hydrotreating catalyst comprising metals of groups viii and vib and preparation with acetic acid and

专利摘要:
invention patent: catalyst usable in hydrotreatment, comprising metals from groups vii and vib and preparation with acetic acid and c1-c4 dialkyl succinate. the present invention relates to a charalizer usable in hydrotreatment processes, which comprises an amorphous support based on alumina, phosphorus, a c1-c4 dialkyl succinate, acetic acid and a hydro-dehydrogenating function, comprising at least one element of group vii and at least one element of group vib, preferably constituted of cobalt and molybdenum, catalyst whose raman spectrum comprises the most intense bands characteristic of keggin heteropolyanions (947 and / or 990 cm ^ -1 ^), of dialkyl succinate c1-c4 and acetic acid (896 cm ^ -1 ^). preferably, the dialkyl succinate referred to is dimethyl succinate and its main range is 853 cm ^ -1 ^. the invention also relates to the process of preparing this catalyst, in which a catalytic precursor comprising the elements of the vib group and the viii group, in particular the molybdenum-cobalt pair, and phosphorus, introduced by impregnation, then dried at a temperature below 180 ° c, it is impregnated with c1-c4 dialkyl succinate, acetic acid and the phosphorus compound, if it has not been introduced in full beforehand, then, after maturation, it is dried at a temperature below 180 ° c before possibly be sulfurised. the invention also relates to the use of this catalyst in any hydrotreating process.
公开号:BR112012014687B1
申请号:R112012014687
申请日:2010-12-08
公开日:2018-05-08
发明作者:Bonduelle Audrey；Hugon Antoine；Guichard Bertrand；Marchand Karin；Digne Mathieu；Rebeilleau Michael；Lopez Sylvie
申请人:Ifp Energies Now；Total Raffinage Marketing；
IPC主号:

专利说明:

