Catalyst suitable for ammoximation of cyclohexanone

Abstract

The disclosure relates to a titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti- MOR, Ti-YNU-5, TM-TS-1, and Fe-TS-1, preferably wherein the titanosilicate is Ti-MWW, and wherein the metal nanoparticles are bound to the titanosilicate. The disclosure also relates to a catalyst comprising the titanosilicate-metal adduct. The disclosure further relates to a process for the preparation of a titanosilicate-metal adduct. Moreover the disclosure further relates to a process comprising reacting a ketone, aldehyde or amide, preferably ketone with H2, O2 and NH3 to form an oxime in the presence of the titanosilicate-metal adduct or catalyst. The disclosure also relates to the use of titanosilicate in ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5 TM- TS-1, or Fe-TS-1.

Description

[0001] Catalyst suitable for ammoximation of cyclohexanone

[0002] The present invention provides titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, a catalyst comprising the titanosilicate-metal adduct, a process for the preparation of a titanosilicate-metal adduct, a process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, and the use of titanosilicate in ketone ammoximation aldehyde ammoximation or amide ammoximation.

[0003]

[0004] Oximes are important synthetic intermediates in organic chemistry, used in the production of many pharmaceutical compounds and polymers. Generally oximes are useful as chemical intermediates in the synthesis of amides and lactams. In particular, cyclohexanone oxime is a key precursor in the production of caprolactam, a commodity chemical used in the synthesis of the polyamide Nylon-6. With global production of Nylon-6 predicted to reach 8.9 million metric tons per annum in 2024, there is significant commercial demand for cyclohexanone oxime.

[0005] Oximes may be produced industrially by the reaction of ketones with hydroxylamine. For example, the classical production of cyclohexanone oxime involves reaction of hydrogen peroxide (H2O2) with ammonia (NH3) in the presence of a titanosilicate catalyst, TS-1. TS-1 was first developed by EniChem, and its use in oxime formation was advantageous to alternative existing methods because it avoided the formation of large quantities of the undesired byproduct ammonium sulphate. It is thought that the high co-ordination ability of Tilvsites present within the TS-1 framework are responsible for the formation of the hydroxylamine intermediate from H2O2 and NH3. Although, there is still some speculation around the true active site responsible for TS-1 catalysed oxidative processes with H2O2 and as such this is an area of ongoing research.

[0006] There is a need for an improved catalysts for ammoximation of ketones, for example the ammoximation of cyclohexanone to the corresponding oxime.

[0007] Brief summary of the disclosure

[0008] The invention is based on the surprising finding that titanosilicate-metal adducts of the invention are especially effective in the catalytic ammoximation of ketones, aldehydes and amides, especially ketones e.g. cyclohexanone. Further, the invention also relates that anumber of particular titanosilicates of the invention are also especially effective in the catalytic ammoximation of ketones, aldehydes and amides, preferably ketones e.g. cyclohexanone.

[0009] In a first aspect, the disclosure provides titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, and Fe-TS-1, preferably wherein the titanosilicate is Ti-MWW, and wherein the metal nanoparticles are bound to the titanosilicate.

[0010] Used herein the term Fe-TS-1 is synonymous with Fe-doped TS-1, i.e. means a titanosilicate of the TS-1 structure wherein some of the silicon atoms are replaced with iron atoms. Fe-TS-1 is an example of an iron-doped zeolite. Used herein the term TM-TS-1 is synonymous with transition metal-doped TS-1, i.e. means a titanosilicate of the TS-1 structure wherein some of the silicon atoms are replaced with atoms of one or more transition metal. TM-TS-1 and Fe-TS-1 are each examples of a transition metal-doped zeolite.

[0011] In a second aspect, the disclosure provides a catalyst for ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, the catalyst comprising the titanosilicate-metal adduct of the first aspect.

[0012] In a third aspect, the disclosure provides a process for the preparation of a titanosilicate-metal adduct the process comprising:

[0013] (a) providing a solution of a first metal salt in a first solvent, preferably wherein the first solvent is acetone, more preferably wherein the first metal salt is a Pd salt, even more preferably wherein the first metal salt is Pd(OAc)2, most preferably wherein the first metal salt is Pd(OAc)2 and the first solvent is acetone;

[0014] (b) combining the solution of first metal salt in first solvent with a titanosilicate to obtain a first slurry, optionally stirring the first slurry for 1 hour at room temperature;

[0015] (c) heating the first slurry above room temperature under conditions allowing the evaporation of the first solvent to obtain a first solid;

[0016] (d) grinding the first solid to obtain a first ground solid;

[0017] (e) optionally dispersing the first ground solid to obtain a second slurry, wherein the second slurry comprises the first ground solid and a second solvent, preferably wherein the second slurry further comprises a second metal salt, more preferably wherein the second solvent is water, even more preferably wherein the second metal salt is HAuCl₄.3H₂O, most preferably wherein the second slurry comprises the ground solid, the second solvent wherein the second solvent is water and the second metal salt wherein the second metal salt isHAuCl₄.3H₂O, followed by heating the second slurry above room temperature under conditions allowing the evaporation of the second solvent to obtain a second solid, followed by grinding the second solid to obtain a second ground solid; and

[0018] (f) reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct, preferably wherein prior to the reducing of the first ground solid or second ground solid the first ground solid or second ground solid is calcined;

[0019] wherein the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, or Fe-TS-1, preferably wherein the titanosilicate is Ti-MWW.

[0020] In a fourth aspect, the disclosure provides a process comprising reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct of the first aspect or the catalyst of the second aspect.

[0021] In a fifth aspect, the disclosure provides the use of titanosilicate in ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, or Fe-TS-1.

[0022] Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of them mean “including but not limited to”, and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps.

[0023] Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

[0024] Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.

[0025] The patent, scientific and technical literature referred to herein establish knowledge that was available to those skilled in the art at the time of filing. The entire disclosures of the issued patents, published and pending patent applications, and other publications that are citedherein are hereby incorporated by reference to the same extent as if each was specifically and individually indicated to be incorporated by reference. In the case of any inconsistencies, the present disclosure will prevail.

[0026] Various aspects of the invention are described in further detail below.

[0027] Detailed Description

[0028] Industrial production of oximes (such as the production of cyclohexanone oxime) by the reaction of H2O2 with NH3, for example in the presence of the titanosilicate catalyst TS-1, where the H2O2 is introduced into the reactor semi- / continuously is associated with a number of disadvantages. Firstly there is a need to purchase the H2O2, which is often a significant proportion of the total cost of production of the oxime. Secondly H2O2 is toxic and reactive, and so special precautions and apparatus are required for the safe handling of H2O2 in this approach. Further, there are safety and performance concerns with using this approach arising from there being areas within the reactor of high concentration of H2O2, referred to as hotspots.

[0029] In the context of the industrial production of oximes, particularly “commodity chemical” oximes such as cyclohexanone oxime, there are high economic and energetic costs associated with the concentration of H2O2 to a form suitable for use in ammoximation. This is because commercial sources of H^C^are relatively dilute, requiring several energy-intensive distillation steps to increase the concentration of before use in chemical synthesis. High concentration H2O2 may be required, for example is required in the production of cyclohexanone oxime, because the water introduced with the H2O2 is an impurity which it may be necessary to be removed from the product for certain applications of the product oxime. Importantly the presence of relatively high water concentration in prior art methods may lead to undesirable dilution of the product stream. Transport and storage of concentrated H2O2in a chemical plant is a serious safety concern. As such, prior art methods of production of oximes are associated with safety concerns. Prior art methods of production of oximes are associated with high energetic costs. Prior art methods of production of oximes are associated with high economic costs. There is a need to provide improved methods of production of oximes, be they ketoximes, aldoximes or amidoximes. There is a need to provide improved catalysts for the production of oximes of all types.

[0030] Additionally, the current industrial processes for production of oximes are associated with a number of drawbacks relating to the instability of H2O2. H2O2 is relatively unstable even atrelatively mild temperatures, and so requires the use of acidic stabilizing agents to prevent decomposition to H2O if it is to be stored. These stabilisers are not required should the H2O2 be formed and reacted in situ. The acidic stabilizing agents present in commercial H2O2 are associated with decreased reactor longevity and can be considered impurities within the product streams that require removal prior to subsequent reaction of the synthesised oxime. As such, the acidic stabilizing agents add significantly to the cost of oxime production in an industrial process setting. Where preformed H2O2 is used in industrial oxime production, a stoichiometric excess of H2O2 is typically required due to its poor stability under ammoximation reaction conditions, namely, elevated temperatures (> 80 °C) and the high pH of the reaction solution, resulting in an associated increase in process costs.

[0031] There have been reports of bi-functional catalysts which can be utilised in an ammoximation processes where the H2O2is generated in situ (see for example Lewis R. J. et al. Science, 5 May 2022, Vol 376, Issue 6593 pp. 615-620; Lewis R. J. et al. ACS Catal. 2023, 13, 3, 1934-1945; and Lewis R. J. etal. Green Chem., 2022, 24, 9496-9507). These bi-functional catalysts enable the production of H2O2 in situ from reaction of H2 with O2, which occurs together with the reaction of ammonia and hydrogen peroxide to form hydroxylamine. In these systems it is thought that the step of reaction of H2 with O2 to form H2O2 is catalysed by the precious metal portion of the catalyst, and the step of reaction of ammonia and H2O2to form hydroxylamine is catalysed by the Ti sites present within the titanosilicate framework portion of the catalyst. It is thought that the reaction of hydroxylamine with a ketone to form an oxime occurs independently of the catalyst spontaneously in an uncatalyzed manner. Development of bi-functional catalysts for ammoximation is highly technically challenging because of the different requirements of each step. Specifically in general there is a substantial gap in the optimal conditions between the two key processes of the reaction sequence (H2O2 synthesis and ketone ammoximation), low pH and sub-ambient temperatures are typically favoured for H2O2 formation, whereas high reaction temperature and high pH conditions are typically favoured for ammoximation, so the conditions of the ammoximation process would in general be expected to be are detrimental to H2O2 stability. In the absence of evidence confirming the reactivity, it would be expected that alternative attempts to prepare a bi-functional catalyst for ammoximation would be unsuccessful due to these challenges. The inventors estimate that bi-functional catalysts offer savings on a material cost basis of approx. 15% over the current commercial system for the ammoximation of cyclohexanone. The previously reported TS-1-precious metal bifunctional catalysts are associated with drawbacks. Specifically, the previous TS-1-precious metal bi-functional catalysts have a relatively low H2 selectivity. Further, the previous TS-1 -precious metal bi-functional catalysts have a relatively low reactivity. The relatively low reactivity means that relatively high catalyst loading and / or relatively high contacttime are required. High catalyst loading is disadvantageous for economic and environmental cost reasons. High contact times are disadvantageous as they provide low throughput and so limit the scale of oxime production.

[0032] The present disclosure relates to a titanosilicate-metal adduct that overcomes the problems associated with the prior art. The titanosilicate-metal adduct of the disclosure has a beneficial combination of properties which makes it especially suitable for ketone ammoximation, aldehyde ammoximation and amide ammoximation, and more especially suitable for ketone ammoximation. The titanosilicate-metal adducts of the invention are highly active as catalysts for ammoximation, including ketone ammoximation. The titanosilicate-metal adducts of the invention may be associated with improved catalytic activity of ammoximation, including ketone ammoximation. The titanosilicate-metal adducts of the invention may be associated with improved yield. The titanosilicate-metal adducts of the invention are active as catalysts for ammoximation, including ketone ammoximation, under conditions of in situ H2O2 synthesis. The titanosilicate-metal adducts of the invention may be associated with improved H2 selectivity. The titanosilicate-metal adducts of the invention may be associated with improved H2 selectivity over a wide range of H2 conversion, e.g. from 30% to 65% H2 conversion. The titanosilicate-metal adducts of the invention may display improved H2 selectivity. The titanosilicate-metal adducts of the invention may display improved H2 selectivity over a wide range of cyclohexanone conversion, e.g. from 50% to 95% cyclohexanone conversion. The titanosilicate-metal adducts of the invention may demonstrate low metal leaching, for example showing no detectable Au leaching. The titanosilicate-metal adducts of the invention demonstrate improved metal leaching, e.g. having lower Pd leaching. The titanosilicate-metal adducts of the invention may be associated with improved oxime selectivity. The titanosilicates of the invention (such as Ti-MWW) are catalytically active for ammoximation, including ketone ammoximation, e.g. under conditions of in situ H2O2 synthesis. The titanosilicate-metal adducts of the invention may be associated with improved catalytic activity in water. The titanosilicate-metal adducts of the invention may be associated with high tolerance to different solvents, e.g. showing high activity in a range of solvents. The titanosilicate-metal adducts of the invention may be associated with high tolerance to different carbonyl substrates, including a high tolerance to different ketones, so a wider range of oximes may be produced than by using previous catalysts.

[0033] Whilst the inventors believe that catalysts of the disclosure may produce H2O2 as an oxidative species as an intermediate in ammoximation, H2O2 is not necessarily the sole oxidative species present, for example, the transition metal nanoparticles may additionally or alternatively produce OOH.Used herein references to a substance being “for ketone ammoximation, aldehyde ammoximation and amide ammoximation” means that the substance may be used for at least any one of ketone ammoximation, aldehyde ammoximation and amide ammoximation. Preferably a substance “for ketone ammoximation, aldehyde ammoximation and amide ammoximation” may be used for all of ketone ammoximation, aldehyde ammoximation and amide ammoximation.

[0034] TM-TS-1, preferably Fe-TS-1, may be associated with improved catalytic activity in ammoximation reactions (for example as demonstrated by Table 14). TM-TS-1 metal nanoparticle adducts, preferably Fe-TS-1 metal nanoparticle adducts, may be associated with high catalytic activity, high H2 selectivity and low metal leaching (e.g. low Pd leaching). TM-TS-1, preferably Fe-TS-1, may be associated with the advantage that when used in ammoximation reactions (for example when TM-TS-1 metal nanoparticle adducts are used) low hydrogen peroxide degradation is observed (as seen in e.g. Table 16).

[0035] The disclosure relates to a titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, and Fe-TS-1, preferably wherein the titanosilicate is Ti-MWW, and wherein the metal nanoparticles are bound to the titanosilicate. In the context of the application the metal nanoparticles being bound to the titanosilicate means that there is a stable interaction between the titanosilicate portion and the metal nanoparticles. Suitably the stable interaction may be a stable non-covalent interaction, a covalent interaction, an ionic interaction, a Van de Waals interaction, among others. Preferably the metal nanoparticles are directly bound to the titanosilicate. In the context of the application the metal nanoparticles being directly bound to the titanosilicate means that there is a stable interaction between the titanosilicate portion and the metal nanoparticles, whereby this interaction arises predominantly or exclusively from the interaction between the surface of the titanosilicate and the surface of the metal nanoparticles. Suitably the metal nanoparticles are indirectly bound to the titanosilicate. Suitably the metal nanoparticles are indirectly bound to the titanosilicate by way of a linker, for example a small molecule linker, e.g. small molecule covalent linker.

[0036] Suitably the titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, and Ti-YNU-5 preferably wherein the titanosilicate is Ti-MWW, and wherein the metal nanoparticles are bound to the titanosilicate.

[0037] Suitably the titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is TM-TS-1, preferably wherein the titanosilicate is Fe-TS-1. In a highly preferred embodiment, the titanosilicate-metal adduct comprises TM-TS-1 and Pd alloy, wherein the Pd alloy comprises palladium and one or more non-palladium metal, and wherein the Pd alloy is bound to the TM-TS-1.

[0038] Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Pd, Au, Pt, Ir, Rh, or Ru, optionally wherein the metal nanoparticles comprise pure Pd, Au, Pt, Ir, Rh, or Ru. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Pd. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Au. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Pt. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Ir. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Rh. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Ru. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising pure Pd. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising pure Au. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising pure Pt. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising pure Ir. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising pure Rh. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising pure Ru.

[0039] Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Pd, Au, Pt, Ir, Rh, or Ru, optionally wherein the metal nanoparticles consist of pure Pd, Au, Pt, Ir, Rh, or Ru. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Pd. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Au. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Pt. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Ir. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Rh. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Ru. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of pure Pd. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of pure Au. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of pure Pt. Suitably the titanosilicate-metal adduct maycomprise metal nanoparticles consisting of pure Ir. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of pure Rh. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of pure Ru.

[0040] Preferably the titanosilicate-metal adduct may have the metal nanoparticles comprising Pd alloy wherein the Pd alloy comprises palladium and one or more non-palladium metal. More preferably the titanosilicate-metal adduct may have the metal nanoparticles consisting of Pd alloy wherein the Pd alloy comprises palladium and one or more non-palladium metal.

[0041] Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPt Aulr, AuRh AuRu, PtNi, PtSn, PtCo, Ptln, or PtZn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPt. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Aulr. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuRh. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuRu. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising PtNi. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising PtSn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising PtCo. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising Ptln. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising PtZn.

[0042] Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPt Aulr, AuRh AuRu, PtNi, PtSn, PtCo, Ptln, or PtZn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPt. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Aulr. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuRh. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuRu. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of PtNi. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of PtSn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of PtCo. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of Ptln. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of PtZn.

[0043] Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPdPt, AuPdNi, AuPdSn, AuPdZn, AuPdCo, AuPdln, or AuPdGa. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPdPt. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPdNi. Suitably the titanosilicate-metaladduct may comprise metal nanoparticles comprising AuPdSn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPdZn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPdCo. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPdln. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles comprising AuPdGa.

[0044] Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdPt, AuPdNi, AuPdSn, AuPdZn, AuPdCo, AuPdln, or AuPdGa. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdPt. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdNi. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdSn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdZn. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdCo. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdln. Suitably the titanosilicate-metal adduct may comprise metal nanoparticles consisting of AuPdGa.

[0045] In a highly preferred embodiment, the titanosilicate-metal adduct comprises Ti-MWW and Pd alloy, wherein the Pd alloy comprises palladium and one or more non-palladium metal, and wherein the Pd alloy is bound to the Ti-MWW. Suitably the titanosilicate-metal adduct comprises Ti-MWW and Pd alloy, wherein the Pd alloy comprises palladium and one or more non-palladium metal. Suitably the titanosilicate-metal adduct comprises Ti-MWW and Pd alloy, wherein the Pd alloy comprises palladium and one or more non-palladium metal, and wherein the Pd alloy is directly bound to the Ti-MWW. In this embodiment, preferably the metal nanoparticles consist of Pd alloy.

[0046] Suitably the titanosilicate-metal adduct comprises metal nanoparticles of 1 nm to 500 nm in diameter, preferably 2 nm to 200 nm in diameter, more preferably 3 nm to 100 nm in diameter, most preferably 5 nm to 50 nm in diameter. Used herein the term “diameter” refers to the length of the longest axis of the nanoparticle. Diameter may be measured using transition electron microscopy. Alternatively diameter may be measured using similar technique. The inventors measured the diameters used herein using transition electron microscopy. Suitably the titanosilicate-metal adduct comprises metal nanoparticles of 1 nm to 500 nm in diameter. Preferably the titanosilicate-metal adduct comprises metal nanoparticles of 2 nm to 200 nm in diameter. More preferably the titanosilicate-metal adduct comprises metal nanoparticles of 3 nm to 100 nm in diameter. Most preferably the titanosilicate-metal adduct comprises metalnanoparticles of 5 nm to 50 nm in diameter. The inventors note that titanosilicate-metal adducts of the invention may also comprise metal species below 1 nm in diameter.

[0047] Preferably the Pd alloy comprises palladium and one non-palladium metal.

[0048] Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is selected from Au, Pt, Fe, Ni, Ir, Cu, Rh, Co, Mn, Ga, Ag, Sn, Ru, In and Zn; preferably wherein the non-palladium metal is selected from Au, Pt, Fe, Ni, Ir, Cu, Co, Mn, Ag, Sn, Ru, In and Zn, more preferably wherein the non-palladium metal is selected from Au, Pt, Ni, Ir, and Sn, In and Zn; even more preferably wherein the non-palladium metal is selected from Au and Pt; most preferably the non-palladium metal is Au. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is selected from Au, Pt, Fe, Ni, Ir, Cu, Rh, Co, Mn, Ga, Ag, Sn, Ru, In and Zn. Preferably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is selected from Au, Pt, Fe, Ni, Ir, Cu, Co, Mn, Ag, Sn, Ru, In and Zn. More preferably metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is selected from Au, Pt, Ni, Ir, and Sn, In and Zn. Even more preferably metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is selected from Au and Pt. Most preferably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Au.

[0049] Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Au. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Pt. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Fe. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Ni. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Ir. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Cu. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Rh. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Co. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Mn. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Ga. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Ag. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Sn. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Ru. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is In. Suitably the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Zn.

[0050] Suitably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 5 wt% to 95 wt%, preferably 10 wt% to 90 wt%, more preferably 20 wt%to 80 wt%, even more preferably 20 wt% to 80 wt%. Suitably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 5 wt% to 95 wt%, preferably 10 wt% to 90 wt%, more preferably 20 wt% to 80 wt%, even more preferably 20 wt% to 80 wt%. Used herein the amount of Pd in the Pd alloy as a weight percentage refers to the amount of Pd as a proportion of the total metal in the metal nanoparticles. Suitably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 5 wt% to 95 wt%. Preferably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 10 wt% to 90 wt%. More preferably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 20 wt% to 80 wt%. Even more preferably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 20 wt% to 80 wt%. Suitably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 5 wt% to 95 wt%. Preferably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 10 wt% to 90 wt%. More preferably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 20 wt% to 80 wt%. Even more preferably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 20 wt% to 80 wt%.

