WO2021229227A1 - Catalyseur pour la production de biaryles - Google Patents

Catalyseur pour la production de biaryles Download PDF

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Publication number
WO2021229227A1
WO2021229227A1 PCT/GB2021/051146 GB2021051146W WO2021229227A1 WO 2021229227 A1 WO2021229227 A1 WO 2021229227A1 GB 2021051146 W GB2021051146 W GB 2021051146W WO 2021229227 A1 WO2021229227 A1 WO 2021229227A1
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Prior art keywords
catalyst
metal
alumina
total weight
group
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PCT/GB2021/051146
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English (en)
Inventor
Ronan Marco BELLABARBA
Laura Cano-Lerida
Stuart Michael SMALL
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Johnson Matthey Public Limited Company
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Priority claimed from GBGB2019932.9A external-priority patent/GB202019932D0/en
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Priority to CN202180019510.1A priority Critical patent/CN115279491B/zh
Publication of WO2021229227A1 publication Critical patent/WO2021229227A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/11—Lithium
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/12—Sodium
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/13—Potassium
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/22—Magnesium
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/23—Calcium

Definitions

  • the present invention relates to catalysts for carrying out the coupling of an aromatic or heteroaromatic substrate to form a corresponding biaryl compound, especially the coupling of pyridine to form 2,2’-bipyridine.
  • Diquat (the organic di-cation 1,T-ethylene-2,2’-bipyridylium) is a non-selective herbicide with a global market of approximately 100 million USD per annum. Diquat is commonly used as the dichloride or dibromide salt, which are manufactured industrially by the reaction between 2,2’-bipyridine (2,2’-bipy, or “bipy”) and 1,2-dibromoethane or 1,2-dichloroethane. 2,2’-bipy itself is manufactured by the catalytic coupling of pyridine.
  • Raney Nickel is known to suffer from handling issues, and when applied to the production of bipy, is known to rapidly lose activity as the reaction proceeds.
  • Efforts have been made to provide Raney Nickel catalysts which have longer activity, such as CN105130883A (Anhui Costar Bio Chemical Co Ltd) which describes a method of producing 2,2’-bipy using a catalyst of Raney nickel in conjunction with a metal salt, such as sodium ethoxide, sodium amide and aluminium isopropoxide.
  • GB1202711 ICI Ltd
  • CN107935919A (Nanjing Red Sun Biochemistry Co Ltd) describes coupling catalysts comprising Ni and at least one other metal on a composite support of AI2O3-S1O2- MgO.
  • Exemplified catalysts comprise Ni and two or all of Ce, Mn and La on a support of Al 2 0 3 -SiC> 2 -Mg0. Tuning of the S1O2 and MgO components is required to control the acidity of the support which can otherwise lead to by-product formation if the acidity of the support is too high.
  • the catalyst uses relatively expensive metals Ce, Mn and La.
  • the present inventors have surprisingly established that a Group 1 or Group 2 metal promoted catalyst of Ni on a support of alumina shows good activity in the conversion of pyridine to bipy, maintains its activity for a longer period, and is more selective for the production of the desired bipy product.
  • alumina rather than a composite support (as for instance in CN107935919A) simplifies the manufacturing process.
  • the instant catalysts only require the presence of the relatively inexpensive Ni and Group 1 or Group 2 metal(s).
  • the invention provides a method of producing a biaryl compound from a heteroaromatic substrate using a catalyst comprising Ni on an alumina support; wherein the content of Ni is 10-30 wt% based on the total weight of catalyst; and wherein the catalyst comprises a promoter metal selected from (i) a Group 1 metal in an amount of 0.5-5.5 wt% based on the total weight of catalyst; or (ii) a Group 2 metal in an amount of 0.5-10 wt% based on the total weight of catalyst.
