WO2020005161A1 - Composition de catalyseur - Google Patents

Composition de catalyseur Download PDF

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Publication number
WO2020005161A1
WO2020005161A1 PCT/SG2019/050320 SG2019050320W WO2020005161A1 WO 2020005161 A1 WO2020005161 A1 WO 2020005161A1 SG 2019050320 W SG2019050320 W SG 2019050320W WO 2020005161 A1 WO2020005161 A1 WO 2020005161A1
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catalyst composition
promoter
catalyst
composition according
metal
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Yan Liu
Wenjin YAN
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Agency for Science, Technology and Research
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/16—Phosphorus; Compounds thereof containing oxygen

Definitions

  • the present invention generally relates to a catalyst composition comprising metal oxides useful in a catalytic oxidative dehydrogenation of the short chains of alkene.
  • the present invention is also directed to a method for preparing the catalyst composition as defined herein.
  • 1,3-butadiene (or abbreviated as“BD”) is regarded as one of the important bulk chemicals with myriads of applications, in particular in the manufacture of polymers.
  • the examples of polymers that can be prepared from 1,3-butadiene include styrene butadiene rubber (SBR), polybutadiene rubber (PB), styrene-butadiene latex (SBL) and acrylonitrile-butadiene- styrene (ABS) resin.
  • SBR styrene butadiene rubber
  • PB polybutadiene rubber
  • SBL styrene-butadiene latex
  • ABS acrylonitrile-butadiene- styrene
  • Today, 1,3-butadiene is primarily synthesized via steam cracking of hydrocarbon feedstock, as a by-product in C4 fraction.
  • thermodynamic equilibrium is low. For instance, at approximately 0.1 bar, the equilibrium conversions for the dehydrogenation reaction are reported to be 35% and 71% at 500°C and 600°C, respectively. Hence, such process operates at relatively low conversion (about 40 to 50%) and selectivity (about 70 to 90%).
  • Other limitations of this process include short on-stream periods to avoid the formation of the coke on the catalysts, which must be then regenerated and release of steam from the process.
  • the present invention therefore provides a catalyst composition used in a catalytic oxidative dehydrogenation (ODH) that overcomes, or at least ameliorates, one or more of the disadvantages described above.
  • ODH catalytic oxidative dehydrogenation
  • a catalyst composition comprising:
  • the catalyst composition as defined herein may enhance the selectivity of the reaction thereby minimizing the side reactions and the formation of side products.
  • said catalyst composition may also advantageously increase the yield of the reaction at a relatively lower reaction temperature.
  • the catalyst composition as defined herein may be stable and may remain highly active after being used in the reaction.
  • step b) drying the mixture obtained in step a) at a drying temperature
  • said catalyst composition comprises:
  • alkene refers to a hydrocarbon compound comprising one carbon-to- carbon double bond. Unless specified otherwise, the term “alkene” used in the present disclosure may be acyclic alkene having only one carbon-to-carbon double bond and no other functional groups. Such alkene may therefore be termed as mono-ene.
  • the term “diene” as used herein refers to a compound having two carbon-to-carbon double bonds. Accordingly, the term “1,3-diene” refers to a compound having two carbon-to- carbon double bonds where these double bonds are in the 1,3 -position.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • a catalyst composition comprising:
  • the present disclosure also provides a catalyst composition consisting essentially of:
  • the metal of the at least one metal oxide of the catalyst composition as defined herein may be a transition metal, a non-transition metal, a combination thereof or an alloy thereof.
  • the transition metals include titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), zirconium (Zr), zinc (Zn), or a combination thereof or an alloy thereof. It is to be understood that other transition metals than those shown above may also be used. Transition metals referred herein are the transition metals found in Group IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the Periodic Table.
  • Non-transition metals may be selected from other metals found in the Periodic Table, which do not form part of the transition metals above. Such non-transition metals may be alkali metals and alkaline earth metals. Non-limiting examples of such non-transition metals include aluminium (Al), cadmium (Cd), indium (In), tin (Sn), lead (Pb), thallium (Tl), bismuth (Bi), a combination thereof or an alloy thereof. It is to be understood that other non-transition metals than those shown above may also be used.