[0051] Suitably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 20 wt% to 60 wt%, preferably 25 wt% to 50 wt%. Suitably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 20 wt% to 60 wt%, preferably 25 wt% to 50 wt%.

[0052] Suitably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 40 wt% to 80 wt%, preferably 50 wt% to 75 wt%. Suitably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 40 wt% to 80 wt%, preferably 50 wt% to 75 wt%.

[0053] Suitably the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 40 wt% to 60 wt%, optionally 50 wt%. Suitably the metal nanoparticles consist of metal nanoparticles wherein the amount of Pd in the Pd alloy is 40 wt% to 60 wt%, optionally 50 wt%.

[0054] In an especially preferred embodiment the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 40 wt% to 80 wt%, more preferably 50 wt% to 75 wt%, wherein the non-palladium metal is Au, and wherein the titanosilicate is Ti-MWW. In a more preferred embodiment, the titanosilicate-metal adduct comprises metalnanoparticles wherein the amount of Pd in the Pd alloy is 50 wt%, wherein the non-palladium metal is Au and wherein the titanosilicate is Ti-MWW.

[0055] In an especially preferred embodiment the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 40 wt% to 80 wt%, more preferably 50 wt% to 75 wt%, wherein the non-palladium metal is Au, and wherein the titanosilicate is Fe-TS-1. In a more preferred embodiment, the titanosilicate-metal adduct comprises metal nanoparticles wherein the amount of Pd in the Pd alloy is 50 wt%, wherein the non-palladium metal is Au and wherein the titanosilicate is Fe-TS-1.

[0056] Suitably the titanosilicate-metal adduct comprises Pd alloy in an amount of is 0.02 wt% to 10 wt%, preferably 0.1 wt% to 8 wt%, more preferably 0.3 wt% to 5 wt%, even more preferably 0.3 wt% to 1 wt%. Used herein the Pd alloy weight percentage refers to the amount of Pd alloy as a proportion of the total weight of all components in the titanosilicate-metal adduct. Suitably the titanosilicate-metal adduct comprises metal nanoparticles consisting of Pd alloy, wherein the titanosilicate-metal adduct comprises Pd alloy in an amount of is 0.01 wt% to 10 wt%, preferably 0.1 wt% to 8 wt%, more preferably 0.5 wt% to 5 wt%.

[0057] Suitably titanosilicate-metal adducts of the disclosure may be prepared by a method comprising:

[0058] (a) providing a solution of a first metal salt in a first solvent, preferably wherein the first solvent is acetone, more preferably wherein the first metal salt is a Pd salt, even more preferably wherein the first metal salt is Pd(OAc)2, most preferably wherein the first metal salt is Pd(OAc)2 and the first solvent is acetone;

[0059] (b) combining the solution of first metal salt in first solvent with a titanosilicate to obtain a first slurry, optionally stirring the first slurry for 1 hour at room temperature;

[0060] (c) heating the first slurry above room temperature under conditions allowing the evaporation of the first solvent to obtain a first solid;

[0061] (d) grinding the first solid to obtain a first ground solid;

[0062] (e) optionally dispersing the first ground solid to obtain a second slurry, wherein the second slurry comprises the first ground solid and a second solvent, preferably wherein the second slurry further comprises a second metal salt, more preferably wherein the second solvent is water, even more preferably wherein the second metal salt is HAuCl₄.3H₂O, most preferably wherein the second slurry comprises the ground solid, the second solvent wherein the second solvent is water and the second metal salt wherein the second metal salt is HAuCl₄.3H₂O, followed by heating the second slurry above room temperature under conditionsallowing the evaporation of the second solvent to obtain a second solid, followed by grinding the second solid to obtain a second ground solid; and

[0063] (f) reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct, preferably wherein prior to the reducing of the first ground solid or second ground solid the first ground solid or second ground solid is calcined. Titanosilicate-metal adducts of the disclosure may be prepared by a method comprising steps (a)-(d) and (f). Titanosilicate-metal adducts of the disclosure may be prepared by a method consisting of steps (a)-(f). Titanosilicate-metal adducts of the disclosure may be prepared by a method consisting of steps (a)-(d) and (f)..

[0064] The disclosure provides a catalyst for ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, wherein the catalyst comprises a titanosilicate-metal adduct of the disclosure, optionally further comprising a support, preferably wherein the support is selected from CeC>2, Nb20s, TiC>2, ZrC>2, SiC>2, AI2O3, or C, more preferably wherein the support is selected from Nb20s, TiC>2, ZrC>2, SiC>2, or AI2O3, even more preferably wherein the support is selected from TiC>2 or ZrC>2. Any titanosilicate-metal adduct of the disclosure may be used in the preparation of a catalyst for ammoximation, such as ketone ammoximation. The disclosure provides a catalyst for ammoximation, such as ketone ammoximation, wherein the catalyst comprises a titanosilicate-metal adduct of the disclosure. The disclosure provides a catalyst for ammoximation, such as ketone ammoximation, wherein the catalyst comprises a titanosilicate-metal adduct of the disclosure further comprising a support. The support may be any suitable catalyst support, optionally catalyst supports known in the art. Preferably the support may be selected from CeC>2, Nb20s, TiC>2, ZrC>2, SiC>2, AI2O3, or C. More preferably the support may be selected from Nb20s, TiC>2, ZrC>2, SiC>2, or AI2O3. Even more preferably the support may be selected from TiC>2 or ZrC>2. The catalyst for ammoximation, such as ketone ammoximation may comprise no support. The catalyst for ammoximation, such as ketone ammoximation may comprise one or more titanosilicate-metal adduct of the disclosure. The catalyst for ammoximation, such as ketone ammoximation may comprise one or more titanosilicate-metal adduct of the disclosure on one or more supports. The catalyst for ammoximation, such as ketone ammoximation may comprise one or more titanosilicate-metal adduct of the disclosure on a single support. Suitably the catalyst consists of a titanosilicate-metal adduct of the disclosure.

[0065] The disclosure provides a catalyst for ammoximation, such as ketone ammoximation wherein the catalyst comprises a H2O2 generating metal and a titanosilicate of the disclosure, wherein the titanosilicate is bound to a support. Suitably the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1 or Fe-TS-1. Suitably the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, or Ti-YNU-5. Preferably the H2O2 generating metal comprises or consists of metal nanoparticles of the disclosure, more preferably wherein the metal nanoparticles comprise Pd alloy. Any metal nanoparticles of the disclosure may be used. The disclosure provides a catalyst for ammoximation, such as ketone ammoximation wherein the catalyst comprises a H2O2 generating metal and a titanosilicate of the disclosure, wherein the H2O2 generating metal is bound to a support. Suitably the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1 or Fe-TS-1. Suitably the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, or Ti-YNU-5. Preferably the H2O2 generating metal comprises or consists of metal nanoparticles of the disclosure, more preferably wherein the metal nanoparticles comprise Pd alloy. Any metal nanoparticles of the disclosure may be used. The disclosure provides a catalyst for ammoximation, such as ketone ammoximation wherein the catalyst comprises a H2O2 generating metal and a titanosilicate of the disclosure, wherein the titanosilicate is bound to a first support, wherein the H2O2 generating metal is bound to a second support. Suitably the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1 or Fe-TS-1. Suitably the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, or Ti-YNU-5. Preferably the H2O2 generating metal comprises or consists of metal nanoparticles of the disclosure, more preferably wherein the metal nanoparticles comprise Pd alloy. Any metal nanoparticles of the disclosure may be used.

[0066] The disclosure provides a process for the preparation of a titanosilicate-metal adduct, the process comprising:

[0067] (a) providing a solution of a first metal salt in a first solvent, preferably wherein the first solvent is acetone, more preferably wherein the first metal salt is a Pd salt, even more preferably wherein the first metal salt is Pd(OAc)2, most preferably wherein the first metal salt is Pd(OAc)2 and the first solvent is acetone;

[0068] (b) combining the solution of first metal salt in first solvent with a titanosilicate to obtain a first slurry, optionally stirring the first slurry for 1 hour at room temperature;

[0069] (c) heating the first slurry above room temperature under conditions allowing the evaporation of the first solvent to obtain a first solid;

[0070] (d) grinding the first solid to obtain a first ground solid;(e) optionally dispersing the first ground solid to obtain a second slurry, wherein the second slurry comprises the first ground solid and a second solvent, preferably wherein the second slurry further comprises a second metal salt, more preferably wherein the second solvent is water, even more preferably wherein the second metal salt is HAuCl₄.3H₂O, most preferably wherein the second slurry comprises the ground solid, the second solvent wherein the second solvent is water and the second metal salt wherein the second metal salt is HAuCl₄.3H₂O, followed by heating the second slurry above room temperature under conditions allowing the evaporation of the second solvent to obtain a second solid, followed by grinding the second solid to obtain a second ground solid; and

[0071] (f) reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct, preferably wherein prior to the reducing of the first ground solid or second ground solid the first ground solid or second ground solid is calcined;

[0072] wherein the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1 or Fe-TS-1, preferably wherein the titanosilicate is Ti-MWW. Suitably the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, or Ti-YNU-5. Where the process does not involves step (e), the reducing in step (f) occurs on the first ground solid and not the second ground solid. This is because in that embodiment there is no second ground solid. Where the process does involves step (e), the reducing in step (f) occurs on the second ground solid. Step (a) may occur by dissolving a first metal salt in a first solvent. Step (b) may occur by addition of the titanosilicate to the solution of first metal salt in first solvent. Steps involving heating the first slurry or the second slurry above room temperature in order to evaporate the solvent may occur by heating the first slurry or the second slurry above room temperature in a vessel open to air. Steps involving heating the first slurry or the second slurry above room temperature in order to evaporate the solvent may occur by heating the first slurry or the second slurry above room temperature in a vessel under reduced pressure. Used herein grinding refers to any mechanical agitation sufficient to obtain a powder. The first ground solid may be a powder. The second ground solid may be a powder. Used herein reducing refers to undergoing a reaction which results in chemical reduction of the substance being reduced. A substance which has been calcined has been heated under an atmosphere of air, enriched air or O2.

[0073] Suitably the first metal salt may be selected from one or more of palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, and tetraammine palladium chloride. Suitably the second metal salt may be a gold salt. Suitably the second metal salt may be selected from one or more of gold chloride, chloroauric acid, and gold acetate.Suitably the first ground solid or second ground solid may be calcined by being heated under an atmosphere of flowing air, flowing enriched air or flowing O2. Preferably the first ground solid or second ground solid may be calcined by being heated under an atmosphere of flowing air. Suitably the first ground solid or second ground solid may be calcined by being heated to between 200 °C and 600 °C, preferably to between 300 °C and 500 °C, more preferably to 400 °C. More preferably the first ground solid or second ground solid may be calcined by being heated under an atmosphere of flowing air for 3 hours. Even more preferably the first ground solid or second ground solid may be calcined by being heated to 400 °C under an atmosphere of flowing air for 3 hours.

[0074] Suitably the reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct may occur at elevated temperatures, preferably 120 °C to 280 °C, more preferably 150 °C to 250 °C, even more preferably 200 °C. Suitably the reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct may occur under an atmosphere comprising H2. Preferably the reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct may occur under an atmosphere comprising H2 / Ar wherein the H2 is present in 1-20 vol%, more preferably 2-10 vol%, even more preferably 5 vol%. It is especially preferable that the reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct occurs at 200 °C under an atmosphere comprising H2 / Ar wherein the H2 is present in 5 vol%.

[0075] Titanosilicate-metal adducts of the disclosure may be prepared a number of alternative methods. Titanosilicate-metal adducts of the disclosure may be prepared by an incipient wetness impregnation protocol, optionally wherein prior to drying occurs at relatively low temperatures (for example 60 °C for 16 h) and reduction occurs using hydrazine. A range of metal precursors and synthetic protocols are suitable to prepare these titanosilicate-metal adducts. Any suitable method for the preparation of titanosilicate-metal adducts may be used, the person skilled in the art will be aware of preparation methods that lead to the immobilisation of Pd-based alloys are immobilised onto the surface of the titanosilicate or within the framework of the titanosilicate. Suitably the metal precursors may be selected from one or more of palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, tetraammine palladium chloride, and the like. Suitably the metal precursors may be selected from one or more of gold chloride, chloroauric acid, gold acetate and the like. Titanosilicate-metal adducts of the disclosure may be prepared by alternative liquid phase routes including for example methods selected from sol immobilisation and deposition precipitation. Titanosilicate-metal adducts of the disclosure may be prepared by dry techniques includingfor example methods selected from physical grinding, chemical vapour deposition or laser / ion ablation.

[0076] The disclosure provides a process comprising reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct of the disclosure or the catalyst of the disclosure. Suitably the ketone is selected from aliphatic ketones, alicyclic ketones, aromatic ketones ora combination thereof, preferably wherein the ketone is a cyclic ketone. Suitably the ketone is a single ketone. Suitably the ketone is a mixture of ketones. Suitably the ketone is an aliphatic ketone. Suitably the ketone is an alicyclic ketone. Suitably the ketone is an aromatic ketones. Suitably the ketone is a cyclic ketone. Suitably the ketone is an acyclic ketone. In an especially preferred embodiment the ketone is cyclohexanone. Suitably the amide is a cyclic amide. Here, cyclic amide refers to its ordinary meaning in the art, i.e. that in the structure R1-(C=O-NH)-R2, where R1and R2link together to form a ring. Suitably the amide is a non-cyclic amide. Suitably the amide is a non-cyclic primary amide. Suitably the amide is a non-cyclic secondary amide. Suitably the amide is a non-cyclic tertiary amide. Suitably the aldehyde is a cyclic aldehyde. Here, cyclic aldehyde refers to its ordinary meaning in the art, i.e. that in the structure there is a ring which is attached to a -C=O-H group. Suitably the aldehyde is a non-cyclic aldehyde. Preferably the ketone is cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone, cyclopentadecanone, 2-octanone, 5-methyl-2-hexanone, 2-butanone, isobutyl methyl ketone, mesityl oxide, propan-2-one, benzophenone, acetophenone, 1-indanone, cyclopentenone, cyclohexenone and the like. Preferably the aldehyde is furfural, citronellal, acetaldehyde, benzaldehyde, 2-chlorobenzaldehyde, or4-methylbenzaldehyde, 5-Isooctyl salicylaldehyde, 5-lsooctyl salicylaldehyde and the like. Preferably the amide is formamide, acetamide, benzamide, dimethylformamide and the like.

[0077] The disclosure provides a process comprising reacting a nitrile with H2, O2 and NH3 to form an amidoxime in the presence of the titanosilicate-metal adduct of the disclosure or the catalyst of the disclosure. Suitable nitriles include benzonitrile, propionitrile, and butyronitrile.

[0078] Suitably the process comprises step (i):

[0079] o

[0080] (i) Reactingnto formvn.

[0081] wherein n is an integer from 1 to 11, preferably from 2 to 10, more preferably 3 to 8, most preferably 4 to 7. Preferably step (i) is:

[0082]

[0083] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct:

[0084] (i) occurs in a solvent, optionally wherein the solvent is a solvent system or a pure solvent, preferably wherein the solvent is a protic solvent, more preferably wherein the solvent is selected from an alcohol, water, an aromatic hydrocarbon or a combination thereof, even more preferably wherein the solvent is methanol, ethanol, propanol, butanol, water, benzene toluene or a combination thereof, even even more preferably wherein the solvent is a combination of water and t-butanol;

[0085] (ii) occurs in a reaction vessel wherein the reaction vessel comprises an inner surface of PTFE, glass or stainless steel;

[0086] (iii) has a reaction temperature 0 to 150 °C, preferably 50 to 120 °C, more preferably 70 to 100 °C;

[0087] (iv) has a reaction pressure of 1 to 200 barg, preferably 10 to 100 barg;

[0088] (v) has a reaction time of 0.017 to 15 h;

[0089] (vi) occurs in batch reaction;

[0090] (vii) occurs in a semi-batch reaction; and / or

[0091] (viii) occurs in a continuous reaction.

[0092] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct occurs in a solvent, optionally wherein the solvent is a solvent system or a pure solvent, preferably wherein the solvent is a protic solvent, more preferably wherein the solvent is selected from an alcohol, water, an aromatic hydrocarbon or a combination thereof, even more preferably wherein the solvent is methanol, ethanol, propanol, butanol, water, benzene toluene or a combination thereof, even even more preferably wherein the solvent is a combination of water and t-butanol. Suitably the solvent may be a protic solvent. Suitably the solvent may be a protic solvent wherein the protic solvent is water, methanol, ethanol, n-propanol, isopropanol, or mixtures thereof.

[0093] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct occurs in areaction vessel wherein the reaction vessel comprises an inner surface of PTFE, glass or stainless steel. Used herein PTFE refers to polytetrafluoroethylene.

[0094] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct has a reaction temperature 0 to 150 °C, preferably 50 to 120 °C, more preferably 70 to 100 °C.

[0095] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct has a reaction pressure of 1 to 200 barg, preferably 10 to 100 barg. Used herein barg refers to gauge pressure measured in bars.

[0096] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct has a reaction time of 0.5 to 15 h.

[0097] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct occurs in batch reaction.

[0098] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct occurs in a semibatch reaction. Used herein a semi-batch reaction refers to a reaction performed in a reactor wherein some reactants are added to the reactor at the start of the batch, while other reactants are added to the reactor intermittently or continuously through time during the course of the reaction.

[0099] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct occurs in a continuous reaction. Used herein continuous reaction refers to a reaction set up where both starting materials and product (oxime) are added and removed respectively in an uninterrupted manner through time.

[0100] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct:

[0101] (i) has air or an enriched air as an O2 source;

[0102] (ii) has a molar ratio of O2:ketone / aldehyde / amide of 0.1: 20, preferably 1: 10, more preferably 1: 5, even more preferably 1: 1;(iii) has a molar ratio of H₂:ketone / aldehyde / amide of 0.1: 20, preferably 1: 10, more preferably 1: 5, even more preferably 1: 1;

[0103] (iv) uses a diluent for gaseous reagents, optionally where in the diluent is N₂, CO₂, Ar, He, Xe, Ne, CH₄, C₂H₆ or NH₃, preferably wherein the diluent is N₂;

[0104] (v) occurs in the presence of an NH₃ source, wherein the NH₃ source is selected from ammonium hydroxide, ammonium carbonate, ammonium acetate, ammonium hydrogen carbonate, ammonium halide, ammonium chloride, gaseous ammonia, and combinations thereof; and / or

[0105] (vi) has a molar ratio of NH₃:ketone / aldehyde / amide of greater than 1: 1, preferably 2: 1, more preferably 1: 1.

[0106] Processes described herein may involve the reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime, and in such cases one or more ketone, aldehyde or amide may be used, including combinations thereof. Preferably a single ketone, a single aldehyde or a single amide is used. References to “ketone / aldehyde / amide” mean the total amount of ketone, aldehyde and amide starting materials in the process.

[0107] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct has air or an enriched air as an O₂ source.

[0108] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct has a molar ratio of O₂: ketone / aldehyde / amide of 0.1: 20, preferably 1: 10, more preferably 1: 5, even more preferably 1: 1.

[0109] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct has a molar ratio of H₂: ketone / aldehyde / amide of 0.1: 20, preferably 1: 10, more preferably 1: 5, even more preferably 1: 1.

[0110] Especially preferably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct has a molar ratio of O₂: H₂:ketone / aldehyde / amide of 1: 1: 1.

[0111] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct uses a diluent for gaseous reagents, optionally where in the diluent is N₂, CO₂, Ar, He, Xe, Ne, CH₄, C₂H₆ or NH₃, preferably wherein the diluent is N₂.

[0112] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct occurs in the presence of an NH₃ source, wherein the NH₃ source is selected from ammonium hydroxide, ammonium carbonate, ammonium acetate, ammonium hydrogen carbonate, ammonium halide, ammonium chloride, gaseous ammonia, and combinations thereof.

[0113] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct has a molar ratio of NH₃:ketone / aldehyde / amide of greater than 1: 1, preferably 2: 1, more preferably 1: 1.

[0114] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct:

[0115] (i) has a weight ratio of titanosilicate-metal adduct: ketone / aldehyde / amide of 0.001:1 to 200:1;

[0116] (ii) occurs in the presence of an ion selected from sulphate, sulfite, phosphate, pyrophosphate, stannate, chloride, bromide, iodide, fluoride and combinations thereof;

[0117] (iii) occurs in the presence of an acid selected from halo acid, HCI, HBr, HF, HI, phosphoric acid, sulphuric acid, nitric acid, tungstic acid, heteropolyacids, solid acids, silico-aluminates, zeolites, alumina, silico-aluminophosphate, sulfated zirconia and combinations thereof;

[0118] (iv) occurs in the presence of a chelating agent, preferably wherein the chelating agent is selected from ethylenediamine tetra(methylene phosphonic acid), ethylenediaminetetraacetic acid, nitrilotriacetic acid and combinations thereof; (v) occurs in the presence of at least one organic compound, preferably wherein the at least one organic compound is selected from organic hydroxy compounds, diglycolic acid, aromatic sulfonic acid, acyl phosphonic acids, phenanthroline, amino-triazine, acetanilide and combinations thereof;

[0119] (vi) occurs in the presence of a radical scavenger preferably wherein the radical scavenger is selected from nitrone compounds, nitroso compounds, dithiocarbamate derivatives, ascorbic acid derivatives and combinations thereof; and / or

[0120] (vii) occurs in the presence of a compound which suppresses H2O2degradation preferably wherein the compound which suppresses H2O2degradation isselected from tantalum species, zirconium species, niobium species and combinations thereof.