  • the invention provides a catalyst comprising Ni on an alumina support; wherein the content of Ni is 10-30 wt% based on the total weight of catalyst; wherein the catalyst comprises a promoter metal selected from (i) a Group 1 metal in an amount of 0.5-5.5 wt% based on the total weight of catalyst; or (ii) a Group 2 metal in an amount of 0.5-10 wt% based on the total weight of catalyst; and wherein the catalyst is in the form of an extrudate and is free from a metal salt or metal oxide cocatalyst.
  • a promoter metal selected from (i) a Group 1 metal in an amount of 0.5-5.5 wt% based on the total weight of catalyst; or (ii) a Group 2 metal in an amount of 0.5-10 wt% based on the total weight of catalyst.
  • EP 0566 197 A1 (Engelhard de Meern B.V.) describes a process for preparing primary amines by hydrogenation of a mono and/or dinitrile with hydrogen in the presence of a nickel and/or cobalt catalyst on a support.
  • Exemplified catalysts have either 5 or 20 wt% nickel on an alumina or silica-alumina support, and include between 3-10 wt% Group 1 and/or Group 2 metals.
  • the catalysts exemplified in EP 0 566 197 A1 differ from those according to the second aspect of the invention because they are prepared by pre-, co- or post-impregnation of the Ni and Group 1 or Group 2 metal salts onto a powdered support material and are therefore not extruded catalysts.
  • the only suggestion within EP 0566 197 A1 to use shaped catalyst bodies is in the context of combining the supported catalyst with a cocatalyst into combined particles.
  • the cocatalyst is generally a metal salt or metal oxide.
  • the catalysts according to the second aspect of the present invention do not include a metal salt or metal oxide as cocatalyst.
  • the invention also relates to the use of a catalyst as defined in the first aspect or according to the second aspect, as a coupling catalyst in the coupling of an aromatic or heteroaromatic substrate to produce a biaryl compound.
  • the invention provides a method of manufacturing a catalyst according to the second aspect, comprising the steps of:
  • step (i) providing a solution comprising a nickel salt and a solution comprising a promoter metal salt; (ii) carrying out incipient wetness impregnation of an extruded alumina support with the solution(s) from step (i);
  • step (iv) calcining the product of step (iii);
  • step (v) reducing the product of step (iv).
  • Figure 1 is a plot of bipy productivity as a function of K content of the catalyst.
  • Figure 2 is a plot of (2-picoline + piperidine) : bipy selectivity as a function of K content of the catalyst.
  • Figure 3a is a plot of K content of the catalyst against product selectivity for the main 4 products of the reaction.
  • Figure 3b is an expanded view of Figure 3a focussing on the product selectivity of the main 3 by-products of the reaction.
  • Figure 4 is a plot of pyridine conversion as a function of time online for various catalysts with different promoter metals.
  • Figure 5 is a plot of (2-picoline + piperidine) : bipy selectivity for various catalysts with different promoter metals.
  • catalyst is used herein to refer to a material in which the support, as defined herein, has been impregnated with Ni and one or more promoter metals.
  • a “promoter metal” is a Group 1 or Group 2 metal.
  • the term “catalyst” can refer to the material formed following incipient wetness impregnation, the material formed following calcination of that material (“calcined material” or “oxidic material”), and the material formed following reduction of the calcined material (“reduced material”). The reduced material may also be passivated before use (“passivated material”).
  • promoter metal means a Group 1 or Group 2 metal.
  • promoted means that the presence of the promoter metal improves one or more of: the lifetime of the catalyst, the activity of the catalyst for bipy formation, or the selectivity of the catalyst for bipy formation, as compared to an equivalent catalyst in which the promoter metal(s) are absent.
  • biasing refers to a molecule having a unit in which two aryl or heteroaryl groups are joined together by a single carbon to carbon bond.
  • aryl group is used to refer to a unit comprising an aromatic ring in which all of the ring atoms are carbon.
  • the ring may be substituted or unsubstituted.
  • An aromatic substrate is a starting material which comprises an aryl group.
  • heteroaryl group is used to refer to a unit comprising an aromatic ring in which at least one of the ring atoms is a heteroatom.
