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    • 专利摘要:
    Catalyst containing an active phase comprising at least one group VIIIB metal selected from cobalt, nickel, ruthenium and iron deposited on a support containing silica, alumina, and at least one simple spinel MAI2O4 or mixed MXM (1-x) Al 2 O 4 partial or not, where M and M 'are distinct metals selected from the group consisting of magnesium, copper, cobalt, nickel, tin, zinc, lithium, calcium , cesium, sodium, potassium, iron and manganese and where x is between 0 and 1, the values 0 and 1 being themselves excluded, characterized in that said active phase further comprises boron, the boron content being between 0.001% and 0.5% by weight relative to the total weight of the catalyst, the value 0.5 itself being excluded.
    公开号:FR3035007A1
    申请号:FR1553399
    申请日:2015-04-16
    公开日:2016-10-21
    发明作者:Romain Chenevier；Dominique Decottignies；Vincent Lecocq；Marie Velly
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to the field of catalysts used for hydrocarbon synthesis reactions from a gas mixture comprising carbon monoxide and hydrogen, generally called Fischer-Tropsch synthesis. STATE OF THE ART The Fischer-Tropsch synthesis methods make it possible to obtain a broad range of hydrocarbon cuts from the CO + H2 mixture, commonly called synthesis gas. The global equation of Fischer-Tropsch synthesis can be written in the following way: n CO + (2n + 1) H2 CnH2n + 2 n H2O Fischer-Tropsch synthesis is at the heart of natural gas conversion processes, coal or biomass into fuels or intermediates for the chemical industry. These processes are called GTL ("Gas to Liquids" in the English terminology) in the case of the use of natural gas as the initial charge, CTL ("Coal to Liquids" in the English terminology) for coal, and BTL (Biomass to Liquids) for biomass. In each of these cases, the initial charge is first gasified to a synthesis gas which comprises a mixture of carbon monoxide and dihydrogen. The synthesis gas is then mainly converted into paraffins by Fischer-Tropsch synthesis, and these paraffins can then be converted into fuels by a hydroisomerization-hydrocracking process. For example, transformation processes such as hydrocracking, dewaxing, and hydroisomerization of heavy cuts (C16 +) make it possible to produce different types of fuels in the range of middle distillates: diesel (180-370 ° C cut) and kerosene (cut 140-300 ° C). The lighter fractions C5-C15 can be distilled and used as solvents. The Fischer-Tropsch synthesis reaction can be carried out in different types of reactors (fixed bed, mobile bed, or triphasic bed (gas, liquid, solid) for example of autoclave type 3035007 2 perfectly stirred, or bubble column), and the products of the reaction has the particular characteristic of being free of sulfur compounds, nitrogen compounds or aromatic type. In an implementation in a bubble column type reactor (or "slurry bubble column" according to the English terminology, or "slurry" in a simplified expression), which uses a divided catalyst in the form of powder very thin, typically of the order of a few tens of micrometers, this powder forming a suspension with the reaction medium.
    [0002] The Fischer-Tropsch reaction proceeds conventionally between 1 and 4 MPa (10 and 40 bar), at temperatures traditionally between 200 ° C and 350 ° C. The reaction is generally exothermic, which requires particular attention to the implementation of the catalyst.
    [0003] The catalysts used for Fischer-Tropsch synthesis are essentially cobalt or iron catalysts, although other metals may be used. Nevertheless, cobalt and iron offer a good performance / price compromise compared to other metals.
    [0004] Conventional methods for preparing supported metal catalysts used for Fischer-Tropsch synthesis include depositing a metal salt or metal-ligand coordination complex on the support, and then performing one or more heat treatment (s) performed. (s) in air, followed by a reductive treatment carried out ex situ or in situ.
    [0005] In order to improve the catalytic properties of the supported metal catalysts used for Fischer-Tropsch synthesis, doping elements may be added either in the active phase of the catalysts or directly in the support. The doping element generally makes it possible to improve the reducibility of the Group VIIIB metal and thus its activity or selectivity, or to slow down its deactivation. Boron falls into the category of doping elements of the active phase of the catalysts. US 6,593,378 discloses a Fischer-Tropsch synthesis process using a catalyst comprising cobalt as the active phase and a carrier prepared from an alumina support and aluminum borate. The document demonstrates that the presence of aluminum borate in the support improves the activity of the catalyst. The article in Journal of Catalysis, 2011, 280, 50-59 by Sayes et al. discloses a catalyst comprising an active phase comprising 20% by weight of cobalt and between 0.5 (3/0 to 2.0% by weight of boron relative to the total weight of the catalyst, and a support of alumina (y-Al 2 O 3 Boron is supplied alone during the final catalyst preparation step, however, the addition between 0.5% and 2% by weight of boron has a limited effect on the cobalt reducibility and on the performance of the catalyst. On the other hand, it makes it possible to significantly improve the stability of the catalyst by limiting the formation of carbonaceous deposits on the catalyst.W002 / 068564 discloses a catalyst comprising an active phase comprising 20% by weight of cobalt and 0 , 5% by weight of boron relative to the total weight of the catalyst, and an alumina support The process for the preparation of this catalyst comprises a step in which the cobalt precursor and the boron precursor are added simultaneously (co-impregnation However, adding boron to such a content in the catalyst does not significantly improve its activity.
    [0006] The Applicant has surprisingly discovered that a catalyst containing an active phase comprising at least one Group VIIIB metal and boron, the boron content of which is strictly less than 0.5% by weight relative to the total weight of the catalyst. , deposited on a support containing silica, alumina and spinel makes it possible to improve their catalytic performances in a Fischer-Tropsch type process, and more particularly makes it possible to significantly increase the activity of said catalyst. Such a catalyst is obtained by a preparation process comprising at least one step in which the precursor of at least one Group VIIIB metal and a boron precursor are added simultaneously in solution. The Fischer-Tropsch process is then carried out in the presence of a catalyst having improved activity, without decreasing its stability and selectivity rate.