[0121] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct has a weight ratio of titanosilicate-metal adduct: ketone / aldehyde / amide of 0.001:1 to 200:1.

[0122] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct occurs in the presence of an ion selected from sulphate, sulfite, phosphate, pyrophosphate, stannate, chloride, bromide, iodide, fluoride and combinations thereof.

[0123] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct occurs in the presence of an acid selected from halo acid, HCl, HBr, HF, HI, phosphoric acid, sulphuric acid, nitric acid, tungstic acid, heteropolyacids, solid acids, silico-aluminates, zeolites, alumina, silico-aluminophosphate, sulfated zirconia and combinations thereof.

[0124] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct occurs in the presence of a chelating agent, preferably wherein the chelating agent is selected from ethylenediamine tetra(methylene phosphonic acid), ethylenediaminetetraacetic acid, nitrilotriacetic acid and combinations thereof.

[0125] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct occurs in the presence of at least one organic compound, preferably wherein the at least one organic compound is selected from organic hydroxy compounds, diglycolic acid, aromatic sulfonic acid, acyl phosphonic acids, phenanthroline, amino-triazine, acetanilide and combinations thereof.

[0126] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct occurs in the presence of a radical scavenger preferably wherein the radical scavenger is selected from nitrone compounds, nitroso compounds, dithiocarbamate derivatives, ascorbic acid derivatives and combinations thereof.Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct occurs in the presence of a compound which suppresses H₂O₂ degradation preferably wherein the compound which suppresses H₂O₂ degradation is selected from tantalum species, zirconium species, niobium species and combinations thereof.

[0127] Suitably the process is for the production of an oxime.

[0128] Suitably the process of reacting a ketone, aldehyde or amide, preferably ketone, with H₂, O₂ and NH₃ to form an oxime in the presence of the titanosilicate-metal adduct process further comprises:

[0129] (ii) Reacting the oxime formed in step (i) to form an amide.

[0130] Preferably step (ii) is:

[0131] HO'N

[0132] (ii) Reacting )nto formH

[0133]

[0134] N4v'n.

[0135] More preferably step (ii) is:

[0136]

[0137] Suitably the process of the disclosure is for the production of polycaprolactam.

[0138] The disclosure relates to the use of titanosilicate in ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, or Ti-YNU-5. In an especially preferred embodiment the titanosilicate is Ti-MWW. Optionally the process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation comprises the addition of H₂O₂. Optionally the process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation comprises synthesis (e.g. in situ synthesis) of H₂O₂, preferably from H₂ and O₂. The use of the titanosilicate may be in any process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation described herein.For example, the use of the titanosilicate may be in any process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation described herein in the presence of a titanosilicate-metal adduct described herein, optionally in the presence of more than one titanosilicate-metal adduct described herein. Alternatively, the use of the titanosilicate may be in any process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, described herein in the absence of a titanosilicate-metal adduct. For example, the use of the titanosilicate may be in any process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, described herein in the absence of a titanosilicate-metal adduct wherein the titanosilicate is the only catalyst present. Alternatively, the use of the titanosilicate may be in any process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, described herein in the absence of a titanosilicate-metal adduct wherein a further hydrogen peroxide forming catalyst is present, optionally wherein the further hydrogen peroxide forming catalyst is selected from Rh, Rh alloy, Pd, Pd alloy, Pt, Pt alloy, or AuPt alloy.

[0139] Suitably the use of the titanosilicate may be in any process of ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, described herein in the absence of a titanosilicate-metal adduct wherein a further hydrogen peroxide forming catalyst is present, wherein the further hydrogen peroxide forming catalyst is selected from Rh, Rh alloy, Pd, Pd alloy, Pt, Pt alloy, or AuPt alloy. Suitably the further hydrogen peroxide forming catalyst is selected from Rh, RhAu, RhSn, RhNi, RhGa, Rhln, RhRu, RhFe, RhCo, RhCu, RhZn, Pd, PdAu, PdSn, PdNi, PdGa, Pdln, PdPt, PdRu, PdRh, PdFe, PdCo, PdCu, PdZn, Pt, PtAu, PtSn, PtNi, PtGa, Ptln, PtRu, PtRh, PtFe, PtCo, PtCu, PtZn, AuPdPt, AuPdSn, AuPdlr, AuPdFe, AuPdZn, AuPdNi, AuPdCo, AuPdCu, AuPdln, AuPdGa, AuPdRh, or AuPdRu. Suitably the further hydrogen peroxide forming catalyst is selected from Rh, RhAu, RhSn, RhNi, RhGa, Rhln, RhRu, RhFe, RhCo, RhCu, or RhZn. Suitably the further hydrogen peroxide forming catalyst is selected from Pd, PdAu, PdSn, PdNi, PdGa, Pdln, PdPt, PdRu, PdRh, PdFe, PdCo, PdCu, or PdZn. Suitably the further hydrogen peroxide forming catalyst is selected from Pt, PtAu, PtSn, PtNi, PtGa, Ptln, PtRu, PtRh, PtFe, PtCo, PtCu, or PtZn. Suitably the further hydrogen peroxide forming catalyst is selected from AuPdPt, AuPdSn, AuPdlr, AuPdFe, AuPdZn, AuPdNi, AuPdCo, AuPdCu, AuPdln, AuPdGa, AuPdRh, or AuPdRu.

[0140] Suitably the further hydrogen peroxide forming catalyst may be supported on a support. Suitably the further hydrogen peroxide forming catalyst may be supported on a supportwherein the support is selected from Carbon, Ga₂O₃, ZrO₂, SiO₂, Al₂O₃, CeO₂, TiO₂, Nb₂O₅, ZrO₂, aluminosilicates, zeolites, ZSM-5, zeolite-Y, zeolite-beta, zeolite-A, S-1 or MCM-41.

[0141] Catalysts of the disclosure, both titanosilicates and titanosilicate-metal adducts, are thought to be especially effective because they comprise titanosilicates of the disclosure (Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1 or Fe-TS-1). It is thought that titanosilicates of the disclosure are especially effective because they comprise frameworks containing medium and / or large pores, allowing for enhanced adsorption and diffusion of reactants and products, for example compared to small pore zeolites including TS-1. In the case of the TM-TS-1 formulations, it is considered that the enhanced performance of these materials (in comparison to the parent TS-1 structure), results from more efficient activation of H₂O₂ (and associated reactive oxygen intermediate species) over the Ti-TM bi-nuclear sites, compared to that offered by the Ti-Si analogues, present within the unmodified titanosilicate (i.e. TS-1). It is considered that this results from the increased electron density of the TM species within the framework (compared to the Si centres), which consequently, augments the electron density of the titanosilicate structure during H₂O₂ (or oxygen-based intermediate) adsorption, which, in turn, reduces the energy of the entire ammoximation system. In addition, silicates of the disclosure may display improved resistance to desilication so can operate in water only solvent mixtures which may allow for improved integration in downstream chemical processes where water is the solvent of choice.

[0142] The inventors found that, surprisingly, the presence of gold in the Au-Pd alloy of the titanosilicate-metal adduct stabilises the titanosilicate-metal adduct. This stabilisation is advantageous as there is improved catalyst lifetimes (the catalyst retains a high level of catalyst activity for a long time). The stabilisation of the titanosilicate-metal adduct is demonstrated by low leaching of Pd. Stabilisation of the titanosilicate-metal adduct is further advantageous as less Pd is present in the final product as a contaminant and / or there is reduced need to remove Pd contaminant from the product.

[0143] The inventors found that titanosilicate-metal adducts prepared according to the disclosure demonstrated low leaching of the non-palladium metal (e.g. Au). As such, the titanosilicate-metal adducts of the disclosure advantageously show low metal leaching in use (as the total metal leaching is the sum of the Pd and Au leaching).

[0144] The inventors believe that the Pd alloy preferentially deposits onto the titanium containing regions of the titanosilicate.H2 selectivity refers to the proportion of H2 being consumed in the generation of oxime relative to the total amount of H2 consumed in the process overall. Low H2 selectivity may occur where a significant portion of H₂ is involved in the undesired reaction of H₂O₂ to H₂O. It is advantageous to have a high H2 selectivity in the context of oxime production because the oxime product formed is purer, for example, there is a reduced need to concentrate the oxime product. The energetic, time, equipment and commercial cost of drying oxime on an industrial scale can be very disadvantageous. It is advantageous to have a high H2 selectivity in the context of oxime production because the overall oxime production process is more economical, due to reduced costs associated with H2 usage.

[0145] The titanosilicate-metal adduct of the disclosure preferably is an adduct between titanosilicate and Au / Pd nanoparticles. The size of the Au / Pd nanoparticles present in the titanosilicate-metal adduct may impact the efficiency of the catalyst. Preferably the Au / Pd nanoparticles are 1 nm to 500 nm in diameter, more preferably 2 nm to 200 nm in diameter, even more preferably 3 nm to 100 nm in diameter, most preferably 5 nm to 50 nm in diameter. Used herein the term “diameter” refers to the length of the longest axis of the nanoparticle. Diameter may be measured using transition electron microscopy or similar technique.

[0146] The titanosilicate-metal adduct of the disclosure may have a uniform distribution of Pd alloy on the Ti-MWW.

[0147] Suitably the titanosilicate-metal adduct of the disclosure has a less than 1% leaching of the one or more non-palladium metal at 3.0 hour reaction time under the conditions of ammoximation of cyclohexanone. Preferably the titanosilicate-metal adduct of the disclosure has a less than 0.5% leaching of the one or more non-palladium metal at 3.0 hour reaction time under the conditions of ammoximation of cyclohexanone. More preferably the titanosilicate-metal adduct of the disclosure has a less than 0.5% leaching of the one or more non-palladium metal at 3.0 hour reaction time under the conditions of ammoximation of cyclohexanone.

[0148] Suitably the titanosilicate-metal adduct of the disclosure has a less than 40% leaching of the palladium at 3.0 hour reaction time under the conditions of ammoximation of cyclohexanone. Preferably the titanosilicate-metal adduct of the disclosure has a less than 20% leaching of the palladium at 3.0 hour reaction time under the conditions of ammoximation of cyclohexanone. More preferably the titanosilicate-metal adduct of the disclosure has a lessthan 10% leaching of the palladium at 3.0 hour reaction time under the conditions of ammoximation of cyclohexanone.

[0149] Suitably the titanosilicate-metal adduct of the disclosure provides 70% or greater yield of cyclohexanone oxime at 1 hour reaction time, preferably 80% or greater yield. Suitably the titanosilicate-metal adduct of the disclosure provides 80% or greater yield of cyclohexanone oxime at 1.5 hour reaction time, preferably 90% or greater yield. Suitably the titanosilicate-metal adduct of the disclosure provides 90% or greater yield of cyclohexanone oxime at 2 hour reaction time.

[0150] Suitably the titanosilicate-metal adduct of the disclosure displays an H2 selectivity of greater than 65% at H2 conversions in the range of 30% to 50%. Suitably the titanosilicate-metal adduct of the disclosure displays an H2 selectivity of greater than 70% at H2 conversions in the range of 30% to 50%. Suitably the titanosilicate-metal adduct of the disclosure displays an H2 selectivity of greater than 75% at H2 conversions in the range of 30% to 50%.

[0151] Suitably the titanosilicate-metal adduct of the disclosure displays an H2 selectivity of greater than 65% at cyclohexanone conversions in the range of 50% to 95%. Suitably the titanosilicate-metal adduct of the disclosure displays an H2 selectivity of greater than 70% at cyclohexanone conversions in the range of 50% to 95%. Suitably the titanosilicate-metal adduct of the disclosure displays an H2 selectivity of greater than 75% at cyclohexanone conversions in the range of 50% to 95%.

[0152] Catalysts of the present disclosure may further comprise a support. Suitably the support may be selected from titanium oxide, activated carbon, silica, alumina and iron oxide or a combination thereof. Catalysts comprise a support bound to a titanosilicate-metal adduct of the present disclosure. In embodiments comprising a titanosilicate-metal adduct of the present disclosure bound to a support, the support may be selected from Al-containing zeolites, Ti-containing zeolites, ZSM-5, TS-2, common oxide supports, TiO₂, Al₂O₃, zirconia, or carbon. In embodiments comprising a titanosilicate-metal adduct of the present disclosure bound to a support, the support may be selected from ZSM-5, TS-2, TiO₂, Al₂O₃, zirconia, or carbon.

[0153] Suitably the form of ammonia supplied to the reaction may be aqueous ammonia solution, gaseous ammonia, ammonium salts, ammonium carbonate, ammonium hydrogen carbonate or a combination thereof.Suitably a titanosilicate-metal adduct of the present disclosure may be prepared by impregnating the titanosilicate (e.g. Ti-MWW) with a solution or a colloidal solution of one or more metals, and drying, calcining, reducing thermally, or carrying out reduction treatment with a reducing agent (e.g. sodium borohydride or hydrazine). Suitably reducing thermally may be conducted through the exposure of the titanosilicate-metal adduct to a H2 containing atmosphere at temperatures exceeding 100 °C. Suitably a titanosilicate-metal adduct of the present disclosure may be prepared by impregnating the titanosilicate (e.g. Ti-MWW) with a solution of palladium salt and non-palladium metal salt; or a colloidal solution of metal nanoparticles (e.g. wherein the metal nanoparticles comprise or consist of Pd alloy), and drying, calcining or carrying out reduction treatment with a reducing agent. Used herein, the term “supporting step” refers to impregnating the titanosilicate (e.g. Ti-MWW) with a solution of one or more metal salts (e.g. combination of palladium metal salt and non-palladium metal salt); or a colloidal solution of metal nanoparticles (e.g. wherein the metal nanoparticles comprise or consist of Pd alloy). Suitably the titanosilicate-metal adduct may be prepared by a supporting step. Suitably the titanosilicate-metal adduct may be prepared by a supporting step wherein the supporting step is impregnating the titanosilicate (e.g. Ti-MWW) with a solution of palladium metal salt and non-palladium metal salt. Suitably the titanosilicate-metal adduct may be prepared by a supporting step wherein the supporting step is impregnating the Ti-MWW with a colloidal solution of Pd alloy. Suitably the non-palladium metal salt may be a gold salt. In the case of palladium and gold, supporting may be accomplished by impregnating the Ti-MWW with a solution of palladium salt and gold salt, or by impregnating the Ti-MWW with a colloidal solution containing an alloy of palladium and gold. After the Ti-MWW is mixed with the aqueous solution of palladium salt and gold salt or palladium / gold alloy colloid, generally water may be removed by filtration or condensation to produce a palladium and gold-supported catalyst.

[0154] Suitably the palladium salt may be selected from palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, tetraammine palladium chloride and combinations thereof. Suitably the gold salt may be selected from gold chloride, chloroauric acid, gold acetate and combinations thereof. Solutions of Pd alloy colloid are not particularly limited as long as Pd alloy particles are dispersed in a liquid. Generally, aqueous solutions are used. The concentration of Pd alloy colloid are not particularly limited.

[0155] Generally, after the supporting step, the titanosilicate-metal adduct is calcined in an O2 atmosphere, an enriched air, or an air atmosphere or reduced with a reducing agent in the liquid phase or gas phase, thereby producing a titanosilicate-metal adduct which is ready for use. Used herein the term enriched air refers to an air / 02 mixture. Suitably the after thesupporting step, the titanosilicate-metal adduct is calcined in ambient atmosphere. Suitably the after the supporting step, the titanosilicate-metal adduct is calcined in an O2 atmosphere or an enriched air atmosphere. Suitably after the supporting step, the titanosilicate-metal adduct is calcined in an O2 atmosphere. Suitably the after the supporting step, the titanosilicate-metal adduct is calcined in an enriched air atmosphere. Suitably the after the supporting step, the titanosilicate-metal adduct is calcined in an air atmosphere. Suitably the after the supporting step, the titanosilicate-metal adduct is thermally treated under an inert atmosphere. Suitably the after the supporting step, the titanosilicate-metal adduct is reduced with a reducing agent in the liquid phase. Suitably the after the supporting step, the titanosilicate-metal adduct is reduced with a reducing agent in the gas phase. The supporting amount of the Pd alloy is generally in the range of 0.01 to 20% by weight, preferably 0.1 to 5% by weight based on the weight of the Ti-MWW. Preferably the titanosilicate-metal adduct is calcined. Embodiments wherein the titanosilicate-metal adduct is calcined may be associated with improved yield.

[0156] Other metals can be supported on supports by the same method. In case that one or more of the other metals are also supported, they are used, for example, in an amount of 0.01 to 10 times by weight based on the total amount of Pd alloy.

[0157] According to the present disclosure the Pd alloy comprises palladium and a non-palladium metal. The Pd alloy may comprise palladium and a non-palladium metal and further nonpalladium metal. The Pd alloy may comprise palladium and two different non-palladium metals. The Pd alloy may comprise palladium and three different non-palladium metals. The Pd alloy may comprise palladium and four different non-palladium metals. Preferably the Pd alloy comprises palladium and one non-palladium metal. Suitably the non-palladium metal may be selected from Au, Pt, Ni, Ir, Cu, Rh, Co, Mn, Ga, Ag, Sn, Ru, In and Zn. Preferably the non-palladium metal is selected from Au, Pt, Ni and Sn. More preferably the non-palladium metal is selected from Au and Pt. Even more preferably the non-palladium metal is Au.

[0158] Titanosilicates are a class of zeolitic substances wherein titanium atoms are substituted for a portion of silicon atoms within the framework. Titanosilicates may be used as molecular sieves.

[0159] The titanosilicate is not particularly limited as long as it is a porous titanosilicate in which a part of Si is replaced with Ti, and the examples thereof include crystalline titanosilicates, layered titanosilicates, and mesoporous titanosilicates.According to the invention, the titanosilicate may be Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, or Fe-TS-1, preferably the titanosilicate is Ti-MWW. Ti-MWW may be Ti-MWW having Framework Type MWW. Ti-MWW having Framework Type MWW is described in Chemistry. Letters. 774-775 (2000) and ChemCatChem., (2024), 16, 19, e202301653. TS-2 may be TS-2 having Framework Type MEL. Ti-ZSM-12 may be Ti-ZSM-12 having Framework Type MTW. Ti-ZSM-12 having Framework Type MTW is described in Zeolites 15, 236-242 (1995). Ti-Beta may be Ti-Beta having Framework Type BEA. Ti-Beta having Framework Type BEA may be Journal of Catalysis 199, 41-47 (2001). Ti-Beta having Framework Type BEA is described in J. Phys. Chem. B, (1998), 102, 1, 75–88, Stud. Surf. Sci. Catal., (1994), 82, 531-540, and Zeolites, (1993), 13, 2, 82-87. Ti-UTD-1 may be Ti-UTD-1 having Framework Type DON. Ti-UTD-1 having Framework Type DON is described in Zeolites 15, 519-525 (1995). The Framework Type Codes used herein are those of the IZA (The International Zeolite Association). Ti-MWW precursor is described in JP 2003-327425 A. Ti-YNU is described in Angewante Chemie International Edition 43, 236-240 (2004). Ti-MCM-41 is described in Microporous Material 10, 259-271 (1997), Chem. Mater., (2000), 12, 10, 3068-3072, Appl. Catal. A Gen. (2015), 507, 14-25, and J. Phys. Chem. 1996, 100, 6, 2178-2182. Ti-MCM-48 is described in Chemical Comunications 145-146 (1996). Ti-SBA-15 is described in Chemistry of Materials 14,1657-1664 (2002). Ti-MMM-1 is described in Microporous and Mesoporous Materials 52, 11-18 (2002). Ti-MOR is described in J. Phys. Chem. B 2001, 105, 15, 2897-2905. Ti-YNU-5 is described in Chem. Lett., 53, 7, upae130. TS-2 is described in J. Catal., (1991), 130, 2, 440-446, and Catal. Lett., (2004), 96, 205-211. TS-1 is described in J. Mater. Sci., (2002), 37, 1959-1965, Catal. Lett., (2003), 91, 123-127, and Science, (2022), 376, 615-620. TM-TS-1, i.e. transition metal doped TS-1, may be prepared according to any suitable method known in the art. Fe-TS-1, i.e. iron doped TS-1, may be prepared according to any suitable method known in the art. TM-TS-1 is preferably doped with one or more of Fe, Sn, Ge, Zr, W, Mo, Hf, B, V, Ga, Ta, Nb, Pb, Pt, Pd, Rh, Ru, Ir or Os. Most preferably TM-TS-1 is doped with Fe. Most preferably TM-TS-1 is Fe-TS-1.

