Process for the preparation of a catalyst which can be used in hydrotreatment and hydroconversion

Abstract

A process for the preparation of a catalyst from a catalytic precursor comprising a support based on alumina and/or silica-alumina and/or zeolite and comprising at least one element of group VIB and optionally at least one element of group VIII, by impregnation of said precursor with a solution of a C1-C4 dialkyl succinate. An impregnation step for impregnation of said precursor which is dried, calcined or regenerated, with at least one solution containing at least one carboxylic acid other than acetic acid, then maturing and drying at a temperature less than or equal to 200° C., optionally a heat treatment at a temperature lower than 350° C., followed by an impregnation step with a solution containing at least one C1-C4 dialkyl succinate followed by maturing and drying at a temperature less than 200° C. without subsequent calcination step. The catalyst is used in hydrotreatment and/or hydroconversion.

Claims

1. A process for the preparation of a catalyst from a catalytic precursor comprising a support and a hydro-dehydrogenating function, wherein the support is based on alumina and/or silica-alumina and/or zeolite and the hydro-dehydrogenating function comprises at least one element of group VIB and optionally at least one element of group VIII, wherein said catalytic precursor contains the entirety of the hydro-dehydrogenating function elements of Group VIB and the entirety of optional elements of Group VIII, wherein the catalytic precursor contains phosphorus and wherein the catalytic precursor has been dried, calcined or regenerated, said process comprising: 1) a first step of impregnating the catalytic precursor with at least one solution consisting of at least one carboxylic acid other than acetic acid, at least one solvent, optionally acetic acid and optionally phosphorus, then maturing and drying at a temperature lower than 200° C., optionally followed by a heat treatment at a temperature lower than 350° C., to obtain a first-impregnated catalytic precursor, and 2) a second and subsequent step of impregnating the first-impregnated catalytic precursor with a solution consisting of at least one C1-C4 dialkyl succinate, at least one solvent, optionally acetic acid and optionally phosphorus, and then maturing and drying at a temperature lower than 200° C., wherein the first and second steps are conducted separately and without a subsequent calcination step.

2. A process according to claim 1 wherein the catalytic precursor is a catalyst which has been regenerated.

3. A process according to claim 1 wherein the C1-C4 dialkyl succinate is dimethyl succinate.

4. A process according to claim 1 wherein the carboxylic acid is citric acid.

5. A process according to claim 1 wherein the first step and/or second step are performed in the presence of water and/or ethanol as the solvent.

6. A process according to claim 1 wherein the maturing in the first step and/or second step is performed, at a temperature between 17 and 60° C.

7. A process according to claim 1 wherein the drying in the first step is performed at a temperature between 100 and 180° C.

8. A process according to claim 1 wherein the drying in the second step is performed at a temperature between 50 and 160° C.

9. A process according to claim 1 further comprising a final sulfuration step after the second step.

10. A process according to claim 1, wherein the hydro-dehydrogenating function is Mo and either Ni or Co or both Ni and Co.

11. A process according to claim 1, wherein: the hydro-dehydrogenating function is Mo and either Ni or Co or both Ni and Co; the C1-C4 dialkyl succinate is dimethyl succinate; and the carboxylic acid is citric acid.

12. A process according to claim 1, wherein the solution in the second step further contains acetic acid.

13. A process according to claim 1, wherein the support is based on alumina.

14. A process for the preparation of a catalyst from a catalytic precursor comprising a support and a hydro-dehydrogenating function, wherein the support is based on alumina and/or silica-alumina and/or zeolite and the hydro-dehydrogenating function comprises at least one element of group VIB and optionally at least one element of group VIII, wherein said catalytic precursor contains the entirety of the hydro-dehydrogenating function elements of Group VIB and the entirety of optional elements of Group VIII and wherein the catalytic precursor has been dried, calcined or regenerated, said process comprising: 1) a first step of impregnating the catalytic precursor with at least one solution consisting of at least one carboxylic acid other than acetic acid, at least one solvent, phosphorus and optionally acetic acid, then maturing and drying at a temperature lower than 200° C., optionally followed by a heat treatment at a temperature lower than 350° C., to obtain a first-impregnated catalytic precursor, and 2) a second and subsequent step of impregnating the first-impregnated catalytic precursor with a solution consisting of at least one C1-C4 dialkyl succinate, at least one solvent, optionally acetic acid and optionally phosphorus, and then maturing and drying at a temperature lower than 200° C., wherein the first and second steps are conducted separately and without a subsequent calcination step.