(54) Title: CATALYST USABLE IN HYDRO TREATMENT, UNDERSTANDING METALS OF GROUPS VIII AND VIB AND PREPARATION WITH ACETIC ACID AND DIALKYL SUCCINATE Cl C4 (51) Int.CI .: B01J 23/882; B01J 27/19; C10G 45/08; B01J 23/28; B01J 23/75; B01J 27/14; B01J 37/02 (30) Unionist Priority: 12/16/2009 FR 09 06103, 12/16/2009 FR 09 06101 (73) Holder (s): IFP ENERGIES NOUVELLES. TOTAL RAFFINAGE MARKETING (72) Inventor (s): KARIN MARCHAND; BERTRAND GUICHARD; MATHIEU DIGNE; MICHAEL REBEILLEAU; SYLVIE LOPEZ; ANTOINE HUGON; AUDREY BONDUELLE
1/48
Descriptive Report of the Invention Patent for CATALYST USEFUL IN HYDRO TREATMENT, UNDERSTANDING METALS OF GROUPS VIII AND VIB AND PREPARATION WITH ACETIC ACID AND DIALKYL SUCCINATE C1-C4.
The present invention relates to a catalyst, the respective method of preparation, and the respective use in the field of hydrotreatments.
Usually, a hydrocarbon cutting hydrotreating catalyst aims to eliminate the sulfur or nitrogen compounds contained therein, in order to place, for example, a petroleum product in the required specifications (sulfur content, aromatics content, etc ...) for a specific application (car fuel, gasoline or fuel oil, household fuel), carbon reactor). It may also be a question of pretreating that load, in order to eliminate impurities, before causing it to undergo different transformation processes to modify its physical-chemical properties, such as, for example, refining, hydrocracking of vacuum distillates, catalytic cracking, hydroconversion of atmospheric residues or vacuum. The composition and use of hydro-treatment catalysts are particularly well described in the article by B.S. Clausen, H.T. Topsoe, and FR.E. Massoth, from Catalysis, Science and Technology, volume 11 (1996), Springer-Verlag. After sulfurization, several surface species are present on the support, which do not all perform well for the desired reactions. These species are particularly well described in the publication by Topsoe, et al., Published in number 26 of the 1984 Catalusis Review Science and Engineering, pages 395 - 420.
The tightening of automobile pollution standards in the European community (Official Journal of the European Union, L76, March 22, 2003, Directive 2003/70 / EC, pages 76/10-L76 / 19) has led refiners to greatly reduce the content of sulfur in diesel and in gasoline fuels (less than 10 parts per million by weight (ppm) of sulfur on 1 January 2009 ^0, 50 ppm against January 1, 2005). On the other hand, the refined2 / 48 res are forced to use loads that are increasingly refractory to hydrotreating processes, on the one hand, because the crude are increasingly heavier and therefore contain more impurities, on the other hand , due to the increase in conversion processes at refineries. In effect, they generate cuts that are more difficult to hydrate than cuts directly from atmospheric distillation. As an example, we can mention cutting fuel oil from catalytic cracking, also called LCO (Light Cycle Oil) with reference to the respective high content of aromatic compounds. These cuts are co-treated with the cutting of fuel oil from atmospheric distillation; they need catalysts that have improved hydrodesulfurizing and hydrogenating functions compared to traditional catalysts, in order to decrease the aromatic content to obtain a density and a cetane number according to specifications.
In addition, conversion processes such as short circuit or hydrocracking use catalysts that have an acidic function, which makes them particularly sensitive to the presence of nitrogenous impurities, and particularly the basic nitrogenous compounds. Therefore, it is necessary to use pre-treatment catalysts for these loads, in order to remove these compounds. This hydrotreating catalyst also requires an improved hydrogenation function as the first hydrodesnitrogenation step is recognized as a hydrogenation step of the aromatic cycle adjacent to the C-N bond.
It therefore appears as interesting to find ways of preparing hydrotreating catalysts, in order to obtain new catalysts with improved performances.
The addition of an organic component over hydrotreating catalysts to improve their activity is then well known to the technician. Numerous patents protect the use of different ranges of organic compounds, such as the etherified mono, di or polyalcohols (WO96 / 41848, WO01 / 76741, US4012340, US3954673, EP601722). Catalysts modified with C2-C14 monoesters are
3/48 described in patent applications EP 466568 and EP 1046424, however, these modifications do not always allow a sufficient increase in the performance of the catalyst in view of the specifications relating to the sulfur content of fuels, which continue to become increasingly problematic for refiners .
To prevent this, Total's patent W02006 / 077326 proposes the use of a catalyst comprising metals of the VIB and VIII groups, a refractory oxide as support, and an organic compound, comprising at least 2 carboxylic ester functions of formula R1-O- CO-R2CO-O-R1 or R1-O-CO-R2-O-CO-R1, in which each R1 independently represents a C1 to C18 alkyl group, C2 to C18 alkenyl, C6 to C18 aryl, C3 alkyl cycle to C8, alkyl aryl or aralkyl in C7 to C20, or the 2 groups R1 together form a divalent group in C2 to C18, and R2 represents an alkylene group in C1 to C18, arylene in C6 to C18, alkylene cycle in C3 to C7 , or a combination thereof, the carbon chain of the hydrocarbon groups represented processing R1 and R2 may contain or carry one or more heteroatoms chosen from N, C and O, and each of the groups R1 and R2 may carry one or more substituents of formula - C (= O) O-R1 or -OC (= O) -R1 in which R1 has the meaning indicated above. A preferred method uses the C1-C4 dialkyl succinate, and in particular, the dimethyl succinate which is exemplified. These compounds can be introduced in the presence of a solvent (an important list of solvents is cited) or a carboxylic acid. Among the three dozen acids mentioned above, there is acetic acid, but it is not mentioned among a dozen preferred acids. It will be noted since then that citric acid is preferred.
The process of preparing the catalyst, as described in patent W02006 / 077326, comprises heat treatment maturation stages that can last up to several days, for example, from 49 to 115 days, which would greatly limit the production of these catalysts and would therefore require , providing improvements.
Other patents in the prior art describe an gain in activity linked to the combined use of an organic acid or an alcohol over a hydrotreating catalyst. Thus, the patent application published under No. JP1995-136523 by KK Japan Energy proposes a solution consisting of:
- to prepare according to a first preferred mode of the invention a solution containing a catalyst support, one or more metals of group Vi of the periodic table of elements, and of group VIII, an organic acid. According to a second preferred mode of the invention, that solution also comprises a phosphorus precursor;
- a heat treatment carried out between 200 and 400 ° C;
- an impregnation of the catalyst obtained previously by an organic acid or an alcohol in a proportion of 0.1 to 2 per mol of metals.
One of the preferred modes of the invention then comprises drying at a temperature below 200 ° C, while a second preferred method comprises a final heat treatment at a temperature greater than or equal to 400 ° C.
It was found that these catalysts do not have enough activity to meet the new environmental standards in view of the increasingly hydrogen-poor loads that refineries have.
Likewise, the patent W02005 / 035691 claims an activation process that schematically reduces the content in crystallized phase of type CoMoO ₄ present on the regenerated catalysts, comprising metal oxides of groups VIII and VIB, a process that includes the placement in contact of the regenerated catalyst with an acid and an organic additive. For this, the use of the citric acid (CA) and polyethylene glycol (PEG) combination was carried out on regenerated catalyst in numerous examples.
The present invention relates to a catalyst and the respective preparation process, the catalyst being usable for hydrotreating and allowing an improvement in the catalytic performances (notably of the catalytic activity) in relation to the catalysts of the prior art. Indeed, it has been shown that the use of the C1-C4 dialkyl succinate pair, and, in particular, of dimethyl, and acetic acid on a dried catalytic precursor, leads, surprisingly, to a markedly improved catalytic activity. in relation to each of the compounds in the pair.
More precisely, the invention relates to a catalyst comprising an amorphous support based on alumina, phosphorus, at least one C1-C4 dialkyl succinate, acetic acid and a hydrodehydrogenating function, comprising at least one element of group VIII and at least one element of the VIB group, a catalyst whose Raman spectrum comprises the 990 and / or 974 cm ' ¹ bands, characteristic of this succinate and the main band at 896 cm' ¹ , characteristic of acetic acid. The hydrodehydrogenating function is preferably composed of cobalt and molybdenum. It can also comprise at least one element of the group VIII and at least one element of the group VIB with the exception of the hydrodehydrogenating function constituted by cobalt and molybdenum.
The catalyst obtained has a characteristic Raman spectrum grouping:
1) characteristic bands of the Keggin heteropolyanions or PXYnO ₄₀ ^x 'and / or PYi2O ₄₀ ^x in which Y is a group VIB metal and X is a group VIII metal.
From Griboval, Blanchard, Payen, Forunier, Dubois in Catalysis Today 45 (1998) 277 fig. 3 e), the main strips of the PCoMoiiO ₄₀ ^x 'structure are over the catalyst dried at 232, 366, 943, 974 cm' ¹ and from MT Pope Heteropoly and Isopoly oxometalates, Springer Verlag, p.8, these strips are not they are characteristic of the nature of the X or Y atom, but rather of the estrutura structure. The most intense range of lacunar Keggin's HPA type is found at 974 cm-1.
From Griboval, Blanchard, Payen, Forunier, Dubois Bernard, Jornal de Catalysis 188 (1999) 102, fig. 1a), the main bands of PMoi ₂ O ₄₀ ^x 'are in the mass state of HPA, for example, with cobalt in counterion at 251, 603, 902, 970, 990 cm' ¹ .The most intense band of this HPA of Keggin is located at 990 cm ' ¹ . MTPope Heteropoly
6/48 and Isopoly oxometalates, Springer Verlag, p.8 ,. it also teaches us that these bands are not characteristic of the nature of the X or Y atom, but rather of the structure of Keggin's HPA, complete, gap or substituted;
2) characteristic bands of the dialkyl succinate (s) used. The Raman spectrum of dimethyl succinate is a unique impression of this molecule. In the spectral zone 300-1800 cm ' ¹ , this spectrum is characterized by the following series of bands (only the most intense bands are reported in cm' ¹ ): 391, 853 (the most intense band), 924, 964, 1739 cm ' ¹ . The spectrum of diethyl succinate comprises the following main bands in the spectral zone: 861 (most intense band), 1101, 1117 cm ' ¹ . Likewise for dibutyl succinate: 843, 1123, 1303, 1439, 1463 cm ¹ and diisopropyl succinate: 833, 876, 1149, 1185, 14.69 (most intense range), 1733 cm '¹;
3) the characteristic bands of acetic acid, the main ones being: 448, 623, 896 cm-1. The most intense band is 896 cm ¹ .
The exact position of the bands, the respective forms and the respective relative intensities can vary to a certain extent depending on the conditions of recording of the spectrum, remaining characteristics of this molecule. The Raman spectra of organic compounds are, on the other hand, well documented, whether on the basis of Raman spectrum fingers (see, for example, Spectral Database for Organic Compounds, HTTP: // riob01 .ibase.aist.go.ip / sdbs / cgibin / direct frame top.cgi), or by the product suppliers (see, for example, www.sigmaldrich.com).
Raman spectra were obtained with a dispersive Raman spectrometer equipped with an ionized argon laser (514 nm). The laser beam is focused on the sample with the aid of a microscope equipped with a long distance working x50 objective. The laser power at the sample level is in the order of 1 mW. The Raman signal emitted by the sample is collected by the same objective and is dispersed as an aid of a 1800 rpm network, then collected by a CCD detector. The spectral resolution obtained is of the order of 0.5 cm ' ¹ . The registered spectral zone is between 300 and 1800 cm ¹ . The acquisition duration was fixed at 120 s
7/48 for each registered Raman spectrum.
Preferably, the dialkyl succinate used is dimethyl succinate, and the catalyst has in its spectrum the main Raman bands in 990 and / or 974 cm ' ¹ characteristic (s) of the Keggin heteropoly (s), and 853 cm ' ¹ characteristic of dimethyl succinate and 896 cm ¹ characteristic of acetic acid.
Preferably, the catalyst of the invention comprises a support consisting of alumina or silica-alumina.
The catalyst according to the invention can also comprise boron and / or fluorine and / or silicon.
Also described in the case described is a process for preparing the catalyst, according to the invention, which comprises at least one step of impregnating a catalytic precursor dried at a temperature below 180 ° C, containing at least one phosphorus and a hydro-function. dehydrogenating agent, as well as an amorphous support, by an impregnation solution, comprising the combination of acetic acid and C1C4 dialkyl succinate, followed by a maturation step of this impregnated catalytic precursor, then a drying step at a temperature below 180 ° C , without subsequent calcination step (heat treatment under air); the catalyst obtained is preferably subjected to a sulfuration step.
The hydrodehydrogenating function comprises at least one element of group VIII and at least one element of group VIB. Preferably, the hydrodehydrogenating function consists of cobalt and molybdenum.
The simple and quick preparation process, with unit steps that do not exceed a few hours, thus allows better productivity on an industrial scale than the processes present in the prior art.
More precisely, the process of preparing a hydrotreating catalyst, according to the invention, comprises the following successive steps that will be detailed in the sequence:
a) at least one step of impregnating an amorphous support based on alumina with at least one solution containing the elements of the hydrodehydrogenating function and phosphorus; will be called the product obtained
8/48 catalytic precursor;
b) drying at a temperature below 180 ° C without subsequent calcination; the product obtained will be called dried catalytic precursor;
c) at least one impregnation step with an impregnation solution comprising at least one C1-C4 dialkyl succinate, acetic acid and at least one phosphorus compound, if this has not been introduced in full in step a); it will be called the product obtained impregnated dried catalytic precursor;
d) a maturation stage;
e) a drying step at a temperature below 180 ° C, without a subsequent calcination step; the product obtained will be called a catalyst.
Preferably, the product obtained from step e) goes through a step f) of sulfuration.
As will be described later, the process, according to the invention, is carried out, preferably, with the following modes considered alone or in combination: the support consists of alumina or silica alumina; the totality of the hydrogenating function is introduced, when in step a); the totality of the phosphorus is introduced during step a); dialkyl succinate is dimethyl succinate; step c) is carried out in the absence of solvent; step d) is carried out at a temperature of 17 to 50 ° C; step c) is carried out at a temperature between 80 and 160 ° C.
Most preferably, the process according to the invention comprises the following successive steps:
a) at least one step of dry impregnation of that support with a solution containing all the elements of the hydrodeshydrogenating function, and all of the phosphorus;
b) drying at a temperature between 75 and 130 ° C without subsequent calcination;
c) at least one dry impregnation step with an impregnation solution, comprising dimethyl succinate and acetic acid;
9/48
d) a maturation stage at 17-50 ° C;
e) a drying step, preferably under nitrogen, at a temperature between 80 and 160 ° C, without a subsequent calcination step.
The catalytic precursor containing the hydrodeshydrogenating function and an amorphous support based on alumina, as well as its method of preparation are described below.
This catalytic precursor obtained at the end of step a) of the process, according to the invention, can be prepared for a large part carrying all the methods well known to the skilled person.
This catalytic precursor contains a hydrodehydrogenating function and contains phosphorus and / or boron and / or fluorine, as a dopant, as well as an amorphous support. The hydrodehydrogenating function comprises at least one element of the VIB group and at least one element of the VIII group. Preferably, the hydrodehydrogenating function consists of cobalt and molybdenum.
The amorphous support of this catalytic precursor is based on alumina, that is, it contains more than 50% of alumina and, in general, it contains only alumina or silica-alumina, as defined below, and eventually the metal (s) ( (s) and / or the dopant (s) that were (were) introduced (s) outside the impregnations (introduced (for example) during preparation - malaxação, peptização ... of the support or its formation). The support is obtained after forming (extrusion, for example) and calcination, generally between 300600 ° C.
Preferably, the support consists of alumina, and preferably extruded alumina. Preferably, alumina is gamma alumina and, preferably, this amorphous support is comprised of gamma alumina.
