Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
  • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
  • C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/44—Palladium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
  • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/396—Distribution of the active metal ingredient
  • B01J35/397—Egg shell like

Definitions

• the present invention relates to a selective hydrogenation catalyst for the transformation of diolefinic unsaturated hydrocarbons into ⁇ -olefinic hydrocarbons, which allows in particular the hydrogenation of diolefinic compounds to ⁇ -olefinic compounds with rates at least 1.5 times, often at at least 3 times or even 5 times greater than the rate of hydrogenation of the ⁇ -olefinic compounds into saturated compounds.
• This catalyst contains palladium and at least one element chosen from tin and lead.
• the invention also relates to the preparation of such a catalyst, as well as to the process for the selective hydrogenation of diolefins to ⁇ -olefins using this catalyst.
• Hydrocarbon conversion processes taking place at high temperatures allow a large production of olefinic compounds, such as ethylene, propylene, n- butene-1, n-butenes-2, isobutene, pentenes and diolefins, such as propadiene-1, 2, butadiene-1, 3, and other compounds whose boiling point is included in the cutting interval "gasoline" and which can be 5 olefinic or diolefinic.
• olefinic compounds such as ethylene, propylene, n- butene-1, n-butenes-2, isobutene, pentenes and diolefins, such as propadiene-1, 2, butadiene-1, 3, and other compounds whose boiling point is included in the cutting interval "gasoline” and which can be 5 olefinic or diolefinic.
• the C4 steam cracking cut contains a high proportion of butadiene-1, 3, butene-1, butenes-2 and isobutene.
• butadiene is separated from the olefinic cut, for example by extractive distillation in the presence of dimethylformamide or N-methylpyrrolidone.
• the olefinic cut thus obtained contains isobutane, isobutene, butene-1, butenes-2, n-butane and butadiene-1, 3, the latter at a content which can vary between 0.1 and 2% by weight.
• the cut can be directly treated on a catalyst in the presence of hydrogen to transform the butadiene into n-butenes.
• butene-1 and isobutene are desired, it is necessary to use processes allowing the significant production of butene-1 and the separation of the various compounds such as the selective hydrogenation of butadiene to butenes with a low isomerization of butene -1 in butene-2, or the separation of isobutene by etherification with methanol leading to methyl-tertiobutyl-ether.
• butene-1 Today there is a strong demand for butene-1. This compound is used as a monomer in the polymer industry. Such use requires almost complete hydrodrogenation of butadiene, the presence of which is tolerated only at contents of less than 10 ppm by weight.
• the object of this invention is therefore a composition of matter allowing the hydrogenation of diolefinic compounds into ⁇ -olefinic compounds.
• Another object of the present invention is a composition of matter allowing a ratio of diolefin / ⁇ -olefin hydrogenation rates at least equal to 1.5: 1.
• a third object of the present invention is a composition of matter allowing good selectivity for butene-1 with respect to all of the n-butenes during the hydrogenation of butadiene-1, 3.
• the invention therefore provides a hydrogenation catalyst characterized in that it comprises particles of a porous support and, as active elements, palladium distributed at the periphery of the particles and at least one element M chosen from l and lead.
• a proportion of at least 80% of the palladium is included in the volume of the particles (for example beads or extrusions) constituting the catalyst defined between the periphery of said particles and a thickness of 500 ⁇ m, as shown in section in the diagram. below:
• the palladium content of the catalyst is between 0.025% and 1.0% by weight, preferably between 0.03 and 0.5% by weight.
• the content of element M (tin and / or lead) in the catalyst is generally between 0.05% and 4% by weight, preferably from 0.2 to 4% for tin and from 1 to 4% by weight for lead.
• the element M / palladium atomic ratio is between 0.1 and 3.
• the support for the hydrogenation catalyst according to the invention can be chosen from the family of compounds containing aluminas, silicas, silico-aluminates and clays.
• the supports of low acidity are chosen, such as, for example, silicas, aluminas of low specific surface or aluminosilicates exchanged with alkalis.
• the support can be, for example, an alumina in particulate form, for example in the form of beads, extrudates, or else pellets. It can for example be in the form of balls with an average diameter generally between 2 and 4 mm.
• the characteristics of the alumina used are, for example, without limitation, the following:
• This precursor is preferably an inorganic compound, such as palladium chloride or palladium nitrate.
• the pH of the solution is advantageously greater than 0.8.
• the element M (tin and / or lead) can also be introduced for example by impregnation of an aqueous or organic solution of a precursor of the element M.