  • Preferred metal of the at least one metal oxide of the catalyst composition may be indium (In).
  • transition metal oxide when the metal of the at least one metal oxide in the catalyst composition as defined above is the transition metal, the metal oxide may therefore be termed as transition metal oxide.
  • Such transition metal oxide may be selected from the group consisting of Ti0 2 , V0 2 , V 2 0 5 , CrO, Cr 2 0 3 , MnO, Mn 2 0 3 , Mn 3 0 4 , Mn 2 0 7 , CoO, Co 2 0 3 , Co 3 0 4 , NiO, Ni 2 0 3 , Zr0 2 , ZnO, a combination thereof and an alloy of such oxides.
  • the metal oxide may be selected from the group consisting of Al 2 0 3 , CdO, ln 2 0 3 , Sn0 2 and PbO, a combination thereof and an alloy of such oxides.
  • the at least one metal oxide may also be a combination of a transition metal oxide with a non -transition metal oxide, which may be in the form of an alloy or a mixture thereof.
  • the promoter of the catalyst composition as defined above may facilitate the catalytic process when said catalyst composition is used in a chemical reaction or transformation, that is, the promoter may enhance the yield of the reaction, increase the selectivity of the reaction or confer other benefits that cannot be obtained if such promoter is absent.
  • the promoter as defined above may be an oxide of a non-metal element, a metal including transition metal, non-transition metal or mixtures thereof.
  • oxide of a non-metal element include R 2( 3 ⁇ 4, R 4( 3 ⁇ 4, As 2 Os, Sb 4 0 6 , Se0 2 , Se0 3 , Bi 2 0 3 , Te0 2 , or Te0 3 .
  • the transition metal may also be used as the promoter.
  • Non-limiting examples of such transition metal may be as defined in the previous section.
  • the examples of the transition metal are not limited to those examples and therefore may also extend to other transition metals found in Group IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the Periodic Table.
  • the promoter may also be an alkali or alkaline earth metal such as sodium (Na), potassium (K), calcium (Ca), or barium (Ba). Further, the promoter as defined herein may also include both the oxide of a non-metal element and a transition metal. Preferred promoter in the present disclosure is P 2 Os and platinum (Pt).
  • each of the promoters may then be termed as a first promoter, a second promoter, a third promoter and so forth.
  • P 2 0 5 may be regarded as the first promoter and platinum (Pt) as the second promoter or vice versa.
  • Pt platinum
  • the presence of one or more promoter in the catalyst composition may provide synergistic effect to the catalyst composition.
  • the present disclosure also provides a catalyst composition comprising:
  • the present disclosure further provides a catalyst composition consisting essentially of:
  • the catalyst composition as defined herein may enhance the selectivity of the reaction thereby minimizing the side reactions and the formation of side products. Further, said catalyst composition may also advantageously increase the yield of the reaction at a relatively lower reaction temperature.
  • the support of the catalyst composition as defined herein may be thermally and / or chemically stable. Moreover, said support of the catalyst composition may be able to withstand process conditions required to prepare or activate pre-catalysts. For instance, if heat treatment such as heating is required in the preparation of the pre -catalysts, the catalyst support used is thermally stable.
  • the support of the catalyst composition as defined above may provide high surface areas useful in heterogeneous catalytic process.
  • Non-limiting examples of the support of the catalyst composition include alumina (Al 2 0 3 ), silica, Ti0 2 , Zr0 2 , zeolite, microporous and mesoporous materials or mixtures thereof.
  • the mesoporous material refers to a material having pore size with diameter between 2 nm to 50 nm and the microporous material refers to a material having pore size with diameter less than 2 nm.
  • the metal used as the catalyst support may be as previously defined. Hence, such metal may be selected from the transition metal, non-transition metal, a combination thereof and an alloy thereof.
  • the support is Al 2 0 3 .
  • the catalyst composition as defined herein may be useful in chemical reactions involving starting materials such as alkanes, alkenes, alcohols and related compounds, where the short- chained alkanes or short-chained alcohols may have 1 to 6 carbon atoms and the short-chained alkenes may have 2 to 6 carbon atoms.
  • Non-limiting examples of the reactions, in which the catalyst composition as disclosed herein may be used include oxidative dehydrogenation of the short chains of alkene.