[0160] Ti-MWW (also known as Titanium-MWW zeolite) refers to a titanosilicate having the having an MEL topology containing titanium atoms substituted in the cage structure (also known as the MWW topology). The MWW topology is described in described in Chemistry Letters 774-775, (2000). Ti-MWW is described in for example Tatsumi et al. Studies in Surface Science and Catalysis Volume 170, 2007, Pages 1051-1058. Ti-MWW is a MWW zeolite. Ti-MWW possesses a structure containing a two-channel system, 10-membered-ring (MR) views to crystallographic direction

[0001] between “layers” (0.48 x 0.35 nm and 0.41 x 0.51 nm), and one pore system is composed of 12MR MWW cages with dimensions of 1.82 x 0.71 x 0.71 nm- see Journal of Catalysis Volume 417, January 2023, Pages 432-444. Suitably Ti-MWW may be Ti-MCM-22. Ti-MCM-22 is described in Phys Chem B, 2001, 105: 2897. Suitably the Ti-MWW may be covalently modified Ti-MWW or unmodified Ti-MWW. Suitably the covalently modified Ti-MWW may be silylized Ti-MWW. Preferably the Ti-MWW is unmodified Ti-MWW. Ti-MWW may have a composition corresponding to the following empirical formula xTiO2.(1-x)SiC>2 where x is between 0.0001 and 0.5, more preferably, the value of x is from 0.01 to 0.125. The molar ratio of Si: Ti in the lattice framework of the zeolite is advantageously from 9.5:1 to 99:1, preferably from 9.5:1 to 60:1. The use of relatively titanium-rich MWW zeolites is desirable. Ti-MWW may be prepared according to US8124555B2. Ti-MWW may be prepared according to J. Phys. Chem. B 2001, 105, 15, 2897-2905.

[0161] The Ti-MWW zeolite preferably contains no elements other than titanium, silicon, and oxygen, although minor amounts of iron, boron, aluminium, sodium, potassium, copper and the like may be present.

[0162] Disclosed herein is a process comprising reacting a ketone, aldehyde or amide, preferably ketone, with H2O2 and NH3 to form an oxime in the presence of a titanosilicate of the disclosure. Disclosed herein is a process comprising reacting a ketone, aldehyde or amide, preferably ketone, with H2O2 and NH3 to form an oxime in the presence of TM-TS-1, preferably Fe-TS-1. In such processes, the any suitable conditions of reactions described herein may be used, and any suitable reagents may be used. For example, with regard to the ketone substrate, any ketone described herein may be used. In these processes the H2O2 may be generated in situ, or may be added as a reagent.

[0163] Titanosilicate-metal adducts comprising titanosilicate, wherein the titanosilicate is TM-TS-1 are preferred. Similarly, processes described herein wherein the titanosilicate-metal adducts comprise titanosilicate, wherein the titanosilicate is TM-TS-1 are preferred. Among TM-TS-1, Fe-TS-1 is most preferred for all titanosilicate-metal adducts and all processes described herein.

[0164] Disclosed herein is a process comprising reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of a titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is TM-TS-1, and wherein the metal nanoparticles are bound to the titanosilicate. Disclosed herein is a process comprising reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of a titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is Fe-TS-1, and wherein the metal nanoparticlesare bound to the titanosilicate. In such processes, the any suitable conditions of reactions described herein may be used, and any suitable reagents may be used. For example, with regard to the ketone substrate, any ketone described herein may be used.

[0165] An especially preferred embodiment described herein is titanosilicate-metal adduct of the disclosure wherein the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Au, and wherein the titanosilicate is TM-TS-1, and wherein the metal nanoparticles are bound to the titanosilicate. Even more preferred is the embodiment described herein of a titanosilicate-metal adduct of the disclosure wherein the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is Au, and wherein the titanosilicate is Fe-TS-1, and wherein the metal nanoparticles are bound to the titanosilicate

[0166] Reactions of oximes to form amides are well known in the art and the skilled person will be readily able to identify them. Any suitable reaction of an oxime to form an amide may be used with the processes of the present disclosure. Suitable reactions of oximes to form amides include the Beckmann rearrangement. Suitable agents that may be used to catalyse / induce the Beckmann rearrangement include acids, strong acids, sulfuric acid, nitric acid, hydrochloric acid, tosyl chloride, thionyl chloride, phosphorus pentachloride, phosphorus pentoxide, triethylamine, sodium hydroxide, trimethylsilyl iodide.

[0167] Titanosilicate-metal adducts of the disclosure may be used to catalyse the transformation of a ketone into an oxime. Suitably the ketone is selected from aliphatic ketones, alicyclic ketones, and aromatic ketones, or a combination thereof. Suitably the ketone is a dialkyl ketone, acetone, ethyl methyl ketone, isobutyl methyl ketone, an alkyl alkenyl ketone, mesityl oxide, an alkyl aryl ketones, acetophenone, a diaryl ketone, benzophenone, a cycloalkanone, cyclopentanone, cyclohexanone, cyclooctanone, cyclododecanone, a cycloalkenone, cyclopentenone, cyclohexenone and combinations thereof. Among these, cycloalkanones are most preferred.

[0168] The above ketones may be those obtained by oxidation of alkanes, oxidation (dehydrogenation) of secondary alcohols, or hydration and oxidation (dehydrogenation) of alkenes.

[0169] The use amount of an ammoximation catalyst to ketones can be varied widely depending on the forms of reaction. For example, in the case of batch reaction, a catalyst may be used in an amount of 0.01 to 200 parts by weight, preferably 0.1 to 100 parts by weight based on 100 parts by weight of ketones. In the case of continuous reaction, starting materials may besupplied such an amount that the space velocity of ketones are in the range about 0.01 to 1000 kg / h per 1kg of catalyst. In addition, in case that a continuous vessel type reactor is used, a catalyst may be used as a dispersion in a reaction mixture in such an amount that the content thereof is about 0.1 to about 20% by weight based on a liquid phase of the reaction mixture. In this case, source materials, solvent and gasses are continuously supplied to the reaction mixture in the reactor in which the catalyst is dispersed, and the liquid phase of the reaction mixture is continuously taken out of the reactor via a filer or the like to obtain a product.

[0170] Used herein the terms Nylon-6, polycaprolactam, poly(azepan-2-one), poly[azanediyl(1-oxohexane-1,6-diyl)] and polyamide 6 are all equivalent terms, used synonymously with one another. Used herein room temperature means ambient temperature, for example about 21 °C. Used herein the term oxime refers to a compound having as part of its structure one or more R1(C=N-OH)R2groups, where R1and R2are independently the point of attachment to the rest of the molecule. As such the term oxime as used herein encompasses aldoximes, ketoximes and amidoximes, being the oximes of aldehydes, ketones and amides respectively. Processes described herein preferably use ketone substrates, and so ketoximes are a preferred type of oxime. Used herein ammoximation refers to the chemical conversion of a carbonyl group to an oxime, preferably ammoximation mean ketone ammoximation, aldehyde ammoximation or amide ammoximation, more preferably ketone ammoximation.

[0171] Although any methods and materials similar or equivalent to those described herein find use in the practice of the present invention, the preferred methods and materials are described herein. Accordingly, the terms defined immediately below are more fully described by reference to the Specification as a whole. Also, as used herein, the singular terms "a", "an," and "the" include the plural reference unless the context clearly indicates otherwise. It is to be understood that this invention is not limited to the particular methodology, protocols, and reagents described, as these may vary, depending upon the context they are used by those of skill in the art.

[0172] Aspects of the invention are demonstrated by the following non-limiting examples.EXAMPLES

[0173] Ti-MWW was obtained from Changzhou Angxing New Carbon Materials Co., Ltd. and used without further purification.

[0174] TS-1 was obtained from HighChem and manufactured by Hengyi Chemical and used without further purification.

[0175] TS-2 was synthesized according to Lin et al., Reversing Titanium Oligomer Formation towards High-Efficiency and Green Synthesis of Titanium-Containing Molecular Sieves, Angew. Chem. Int. Ed., (2021), 60, 7, 3443-3448,

[0176]

[0177] (https: / / doi.org / 10.1002 / anie.202011821), using the synthetic protocol reported in the supporting information of this paper at page S5 lines 1 - 9 (which is incorporated herein by reference) and used without further purification.

[0178] Ti-beta was sourced from the Universidad Politecnica de Valencia, Spain, and was synthesised via a protocol based on that outlined in Camblor et al., A new highly efficient method for the synthesis of Ti-Beta zeolite oxidation catalyst, Appl. Catal., A., (1995), 133, L185-L189, (https: / / doi.org / 10.1016 / 0926-860X(95)00252-9), using the synthetic protocol reported on page L185, line 16-32 (which is incorporated herein by reference) and used without further purification.

[0179] Ti-MCM-41 was sourced from the by Universidad Politecnica de Valencia, Spain, and was synthesised via a protocol based on that outlined in Corma et al., One step synthesis of highly active and selective epoxidation catalysts formed by organic-inorganic Ti containing mesoporous composites, Chem. Commun., 1998, 1899-1900 (https: / / doi.org / 10.1039 / A804801K), using the synthetic protocol reported page 1899 column 1, line 33-page 1899, column 2, line 9 (which is incorporated herein by reference) and used without further purification.

[0180] Titanosilicate-metal adduct synthesis

[0181] Ti-MWW supported AuPd catalysts were prepared (on a weight basis) based on a methodology previously reported in the literature (see Lewis R. J. et al. Science, 5 May 2022, Vol 376, Issue 6593 pp. 615-620) using Pd(OAc)2 and HAuCl₄ as metal precursors via a sequential wet impregnation methodology. The procedure to produce 2 g of the 0.33%Au-0.33% Pd / Ti-MWW catalyst is outlined below.

[0182] Pd(OAc)2 (0.0139 g, Merck) was charged into a 50 mL round bottom flask, with the total solution volume fixed to 20 mL with acetone (Merck). Once fully dissolved, Ti-MWW (1.987 g) was added and the vessel stoppered. The resulting slurry was stirred in a room-temperatureoil bath for 1 h, (600 rpm). Following this the stopper was removed and temperature was raised to 70 °C and the acetone allowed to evaporate. The resulting solid was ground and redispersed in water (20 mL, HPLC grade, Fisher Scientific), to which a HAuCl₄.3H₂O solution (0.539 mL, [Au] = 12.25 mgmL'1, Strem Chemicals) was added and the vessel again stoppered. The resulting slurry was stirred (600 rpm) at room temperature, in an oil bath for 1 h, prior to the temperature being raised to 85 °C for 16 h. The as-obtained solid was ground prior to calcination in flowing air (400 °C, 3h, 10 °Cmin-1) and was subsequently reduced (200 °C, 2 h, 10 °Cmin-1, 5% H2 / Ar,).

[0183] The titanosilicate-metal adducts of Table S.1 were prepared analogously to the 0.33%Au-0.33%Pd / Ti-MWW adduct using the details provided in the table. Where appropriate, alternative formulations were prepared on the titanosilicate TS-1 for comparative purposes.Table S.1. Synthesis details of the precursors used in the preparation of key mono- and bimetallic Pd-based catalysts.

[0184] Catalyst Pd Precursor Metal X Precursor precursor volume / mL precursor volume / mL (mgml_-1) (mgmL1) 0.66%Pd / Ti-MWW PdCI22.200 (6.00) N. A N. A 0.33%Pd-0.33%Au / Ti- PdCl21.100 (6.00) HAuCl4.3H2O 0.539 (12.25) MWW

[0185] 0.33%Pd-0.33%Pt / Ti- PdCI21.100 (6.00) H2PtCI6.6H2O 0.6947 (9.50) MWW

[0186] 0.33%Pd-0.33%Ni / Ti- PdCI21.100 (6.00) NiCI2.6H2O 1.626 (4.06) MWW

[0187] 0.33%Pd-0.33%Cu / Ti- PdCI21.100 (6.00) CuCI22.510 (2.63) MWW

[0188] 0.33%Pd-0.33%lr / Ti- PdCI21.100 (6.00) IrCl3.xH2O 1.100 (6.00) MWW

[0189] 0.33%Pd-0.33%Co / Ti- PdCI21.100 (6.00) COCI2.6H2O 0.767 (8.60) MWW

[0190] 0.33%Pd-0.33%Mn / Ti- PdCI21.100 (6.00) MnCI2.4H2O 0.815 (8.10) MWW

[0191] 0.33%Pd-0.33%Ag / Ti- Pd(NO3)21.100 (6.00) AgNO31.638 (4.03) MWW

[0192] 0.33%Pd-0.33%Sn / Ti- PdCI21.100 (6.00) SnCI21.363 (4.84) MWW

[0193] 0.33%Pd-0.33%Ru / Ti- PdCI21.100 (6.00) RuCl3xH2O 2.143 (3.08) MWW

[0194] 0.33%Pd-0.33%ln / Ti- PdCI21.100 (6.00) InCl31.292 (5.11) MWW

[0195]

[0196] Note: Volumes of metal precursors are for the preparation of 2 g of catalyst, precursor concentrations relate to the metal rather than the precursor salt. N. A: Not applicable.

[0197] Fe-TS-1 Synthesis

[0198] The synthesis of Fe-TS-1 was based on the in situ hydrothermal synthesis method. In the typical synthesis, 22.7 g of solution of tetrapropylammonium hydroxide (25 wt.%, TPAOH), 28.6 g of deionized water (18.2 MΩ·cm, H₂O), 30.0 g of tetraethyl orthosilicate (98.5 wt.%,TEOS) and 0.96 g of tetrabutyl titanate (99.0 wt.%, TBOT) were mixed directly. The mixed solution was irradiated by the ultraviolet light (500 W) for 1 h under vigorous stirring. Afterwards, the pre-mixed solution containing 1.0 g of ethylenediaminetetraacetic acid (99.2 wt.%, EDTA) and specific content of ferric nitrate (98.9 wt.%, Fe(NO₃)₃) was added dropwise into the obtained clear solution. Then, the obtained gel was crystallized at 170 °C for 3 days. Subsequently, the as-synthesized Fe-TS-1 catalyst was washed by the deionized water and dried at 80°C overnight for 16 h. The dried sample was calcined at 550 °C for 6 h with a heating rate of 2 °Cmin-1to obtain the Fe-TS-1 catalyst. Metals were subsequently immobilised onto the Fe-TS-1 support following a similar protocol to that outlined above.

[0199] The preparation of catalysts by the incipient wetness method.

[0200] A series of key catalyst formulations were prepared on a TS-1 or Ti-MWW support via an incipient wetness method, based on that reported in Li et al. Oxidative Degradation of Phenol via In situ Generation of H2O2 in a Flow Reactor, Catal. Lett., (2025) 155, 373 (https: / / doi.org / 10.1007 / s10562-025-05221-3). These formulations include: 0.33%Pd-0.33%Au / TS-1, 0.33%Pd-0.33%Au / Ti-MWW, 0.66%Pd / Ti-MWW and 0.33%Pd-0.33%Pt / Ti-MWW. The procedure to produce 10 g of the 0.33%Pd-0.33%Au / Ti-MWW catalyst is reported below, with a similar protocol utilised for all formulations.

[0201] A Au solution (HAuCl₄·3H₂O, 3.37 mL, [Au] = 9.8 mgmL'1> 99.9% trace metals basis) was added to 10 g of deionized water. A Pd solution was separately produced by adding PdCh (0.055 g > 99.9% trace metals basis) to 10 g of deionized water containing 2 g of hydrochloric acid (37 wt.%) and heated to 80 °C until fully dissolved. Additional water was added to bring the total amount to 24 g, based on the determined pore volume of the support material. The resulting Au and Pd precursor solutions were then combined and slowly added to 10 g of Ti-MWW under continuous stirring. The suspension was subsequently dried in air at 60 °C (typically for 16 h). The dried material (10 g) was then redispersed in 100 mL of deionized water, followed by the addition of 5 mL of hydrazine solution (5 wt.%) to reduce the metal species to the metallic state. After stirring and completion of the reduction, the solid catalyst was recovered by filtration, washed three times with deionized water until a neutral pH was reached, and dried in air at 60 °C (typically for 16 h).

[0202] In the case of the TS-1 based catalysts the total volume of water was modified based on the pore volume determined for the support. In the case of the Pt-based catalysts H₂PtCl₆·6H₂O was used as the metal precursor.Direct synthesis of H2O2

[0203] Hydrogen peroxide synthesis was evaluated using a Parr Instruments stainless steel autoclave with a nominal volume of 100 mL, equipped with a PTFE liner and a maximum working pressure of 2000 psi. To test each catalyst for H2O2 synthesis, the autoclave was charged with catalyst (0.01 g), solvent (5.6 g MeOH and 2.9 g H2O, both HPLC grade, Fischer Scientific). The charged autoclave was then purged three times with 5%H2 / CC>2 (100 psi) before filling with 5% H₂ / CO₂ (420 psi), followed by the addition of 25%O2 / CC>2 (160 psi) to give a H2: O2 ratio of 1: 2. All pressures are provided as gauge pressures, reactant gases were not continuously introduced into the reactor. The temperature was then decreased to 2 °C (using a HAAKE K50 bath / circulator and an appropriate coolant) followed by stirring (1200 rpm) of the reaction mixture for 0.5 h. The above reaction parameters represent the optimum conditions we have previously used for the synthesis of H2O2. H2O2 productivity was determined by titrating aliquots of the final solution after reaction with acidified Ce(SC>4)2 (0.01 M) in the presence of ferroin indicator.

[0204] The catalytic conversion of H2 and selectivity towards H2O2 were determined using a Varian 3800 GC fitted with TCD and equipped with a Porapak Q column.

[0205] H2 conversion (Equation 1) and H2O2 selectivity (Equation 2) are defined as follows:

[0206] mmolH₂ (t(0))− mmolH₂ (t(1))

[0207] H2Conversion (%) × 100 (1)

[0208] mmolH₂ (t(0))

[0209] H2O2detected (mmol)

[0210] H2O2Selectivity (%) = x 100 (2)

[0211] H2consumed (mmol)

[0212] The total autoclave capacity was determined via water displacement to allow for accurate determination of H2 conversion and H2O2 selectivity. When equipped with the PTFE liner the total volume of an unfilled autoclave was determined to be 93 mL, which includes all available gaseous space within the autoclave.

[0213] Degradation of H2O2

[0214] Catalytic activity towards H2O2 degradation (via hydrogenation and decomposition pathways) was determined in a manner similar to that used for measuring the H2O2 direct synthesis activity of a catalyst. The autoclave was charged with methanol (5.6 g, HPLC grade, Fisher Scientific), H2O2 (50 wt.% 0.69 g, Merck), H2O (2.21 g, HPLC grade, Fisher Scientific) and catalyst (0.01 g), with the solvent composition equivalent to a 4 wt.% H2O2 solution. From thesolution, two aliquots of 0.05 g were removed and titrated with acidified Ce(SC>4)2 solution using ferroin as an indicator to determine an accurate concentration of H2O2 at the start of the reaction. The charged autoclave was then purged three times with 5%H2 / CC>2 (100 psi) before filling with 5%H2 / CC>2 (420 psi). All pressures are provided as gauge pressures, reactant gases were not continuously introduced into the reactor. The reaction mixture was cooled to 2 °C prior to the reaction commencing upon stirring (1200 rpm). The reaction was allowed to proceed for 0.5 h, after which, the catalyst was removed from the reaction solvents via filtration and as described previously, two aliquots of 0.05 g were titrated against the acidified Ce(SC>4)2 solution using ferroin as an indicator. Catalyst degradation activity is reported as molH202kgcat ’1h’1and %.Ketone ammoximation via the in situ synthesis of H2O2.

[0215] Catalysts were evaluated for their activity towards ketone ammoximation with the procedure for cyclohexanone ammoximation outlined below using a stainless-steel autoclave (Parr Instruments) with a nominal volume of 100 mL, equipped with a PTFE liner and a maximum working pressure of 2000 psi.

[0216] The autoclave was typically charged with the catalyst (0.075 g), solvent (H2O (7.5 g, HPLC grade, Fisher Scientific) and t-BuOH (5.9 g, Merck)), ketone (2.0 mmol, Merck) and ammonium bicarbonate (0.32 g, 4.0 mmol, Merck). The reactor was purged three times with 5%H2 / N2 (100 psi) and then filled with 5%H2 / N2 (420 psi) and 25%C>2 / N2 (160 psi) to give a H2: O2 ratio of 1: 2. All pressures are provided as gauge pressures, reactant gases were not continuously introduced into the reactor. The reactor was stirred (100 rpm) while the reaction temperature was raised to 80 °C at which time stirring was increased to 800 rpm. The reaction was allowed to run for 6 h, unless otherwise stated, after which the reactor was cooled to 25 °C while stirring (100 rpm), using ice water. The reactant gas was collected for analysis after which a gas sample was taken for analysis by gas chromatography using a Varian CP-3380 equipped with a TCD and a Porapak Q column. To the reaction solution EtOH (6 g, HPLC grade, Fischer Scientific) and diethylene glycol monoethyl ether (external standard, 0.15 g, Merck) were added, the catalyst was removed by filtration and the resulting solution was analysed by gas chromatography using a Varian 3800 equipped with FID and a CP-Wax 52 CB column.

[0217] In the case of experiments where a physical mixture of H2O2 synthesising catalyst (i.e. metal sites responsible for H2O2 production) and bare Ti-MWW, 0.075 g of each solid was added to the autoclave liner.

[0218] Ketone conversion and selectivity towards the corresponding oxime were calculated on the basis of the starting amount of the ketone, according to Eqs. (3) and (4), respectively.