    [0007] OBJECTS OF THE INVENTION A first object of the invention relates to a catalyst containing an active phase comprising at least one Group VIIIB metal chosen from cobalt, nickel, ruthenium and iron deposited on a support containing silica, alumina, and at least one simple spinel MAI204 or mixed MxM '(1-x) Al 2 O 4 partial or not, where M and M' are separate metals selected from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co), nickel (Ni), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), cesium (Cs), sodium (Na), potassium (K), iron (Fe) and manganese (Mn) and where x is between 0 10 and 1, the values 0 and 1 being themselves excluded, characterized in that said active phase further comprises boron, the boron content being between 0.001% and 0.5% by weight relative to the total weight of the catalyst, the value 0.5 itself being excluded.
    [0008] Advantageously, said support is a silica-alumina in which the spinel is included. Preferably, the spinel content is between 3 and 50% by weight relative to the weight of the support. Preferably, the content of metal M or M 'is between 1 and 20% by weight relative to the weight of the support. Advantageously, M is cobalt in the case of a simple spinel, and M is cobalt and M 'is magnesium or zinc in the case of a mixed spinel.
    [0009] Preferably, the group VIIIB metal content of the active phase is between 0.01 and 60% by weight based on the weight of the catalyst. Another object relates to a process for preparing a catalyst according to the invention, which process comprises at least one step in which said support containing silica, alumina and spinel is impregnated with an aqueous or organic solution comprising at least one group VIIIB metal salt selected from cobalt, nickel, ruthenium and iron, and at least one boron precursor. Advantageously, the process according to the invention comprises the following steps: a support containing silica and alumina is provided; said support is impregnated with an aqueous or organic solution comprising at least one metal salt M or M 'selected from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co), nickel (Ni) , tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), cesium (Cs), sodium (Na), potassium (K), iron (Fe) and manganese (Mn), then dried and calcined at a temperature between 700 and 1200 ° C, so as to obtain a simple spinel MAI204 or mixed MxM '(1-x) A1204 partial or not, where M and M' are distinct metals and where x is between 0 and 1, the values 0 and 1 being themselves excluded; said support containing silica, alumina and spinel 10 is impregnated with an aqueous or organic solution comprising at least one group VIIIB metal salt selected from cobalt, nickel, ruthenium and iron; said support containing silica, alumina and spinel is impregnated a second time with an aqueous or organic solution comprising at least one group VIIIB metal salt chosen from cobalt, nickel, ruthenium and iron; Wherein said aqueous or organic solution impregnated in step c) and / or d) further comprises the boron precursor. Preferably, the boron precursor is introduced only into the aqueous or organic solution supplied in step d).
    [0010] Advantageously, the content of the group VIIIB metal (s) supplied in step c) is between 0.005 and 30% by weight relative to the weight of the catalyst. Advantageously, the content of the Group VIIIB metal (s) supplied in step d) is between 0.005 and 30% by weight relative to the total weight of the catalyst. Preferably, the boron precursor is boric acid. Advantageously, the catalyst obtained in step d) is dried at a temperature of between 30 minutes and 3 hours, and then said dried catalyst is calcined under an oxidizing atmosphere at a temperature of between 320 ° C. and 460 ° C. Preferably, the dried and calcined catalyst is reduced to a temperature between 200 ° C and 500 ° C.
    [0011] Another object relates to a Fischer-Tropsch hydrocarbon synthesis process in which the catalyst according to the invention or prepared by the process according to the invention is brought into contact with a feedstock comprising synthesis gas at a total pressure of Between 0.1 and 15 MPa, at a temperature of between 150 and 350 ° C., and at an hourly space velocity of between 100 and 20000 volumes of synthesis gas per volume of catalyst and per hour with a molar ratio of H2 / CO Synthetic gas between 0.5 and 4. Detailed Description of the Invention In the following description, groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR Lide, 81st edition, 2000-2001). For example, group VIIIB according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification. The textural and structural properties of the support and the catalyst described below are determined by the characterization methods known to those skilled in the art. The total pore volume and the porous distribution are determined in the present invention by mercury porosimetry (see Rouquerol F. Rouquerol J. Singh K. "Adsorption by Powders & Porous Solids: Principle, methodology and applications", Academic Press , 1999). More particularly, the total pore volume is measured by mercury porosimetry according to the ASTM D4284-92 standard with a wetting angle of 140 °, for example by means of an Autopore IIITM model apparatus of the MicromeriticsTM brand. The specific surface is determined in the present invention by the B.E.T. method, described in the same reference work as mercury porosimetry, and more particularly according to ASTM D3663-03. Catalyst 30 The invention relates to a catalyst containing an active phase comprising at least one group VIIIB metal deposited on a support containing silica, alumina and at least one MAI204 or mixed (1-x) -x single spinel. - MM AI2 -4 partial or not, where M and M 'are - 0 distinct metals selected from the group consisting of magnesium (Mg), copper (Cu), 3035007 7 cobalt (Co), nickel (Ni ), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), cesium (Cs), sodium (Na), potassium (K), iron (Fe) and manganese (Mn) and where x is between 0 and 1, the values 0 and 1 being themselves excluded, the active phase of said catalyst further comprising boron, the boron content being between 0.001% and 0, 5% by weight relative to the total weight of the catalyst, the value 0.5 itself being excluded. The group VIIIB metal content of the active phase selected from cobalt, nickel, ruthenium and iron is between 0.01 and 60% by weight relative to the weight of the catalyst.