In another preferred case, it is a silica-alumina containing at least 50% alumina. The silica content in the support is a maximum of 50% by weight, more often less than or equal to 45% by weight, preferably less than or equal to 40%.
Silicon sources are well known to the person skilled in the art. You can
10/48 mention, for example, silicic acid, silica in powder form or in colloidal form (silica soil), tetraethyl orthosilicate Si (OEt) ₄ .
The hydrodehydrogenating function of this catalytic precursor is ensured by at least one element of the VIB group and by at least one element of the VIB group and by at least one element of the VIII group. The pair consisting of cobalt and molybdenum is preferred. The total content of hydrodeshydrogenating elements is advantageously greater than 6% by weight in relation to the total weight of the catalyst. The preferred elements of the VIB group are molybdenum and tungsten, and generally molybdenum. The preferred group VIII elements are non-noble elements and, in particular, cobalt and nickel.
Advantageously, the hydrogenating function is chosen from the group formed by the combinations of the elements cobalt-molybdenum, nickel-molybdenum, or nickel-cobalt-molybdenum, or nickel-molybdenum-tungsten.
In the event that an important activity in hydrodesulfurization, or in hydrodesnitrogenation and aromatics hydrogenation is desired, the hydrodeshydrogenating function is advantageously ensured by the combination of nickel and molybdenum; a combination of nickel and tungsten in the presence of molybdenum can also be advantageous. In the case of vacuum distilled or heavier fillers, combinations of the cobalt-nickel-molybdenum type can be advantageously used.
Molybdenum precursors that can be used are also well known to the person skilled in the art. For example, among the sources of molybdenum, oxides and hydroxides, molybdic acids and their salts, in particular, ammonium salts, such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid (H3PM012O40 ) and its salts, and eventually the silico-molybdic acid (H4S1M012O40) and the salts. Molybdenum sources can also be any heteropolic compound of the Keggin type, lacunar Keggin, substituted Keggin, Dawson, Anderson, Strandberg, for example. Preferably, 0 molybdenum trioxide and heteropoly compounds (hetero polyanions) of the type Strandberg, Keggin ,, Keggin
11/48 gap, or Keggin replaced.
The tungsten precursors that can be used are also known to the person skilled in the art. For example, among the sources of tungsten, oxides and hydroxides, tungstic acids and their salts can be used, in particular, ammonium salts, such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and its salts, and possibly silicotungstic acid (H4S1W12O40) and salts. The tungsten sources can also be any heteropolic compound of the Keggin type, lacunar Keggin, substituted Keggin, Dawson, for example ,. Preferably, ammonium oxides and salts are used, such as ammonium metatungstate or Keggin, lacunar Keggin or substituted Keggin heteropolyanions.
The amount of precursor (s) of element (s) of the VIB group is advantageously comprised between 5 and 40% by weight of oxides of the VIB group in relation to the total mass of the catalytic precursor, preferably between 8 and 35% by weight and of most preferably between 10 and 30% by weight.
The group VIII element (s) precursors that can be used are advantageously chosen from oxides, hydroxides, hydroxide carbonates, carbonates and nitrates, for example nickel hydroxide carbonate, cobalt carbonate or hydroxide cobalt are used in a preferred manner.
The amount of group VIII element precursor (s) is advantageously between 1 and 10% by weight of group VIII oxides in relation to the total mass of the catalytic precursor, preferably between 1.5 and 9% by weight and most preferably, between 2 and 8% by weight.
The hydrodehydrogenating function of this catalytic precursor can be introduced into the catalyst at different levels of the preparation and in different ways. This hydrodehydrogenating function is always introduced, at least in part and, preferably in full, by impregnating the shaped support. It can also be introduced in part when forming this amorphous support.
In the case where the hydrodehydrogenating function is introduced in part, when forming this amorphous support, it can be introduced in part (for example, at most 10% of element (s) of the VIB group, for example, introduced by malaxagem) only at the moment of malaxamento with an alumina gel chosen as matrix, the rest of the hydrogenating element (s) being then introduced later. Preferably, when the hydrodehydrogenating function is introduced in part at the time of packing, the proportion of element (s) of the VIB group introduced during this step is less than 5% of the total amount of element (s) of the VIB group introduced over the final catalyst. Preferably, at least one element (or all) of the VIB group is introduced at the same time as at least one element (or all) of the group VIII, regardless of the mode of introduction. These methods and quantities for the introduction of the elements are used notably in the case where the hydrodehydrogenating function consists of CoMo.
In the case where the hydrodehydrogenating function is introduced at least in part and, preferably, in full, after the formation of this amorphous support, the introduction of this hydrodehydrating function on the amorphous support can be advantageously carried out by one or more impregnations in excess of solution on the shaped and calcined support, or, preferably, by one or more dry impregnations and, preferably, by a dry impregnation of this shaped and calcined support, with the aid of solutions containing the metal precursor salts. Most preferably, the hydrodehydrogenating function is introduced in its entirety after the formation of this amorphous support, by a dry impregnation of that support with the aid of an impregnation solution, containing the metal precursor salts. The introduction of this hydrodehydrogenating function can also be advantageously carried out by one or more impregnations of the shaped and calcined support, carrying a solution of the precursor (s) of the active phase. In the event that the elements are introduced into various impregnations of the corresponding precursor salts, an intermediate drying step of the catalyst is generally carried out at a temperature between 50 and 180 ° C, preferably between 60 and 150 ° C and, most preferably between 75 and 130 ° C.
13/48
Phosphorus is also introduced into the catalyst. Another catalyst dopant can also be introduced, which is chosen from boron, fluorine alone or in mixture. The dopant is an added element, which itself does not have a catalytic character, but which increases the catalytic activity of the metal (s).
This dopant can advantageously be introduced alone or in admixture with at least one of the elements of the hydrodehydrogenating function
It can also be entered from the support synthesis.
It can also be introduced just before or after the peptization of the chosen matrix, such as, for example, and preferably the aluminum oxide hydroxide (bohemite) precursor to alumina.
This dopant can also be advantageously introduced in mixture with the precursor (s) of the hydrodeshydrogenating function, in whole or in part, on the shaped amorphous support, preferably alumina or silica-alumina in extruded form, by impregnation at dry of this amorphous support as aid of a solution containing the precursor salts of the metals and the precusor (s) of the dopant (s).
The source of boron can be boric acid, preferably H3BO3 ortho-boric acid, ammonium biborate or pentaborate, boron oxide, boric esters. Boron can be introduced, for example, by a solution of boric acid in a water / alcohol mixture or in a water / ethanol amine mixture.
The preferred phosphorus source is orthophosphoric acid H ₃ PO ₄ , but its salts and esters such as ammonium phosphates are convenient as well. The phosphorus can also be introduced at the same time as the element (s) of the VIB group in the form of Keggin heteropolyanions, lacunar Keggin, substituted Keggin or Strandberg type.
The sources of fluorine that can be used are well known to the person skilled in the art. For example, fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. In the latter case, the
14/48 salt is advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid. Fluorine can be introduced, for example, by impregnating an aqueous solution of hydrofluoric acid, or ammonium fluoride or ammonium bifluoride.
The dopant is advantageously introduced into the catalytic precursor in an amount of oxide of that dopant in relation to the catalyst:
- comprised between 0 and 40%, preferably between 0 and 30% and even more preferably between 0 and 20%, preferably between 0 and 15% and even more preferably between 0 and 10%, when that dope is boron; when boron is present, preferably the minimum amount is 0.1% by weight;
- comprised between 0.1 to 20%, preferably between 0.1 and 15% and even more preferably between 0.1 and 10% by weight, when that dopant is phosphorus,
- between 0 and 20%, preferably between 0 and 15% and, even more preferably, between 0 and 10%, when that dopant is fluorine; when fluorine is present, preferably the minimum amount is 0.1% by weight.
Phosphorus is always present. It is introduced at least in part (and preferably in whole) by impregnation over the catalytic precursor, in step a) and eventually over the dried catalytic precursor in step c). Preferably, the same is true for the other dopants. However, as previously mentioned, dopants can be introduced partly when preparing the substrate (understood formation) or in full (with the exception of phosphorus).
The introduction of this hydrodehydrogenating function and possibly a dopant in or on the formed calcined support is then advantageously followed by a drying step b) during which the solvent of the metal salts precursor to the metal oxide (s) ( is) (solvent which is generally water) is eliminated, at a temperature between 50 and 180 ° C, preferably between 60 and 150 ° C or still between 65 and 145 ° C, and most preferably between 70 and 140 ° C or between 75 and
15/48
130 ° C. The drying step of the dried catalytic precursor thus obtained is never followed by a step of calcination under air at a temperature above 200 ° C. Advantageously, it operates in these temperature ranges at a maximum temperature of 150 ° C, and without subsequent calcination at a temperature above 180 ° C.
Preferably, in step a) of the procedure, according to the invention, that catalytic precursor is obtained by dry impregnation of a solution comprising one (a) precursor (s) of the hydrodeshydrogenating function, and of phosphorus on an amorphous support to shaped calcined alumina base, followed by drying at a temperature below 180 ° C, preferably between 50 and 180 ° C, preferably between 60 and 150 ° C and most preferably between 75 and 130 ° Ç.
A dried catalytic precursor is thus obtained at the end of step b) It is possible in step a) of the process, according to the invention, to prepare an impregnation solution containing at least one dopant chosen from boron, fluorine, considered alone or in combination. mixture.,
Even more preferably, the catalytic precursor in step a) of the process, according to the invention, is prepared with an impregnation solution containing at least one precursor of each element of the hydrodehydrogenating function, in the presence of a phosphorus precursor, the amorphous support consisting of alumina or silica alumina.
According to step c) of the process, according to the invention, that dried catalytic precursor is impregnated by an impregnation solution, comprising at least one C1-C4 dialkyl succinate (and, in particular, dimethyl succinate) and acid acetic.
These compounds are advantageously introduced into the impregnation solution of step c) of the process, according to the invention, in a corresponding amount:
- a molar ratio of dialkyl succinate (for example dimethyl) per GVIB element (s) impregnated with the catalytic precursor between 0.15 to 2 moles / mol, preferably between 0.3
16/48 to 1.8 mmol / mol, preferably comprised between 0.5 and 1.5 moles / mol and most preferably comprised between 0.8 and 1.2 moles / mol; and
- an acetic acid molar ratio per element (s) of the GVIB impregnated with the catalytic precursor between 0.1 to 5 moles / mol, preferably between 0.5 to 4 moles / mol, preferably between 1.3 and 3 moles / mol and most preferably comprised between 1.5 and 2.5 moles / mol. This is notably the case in which the hydrodehydrogenating function is made up of CoMo.
According to step c) of the process, according to the invention, the combination of dialkyl succinate and acetic acid is introduced over the dried catalytic precursor by at least one impregnation step and, preferably, by a single impregnation step of an impregnation solution on that dried catalytic precursor.
This combination can advantageously be deposited in one or more stages, either by impregnation in slurry, either by excess impregnation, or by dry impregnation, or by any other means known to the technician.
According to a preferred embodiment of step c) of the preparation process, according to the invention, step c) is a single dry impregnation step.
According to step c) of the process, according to the invention, the impregnation solution of step c) comprises at least the combination of the C1-C4 dialkyl succinate (in particular, dimethyl) of acetic acid.
The impregnation solution used in step c) of the process, according to the invention, can be supplemented by any non-protic solvent known to the person skilled in the art, notably comprising toluene, xylene.
The impregnation solution used in step c) of the process, according to the invention, can be supplemented by any polar solvent known to the person skilled in the art. This polar solvent used is advantageously chosen from the group formed by methanol, ethanol, water, phenol,
17/48 cyclohexanol, considered alone or in mixture. That polar solvent used in step c) of the process, according to the invention, can also be advantageously chosen from the group formed by propylene carbonate, DMSOP (dimethyl sulfoxide), sulfolane, considered alone or in mixture. Preferably, a polar protic solvent is used. A list of the usual polar solvents, as well as its dielectric constant can be found in the book Solvents and Solvent Effects in Organic Chemistry, C.Reichardt, Wiley-VCH, 3rd edition, 2003, 472-474 pages). Most preferably, the solvent used is ethanol.
Preferably, there is no solvent in the impregnation solution used in step c) of the process, according to the invention, which facilitates use on an industrial scale. Preferably, it contains only dialkyl succinate and acetic acid.
The dialkyl succinate used is preferably included in the group consisting of dimethyl succinate, diethyl succinate, dipropyl succinate, diisopropyl succinate and dibutyl succinate. Preferably, the C1-C4 dialkyl succinate used is dimethyl succinate or diethyl succinate. Most preferably, the C1-C4 dialkyl succinate used is dimethyl succinate. At least one C1-C4 dialkyl succinate is used, preferably a single one, and preferably dimethyl succinate.
According to step d) of the preparation process, according to the invention, the impregnated catalytic precursor from step c) is subjected to a maturation step. It is advantageously carried out at atmospheric pressure and at a temperature between 17 ° C and 50 ° C, and generally a maturation period between ten minutes and forty-eight hours, preferably between thirty minutes and five hours, is sufficient . Longer durations are not excluded. A simple way to adjust the maturation duration is to characterize the formation of Keggin heteropolyanions, by Raman spectroscopy in the impregnated dried catalytic precursor from step c) of the process, according to the invention. In a very preferred way, to increase 'roductivity, without
18/48 modifying the amount of reformed heteropolyanions, the maturation period is between thirty minutes and four hours. Even more preferably, the duration of maturation is between thirty minutes and four hours. Even more preferably, the maturation period is between thirty minutes and three hours.
According to step e) of the preparation process, according to the invention, the catalytic precursor from step d) is subjected to a drying step at a temperature below 180 ° C, without a subsequent calcination step at a temperature greater than 200 ° C.
The purpose of this step is to obtain a transportable, stockable and manipulable catalyst, in particular for loading the hydrotreating unit. It is advantageous, according to the chosen embodiment of the invention, to remove all or part of the eventual solvent that allowed the introduction of the combination of the C1-C $ dialkyl succinate (in particular, dimethyl) and acetic acid. In all cases, and in particular, in the case where the combination of C1-C4 dialkyl succinate (in particular, dimethyl) and acetic acid is used alone, it is a matter of giving the catalyst a dry appearance in order to prevent the extrudates from sticking to each other during the stages of transport, storage, handling or loading.
The drying step e) of the process according to the invention is advantageously performed by any technique known to the person skilled in the art. It is advantageously made at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure.
This step e) is advantageously carried out at a temperature between 50 ° C and below 180 ° C, preferably between 60 and 170 ° C and, most preferably, between 80 and 160 ° C. Advantageously, it operates in these temperature ranges at a maximum temperature of 160 ° C (the preferred range being 80 - 180 ° C) and without subsequent calcination at a temperature above 180 ° C.