[0219] ^ketone ^ketone ( t (1))

[0220] X ketone = - - — X 100 (3)

[0221] ‘‘’ketone (t(0))

[0222] > >noxime. „„ oxime _ ±vv (4)

[0223]

[0224] ketone (t(0)) ‘‘'ketone (t(l))

[0225] Oxime yield was calculated using Eq. (5).

[0226] Yoxime = -m°loxime- X100 (5)

[0227]

[0228] + molox[meH2 conversion and oxime selectivity based on H2 were calculated based on the starting amount of H2 and the yield of oxime as determined from Eqs. (6) and (7).

[0229] >nH2 (t(0)) -nH2 (t(l))

[0230] — - X 100

[0231] nH2 (t(0))

[0232] noxime

[0233] nH2 ~nH2 (t(l))

[0234]

[0235] nH2 (t(0))

[0236] Catalyst reusability in the ammoximation of ketones via the in situ synthesis of H2O2 in a batch regime.

[0237] In order to determine catalyst reusability, a similar procedure to that outlined above for ketone ammoximation via the in situ production of H2O2 was followed utilizing 0.3 g of catalyst. Following the initial test, the catalyst was recovered by filtration, washed with EtOH (6 g, Fischer Scientific) and dried (30 °C, 17 h, under vacuum). Next, 0.075 g of material from the recovered catalyst sample was used to conduct a standard ammoximation experiment. A similar protocol was utilised for the evaluation of key catalytic formulations over successive uses.

[0238] Ketone ammoximation via the in situ synthesis of H2O2 in a fixed bed, continuous flow regime

[0239] A typical cyclohexanone ammoximation reaction, was carried out using 2.0 g of a mixture of catalyst and powdered Y-AI2O3 (Daqiu New Materials (China) Co., Ltd.) (catalyst: binder = 4: 1), which had been pressed (5 T, 15 min) into a disk, crushed and sieved to a particle size of 0.45-0.9 mm± 0.1 mm. The catalyst and diluent (Y-AI2O3, grain size ~ 1.0 mm, (Daqiu New Materials (China) Co., Ltd.)) were contained within a stainless-steel reactor bed, with catalyst bed volume determined to be 3.5 mL (bed length = 7 cm, internal bed diameter = 0.8 cm). A liquid reactant feed of H2O and t-BuOH (1: 9 (v / v)), cyclohexanone and ammonia water (cyclohexanone: ammonia = 1: 1, concentration of cyclohexanone was adjusted to 19 wt.%) was utilized with a liquid flow rate of 0.048 mLmin-1. The reactant gas feed consisted of 2.8% H2, 6.4% O2 and 90.8 % N2 (130 psi) with a gas flow rate of 88 mLmin-1. The reactor was heated to 80 °C. Liquid sampling was conducted on-line. To the liquid sample (1.0 g), diethylene glycol monoethyl ether (0.15 g) was added as an internal standard and the solution was diluted with EtOH, the resulting solution was analyzed by gas chromatography equipped with FID and a TC-WAX column.Model Leaching Studies.

[0240] To provide an indication of catalyst stability during the ammoximation of ketones via the in situ production of H2O2, indicative model studies were conducted utilising 0.1 g of the 0.33%Au-0.33%Pd / Ti-MWW catalyst, in the presence of ammonia (aq., 60 mmol, Merck, 25 wt.%), preformed H2O2 (50 mmol, Fischer Scientific, 50 wt.%), H2O (7.5 g, Fischer Scientific, HPLC grade), t-BuOH (5.9 g, Merck, >99.5%), for 1 h, at a temperature of 80 °C and a reaction time of 1 h. After the desired reaction time, the reaction solution was cooled in ice water to 20 °C, the catalyst was removed via filtration and the reaction solution analysed by ICP-MS.

[0241] ICP-MS analysis to establish metal leaching.

[0242] Total metal leaching from the supported catalyst was quantified via inductively coupled plasma mass spectrometry (ICP-MS). Post-reaction solutions were analysed using an Agilent 7900 ICP-MS equipped with I-AS auto-sampler. All samples were diluted by a factor of 10 using HPLC grade H2O (1%HNOs and 0.5% HCI matrix). All calibrants were matrix-matched and measured against a five-point calibration using certified reference materials purchased from PerkinElmer and certified internal standards acquired from Agilent.Results

[0243] Table 1. Comparative activity of 0.33%Au-0.33%Pd / Ti-MWW and 0.33%Au-0.33%Pd / TS-1 catalysts towards the ammoximation of cyclohexanone via in situ H2O2 synthesis.

[0244] Catalyst Reaction Cyclo. Oxime Oxime H2H2Au Pd formulation time / h Conv. Sei. / Yield / Conv. Sei leaching leaching / % % % / % / % / %* / %* 0.33%Pd- 0.5 50.1 99.2 49.7 28.6 76.2 0.0 5.5 0.33%Au / Ti- MWW

[0245] 1 81.5 99.4 81.0 50.1 75.6 0.0 6.8 2 97.0 99.6 96.6 55.7 75.6 0.0 7.8 3 98.0 99.4 97.4 65.0 64.9 0.0 9.4 Ti-MWW 3 3.0 98.1 3.0 B. D. L - N. A N. A 0.33%Pd- 0.5 22.1 99.5 22.0 15.5 61.5 0.0 25.6 0.33%Au / TS

[0246] -1

[0247] 1 44.5 97.8 43.5 32.6 56.4 0.0 38.4 2 71.8 99.4 71.4 53.7 56.9 0.0 44.0 3 84.1 98.2 82.6 63.8 57.4 0.0 48.2 TS-1 3 11.0 8.0 1.0 B. D. L - N. A N. A

[0248]

[0249] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5 - 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A = not applicable. *As established by ICP-MS analysis of post-reaction solutions.

[0250] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2 Conv. = H2 conversion; H2 Sel = H2 selectivity.

[0251] The results of table 1 demonstrate that titanosilicate-metal adducts of the invention are active as catalysts for ketone ammoximation. These results demonstrate that titanosilicate-metal adducts of the invention are active as catalysts for ketone ammoximation under conditions of in situ H2O2 synthesis. These results demonstrate that titanosilicate-metal adducts of theinvention may have improved H2 selectivity (e.g. improved relative to that titanosilicate-metal adducts having TS-1 as the titanosilicate), for example over a wide range of H2 conversion, e.g. from 30% to 65% H2 conversion. These results demonstrate that titanosilicate-metal adducts of the invention may have improved H2 selectivity (e.g. improved relative to that titanosilicate-metal adducts having TS-1 as the titanosilicate), for example over a wide range of cyclohexanone conversion, e.g. from 50% to 95% cyclohexanone conversion. These results demonstrate that titanosilicate-metal adducts of the invention demonstrate low metal leaching, for example showing no measurable Au leaching. These results demonstrate that titanosilicate-metal adducts of the invention demonstrate improved (i.e. reduced) metal leaching (e.g. improved relative to that titanosilicate-metal adducts having TS-1 as the titanosilicate), having lower Pd leaching. These results demonstrate that titanosilicate-metal adducts of the invention demonstrate improved catalytic activity (e.g. improved relative to that titanosilicate-metal adducts having TS-1 as the titanosilicate), as demonstrated by the higher oxime yield at a particular time point. These results demonstrate that titanosilicate-metal adducts of the invention demonstrate improved oxime selectivity (e.g. improved relative to that titanosilicate-metal adducts having TS-1 as the titanosilicate). These results indicate that titanosilicates of the invention, e.g. Ti-MWW are catalytically active for ketone ammoximation, e.g. under conditions of in situ H2O2 synthesis. These results when considered with the results presented in table 2 also demonstrate the improved reactivity of Ti-MWW over TS-1 for ketone ammoximation as table 2 shows similar H2O2 synthesising activity and so the enhanced reactivity arises from the titanosilicate used.

[0252] Table 2. Comparative activity of 0.33%Au-0.33%Pd / Ti-MWW and 0.33%Au-0.33%Pd / TS-1 catalysts towards direct synthesis of H2O2 synthesis from the elements, under conditions optimised for H2O2 stability.

[0253] Catalyst Productivity / H2H2O2 Degradation / Degradation formulation molH₂O₂kgcat-1h-1Conv. Sei. / molH₂O₂kgcat-1h-1 / %

[0254] / % %

[0255] 0.33%Pd- 28 9 46 136 7 0.33%Au / Ti- MWW

[0256] 0.33%Pd- 33 8 45 102 5 0.33%Au / TS-1

[0257]

[0258] H2O2 synthesis conditions: Catalyst (0.01g), H2O (2.9 g), MeOH (5.6 g), 5% H2 / CO2 (420 psi), 25% O2 / CO2 (160 psi), reaction time 0.5 h, reaction temperature 2°C, stirring speed 1200 rpm.H2O2 degradation conditions: Catalyst (0.01 g), H2O2 (50 wt.% 0.68 g) H2O (2.22 g), MeOH (5.6 g), 5% H2 / CO2 (420 psi), reaction time 0.5 h, reaction temperature 2°C, stirring speed 1200 rpm.

[0259] The results of table 2 indicate that the PdAu / Ti-MWW catalyst is able to synthesise H2O2 from H2 and O2, and that regardless of titanosilicate support utilised to immobilise the H2O2 synthesising component of the catalyst, similar reactivity towards the direct synthesis of H2O2 (under conditions optimised for H2O2 stability) is achieved. That is, it demonstrates the H2O2 direct synthesis property is present in the titanosilicate-metal adducts of the invention. Such data, when considered with the data reported in table 1 and table 12 indicate that the improved performance of the 0.33%Au-0.33%Pd / Ti-MWW catalyst, compared to the TS-1 analogue, when utilised in the in situ ketone ammoximation reaction may be attributed to the hydroxylamine synthesising component of the catalyst. That is catalytic performance towards in situ ketone ammoximation may be improved through catalyst design and specifically through careful selection of the titanosilicate component.

[0260] Table 3. Activity of the 0.33%Au-0.33%Pd / Ti-MWW catalyst towards the ammoximation of cyclohexanone via in situ H2O2 synthesis, as a function of solvent.

[0261] Solvent Reaction time Cyclo. Oxime Oxime H2H2Sei /

[0262] Z h Conv. / Sei. / % Yield / % Conv. / %

[0263] % %

[0264] H2O / t-BuOH 0.5 50.1 99.2 49.7 28.6 76.2

[0265] 1 81.5 99.4 81.0 50.1 75.6 2 97.0 99.6 96.6 55.7 75.6 3 98.0 99.4 97.4 65.0 64.9

[0266] H2O 0.5 49.1 97.6 47.9 25.3 76.8

[0267] 1 75.2 98.3 73.9 41.9 74.1 2 91.4 97.1 88.8 58.0 62.3 3 96.3 97.9 94.3 72.7 60.4

[0268]

[0269] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), solvent (t-BuOH (5.9 g), H2O (7.5 g) or H2O (13.4 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0270] The results of table 3 demonstrate that the solvent used for ketone ammoximation using titanosilicate-metal adducts of the invention is not particularly limited. These results indicatethat the solvent for ketone ammoximation may be water, e.g. pure water. Surprisingly, the titanosilicate-metal adducts of the invention show very high catalytic activity in water. These results indicate that the solvent for ketone ammoximation may be a t-butanol-water mixture.

[0271] Table 4. The effect of Au: Pd ratio on the ammoximation of cyclohexanone via in situ H2O2 synthesis over 0.66%AuPd / Ti-MWW, where total metal loading is maintained at 0.66 wt.%. Total metal loading is maintained at 0.66wt.% but Au: Pd ratio is altered - i.e. these experiments where performed in order to determine the effect of elemental composition on catalytic performance towards in situ ketone ammoximation.

[0272] Catalyst Cyclo. Oxime Sei. Oxime H2 Conv. / H2Sei / % formulation Conv. / % / % Yield / % %

[0273] 0.66%Pd / Ti-MWW 96.9 99.4 96.3 69.3 61.1 0.55%Pd- 97.4 97.8 95.2 75.4 67.6 0.11%Au / Ti-MWW

[0274] 0.495%Pd- 96.7 99.4 96.5 74.2 59.9 0.165%Au / Ti- MWW

[0275] 0.44%Pd- 97.4 98.3 95.8 62.5 62.6 0.22%Au / Ti-MWW

[0276] 0.33%Pd- 98.0 99.4 97.4 65.0 64.9 0.33%Au / Ti-MWW

[0277] 0.22%Pd- 97.6 97.4 95.1 57.8 66.7 0.44%Au / Ti-MWW

[0278] 0.165%Pd- 98.6 99.8 98.3 71.3 64.8 0.495%Au / Ti- MWW

[0279] 0.11%Pd- 13.9 97.5 13.4 10.9 60.7 0.55%Au / Ti-MWW

[0280] 0.66%Au / Ti-MWW 4.2 9.4 0.4 1.0 9.8 Ti-MWW 3.0 98.1 3.0 B. D. L -

[0281]

[0282] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit.

[0283] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2 Conv. = H2 conversion; H2 Sel = H2 selectivity.The results of table 4 demonstrate that a wide range of Pd alloys in titanosilicate-metal adducts of the invention are highly catalytically active, as are pure monometallic compositions (e.g. Au / Ti-MWW and Pd / Ti-MWW adducts). These results demonstrate that titanosilicate-metal adducts having 40 wt% to 80 wt%, for example 50 wt% to 75 wt%, of Pd in the Pd alloy may be associated with improved catalytic activity (and so improved yield), for example wherein the Pd alloy is a PdAu alloy.

[0284] Table 5. The effect of Au: Pd ratio on the ammoximation of cyclohexanone via in situ H2O2 synthesis over 0.66%AuPd / Ti-MWW, as a function of reaction time.

[0285] Catalyst Reaction Cycl Oxi Oxim H2H2Sei / Pd Au formulation time / h 0. me e Conv % leachi leachi Con Sei. Yield. / % ng / ng / v. / / % / % %* %* %

[0286] 0.66%Pd / Ti- 0.25 12.0 96.2 11.5 5.1 89.8 4.2 N. A MWW

[0287] 0.5 26.4 99.6 26.3 13.4 88.8 6.9 N. A 1 57.7 97.4 56.2 30.6 78.7 9.9 N. A 2 74.6 99.2 74.0 54.9 64.7 13.0 N. A 3 96.9 99.4 96.3 69.3 61.1 22.4 N. A 0.495%Pd- 0.25 44.2 97.9 43.3 18.5 91.9 3.1 0.0 0.165%Au / Ti- MWW

[0288] 0.5 73.0 99.6 72.7 48.0 67.7 7.1 0.0 1 78.9 99.4 78.4 54.5 66.6 9.0 0.0 2 96.4 99.6 96.0 65.5 63.6 14.1 0.0 3 96.9 99.4 96.5 74.2 59.9 16.4 0.0 0.33%Pd- 0.25 34.0 97.8 33.3 17.7 71.9 2.6 0.0 0.33%Au / Ti- MWW

[0289] 0.5 50.3 99.8 50.2 28.6 76.2 5.5 0.0 1 82.0 99.9 81.9 50.1 75.6 6.8 0.0 2 97.0 99.7 96.7 55.7 76.7 7.8 0.0 3 98.0 99.4 97.4 65.0 64.9 9.4 0.0

[0290]

[0291] 0.165%Pd- 0.25 16.4 97.9 16.0 8.2 78.6 1.9 0.0 0.495%Au / Ti- MWW

[0292] 0.5 32.6 98.2 32.0 16.7 78.0 4.5 0.0 1 46.5 99.6 46.3 28.4 67.4 7.1 0.0 2 98.0 99.9 97.7 69.3 67.4 7.2 0.0 3 98.6 99.8 98.3 71.3 64.8 8.4 0.0 0.66%Au / Ti- 3 4.2 9.4 0.4 1.0 9.8 N. A 0.0 MWW

[0293] Ti-MWW 3 3.0 98.1 3.0 B. D. L N. A N. A N. A

[0294]

[0295] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5 - 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A = not applicable. *As established by ICP-MS analysis of post-reaction solutions.

[0296] The results of table 5 demonstrate that titanosilicate-metal adducts of the invention may be associated with the advantage of improved (i.e. reduced) metal leaching, for example Pd leaching, especially wherein the amount of Pd in the Pd alloy is 20 wt% to 60 wt%, preferably 25 wt% to 50 wt%, for example wherein the Pd alloy is a PdAu alloy.

[0297] Table 6. The effect of adding Ti-MWW to the 0.33%Au-0.33%Pd / Ti-MWW catalyst toward the ammoximation of cyclohexanone via in situ H2O2synthesis.

[0298] AuPd / Ti- Ti-MWW Cyclo. Oxime Oxime H2Conv. H2Sei / % MWW mass / g Conv. / % Sei. / % Yield / % / %

[0299] mass / g

[0300] 0.075 - 50.1 99.2 49.7 28.6 76.2 0.075 0.075 52.1 99.4 51.8 24.6 80.3 0.075 0.150 53.1 97.2 51.7 24.3 82.2 - 0.075 3.0 98.1 3.0 B. D. L -

[0301]

[0302] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), Ti-MWW (0.075 - 0.15 g) t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit.The results of table 6 demonstrate that the presence of titanosilicate (e.g. pure titanosilicate, such as Ti-MWW) in addition to the titanosilicate-metal adduct may be associated with improved H2 selectivity.

[0303] Table 7. Catalytic activity of Ti-MWW supported Pd-based catalysts toward the ammoximation of cyclohexanone via the in situ synthesis of H2O2, as a function of the secondary metal, where the catalyst is being used for the first time.

[0304] Catalyst Cyclo. Oxime Oxime H2H2Sel Pd Secondary formulation Conv. / Sel. / % Yield / Conv. / / % leaching metal % % % / %* leaching /

[0305] %* 0.66%Pd / Ti- 96.9 99.4 96.3 69.3 61.1 22.4 N. A MWW

[0306] 0.33%Pd / Ti- 90.4 99.9 90.4 58.8 66.3 21.0 N. A MWW

[0307] 0.33%Pd- 98.0 99.4 97.4 65.0 64.9 9.4 B. D. L 0.33%Au / Ti- MWW

[0308] 0.33%Pd- 78.1 96.4 75.3 56.1 56.5 24.8 27.4 0.33%Ni / Ti- MWW

[0309] 0.33%Pd- 88.5 96.9 75.3 54.9 62.2

[0310] 0.33%Zn / Ti- MWW

[0311] 0.33%Pd- 1.2 95.8 1.1 16.2 2.7

[0312] 0.33%Mn / Ti- MWW

[0313] 0.33%Pd- 77.2 97.6 75.2 49.8 59.9 25.5 7.7 0.33%Sn / Ti- MWW

[0314] 0.33%Pd- 88.3 95.0 83.9 58.1 61.4 12.3 1.9 0.33%lr / Ti- MWW

[0315]

[0316] 0.33%Pd- 70.1 85.7 60.1 37.2 70.9

[0317] 0.33%Fe / Ti- MWW

[0318] 0.33%Pd- 85.0 95.3 81.0 77.3 44.1 11.2 7.5 0.33%Pt / Ti- MWW

[0319] 0.33%Pd- 31.8 94.5 30.1 20.9 55.5

[0320] 0.33%Ru / Ti- MWW

[0321] 0.33%Pd- 0.1 85.7 0.1 12.3 0.4

[0322] 0.33%Cu / Ti- MWW

[0323] 0.33%Pd- 0.5 86.7 0.4 1.1 15.0

[0324] 0.33%Ag / Ti- MWW

[0325] 0.33%Pd- 46.5 95.1 44.3 35.8 46.9

[0326] 0.33%Co / Ti- MWW

[0327] 0.33%Pd- 93.3 98.5 92.0 69.9 57.0 29.3 B. D. L 0.33%ln / Ti- MWW

[0328] Ti-MWW 3.0 98.1 3.0 B. D. L - N. A N. A

[0329]

[0330] Ammoximation reaction conditions: Cyclohexanone (2 mmo), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A. = Not applicable. *As established by ICP-MS analysis of post-reaction solutions. Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.

[0331] The results of table 7.1 demonstrate that a wide range of titanosilicate-metal adducts are catalytically active. In particular, a wide range of titanosilicate-metal adducts wherein the metal nanoparticles comprise Pd alloy have been demonstrated, for example where the nonpalladium metal is selected from Au, Pt, Fe, Ni, Ir, Cu, Co, Mn, Ag, Sn, Ru, In and Zn are active. These results indicate the possibility of lowering catalyst synthesis costs through the alloying of Pd with secondary metals considered to be more abundant than, for example, Au or Pt. The incorporation of several secondary metals, very effectively Au, Pt, and Ir, especiallyeffectively Au inhibits the leaching of Pd. Notably, unlike other secondary metals the incorporation of Au inhibits Pd leaching, while not leaching itself, making Au especially preferred in the present disclosure.

[0332] Table 7.2 Catalytic activity of key Ti-MWW supported Pd-based catalysts toward the ammoximation of cyclohexanone via the in situ synthesis of H2O2, as a function of the secondary metal, upon second use of the catalyst.