  • the oxidative dehydrogenation of the short chains of alkene disclosed herein may produce corresponding dienes.
  • the catalyst composition as defined herein may be used in the oxidative dehydrogenation of 1- butene to produce 1,3 -butadiene.
  • the present disclosure provides a catalyst composition consisting essentially of:
  • the conversion of 1 -butene to valuable chemicals such as 1, 3-butadiene may be carried out in the presence of an oxidant such as oxygen, carbon dioxide or a mixture thereof.
  • an oxidant such as oxygen, carbon dioxide or a mixture thereof.
  • suitable oxidants than the above may also be used as appropriate.
  • Use of a soft oxidant for instance carbon dioxide has several benefits over molecular oxygen including minimization of total oxidation, reduction of hot spots as well as being environmentally benign.
  • the preferred oxidant used in the present disclosure is carbon dioxide.
  • the catalyst composition as defined herein may be stable and remain highly active after being used in the reaction i.e. one or more cycles of reaction. Therefore, when desired, it may be possible to regenerate said catalyst composition to be used for a further cycle of reaction.
  • the catalyst composition as defined herein may comprise active components or ingredients or constituents that may determine the catalytic performance of said catalyst composition. Such active ingredients may therefore be termed as active catalytic ingredients.
  • active catalytic ingredients of the catalyst components described above may be metal oxide(s) and / or promoter(s). Hence, the active catalytic ingredients may therefore refer to the catalyst composition excluding or in the absence of the catalyst support.
  • a catalyst composition consisting essentially of:
  • the active catalytic ingredients of the above catalyst composition are indium oxide (ln 2 0 3 ) and promoters (Pt and P 2 0 5 ).
  • the active catalytic ingredients of the catalyst composition as defined above may be present in an amount ranging from about 0.01 wt.% to about 60 wt.%, for example about 0.05 wt.%, about 0.1 wt.%, about 0.5 wt.%, about 1 wt.%, about 2 wt.%, about 5 wt.%, about 8 wt.%, about 10 wt.%, about 20 wt.%, about 25 wt.%, about 25.5 wt.%, about 26 wt.%, about 27 wt.%, about 28 wt.%, about 30 wt.%, about 32 wt.%, about 35 wt.%, about 40 wt.%, about 45 wt.%, or about 50 wt.%, based on the weight of the catalyst composition.
  • the amount above corresponds to the amount of the metal oxide(s) present in the catalyst composition.
  • the active catalytic ingredients consist essentially of the metal oxide(s) and at least one promoter
  • the amount above corresponds to the total amount of the metal oxide(s) and the at least one promoter present in the catalyst composition.
  • the amount of the at least one metal oxide in the catalyst composition may be in a range of about 5 wt.% to about 50 wt.% of the total weight of the catalyst composition, such as about 5 wt.%, about 10 wt.%, about 15 wt.%, about 20 wt.%, about 25 wt.% and about 50 wt.%.
  • the promoter of the catalyst composition as defined herein may be present in the amount ranging from 0 wt.% to about 20 wt.% of the total weight of the catalyst composition, such as 0 wt.%, about 1 wt.%, about 2 wt.%, about 3 wt.%, about 5 wt.%, about 10 wt.%, about 15 wt.% and about 20 wt.%. It should be noted that the range shown above may also be applicable when more than one promoter is used. Hence, the above range may refer to the total amount of the promoters used.
  • the total amount of these two promoters may be in a range of 0 wt.% to about 20 wt.% of the total weight of the catalyst composition.
  • the amount of the support (also termed as “catalyst support”) available in the catalyst composition may be derived from the amount of the at least one metal oxide and the promoter, which altogether make up 100 wt.% of the catalyst composition. For avoidance of doubt, if the at least one metal oxide is present at about 15 wt.% and there is only one promoter being used of about 3 wt.%, it then follows the amount of the catalyst support is about 82 wt.%.
  • the reaction may be undertaken at the temperature of about 450°C to about 700°C, such as about 500°C, about 525°C, about 550°C, about 575°C, about 600°C, about 625°C, about 650°C, and about 700°C.