  • the ring may be substituted or unsubstituted.
  • a heteroaromatic substrate is a starting material which comprises a heteroaryl group.
  • the first aspect of the invention is a method of producing a biaryl compound from a heteroaromatic substrate using a nickel catalyst on an alumina support which is promoted with a Group 1 or Group 2 metal.
  • the catalysts described in the present specification have a Ni content of 10-30 wt% based on the total weight of the catalyst.
  • the content of Ni is preferably 12-28 wt%, such as 15-25 wt%.
  • a Ni content of 25 wt% ⁇ 2 wt% is especially preferred.
  • the Ni in the catalyst will be present as a mixture of metallic Ni and nickel oxide.
  • the Ni content referred to herein is the total amount of Ni based on the amount of the catalyst, whether in the metallic state (Ni(0)) or in another state, such as Ni(ll) e.g. in the form of nickel oxide).
  • the Ni content of the catalyst can be measured by inductively coupled plasma analysis (ICP analysis) as is well known in the art.
  • the catalyst has a Ni surface area of 100-150 m 2 / g Ni, preferably of 110-140 m 2 / g Ni, preferably of 120-140 m 2 / g Ni. In preferred embodiments the catalyst has a Ni surface area of 15-40 m 2 / g catalyst, preferably of 20-40 m 2 / g catalyst, preferably of 20-35 m 2 / g catalyst. Ni surface is measured by H2 chemisorption, by reducing the oxidic catalyst in flowing hydrogen at a temperature of 430°C for 1 h followed by a 6 h evacuation, then Ni surface area analysis at 50°C using a Micromeritics Chemisorb HTP unit, ASAP 2480.
  • the catalysts described in the present specification comprise a promoter metal selected from a Group 1 metal or a Group 2 metal.
  • the present inventors have surprisingly established that the inclusion of a Group 1 or Group 2 metal increases the lifetime of catalyst, improves catalyst activity and improves the selectivity of the catalyst towards the biaryl product.
  • a Group 1 metal is a metal selected from the group consisting of Li, Na, K, Rb and Cs. Where a Group 1 metal is used as the promoter metal then the catalyst includes a Group 1 metal in an amount of 0.5-5.5 wt% based on the total weight of catalyst.
  • the Group 1 metal content is preferably 1.0-5.5 wt%, more preferably 1-5 wt%, more preferably 1.5-3.5 wt%. Where a mixture of Group 1 metals are used, these ranges refer to the combined amounts of Group 1 metals.
  • the Group 1 metal is preferably one or more of Li, Na or K, more preferably Na or K, most preferably K. Where a mixture of Group 1 metals are used, it is preferred that at least one of Li, Na or K is present, more preferably at least one of Na or K is present, most preferably K is present. It is preferred that a single Group 1 metal is used, most preferably the only Group 1 metal present is K.
  • the Group 1 metal content can be measured by inductively coupled plasma analysis (ICP analysis) as is well known in the art. It is particularly preferred that the promoter metal is K. When the promoter metal is K, a particularly preferred content of K is 1-4 wt%, preferably 1.5-3.5 wt%, preferably 2-3 wt%. These values of K content provide a catalyst which has a good balance of productivity and selectivity, particularly when used for the conversion of pyridine to bipy.
  • a Group 2 metal is a metal selected from the group consisting of Be, Mg, Ca, Sr, Ba and Ra. Where a Group 2 metal is used as the promoter metal then the catalyst includes a Group 2 metal in an amount of 0.5-10 wt% based on the total weight of catalyst.
  • the catalyst includes a mixture of Group 2 metals as promoter metals then the total content of Group 2 metals is 0.5-10 wt%, preferably 0.5-8 wt%, more preferably 0.5-5 wt%. It is preferred that a single Group 2 metal is used.
  • the catalyst preferably comprises one or more of Mg, Ca and Sr, more preferably Mg or Ca. Where a mixture of Group 2 metals are used, it is preferred that at least one of Mg or Ca is present. It is preferred that a single Group 2 metal is used.