[0333] Catalyst Cyclo. Oxime Oxime H2H2Sel Pd Secondary formulation Conv. / Sel. / % Yield / Conv. / / % leaching metal % % % / %* leaching /

[0334] %* 0.66%Pd / Ti- 93.9 97.2 91.3 68.1 59.5 38.1 N. A MWW

[0335] 0.33%Pd / Ti- 89.3 96.1 85.8 56.6 66.5 25.0 N. A MWW

[0336] 0.33%Pd- 98.0 98.8 96.8 74.0 56.5 8.4 B. D. L 0.33%Au / Ti- MWW

[0337] 0.33%Pd- 78.0 96.2 75.1 57.0 59.7 24.8 27.4 0.33%Ni / Ti- MWW

[0338] 0.33%Pd- 66.2 96.6 63.9 39.8 73.8 24.7 8.6 0.33%Sn / Ti- MWW

[0339] 0.33%Pd- 80.1 97.2 77.9 62.4 53.9 10.4 2.1 0.33%lr / Ti- MWW

[0340] 0.33%Pd- 84.5 94.9 80.1 63.4 54.9 10.5 6.0 0.33%Pt / Ti- MWW

[0341] 0.33%Pd- 74.7 97.1 72.5 45.9 69.6 32.6 B. D. L 0.33%ln / Ti- MWW

[0342]

[0343] Ammoximation reaction conditions: Cyclohexanone (2 mmo), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g),reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A. = Not Applicable. *As established by ICP-MS analysis of post-reaction solutions. Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2 Conv. = H2 conversion; H2 Sel = H2 selectivity.

[0344] Collectively the data in Table 7.1 and 7.2 demonstrates that the incorporation of secondary metals including Au, Pt, and Ir, but particularly Au promotes catalyst stability through the inhibition of Pd leaching.

[0345] Table 8. The effect of support on the catalytic performance of supported AuPd nanoparticles (0.33%Au-0.33%Pd) towards the ammoximation of cyclohexanone via in situ H2O2 synthesis, when used in conjunction with Ti-MWW.

[0346] Cyclo. Oxime Oxime H2 Conv. / % H2Sel / % Catalyst Conv. / % Sel. / % Yield / %

[0347] formulation

[0348] 0.33%Pd- 98.0 99.4 97.4 65.0 64.9 0.33%Au / Ti- MWW

[0349] 0.33%Pd- 42.2 98.0 41.4 25.2 72.5 0.33%Au / CeO2

[0350] 0.33%Pd- 97.0 99.5 96.5 59.1 70.1 0.33%Au / Nb2O5

[0351] 0.33%Pd- 98.4 99.6 98.0 67.3 61.6 0.33%Au / TiO2

[0352] 0.33%Pd- 98.3 99.8 98.1 68.7 63.6 0.33%Au / ZrO2

[0353] 0.33%Pd- 97.9 95.1 93.1 74.8 53.2 0.33%Au / SiO2

[0354] 0.33%Pd- 97.7 99.0 96.8 74.7 53.5 0.33%Au / Al2O3

[0355] 0.33%Pd- 22.2 95.6 21.2 18.1 53.7 0.33%Au / C

[0356] 0.33%Pd- 0.4 98.5 0.4 40.6 0.4 0.33%Au / TiO2*

[0357] 0.33%Pd- 0.1 92.1 0.1 60.4 0.1 0.33%Au / SiO2*

[0358]

[0359] Ti-MWW** 3.0 98.1 3.0 B. D. L -

[0360]

[0361] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), Ti-MWW (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.* Reactions run in the absence of Ti-MWW, with all other conditions as outlined above.** Reactions run in the absence of the AuPd / X catalyst, with all other conditions as outlined above. B. D. L = below detection limit.

[0362] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.

[0363] The results of table 8 indicate that when used in conjunction with the titanosilicate catalysts comprising metal adducts responsible for H2O2synthesis immobilised on a range of supports, for example CeO2, Nb2O5, TiO2, ZrO2, SiO2, Al2O3, or C may be catalytically active for the in situ ammoximation of ketones. Catalysts comprising Nb2O5, TiO2, ZrO2, SiO2, or Al2O3as a support (even more especially TiO2or ZrO2) may be associated with especially high catalytic activity and so especially high yield. These results indicate that both the H2O2synthesis and ammoximation components are required to achieve high efficacy towards ketone ammoximation.

[0364] Table 8a. A comparison of 0.33%Pd-0.33%Au / TS-1 and 0.33%Pd-0.33%Au / Ti-MWW catalyst activity towards the ammoximation of cyclohexanone via the in situ synthesis of H2O2, in a flow regime.

[0365] Catalyst Reaction Oxime Catalyst Reaction Oxime formulation time / h Yield / % formulation time / h Yield / % 0.33%Pd- 12 14.4 0.33%Pd- 12 19.5 0.33%Au / TS-1 0.33%Au / Ti- MWW

[0366] 24 16.5 24 31.5 36 16.6 36 33.9 48 16.1 48 37.1 60 15.1 60 38.2 72 15.2 70 39.3 84 15.7 84 40.8 96 15.1 94 42.0 108 15.0 109 43.0 120 14.4

[0367]

[0368] 132 14.4 132 44.3

[0369] 152 13.7 156

[0370] 166 13.5 164 46.4 180 13.1 180 47.2 190 12.9

[0371] 204 12.7 204 47.5 214 12.6 216 47.2 230 12.5 228 47.2 234 234 47.3

[0372]

[0373] Ammoximation reaction conditions: Cyclohexanone (19 wt.%): NH3 (aq.) (1: 1 (mol / mol)), 2.8% H2, 6.4% O2, 90.8% N2 (gas flow rate = 88 mLmin-1), catalyst (0.45 - 0.9 mm, catalyst: Al2O3binder = 4:1 (g / g), total mass = 2.0 g), t-BuOH: H2O (9:1 (vol / vol)), liquid flow rate = 0.048 mLmin-1, reaction temperature 80 °C.

[0374] The results of table 8a demonstrates the Ti-MWW support offers a clear enhancement in reactivity, achieving an approximate 4 times greater yield than the TS-1 -based analogue. Importantly, the Ti-MWW-based catalyst also offers improved stability, compared to the TS-1-based formulation, showing no loss in performance over approximately 230 h on-stream, whereas there is clear deactivation of the TS-1 formulation.

[0375] Table 9. The effect of metal loading on the catalytic performance of supported AuPd / Ti-MWW catalysts towards the ammoximation of cyclohexanone via in situ H2O2 synthesis.

[0376] Reaction Cyclo. Oxime Oxime H2 Conv. / H2Sei / % Catalyst time / h Conv. / % Sei. / % Yield / % %

[0377] formulation

[0378] 0.33%Pd- 0.5 50.1 99.2 49.7 28.6 76.2 0.33%Au / Ti-MWW

[0379] 1 81.5 99.4 81.0 50.1 75.6 2 97.0 99.6 96.6 55.7 76.7 3 98.0 99.4 97.4 65.0 64.9

[0380] 0.165%Pd- 0.5 40.7 98.4 40.1 22.8 79.7 0.165%Au / Ti- MWW

[0381] 1 67.6 98.9 66.9 37.0 77.9 2 90.9 99.6 90.6 51.7 74.7

[0382]

[0383] 3 98.1 98.8 96.9 60.9 73.6

[0384] 0.083%Pd- 0.5 22.3 97.8 21.8 13.6 79.7 0.083%Au / Ti- MWW

[0385] 1 54.2 98.7 53.5 31.5 77.1 2 74.6 97.6 72.8 45.2 75.1 3 96.2 98.9 95.1 53.3 80.7

[0386] 0.041 %Pd- 0.5 29.8 99.1 29.5 13.8 84.1 0.041 %Au / Ti- MWW

[0387] 1 33.8 98.4 33.3 16.1 83.5 2 70.1 98.1 68.8 34.4 82.8 3 89.1 99.2 88.4 44.3 84.5

[0388] 0.021Pd%- 0.5 13.6 96.4 13.1 6.1 83.4 0.021 %Au / Ti- MWW

[0389] 1 18.9 97.0 18.3 8.5 80.7 2 36.3 95.3 34.6 20.9 75.1 3 40.2 95.6 38.4 20.0 75.6

[0390]

[0391] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5-3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0392] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.

[0393] The results of table 9 indicate that titanosilicate-metal adducts of the invention may be catalytically active with a broad range of metal loadings. For example, 0.042 wt% to 0.66 wt%, e.g. 0.165 wt% to 0.66 wt% metal nanoparticles in the titanosilicate-metal adducts are shown to be catalytically active. Lower metal loading may offer improved H2selectivities.

[0394] Table 9a. The effect of metal loading on the catalytic performance of supported AuPd / Ti-MWW catalysts towards the ammoximation of cyclohexanone via in situ H2O2synthesis.Reactio Cyclo Oxim Oxim H2 Con H2Se Pd Au Catalyst n time / e Sel. e v. / % l / % leachin leachin formulation h Conv. / % Yield g / %* g / %*

[0395] / % / %

[0396] 0.66%Pd / Ti- 0.25 12.0 96.2 11.5 5.1 89.8 4.2 N. A MWW

[0397] 0.5 26.4 99.6 26.3 13.4 88.8 6.9 N. A 1 57.7 97.4 56.2 30.6 78.7 9.9 N. A 2 74.6 99.2 74.0 54.9 64.7 13.0 N. A 3 96.9 99.4 96.3 69.3 61.1 22.4 N. A 0.55%Pd- 0.25 24.2 99.0 23.9 29.7 34.1

[0398] 0.11%Au / Ti- MWW

[0399] 0.5 42.9 99.6 42.7 37.9 47.4

[0400] 1 66.7 98.4 65.6 53.0 53.8

[0401] 2 89.6 98.4 88.2 71.1 52.9

[0402] 3 97.4 97.8 95.2 75.4 67.6

[0403] 0.495%Pd- 0.25 44.2 97.9 43.3 18.5 91.9 3.1 B. D. L 0.165%Au / T

[0404] i-MWW

[0405] 0.5 73.0 99.6 72.7 48.0 67.7 7.1 B. D. L 1 78.9 99.4 78.4 54.5 66.6 9.0 B. D. L 2 96.4 99.6 96.0 65.5 63.6 14.1 B. D. L 3 96.9 99.4 96.5 74.2 59.9 16.4 B. D. L 0.44%Pd- 0.25 35.3 98.7 34.9 32.7 45.4

[0406] 0.22%Au / Ti- MWW

[0407] 0.5 59.3 98.5 58.4 38.8 64.1

[0408] 1 81.4 99.7 81.2 54.3 64.4

[0409] 2 97.2 99.2 96.4 64.9 66.1

[0410] 3 97.4 98.3 95.8 62.5 62.6

[0411] 0.33%Pd- 0.25 34.0 97.8 33.3 17.7 71.9 2.6 B. D. L 0.33%Au / Ti- MWW

[0412] 0.5 50.3 99.8 50.2 28.6 76.2 5.5 B. D. L 1 82.0 99.9 81.9 50.1 75.6 6.8 B. D. L

[0413]

[0414] 2 97.0 99.7 96.7 55.7 76.7 7.8 B. D. L 3 98.0 99.4 97.4 65.0 64.9 9.4 B. D. L 0.22%Pd- 0.25 30.2 99.2 29.9 16.8 73.3

[0415] 0.44%Au / Ti- MWW

[0416] 0.5 37.9 99.4 37.7 28.9 56.9

[0417] 1 49.5 99.3 49.2 36.3 58.8

[0418] 2 95.8 99.2 94.9 50.7 73.4

[0419] 3 97.6 97.4 95.1 57.8 66.7 B. D. L 0.165%Pd- 0.25 16.4 97.9 16.0 8.2 78.6 1.9 B. D. L 0.495%Au / T

[0420] i-MWW

[0421] 0.5 32.6 98.2 32.0 16.7 78.0 4.5 B. D. L 1 46.5 99.6 46.3 28.4 67.4 7.1 B. D. L 2 98.0 99.9 97.7 69.3 67.4 7.2 B. D. L 3 98.6 99.8 98.3 71.3 64.8 8.4 B. D. L 0.11%Pd- 0.25 0.14 97.9 0.14 10.6 0.57

[0422] 0.55%Au / Ti- MWW

[0423] 0.5 2.53 98.5 2.49 14.9 7.37

[0424] 1 7.72 99.8 7.70 16.8 19.4

[0425] 2 11.7 99.9 11.7 22.3 21.7

[0426] 3 13.9 97.5 13.4 10.9 60.7

[0427] 0.66%Au / Ti- 3 4.2 9.4 0.4 1.0 9.8 N. A B. D. L MWW

[0428] Ti-MWW 3 3.0 98.1 3.0 B. D. L - N. A N. A

[0429]

[0430] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5-3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A = not applicable. *As established by ICP-MS analysis of post-reaction solutions.

[0431] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.

[0432] The results of table 9a demonstrate that the introduction of Au into a supported Pd / Ti-MWW catalyst promotes catalytic reactivity. The results in this table demonstrate Pd-only catalystsprepared on titanosilicates are active towards in situ ammoximation but the introduction of Au into a supported Pd / Ti-MWW catalyst promotes catalytic reactivity considerably, while the activity of Au / T-MWW is limited. The introduction of Au also promotes catalytic stability as evidenced by a decrease in Pd leaching upon alloying with Au. Advantageously, unlike with other bimetallic formulations (eg Pd-Pt / Ti-MWW), the secondary metal Au is stable, no leaching is observed.

[0433] Table 10. Catalytic activity of the 0.33%Au-0.33% Pd / Ti-MWW catalyst toward the ammoximation of a range of ketones via in situ H2O2 synthesis.

[0434] Cyclo. Oxime Sei. Oxime H2 Conv. / H2Sei / % Ketone Conv. / % / % Yield / % % Cyclopentanone 79.5 97.1 77.2 64.8 37.9 Cyclohexanone 98.0 99.4 97.4 65.0 64.9 Cycloheptanone 80.6 98.2 97.4 64.8 58.5 Cyclooctanone 59.6 96.1 57.3 64.8 43.8 Cyclododecanone 22.1 95.1 21.0 79.0 18.9 2-Octanone 55.3 95.8 53.0 78.2 32.7 5-methyl-2- 64.1 96.4 61.8 81.3 30.9 hexanone

[0435] Cyclododecanone 22.1 95.1 21.0 79.0 10.8 2-butanone 90.1 98.9 89.1 71.8 50.2 Acetophenone 6.9 96.9 6.8 54.2 5.3 1-lndanone 8.7 93.2 8.01 79.53 4.10 Cyclopentadecanone 8.6 97.9 8.4 79.20 2.14 Benzaldehyde 99.1 99.3 98.4 71.9 55.1 2- 99.6 98.9 98.4 80.4 49.4 chlorobenzaldehyde

[0436] 4- 97.0 99.6 96.7 75.4 52.3 methylbenzaldehyde

[0437] Benzamide 4.5 98.9 4.4 65.7 2.7

[0438]

[0439] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0440] The results of table 10 demonstrate that the titanosilicate-metal adducts of the invention may be used in the in situ ammoximation of a range of ketones and aldehydes. The results of table10 demonstrate that the titanosilicate-metal adducts of the invention may be used in the ketone ammoximation of a range of cyclic ketones, as well as a range of linear ketones.

[0441] Table 11. The effect of H2O2 synthesizing metals in in situ ammoximation of cyclohexanone Catalyst formulation Cyclo. Conv. / % Oxime Sei. / % Oxime Yield / % Ti-MWW 3.0 98.1 3.0 0.33%Pd-0.33%Au / Ti- 98.0 99.4 97.4

[0442] MWW

[0443]

[0444] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0445] The results of table 11 demonstrate that titanosilicates of the invention (for example Ti-MWW) are effective for ketone ammoximation under in situ H2O2 generating conditions, and they are effective ketone ammoximation under in situ H2O2 generating conditions in the absence of a further catalyst (such as H2O2 synthesizing catalyst, e.g. H2O2 synthesizing metals). The results of table 11 also demonstrate that titanosilicate-metal adducts of the invention (for example 0.33%Pd-0.33%Au / Ti-MWW) may be especially effective in ketone ammoximation under in situ H2O2 generating conditions.

[0446] Table 12. Catalytic activity towards the ammoximation of cyclohexanone to cyclohexanone oxime in the presence of preformed H2O2, a comparison of titanosilicate framework.

[0447] Catalyst formulation Cyclo. Conv. / % Oxime Sei. / % Oxime Yield / % Ti-MWW 70.2 98.2 69.0

[0448] TS-1 58.3 97.4 56.8

[0449]

[0450] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), N2 (580 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), H2O2 (50 wt.%, 0.34 g) reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0451] The results of table 12 demonstrate that titanosilicates of the invention (for example Ti-MWW) are especially effective (e.g. high yielding) for ketone ammoximation under conditions where H2O2 is added to the reaction as opposed to generated in situ. The results of table 12 demonstrate that titanosilicates of the invention (for example Ti-MWW) may be higher yielding than TS-1 for ketone ammoximation under conditions where H2O2 is added to the reaction as opposed to generated in situ.Table 13. The effect of solvent on the catalytic performance of the 0.33%Au-0.33%Pd / Ti-MWW catalyst towards the ammoximation of cyclohexanone via in situ H2O2 synthesis.

[0452] Cyclo. Oxime Oxime H2 Conv. / % H2Sei / % Solvent Conv. / % Sei. / % Yield / %

[0453] H2O 98.0 99.6 97.6 72.3 62.9 CH3OH 84.5 99.3 84.0 86.6 39.7 CH3OH + H2O 96.6 99.8 96.4 74.8 54.0 C2H5OH 73.6 99.5 73.2 85.4 37.4 C2H5OH + H2O 84.0 99.1 83.2 81.6 41.5 C3H7OH 90.6 99.6 90.2 83.5 44.6 C3H7OH + H2O 98.1 99.2 97.2 76.3 55.7 (CH3)3COH +

[0454] 98.0 99.4 97.4 65.0 64.9 H2O

[0455]

[0456] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%C>2 / N2 (160 psi), catalyst (0.075 g), solvent (single solvent = 13.4 g, mixed solvent = 7.5 g H2O and 5.9 g alcohol) t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0457] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2 Conv. = H2 conversion; H2 Sel = H2 selectivity.

[0458] The results of table 13 demonstrates that a range of protic solvents are compatible with the in situ H2O2 synthesis process of the disclosure.

[0459] Table 14. Catalytic activity of different titanosilicate supports toward the ammoximation of cyclohexanone, using ex-situ generated H2O2.

[0460] Ketone Cyclo. Conv. / % Oxime Sei. / % Oxime Yield / %

[0461] Fe-TS-1 58.4 99.5 58.1 TS-1 37.5 98.3 36.9 Fe-S-1 0.5 95.2 0.5

[0462]

[0463] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), H2O2 (50 wt.%, 0.32g), N2 (580 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), 3 h, reaction temperature 80°C, stirring speed 800 rpm.

[0464] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2 Conv. = H2 conversion; H2 Sel = H2 selectivity.This table demonstrates there is a need for Ti species within the support structure to achieve high ammoximation activity. Fe alone does not offer significant activity towards ketone ammoximation (see Fe-S-1 results). The incorporation of a transition metal dopant, e.g. Fe, into the TS-1 framework, which contains Ti species improves catalytic performance (Fe-TS-1 results).Table 15. Comparative activity of 0.33%Au-0.33%Pd / Ti-MWW, 0.33%Au-0.33%Pd / Fe-TS-1 and 0.33%Au-0.33%Pd / TS-1 catalysts towards the ammoximation of cyclohexanone via in situ H2O2 synthesis.

[0465] Catalyst Reaction Cyclo. Oxime Sei. Oxime H2H2Au Pd formulation time / h Conv. / % / % Yield / Conv. Sei leaching leaching % / % / % / %* / %* 0.33%Pd- 0.5 50.1 99.2 49.7 28.6 76.2 B. D. L 5.5 0.33%Au / Ti- MWW

[0466] 1 81.5 99.4 81.0 50.1 75.6 B. D. L 6.8 2 97.0 99.6 96.6 55.7 75.6 B. D. L 7.8 3 98.0 99.4 97.4 65.0 64.9 B. D. L 9.4 Ti-MWW 3 3.0 98.1 3.0 B. D. L - N. A N. A 0.33%Pd- 0.5 22.1 99.5 22.0 15.5 61.5 B. D. L 25.6.33%Au / TS-1

[0467] 1 44.5 97.8 43.5 32.6 56.4 B. D. L 38.4 2 71.8 99.4 71.4 53.7 56.9 B. D. L 44.0 3 84.1 98.2 82.6 63.8 57.4 B. D. L 48.2 TS-1 3 11.0 8.0 1.0 B. D. L - N. A N. A 0.33%Pd- 0.5 B. D. L

[0468] 22.4 3%Au / Fe-TS-1 29.4 99.1 29.2 14.6 79.3

[0469] 1 45.5 98.3 44.7 25.0 76.4 B. D. L 24.2 2 68.4 98.7 67.6 41.7 68.8 B. D. L 26.5 3 93.6 97.4 91.1 61.9 63.8 B. D. L 29.2 Fe-TS-1 3 0.3 97.8 0.3 B. D. L - N. A N. A 0.33%Pd- 3 0.2 95.5 0.2 47.0 0.2 B. D. L 20.7 33%Au / Fe-S-1

[0470] Fe-S-1 3 0.5 98.6 0.5 B. D. L - N. A N. A

[0471]

[0472] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5 - 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A = not applicable. *As established by ICP-MS analysis of post-reaction solutions.