15. A process according to claim 14, wherein the catalytic precursor is a catalyst which has been regenerated.

16. A process according to claim 14, wherein the C1-C4 dialkyl succinate is dimethyl succinate.

17. A process according to claim 14, wherein the carboxylic acid is citric acid.

18. A process according to claim 14, wherein the first step and/or second step are performed in the presence of water and/or ethanol as the solvent.

19. A process according to claim 14, wherein the maturing in the first step and/or second step is performed, at a temperature between 17 and 60° C.

20. A process according to claim 14, wherein the drying in the first step is performed at a temperature between 100 and 180° C.

21. A process according to claim 14, wherein the drying in the second step is performed at a temperature between 50 and 160° C.

22. A process according to claim 14, further comprising a final sulfuration step after the second step.

23. A process according to claim 14, wherein the hydro-dehydrogenating function is Mo and either Ni or Co or both Ni and Co.

24. A process according to claim 14, wherein: the hydro-dehydrogenating function is Mo and either Ni or Co or both Ni and Co; the C1-C4 dialkyl succinate is dimethyl succinate; and the carboxylic acid is citric acid.

25. A process according to claim 14, wherein the solution in the second step further contains acetic acid.

26. A process according to claim 14, wherein the support is based on alumina.

27. A process according to claim 14, wherein the catalytic precursor contains phosphorus.

28. A process for the preparation of a catalyst from a catalytic precursor comprising a support and a hydro-dehydrogenating function, wherein the support is based on alumina and/or silica-alumina and/or zeolite and the hydro-dehydrogenating function comprises at least one element of group VIB and optionally at least one element of group VIII, wherein said catalytic precursor contains the entirety of the hydro-dehydrogenating function elements of Group VIB and the entirety of optional elements of Group VIII and wherein the catalytic precursor has been dried, calcined or regenerated, said process comprising: 1) a first step of impregnating the catalytic precursor with at least one solution consisting of at least one carboxylic acid other than acetic acid, at least one solvent, optionally acetic acid and optionally phosphorus, and then maturing and drying at a temperature lower than 200° C., optionally followed by a heat treatment at a temperature lower than 350° C., to obtain a first-impregnated catalytic precursor, and 2) a second and subsequent step of impregnating the first-impregnated catalytic precursor with a solution consisting of at least one C1-C4 dialkyl succinate, phosphorus, at least one solvent and optionally acetic acid, and then maturing and drying at a temperature lower than 200° C., wherein the first and second steps are conducted separately and without a subsequent calcination step.

29. A process according to claim 28, wherein the catalytic precursor is a catalyst which has been regenerated.

30. A process according to claim 28, wherein the C1-C4 dialkyl succinate is dimethyl succinate.

31. A process according to claim 28, wherein the carboxylic acid is citric acid.

32. A process according to claim 28, wherein the first step and/or second step are performed in the presence of water and/or ethanol as the solvent.

33. A process according to claim 28, wherein the maturing in the first step and/or second step is performed, at a temperature between 17 and 60° C.

34. A process according to claim 28, wherein the drying in the first step is performed at a temperature between 100 and 180° C.

35. A process according to claim 28, wherein the drying in the second step is performed at a temperature between 50 and 160° C.

36. A process according to claim 28, further comprising a final sulfuration step after the second step.

37. A process according to claim 28, wherein the hydro-dehydrogenating function is Mo and either Ni or Co or both Ni and Co.

38. A process according to claim 28, wherein: the hydro-dehydrogenating function is Mo and either Ni or Co or both Ni and Co; the dialkyl succinate is dimethyl succinate; and the carboxylic acid is citric acid.

39. A process according to claim 28, wherein the solution in the second step contains acetic acid.

40. A process according to claim 28, wherein the support is based on alumina.

41. A process according to claim 28, wherein the catalytic precursor contains phosphorus.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 represents Raman spectra of materials in accordance with the invention.