  • the present disclosure provides a method of preparing the catalyst composition as defined herein comprising the steps of:
  • step b) drying the mixture obtained in step a) at a drying temperature
  • the solvent used in the method as defined herein may include aqueous solvent, organic solvent or a mixture thereof. More importantly, the at least one metal precursor should be dissolved or substantially dissolved in said solvent.
  • the organic solvent to dissolve the at least one metal precursor include methanol, ethanol, acetone, l,2-dichloroethane, acetonitrile, dimethylformamide (DMF).
  • DMF dimethylformamide
  • suitable organic solvents that are not shown above may also be used.
  • the aqueous solvent used in the above method may be water.
  • the drying temperature in step b) may be from about 50°C to l20°C, such as about 60°C, about 70°C, about 80°C, about 90°C, about l00°C or about ll0°C.
  • the drying process in step b) may be undertaken for a period ranging from about 1 hour to about 20 hours such as about one hour, about 2 hours, about 3 hours, about 5 hours, about 10 hours, or about 20 hours.
  • the drying process in step b) may be repeated when desired with the same or different drying temperature and duration.
  • the drying in step b) comprises drying at about 50°C and a further drying at about 1 l0°C for approximately 12 hours.
  • the objective of the drying process above is to substantially remove the solvent prior to the heating process of step c).
  • the heating process in step c) may be undertaken under a heating temperature ranging from about 400°C to 800°C, such as about 450°C, about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, or about 750°C.
  • step b) as defined above and / or the heating process of step c) may be undertaken at a constant or variable temperature.
  • variable temperature the heating or drying temperature is varied during the course of heating or drying.
  • the heating process in step c) may be undertaken for a period ranging from about 1 hour to about 20 hours such as about one hour, about 2 hours, about 3 hours, about 5 hours, about 10 hours, or about 20 hours.
  • the above heating process may be in the form of calcining, which comprise heating the dried mixture of step b) in static or continuous flow of air or oxygen or inert gas.
  • step a) of the method above may be modified accordingly, that is step a) may comprise adding a support to at least one metal precursor and at least one promoter precursor, wherein said at least one metal precursor and at least one promoter precursor are dissolved in a solvent or a mixture of solvents.
  • the above method for preparing the catalyst composition may be termed as wet impregnation technology.
  • the present disclosure provides a method for converting an alkene to a diene comprising the step of
  • the present disclosure provides a method for converting an alkene to a diene comprising the step of
  • the present disclosure provides a method for converting an alkene to a diene comprising the step of
  • the present disclosure additionally provides a method for converting an alkene to a diene comprising the step of
  • the step of converting the alkene to the diene may be undertaken until a substantial deactivation of the catalyst occurs, wherein the substantial deactivation is about 20 to 30% decrease from the initial activity of the catalyst.
  • the catalyst composition as defined herein may be regenerated and reused.
  • the reaction chamber Prior to a regeneration step, the reaction chamber may be purged with inert gas (which may be nitrogen, argon or helium) followed by charging the oxygen or other suitable gas to the reactor in order to remove the unwanted residues on the catalyst such as coke and at the same time to regenerate the catalyst.
  • inert gas may then be introduced to the reaction chamber to remove the oxygen residue before the regenerated catalyst is used for the next cycle of the reaction.
  • the method for converting the alkene to the diene in the presence of the catalyst composition as defined above may be undertaken under process conditions such as the amount of the at least one metal oxide, a promoter and a support as defined above as well as at the temperature range previously defined.
  • the above method may be useful for converting 1 -butene to 1, 3-butadiene.
  • the present disclosure also provides a method for preparing 1,3 -butadiene from 1 -butene comprising the step of
  • the present disclosure also provides a method for converting 1 -butene to 1, 3-butadiene comprising the step of exposing a reactant stream of the 1 -butene to a catalyst composition at a temperature of at least 500°C, wherein said catalyst composition consists essentially of:
  • the method for converting 1 -butene to 1, 3-butadiene in the presence of the catalyst composition as defined above may be undertaken under process conditions such as the amount of indium oxide, Pt and P 2 0 5 as promoters and Al 2 0 3 as catalyst support as defined above as well as at the temperature range previously defined.
  • oxidative dehydrogenation has advantages compared to other processes such as direct dehydrogenation, mainly due to less energy consumption, higher theoretical conversion and longer catalyst life.