[0473] Cyclo. Conv. = cyclohexanone conversion; Oxime Sei. = oxime selectivity; H2 Conv. = H2 conversion; H2 Sei. = H2 selectivityThe results of table 15 demonstrates there is a need for the H2O2 synthesising component (e.g. the metal nanoparticles) and the titanosilicate to achieve ketone ammoximation, as evidenced by a comparison to the metal loaded catalysts and the bare supports. There is a need for isolated Ti species to also be incorporated into the support (i.e. the support must be a titanosilicate) to achieve ketone ammoximation, as evidenced by a comparison of the PdAu / Fe-TS-1 and PdAu / Fe-S-1 catalysts. Fe incorporation into the titanosilicate inhibits the leaching of Pd, as evidenced by a comparison of PdAu / Fe-TS-1 and PdAu / TS-1.

[0474] Table 16. Comparative activity of 0.33%Au-0.33%Pd / Ti-MWW, 0.33%Au-0.33%Pd / TS-1, 0.33%Au-0.33%Pd / Fe-TS-1 and 0.33%Au-0.33%Pd / Fe-S-1 catalysts towards the direct synthesis of H2O2 synthesis from the elements, under conditions optimised for H2O2 stability.

[0475] Catalyst Productivity / H2H2O2 Degradation / Degradation formulation molH₂O₂kgcat-1h-1Conv. Sei. / molH₂O₂kgcat-1h-1 / %

[0476] / % %

[0477] 0.33%Pd- 28 9 46 136 7 0.33%Au / Ti- MWW

[0478] 0.33%Pd- 33 8 45 102 5 0.33%Au / TS-1

[0479] 0.33%Au- 22 6 29 20 1 0.33%Pd / Fe-TS- 1

[0480] 0.33%Au- 21 5 30 20 1 0.33%Pd / Fe-S-1

[0481]

[0482] H2O2 synthesis conditions: Catalyst (0.01g), H2O (2.9 g), MeOH (5.6 g), 5% H2 / CO2 (420 psi), 25% O2 / CO2 (160 psi), reaction time 0.5 h, reaction temperature 2°C, stirring speed 1200 rpm. H2O2 degradation conditions: Catalyst (0.01 g), H2O2 (50 wt.% 0.68 g) H2O (2.22 g), MeOH (5.6 g), 5% H2 / CO2 (420 psi), reaction time 0.5 h, reaction temperature 2°C, stirring speed 1200 rpm.

[0483] This results of table 16 demonstrates under these reaction conditions the choice of catalyst support offers minimal variation in H2O2 synthesis rate, but the incorporation of Fe lowers H2O2 degradation rate considerably.Table 17. The effect of Au: Pd ratio on the ammoximation of cyclohexanone via in situ H2O2 synthesis over 0.66%AuPd / Fe-TS-1, as a function of reaction time.

[0484] Catalyst Reaction Cyclo. Oxime Oxime H2 Conv. H2Sei. / Pd Au formulati time / h Conv. / Sei. / % Yield / % / % % leaching leaching on % / %* / %* 0.66%Pd 0.5 4.3 63.7 N. A.

[0485] 7.0 94.4 6.7 43.8

[0486] / Fe-TS-1

[0487] 1 12.1 9.4 56.6 N. A.

[0488] 43.7

[0489] 12.1 99.7

[0490] 2 26.9 22.1 50.9 N. A.

[0491] 45.2

[0492] 27.3 98.9

[0493] 3 35.6 98.3 35.0 31.6 45.5 45.4 N. A.

[0494] 0.495%P 0.5 31.0 21.4 20.0 B. D. L d- 0.165%A

[0495] u / Fe-TS- 1 31.9 97.4 71.9

[0496] 1 59.2 99.5 58.9 35.1 66.9 24.9 B. D. L 2 94.1 99.1 93.3 60.7 61.0 30.8 B. D. L 3 97.7 98.3 96.1 71.1 58.0 30.8 B. D. L 0.33%Pd 0.5 29.2 14.6

[0497] 22.4 B. D. L 0.33%Au

[0498] / Fe-TS-1 29.4 99.1 79.3

[0499] 1 45.5 98.3 44.7 25.0 76.4 24.2 B. D. L 2 68.4 98.7 67.6 41.7 68.8 26.5 B. D. L 3 93.6 97.4 91.1 61.9 63.8 29.2 B. D. L 0.165%P 0.5 10.0 4.1 18.1 B. D. L d- 0.495%A

[0500] u / Fe-TS- 1 10.0 99.2 91.4

[0501] 1 24.8 97.2 24.1 11.7 78.7 19.7 B. D. L 2 50.3 98.3 49.5 27.1 77.0 20.5 B. D. L 3 84.4 98.1 82.8 43.5 74.8 21.0 B. D. L

[0502]

[0503] 0.66%Au 0.5 N. A. B. D. L / Fe-TS-1 0.4 99.1 0.4 B. D. L - 1 0.2 97.2 0.2 B. D. L - N. A. B. D. L 2 0.3 99.8 0.3 B. D. L - N. A. B. D. L 3 0.4 99.6 0.4 B. D. L - N. A. B. D. L Fe-TS-1 3 0.3 97.8 0.3 B. D. L - N. A. N. A.

[0504]

[0505] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5 - 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A. = not applicable. *As established by ICP-MS analysis of post-reaction 5 solutions.

[0506] The results of table 17 demonstrates the incorporation of Au promotes catalytic performance (increased yield), improved selective utilisation of H2and lower Pd leaching.

[0507] 10 Table 18. The effect of support on the catalytic performance of supported AuPd nanoparticles (0.33%Au-0.33%Pd) towards the ammoximation of cyclohexanone via in situ H2O2synthesis, when used in conjunction with Fe-TS-1.

[0508] Cyclo. Oxime Oxime H2Conv. / % H2Sel / % Catalyst Conv. / % Sel. / % Yield / %

[0509] formulation

[0510] 0.33%Pd- 93.6 97.4 91.1 61.9 63.8 0.33%Au / Fe-TS-1

[0511] 0.33%Pd- 48.4 98.4 47.6 44.9 43.7 0.33%Au / CeO2

[0512] 0.33%Pd- 68.7 99.9 68.6 43.4 67.7 0.33%Au / Nb2O5

[0513] 0.33%Pd- 93.3 98.6 92.0 71.1 56.4 0.33%Au / TiO2

[0514] 0.33%Pd- 95.0 99.2 94.3 70.4 58.1 0.33%Au / ZrO2

[0515] 0.33%Pd- 91.9 99.6 91.5 66.4 58.3 0.33%Au / SiO2

[0516] 0.33%Pd- 91.4 99.4 90.8 57.3 67.8

[0517] 0.33%Au / Al2O3

[0518]

[0519] 0.33%Pd- 24.1 99.8 24.1 16.1 61.8 0.33%Au / C

[0520]

[0521] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), Fe-TS-1 (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0522] The results of table 18 demonstrates a physical mixture of H2O2synthesising catalyst and Fe- TS-1 is effective for the in situ ammoximation of ketones.

[0523] Table 19. Catalytic activity of Fe-TS-1 supported Pd-based catalysts toward the ammoximation of cyclohexanone via the in situ synthesis of H2O2, as a function of the secondary metal.

[0524] Catalyst Cyclo. Oxime Sei. Oxime H2Conv. / H2Sei / % formulation Conv. / % / % Yield / % %

[0525] 0.66%Pd / Fe-TS-1 35.6 98.3 35.0 31.6 45.5 0.33%Pd- 93.6 97.4 91.1 61.9 63.8 0.33%Au / Fe-TS-1

[0526] 0.33%Pd- 40.5 99.5 40.3 23.8 71.6 0.33%Ni / Fe-TS-1

[0527] 0.33%Pd- 45.9 99.8 45.8 27.2 73.6 0.33%Zn / Fe-TS-1

[0528] 0.33%Pd- 3.1 87.9 2.7 18.6 6.0 0.33%Mn / Fe-TS-1

[0529] 0.33%Pd- 85.7 100.0 85.7 51.6 58.3 0.33%Sn / Fe-TS-1

[0530] 0.33%Pd- 34.9 98.5 34.4 22.6 64.5 0.33%Fe / Fe-TS-1

[0531] 0.33%Pd- 89.2 99.1 88.4 65.6 56.3 0.33%Pt / Fe-TS-1

[0532] 0.33%Pd- 10.9 94.7 10.3 17.5 24.0 0.33%Ru / Fe-TS-1

[0533] 0.33%Pd- 0.5 90.1 0.5 2.7 7.0 0.33%Cu / Fe-TS-1

[0534] 0.33%Pd- 2.5 86.7 2.2 4.6 19.8 0.33%Ag / Fe-TS-1

[0535]

[0536] 0.33%Pd- 9.9 94.5 9.4 6.0 63.9 0.33%Co / Fe-TS-1

[0537] 0.33%Pd- 67.9 99.2 67.4 39.4 69.7 0.33%ln / Fe-TS-1

[0538] Fe-TS-1 0.3 97.8 0.3 B. D. L -

[0539]

[0540] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limits of the equipment.

[0541] The results of table 19 demonstrates the incorporation of a range of secondary metals (particularly Au, Pt, In, Sn, Ni and Fe), into a Fe-TS-1 supported Pd catalyst results in improved catalytic performance, compared to the monometallic Pd / Fe-TS-1 catalyst.

[0542] Table 20. Catalytic activity of the 0.33%Au-0.33%Pd / Fe-TS-1 catalyst toward the ammoximation of a range of ketones via in situ H2O2synthesis.

[0543] Ketone Cyclo. Oxime Oxime H2Conv. / % H2Sei / % Conv. / % Sei. / % Yield / %

[0544] Cyclopentanone 63.3 96.6 61.2 60.8 34.3 Cyclohexanone 93.6 97.4 91.1 61.9 63.8 Cycloheptanone 79.7 96.7 77.0 65.9 55.0 Cyclooctanone 52.2 95.8 50.0 72.2 37.1 2-octanone 67.1 98.2 65.8 65.9 47.0 5-methyl-2- 56.7 97.6 55.4 65.9 34.9 hexanone

[0545]

[0546] Ammoximation reaction conditions: Ketone (2 mmol), NH4HCO3(4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0547] The results of table 20 demonstrates (analogously to the Ti-MWW supported catalyst) the Fe-TS-1 supported analogues offer activity towards the in situ ammoximation of a range of cyclic and linear ketones.Table 21. The effect of Fe incorporation into the TS-1 support on catalytic performance towards the in situ ammoximation of cyclohexanone and catalyst stability.

[0548] Catalyst formulation Cyclo. Oxime Oxime H2H2Sei. / Pd Conv. / Sei. / % Yield / Conv. / % leaching / % % % %* 0.33%Pd / TS-1 20.7 97.8 20.2 22.4 38.3 87.5 0.33%Pd / Fe-S-1 3.0 7.3 0.2 26.7 0.3 33.1 0.33%Pd / Fe-TS-1 25.4 97.9 24.8 26.8 38.3 43.0

[0549]

[0550] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm. *As established by ICP- MS analysis of post-reaction solutions.

[0551] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.

[0552] The results of table 21 demonstrates the incorporation of Fe into the TS-1 structure offers improved catalytic performance and reduced leaching, as evidenced by comparison of the TS- 1 supported analogue. This table also demonstrates Ti incorporation into the silicate support structure is beneficial (e.g. from the perspective of oxime yield) as evidenced by comparison of the Fe-TS-1 and TS-1 supported catalyst, with the Ti-free Fe-S-1 analogue.

[0553] Table 22. The effect of metal loading on the ammoximation of cyclohexanone via in situ H2O2synthesis over AuPd / Fe-TS-1, as a function of reaction time.

[0554] Catalyst formulation Reaction time Cyclo. Oxime Oxime H2H2Sei / % Z h Conv. Sei. / Yield / Conv. /

[0555] / % % % %

[0556] 0.33%Pd / Fe-TS-1 3 25.4 97.9 24.8 26.8 38.3

[0557] 0.33%Au-0.33%Pd / Fe- 0.5 29.2 14.6

[0558] TS-1

[0559] 29.4 99.1 79.3

[0560]

[0561] 1 44.7 25.0

[0562] 45.5 98.3 76.4 2 67.6 41.7

[0563] 68.4 98.7 68.8 3 93.6 97.4 91.1 61.9 63.8

[0564] 0.083%Au-0.248%Pd / Fe- 0.5

[0565] 40.1 97.9 39.3 18.8 85.2 TS-1

[0566] 1

[0567] 57.3 99.9 57.3 31.8 75.5

[0568] 2

[0569] 85.4 99.9 85.4 44.1 79.8

[0570] 3

[0571] 96.5 99.0 95.5 58.7 66.8

[0572] 0.0413%Au- 0.5

[0573] 0.1238%Pd / Fe-TS-1 24.0 97.6 23.4 10.6 94.2

[0574] 1

[0575] 56.5 99.6 56.3 28.5 83.9

[0576] 2

[0577] 75.7 99.3 75.2 39.4 78.1

[0578] 3

[0579] 91.2 98.7 90.1 50.0 73.3

[0580]

[0581] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3(4 mmol) 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5-3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0582] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.

[0583] The results of table 22 demonstrates the incorporation of Au promotes catalytic performance (increased yield), improved selective utilisation of H2and that the titanosilicate-metal adducts of the invention may be catalytically active with a broad range of metal loadings. For example,0.165 wt% to 0.66 wt%, metal nanoparticles in the titanosilicate-metal adducts are shown to be catalytically active. Lower metal loading may offer improved H2 selectivities.

[0584] Table 23. Catalytic activity of key Ti-MWW supported Pd-based bimetallic catalysts and corresponding monometallic catalysts, toward the ammoximation of cyclohexanone via the in situ synthesis of H2O2, as a function of reaction time, over successive reactions.

[0585] Catalyst Reacti Reacti Cycl Oxim Oxim H2H2Pd Seconda formulati on on time 0. e e Con Sei leachi ry metal on numbe Z h Conv Sei. / Yield v. / / % ng / %* leaching r. / % % / % % / %* 0.66%Au / 1 3 4.2 9.4 0.4 B. D. - N. A B. D. L Ti-MWW L

[0586] 0.66%Au / 2 3 1.1 11.5 0.1 B. D. - N. A B. D. L Ti-MWW L

[0587] 0.66%Pd / 1 0.5 26.4 99.6 26.3 13.4 88. 6.9 N. A Ti-MWW 8

[0588] 1 57.7 97.4 56.2 30.6 78. 9.9 N. A 7

[0589] 2 74.6 99.2 74.0 54.9 64. 13.0 N. A 7

[0590] 3 96.9 99.4 96.3 69.3 61. 22.4 N. A 1

[0591] 0.66%Pd / 2 0.5 62. 15.1 N. A 43.8 97.3 42.6 29.8

[0592] Ti-MWW 0

[0593] 1 66. 19.6 N. A 65.5 96.4 63.1 43.2

[0594] 0

[0595] 2 63. 28.2 N. A 89.5 99.1 88.7 60.4

[0596] 7

[0597] 3 59. 38.1 N. A 93.9 97.2 91.3 68.1

[0598] 5

[0599] 0.66%Pt / 1 0.5 62. N. A

[0600] 45.0 86.3 38.8 28.3 1.9 Ti-MWW 1

[0601] 1 62. N. A

[0602] 62.9 92.8 58.4 42.6 2.2

[0603] 7

[0604] 2 55. N. A

[0605] 93.2 96.8 90.2 72.3 3.2

[0606] 6

[0607]

[0608] 3 46. N. A

[0609] 93.1 97.1 90.4 86.8 3.3

[0610] 0

[0611] 0.66%Pt / 2 0.5 42. N. A

[0612] 63.2 95.1 60.1 63.1 1.2 Ti-MWW 1

[0613] 1 42. N. A

[0614] 72.6 95.2 69.2 73.3 1.3

[0615] 5

[0616] 2 43. N. A

[0617] 79.5 98.6 78.3 81.3 1.5

[0618] 4

[0619] 3 42. N. A

[0620] 87.5 98.3 86.0 87.6 1.6

[0621] 5

[0622] .33%Pd- 1 0.5 50.3 99.8 50.2 28.6 76. 5.5 B. D. L.33%Au / 2

[0623] Ti-MWW

[0624] 1 82.0 99.9 81.9 50.1 75. 6.8 B. D. L 6

[0625] 2 97.0 99.7 96.7 55.7 76. 7.8 B. D. L 7

[0626] 3 98.0 99.4 97.4 65.0 64. 9.4 B. D. L

[0627] 9

[0628] .33%Pd- 2 0.5

[0629] 80.

[0630] .33%Au / 48.7 94.5 46.1 26.4 2.9 B. D. L 3

[0631] Ti-MWW

[0632] 1 79.

[0633] 82.0 98.2 80.4 45.8 3.2 B. D. L 3

[0634] 2 68.

[0635] 97.4 99.5 96.8 63.4 5.5 B. D. L 3

[0636] 3 56.

[0637] 98.0 98.8 96.8 74.0 8.4 B. D. L

[0638] 5

[0639] .33%Pd- 3 0.5

[0640] 75.

[0641] .33%Au / 57.2 98.0 56.1 56.1

[0642] 2

[0643] Ti-MWW

[0644] 1 75.

[0645] 85.6 99.2 84.9 33.1

[0646] 2

[0647] 2 75.

[0648] 96.7 98.7 95.4 50.9

[0649] 4

[0650]

[0651] 3 66.

[0652] 99.5 98.4 97.9 65.1

[0653] 0

[0654] 0.33%Pd- 1 0.5 44.4 89.5 39.7 30.2 57. 4.4 3.9 0.33%Pt / 9

[0655] Ti-MWW

[0656] 1 76.9 96.0 73.9 44.5 72. 5.0 4.4 0

[0657] 2 83.4 94.4 78.7 60.1 60. 8.8 5.5

[0658] 6

[0659] 3 85.0 95.3 81.0 77.3 44. 11.2 7.5

[0660] 1

[0661] 0.33%Pd- 2 0.5

[0662] 65.

[0663] 0.33%Pt / 50.9 89.3 45.5 31.1 6.1 3.9

[0664] 8

[0665] Ti-MWW

[0666] 1 71.

[0667] 73.1 94.2 68.9 43.9 6.6 4.7

[0668] 2

[0669] 2 59.

[0670] 77.7 93.2 72.5 54.4 8.6 5.3

[0671] 1

[0672] 3 54.

[0673] 84.5 94.8 80.1 63.4 10.5 6.0

[0674] 9

[0675] 0.33%Pd- 3 0.5

[0676] 81.

[0677] 0.33%Pt / 52.2 95.7 50.0 27.4

[0678] 7

[0679] Ti-MWW

[0680] 1 82.

[0681] 74.1 95.7 70.9 38.7

[0682] 1

[0683] 2 66.

[0684] 84.5 95.1 80.4 56.0

[0685] 9

[0686] 3 61.

[0687] 84.9 97.0 82.3 60.3

[0688] 9

[0689]

[0690] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5-3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A. = not applicable. *As established by ICP-MS analysis of post-reaction solutions.

[0691] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.The results of table 23 demonstrates, similarly to that which is shown in table 7.1 and 7.2 the introduction of Au inhibits the leaching of Pd and also Pt has a similar (but smaller) effect on reducing Pd leaching. Unlike Pt, Au does not itself leach under the reaction conditions. A comparison of the 0.66%Pd / Ti-MWW, 0.33%Pd-0.33%Au / Ti-MWW and 0.33%Pd-0.33%Pt / Ti-MWW catalysts at similar levels of H2 conversion indicate that the incorporation of Au is key in promoting improved H2 selectivity. As such the incorporation of Au improves catalytic activity (as indicated by oxime yield), selectivity of H2 (a key feedstock, lowering costs) and improves catalyst stability, through the inhibition of Pd leaching, while not leaching itself (unlike Pt).

[0692] Table 24. A comparison of 0.66%Pd / Ti-MWW, 0.33%Pd-0.33%Au / Ti-MWW and 0.33%Pd-0.33%Pt / Ti-MWW catalyst activity towards the ammoximation of cyclohexanone via the in situ synthesis of H2O2, in a flow regime.

[0693] Catalyst Reacti Oxim Catalyst Reacti Oxim Catalyst Reacti Oxim formulati on e formulati on e formulati on e on time / h Yield on time / h Yield on time / h Yield / % / % / % 0.66%Pd / 6 18.7 0.33%Pd- 12 19.5 0.33%Pd- 12 30.2 Ti-MWW 0.33%Au / 0.33% Pt /

[0694] Ti-MWW Ti-MWW

[0695] 18 23.2 24 31.5 24 27.0

[0696] 36 33.9 36 27.1 30 23.3 48 37.1 42 26.5 42 15.2 60 38.2 54 26.5 48 13.4 70 39.3 66 27.0 54 12.9 84 40.8 78 27.1 66 12.7 94 42.0 90 27.2 72 11.8 109 43.0 114 27.6 96 10.8

[0697] 102 10.2 132 44.3

[0698] 114 9.5 156

[0699] 164 46.4

[0700] 180 47.2

[0701] 204 47.5

[0702]

[0703] 216 47.2

[0704] 228 47.2

[0705] 234 47.3

[0706]

[0707] Ammoximal ion reaction conditions: Cyclohexanone (19 wt.%): NH3(aq.) (1: 1 (mol / mol)), 2.8% H2, 6.4% O2, 90.8% N2 (gas flow rate = 88 mLmin-1), catalyst (0.45 - 0.9 mm, catalyst: Al2O3binder = 4:1 (g / g), total mass = 2.0 g), t-BuOH: H2O (9:1 (vol / vol)), liquid flow rate = 0.048 mLmin-1, reaction temperature 80 °C.