It is advantageously made in a crossed layer, using air or any other hot gas. Preferably, when drying is
19/48 made in a fixed layer, the gas used is either air or an inert gas, such as argon or nitrogen. Most preferably, drying is carried out in a crossed layer in the presence of nitrogen.
Preferably, this step lasts between 30 minutes and 4 hours and, preferably, between 1 and 3 hours.
At the end of step e) of the process, according to the invention, a dried catalyst is obtained, which is not subjected to any subsequent calcination step under air, for example, at a temperature above 200 ° C.
The catalyst obtained in step d) or in step e) has a Raman spectrum, comprising the most intense bands at 990, 974 cm ' ¹ (Keggin type polyanions), the bands corresponding to succinate (for dimethyl succinate to the most intense is at 853 cm ¹ ), and the characteristic bands of acetic acid, of which the most intense is at 896 cm ' ¹ .
Before use, it is advantageous to transform a dry or calcined catalyst into a sulfur catalyst in order to form its active species. This activation or sulfurization phase is carried out by methods well known to the technician, and advantageously under a sulforeductive atmosphere in the presence of hydrogen and sulfuric hydrogen.
At the end of step e) of the process, according to the invention, that dried catalyst obtained is therefore advantageously subjected to a sulfurization step f), without intermediate calcination step.
This dried catalyst is advantageously sulfated in an ex situ or in situ manner. Sulfurants are H ₂ S gas or any other sulfur-containing compound used for the activation of hydrocarbon charges, with a view to sulfurizing the catalyst. These sulfur-containing compounds are advantageously chosen from alkyldisulfides, such as, for example, disulfide (DMDS), alkylsulfides, such as, for example, dimethyl sulfide, n-butyl mercaptan, tertiononyl polysulfide polysulfide compounds , such as, for example, TPS-37 or TPS-54 marketed by ARKEMA, or any other compound known to the person skilled in the art, allowing good sulfurization of the catalyst. Preferably, the catalyst is sulfurized in situ in the presence of a sulfurizing agent and a hydrocarbon filler. Most preferably, the catalyst is sulfurized in situ in the presence of an additive hydrocarbon charge with dimethyl disulfide.
Finally, another object of the invention is the use of the catalyst, according to the invention, in hydrotreating processes, notably in the hydrodesulphurisation, hydrodesnitrogenation processes, and hydrogenation of the hydroconversion aromatics from oil cuts.
The dried catalysts obtained by the process, according to the invention, and having preferably undergone a f) sulfurization step, are advantageously used for the hydrotreating reactions of hydrocarbon charges, such as oil cuts, coal cuts or hydrocarbons produced from natural gas and more particularly for the reactions of hydrogenation, hydrodesnitrogenation, hydrodesarmatization, hydrodesulphurisation, hydrodesmetallization or hydroconversion of hydrocarbon charges.
In these uses, the catalysts obtained by the process, according to the invention, and having preferably undergone a sulfuration step f) previously have an improved activity in relation to the catalysts of the prior art. These catalysts can also be advantageously used, when pretreating the catalytic cracking loads or the hydrodesulphurization of residues or hydrodesulphurisation of fuel oils (ULSD Ultra Low Sulfur Diesel).
The loads used in the hydrotreating processes are, for example, gasolines, gasolines under vacuum, atmospheric residues, residues under vacuum, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, waste oils, unburdened residues or crude, from the processes of thermal or catalytic conversions, considered alone or in mixtures. The loads that are treated, and in particular those mentioned above, generally contain heteroatoms, such as sulfur, oxygen and nitrogen, and for heavy loads, they contain more often also metals.
21/48
The operating conditions used in the processes that use the hydrocarbon loading reactions described above are generally as follows: the temperature is advantageously between 180 and 450 ° C and, preferably, between 250 and 440 ° C, the pressure is advantageously understood between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the density between 0.2 and 5 h ¹ , and the hydrogen / charge ratio, expressed in volume of hydrogen, measured under normal temperature conditions and pressure, per volume of net charge is advantageously between 50 l / l and 2000 l / l.
The following examples demonstrate the important activity gain over the catalysts prepared according to the process, according to the invention, in relation to the catalysts of the prior art and need the invention, without, however, limiting its scope.
EXAMPLE 1: preparation of catalysts (NiMoP / alumina) calcined C1A, (NiMoP / alumina) dried with citric acid (CA) and polyethylene glycol (PEG) C1E, (C1A and C1E being not according to the invention), thus as dried (NiMoP / alumina) catalysts, added with acetic acid and dimethyl succinate C1B and C1F, (which are in accordance with the invention).
A matrix composed of ultrafine tabular bohemite or alumina gel, marketed by the company Condéa 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 salt), then mixed for 15 minutes. At the end of this mixing, the obtained paste is passed through a row that has cylindrical holes with a diameter of 1.6 mm. The extrudates are then dried overnight at 120 ° C, then calcined at 600 ° C for 2 hours in moist air containing 50 g of water per kg of dry air. In this way, support extrudates are obtained, having a specific surface area of 300 m ² / g. X-ray diffraction analysis reveals that the support is only composed of low crystalline cubic gamma alumina.
Nickel, molybdenum and nickel are added to the alumina support described above and in the form of an extrudate.
22/48 phosphorus. The impregnation solution is prepared by hot dissolving molybdenum oxide and nickel hydroxy carbonate in the phosphoric acid solution in aqueous solution in order to obtain a formulation of approximately 4 / 22.5 / 4 expressed in% by weight of oxides of nickel, molybdenum and in% by weight of phosphoric anhydride in relation to the amount of dry matter in the final catalyst. After dry impregnation, the extrudates are allowed to mature in an atmosphere saturated in water for 12 hours, then they are dried overnight at 90 ° C. The dried catalytic precursor thus obtained is noted with C1. The calcination of C1 at 450 ° C for 2 hours leads to the calcined catalyst C1A. The final composition of the catalysts C1 and C1A expressed as oxides is then as follows: MoO ₃ = 22.4 + 0.2 (% by weight), NiO = 4.1 +0.1 (% by weight)
The catalyst C1E is prepared by impregnating the dried catalytic precursor C1 with a solution containing citric acid (CA) and polyethylene glycol (PEG) in solution in ethanol, in order to have a volume of solution to be impregnated equal to the porous volume of the dried catalytic precursor. C1. the target contents of citric acid (CA) and polyethylene glycol (PEG) are both 10% by weight.
The catalyst C1B, according to the invention, is made from the dried catalytic precursor C1 by dry impregnation of a solution containing the mixture of dimethyl succinate and acetic acid in ethanol, so as to obtain also 10% by weight of acid acetic and 10% by weight of acetic acid and 10% by weight of dimethyl succinate on the final catalyst.
The C1F catalyst, according to the invention, is made in the same way, but in the absence of ethanol. A final content of acetic acid of 13% by weight and a final content of dimethyl succinate of 20% by weight are envisaged.
The catalysts also undergo a 3-hour maturation stage at 20 ° C under air, then heat treatment in a layer-type oven at 110 ° C for 3 hours.
EXAMPLE 2: Evaluation of NiMoP / alumina catalysts C1A (not according), C1E (not according) in hydrotreating fuel oil distillation23 / 48
Sulfuration of the catalyst (30 cm ³ of catalyst in the form of extrudates mixed with 10 cm ³ of SiC of 0.8 mm size) is carried out at 50 bariums, at WH = 2 h ' ¹ , with a ratio (of volume flow ) H ₂ / HC input = 400 Std l / l. The sulfuration charge (fuel oil with 2% DMDS Evolution from Arkéma) is introduced into the reactor under H ₂ , when it reaches 150 ° C. After an hour at 150 ° C, the temperature is raised with a ramp of 25 ° C / hour, until reaching a range of 350 ° C, then with a ramp of 12 ° C / hour until reaching a level of 350 ° C, maintained 12 hours.
After sulfurization, the temperature is lowered to 330 ° C and the test load is injected. The catalytic test is performed at a total pressure of 50 bariums, with hydrogen lost, with WH = 2 h ' ¹ , with an H ₂ / HC ratio at the entrance of 400 Std l / l (flow H ₂ = 24 Std 1.h ' ¹ , load flow = 60 cm ³ .h ¹ ), and at 330 ° C, 340 ° C and 350 ° C.
In order to be able to evaluate the performance of HDS catalysts, and to get rid of the presence of H ₂ S in recipes, the recipe container is gutted to nitrogen at a rate of 10 L.h ' ¹ .
The fuel oil used in the case of a heavy Arab crude. It contains 0.89% by weight of sulfur, 100 ppm by weight of nitrogen and its TMP [(T ₅ + 2T ₅₀ + 4Tg ₅ ) / 7] is 324 ° C and its density is 0.848 g / cm ³ .
HDS activity is measured from HDS conversion, according to the formula:
₁ 100 -% / fflS and HDS conversion (% HDS) is given by% HDS = _x i oo
Q ° load
During the test, the density of the effluents obtained at each temperature is measured at 15 ° C. The evolution of density was represented in figure 1. This graph allows to determine the temperature at which it is necessary
24/48 operate to have a specific density, the refiner having a strong interest in using the catalyst that will provide this performance at the lowest temperature. It can be seen in figure 1 that the catalyst, according to the invention, allows the effluent isodensity to decrease the operating temperature of approximately 15 ° C in relation to the prior art C1A catalyst. The results obtained in hydrodesulfurization during this test were reported in the table below:
Reference Catalyst Temperature 330 ° C 340 ° C 350 ° C HDS activity related to isovolume in relation to C1A (%) C1A NiMoP / aluminacalcined not ofwake up - 100 100 100 C1E NiMoP / aluminadried additivenot in agreement PEG + CAin EtOH 104 105 106 C1B NiMoP / aluminadried additiveaccording DMSU + AAin EtOH 121 123 126
The results obtained show that, in hydrotreating fuel oil, it is interesting both in terms of hydrodesulfurization. As for hydroaromatization (which translates into the evolution of the density of effluents), add the catalyst by dimethyl succinate in combination as acetic acid according to the process of the invention. In effect, according to the preceding table, the HDS activity obtained is 126 at high temperature (corresponding to the ULSD domain, that is, for a sulfur content close to
10 ppm by weight) for the catalyst according to the invention, while the calcined catalyst is at 100 (reference) and the prior art catalyst C1E at 106.
EXAMPLE 3: Evaluation of NiMoP / alumina catalysts C1A (not according), C1E (not according) in vacuum distillate hydrodesnitrogenation (DSV) for a hydrocracking pretreatment application
25/48
The main characteristics of the vacuum distillate used are given below:
Density at 20 ° C: 0.9365 Sulfur: 2.92% by weight Total nitrogen: 1400 ppm in pesop Simulated distillation: PI: 361 ° C 10%: 430 ° C 50%: 492 ° C 90%: 567 ° C FEDERAL POLICE: 598 ° C
The test was done in an isothermal pilot reactor with a fixed layer crossed, the fluids circulating from the bottom up. After sulfurization in situ at 350 ° C in the unit under pressure using a direct distillation fuel oil to which 2% by weight of dimethyl disulfide is added, the hydrotreatment test was conducted under the following operating conditions:
Total pressure: 12Mpa Catalyst volume: 40 cm ³ Temperature: 380 ° C Hydrogen flow rate: 40 l / h Load flow: 40 cm ³ / h The catalytic performances of the tested catalysts are given
in the following table. They are expressed in relative activity, placing that of the catalyst C1A is equal to 100 and considering that they are of the order 1.5. The relationship linking activity and conversion to hydrodesulphurization (% HDS) is as follows:
A M-ids - ^{1 100} -1 _or % HDS = ^Scarsa ^ ¹¹ °° ¹¹ ° x100
100-% ffl) S s _c , ₈ ,
The same relationship is applicable for hydrodesnitrogenation (% HDN and Ahdn).
On the other hand, it is also evaluated the crude conversion to fraction that has a boiling point below 380 ° C obtained with each catalyst.
26/48
It is expressed from the results of simulated distillation (ASTM D86 method) by the relation:
Conversion =% 380; _ai8 , -% 380; _flumte % 38o: ^ _t
The table below provides the test results obtained for the three catalysts:
Catalyst Ahds relative to C1A (%) Ahdn relative to C1A (%) Conversionat 380 ° C- (%) C1A NiMoP / calcined alumina (not according) 100 100 25 C1F NiMoP / alumina DMSU + AA (according) 145 151 29
The catalytic results show that in the case of a hydrocracking pretreatment application, the catalyst, according to the invention, performs better than a calcined NiMoP catalyst as the catalyst, according to the invention, allows for a gain and , hydrodesulfurization, but also in hydrodesnitrogenation and what is most surprising in conversion.
EXAMPLE 4: Preparation of a NiMoP catalyst on calcined silica alumina C2A (not according) and a NiMoP catalyst on silica alumina dried and added to acetic acid and C2B dimethyl succinat (according)
Two NiMoP catalysts were made with a formulation
3.6 / 18 / 1.6 on a silica alumina of the SIRALOX type marketed by SASOL, with 25% silica content. A dried catalytic precursor of the NiMoP / silica alumina type was prepared from the precursors MOO3 and Ni (OH) ₂ solubilized with the aid of H3PO4 and a reflux assembly for two hours at 90 ° C. The clear solution was then concentrated by evaporation of the water, in order to reach the impregnation volume, then it was impregnated at room temperature on silica alumina. The support extrudates thus impregnated undergo a maturation stage in a
27/48 closed compartment saturated with water, overnight, then dried in the oven at 120 ° C for 24 hours. This catalytic precursor was then divided into two batches:
the first was calcined at 450 ° C for two hours under fixed layer air to give the catalyst C2A (not according);
the second was used according to the protocol, according to the invention, impregnating dropwise a solution containing acetic acid and dimethyl succinate / acetic acid of 0.58 until the emergence of the rising humidity that shows that all the porosity was filled. The catalyst was then left to mature for 3 hours and underwent heat treatment at 125 ° C for two hours to give the C2B catalyst according to the invention.
EXAMPLE 5: Evaluation in hydrogenation of toluene in the presence of aniline and hydrocracking of DSV catalysts calcined on silica alumina C2A (not according to agreement) and NiMoP on silica alumina dried and added with acetic acid and with C2B methyl succinate (according to agreement) ).
The hydrogenation test of toluene in the presence of aniline (test ΉΤΑ) aims to evaluate the HYDrogenating activity (HYD) of supported sulfur catalysts or mass, in the presence of H ₂ S and under hydrogen pressure. The isomerization and cracking that characterize the acid function of the catalyst supported on silica-alumina are inhibited by the presence of NH ₃ (following the decomposition of aniline). Aniline and / or NH ₃ will thus react via an acid-base reaction with the acidic sites of the support. All tests presented were performed on a unit that holds several micro-reactors in parallel. When testing ΉΤΑ, the same charge is used for the sulfurization of the catalyst and the catalytic test phase itself. Before loading, the catalyst is packaged: it is stacked and sorted so that the sample size is between two and four mm. 4 cm ³ of heaped catalyst mixed with 4 cm ³ of carborundum (SiC, 500 pm) are loaded into the reactors.
28/48
The load used for this test is as follows:
Toluene 20% by weight;
Cyclohexane 73.62% by weight;
DMDS (Dimethyl Disulfide) 5.88% by weight (3.8% by weight in S);
Aniline 0.5% by weight (750 ppm N)
The catalyst is loaded into the reactor in its dried, non-active form. Activation (sulfurization) is carried out on the unit with the same charge. It is the H ₂ S that, formed after the DMDS decomposition, sulfurizes the oxidized phase. The amount of aniline present in the load was chosen to obtain, after decomposition, approximately 750 ppm NH ₃ .
The operational conditions for the toluene hydrogenation test are as follows:
P = 6 MPa
WH = 2 h ' ¹ (load flow = 8 cm ³ / h)
H ₂ / HC = 450 Nl / I, (flow H ₂ = 3.6 Nl / I)
T = 350 ° C
The percentage of converted toluene is evaluated and, assuming the hypothesis of an order 1 of the reaction, the activity is deduced from the following relation:
AHordem. 1 ⁼ IΠ 100 / (100 -% HYDtoluene) with% HYDtoluene = percentage of converted toluene.
The C2A catalyst (not according) has an activity of 0.52 and the C2B catalyst (according to the invention) 0.93, which represents a considerable gain and shows interest in the combination of acetic acid and dimethyl succinate for increase the hydrogenating activity of NiMoP type catalysts on silica alumina for sweet hydrocracking. In order to quantify the gain in conversion and in hydrodesulfurization, a hydrotreatment test under vacuum type distilled under load (DSV) was performed.