  • FIG. 1 is a number of graphs describing the catalytic performance of In 2 0 3 /Al 2 0 3 in Example 2a in terms of 1,3 -butadiene (BD) yield, BD selectivity and conversion at different reaction temperatures.
  • Fig. 1(A) illustrates the (BD) yield, BD selectivity and conversion at four different reaction temperatures.
  • Fig. 1(B) depicts the selectivity of the three products i.e. cA-2-butene, rra/rv-2-butene and 1,3-butadiene (BD).
  • the values of the selectivity for cA-2-butene at four different temperatures are 41, 36, 22 and 12, respectively.
  • the values of the selectivity for trans- 2-butene at four different temperatures are 58, 48, 29 and 15, respectively.
  • the values of the selectivity for 1,3-butadiene (BD) at four different temperatures are 5, 14, 34 and 41, respectively.
  • FIG. 2 is a number of graphs describing the catalytic performance of the catalyst composition in Example 2a based on the concentration of ln 2 0 3 in In 2 0 3 /Al 2 0 3 catalyst at constant temperature of 600°C.
  • Fig. 2(A) depicts the conversion achieved with 0 wt%, 5 wt%, 10 wt%, 25 wt%, 50 wt% of ln 2 0 in In 2 0 /Al 2 0 catalyst.
  • Fig. 2(A) depicts the conversion achieved with 0 wt%, 5 wt%, 10 wt%, 25 wt%, 50 wt% of ln 2 0 in In 2 0 /Al 2 0 catalyst.
  • FIG. 2(B) shows the 1,3- butadiene (BD) selectivity achieved with 0 wt%, 5 wt%, 10 wt%, 25 wt%, 50 wt% of ln 2 0 3 in Ih 2 q 3 /A1 2 q 3 catalyst.
  • Fig. 2(C) depicts the BD yield achieved with 0 wt%, 5 wt%, 10 wt%, 25 wt%, 50 wt% of ln 2 0 3 in In 2 0 3 /Al 2 0 3 catalyst.
  • FIG. 3 is a number of graphs describing the effect of the concentration of P 2 0 5 (as promoter) in In 2 0 3 /Al 2 0 3 catalyst of Example 2b on the catalytic performance of the catalyst composition at constant temperature of 600°C and constant concentration of ln 2 0 3 at 25 wt%.
  • Fig. 3(A) depicts the conversion achieved with 0 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt% of P 2 0 5 in In 2 0 3 /Al 2 0 3 catalyst.
  • Fig. 3 is a number of graphs describing the effect of the concentration of P 2 0 5 (as promoter) in In 2 0 3 /Al 2 0 3 catalyst of Example 2b on the catalytic performance of the catalyst composition at constant temperature of 600°C and constant concentration of ln 2 0 3 at 25 wt%.
  • FIG. 3(B) shows the 1,3-butadiene (BD) selectivity achieved with 0 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt% of P 2 0 5 in In 2 0 3 /Al 2 0 3 catalyst.
  • Fig. 3(C) depicts the BD yield achieved with 0 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt% of P 2 0 5 in In 2 0 3 /Al 2 0 3 catalyst.
  • FIG. 4 is a histogram to compare the BD yield achieved in the oxidative dehydrogenation of 1-butene performed at two reaction temperatures 550°C and 600°C as described in Example 2b.
  • FIG. 5 is a histogram describing the effect of the type of promoter and its concentration on the catalytic performance of In 2 0 3 /Al 2 0 3 catalyst described in Example 2c. Specifically, this fig. depicts the BD yield achieved with various promoters (La, Pt, Ni, Zn, Ag, P 2 0 5 , Ce, Mn or Mo) in In 2 0 3 /Al 2 0 3 catalyst at three different temperatures 550°C, 600°C and 650°C.
  • various promoters La, Pt, Ni, Zn, Ag, P 2 0 5 , Ce, Mn or Mo
  • FIG. 6 is a number of graphs describing the catalytic performance of the catalyst composition comprising P and Pt (as two promoters) in In 2 0 3 /Al 2 0 3 catalyst at constant concentration of ln 2 0 3 of 25 wt% and at reaction temperatures of 500°C, 550°C and 600°C as described in Example 2d.