EXAMPLES

(2) The following examples demonstrate the considerable gain in activity on the catalysts prepared with the process according to the invention in relation to the catalysts in the prior art and set forth the invention more precisely without however limiting the scope thereof.

Example 1

Preparation of the Catalysts A1, A2 and A3 (not According) and A4 (According)

(3) A matrix composed of ultrafine tabular boehmite or alumina gel marketed by Condéa Chemie GmbH was used. That gel was mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel) then worked for 15 minutes. At the end of that working operation the paste obtained is passed through a die having cylindrical orifices of a diameter equal to 1.6 mm. The extrudates are then dried for one night at 120° C. and then calcined at 600° C. for 2 hours in moist air containing 50 g of water per kg of dry air. That gives support extrudates solely composed of cubic gamma alumina of low crystallinity.

(4) Cobalt, molybdenum and phosphorus are added to the above-described alumina support which is in the extruded form. The impregnation solution is prepared by hot dissolution of molybdenum oxide (24.34 g) and cobalt hydroxide (5.34 g) in the solution of phosphoric acid (7.74 g) in aqueous solution. After dry impregnation the extrudates are left to mature at ambient temperature (20° C.) in a water-saturated atmosphere for a period of 12 hours and then they are dried for one night at 90° C. The dried catalytic precursor A1 is obtained. A fraction of the dried catalyst is then calcined at 450° C. for 2 hours. The calcined catalyst A2 is obtained. The final composition of the catalysts A1 and A2 expressed in the form of oxides is then as follows: MoO.sub.3=22.5±0.2 (% by weight), CoO=4.1±0.1 (% by weight) and P.sub.2O.sub.5=4.0±0.1 (% by weight).

(5) The catalyst A3 is prepared by dry impregnation of the dried precursor A1 with a solution comprising dimethyl succinate and acetic acid which are diluted in water. The intended contents of dimethyl succinate (DMSU) and acetic acid (AA) are respectively 27% by weight and 18% by weight (that is to say AA/Mo=1.9 mol/mol and DMSU/Mo=1.2 mol/mol). After a maturing period of 3 hours in a closed vessel at ambient temperature the catalyst is again dried in a flow of nitrogen (1 NL/g/g) for a period of 1 hour in a cross-flow bed at 140° C.

(6) The catalyst A4 is prepared by dry impregnation of the calcined precursor A2 with a solution of citric acid diluted in water. The intended contents of citric acid (CA) are 10% by weight (that is to say CA/Mo=0.35 mol/mol). After a maturing period of 12 hours in a closed vessel at ambient temperature the catalyst is dried in a flow of nitrogen (1 NL/g/g) for a period of 2 hours in a furnace of the cross-flow bed type at 180° C. The catalyst is then impregnated dry with a solution comprising dimethyl succinate and acetic acid which are diluted in water. The intended contents of dimethyl succinate (DMSU) and acetic acid (AA) are respectively 18% by weight and 17% by weight (that is to say AA/Mo=1.8 mol/mol and DMSU/Mo=0.8 mol/mol). After a maturing period of 3 hours in a closed vessel at ambient temperature the catalyst is again dried in a flow of nitrogen (1 NL/g/g) for a period of 1 hour in a cross-flow bed at 140° C.

Example 2

Preparation of the Regenerated Catalyst B31

(7) The catalyst A3 is loaded into a cross-flow bed unit and sulphurated by a direct distillation diesel with the addition of 2% by weight of dimethyl disulphide. An HDS test on a mixture of direct distillation diesel and a diesel from catalytic cracking is then implemented for 600 hours. After the test the spent catalyst is discharged, collected and washed with toluene under reflux for 12 hours and then separated into two batches. The first batch is regenerated in a controlled combustion furnace while introducing for each temperature stage increasing amounts of oxygen, which makes it possible to limit the exothermy linked to combustion of the coke. The final regeneration stage is at 480° C. The catalyst regenerated in that way is analysed by DRX. The presence of a line at 26° characteristic of the presence of crystallised CoMoO.sub.4 is noted. In addition this catalyst which hereinafter will be referred to as B31 is of a very pronounced bright blue colour.