The load used is a DSV type load, whose main characteristics are recorded in the following table:
29/48
Charge DSV Density 15/4 (g / cm ³ ) 0.897 Organic S (% by weight) 0.2374 Organic N (ppm) 450 TMP * (° C) 467 Weight% of 370 ° C- 15.9
*: Weighted average temperature = 1T ₅ % + 2T ₅₀ % + 4T g ₅ o _{/ o} / 7 with T _x % at the boiling temperature of x% of the net cut.
The fraction of the extrudates between 2 and 4 mm in length is tested. The 4 cm ³ of catalyst is loaded into the reactor in its non-active oxide form. The activation (sulfurization) is carried out in the unit, before starting the test with a so-called sulfuration charge (direct distillation fuel oil + 2% by weight of DMDS). It is the H ₂ S that, formed following the DMDS decomposition, sulfurizes the catalysts.
The operational conditions applied when testing are as follows:
P = 6 MPa
WH = 0.6 h ' ¹
H ₂ / HC output = 480 Nl / I
T = 380 ° C
Thanks to this test, a classification of the catalysts is obtained by evaluating the gross conversion of the fraction 370 ⁺ into 370 =% by weight 370 ° C effluents.
The catalytic results are shown in the table below. The C2B catalyst, according to the invention, allows a gain in conversion of 5% and, above all, in HDS in relation to the C2A catalyst (not according), since the S content in liquid effluents goes from 60 ppm to 32 ppm when the catalyst used is activated by dimethyl succinate in combination with acetic acid, using a protocol, according to the invention.
30/48
Gross conversion(%) Total sulfur ineffluent (ppm) C2ANiMoP / calcined alumina silicanot in agreement 32 60 C2BNiMoP / dried alumina silicaadditive DMSU + AAaccording 37 32
These results show that, in addition to a gain in hydrogenation, the catalyst, according to the invention, can allow to obtain interesting gains in hydrocracking compared to a conventional calcined catalyst, having a similar formulation.
EXAMPLE 6: Preparation of a CoMoNiP / calcined alumina C3A catalyst (not according) and a dried CoMoNiP / alumina catalyst added to dimethyl succinate and C3B acetic acid (according to), as well as a dried CoMoNiP / alumina catalyst added to C3C dimethyl succinate (not according)
The alumina used in example 1 was also used in the case to make a dried catalytic precursor of the NiCoMoP / alumina formulation. The precursors used are molybdenum trioxide, cobalt carbonate, nickel hydroxy carbonate and phosphoric acid. The impregnation solution is carried out in one step by heating to reflux of these precursors. The target corresponds to a content expressed in% oxide weight in relation to the dry catalyst (after browning at 550 ° C): NiO / COO / MOO3 / P2O5 ¹ Λ, 3/15 / 4.4. At the end of the impregnation, the extrudates are left to mature for one night in an atmosphere saturated with water, then placed for two hours in an oven at 120 ° C. The dried catalytic precursor is then obtained, which, in the same way as in example 4, is divided into three batches:
a first batch is calcined at 450 ° C for 3 hours to give the catalyst C3A (not according);
the second batch is impregnated with a solution containing 31/48 of acetic acid and methyl succinate, according to the protocol of the invention: the ratio of dimethyl succinate / acetic acid in solution is 0.58 and the dried catalytic precursor is impregnated by this solution until the appearance until the appearance of nascent moisture, which shows that the porosity of the catalytic precursor was filled by the solution containing the dimethyl succinate and acetic acid. Then, a maturation of 2 hours is performed, followed by a heat treatment at 140 ° C for one hour. The catalyst thus obtained is the C3B catalyst, according to the invention.
The third batch is impregnated with dimethyl succinate until the emergence of nascent moisture, which shows the porosity of the catalytic precursor was filled with the solution of dimethyl succinate. Then, a maturation of two hours is performed, followed by a heat treatment at 140 ° C for one hour. The catalyst thus obtained is the C3C catalyst, not according to the invention.
EXAMPLE 7: Evaluation of CoMoNiP / calcined alumina C3A catalysts (not according) and a dried CoMoNiP / alumina catalyst added to dimethyl succinate and C3B acetic acid (according), and dried CoMoNiP / alumina catalyst added to dimethyl succinate C3C (not in agreement) in toluene hydrogenation model molecule test
In applications such as hydrotreating vacuum distillates and residues, the hydrodehydrogenating function plays a critical role, considering the important content in aromatic composites of these fillers. The toluene hydrogenation test was therefore used to discover the interest in catalysts for applications such as pretreatment of catalytic cracking or hydrodesulfurization of waste.
The catalysts previously described in example 6, are dynamically sulfurized in situ in the tubular reactor with a fixed layer traversed by a pilot unit of the Microcat type (manufacturer: Vinci company), the fluids circulating from top to bottom. Measurements of hydrogenating activity are carried out immediately after sulfuration under pressure and without replacement in the air with the hydrocarbon charge that served to sulfur the catalysts.
32/48
The sulfur and test load is composed of 5.8% dimethyl disudisulfide (DMDS) 20% toluene and 74.2% cyclohexane (by weight).
Sulfurization takes place at room temperature up to 350 ° C, with a temperature distributor of 2 ° C / min, a WH = 4 h ' ¹ and H2 / HC = 450 Nl / I. The catalytic test is performed at 350 ° C with WH = 2 h ' ¹ and H2 / HC equivalent to that of sulfurization, with a minimum of 4 recipes that are analyzed by gas chromatography.
Thus, the stabilized catalytic activities of equal volumes of catalysts in the toluene hydrogenation reaction are measured.
The detailed conditions for measuring activity are as follows:
Total pressure:
Toluene pressure: Cyclohexane pressure Methane pressure Hydrogen pressure H ₂ S pressure Catalyst volume
6.0 MPa 0.37 MPa 1.42 MPa 0.22 MPa 3.68 MPa 0.22 MPa cm ³ (extruded in lengths between 2 and 4 mm) Hourly space speed 2 h ' ¹
Sulfuration and test temperature 350 ° C
Withdrawals of the liquid effluent are analyzed by gas chromatography. The determination of molar concentrations in unconverted toluene (T) and their hydrogenation products concentrations (methyl cyclohexane (MCC6), ethyl cyclopentane (EtCC5) and dimethyl cyclopentanes (DMCC5)) allows the calculation of a toluene hydrogenation rate Xhyd defined by:
znzx MCC6 + EtCC5 + DMCC5
X _mn (%) = 100 X ^mD T + MCC6 + EtCC5 + DMCC5
The hydrogenation reaction of toluene being of order 1 in the applied test conditions and the reactor behaving like an ideal piston reactor, the hydrogenating activity A _H yd of the catalysts is calculated, applying the formula:
HYD ln
100 <100 HYD J
The table below allows to compare the relative hydrogenating activities of the catalysts prepared in example 6.
Catalyst Acid type Amount of acid (% by weight with respect to the final catalyst) Type of organic additive Amount of organic additive (% by weight in relation to the final catalyst) Relative ahyd in relation to C3A (%) C3Anot in agreement - 0 - 0 100 C3Baccording AA 13 DMSU 20 127 C3Cnot in agreement - 0 DMSU 25 110
These catalytic results show the particular effect at level 5 of the hydrogenating activity of the combination acetic acid (AA) and dimethyl succinate (DMSU) on the dried catalytic precursor CoMoNiP / alumina (according to the invention) in relation to a CoMoNiP / alumina catalyst calcined from the prior art. This gain in hydrogenation activity is particularly advantageous for heavy load applications such as pre-treatment of catalytic cracking or the hydrodesulfurization of waste.
Raman spectra were obtained with a dispersive Raman spectrometer equipped with an ionized argon laser (514 nm). The laser beam is focused on the sample with the aid of an e15 microscope equipped with a long-distance x 50 objective. The laser power at the sample level is in the order of 1 mW. The Raman signal emitted by the sample is collected by the same objective and is dispersed with the aid of an 1800 rpm network, then collected by a CCD detector. The spectral resolution obtained is of the order of 0.5 cm ' ¹ . The registered spectral zone is between 20 and 1800 cm ' ¹ . The acquisition duration was fixed at 120 s for each registered Raman spectrum.
34/48
Raman analyzes were made on catalysts C16 to C19 and allowed to show for catalysts, according to the invention, the presence on the Raman spectrum of the bands the most intense characteristics of Keggin's HPA, dimethyl succinate and acetic acid. The exact position of the bands, their shapes and their relative intensities can vary to a certain extent depending on the conditions of recording the spectrum, remaining characteristics of this molecule. The Raman spectra of the compounds, on the other hand, are well documented, whether in the Raman spectrum databases (see, for example, Spectral Database for Organic Compounds,
HTTP://riodb01.ibase.aist.go.jp/sdbs/cgibin/direct_frame_top.cgi), or by the product suppliers (see, for example, www.sigmaaldrich.com).
Raman spectra were recorded for C3B (DMSU + AA) and C3C (pure DMSU) catalysts and reported in figure 2. Each measurement was repeated over 3 different extruded zones. In the case of catalyst C3B, the presence of two bands in 990 and 971 cm ¹ , characteristic of Keggin heteropolyanions, is observed. The less intense bands also attributable to species on the 970, 902, 602 cm ' ¹ straps for the Keggin heteropolyanion. The presence of an intense band of dimethyl succinate at 851 cm ' ¹ can also be seen on these two spectra. In contrast, the 896 cm ' ¹ strip is only present on the catalyst, according to the invention.
In short, the Raman spectrum of the C3B catalyst, according to the invention, has characteristic bands of Keggin heteropolyanions, dimethyl succinate and acetic acid, while the C3C catalyst only has the characteristic bands of Keggin and dimethyl succinate.
EXAMPLE 8: Preparation of CoMoP catalysts on C1, C2, C3, C4 alumina (not according to the invention)
A matrix composed of ultrafine tabular bohemite or alumina gel, marketed by the company Condéa Chemie GmbH was used. This gel was mixed with an aqueous solution containing 66% nitric acid
35/48 (7% by weight of acid per gram of dry gel), then kneaded for 15 minutes. At the end of this mixing, the paste obtained is passed through a row that has cylindrical holes with a diameter equal to 1.6 mm. The extrudates are then dried overnight at 120 ° C, then calcined at 600 ° C for 2 hours in moist air containing 50 g of water per kg of dry air. Thus, extruded support is obtained, having a specific surface of 300 m ² / g. X-ray diffraction analysis reveals that the support is only composed of low crystalline cubic gamma alumina.
Cobalt, molybdenum and phosphorus are added to the alumina support described above, which is presented in the form and extruded. The impregnation solution is prepared by hot dissolving molybdenum oxide (24, 34 g) and cobalt hydroxide (5.34 g) in the phosphoric acid solution (7.47 g) in aqueous solution. After dry impregnation, the extrudates are left to mature in a water-saturated atmosphere for 12 hours, then are dried overnight at 90 ° C. The dried catalytic precursor thus obtained is at night. The calcination of the catalytic precursor C1 at 450 ° C for two hours leads to the calcined catalyst C2. The final composition of the catalysts C1 and C2 expressed as oxides is then as follows: MoO ₃ = 22.5 + 0.2 (% by weight), Côo = 4.1 +0.1 (% by weight) and P ₂ O ₅ = 4.0 + 0.1 (wt%).
The calcined catalyst C2 is loaded in a cross-layer unit and sulfurized by a direct distillate fuel oil of 2% by weight of dimethyl disulfide. An HDS test of a mixture of direct distillation fuel oil and fuel oil from catalytic cracking is then conducted for 300 hours. After testing, the used catalyst is discharged, collected and washed with reflux toluene, then separated into two batches. The first batch is regenerated in a controlled combustion oven, introducing increasing amounts of oxygen for each temperature range, which allows limiting the exotherm associated with the combustion of coke. The final regeneration range is 450 ° C. The catalyst thus regenerated is analyzed by XRD. It is noted in the absence of a 26 ° risk characteristic of the presence of crystallized CoMoO ₄ .
36/48
This catalyst will then be annotated with C3. The second batch of used washed catalyst is regenerated in an oven with a booklet at 400 ° C, without controlling the coke combustion exotherm. The XRD analysis performed after regeneration shows the presence of a fine scratch at 26 ° C, characteristic of the presence of crystallized CoMoO ₄ . In addition, this catalyst that will be annotated hereinafter with C4 has a very pronounced bright blue color.
EXAMPLE 9: Preparation of C0M0P catalysts on alumina with C5, C6, C7, C8, C9, C10, C11, C12 additives (not according to the invention).
The catalyst C5 is prepared by impregnating the dried catalytic precursor C1 with a solution containing citric acid (CA) and polyethylene glycol (PEG) in solution in ethanol, in order to have a volume of solution to be impregnated equal to the porous volume of the dried catalytic precursor. C1. The target contents of citric acid (CA) and polyethylene glycol (PEG) are all two of 10%.
The catalyst C6 is prepared by impregnating the dried catalytic precursor C1 with a solution containing citric acid (CA) and polyethylene glycol (PEG) in solution in ethanol. The target contents of citric acid (CA) and polyethylene glycol (PEG) are 4 and 10% by weight, respectively.
The catalyst C7 is prepared by impregnating the calcined catalyst C2 with a solution containing citric acid and polyethylene glycol in solution in ethanol, in order to have a volume of solution to be impregnated equal to the porous volume of the calcined catalyst C2. The target contents of citric acid (CA) and polyethylene glycol (PEG) are all two of 10% by weight.
The catalyst C8 is prepared by impregnating the calcined catalyst C2 with a solution containing citric acid and polyethylene glycol in solution in ethanol. The target contents of citric acid (CA) and polyethylene glycol (PEG) are all two of 10% by weight.
The catalyst C9 is prepared by impregnating the calcined catalyst C2 with a solution containing acetic acid (AA) and dimethyl succinate (DMSU) in solution in ethanol. The target levels of acetic acid
37/48 (AA) and dimethyl succinate (DMSU) are respectively 4 to 10% by weight.
The catalyst C10 is prepared by impregnating the regenerated catalyst, not having a refractory phase of type CoMoO ₄ , C3, by a solution containing citric acid (CA) and polyethylene glycol (PEG) in ethanol in order to have an equal volume of solution to be impregnated porous volume of C3. The target contents of citric acid (CA) and polyethylene glycol (PEG) are both 10%.
The catalyst C11 is prepared by impregnating the regenerated catalyst, not having a refractory phase of type CoMoO ₄ , C3, with a solution containing citric acid (CA) and polyethylene glycol (PEG) in ethanol. The target contents of citric acid and methyl succinate are 4 and 10% by weight respectively.
The catalyst C12 is prepared by impregnating the regenerated catalyst, not containing refractory phase type C0M004, C3, by a solution containing acetic acid and dimethyl succinate in ethanol. The target contents of acetic acid and dimethyl succinate are 4 and 10% by weight respectively.
The catalyst C13 is prepared by impregnating the regenerated catalyst comprising CoMoO ₄ , C4, with a solution containing citric acid and polyethylene glycol in ethanol, in order to have a volume of solution to be impregnated equal to the porous volume of C4. The target contents of citric acid and polyethylene glycol are both 10% by weight.
The catalyst C14 is prepared by impregnating the regenerated catalyst containing CoMoO ₄ , C4, with a solution containing citric acid and polyethylene glycol in ethanol. The target contents of citric acid and polyethylene glycol are 4 and 10% by weight respectively.
The catalyst C15 is prepared by impregnating the regenerated catalyst containing C0M004, C4, with a solution containing acetic acid and dimethyl succinate in ethanol. The target contents of acetic acid and dimethyl succinate are 4 and 10% by weight respectively.
38/48
The catalysts C5 to C15 are then subjected to a maturation stage of 3 hours followed by a thermal treatment (drying) stage of 1 hour at 140 ° C under nitrogen.
EXAMPLE 10: Preparation of the C16 CoMoP additive catalyst (according to the invention)
The catalyst C16 is prepared by impregnating the dried catalytic precursor C1 with a solution containing acetic acid, dimethyl succinate and ethanol. The target contents of acetic acid and dimethyl succinate are 4 and 10% by weight respectively. The catalyst is then subjected to a 3-hour maturation stage under air at room temperature, followed by a heat treatment (drying) stage at 140 ° C for one hour under nitrogen.
EXAMPLE 11: Comparative test of catalysts C1 to C16 in hydrogenation of toluene in cyclohexane under pressure and in the presence of sulfuric hydrogen.
The catalysts previously described, are dynamically sulfurized in situ in the tubular reactor with a fixed layer crossed by a pilot unit of the Microcat type (manufacturer: Sociedade Vinci), the fluids circulating from top to bottom. Measurements of hydrogenating activity are made immediately after sulfurisation under pressure and without replacement to air with the hydrocarbon filler that served to sulfurize the catalysts.
The sulfur and test load is composed of 5.8% dimethyl disulfide (DMDS), 20% toluene and 74.2% cyclohexane (by weight).