    [0012] In the case where the active phase comprises at least one metal chosen from cobalt, nickel and iron, the content of said metal represents from 1 to 60% by weight, preferably from 5 to 30% by weight, and very preferred from 10 to 30% by weight relative to the weight of the catalyst. In the case where the active phase comprises ruthenium, the ruthenium content is between 0.01 and 10% by weight, and preferably between 0.05 and 5% by weight relative to the weight of the catalyst. The boron content is between 0.001% and 0.5% by weight, the value 0.5 being itself excluded, and preferably between 0.01 and 0.4% by weight relative to the weight of the catalyst, more preferably between 0.02 and 0.35%, and even more preferably between 0.02 and 0.2% by weight relative to the total weight of the catalyst.The active phase of said catalyst may advantageously also comprise at least one element. additional dopant selected from a noble metal of groups VIIB or VIIIB.
    [0013] The additional doping element makes it possible to improve the reducibility of the Group VIIIB metal, and hence its activity or selectivity, or to slow down its deactivation. When at least one additional dopant is present, the additional dopant content (s) is generally between 20 ppm and 1% by weight, and preferably between 0.01 and 0.5% by weight relative to the weight of the catalyst. In the case where the dopant is selected from a noble metal 30 groups VIIB or VIIIB, it is preferably selected from platinum (Pt), palladium (Pd), rhodium (Rh) or rhenium (Re). More preferably, the dopant is platinum (Pt).
    [0014] The active phase thus comprises boron and at least one Group VIIIB metal selected from cobalt, nickel, ruthenium and iron, and optionally an additional doping element. Preferably, said active phase comprises cobalt, boron and platinum. Preferably, said active phase consists of cobalt and boron. Even more preferably, said active phase is cobalt, boron and platinum. The support of said catalyst employed for carrying out the hydrocarbon synthesis process according to the invention is an oxide support containing alumina, silica, and at least one spinel as described above. The alumina present in the oxide support generally has a crystallographic structure of the alumina delta (8), gamma (y), theta (0) or alpha (a) type, alone or as a mixture.
    [0015] The support containing alumina, silica, at least one spinel as described above can be prepared from alumina irrespective of its specific surface and the nature of its porous distribution. The specific surface area of the alumina from which the carrier is prepared is generally from 50 m 2 / g to 500 m 2 / g, preferably from 100 m 2 / g to 300 m 2 / g, more preferably from 150 m 2 / g / g and 250 m2 / g. The total pore volume of the alumina from which the support is prepared is generally between 0.4 ml / g and 1.2 ml / g, and preferably between 0.45 ml / g and 1 ml / g. . The porous distribution of the pores in the alumina from which the support is prepared may be monomodal, bimodal or plurimodal. Preferably, it is of monomodal type. The pore size is on the order of 2 to 50 nm, with an average pore size between 5 and 25 nm, preferably between 8 and 20 nm. The characteristics of the alumina mentioned above correspond to the characteristics of the alumina from which the support is prepared, that is to say before the introduction of silica, metals M and optionally M 'for the formation of the spinel phase, the active phase.
    [0016] The silica content in the support varies from 0.5% by weight to 30% by weight, preferably from 1% by weight to 25% by weight, and even more preferably from 1.5 to 20% by weight relative to weight of the support.
    [0017] By a support containing alumina and silica is meant a support in which the silicon and aluminum are in the form of agglomerates of silica or alumina respectively, amorphous aluminosilicate or any other mixed phase containing silicon and aluminum. Preferably, the alumina and the silica are present in the form of a mixture of SiO 2 -Al 2 O 3 oxides called silica-alumina. Silica-alumina is understood to mean an alumina comprising a percentage of silica that is strictly greater than 10% by weight and up to 30% by weight relative to the weight of the support. Said silica-alumina is homogeneous on a micrometer scale, and even more preferably, homogeneous on a nanometer scale. The spinel present in the oxide support is a simple MAI204 or mixed MxM '(1-x) Al 2 O 4 partial spinel, where M and M' are distinct metals selected from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co), nickel (Ni), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), cesium (Cs), sodium (Na), potassium (K), iron (Fe) and manganese (Mn) and where x is between 0 and 1, the values 0 and 1 being themselves excluded.
    [0018] The use of phases of MAI204 spinel structures or mixed spinels MxM '(1- x) Al 2 O 4 has been described in documents FR2879478 and WO 2005/072866, M and M' being generally divalent metals such as Mg, Sn , Ni, Co, Cu. Other publications include Rotan et al. in Journal of the European Ceramic Society 33 (2013) 1-6 and Rytter et al. in Top. Catal. 54 (2011) 801-810. In this case, the divalent metal (in particular nickel) is introduced in the form of a precursor of the nitrate type, for example up to a few percent on the initial support containing alumina. By calcination at a very high temperature, the spinel phase is formed and stabilizes the entire support.
    [0019] Most preferably, M is cobalt or nickel in the case of a single spinel. Very preferably, M is cobalt and M 'is magnesium or zinc in the case of a mixed spinel.
    [0020] In a particularly preferred manner, the spinel is a simple spinel MAI204 in which M is cobalt. The content of the spinel is generally between 3 and 50% by weight, and preferably between 5 and 40% by weight relative to the weight of the support. The metal content M or M 'is between 1 and 20% by weight, and preferably between 2 and 10% by weight relative to the weight of the support. The formation of the simple or mixed spinel structure in said support, often referred to as a stabilization stage of the support, can be carried out by any method known to those skilled in the art. It is generally carried out by introducing the metal M or M 'in the form of a salt precursor, for example of the nitrate type, onto the initial support containing the alumina. By calcination at a very high temperature, the spinel phase, in which the metal M or M 'is in aluminate form, is formed and stabilizes the entire support. The presence of spinel phase in the catalyst used in the Fischer-Tropsch process according to the invention is measured by the programmed temperature reduction RTP (or TPR for "temperature program reduction" according to the English terminology) as for example described in US Pat. Oil & Gas Science and Technology, Rev. IFP, Vol. 64 (2009), No. 1, pp. 11-12. According to this technique, the catalyst is heated under a stream of a reducing agent, for example under a flow of dihydrogen. The measurement of dihydrogen consumed as a function of temperature gives quantitative information on the reducibility of the species present. The presence of a spinel phase in the catalyst is thus manifested by a dihydrogen consumption at a temperature above about 800 ° C. Preferably, the oxide support containing alumina, silica, at least one spinel as described above is a silica-alumina in which the spinel is included, said support preferably having a silica content between 0.5% by weight to 30% by weight relative to the weight of the support, said support additionally containing at least one spinel as described above. Preferably, the silica content is greater than 10% by weight up to 30% by weight relative to the weight of the support, said support also containing at least one spinel as described above.