  • the Group 2 metal content can be measured by inductively coupled plasma analysis (ICP analysis) as is well known in the art.
  • the catalysts include a mixture of Group 1 and Group 2 as promoter metals, in which case the total content of promoter metals is 0.5-10 wt%.
  • a single type of promoter metal is used (Group 1 or Group 2 metals), more preferably only a single promoter metal is used.
  • the catalysts described in the present specification comprise an alumina support.
  • the alumina support is substantially free of other materials, e.g. metal oxides other than alumina.
  • the support is at least 90 wt% alumina, preferably at least 95 wt% alumina, such as at least 98 wt% alumina.
  • Alumina exists in a variety of different forms (phases) which are well known in the literature, any of which may be used as the support in the present invention.
  • the support may comprise alumina in a single phase, or may comprise a mixture of different phases. Where the support comprises different alumina phases the support may comprise separate crystallites of each alumina phase, or may comprise crystallites having two or more phases within each crystallite.
  • the alumina comprises one or more of g- , d- or q-alumina. In an embodiment the alumina comprises g-alumina. In an embodiment the alumina comprises a mixture of d-alumina and q-alumina.
  • the catalyst consists essentially of, or consists of, the Ni component (which is typically a mixture of metallic Ni(0) and nickel oxide), the promoter metal component and the support.
  • “consists essentially of” means that the catalyst includes less than 2 wt% of components other than the Ni-component, promoter metal component and the support, preferably less than 1 wt% of other components, preferably less than 0.5 wt% of other components, preferably less than 0.1 wt% of other components.
  • the catalyst consists of the Ni, the promoter metal component and the support.
  • the catalyst comprises 15-25 wt% Ni based on the total weight of catalyst, 1-5 wt% K based on the total weight of catalyst and the support is at least 95 wt% alumina.
  • the support is preferably a mixture of d-alumina and Q- alumina. It is further preferred in this embodiment that the catalyst consists essentially of, or consists of, the Ni, K and alumina support.
  • the catalyst comprises 15-25 wt% Ni based on the total weight of catalyst and 1.5-3.5 wt% K based on the total weight of catalyst and the support is at least 95 wt% alumina.
  • the support is preferably a mixture of d-alumina and q-alumina. It is further preferred in this embodiment that the catalyst consists essentially of, or consists of, the Ni, K and alumina support.
  • the catalyst is in the form of granules, pellets or extrudates, preferably pellets or extrudates. It is preferred that the catalyst is in the form of an extrudate, because extrudates offer higher geometric surface area than pellets or granules. It is especially preferred that the catalyst is in the form of a trilobe extrudate.
  • the catalysts according to the second aspect of the invention are in the form of extrudates.
  • the catalysts of the second aspect are also free from a metal salt or metal oxide cocatalyst; that is, the extrudates do not include separate particles of a metal salt or metal oxide cocatalyst.
  • Catalysts according to the invention can be prepared by incipient wetness impregnation. This procedure will be known to those skilled in the art and as is described for instance in WO2011/080515. In this technique a support material is combined with an aqueous solution of metal salt(s), using a volume of aqueous solution which is sufficient to fill the pores of the support. The impregnated support is then dried. This process leads to the metal salt(s) becoming supported on the support material. The steps of impregnation and drying may be repeated several times.
  • a solution comprising a nickel salt and a promoter metal salt is provided.
  • the nickel salt and the promoter metal salt may be present as separate solutions or may be present in a single solution. Preferably, the nickel and promoter metal salts are present together in the same solution.
  • Incipient wetness impregnation is preferably carried out by impregnation using a single solution comprising both a nickel salt and a promoter metal salt (co-impregnation).
  • the amount of solution is chosen to be approximately equal to the pore volume of the support material.