[0708] The results of table 24 demonstrates that the incorporation of Au into a Pd-based Ti-MWW supported catalyst results in improved stability in comparison to the Pd-only formulation and increased activity compared to the PdPt analogue.

[0709] Table 25. The effect of titanosilicate framework on the catalytic performance of supported AuPd nanoparticles (0.33%Au-0.33%Pd) towards the ammoximation of cyclohexanone via in situ H2O2 synthesis.

[0710] Cyclo. Oxime Oxime H2 Conv. / % H2Sel / % Catalyst Conv. / % Sel. / % Yield / %

[0711] formulation

[0712] 0.33%Pd- 98.0 99.4 97.4 65.0 64.9 0.33%Au / Ti- MWW

[0713] 0.33%Pd- 84.1 98.2 82.6 63.8 57.4 0.33%Au / TS-1

[0714] 0.33%Pd- 74.4 98.3 73.1 65.3 47.8 0.33%Au / TS-2

[0715] 0.33%Pd- 40.0 96.5 38.6 50.3 32.1 0.33%Au / Ti-beta

[0716] 0.33%Pd- 7.4 98.0 7.3 59.5 5.0 0.33%Au / Ti- MCM-41

[0717]

[0718] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 3 h, reaction temperature 80 °C, stirring speed 800 rpm.

[0719] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2 Conv. = H2 conversion; H2 Sel = H2 selectivity.The results of table 25 demonstrates that the in situ approach to ketone ammoximation is possible over a range of titanosilicate structures, but the Ti-MWW framework offers optimal performance.

[0720] Table 26. The effect of Au loading (Pd fixed at 0.33%), on the catalytic performance of supported AuPd nanoparticles towards the ammoximation of cyclohexanone via in situ H2O2 synthesis, as a function of time.

[0721] Catalyst Reaction Cyclo. Oxime Oxime H2H2Au Pd formulation time / h Conv. Sei. / Yield / Conv. Sei. leaching leaching / % % % / % / % / %* / %* 0.33%Pd / Ti- 0.5 30.1 99.0 29.8 21.4 61.1 N. A. 10.5 MWW

[0722] 1 47.8 97.9 46.8 31.5 62.5 N. A. 13.3 2 82.1 99.6 81.8 52.1 65.7 N. A. 20.3 3 90.4 99.9 90.4 58.8 66.3 N. A. 24.3 0.33%Pd- B. D. L 10.1.0825%Au / Ti- MWW 0.5 51.0 98.8 50.4 36.6 56.5

[0723] 1 80.0 99.2 79.4 55.4 59.9 B. D. L 12.3 2 95.2 99.2 94.4 60.0 67.3 B. D. L 15.0 3 97.2 99.4 96.6 71.9 56.1 B. D. L 20.6 0.33%Pd- 0.5 49.7 99.0 49.2 32.0 65.9 B. D. L 8.0.165%Au / Ti- MWW

[0724] 1 81.2 98.1 79.7 52.0 67.1 B. D. L 10.7 2 97.9 98.1 96.1 61.8 63.7 B. D. L 14.4 3 98.9 98.6 97.6 80.2 51.7 B. D. L 19.0 0.33%Pd- 0.5 50.1 99.2 49.7 28.6 76.2 B. D. L 5.5 0.33%Au / Ti- MWW

[0725] 1 81.5 99.5 81.0 50.1 75.6 B. D. L 6.8 2 97.0 99.6 96.6 55.7 76.7 B. D. L 7.8 3 98.0 99.4 97.4 65.0 64.9 B. D. L 9.4 0.33%Pd- 0.5 48.9 99.9 48.8 27.4 74.7 B. D. L 5.2 0.66%Au / Ti- MWW

[0726]

[0727] 1 80.8 99.1 80.1 42.6 81.4 B. D. L 6.3

[0728] 2 98.3 97.8 96.1 55.3 72.8 B. D. L 7.7 3 98.9 98.5 97.4 64.8 62.6 B. D. L 8.60.33%Pd- 0.5 15.1 99.0 14.9 15.1 41.4 B. D. L 4.21.65%Au / Ti- MWW

[0729] 1 70.5 98.0 69.1 35.9 78.8 B. D. L 5.1 2 94.5 99.6 94.1 53.2 74.1 B. D. L 6.6 3 98.7 99.0 97.8 59.4 71.1 B. D. L 6.7

[0730]

[0731] Ammoximation reaction conditions: Cyclohexanone (2 mmol), NH4HCO3 (4 mmol), 5%H2 / N2(420 psi), 25%O2 / N2(160 psi), catalyst (0.075 g), t-BuOH (5.9 g), H2O (7.5 g), reaction time 0.5-3 h, reaction temperature 80 °C, stirring speed 800 rpm. B. D. L = below detection limit. N. A. = not applicable. *As established by ICP-MS analysis of post-reaction solutions.

[0732] Cyclo. Conv. = cyclohexanone conversion; Oxime Sel. = oxime selectivity; H2Conv. = H2conversion; H2Sel = H2selectivity.

[0733] The results of table 26 highlights that the incorporation of Au offers improved performance, with a Au: Pd ranging from 0.25 to 5 shown to result in a higher yield of oxime. Comparison of H2selectivity, at comparable rates of H2conversion rates (~ 30%), across the series shows that the inclusion of Au promotes the effective utilisation of H2. The introduction of increasing Au content inhibits the leaching of Pd.Table 27. Comparison of catalytic stability after treatment with reagents used in the ammoximation of cyclohexanone, as determined by ICP-MS analysis of recovered catalysts after exposure to model reaction conditions.

[0734] Cyclohexanone + NH3 Cyclohexanone + Cyclohexanone + NH3

[0735] H2O2 + H2O2

[0736] Catalyst Pd Secondar Pd Secondar Pd Secondar Leachin y metal Leachin y metal Leachin y metal g / % leaching / g / % leaching / g / % leaching /

[0737] % % % 0.33%Pd / Ti- 1.88 N. A. 3.27 N. A. 4.08 N. A. MWW

[0738] 0.33%Pd- 0.33%Au / Ti- 1.16 B. D. L 1.25 B. D. L 2.53 B. D. L MWW

[0739] 0.33%Pd- 0.33%Ni / Ti- 2.0 0.9 MWW

[0740] 0.33%Pd- 0.33%Zn / Ti- 0.6 1.2 MWW

[0741] 0.33%Pd- 0.33%Mn / Ti 2.5 0.1 -MWW

[0742] 0.33%Pd- 0.33%Sn / Ti- 1.6 0.1 MWW

[0743] 0.33%Pd- 0.33%lr / Ti- 1.1 0.2 MWW

[0744] 0.33%Pd- 0.33%Fe / Ti- 10.8 0.7 MWW

[0745] 0.33%Pd- 0.33%Pt / Ti- 3.2 3.9 MWW

[0746]

[0747] 0.33%Pd- 0.33%Ru / Ti- 5.1 0.2 MWW

[0748] 0.33%Pd- 0.33%Cu / Ti- 1.2 11.2 MWW

[0749] 0.33%Pd- 0.33%Ag / Ti- 4.3 21.7 MWW

[0750] 0.33%Pd- 0.33%Co / Ti- 9.2 2.0 MWW

[0751] 0.33%Pd- 0.33%ln / Ti- N. D* 4.3 MWW

[0752]

[0753] Ammoximation reaction conditions: Cyclohexanone (50 mmol), NH3 (25 wt.%, 60 mmol), H2O2 (50 wt.%, 50 mmol), catalyst (0.1g), t-BuOH (5.9 g), H2O (7.5 g), reaction temperature 80°C, stirring speed 800 rpm, 1h. B. D. L = below detection limit. N. A. = not applicable. N. D* = not determined as In is utilised was utilised as the standard for ICP-MS analysis.

[0754] The data in this table demonstrate that the introduction of Au inhibits Pd leaching. The data in this table demonstrate that the introduction of a range of secondary metals (including e.g. Au, Ni, Zn, Mn, Sn, Ir, Pt, and Cu) inhibits the leaching of Pd, and so a range of secondary metals are advantageous. With the exception of Au all of these secondary metals are found to show some degree of instability under these reaction conditions, so whilst all secondary metals are advantageous, Au is the most advantageous. When this data is assessed along with that above (activity and stability of PdX catalysts) there is a clear enhancement in both metrics as a result of Au incorporation.

[0755] The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0756] All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and / or all of the steps of any method or process so disclosed, may becombined in any combination, except combinations where at least some of such features and / or steps are mutually exclusive.

[0757] Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent, or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[0758] The invention is not restricted to the details of any foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

Claims1. A titanosilicate-metal adduct comprising titanosilicate and metal nanoparticles, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-LITD- 1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, and Fe-TS-1, preferably wherein the titanosilicate is Ti- MWW, and wherein the metal nanoparticles are bound to the titanosilicate.

2. The titanosilicate-metal adduct according to claim 1 wherein the metal nanoparticles comprise Pd, Au, Pt, Ir, Rh, or Ru, optionally wherein the metal nanoparticles comprise pure Pd, Au, Pt, Ir, Rh, or Ru.

3. The titanosilicate-metal adduct according to claim 1 or 2 wherein the metal nanoparticles comprise Pd alloy wherein the Pd alloy comprises palladium and one or more non-palladium metal.

4. The titanosilicate-metal adduct according to any preceding claim wherein the metal nanoparticles comprise AuPt, Aulr, AuRh, AuRu, PtNi, PtSn, PtCo, Ptln, or PtZn.

5. The titanosilicate-metal adduct according to any preceding claim comprising Ti-MWW and Pd alloy, wherein the Pd alloy comprises palladium and one or more non-palladium metal, and wherein the Pd alloy is bound to the Ti-MWW.

6. The titanosilicate-metal adduct according to any preceding claim wherein the metal nanoparticles are 1 nm to 500 nm in diameter, preferably 2 nm to 200 nm in diameter, more preferably 3 nm to 100 nm in diameter, most preferably 5 nm to 50 nm in diameter.

7. The titanosilicate-metal adduct according to any preceding claim wherein the Pd alloy comprises palladium and one non-palladium metal.

8. The titanosilicate-metal adduct of any preceding claim wherein the metal nanoparticles comprise Pd alloy, wherein the non-palladium metal is selected from Au, Pt, Fe, Ni, Ir, Cu, Rh, Co, Mn, Ga, Ag, Sn, Ru, In, and Zn; preferably wherein the non-palladium metal is selected from Au, Pt, Fe, Ni, Ir, Cu, Co, Mn, Ag, Sn, Ru, In and Zn, more preferably wherein the non-palladium metal is selected from Au, Pt, Ni, Ir, Sn, In andZn; even more preferably wherein the non-palladium metal is selected from Au and Pt; most preferably the non-palladium metal is Au.

9. The titanosilicate-metal adduct according to any preceding claim wherein the amount of Pd in the Pd alloy is 5 wt% to 95 wt%, preferably 10 wt% to 90 wt%, more preferably 20 wt% to 80 wt%, even more preferably 20 wt% to 80 wt%.

10. The titanosilicate-metal adduct of claim 9 wherein the amount of Pd in the Pd alloy is 20 wt% to 60 wt%, preferably 25 wt% to 50 wt%.

11. The titanosilicate-metal adduct of claim 9 wherein the amount of Pd in the Pd alloy is 40 wt% to 80 wt%, preferably 50 wt% to 75 wt%.

12. The titanosilicate-metal adduct of claim 9 wherein the amount of Pd in the Pd alloy is 40 wt% to 60 wt%, optionally 50 wt%.

13. The titanosilicate-metal adduct according to any preceding claim wherein amount of Pd alloy is 0.02 wt% to 10 wt%, preferably 0.1 wt% to 8 wt%, more preferably 0.3 wt% to 5 wt%, even more preferably 0.3 wt% to 1 wt%.

14. The titanosilicate-metal adduct according to any preceding claim wherein the titanosilicate is TM-TS-1, preferably wherein the titanosilicate is Fe-TS-1.

15. The titanosilicate-metal adduct according to any preceding claim prepared by a method comprising:(a) providing a solution of a first metal salt in a first solvent, preferably wherein the first solvent is acetone, more preferably wherein the first metal salt is a Pd salt, even more preferably wherein the first metal salt is Pd(OAc)2, most preferably wherein the first metal salt is Pd(OAc)2 and the first solvent is acetone;(b) combining the solution of first metal salt in first solvent with a titanosilicate to obtain a first slurry, optionally stirring the first slurry for 1 hour at room temperature;(c) heating the first slurry above room temperature under conditions allowing the evaporation of the first solvent to obtain a first solid;(d) grinding the first solid to obtain a first ground solid;(e) optionally dispersing the first ground solid to obtain a second slurry, wherein the second slurry comprises the first ground solid and a second solvent, preferably wherein thesecond slurry further comprises a second metal salt, more preferably wherein the second solvent is water, even more preferably wherein the second metal salt is HAuCl₄.3H₂O, most preferably wherein the second slurry comprises the ground solid, the second solvent wherein the second solvent is water and the second metal salt wherein the second metal salt is HAuCl₄.3H₂O, followed by heating the second slurry above room temperature under conditions allowing the evaporation of the second solvent to obtain a second solid, followed by grinding the second solid to obtain a second ground solid; and(f) reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct, preferably wherein prior to the reducing of the first ground solid or second ground solid the first ground solid or second ground solid is calcined.

16. A catalyst for ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, wherein the catalyst comprises a titanosilicate-metal adduct of any one of claims 1-15, optionally further comprising a support, preferably wherein the support is selected from CeC>2, Nb20s, TiC>2, ZrC>2, SiC>2, AI2O3, or C, more preferably wherein the support is selected from Nb20s, TiC>2, ZrC>2, SiC>2, or AI2O3, even more preferably wherein the support is selected from TiC>2 or ZrC>2.

17. The catalyst of claim 16, wherein the catalyst consists of a titanosilicate-metal adduct of any one of claims 1-15.

18. A process for the preparation of a titanosilicate-metal adduct, the process comprising: (a) providing a solution of a first metal salt in a first solvent, preferably wherein the first solvent is acetone, more preferably wherein the first metal salt is a Pd salt, even more preferably wherein the first metal salt is Pd(OAc)2, most preferably wherein the first metal salt is Pd(OAc)2 and the first solvent is acetone;(b) combining the solution of first metal salt in first solvent with a titanosilicate to obtain a first slurry, optionally stirring the first slurry for 1 hour at room temperature;(c) heating the first slurry above room temperature under conditions allowing the evaporation of the first solvent to obtain a first solid;(d) grinding the first solid to obtain a first ground solid;(e) optionally dispersing the first ground solid to obtain a second slurry, wherein the second slurry comprises the first ground solid and a second solvent, preferably wherein the second slurry further comprises a second metal salt, more preferably wherein the second solvent is water, even more preferably wherein the second metal salt is HAuCl₄.3H₂O, most preferably wherein the second slurry comprises the ground solid, the second solvent whereinthe second solvent is water and the second metal salt wherein the second metal salt is HAuCl₄.3H₂O, followed by heating the second slurry above room temperature under conditions allowing the evaporation of the second solvent to obtain a second solid, followed by grinding the second solid to obtain a second ground solid; and(f) reducing the first ground solid or the second ground solid to obtain the titanosilicate-metal adduct, preferably wherein prior to the reducing of the first ground solid or second ground solid the first ground solid or second ground solid is calcined;wherein the titanosilicate is Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, or Fe-TS-1, preferably wherein the titanosilicate is Ti-MWW.

19. A process comprising reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct according to any one of claims 1-15 or the catalyst according to claim 16 or 17.

20. The process according to claim 19 wherein the ketone is selected from aliphatic ketones, alicyclic ketones, aromatic ketones or a combination thereof, preferably wherein the ketone is a cyclic ketone.

21. The process according to claim 20 comprising step (i):oHO'N(ii) Reactingnto formvn ■wherein n is an integer from 1 to 11, preferably from 2 to 10, more preferably 3 to 8, most preferably 4 to 7.

22. The process according to claim 21 wherein step (i) is:o HCXNReacting to form23. The process according to any one of claims 19-22 wherein the reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct:(ix) occurs in a solvent, optionally wherein the solvent is a solvent system or a pure solvent, preferably wherein the solvent is a protic solvent, more preferablywherein the solvent is selected from an alcohol, water, an aromatic hydrocarbon or a combination thereof, even more preferably wherein the solvent is methanol, ethanol, propanol, butanol, water, benzene toluene or a combination thereof, even more preferably wherein the solvent is a combination of water and t-butanol;(x) occurs in a reaction vessel wherein the reaction vessel comprises an inner surface of PTFE, glass or stainless steel;(xi) has a reaction temperature 0 to 150 °C, preferably 50 to 120 °C, more preferably 70 to 100 °C;(xii) has a reaction pressure of 1 to 200 barg, preferably 10 to 100 barg;(xiii) has a reaction time of 0.017 to 15 h;(xiv) occurs in batch reaction;(xv) occurs in a semi-batch reaction; and / or(xvi) occurs in a continuous reaction.

24. The process according to any one of claims 19-23 wherein the reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct:(vii) has air or an enriched air as an O2 source;(viii) has a molar ratio of O2:ketone / aldehyde / amide of 0.1: 20, preferably 1: 10, more preferably 1: 5;(ix) has a molar ratio of H2:ketone / aldehyde / amide of 0.1: 20, preferably 1: 10, more preferably 1: 5;(x) uses a diluent for gaseous reagents, optionally where in the diluent is N2, CO2, Ar, He, Xe, Ne, CH4, C2H6or NH3, preferably wherein the diluent is N2;(xi) occurs in the presence of an NH3 source, wherein the NH3 source is selected from ammonium hydroxide, ammonium carbonate, ammonium acetate, ammonium hydrogen carbonate, ammonium halide, ammonium chloride, gaseous ammonia, and combinations thereof; and / or(xii) has a molar ratio of ammonia:ketone / aldehyde / amide of greater than 1: 1, preferably 2: 1, more preferably 1: 1.

25. The process according to any one of claims 19-24 wherein the reacting a ketone, aldehyde or amide, preferably ketone, with H2, O2and NH3to form an oxime in the presence of the titanosilicate-metal adduct:(viii) has a weight ratio of titanosilicate-metal adduct: ketone / aldehyde / amide of 0.001:1 to 200:1;(ix) occurs in the presence of an ion selected from sulphate, sulfite, phosphate, pyrophosphate, stannate, chloride, bromide, iodide, fluoride and combinations thereof;(x) occurs in the presence of an acid selected from halo acid, HCI, HBr, HF, HI, phosphoric acid, sulphuric acid, nitric acid, tungstic acid, heteropolyacids, solid acids, silico-aluminates, zeolites, alumina, silico-aluminophosphate, sulfated zirconia and combinations thereof;(xi) occurs in the presence of a chelating agent, preferably wherein the chelating agent is selected from ethylenediamine tetra(methylene phosphonic acid), ethylenediaminetetraacetic acid, nitrilotriacetic acid and combinations thereof; (xii) occurs in the presence of at least one organic compound, preferably wherein the at least one organic compound is selected from organic hydroxy compounds, diglycolic acid, aromatic sulfonic acid, acyl phosphonic acids, phenanthroline, amino-triazine, acetanilide and combinations thereof; (xiii) occurs in the presence of a radical scavenger preferably wherein the radical scavenger is selected from nitrone compounds, nitroso compounds, dithiocarbamate derivatives, ascorbic acid derivatives and combinations thereof; and / or(xiv) occurs in the presence of a compound which suppresses H2O2degradation preferably wherein the compound which suppresses H2O2degradation is selected from tantalum species, zirconium species, niobium species and combinations thereof.

26. The process according to any one of claims 19-25 wherein the process is for the production of an oxime.

27. The process according to any one of claims 19-25 wherein the process further comprises:(iv) Reacting the oxime formed in step (i) to form an amide.

28. The process according to claim 27 wherein step (ii) is:HO'N)(ii) Reactingnto formHN' 'n.

29. The process according to claim 27 wherein step (ii) is:

30. The process according to any one of claims 27-29 wherein the process is for the production of polycaprolactam.

31. The use of titanosilicate in ketone ammoximation, aldehyde ammoximation or amide ammoximation, preferably ketone ammoximation, wherein the titanosilicate is selected from Ti-MWW, TS-2, Ti-ZSM-12, Ti-Beta, Ti-UTD-1, Ti-MWW precursor, Ti-YNU, Ti- MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-MMM-1, Ti-MOR, Ti-YNU-5, TM-TS-1, or Fe-TS- 1.

32. The use according to claim 31 wherein the titanosilicate is Ti-MWW.

33. The use according to claim 31 wherein the titanosilicate is TM-TS-1, preferably wherein the titanosilicate is Fe-TS-1.

34. The use according to claim 31, 32 or 33 wherein the use is in a process of any one of claims 19-30 in the presence of a titanosilicate-metal adduct.

35. The use according to claim 31, 32 or 33 wherein the use is in a process of any one of claims 19-30 in the absence of a titanosilicate-metal adduct.

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