    [0021] The specific surface of the oxide support containing alumina, silica, and at least one spinel as described above is generally between 50 m 2 / g and 500 m 2 / g, preferably between 100 m 2 and 300 m2 / g, more preferably between 150 m2 / g and 250 m2 / g. The pore volume of said support is generally between 0.3 ml / g and 1.2 ml / g, and preferably between 0.4 ml / g and 1 ml / g. The support on which said active phase is deposited may have a morphology in the form of beads, extrudates (for example trilobes or quadrilobes) or pellets, especially when said catalyst is used in a reactor operating in a fixed bed. or have a morphology in the form of a powder of variable particle size, especially when said catalyst is used in a bubble column type reactor. The specific surface of the catalyst containing the active phase and the support of oxides containing alumina, silica, and at least one spinel as described above is generally between 50 m 2 / g and 500 m 2 / g preferably between 80 m2 / g and 250 m2 / g, more preferably between 90 m2 / g and 150 m2 / g. The pore volume of said catalyst is generally between 0.2 ml / g and 1 ml / g, and preferably between 0.25 ml / g and 0.8 ml / g. Preferably, the porous distribution is monomodal.
    [0022] Preferably, the catalyst according to the invention contains an active phase comprising cobalt and boron, and optionally an additional doping element, preferably platinum, the boron content being between 0.001 and 0.5% by weight per relative to the total weight of the catalyst, the value 0.5 being itself excluded, preferably between 0.01 to 0.4 cY0 weight, more preferably between 0.02 and 0.35%, and even more preferentially between 0 , 02 and 0.2% by weight, and a silica-alumina support in which a spinel is included, the silica content of the support being preferably between 1.5 and 20% by weight relative to the weight of the support, said spinel being a simple MAI204 or mixed MxM '(1-x) Al 2 O 4 partial spinel, where M and M' are distinct metals selected from the group consisting of magnesium (Mg), copper (Cu), cobalt ( Co), nickel (Ni), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), esium (Cs), sodium (Na), potassium (K), iron (Fe) and manganese (Mn) and where x is between 0 and 1, the values 0 and 1 being themselves excluded.
    [0023] In a particularly preferred manner, the catalyst used for carrying out the Fischer-Tropsch process according to the invention is a catalyst in which the active phase consists of cobalt and boron, and possibly platinum, and the support of oxides is comprised of a silica-alumina in which a spinel is included, the silica content of the support is between 1.5% and 20% by weight relative to the weight of the support, said spinel being CoA1204, the content of boron being between 0.001 and 0.5% by weight relative to the total weight of the catalyst, the value 0.5 itself being excluded. Preferably, the boron content is between 0.01 and 0.4% by weight relative to the total weight of the catalyst, more preferably between 0.02 and 0.35%, and even more preferably between 0.02 and 0.2% by weight. Process for the preparation of the catalyst The preparation of the catalyst generally comprises, in a first step, the preparation of the support of oxides containing alumina, silica, at least one spinel and then, in a second stage, the introduction of the phase active. According to the invention, the process for preparing the catalyst comprises at least one step in which said support containing silica, alumina and spinel is impregnated with an aqueous or organic solution comprising at least one metal salt of the group VIIIB selected from cobalt, nickel, ruthenium and iron, and at least one boron precursor (co-impregnation). Preferably, the impregnation of the Group VIIIB metal precursor selected from cobalt, nickel, ruthenium and iron may be carried out in several steps, preferably in two steps. Between each of the impregnation steps, it is preferred to optionally carry out at least one drying and / or calcination step under the conditions described below, and / or reduction under the conditions described below.
    [0024] More particularly, the process for preparing the catalyst according to the invention comprises the following steps: providing an oxide support containing alumina and silica; the carrier containing alumina and silica is impregnated with an aqueous or organic solution comprising at least one metal salt M or M 'selected from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co), nickel (Ni), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), cesium (Cs), sodium (Na), potassium (K), iron (Fe) and manganese (Mn), then dried and calcined at a temperature between 700 and 1200 ° C, so as to obtain a simple spinel MAI204 or mixed MxM '(1-x) A1204 partial or not, where 5 M and M 'are distinct metals and where x is between 0 and 1, the values 0 and 1 being themselves excluded; the oxide support containing alumina, silica and a spinel are impregnated a first time with an aqueous or organic solution comprising at least one group VIIIB metal salt chosen from cobalt, nickel, ruthenium and the iron ; The oxide support containing alumina, silica and a spinel are impregnated a second time with an aqueous or organic solution comprising at least one group VIIIB metal salt chosen from cobalt, nickel and ruthenium. and iron; and the aqueous or organic solution impregnated in step c) and / or d) comprises a boron precursor.
    [0025] According to step a), a carrier containing alumina and silica is provided. The SiO 2 silica content can vary from 0.5% by weight to 30% by weight, preferably from 1% by weight to 30% by weight, and even more preferably from 1.5 to 20% by weight relative to the weight of the support. . Preferably, a silica-alumina support is provided. Such a carrier can be purchased or manufactured, for example by atomizing an alumina precursor in the presence of a compound comprising silicon. The support containing alumina and silica may be prepared by any other means known to those skilled in the art, for example by impregnation of an organosilyl compound of TEOS (tetraethylorthosilicate) type on an alumina. In this case, this impregnation, followed by drying and calcination, is preliminary to step a) described above. The solid containing alumina, silica can then be dried and calcined. The drying is advantageously carried out at a temperature of between 60 ° C. and 200 ° C., preferably for a period ranging from 30 minutes to three hours. The calcination is suitably carried out at a temperature of from 200 ° C to 1100 ° C, preferably from 1 hour to 24 hours, and preferably from 2 hours to 8 hours. The calcination is generally carried out under an oxidizing atmosphere, for example under air, or under oxygen-depleted air; it can also be carried out at least partly under nitrogen.