  • Co-impregnation is particularly suitable in the case where the promoter metal is a Group 1 metal, especially where an aqueous ammoniacal solution comprising nickel carbonate and potassium carbonate is used for co-impregnation, since these salts readily dissolve in aqueous ammoniacal solution.
  • the support material may be impregnated sequentially with separate solutions of a nickel salt and a promoter metal salt, in any order.
  • aqueous ammoniacal solutions comprising both a nickel salt and a promoter metal salt are difficult to form, e.g. because of poor solubility of the promoter metal salt is aqueous ammoniacal solution.
  • the impregnation may be a post-impregnation (impregnation of the Ni salt before the promoter metal salt) or a pre-impregnation (impregnation of the Ni salt after the promoter metal salt), preferably a post-impregnation. Post-impregnation is particularly appropriate where the promoter metal is a Group 2 metal.
  • a drying step will typically be performed between each impregnation.
  • the solution of metal salt (or metal salts) used during the impregnation step is typically aqueous and preferably has a pH above 7, preferably from 8-12 such as from 9-12.
  • the desired pH can be achieved by the addition of a metal-free base to the impregnation solution, such as ammonium hydroxide.
  • Ni salts can be used.
  • the counterion (anion) is preferably one which can be converted to oxide in a subsequent calcination step.
  • Preferred Ni salts are carbonate, nitrate, acetate and halide (e.g. chloride).
  • a preferred Ni salt is nickel carbonate.
  • the concentration of Ni in the impregnation solution is not especially limited. However, it will be appreciated that if using a dilute solution of Ni the impregnation step may have to be repeated more times compared with using a more concentrated solution of Ni.
  • a suitable Ni concentration is 5-20 wt%, this value being the wt% of Ni in the solution rather than the wt% of Ni salt.
  • a particularly preferred concentration of Ni is 5-15 wt%.
  • the promoter metal salt is water soluble.
  • the counterion (anion) is preferably one which can be converted to oxide in a subsequent calcination step.
  • Preferred promoter salts are carbonates, nitrates, acetate, hydroxide and halide (e.g. chloride). It is preferred that the promoter metal salt is a carbonate, preferably NaaCChor K 2 CO 3 , especially K 2 CO 3 .
  • the concentration of promoter metal salt in the solution is not especially limited. However, it will be appreciated that if using a dilute solution of promoter metal the impregnation steps may have to be repeated more times to achieve the desired content of metals in the catalyst compared with using a more concentrated solution of promoter metal.
  • a suitable concentration is 0.5-5 wt%, this value being the wt% of K rather than the wt% of K salt.
  • a particularly preferred concentration for K is 1-3 wt%.
  • the process includes at least 1 impregnation step. Preferably the process includes 2, 3, 4 or 5 impregnation steps. Most preferably the process includes 2 or 3 impregnation steps.
  • step (iii) the product of incipient wetness impregnation is dried.
  • the catalyst will be allowed to dry after each successive impregnation step. Drying is typically performed at an elevated temperature for several hours, preferably at a temperature of 50-150 °C for
  • steps (ii) and (iii) are repeated at least once, preferably twice.
  • the material is calcined (step (iv)). This typically involves heating the catalyst to a temperature of 200-600 °C for a period of 2-6 hours in an atmosphere containing oxygen, preferably at a temperature of 300-500 °C for a period of 2-6 hours. In a preferred embodiment calcination is performed in air. Following calcination the catalyst is reduced (step (v)). The purpose of this step is to convert at least a portion of the nickel oxide formed in the drying and calcination steps back into active nickel metal.
  • the reduction step is carried out by treating the calcined material under an atmosphere of H2 at an elevated temperature.
  • the atmosphere may be 100% H2 or a mixture of H2 with an inert diluent.
  • a suitable range of temperatures is 200- 700 °C, preferably 350-500 °C, for a period of 1-5 hours, preferably 1-3 hours.
  • the catalyst produced following reduction may be passivated.