Example 3

Preparation of the Catalysts C31 and C31bis (not According) from the Regenerated Precursor B31—Implementation with Citric Acid Alone

(8) The catalysts C31 and C31 bis are prepared by dry impregnation of the regenerated catalyst B31 with a solution of citric acid diluted in water. The intended contents of citric acid (CA) are 10% by weight (CA/Mo=0.35 mol/mol). After a maturing period of 12 hours in a closed vessel at ambient temperature the catalyst is divided into 2 batches: the first is dried in a flow of nitrogen (1 NL/g/g) for a period of 2 hours in a furnace of cross-flow bed type at 180° C., resulting in the catalyst C31. The second batch is dried in identical fashion but with a reference temperature of 140° C., resulting in the catalyst C31bis.

Example 4

Preparation of a Catalyst D31 and D31bis (According) from the Regenerated Precursor—Implementation with DMSU

(9) The catalyst D31 is prepared by dry impregnation of the regenerated catalyst C31 with a solution comprising pure dimethyl succinate (DMSU). That amounts to aiming at 32% by weight of dimethyl succinate on the final catalyst (that is to say DMSU/Mo=1.4 mol/mol). After a maturing time of 3 hours in a closed vessel at ambient temperature the catalyst is again dried in a flow of nitrogen (1 NL/g/g) for a period of 1 hour in a cross-flow bed at 140° C.

(10) The catalyst D31bis is prepared by dry impregnation of the regenerated catalyst C31 with a solution comprising pure dimethyl succinate (DMSU). That amounts to aiming at 30% by weight of dimethyl succinate on the final catalyst (that is to say DMSU/Mo=1.3 mol/mol). After a maturing time of 3 hours in a closed vessel at ambient temperature the catalyst is again dried in a flow of nitrogen (1 NL/g/g) for a period of 1 hour in a cross-flow bed at 140° C.

(11) The catalysts D31 and D31bis were analysed by Raman spectroscopy. They both have in particular the main band of Keggin HPA at 990 cm.sup.−1.

Example 5

Preparation of a Regenerated Catalyst E31 and E31bis (According)—Implementation with DMSU and Acetic Acid

(12) The catalyst E31 is prepared by dry impregnation of the regenerated catalyst C31 with a solution comprising dimethyl succinate and acetic acid which are diluted in water. The intended contents of dimethyl succinate (DMSU) and acetic acid (AA) are respectively 18% by weight and 17% by weight (that is to say AA/Mo=1.8 mol/mol and DMSU/Mo=0.8 mol/mol). After a maturing period of 3 hours in a closed vessel at ambient temperature the catalyst is again dried in a flow of nitrogen (1 NL/g/g) for a period of 1 hour in a cross-flow bed at 140° C.

(13) The catalyst E31bis is prepared by dry impregnation of the regenerated catalyst C31 bis with the same solution as for E31, comprising dimethyl succinate and acetic acid which are diluted in water. The intended contents of dimethyl succinate (DMSU) and acetic acid (AA) are respectively 17% by weight and 17% by weight (that is to say AA/Mo=1.8 mol/mol and DMSU/Mo=0.7 mol/mol). After a maturing period of 3 hours in a closed vessel at ambient temperature the catalyst is again dried in a flow of nitrogen (1 NL/g/g) for a period of 1 hour in a cross-flow bed at 140° C.

(14) The catalysts E31 and E31bis were analysed by Raman spectroscopy. They have in particular the main band of the Keggin HPA at 990 cm.sup.−1, but also a shoulder at 850 cm.sup.−1 characteristic of dimethyl succinate (FIG. 1).

Example 6

Preparation of a Regenerated Catalyst F31 (not According)—Implementation in One Step

(15) The catalyst F31 is prepared by dry impregnation of the regenerated catalyst B31 with a solution comprising dimethyl succinate, citric acid and acetic acid which are diluted in water. The intended contents of citric acid (CA), dimethyl succinate (DMSU) and acetic acid (AA) are respectively 10% by weight, 18% by weight and 17% by weight (that is to say CA/Mo=0.3 mol/mol, DMSU/Mo=0.8 mol/mol and AA/Mo=1.8 mol/mol). After a maturing period of 12 hours in a closed vessel at ambient temperature the catalyst is again dried in a flow of nitrogen (1 NL/g/g) for a period of 2 hours in a cross-flow bed at 160° C.