    [0026] All the drying and calcination steps described in the present description can be carried out by any technique known to those skilled in the art: fixed bed, fluidized bed, oven, muffle furnace, rotary kiln.
    [0027] Step b) consists of impregnating, preferably dry, said support containing alumina, silica, with an aqueous solution of one or more salts of a metal M or M 'chosen from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co), nickel (Ni), tin (Sn), zinc (Zn), lithium (Li), calcium ( Ca), cesium (Cs), sodium (Na), potassium K, iron (Fe) and manganese (Mn), preferably cobalt, nickel, magnesium, calcium and zinc, and very preferably cobalt and nickel, and particularly preferably cobalt, followed by drying and calcination at a temperature between 700 and 1200 ° C.
    [0028] The metal M or M 'is contacted with the support via any soluble metal precursor in the aqueous phase. Preferably, when the metal M or M 'belongs to the group VIIIB, then the precursor of the group VIIIB metal is introduced in aqueous solution, preferably in the form of nitrate, carbonate, acetate, chloride, oxalate complexes formed by a polyacid or an alcoholic acid and its salts, complexes formed with acetylacetonates, or any other soluble inorganic derivative in aqueous solution, which is brought into contact with said support. In the preferred case where the metal M is cobalt, the cobalt precursor advantageously used is cobalt nitrate, cobalt oxalate or cobalt acetate.
    [0029] The metal content M or M 'is advantageously between 1 and 20% by weight and preferably between 2 and 10% by weight relative to the total mass of the final support. The drying is advantageously carried out at a temperature of between 60 ° C. and 200 ° C., preferably for a period ranging from 30 minutes to three hours.
    [0030] The calcination is carried out at a temperature between 700 and 1200 ° C, preferably between 850 and 1200 ° C, and preferably between 850 and 900 ° C, generally for a period of between one hour and 24 hours and preferably between 2 hours and 5 hours. The calcination is generally carried out under an oxidizing atmosphere, for example under air, or under oxygen-depleted air; it can also be carried out at least partly under nitrogen. It makes it possible to transform the precursors M and M 'and alumina into a spinel type structure (aluminate of M and M').
    [0031] According to one variant, the calcination can also be carried out in two stages, said calcination is advantageously carried out at a temperature of between 300 ° C. and 600 ° C. in air for a period of between half an hour and three hours, and then at a temperature of temperature of between 700 ° C. and 1200 ° C., preferably between 850 and 1200 ° C. and preferably between 850 and 900 ° C., generally for a period of between one hour and 24 hours, and preferably between 2 hours and hours and 5 hours. Thus, at the end of said step b), said support containing alumina and silica also contains at least one simple MAI2O4 spinel or mixed MxM '(1-x) Al2O4 partial or not, in which the metals M and M 'are in the form of aluminates.
    [0032] Preferably, in step c), said support is impregnated with a solution comprising only the group VIIIB metal precursor selected from cobalt, nickel, ruthenium and iron; and in step d), said support of step c) is impregnated with a solution comprising the boron precursor and the group VIIIB metal precursor selected from cobalt, nickel, ruthenium and iron. In particular, the impregnation stages c) and d) are carried out by dry impregnation, by excess impregnation, or by deposition-precipitation according to methods that are well known to a person skilled in the art. Preferably, the impregnation steps c) and d) are carried out by dry impregnation, preferably at room temperature, and preferably at a temperature of 20 ° C. More particularly, the impregnation steps c) and / or d) comprise contacting said support with a solution comprising at least one precursor of said group VIIIB metal and a solution comprising a boron precursor (supplied at the stage c) and / or d)). The total volume of solutions impregnated in steps c) and d) is equal to the pore volume of said support to be impregnated.
    [0033] The metal precursor of the group VIIIB metal (s) is supplied with solution at a desired concentration in order to obtain on the final catalyst the target metal content, advantageously a metal content of between 0.01 and 60% by weight, and preferably between 5 and 30% by weight relative to the weight of the catalyst. Preferably, the metal content of the group VIIIB metal (s) supplied in step c) is between 0.005 and 30% by weight relative to the total weight of the catalyst, preferably between 1 and 30% by weight. , and even more preferably between 2.5 and 15% by weight, the metal content of the group VIIIB metal (s) supplied in stage d) is between 0.005 and 30% by weight relative to the total weight of the catalyst, preferably between 1 and 30% by weight, and even more preferably between 2.5 and 15% by weight. The solution containing the boron precursor is supplied to a desired concentration in order to obtain on the final catalyst a boron content of between 0.001 and 0.5% by weight, the value 0.5 being itself excluded, preferably between 0.02 and 0.02. and 0.4% by weight based on the weight of the catalyst, more preferably between 0.02 and 0.35%, and even more preferably between 0.02 and 0.2% by weight relative to the weight of the catalyst. Preferably, the boron precursor is supplied with solution in step d), simultaneously with the precursor of the group VIIIB metal (co-impregnation).
    [0034] The Group VIIIB metal or metals are contacted with the support via any soluble metal precursor in the aqueous phase or in the organic phase. When introduced in organic solution, the group VIIIB metal precursor is preferably the oxalate or the acetate of said group VIIIB metal. Preferably, the group VIIIB metal precursor is introduced in aqueous solution, preferably in the form of nitrate, carbonate, acetate, chloride, oxalate, complexes formed by a polyacid or an alcoholic acid. and its salts, complexes formed with acetylacetonates, or any other soluble inorganic derivative in aqueous solution, which is brought into contact with said support. In the preferred case where the Group VIIIB metal is cobalt, the cobalt precursor advantageously used is cobalt nitrate, cobalt oxalate or cobalt acetate. Most preferably, the precursor used is cobalt nitrate. The boron source may be boric acid, preferably orthoboric acid H3B03, biborate or ammonium pentaborate, boron oxide, boric esters. Boron may for example be introduced in the form of a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines. compounds of the family of pyridine and quinolines and compounds of the pyrrole family. Boron may be introduced for example by a boric acid solution in a water / alcohol mixture.