  • a typical method for producing biaryls involves treating a substrate having an aryl or heteroaryl group with the catalyst at an elevated temperature. It is preferred that the substrate includes a 6-membered aromatic or heteroaromatic ring, which may be substituted or unsubstituted, and which may be part of a fused system (e.g. naphthalene, quinoline, etc.).
  • a fused system e.g. naphthalene, quinoline, etc.
  • the substrate is a heteroaromatic substrate, preferably comprising a 6-membered heteroaromatic ring in which one of the ring atoms is a heteroatom.
  • the heteroatom is N.
  • the substrate is a substituted or unsubstituted pyridine.
  • the substrate is pyridine and the biaryl product is 2,2’-bipyridine.
  • the coupling reaction will typically give rise to a mixture of biaryl products, predominantly mono- and di-substituted products.
  • catalysts of the invention when applied to pyridine may give a mixture of 2,2’-bipyridine and 2,2’,6’,2”-terpyridine, predominantly 2,2’- bipyridine.
  • a method of producing a biaryl compound from an aromatic or heteroaromatic substrate using a coupling catalyst wherein the catalyst comprises Ni on an alumina support; wherein the content of Ni is 10-30 wt% based on the total weight of catalyst; and wherein the catalyst comprises a promoter metal selected from (i) a Group 1 metal in an amount of 0.5-5.5 wt% based on the total weight of catalyst; or (ii) a Group 2 metal in an amount of 0.5-10 wt% based on the total weight of catalyst.
  • the promoter metal is a Group 1 metal selected from Li, Na and K.
  • a method according to embodiment 2, wherein the promoter metal is K. 4. A method according to embodiment 2 or embodiment 3, wherein the content of promoter metal(s) is 1-5 wt% based on the total weight of catalyst.
  • the catalyst satisfies the following: the content of Ni is 15-25 wt% based on the total weight of catalyst; the promoter metal is K and is present in an amount of 1.5-3.5 wt% based on the total weight of catalyst; and the support is at least 95 wt% alumina.
  • a catalyst comprising Ni on an alumina support; wherein the content of Ni is 10-30 wt% based on the total weight of catalyst; wherein the catalyst comprises a promoter metal selected from (i) a Group 1 metal in an amount of 0.5-5.5 wt% based on the total weight of catalyst; or (ii) a Group 2 metal in an amount of 0.5-10 wt% based on the total weight of catalyst; and wherein the catalyst is in the form of an extrudate and is free from a metal salt or metal oxide cocatalyst.
  • a catalyst according to embodiment 20, wherein the promoter metal is K. 22. A catalyst according to embodiment 20 or embodiment 21 , wherein the content of promoter metal(s) is 1-5 wt% based on the total weight of catalyst.
  • a catalyst according to embodiment 19, wherein the promoter metal is Group 2 metal selected from Mg and Ca.
  • step (ii) carrying out incipient wetness impregnation of an extruded alumina support with the solution(s) from step (i);
  • step (iv) calcining the product of step (iii);
  • step (v) reducing the product of step (iv).
  • step (i) A method according to embodiment 35, wherein the nickel salt and the promoter metal salt are present in a single solution in step (i).
  • step (ii) involves sequential treatment of the support with the solution of promoter metal salt and solution of nickel salt, in any order.
  • H ⁇ chemisorption Ni surface area was measured via H2 chemisorption using a Micromeritics Chemisorb HTP unit, ASAP 2480.
  • the samples were reduced in flowing hydrogen at the temperature specified (430°C or 230 °C if they were pre-reduced and passivated) for 1 h followed by a 6 h evacuation, prior to nickel surface area analysis at 50°C. Uncertainty on metal area is +/- 1%. The limit of detection was 0.10 m 2 /g.
  • Aqueous ammonium hydroxide was placed in a glass beaker with a magnetic stirrer. Ammonium carbonate and nickel carbonate were added gradually and alternating each other (to avoid the solution becoming too hot) to this beaker with mild agitation. The amount of ammonium carbonate was sufficient to achieve a pH of approximately 11.0. The stirring was maintained overnight. The morning after the solution was homogeneous with no solids, and of the characteristic intense blue colour. Potassium carbonate was added to this solution.