Sulfurization is carried out from room temperature to 350 ° C, with a temperature distributor of 2 ° C / min, a WH = 4 h ' ¹ and H2 / HC = 450 Nl / I. The catalytic test is performed at 350 ° C with WH = 2h ' ¹ and H2 / HC equivalent to that of sulfurization with a minimum removal of 4 recipes that are analyzed by gas chromatography.
Thus, the stabilized catalytic activities of equal volumes of catalysts in the toluene hydrogenation reaction are measured.
The detailed conditions for measuring activity are as follows:
39/48
Total pressure:
Toluene pressure: Cyclohexane pressure Methane pressure Hydrogen pressure H ₂ S pressure Catalyst volume
6.0 MPa 0.37 MPa 1.42 MPa 0.22 MPa 3.68 MPa 0.22 MPa cm ³ (extruded in lengths between 2 and 4 mm) Hourly space speed 2 h ' ¹
Sulfuration and test temperature 350 ° C
Withdrawals of the liquid effluent are analyzed by gas chromatography. The determination of molar concentrations in unconverted toluene (T) and concentrations of its hydrogenation products (methyl cyclohexane (MCC6), ethyl cyclopentane (EtCC5) and dimethyl cyclopentanes (DMCC5)) allows to calculate a hydrogenation rate of toluene Xhyd defined by:
Ύ _ΗίΏ (%) = 100χ
MCC6 + EtCC5 + DMCC5
T + MCC6 + EtCC5 + DMCC5 The hydrogenation reaction of toluene being of order 1 under the applied test conditions and the reactor behaving like an ideal piston reactor, the hydrogenating activity A _H yd of the catalysts is calculated, applying to formula:
HYD ln
100
Table 1 compares the relative hydrogenating activities of the catalysts added from the dried catalytic precursor C1 (not according), equal to the ratio of the activity of the catalyst added to the activity of the calcined starting catalyst C2 (not according) taken with reference ( 100% activity).
40/48
Table 1:
Relative activities in relation to calcined catalyst C2 (not according) in hydrogenation of toluene of the additives catalysts C5, C6 (not according) and C16 (according) prepared from the dried catalyst C1 (not according).
Catalyst Kind ofacid Amount of acid (% by weight with respect to the final catalyst) Kind ofadditiveorganic Amount of organic additive (% by weight in relation to the catalystfinal user) Relative ahyd inrelation to C3A (%) Calcined C2not in agreement - 0 - 0 100 Dried C1not in agreement - 0 - 0 75 C5not in agreement HERE 10 PEG 10 - C6not in agreement HERE 4 PEG 10 105 C16 according AA 4 DMSU 10 138
Table 1 shows that the dried catalytic precursor C1 (not according) has less activity than the calcined catalyst C2 (not according). The additive catalyst C5 (not in agreement) prepared by adding 10% by weight of citric acid (CA) and 10% polyethylene glycol (PEG) in the dried catalyst C1 could not be tested, since the extrudates were glued in bulk in the end of drying, which shows that an excess of acid and additive is not convenient in the case where the starting catalyst is a dried catalyst. The catalyst C6 (not according) prepared by adding 4% citric acid (CA) and 10% polyethylene glycol (PEG) to the dried catalyst C1 has an improved activity compared to the dried catalyst starting by 40%. However, as the dried starter catalyst C1 has a withdrawal activity of 25% compared to the conventional calcined catalyst C2, the relative hydrogenating activity of catalyst C6 in relation to catalyst C2 shows only a gain of 5%, which represents the margin error for this test. There is therefore no interest
41/48 to add the dried catalyst by the combination PEG + CA. Finally, the catalyst C16 (in accordance) prepared by adding 4% acetic acid (AA) and 10% of dimethyl succinate (DMSU) shows a gain of 84% in relation to the dry catalyst C1 (not in agreement) of match. In relation to the calcined catalyst C2 (not according to agreement) used conventionally, the activity of this catalyst C16 (according to agreement) has a gain of 38%, which is superior to a new generation of catalyst (gain of 25 to 30%). These catalytic results show the particular and surprising effect of the combination acetic acid (AA) and dimethyl succinate (DMSU) on dried catalyst (according to the invention) in relation to the combination of citric acid (CA) and polyethylene glycol (PEG) (not according to the invention).
In the same way, table 2 compares the relative hydrogenating activities of the catalysts added from the dried catalyst C1 (not according), equal to the ratio of the activity of the catalyst added to the activity of the calcined catalyst starting C2 (not according) taken as a reference (100% activity).
Table 2:
Relative activities in relation to the calcined catalyst C2 (not according) in hydrogenation of the toluene of the additives catalysts C7, C8, C9 (not according) prepared from the calcined catalyst C2 (not according).
Catalyst Typeinacid Amount of acid (%by weight in relation to the catalyst) Kind ofadditiveorganic Amount of organic additive (% by weight with respect to the catalyst) Relative ahyd inrelation to C2 (%) Calcined C2not in agreement - 0 - 0 100 C7not in agreement HERE 10 PEG 10 102 C8not in agreement HERE 4 PEG 10 114 C9not in agreement AA 4 DMSU 10 105
42/48
Table 2 shows, surprisingly, that the additive catalyst C7 (not according) prepared by adding 10% by weight of citric acid (AC) and 10% polyethylene glycol (PEG) to the calcined catalyst C2 has a similar activity , even equivalent, to that of the calcined starting catalyst C2 (not according), which shows that an excess of acid and additive that was not suitable in the case where the starting catalyst was a dried catalyst is of little use in the case of a calcined catalyst. The catalyst C8 (not according) prepared by adding 4% citric acid (CA) and 10% polyethylene glycol (PEG) to the calcined catalyst C2 has an improved activity compared to the calcined starting catalyst of 14%. Finally, catalyst C9 (not in agreement) prepared by adding 4% acetic acid (AA) and 10% dimethyl succinate (DMSU) has an activity close (5% gain) to that of calcined catalyst C2 (no agreement) of departure. These catalytic results show the particular interest of the combination acetic acid (AA) and dimethyl succinate (DMSU) only on dried catalytic precursor C1 (combination according to the invention) and not on calcined catalyst C2 (combination not according to the invention) ).
Likewise, Table 3 compares the relative hydrogenating activities of additive catalysts (not according) prepared from the regenerated catalyst containing no refractory phase of type CoMoO ₄ , C3.
Table 3:
Relative activities in relation to calcined catalyst C2 (not according) in hydrogenation of toluene of the additives catalysts C10, C11, C12 (not according) prepared from regenerated catalyst C3 (not according), without crystallized phase C0M004
Catalyst Typeinacid Amount of acid (% by weight with respect to the catalyst) Kind ofadditiveorganic Amount of organic additive (% by weight with respect to catalyst I) A _H yd relative to C2 (%) Regenerated C3 not containing crystallized phase not according - 0 - 0 97
43/48
Catalyst Typeinacid Amount of acid (% by weight with respect to the catalyst) Kind ofadditiveorganic Amount of organic additive (% by weight with respect to catalyst I) Relative ahyd in relation to C2(%) C10not in agreement HERE 10 PEG 10 104 C11not in agreement HERE 4 PEG 10 109 C12not in agreement AA 4 DMSU 10 99
Table 3 shows that the additive catalyst C10 (not according) prepared by adding 10% by weight of citric acid (CA) and 10% polyethylene glycol (PEG) to the regenerated catalyst C3, without containing refractory phase of type C0M004 , has an activity close, even e5 equivalent, to that of the calcined starting catalyst C2 (not according), which shows that an excess of acid and additive is also of little use in the case where the regenerated catalyst does not have a crystallized phase C0M004. The catalyst C11 (not according) prepared by adding 4% citric acid (CA) and 10% polyethylene glycol (PEG) to the catalyst re10 generated C3, without containing refractory phase of type C0M004, has an improved activity in relation to 12% starting catalyst C3 (not in agreement), which gives it a 9% improved activity compared to the new calcined catalyst C2. Finally, the catalyst C12 (not according) prepared by adding 4% acetic acid (AA) and 10% dimethyl succinate (DMSU) has an activity close to that of the calcined catalyst C2 (not according). These catalytic results show well the particular interest of the combination acetic acid (AA) and dimethyl succinate (DMSU) on dried catalyst C1 (according to the invention) in relation to the same combination on regenerated catalyst C3 not presenting crystallized phase of type CoMoO ₄ (not according to the invention).
In the same way, table 4 compares the relative hydrogenating activities of catalysts added from the regenerated catalyst C4 (not according) presenting CoMoO ₄ . The presence of C0M004 is confirmed by XRD analysis.
44/48
Table 4:
Relative activities in relation to the calcined catalyst C2 (not according) in hydrogenation of toluene of the additives catalysts C4, C13, C14, C15 (not according) prepared from the regenerated catalyst C4 (not according), having crystallized phases of type C0M0O4
Catalyst Typeinacid Amount of acid (% by weight with respect to the catalyst) Kind ofadditiveorganic Amount of organic additive (% by weight with respect to the catalyst) Relative ahyd in relation to C2 (%) Regenerated C4containingC0M004 crystallized not according - 0 - 0 73 C13not in agreement HERE 10 PEG 10 103 C14not in agreement HERE 4 PEG 10 85 C15not in agreement AA 4 DMSU 10 75
Table 4 shows that the additive catalyst C13 (not according) prepared by adding 10% by weight of citric acid (CA) and 10% polyethylene glycol (PEG) to the regenerated catalyst, containing CoMoO ₄ , C4 has a activity close, even equivalent, to that of the calcined starting catalyst C2 (not according), which shows that an excess of acid and additive is usable in the case where the regenerated catalyst having crystallized phases CoMoO ₄ . Indeed, the catalyst C14 (not according) prepared by adding 4% citric acid (CA) and 10% polyethylene glycol (PEG) to the regenerated catalyst, having crystalline phases of type C0M004 (not according) an insufficient activity improved in relation to the starting catalyst C4 (not in agreement), since its activity remains inferior to that of the new calcined catalyst C2. Finally, catalyst C15 (not in agreement) prepared by adding 4% acetic acid (AA) and 10% dimethyl succinate (DMSU) shows an activity close (gain of 3%) to that of catalyst C4 (no
45/48 accordingly) and much lower compared to the new calcined catalyst C2. These catalytic results show the particular interest of the combination acetic acid (AA) and dimethyl succinate (DMSU) on dried catalyst C1 (according to the invention) in relation to the same combination on regenerated catalyst presenting crystallized phases of type CoMoO ₄ C4 ( which is not in accordance with the invention). This combination is, in particular, inoperative on catalysts containing crystallized refractory phases of type CoMoO ₄ , contrary to the combination of citric acid (CA) and polyethylene glycol (PEG).
EXAMPLE 12: Preparation of catalysts C17 and C18 (not according to the invention), C19 (according to the invention) and comparison in HDS of fuel oil of catalysts C2 (not according to), C17 and C18 (not according) , C16 and C19 (according).
The C17 catalyst is prepared by impregnating the catalytic precursor C1 with pure dimethyl succinate (DMSU). This amounts to 30% by weight of dimethyl succinate on the final catalyst. The catalyst then undergoes a 3 hour maturation stage at 20 ° C, then a heat treatment of 140 ° C for one hour under air in the cross-layer oven. The catalyst obtained at the end of this heat treatment is noted with C17. This catalyst is not in accordance with the invention, as it does not contain acetic acid in combination with methyl succinate.
The catalyst C18 is prepared in the same way, but filling the porosity of the catalytic precursor C1 with acetic acid. 31% by weight relative to the weight of the catalyst is obtained. The maturation / heat treatment steps are similar to C17.
The catalyst C19 is prepared by impregnating the catalytic precursor C1 with a solution containing only the mixture of dimethyl succinate and acetic acid with a dimethyl succinate to molybdenum molar ratio of 1.1. This even reaches levels in relation to the final catalyst of respectively 25 and 18% by weight for dimethyl succinate and acetic acid. The catalyst then undergoes a maturation stage of 3 hours at room temperature, then a heat treatment of 140 ° C for 46/48 hours for one hour under air in a cross-layer oven. The catalyst obtained at the end of this heat treatment is noted with C19. This catalyst is in accordance with the invention.
The catalysts C2 (not according), C16 (according), C17 (not according and C19 (according) were tested in fuel oil HDS.
Characteristics of the fuel oil load used:
- Intended for 15 ° C: 0.8522 - sulfur: 1.44% by weight - Simulated distillation: • PI: 155 ° C • 10%: 247 ° C • 50%: 315 ° C • 90%: 392 ° C • FEDERAL POLICE: 444 ° C
The test was carried out in an isothermal pilot reactor with a fixed layer crossed, the fluids circulating from bottom to top. After sulfurization in situ at 350 ° C in the unit under pressure by means of the test fuel oil to which 2% by weight of dimethyl disulfide is added, the hydrodesulphurisation test led to the following operational conditions:
- Total pressure: 7 MPa - Catalyst volume: 30 cm ³ - Temperature: 340 ° C - Hydrogen flow: 24 l / h - Load flow: 60 cm ³ / h Catalytic performances of the tested catalysts are
in table 3. They are expressed in relative activity, putting that of the calcined catalyst C2 is equal to 100 and considering that they are of order 1.5. The relationship linking activity and conversion to hydrodesulphurization (noted with% HDS) is as follows:
^HDS JlOO-% HDS
The results obtained are reported in table 5.
47/48
Table 5:
Activity related to isovolume in hydrodesulfurization of fuel oil of catalysts C16 (according), C17 (not according), C18 (according) in relation to calcined catalyst C2 (not according).
Catalyst Summary of the main differences in the preparation process Ahds relative to C2 (%) The most intense Raman bands (cm - ¹ ) C16(according) DMSU (23% of the porous volume of the catalytic precursor) + AA (9% of the porous volume of the catalytic precursor) + EtOH (68% of the porous volume of the catalytic precursor) 119 990, 972 (heteropolyanions)853 (DMSU)896 (AA) C17(not in agreement) Pure DMSU (100% of the porous volume of the catalytic precursor) 109 990 (Keggin heteropolyanion)853 (DMSU) C18(not in agreement) Pure AA (100% of the porous volume of the catalytic precursor 85 952 (Anderson heteropolyanion)896 (AA) C19(according) DMSU (58% of the porous volume of the catalytic precursor) + AA (42% of the porous volume of the catalytic precursor) 138 990, 971 (Keggin heteropolyanion) 851 (DMSU)895 (AA)
Table 5 clearly shows the synergy effect and the particular interest of the combination of acetic acid and dimethyl succinate on a dried catalytic precursor. In effect, catalysts C17 and C18 (not according to) have lower activities than those obtained for catalysts C16 and C19, according to the invention. In addition, it is interesting to note that, in the case of catalyst C19, a more important amount of additive DMSU is more impregnated than in the case of catalyst C16, however, the gain in activity increases contrary to what could be highlighted in the case of PEG and citric acid in example 1.
Raman spectra were obtained with a dispersive Raman spectrometer equipped with an ionized argon laser (514 nm). The lesion beam is focused on the sample with the aid of a microscope equipped with a long working distance x50 objective. The laser power at the sample level is in the order of 1 mW. The Raman signal emitted by the sample is collected by the same objective and is dispersed with the aid of a 1800 rpm network, then collected by a CCD detector. The spectral resolution obtained in the order of 0.5 cm ' ¹ . The registered spectral zone is between 300 and 1800 cm ' ¹ . The acquisition duration was fixed at 120 S for each registered Raman spectrum.
Raman analyzes were made on catalysts C16 to C19 and allowed to show for catalysts, according to the invention, the presence on the Raman spectrum of the bands the most intense characteristics of Keggin's HPA, dimethyl succinate and acetic acid. The exact position of the bands, their shapes and their relative intensities can vary to a certain extent depending on the conditions of recording the spectrum, remaining characteristics of this molecule. The Raman spectra of organic compounds are, on the other hand, well documented, whether in the Raman spectrum databases (see, for example, Spectral Database for Organic Compounds, http://riodb01.ibase.aist.go.jp/sdbs/ cgibin / direct_frame_top.cgi), or by the product suppliers (see, for example, www.sigmaaldrich.com).
Without being linked to any theory, it was found that non-complexing organic additives allowed the reformulation of heteropolyanions in solution in the pores of the catalyst. It is typically this phenomenon that is highlighted with the appearance of the heteropolyanium bands, after impregnation of the solution that comprises the mixture of dialkyl succinate and acetic acid. This effect was classified as reforming the heteropolyanions, as they are initially present in the impregnation solution, but are not present on the recently impregnated dried catalytic precursor, on the contrary they reform when the additive impregnates. In the case of PEG in the presence of citric acid, the complexing effect allows the crystallized phases to disappear, easily characterized by XRD, but no heteropolyanion is reformed.
1/4