    [0035] Said impregnation steps c) and d) of the support with the active phase may also advantageously comprise at least one additional step of depositing at least one additional doping element chosen from a noble metal of groups VIIB or VIIIB on said support oxides. The dopant is preferably selected from platinum (Pt), palladium (Pd), rhodium (Rh) or rhenium (Re). More preferably, the additional doping element is platinum (Pt). The deposition of the additional dopant on the support can advantageously be carried out by any method known to those skilled in the art, preferably by impregnation of said oxide support with at least one solution containing at least one precursor of said additional dopant, and preferably by Dry or impregnated impregnation in excess. This solution contains at least one precursor of said additional dopant at the desired concentration to obtain on the final catalyst the additional dopant content of between 20 ppm and 1% by weight, and preferably between 0.01 and 0.5% by weight relative to the catalyst weight. Subsequently, the catalyst containing the dopant is dried and calcined under the same conditions as those described in the drying and calcination steps during the impregnation of the active phase. The introduction of the additional doping element may be carried out at the same time as the impregnation of the aqueous or organic solution comprising said group VIIIB metal salt selected from cobalt, nickel, ruthenium and iron, and said boron precursor, ie in step c) and / or d), or in an additional step (after step d)). Preferably, the additional doping element is introduced at the same time as the impregnation of said aqueous or organic solution comprising said group VIIIB metal salt selected from cobalt, nickel, ruthenium and iron, and said boron precursor .
    [0036] The catalyst thus obtained is then dried and calcined. The drying is advantageously carried out at a temperature of between 60 ° C. and 200 ° C., preferably for a period ranging from 30 minutes to three hours. The calcination is advantageously carried out at a temperature between 320 ° C and 460 ° C, preferably between 350 and 440 ° C and preferably between 360 and 420 ° C. It is preferably carried out for a period of between 15 min and 15 h and preferably between 30 min and 12 h and even more preferably between 1 h and 6 h. The calcination is generally carried out under an oxidizing atmosphere, for example under air, or under oxygen-depleted air; it can also be carried out at least partly under nitrogen. Prior to its use in the Fischer-Tropsch synthesis catalytic reactor, the catalyst is generally subjected to a reducing treatment, for example in pure or dilute hydrogen, at high temperature, for activating the catalyst and forming metal particles 10 to 10. zero state are worth (in metallic form). This treatment can be carried out in situ (in the same reactor as that where the Fischer-Tropsch synthesis is performed), or ex situ before being loaded into the reactor. The temperature of this reducing treatment is preferably between 200 ° C. and 500 ° C. and its duration is generally between 2 and 20 hours.
    [0037] Fischer-Tropsch Process The present invention also relates to a Fischer-Tropsch process by contacting a filler comprising synthesis gas under Fischer-Tropsch synthesis operating conditions with at least one catalyst according to the invention or prepared according to the preparation process of the invention. The Fischer-Tropsch process allows the production of essentially linear and saturated hydrocarbons C5 +. According to the invention, the term "substantially linear and saturated hydrocarbons C5 +" is intended to mean hydrocarbons whose proportion of hydrocarbon compounds having at least 5 carbon atoms per molecule represents at least 50% by weight, preferably at least 80% by weight. of all the hydrocarbons formed, the total content of olefinic compounds present among said hydrocarbon compounds having at least 5 carbon atoms per molecule being less than 15% by weight. The hydrocarbons produced by the process of the invention are thus essentially paraffinic hydrocarbons, of which the fraction having the highest boiling points can be converted with a high yield of middle distillates (diesel and kerosene cuts) by a catalytic process. hydroconversion such as hydrocracking and / or hydroisomerization.
    [0038] Preferably, the feedstock used for carrying out the process of the invention is constituted by the synthesis gas, which is a mixture of carbon monoxide and hydrogen of molar ratios H 2 / CO, which can vary between 0.degree. , 5 and 4 depending on the manufacturing process from which it is derived. The H2 / CO molar ratio of the synthesis gas is generally close to 3 when the synthesis gas is obtained from the process of steam reforming hydrocarbons or alcohol. The H2 / CO molar ratio of the synthesis gas is of the order of 1.5 to 2 when the synthesis gas is obtained from a partial oxidation process. The H2 / CO molar ratio of the synthesis gas is generally close to 2.5 when it is obtained from an autothermal reforming process. The H 2 / CO molar ratio of the synthesis gas is generally close to 1 when it is obtained from a CO2 gasification and reforming process (called dry reforming). The Fischer-Tropsch process according to the invention is carried out under a total pressure of between 0.1 and 15 MPa, preferably between 0.5 and 10 MPa, at a temperature of between 150 and 350 ° C., preferably between 180 and 350 ° C. and 270 ° C. The hourly volume velocity is advantageously between 100 and 20000 volumes of synthesis gas per volume of catalyst and per hour (100 to 20000 h -1) and preferably between 400 and 10,000 volumes of synthesis gas per volume of catalyst and per hour (400 to 10000 h-1).
    [0039] The Fischer-Tropsch process according to the invention can be carried out in a perfectly stirred autoclave type reactor, bubbling bed, bubble column, fixed bed or moving bed. Preferably, it is carried out in a bubble column reactor. As a result, the grain size of the catalyst used in the Fischer-Tropsch process may be between a few microns and 2 millimeters. Typically, for use in a three-phase "slurry" reactor (in a bubble column), the catalyst is finely divided and is in the form of particles. The size of the catalyst particles will be between 10 and 500 micrometers (μm), preferably between 10 and 300 μm and very preferably between 20 and 150 μm, and even more preferably between 20 and 120 μm.