  • Examples 1R and 2R were prepared from a commercially available Ni on alumina catalyst (HTCTM Ni500 RP, 1.2 mm trilobes, batch D600319 from Johnson Matthey).
  • Example 9R was prepared from a commercially available catalyst of Ni on a support of calcium aluminate / kaolin (KatalcoTM 11-4R, batch 121820 from Johnson Matthey).
  • Examples 10-13 were prepared by a post-impregnation procedure using HTCTM Ni 500 (oxidic form, 1.2 mm trilobes, batch D502041 from Johnson Matthey).
  • a solution of the appropriate promoter metal salt was prepared by dissolving the promoter metal in demineralised water.
  • the HTCTM Ni 500 trilobes were impregnated with the solution of promoter metal salt by incipient wetness impregnation in a Pascal mixer with gentle rotation. The volume of solution used was approximately equal to the pore volume of the trilobes.
  • the samples were dried at 105 °C for 3 hours then calcined at 430 °C (example 10) and 400°C (examples 11-13) for 4 hours.
  • Example 10 used lithium hydroxide monohydrate (Acros Organics).
  • Example 11 used sodium nitrate (Acros Organics).
  • Example 12 used magnesium nitrate hexahydrate (Acros Organics).
  • Example 13 used calcium nitrate tetrahydrate (Acros Organics).
  • Catalyst testing was carried out using a Falling Basket Rig (manufactured by Autoclave Engineers). Once cool, the reduced catalyst in a glass reduction vessel was transferred to a nitrogen glove box. The catalyst was charged in the basket of the Falling Basket Rig and submerged in a container of pyridine. The container was sealed, removed from the glovebox and transferred to the upper portion of the Falling Basket Rig. The autoclave body of the rig was filled with 500 ml of pyridine, purged with nitrogen then pressure tested. Pressure testing was completed under nitrogen up to 10 barg. The autoclave was subsequently depressurized to 1 barg, then heated to 200 °C at a ramp rate of 180 °C/h.
  • Catalysts 3R to 7R having K contents between 1.6 and 4.4 wt% showed much higher productivities for bipy formation than either of the comparative catalysts Ni HTCTM 500 (Comparatives 1R and 2R) or KatalcoTM 11-4R (Comparative 9R).
  • K reduced the catalyst productivity.
  • Catalysts 10R to 13R promoted respectively with Li, Na, Mg and Ca, also had a higher productivity than either of the Comparative catalysts.
  • Figure 1 shows that at an approximately constant Ni content, promoting the catalyst with K caused a gradual increase in catalyst productivity for bipy formation, with the highest productivity achieved by catalyst 5R with a K content of 2.55 wt% (in its oxidic form). As K content was increased further the productivity of the catalyst reduced.
  • Figure 2 shows the selectivity ratio (2-picoline + piperidine) : (bipy) for catalysts 3R-8R. Promoting the catalyst with K up to a loading of approximately 2.5 wt% caused an increase in catalyst selectivity for bipy formation. As K content was increased further the selectivity of the catalyst for bipy formation increased only moderately.
  • Figures 4 and 5 show the pyridine conversion ( Figure 4) and selectivity ratio (2-picoline + piperidine) : (bipy) ( Figure 5) for catalysts 6R (K promoted), 10R (Li promoted), 11R (Na promoted), 12R (Mg promoted) and 13R (Ca promoted). Each of these catalysts had a pyridine conversion above that of reference catalyst 2R and showed a greater selectivity for pyridine.