权利要求:
Claims (23)
[1]
1. Catalyst, comprising an amorphous support based on alumina, phosphorus, at least one C1-C4 dialkyl succinate, acetic acid and a hydrodeshydrogenating function, comprising at least one element of the VIB group and at least one element of the group VIII, catalyst whose Raman spectrum comprises the bands at 990 and / or 974 cm ' ¹ , characteristic of at least one Keggin heteropolyanion, the characteristic bands of this succinate and the main band at 896 cm' ¹ characteristic of acetic acid.
[2]
2. Catalyst according to claim 1, in which the dialkyl succinate is dimethyl succinate and in which the catalyst has in its spectrum main Raman bands at 990 and / or 974 cm ' ¹ , characteristic of the Keggin heteropolyranions, and 853 cm ¹ , characteristic of dimethyl succinate and 896 cm ' ¹ characteristic of acetic acid.
[3]
Catalyst according to claim 1, in which the dialkyl succinate is diethyl succinate, dibutyl succinate or diisopropyl succinate.
[4]
Catalyst according to one of the preceding claims, comprising a support consisting of alumina.
[5]
Catalyst according to one of the preceding claims, comprising a support consisting of silica-alumina.
[6]
Catalyst according to one of the preceding claims, also comprising boron and / or fluorine.
[7]
Catalyst according to one of claims 1 to 4 and 6, in which the hydrodehydrogenating function is made up of cobalt and molybdenum and the support is made up of alumina.
[8]
8. Catalyst according to one of claims 1 to 6 and 7, in which the hydrogenating function is chosen from the group formed by the combinations of the elements nickel - molybdenum, or nickel - cobalt - molybdenum, or nickel - molybdenum - tungsten.
[9]
Catalyst according to one of the preceding claims, and sulfurized.
2/4
[10]
10. Process for preparing a catalyst, as defined in one of the preceding claims, that process comprising the following successive steps:
a) at least one step of impregnating an amorphous support based on alumina with at least one solution containing the elements of the hydrodehydrogenating function, and phosphorus;
b) drying at a temperature below 180 ° C, without subsequent calcination;
c) at least one impregnation step with an impregnation solution, comprising at least one C1-C4 dialkyl succinate, acetic acid and at least one phosphorus compound, if this has not been fully introduced in step a);
d) a maturation stage;
e) a drying step at a temperature below 180 ° C, without a subsequent calcination step.
[11]
Process according to claim 10, in which the totality of the hydrodeshydrogenating function is introduced, during step a).
[12]
Process according to one of claims 10 and 11, in which step c) is carried out in the absence of solvent.
[13]
Process according to one of claims 10 to 12, in which step c) is carried out in the presence of a solvent chosen from the group formed by methanol, ethanol, water, phenol, cyclohexanol, considered alone or in mixture.
[14]
Process according to one of claims 10 to 13, in which the dialkyl succinate and acetic acid are introduced into the impregnation solution of step c) in an amount corresponding to a molar ratio of dialkyl succinate per element (s ) of the VIB group impregnated with the catalytic precursor comprised between 0.15 and 2 moles / mol, and a molar ratio of acetic acid per element (s) of the VIB group impregnated with the catalytic precursor comprised between 0.1 and 5 moles / mol.
[15]
Process according to one of claims 10 to 14, in which step d) is carried out at a temperature of 17 to 50 ° C.
3/4
[16]
16. Process according to one of claims 10 to 15, in which step e) is carried out at a temperature of 80 to 160 ° C, without subsequent calcination at a temperature greater than 180 ° C.
[17]
17. Process according to one of claims 10 to 16, that process comprising the following successive steps:
a) at least one step of dry impregnating this support with a solution, containing all the elements of the hydrodeshydrogenating function, and phosphorus;
b) drying at a temperature between 75 and 130 ° C without subsequent calcination;
c) at least one dry impregnation step with an impregnation solution, comprising dimethyl succinate and acetic acid;
d) a maturation stage at 17-50 ° C;
e) a drying step at a temperature between 80 and 160 ° C, without a subsequent calcination step.
[18]
Process according to one of claims 10 to 17, in which the quantity of phosphorus introduced in step a) or in step c), if it has not been introduced in full in step a), the quantity introduced in step a ) expressed in quantity of oxide in relation to the catalyst is comprised between 0.1 to 20%, preferably between 0.1 and 15% and even more preferably between 0.1 and 10% by weight.
[19]
19. Process according to one of claims 10 to 18, in which step e) is carried out under nitrogen.
[20]
20. Process according to one of claims 10 to 19, in which the product obtained at the end of step e) undergoes a sulfuration step.
[21]
21. Process for hydrotreating hydrocarbon charges in the presence of a catalyst, as defined in one of claims 1 to 9, or prepared by the process, as defined in one of claims 10 to 20.
[22]
22. The process of claim 21, wherein the hydro4 / 4 treatment is a hydrodesulphurisation, a hydrodesnitrogenation, a hydrodesmetalization, a hydrogenation of the aromatics or a hydro conversion.
[23]
23. The process of claim 22, wherein the hydrotreatment is a hydrodesulphurisation driven by fuel oils.
1/2 ( _ε ωο / β) ^ ψ (0 _ο ) i ♦ CIAclacinado C1E PEG + CA to C1B DMSU + A
Fig 1 (ex 2)
2/2
Fig 2 (ex 7)