  • the catalytic performance was evaluated in terms of the BD yield.
  • FIG. 7 is a number of graphs showing the catalytic performance of the regenerated catalyst composition at 600°C as described in Example 3. refers to the number of reaction cycle. For clarity, #2 means that the catalyst composition has been used once before and regenerated prior to being subjected to the second reaction cyle.
  • Fig. 7(A) describes the conversion of the regenerated catalyst composition (25 wt% of ln 2 0 3 , 5 wt% of R 2( 3 ⁇ 4 and 2 wt% of Pt/Al 2 0 3 ).
  • Fig. 7(A) describes the conversion of the regenerated catalyst composition (25 wt% of ln 2 0 3 , 5 wt% of R 2( 3 ⁇ 4 and 2 wt% of Pt/Al 2 0 3 ).
  • FIG. 7(b) shows the BD selectivity of the regenerated catalyst composition (25 wt% of ln 2 0 3 , 5 wt% of R 2( 3 ⁇ 4 and 2 wt% of Pt/Al 2 0 3 ).
  • Fig. 7(C) describes the BD yield of the regenerated catalyst composition (25 wt% of ln 2 0 3 , 5 wt% of P 2 0 5 and 2 wt% of Pt/Al 2 0 3 ).
  • Non-limiting examples of the invention and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.
  • Example 1 Preparation of A1 2 0 3 Supported ln 2 0 3 Catalyst a) A1 2 0 3 Supported ln 2 0 3 Catalyst of Different ln 2 0 3 Loading (Al 2 0 3 /In 2 0 3 )
  • a required amount of In(N0 3 ) 3 xH 2 0 (purity 99.9%, purchased from Sigma-Aldrich of St. Louis, Missouri of the United States of America), depending on the desired wt% of ln 2 0 , was dissolved in 20 mL deionized (DI) water. The mixture was then transferred into a round bottom flask (RBF). The RBF was rotated at about 100 rpm for about 30 minutes to obtain a homogeneous solution. About 1 gram of solid A1 2 0 support was then added, and the mixture was stirred at 30 rpm for about 3 hours to achieve uniform immersion.
  • DI deionized
  • Example 2 Activity Testing of A1 2 0 3 Supported ln 2 0 3 Catalyst a) A1 2 0 3 Supported ln 2 0 3 Catalyst of Different ln 2 0 3 Loading (Al 2 0 3 /In 2 0 3 )
  • the catalytic activity of Al 2 0 3 /In 2 0 3 was evaluated in a fixed-bed continuous flow reactor. About 100 mg of catalyst was loaded into and packed in a quartz tube. The catalyst was first pre-treated with a continuous flow of helium at about 30 mL/min and at 400°C for one hour prior to the actual reaction.
  • the feeding rate of the reactant mixture was maintained at 30 mL/min (Weight hourly space velocity or“WHSV” was set at about 4.5 h 1 ).
  • WHSV Weight hourly space velocity
  • Fig. 2(A) The results of the experiment performed at 600°C, which include the conversion, 1,3- butadiene (BD) selectivity and BD yield are shown in Fig. 2.
  • Fig. 2(A) in general, the longer the duration of the reaction, the conversion tends to decrease. Significant erosion in the conversion was observed with the 50 wt% of ln 2 0 3 in the catalyst.
  • Fig. 2(B) the 1,3-butadiene (BD) selectivity increases slightly as the duration of the reaction was increased.
  • BD 1,3-butadiene
  • the catalytic activity of P-Al 2 0 3 /In 2 0 3 was evaluated in a similar manner as section a). About 100 mg of catalyst was loaded into and packed in a quartz tube to obtain a fixed-bed reactor system. The catalyst was first pre-treated with a continuous flow of helium at about 30 mL/min and at 400°C for one hour prior to the actual reaction.
  • the feeding rate of the reactant mixture was maintained at 30 mL/min (Weight hourly space velocity or“WHSV” was set at about 4.5 h -1 ).
  • the catalytic activity of Al 2 0 3 /In 2 0 3 comprising different promoter (including phosphorous) was evaluated in a similar manner as section a). About 100 mg of catalyst was loaded into and packed in a quartz tube to obtain a fixed-bed reactor system. The catalyst was first pre-treated with a continuous flow of helium at about 30 mL/min and at 400°C for one hour prior to the actual reaction.