    [0040] To illustrate the invention and to enable those skilled in the art to perform it, we will hereinafter show various embodiments of the process for preparing a catalyst used for Fischer-Tropsch synthesis; however this can not limit the scope of the invention.
    [0041] EXAMPLE 1 Preparation of Catalysts A and B (Comparative) and Catalyst C (According to the Invention) Catalyst A (Non-Conforming) Catalyst 25% Co on Silica-Alumina at 5% SiO 2 and 5 (3/0) CO in aluminate form (spinel) On a Siralox® 5 commercial support (Sasol Germany), containing 5% by weight of SiO 2, a solution of cobalt nitrate is impregnated, then the solid is dried in an oven for 12 hours at 120 ° C. and calcined in a fixed-bed tubular reactor at 800 ° C. for 2 hours This high temperature calcination makes it possible to form the cobalt aluminate spinel phase (5% by weight of cobalt) on this support stabilized with silicon and with cobalt in the form of spinel, a cobalt nitrate solution is impregnated in. The solid obtained is then dried in an oven for 12 hours and then calcined in air in a fixed-bed tubular reactor at 420 ° C. for 2 hours. 0% by weight of cobalt This intermediate solid undergoes a new impregnated followed by a solution of cobalt nitrate, followed by drying and calcination identical to the previous step. The final catalyst A which contains 25.0% by weight of cobalt (the content of Co present in the spinel phase being included) is obtained in two stages of preparation and a reducible cobalt content of 20.0% by weight.
    [0042] Catalyst B (non-compliant): 25% Co + 5% B catalyst on silica-alumina at 5% SiO 2 and 5 (3/0 Co in aluminate form (spinel) On a Siralox® 5 commercial support (Sasol Germany) containing 5% by weight of SiO 2, a solution of cobalt nitrate is impregnated, the solid is then dried in an oven for 12 hours at 120 ° C., and calcined in a fixed-bed tubular reactor at 800 ° C. for 2 hours. This calcination at high temperature makes it possible to form the cobalt aluminate spinel phase (5% by weight of cobalt), on this support stabilized with silicon and with cobalt in the form of spinel, a solution containing cobalt nitrate and cobalt nitrate is impregnated. The solid obtained is then dried in an oven for 12 hours and then calcined in air in a fixed-bed tubular reactor at 420 ° C. for 2 hours, containing 15.0% by weight of cobalt and 0.27% by weight. weight of boron This intermediate solid undergoes a new impregnation with a solution of cobalt nitrate and of boric acid, followed by drying and calcination identical to the previous step. The final catalyst B which is obtained in two stages of preparation contains 25.0% by weight of cobalt and 0.5% by weight of boron (the content of Co present in the spinel phase being included) and a reducible cobalt content of 20.0% by weight. Catalyst C (according to the invention): Catalyst 25% Co + 0.2% B on Silica-Alumina at 5% SiO 2 5 and 5% Co in Aluminate Form (Spinel) On a commercial support Siralox® 5 (Sasol Germany), containing 5% by weight of SiO 2, a solution of cobalt nitrate is impregnated, then the solid is dried in an oven for 12 hours at 120 ° C., and calcined in a fixed-bed tubular reactor at 800 ° C. for 2 hours. This calcination at high temperature makes it possible to form the cobalt aluminate spinel phase (5% by weight of cobalt). On this support stabilized with silicon and with cobalt in the form of spinel, a solution containing cobalt nitrate and boric acid is impregnated. The solid obtained is then dried in an oven for 12 h and then calcined in air in a fixed-bed tubular reactor at 420 ° C. for 2 hours. It contains 15.0% by weight of cobalt and 0.11% by weight of boron. This intermediate solid undergoes a new impregnation with a solution of cobalt nitrate and boric acid, followed by drying and calcination identical to the previous step. The final catalyst C which contains 25.0% by weight of cobalt and 0.2% by weight of boron (the content of Co present in the spinel phase being included) is obtained in two stages of preparation and a reducible cobalt content of 20. 0% weight
    [0043] EXAMPLE 2 Fischer-Tropsch catalytic performances of catalysts A to C Catalysts A to C, before being successively tested in conversion of synthesis gas, are reduced ex situ under a stream of pure hydrogen at 400 ° C. C for 16 hours in a tubular reactor. Once the catalyst is reduced, it is discharged under an argon atmosphere and coated with SasoIwax® wax to be stored protected from the air before testing. The Fischer-Tropsch synthesis reaction is carried out in a slurry-type reactor operating continuously and operating with a concentration of 10% (vol) of catalyst in the slurry phase.
    [0044] Each of the catalysts is in powder form with a diameter of about 30 to 170 microns. The test conditions are as follows: Temperature = 220 ° C. 3035007 22 Total pressure = 2 MPa Molar ratio H2 / CO = 2 The conversion of CO is maintained between 45 and 50% throughout the test.
    [0045] The test conditions are adjusted to be iso CO conversion regardless of the activity of the catalyst. The results were calculated for Catalysts A to C relative to Catalyst A as a reference and are shown in Table 1 below. The paraffin alpha selectivities are also given as well as the methane selectivity. The measurement of the alpha paraffin selectivity is carried out by gas chromatographic analysis of the reaction effluents, paraffin measurement and calculation of the slope of the corresponding log-mol (%) = f (carbon number) curve. at the alpha coefficient. Table 1 Cat. Target Formulation Relative Activity after Selectivity of Selectivity at (') wt.% Per 300 h of paraffin-based test versus weight load syngas methane (%) long total catalyst) A 25% Co 100 (base) 10 0.894 B 25% Co + 0.5% B 104 10.5 0.892 C 25% Co + 0.2% B 145 10 0.896 The results in Table 1 show the catalytic performances of catalysts A to C; It appears that the catalyst C according to the invention shows significant gains in activity relative to the comparative catalysts while keeping a selectivity equivalent to the catalyst A.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. Catalyst containing an active phase comprising at least one Group VIIIB metal selected from cobalt, nickel, ruthenium and iron deposited on a support containing silica, alumina, and at least one MAI204 or mixed MxIM simple spinel (p-x) Al 2 O 4, partial or not, where M and M 'are distinct metals selected from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co), nickel (Ni), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), cesium (Cs), sodium (Na), potassium (K), iron (Fe) and manganese (Mn) and where x is between 0 and 1, the values 0 and 1 being themselves excluded, characterized in that said active phase further comprises boron, the boron content being between 0.001% and 0, 5% by weight relative to the total weight of the catalyst, the value 0.5 itself being excluded.