• Acetates, chlorides, alkyl complexes, nitrates, alcoholates can for example be used.
• the alkyl complexes can be tetrabutyl tin or tetrabutyl lead.
• the two metals can be introduced from a common solution of the two precursors or from separate solutions. In the latter case, drying, calcination or reduction treatments at temperatures between 120 ° C. and 900 ° C. may possibly be carried out between the two impregnation steps.
• the distribution of the metal M in the particles, for example beads or extrusions, of catalyst corresponds to that defined for palladium, that is to say that at least 80% of the tin and / or lead is included in the volume of the particle, for example ball or extruded, constituting the catalyst defined between the periphery of said particle and a thickness of 500 ⁇ m as shown above.
• the catalyst thus obtained is generally dried at temperatures between room temperature and 150 ° C.
• the catalyst thus dried can be used as it is; most often it is calcined in order to decompose the metal precursors and / or it is reduced before its use.
• Calcination is generally carried out by treating the catalyst under an air flow at a temperature between 400 ° C and 900 ° C.
• the reduction can be carried out by treatment of the catalyst with a gas containing hydrogen, for example at a temperature between room temperature and 500 ° C.
• the selective hydrogenation process using the catalysts of the invention can be carried out under the usual conditions.
• the charge generally consisting of a C4 cut coming from a steam cracking operation passes through the catalyst placed in a fixed bed, at a temperature generally between 40 and 100 ° C, under a pressure of 5 to 40 bar, preferably 10 at 30 bar and at an hourly volume speed from 1 to 20 h ⁇ 1 , preferably from 4 to 10 h -1 .
• a palladium-based catalyst A is prepared by impregnating
• the support is in the form of beads 2 mm in diameter, its specific surface is 60 m 2 / g and the pore volume is 0.6 ml / g.
• the catalyst is dried at 120 ° C, calcined at 450 ° C and reduced for 2 hours at 150 ° C.
• Part of the catalyst A (1.00 g) is then introduced into a perfectly stirred reactor containing 10 g of butadiene-1, 3 and 100 g of n-heptane.
• the reactor is then purged with nitrogen and brought to hydrogen pressure (10 bar) with stirring at 20 ° C.
• the experimental device makes it possible to work with catalyst balls without the latter undergoing attrition during the test (use of Carbery type basket).
• the experimental system used makes it possible to work at constant pressure, to measure the consumption of hydrogen as a function of time and to take liquid samples at regular intervals whose analysis by chromatography makes it possible to determine the composition of the medium. From these data, we define different parameters:
• Kbd the rate of hydrogenation of butadiene
• catalysts B and C Two catalysts (catalysts B and C) based on palladium and tin are prepared from 100 g of catalyst A. The tin is then introduced by impregnating 60 ml of a solution of tetrabutyl- tin containing the desired content of this element. The catalysts are then dried at 120 ° C, calcined at 450 ° C and reduced for 2 hours at 150 ° C.
• Catalyst C which contains 0.53% by weight of tin therefore allows the hydrogenation of butadiene with a speed at least five times greater than that of the hydrogenation of butene-1.
• a Cbis catalyst based on palladium and tin is prepared according to the following protocol:
• Example 1 100 g of support described in Example 1 are impregnated with an aqueous solution of tin (II) acetate.
• the volume of solution used corresponds to the volume of the support and the tin concentration of the solution is adjusted to obtain a final tin content of 0.53% by weight relative to the support.
• the sample is then dried at 120 ° C and calcined at 450 ° C.
• the palladium is then deposited on this catalyst according to the same impregnation technique as that described in Example 1.
• the final palladium content is 0.3% by weight.
• the activity of the catalyst Cbis is then evaluated under the conditions described in Example 1. The results obtained under these conditions are reported in the following table:
• the catalyst Cbis which contains 0.53% by weight of tin therefore allows the hydrogenation of butadiene with a speed at least 1.5 times greater than that of the hydrogenation of butene-1.
• the Kbd Kb1 ratio is lower than that obtained with catalyst C.
• a Cter catalyst based on palladium and tin is prepared according to the following protocol:
• Example 1 100 g of support described in Example 1 are impregnated with an organic solution of palladium bis acetylacetonate.
• the volume of solution used corresponds to 5 times the volume of the support and the palladium concentration of the solution is adjusted to obtain a final palladium content of 0.3% by weight relative to the support.
• the sample is then dried at 120 ° C and calcined at 450 ° C.