Example 7

Comparative Test of Catalysts A1, A2, A3, A4, B31, C31, C31bis, D31, D31bis, E31, E31 bis, F31 in Hydrogenation of Toluene in Cyclohexane Under Pressure and in the Presence of Hydrogen Sulphide

(16) The above-described catalysts are sulphurated in situ in a dynamic process in a tubular reactor with a fixed cross-flow bed of a pilot unit of Microcat type (manufacturer: Vinci), the fluids circulating in a downward direction. The hydrogenating activity measurements are made immediately after sulphuration under pressure and without decompression air venting with the hydrocarbons charge which served to sulphurate the catalysts.

(17) The sulphuration and test charge is composed of 5.8% of dimethyl disulphide (DMDS), 20% of toluene and 74.2% of cyclohexane (by weight).

(18) Sulphuration is effected from ambient temperature to 350° C. with a temperature ramp of 2° C./min, an HSV=4 h.sup.−1 and H.sub.2/HC=450 NL/L. The catalytic test is effected at 350° C. at an HSV=2 h.sup.−1 and H.sub.2/HC equivalent to that of the sulphuration process, with a minimum sampling of 4 compositions which are analysed by gaseous phase chromatography.

(19) This therefore provides for measuring the stabilised catalytic activities of equal volumes of catalysts in the toluene hydrogenation reaction.

(20) The detailed operating conditions under which the activity measurements are implemented are as follows: Total pressure: 6.0 MPa Toluene pressure: 0.37 MPa Cyclohexane pressure: 1.42 MPa Methane pressure: 0.22 MPa Hydrogen pressure: 3.68 MPa H.sub.2S pressure: 0.22 MPa Catalyst volume: 4 cm.sup.3 (extrudates of a length of between 2 and 4 mm) Hour space velocity: 2 h.sup.− Sulphuration and test temperature: 350° C.

(21) Samples of the liquid effluent are analysed by gaseous phase chromatography. Determining the molar concentrations of unconverted toluene (T) and the concentrations in respect of its hydrogenation products (methyl cyclohexane (MCC6), ethyl cyclopentane (EtCC5) and dimethyl cyclopentanes (DMCC5)) make it possible to calculate a toluene hydrogenation rate X.sub.HYD defined by:

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

(23) The toluene hydrogenation reaction being of an order 1 under the test conditions used and the reactor behaving like an ideal plug flow reactor, the hydrogenating activity A.sub.HYD of the catalysts is calculated by applying the formula:

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

(25) Table 1 compares the relative hydrogenating activities, that is to say which are equal to the ratio of the activity of the catalyst to the activity of the catalyst B2 (not according) taken as a reference (activity 100%) for all the catalysts prepared here.

(26) The results of the tests are set out in Table 1.

(27) Table 1 shows that the additived catalysts D31 and E31 (according to the invention) prepared by the addition respectively of 32% by weight of dimethyl succinate (DMSU) and 18% by weight of dimethyl succinate (DMSU) plus 10% by weight of acetic acid to the catalyst C31 itself prepared by the addition of 10% by weight of citric acid (CA) to the catalyst B1 enjoy improved activity in relation to the starting catalyst of 52 and 62% respectively.

(28) In comparative terms the catalysts which are not according to the invention C31 (CA alone) or F31 (simultaneous impregnation of CA, DMSU and AA) have respective gains in activity of 38 and 40%.

(29) A reduction in the heat treatment temperature after the citric acid impregnation step leads to catalysts D31bis and E31bis(according to the invention) with levels of activity similar to or slightly less than D31 and E31 respectively. Those catalysts have in particular activities greater by 10% and 17% than the catalyst F31 impregnated in a single step.

(30) Impregnation in two steps of a carboxylic acid then a dialkyl succinate is also advantageous on a calcined precursor, as is testified by the performances of the catalyst A4.