    [0002]
    2. Catalyst according to claim 1, characterized in that said support is a silica-alumina in which the spinel is included.
    [0003]
    3. Catalyst according to claims 1 or 2, wherein the spinel content is between 3 and 50% by weight relative to the weight of the support.
    [0004]
    4. Catalyst according to any one of claims 1 to 3, wherein the metal content M or M 'is between 1 and 20% by weight relative to the weight of the support.
    [0005]
    5. Catalyst according to any one of claims 1 to 4, wherein M is cobalt in the case of a simple spinel, and M is cobalt and M 'is magnesium or zinc in the case of a spinel mixed.
    [0006]
    6. Catalyst according to any one of claims 1 to 5, wherein the group VIIIB metal content of the active phase is between 0.01 and 60% by weight relative to the weight of the catalyst.
    [0007]
    7. Process for the preparation of a catalyst according to any one of claims 1 to 6, which process comprising at least one step in which said support containing silica, alumina and spinel is impregnated with an aqueous solution or An organic compound comprising at least one group VIIIB metal salt selected from cobalt, nickel, ruthenium and iron, and at least one boron precursor.
    [0008]
    The process of claim 7 comprising the steps of: a) providing a support containing silica and alumina; b) said support is impregnated with an aqueous or organic solution comprising at least one metal salt M or M 'chosen from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co), nickel ( Ni), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), cesium (Cs), sodium (Na), potassium (K), iron ( Fe) and manganese (Mn), then dried and calcined at a temperature between 700 and 1200 ° C, so as to obtain a simple spinel MAI204 or mixed MxM '(, - x) Al204 partial or not, where M and M 'are distinct metals and where x is between 0 and 1, the values 0 and 1 being themselves excluded; c) first impregnating said support containing silica, alumina and spinel with an aqueous or organic solution comprising at least one group VIIIB metal salt selected from cobalt, nickel, ruthenium and iron ; d) a second impregnation said support containing silica, alumina and spinel with an aqueous or organic solution comprising at least one group VIIIB metal salt selected from cobalt, nickel, ruthenium and iron ; Wherein said aqueous or organic solution impregnated in step c) and / or d) further comprises the boron precursor.
    [0009]
    9. The method of claim 8, wherein the boron precursor is introduced only into the aqueous or organic solution supplied in step d). 25-
    [0010]
    10. The method of claim 8 or 9, wherein the content content of the Group VIIIB metal (s) supplied in step c) is between 0.005 and 30% by weight relative to the weight of the catalyst. 30
    [0011]
    11. A method according to any one of claims 8 to 10, wherein the content of Group VIIIB metal (s) supplied in step d) is between 0.005 and 30% by weight relative to the total weight of the catalyst.
    [0012]
    12. A process according to any one of claims 7 to 11, wherein the boron precursor is boric acid.
    [0013]
    13. A process according to any one of claims 8 to 12, wherein the catalyst obtained in step d) is dried at a temperature of between 30 minutes and 35 hours, and then said dried catalyst is calcined under an oxidizing atmosphere at a temperature of between 30 minutes and 35 hours. temperature between 320 ° C and 460 ° C.
    [0014]
    The process according to claim 13, wherein the dried and calcined catalyst is reduced to a temperature between 200 ° C and 500 ° C. 10
    [0015]
    A hydrocarbon synthesis Fischer-Tropsch process wherein the catalyst of any one of claims 1 to 6 or prepared according to any one of claims 7 to 14 is contacted with a feed comprising synthesis gas under a total pressure of between 0.1 and 15 MPa, at a temperature between 150 and 350 ° C, and at an hourly space velocity of between 100 and 20000 volumes of synthesis gas per volume of catalyst and per hour with a ratio of molar H2 / CO synthesis gas between 0.5 and 4.
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    同族专利:
    公开号 | 公开日
    DK3283216T3|2020-03-23|
    CN107438481A|2017-12-05|
    US11020728B2|2021-06-01|
    WO2016165859A1|2016-10-20|
    EP3283216B1|2020-01-01|
    US20180104672A1|2018-04-19|
    EP3283216A1|2018-02-21|
    FR3035007B1|2019-04-19|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1553399|2015-04-16|
    FR1553399A|FR3035007B1|2015-04-16|2015-04-16|CATALYST COMPRISING AN ACTIVE DOPED PHASE|FR1553399A| FR3035007B1|2015-04-16|2015-04-16|CATALYST COMPRISING AN ACTIVE DOPED PHASE|
    US15/565,913| US11020728B2|2015-04-16|2016-02-22|Catalyst comprising a boron-doped active phase|
    DK16707672.8T| DK3283216T3|2015-04-16|2016-02-22|CATALYST, INCLUDING A BOREDOTIC ACTIVE PHASE|
    PCT/EP2016/053631| WO2016165859A1|2015-04-16|2016-02-22|Catalyst including a boron-doped active phase|
    EP16707672.8A| EP3283216B1|2015-04-16|2016-02-22|Catalyst comprising a boron doped phase|
    CN201680022111.XA| CN107438481A|2015-04-16|2016-02-22|Include the catalyst of boron doped active phase|
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