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112012014687B1|2018-05-08|hydrotreating catalyst comprising metals of groups viii and vib and preparation with acetic acid and c1-c4 dialkyl succinate

---

BR112013023877B1|2019-07-02|CATALYST, EVEN PREPARATION AND HYDROCARBON LOADING PROCESSES

---

JP4491677B2|2010-06-30|Hydroprocessing catalyst containing nitrogen organic compound and use thereof

---

KR100653505B1|2006-12-04|Process for sulphiding a hydrotreating catalyst comprising an organic compound comprising n and carbonyl

---

JP6706629B2|2020-06-10|Catalysts based on γ-valerolactone and/or its hydrolysis products and their use in hydrotreating and/or hydrocracking processes

---

BR112014015330B1|2020-10-27|catalyst preparation process usable in hydrotreating and hydroconversion

---

BRPI1011677B1|2018-03-06|METHOD FOR HYDROPROCESSING A CARBONARY FOOD LOAD AND HYDROPROCESSING CATALYST

---

TW201701951A|2017-01-16|Catalyst based on [gamma]-ketovaleric acid and use thereof in a hydrotreatment and/or hydrocracking process

---

BR112013003002B1|2019-04-02|COMPOSITION CONTAINING POLAR ADDITIVE AND USEFUL CHELING AGENT IN HYDROPROCESSING HYDROCARBON SUPPLIES AND THE METHOD OF THEIR PRODUCTION AND USE

---

RU2678456C2|2019-01-29|Process for preparing hydrotreating catalyst

---

BR112013002168B1|2018-11-21|hydrotreating process of a boiling hydrocarbon cut-off point greater than 250 ° C in the presence of a sulfide catalyst prepared by means of a cyclic oligosaccharide

---

FR2953740A1|2011-06-17|New catalyst comprising amorphous support made of alumina, phosphorus, at dialkyl succinate, acetic acid and hydro-dehydrogenating function containing e.g. element of group VIB, useful for the hydrotreatment of hydrocarbon feedstocks

---

US10828627B2|2020-11-10|Catalyst containing 2-acetylbutyrolactone and/or the hydrolysis products thereof, and use thereof in a hydrotreatment and/or hydrocracking process

---

JP2021504102A|2021-02-15|Its use in catalysts containing furan compounds and methods of hydrogenation and / or hydrocracking

---

JP6454708B2|2019-01-16|Catalyst preparation method, catalyst and its use in hydroconversion and / or hydroprocessing methods

---

González-Cortés et al.2014|Solution combustion method: a convenient approach for preparing Ni promoted Mo and MoW sulphide hydrotreating catalysts

---

RU2574389C2|2016-02-10|Catalyst, suitable for hydroprocessing, containing metals of groups viii and vib, phosphorus, and its obtaining with application of citric acid and c1-c4-dialkylsuccinate

---

van Haandel et al.2017|Structure and Performance of Hydrotreating Catalysts: A Refinement of the Co-Mo-S Model

---

JP2021528245A|2021-10-21|Catalysts supplemented with alkyl lactate, their preparation and their use in hydrogenation and / or methods of hydrocracking

同族专利:

---

公开号 | 公开日

---

KR101788700B1|2017-10-20|

---

WO2011080407A1|2011-07-07|

---

BR112012014687A2|2016-04-05|

---

EP2512662B1|2014-05-07|

---

US20130008829A1|2013-01-10|

---

DK2512662T3|2014-08-11|

---

ZA201204137B|2013-03-27|

---

CN102933298B|2016-08-03|

---

JP2013514169A|2013-04-25|

---

KR20120098884A|2012-09-05|

---

RU2551857C2|2015-05-27|

---

CN102933298A|2013-02-13|

---

US9174202B2|2015-11-03|

---

JP5732470B2|2015-06-10|

---

RU2012130027A|2014-01-27|

---

EP2512662A1|2012-10-24|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US4012340A|1971-02-01|1977-03-15|Chiyoda Kako Kensetsu Kabushiki Kaisha|Process for preparing catalysts for hydrodesulfurization|

---

JPS526711B1|1971-02-01|1977-02-24|

---

FR2664507B1|1990-07-13|1995-04-14|Eurecat Europ Retrait Catalys|PROCESS FOR PRETREATING A CATALYST WITH A MIXTURE OF A SULFUR AGENT AND AN ORGANIC REDUCING AGENT.|

---

US5198100A|1990-12-24|1993-03-30|Exxon Research And Engineering Company|Hydrotreating using novel hydrotreating catalyst|

---

JPH04243547A|1991-01-22|1992-08-31|Sumitomo Metal Mining Co Ltd|Manufacture of hydrogenation catalyst for hydrocarbon oil|

---

JP2900771B2|1992-11-18|1999-06-02|住友金属鉱山株式会社|Method for producing catalyst for hydrotreating hydrocarbon oil|

---

JPH06339635A|1993-06-01|1994-12-13|Japan Energy Corp|Preparation of hydrogenation catalyst|

---

JPH07136523A|1993-11-12|1995-05-30|Japan Energy Corp|Production of hydrogenation catalyst|

---

DE69534311T2|1994-05-13|2006-04-20|Shell Oil Co., Houston|Process for improving the activity of catalysts|

---

JP3802106B2|1995-06-08|2006-07-26|日本ケッチェン株式会社|Hydrocarbon oil hydrotreating catalyst, production method thereof and activation method thereof|

---

FR2792551B1|1999-04-20|2001-06-08|Atochem Elf Sa|PROCESS FOR SULFURIZING HYDROTREATMENT CATALYSTS|

---

CA2405841C|2000-04-11|2010-02-09|Akzo Nobel N.V.|Process for sulphiding an additive-containing catalyst|

---

WO2003002253A1|2001-06-27|2003-01-09|Japan Energy Corporation|Method for producing hydro-refining catalyst|

---

CA2540286C|2003-10-03|2014-04-15|Albemarle Netherlands B.V.|Process for activating a hydrotreating catalyst|

---

FR2880823B1|2005-01-20|2008-02-22|Total France Sa|HYDROTREATING CATALYST, PROCESS FOR PREPARING THE SAME AND USE THEREOF|

---

FR2904242B1|2006-07-28|2012-09-28|Inst Francais Du Petrole|PROCESS FOR HYDRODESULFURING CUTS CONTAINING SULFUR COMPOUNDS AND OLEFINS IN THE PRESENCE OF A SUPPORTED CATALYST COMPRISING ELEMENTS OF GROUPS VIII AND VIB|

---

CN100450612C|2006-09-30|2009-01-14|厦门大学|Heteropoly acid containing hydrocracking catalyst and its preparation method|

---

FR2910351B1|2006-12-22|2009-02-27|Total France Sa|HYDROTREATING CATALYST, PROCESS FOR PREPARING THE SAME AND USE THEREOF|

---

FR2917647B1|2007-06-25|2011-05-06|Inst Francais Du Petrole|PROCESS FOR PREPARING HYDROTREATMENT CATALYST BY IMPREGNATING A PHOSPHORIC COMPOUND|

---

CN100584458C|2007-07-26|2010-01-27|厦门大学|Hydrocracking catalyzer containing heteropoly acid and method of manufacturing the same|

---

FR2972648B1|2011-03-18|2013-04-26|Ifp Energies Now|CATALYST FOR USE IN HYDROTREATMENT COMPRISING METALS OF GROUP VIII AND VIB AND PREPARATION WITH CITRIC ACID AND C1-C4 DIALKYL SUCCINATE|FR2972648B1|2011-03-18|2013-04-26|Ifp Energies Now|CATALYST FOR USE IN HYDROTREATMENT COMPRISING METALS OF GROUP VIII AND VIB AND PREPARATION WITH CITRIC ACID AND C1-C4 DIALKYL SUCCINATE|

---

JP5906634B2|2011-09-26|2016-04-20|宇部興産株式会社|Method for producing 1,3-diol compound|

---

FR2984760B1|2011-12-22|2014-01-17|IFP Energies Nouvelles|HYDROCONVERSION USING CATALYST COMPRISING AT LEAST ONE ZEOLITHE AND METALS OF GROUP VIII AND VIB AND PREPARATION OF CATALYST|

---

FR2984764B1|2011-12-22|2014-01-17|IFP Energies Nouvelles|PROCESS FOR PREPARING A CATALYST FOR USE IN HYDROTREATMENT AND HYDROCONVERSION|

---

FR3013721B1|2013-11-28|2015-11-13|Ifp Energies Now|GASOLINE HYDROTREATMENT PROCESS USING A CATALYST SURFACE|

---

FR3013720B1|2013-11-28|2015-11-13|IFP Energies Nouvelles|METHOD FOR HYDROPROCESSING VACUUM DISTILLATES USING A CATALYST SURFACE|

---

FR3015514B1|2013-12-23|2016-10-28|Total Marketing Services|IMPROVED PROCESS FOR DESAROMATIZATION OF PETROLEUM CUTTERS|

---

FR3017875B1|2014-02-24|2016-03-11|Total Marketing Services|COMPOSITION OF ADDITIVES AND PERFORMANCE FUEL COMPRISING SUCH A COMPOSITION|

---

FR3017876B1|2014-02-24|2016-03-11|Total Marketing Services|COMPOSITION OF ADDITIVES AND PERFORMANCE FUEL COMPRISING SUCH A COMPOSITION|

---

JP6306370B2|2014-02-25|2018-04-04|千代田化工建設株式会社|Aromatic compound hydrogenation system and hydrogenation method|

---

FR3023184B1|2014-07-04|2019-12-27|IFP Energies Nouvelles|HIGH MOLYBDEN DENSITY HYDROTREATMENT CATALYST AND PREPARATION METHOD.|

---

WO2016064938A1|2014-10-22|2016-04-28|Shell Oil Company|A hydroprocessing catalyst composition containing an acetoacetic acid compound, a method of making such a catalyst, and a process of using such catalyst catalyst|

---

US20180126362A1|2015-04-24|2018-05-10|Albemarle Europe Sprl|Hydrotreating catalyst containing metal organic sulfides on doped supports|

---

FR3065888B1|2017-05-04|2020-05-29|IFP Energies Nouvelles|PROCESS FOR THE INDIRECT ADDITION OF AN ORGANIC COMPOUND TO A POROUS SOLID.|

---

FR3074699B1|2017-12-13|2019-12-20|IFP Energies Nouvelles|PROCESS FOR HYDROCONVERSION OF HEAVY HYDROCARBON CHARGE INTO HYBRID REACTOR|

---

FR3075072B1|2017-12-14|2021-11-26|Ifp Energies Now|FCC GASOLINE SELECTIVE HYDRODESULFURATION CATALYST|

---

FR3083139A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON PIPERIDINONES, PIPERIDINEDIONES AND / OR AZEPANONES AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|

---

FR3083132A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON 1--2-PYRROLIDONE AND / OR 1--2,5-PYRROLIDINEDIONE AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|

---

FR3083131A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON IMIDAZOLIDINONES, IMIDAZOLIDINEDIONES, PYRIMIDINONES AND / OR PYRIMIDINETRIONES AND ITS USE IN A HYDROPROCESSING AND / OR HYDROCRACKING PROCESS|

---

FR3083134A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON 1-VINYL-2-PYRROLIDONE AND / OR 1-ETHYL-2-PYRROLIDONE AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|

---

RU2714810C1|2018-10-15|2020-02-19|федеральное государственное бюджетное образовательное учреждение высшего образования "Самарский государственный технический университет"|Method for selective hydrogenation of styrene oligomers and still residues of reaction resins , use thereof as liquid organic hydrogen carrier and hydrogen cycle based thereon|

---

FR3089135A1|2018-11-30|2020-06-05|IFP Energies Nouvelles|Process for the preparation of a catalytic material based on a W or Mo type mononuclear precursor for electrochemical reduction reactions|

---

FR3089132A1|2018-11-30|2020-06-05|IFP Energies Nouvelles|Process for the preparation of a catalytic material for electrochemical reduction reactions comprising a group VI and group VIII metal obtained by chemical reduction|

---

FR3089133A1|2018-11-30|2020-06-05|IFP Energies Nouvelles|Method of preparing an active electrode layer for electrochemical reduction reactions|

---

FR3089134B1|2018-11-30|2020-11-13|Ifp Energies Now|A method of preparing an electrode catalytic material for electrochemical reduction reactions prepared by electroreduction.|

---

FR3106506A1|2020-01-28|2021-07-30|IFP Energies Nouvelles|Finishing hydrodesulfurization process in the presence of a catalyst obtained by additivation|

法律状态:
2018-03-13| B09A| Decision: intention to grant|

---

2018-05-08| B16A| Patent or certificate of addition of invention granted|

优先权:

---

申请号 | 申请日 | 专利标题

---

FR0906103A|FR2953740B1|2009-12-16|2009-12-16|CATALYST FOR USE IN HYDROTREATMENT COMPRISING METALS OF GROUP VIII AND VIB EXCEPT COBALT-MOLYBDENE TORQUE, AND PREPARATION WITH ACETIC ACID AND C1-C4 DIALKYL SUCCINATE|

---

FR0906101A|FR2953739B1|2009-12-16|2009-12-16|HYDROTREATABLE CATALYST COMPRISING COBALT AND MOLYBDENUM, PROCESS FOR THE PREPARATION THEREOF WITH ACETIC ACID AND C1-C4 DIALKYL SUCCINATE|

---

PCT/FR2010/000819|WO2011080407A1|2009-12-16|2010-12-08|Catalyst that can be used in hydrotreatment, comprising metals of groups viii and vib, and preparation with acetic acid and dialkyl succinate c1-c4|

---