  • the feeding rate of the reactant mixture was maintained at 30 mL/min (Weight hourly space velocity or“WHSV” was set at about 4.5 h 1 ).
  • BD 1,3-butadiene
  • the catalytic activity of Al 2 0 3 /In 2 0 3 having phosphorous and platinum as promoters was assessed in a similar manner as section a). About 100 mg of catalyst was loaded into and packed in a quartz tube to obtain a fixed-bed reactor. The catalyst was first pre-treated with a continuous flow of helium at about 30 mL/min and at 400°C for one hour prior to the actual reaction.
  • the feeding rate of the reactant mixture was maintained at 30 mL/min (Weight hourly space velocity or“WHSV” was set at about 4.5 h -1 ).
  • the catalytic activity was evaluated in an automatic fixed-bed continuous flow reactor with cyclic program. About 200 mg of the catalyst composition was mixed with 730 mg quartz sands. The mixture was then loaded into and packed in a quartz tube.
  • the reaction was carried out for 150 minutes at about 600°C.
  • the feeding gas was switched from the reaction gas to helium.
  • the system was then cooled down to 500°C and maintained at this condition for about one hour.
  • Purified air (PA) having a flow rate of 30 mL/min was fed into the reactor for regeneration process at 500°C for approximately one hour.
  • the reactor system was subjected to a further cooling under continuous flow of helium to 400°C.
  • the catalyst composition was regenerated and ready to be used for next cycle of pre-treatment and reaction.
  • the catalytic performance of the regenerated catalyst compositions i.e. first one being 25 wt% of ln 2 0 3 , 5 wt% of P 2 0 5 and 2 wt% of Pt/Al 2 0 3 and the second one being 25 wt% of ln 2 0 3 , 2 wt% of R 2( 3 ⁇ 4 and 2 wt% of Pt/Al 2 0 3 at 600°C is depicted in Figs.
  • catalyst composition as defined herein confers benefits and/ or advantages described above, such catalyst composition may be used for converting short chains of alkene into its corresponding diene in industrial setting.
  • 1,3-butadiene is used primarily in the production of synthetic rubber such as styrene-butadiene rubber (SBR), polybutadiene rubber, and nylon intermediate i.e. adiponitrile. It is also known that a copolymer of styrene and butadiene such as acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene (NBR) and styrene -butadiene (SBR) can be used in automobile tires.
  • ABS acrylonitrile butadiene styrene
  • NBR acrylonitrile butadiene
  • SBR styrene -butadiene
  • 1,3-butadiene is also useful in the manufacture of other synthetic rubber materials such as chloroprene, solvent such as sulfolane and the synthesis of cycloalkanes and cycloalkenes.
  • the catalyst composition as defined herein is industrially applicable at least in the processes or manufacture of the chemicals outlined above.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne une composition de catalyseur comprenant des oxydes métalliques utiles dans une déshydrogénation oxydative catalytique des chaînes courtes d'alcène dans son diène correspondant, en particulier la déshydrogénation oxydative catalytique de 1-butène en 1,3-butadiène (BD). Dans un mode de réalisation préféré, le catalyseur est de l'oxyde d'indium (ln2O3) supporté sur de l'alumine (Al2O3) et éventuellement favorisé par du pentoxyde de diphosphore ((P2O5)) et/ou du platine (Pt). La présente invention concerne également un procédé de préparation de la composition de catalyseur telle que définie dans la description.
PCT/SG2019/050320 2018-06-27 2019-06-27 Composition de catalyseur Ceased WO2020005161A1 (fr)

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CN119565601A (zh) * 2024-12-02 2025-03-07 广东工业大学 一种抑制正丁烷脱氢异构化的催化剂及其制备方法和应用

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CN112239391A (zh) * 2019-07-16 2021-01-19 中国石油化工股份有限公司 丁烯脱氢制备1,3-丁二烯的方法
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CN119565601A (zh) * 2024-12-02 2025-03-07 广东工业大学 一种抑制正丁烷脱氢异构化的催化剂及其制备方法和应用

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