(31) TABLE-US-00001 TABLE 1 Relative hydrogenating activities with respect to the calcined catalyst A2 (not according) Type Amount of Impregnation Amount of acid of organic organic additive number Relative A.sub.HYD (% by wt with respect additive (% by wt with respect (acid and/or with respect Catalyst Type of acid to the final catalyst) (step 2) to the final catalyst) additive) to A2 (%) A1 (dried, not according) — — — — — 95 A2 (calcined, not according) — — — — — 100 A3 (dried, not according) AA 18 DMSU 27 1 170 A4 (calcined, according) CA(step1) + CA = 10; AA = 17 DMSU 18 2 167 AA(step2) B31 regenerated —  0 —  0 — 110 (not according) C31 (not according) CA 10 — — 1 148 C31bis (not according) CA 10 — — 1 151 D31 (according) CA 10 DMSU 32 2 162 D31 bis (according) AC 10 DMSU 32 2 160 E31 (according) CA(step1) + CA = 10; AA = 17 DMSU 18 2 172 AA(step2) E31bis (according) CA(step1) + CA = 10; AA = 17 DMSU 17 2 167 AA(step2) F31 (not according) CA + AA CA = 10; AA = 17 DMSU 18 1 150

Example 8

Comparative Test of the Catalysts A2, A3, B31, C31, C31bis, E31, E31bis, F31, in Respect of Diesel HDS

(32) The above-described catalysts are sulphurated in situ in a dynamic process in a tubular reactor with a fixed cross-flow bed of a pilot unit of Microcat type (manufacturer: Vinci), the fluids circulating in a downward direction. The activity measurements are made immediately after sulphuration under pressure and without decompression air venting with a direct distillation diesel.

(33) The sulphuration charge is composed of 2% of dimethyl disulphide (DMDS) added to a direct distillation diesel. Sulphuration is effected from ambient temperature to 350° C. A 12 hour stage at 350° C. is observed for that.

(34) The catalytic test is effected at three temperatures: chronologically 330-335-340° C. at HSV=1 h.sup.−1 and H.sub.2/HC of 450 NI/I, with sampling of liquid compositions every 24 hours. When the sulphur contents in the compositions are stable the temperature is changed. The test lasts about 400-450 hours in total.

(35) The sulphur in the effluents is analysed by FX. By tracing the variation in the sulphur content in the effluents in dependence on temperature it is possible to measure the relative differences in temperatures between catalysts. The choice here is to put a figure on the differences in performance in degrees Celsius at 50 ppm: noted as T.sub.50-HDS. Table 2 compares the activities in relation to the activity of the catalyst A2 (not according) taken as a base. For a sulphur content in the effluent of 50 ppm the catalysts having a temperature lower than that of the base catalyst are more active.

(36) The attraction of the sequential introduction of the carboxylic acids and succinates is confirmed. E31 and E31bis prepared according to the invention thus make it possible to improve the activity of the regenerated catalyst B31 by 5 and 6° C. respectively while impregnation of citric acid alone C31 (or C31bis) makes it possible to gain only 2° C. (or 3° C.) and simultaneous impregnation of the mixture DMSU, CA, AA makes it possible to gain only 3° C.

(37) TABLE-US-00002 TABLE 2 Relative HDS activities with respect to the calcined catalyst A2 (not according) Type Amount of Amount of acid of organic organic additive (% by wt with respect additive (% by wt with respect Impregnation number T.sub.50-HDS Catalyst Type of acid to the final catalyst) (step 2) to the final catalyst) (acid and/or additive) (° C.) A2 (calcined, not — — — — — base according) A3 (dried, not according) AA 18 DMSU 27 1 base - 6 B31 Regenerated —  0 —  0 — base - 1 (not according) C31 (not according) CA 10 — — 1 base - 3 C31bis (not according) CA 10 — — 1 base - 4 E31 (according) CA(step1) + CA = 10; AA = 17 DMSU 18 2 base - 7 AA(step2) E31bis (according) CA(step1) + CA = 10; AA = 17 DMSU 17 2 base - 6 AA(step2) F31 (not according) CA + AA 10 + 17 DMSU 18 1 base - 4

(38) Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

(39) In the foregoing and in the examples, all temperatures are set forth uncorrected in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.

(40) The entire disclosures of all applications, patents and publications, cited herein and of corresponding French application Ser. No. 11/04.026, filed Dec. 22, 2011, are incorporated by reference herein.

(41) The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

(42) From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.