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Abstract

La spécification décrit un procédé de production d'un composé biaryle à l'aide d'un catalyseur comprenant du Ni sur un support d'alumine ; la teneur en Ni étant de 10 à 30 % en poids sur la base du poids total du catalyseur ; et le catalyseur comprenant un métal promoteur choisi parmi (i) un métal du Groupe 1 en une quantité de 0,5 à 5,5 % en poids sur la base du poids total du catalyseur ; ou (ii) un métal du Groupe 2 en une quantité de 0,5 à 10 % en poids sur la base du poids total du catalyseur. L'invention concerne également des catalyseurs permettant de mettre en œuvre des réactions de couplage et un procédé de production de tels catalyseurs. Les catalyseurs sont particulièrement appropriés pour la conversion de pyridine en 2,2 '-bipyridine.
PCT/GB2021/051146 2020-05-14 2021-05-13 Catalyseur pour la production de biaryles WO2021229227A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1202711A (en) 1967-01-20 1970-08-19 Ici Ltd Catalyst regeneration process
US5221747A (en) 1989-01-19 1993-06-22 Reilly Industries, Inc. Improved process and catalyst for the preparation of 2,2' bipyridyls
EP0566197A1 (fr) 1992-04-13 1993-10-20 Engelhard De Meern B.V. Procédé de préparation d'amines primaires et système catalytique apte à ce procédé
EP0539505B1 (fr) 1990-07-18 1999-12-08 Zeneca Limited Procedes ameliores pour la preparation de 2,2'-bipyridyles
WO2011080515A2 (fr) 2010-01-04 2011-07-07 Johnson Matthey Plc Catalyseur et procédé de fabrication de catalyseur
WO2014048740A1 (fr) * 2012-09-25 2014-04-03 Haldor Topsøe A/S Catalyseur de reformage à la vapeur et son procédé de fabrication
CN105130883A (zh) 2015-08-10 2015-12-09 安徽国星生物化学有限公司 一种2，2′-联吡啶及其催化偶联合成方法与应用
CN107935919A (zh) 2017-11-17 2018-04-20 南京红太阳生物化学有限责任公司 一种2,2’‑联吡啶及其衍生物的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4966972A (en) * 1989-01-19 1990-10-30 Reilly Industries, Inc. Process and catalyst for the preparation of 2,2'-bipyridyls
FR2998488B1 (fr) * 2012-11-29 2015-02-06 Ifp Energies Now Catalyseur d hydrotraitement a partir d alumine gel et methode de preparation d un tel catalyseur
CN106380444B (zh) * 2016-08-17 2018-08-28 南京红太阳生物化学有限责任公司 一种2,2’-联吡啶的制备方法
CN110801841A (zh) * 2019-11-27 2020-02-18 中国科学院大连化学物理研究所 一种用于合成吡啶偶联制2,2’-联吡啶的催化剂及其制备方法和应用

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1202711A (en) 1967-01-20 1970-08-19 Ici Ltd Catalyst regeneration process
US5221747A (en) 1989-01-19 1993-06-22 Reilly Industries, Inc. Improved process and catalyst for the preparation of 2,2' bipyridyls
US5416217A (en) 1989-01-19 1995-05-16 Reilly Industries Inc. Process for the preparation of 2,2'-bipyridyls
EP0539505B1 (fr) 1990-07-18 1999-12-08 Zeneca Limited Procedes ameliores pour la preparation de 2,2'-bipyridyles
EP0566197A1 (fr) 1992-04-13 1993-10-20 Engelhard De Meern B.V. Procédé de préparation d'amines primaires et système catalytique apte à ce procédé
WO2011080515A2 (fr) 2010-01-04 2011-07-07 Johnson Matthey Plc Catalyseur et procédé de fabrication de catalyseur
WO2014048740A1 (fr) * 2012-09-25 2014-04-03 Haldor Topsøe A/S Catalyseur de reformage à la vapeur et son procédé de fabrication
CN105130883A (zh) 2015-08-10 2015-12-09 安徽国星生物化学有限公司 一种2，2′-联吡啶及其催化偶联合成方法与应用
CN107935919A (zh) 2017-11-17 2018-04-20 南京红太阳生物化学有限责任公司 一种2,2’‑联吡啶及其衍生物的制备方法

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