• the tin is then deposited on this catalyst using the same impregnation technique as that described in Example 2.
• the final palladium content is 0.3% by weight of palladium.
• a series of catalysts (catalysts D to J) based on palladium and lead are prepared by impregnating 100 g of alumina support with 60 ml of an aqueous solution of dissolved lead nitrate. The amount of lead nitrate is adjusted to have catalysts with variable content of this element.
• the support has the same characteristics as that used in Example 1.
• the catalyst is dried at 120 ° C, then calcined at 450 ° C.
• Palladium is then introduced by impregnating the catalysts with 60 ml of a solution of palladium nitrate dissolved in nitric acid to obtain a final catalyst at 0.3% by weight of palladium.
• the catalysts are then dried at 120 ° C, calcined at 450 ° C and reduced for 2 hours at 150 ° C.
• catalysts containing lead contents greater than 2% by weight therefore allow the hydrogenation of butadiene with a speed at least five times greater than that of the hydrogenation of butene-1.
• a catalyst (Gbis catalyst) based on palladium and lead is prepared from 100 g of catalyst A. Catalyst A is reduced to 150 ° C., then the introduction of lead is carried out by impregnation of 60 ml of a tetrabutyl-lead solution containing the desired content of this element. The catalyst is then dried at 120 ° C, and reduced for 2 hours at 150 ° C.
• the catalyst Gbis which contains 0.99% by weight of lead therefore allows the hydrogenation of butadiene with a speed at least 1.5 times greater than that of the hydrogenation of butene-1. Compared to catalyst G, this catalyst has a higher Kbd / Kb1 ratio.
• a catalyst K based on palladium and silver is prepared according to the conditions described in patent US-A-4 409 410.
• Catalyst K is prepared by impregnating 100 g of the alumina used in Example 1 with 60 ml of a solution of nitric acid, palladium nitrate and silver nitrate, to obtain a final catalyst containing 0 , 3% by weight of palladium and 0.5% by weight of silver. The catalyst is then dried at 120 ° C, calcined at 450 ° C and reduced for 2 hours at 150 ° C.
• the catalyst K makes it possible to obtain a better selectivity for butene-1 compared to the monometallic catalyst, which corresponds to the properties announced in the previously cited patent, but the ratio of the speed constants Kbd Kb1 is close to 1, which means that on this catalyst, the rate of hydrogenation of butadiene is practically equivalent to the rate of hydrogenation of butene-1.
• Example 5 comparative
• a catalyst L based on palladium and gold is prepared according to the conditions described in US-A-4,533,779.
• Catalyst L is prepared by impregnating 100 g of the alumina used in Example 1 with 60 ml of a solution of nitric acid and palladium nitrate, to obtain a catalyst containing 0.3% by weight of palladium. The catalyst is then dried at 120 ° C, calcined at 300 ° C and reduced for 2 hours at 300 ° C. The catalyst is then impregnated with an aqueous solution of chloroauric acid (HAuCU), to obtain a final catalyst at 0.5% by weight of gold.
• HAuCU chloroauric acid
• catalyst L The activity of catalyst L is then evaluated under the conditions described in Example 1.
• Catalyst L makes it possible to obtain a better selectivity for butene-1 relative to the monometallic catalyst, but the ratio of the speed constants Kbd Kb1 is close to 1, which means that on this catalyst the rate of hydrogenation of butadiene is practically equivalent to the rate of hydrogenation of butene-1.

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• 1996
  • 1996-11-07 FR FR9613576A patent/FR2755378B1/fr not_active Expired - Fee Related
• 1997
  • 1997-10-28 AU AU49524/97A patent/AU731009B2/en not_active Ceased
  • 1997-10-28 WO PCT/FR1997/001929 patent/WO1998019793A1/fr active IP Right Grant
  • 1997-10-28 EP EP97912269A patent/EP0946299A1/de not_active Withdrawn
  • 1997-10-28 CN CN97199547A patent/CN1107547C/zh not_active Expired - Fee Related
  • 1997-10-28 JP JP52109298A patent/JP2001503324A/ja active Pending
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  • 1997-10-28 KR KR10-1999-7004008A patent/KR100485239B1/ko not_active IP Right Cessation
  • 1997-10-28 RU RU99112176/04A patent/RU2192306C2/ru not_active IP Right Cessation
  • 1997-10-28 CA CA002270574A patent/CA2270574A1/fr not_active Abandoned
  • 1997-11-06 US US08/964,129 patent/US5955397A/en not_active Expired - Lifetime
• 1999
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