NZ508844A

NZ508844A - Homogenous amorphous silicate catalyst containing a metal cationic species such as rhodium for catalysing the hydroformylation of olefins

Info

Publication number: NZ508844A
Application number: NZ508844A
Authority: NZ
Inventors: Thomas Borrmann; James Howard Johnston
Original assignee: Victoria Link Ltd
Priority date: 2000-12-13
Filing date: 2000-12-13
Publication date: 2003-07-25
Also published as: AU2002216493A1; WO2002048039A1; WO2002048039A8

Abstract

A homogeneous catalyst for hydroformylation reactions comprising or including: a) a substantially amorphous calcium silicate host, and b) a plurality of metal cationic species (preferably rhodium Rh(III) species) capable of catalysing a hydroformylation reaction, coordinated or bound to the host is disclosed. Also disclosed are the methods for making such a catalyst and applications for these catalysts for the synthesis of a transition metal-containing silicate matrix, with rhodium as the metal in the form of rhodium containing calcium silicate, for catalysts in a continuous hydroformylation process.

Description

<div class="application article clearfix" id="description"> 1 NEW ZEALAND PATENTS ACT, 1953 No: 508844 Date: 13 December 2000 COMPLETE SPECIFICATION "Catalysts and the Hydroformylation of Olefins" We, VICTORIA LINK LIMITED a company duly incorporated under the laws of New Zealand of 15 Mount Street, Kelburn, Wellington, New Zealand do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: Intellectual Property | Office »f N.Z- ! 12 DEC 2001 received FIELD OF THE INVENTION The invention relates to novel catalyst materials. More particularly but not exclusively it relates to novel homogeneous catalysts for use in hydroformylation reactions. BACKGROUND TO THE INVENTION The Hydroformylation Reaction With several million tons of products per year, the conversion of olefins to aldehydes and alcohols using the hydroformylation process is an important industrial chemistry process [1~4]. Various catalytic processes are used to effect these reactions. Initially, only single phase processes were used whereby the catalyst, in most cases a soluble cobalt-containing carbonyl complex, was carried through the reaction in the same phase as the substrates and products. This procedure has obvious disadvantages in terms of product separation and recovery, and the loss of catalytic material. Therefore more economically and environmentally benign hydroformylation processes applying biphasic systems have been introduced in recent times [M]. The Catalyst For a biphasic liquid hydroformylation system, the catalyst, in general a rhodium-containing carbonyl compound, is dissolved in a polar phase, preferably water. Phosphine ligands are added to increase the activity, stabilise the catalyst and minimise the loss of catalytic material C1"4]. During the hydroformylation reaction, either the substrate becomes soluble in the polar phase, or the catalyst becomes soluble in the substrate phase. Industrial chemical processes utilising this approach work well for short chained linear olefins. However, longer chained and branched olefins present a problem as they are not soluble in water and therefore show only a very low activity for the conversion of these substrates. Later approaches utilising a phase transfer catalyst may provide a new perspective in this field of research [5'6]. Several research groups have attempted the formation of rhodium catalysts on zeolite substrates [7"12]. Hanson et al.[10] attempted to substitute rhodium for aluminium in an aluminosilicate matrix. The resulting compounds were catalytically active but were unstable to the extent that they degraded after a few turnovers. Other approaches studied the application of silica or silicate as carrier material for various rhodium 508844' compounds [131. The catalytic systems generated this way also proved to be unstable and they showed only a low activity in hydroformylation reactions. OBJECT OF THE INVENTION It is an object of the invention to provide a novel catalyst for use in hydroformylation reactions using one of Rh, Co, Mo, V, Cr, Mn, or Fe as the catalytic entity. It is a further object of this invention to provide a silicate catalytic matrix that overcomes or addresses some of the above disadvantages or which at least provides the public with a useful choice. Other objects of the present invention are: ■ to provide a process for the preparation of a silicate catalytic matrix ■ to provide a hydroformylation process utilising a silicate catalytic matrix; ■ to provide a catalytic vessel for use in a hydroformylation process ■ to provide a continuous flow hydroformylation process; or again ■ at least to provide the public with a useful choice. DESCRIPTION OF THE INVENTION Described herein is a homogeneous catalyst for hydroformylation reactions comprising or including: a) a substantially amorphous silicate host, and b) a plurality of metal cationic species capable of catalysing a hydroformylation reaction, coordinated or otherwise bound to the host. Preferably the amorphous silicate host comprises a silicate structure bridged or linked by a metal linker species. Preferably the metal linker species is a group II or transition metal, each of which has on average a valency of +2 or more in the structure. Preferably the metal linker species are or include Ca(II) cations, and the silicate host is an amorphous calcium silicate. More specifically, in a first aspect of the invention there is provided a homogeneous catalyst for hydroformylation reactions comprising or including: IPONZ 26 m 2003 5 0 8 8 4 A a) a substantially amorphous calcium silicate hoStf ana b) a plurality of metal cationic species capable of catalysing a hydroformylation reaction, coordinated or bound to the host. Preferably the calcium silicate host is porous in nature and wherein, relative to a non-porous host, the porosity gives rise to: i) an increased number of chemical binding sites for the metal cationic species to the calcium silicate host, and ii) increased access to and/or the metal cationic species (and pre-cursor species and/or products thereof) by reactants in a hydroformylation reaction. Preferably the metal cationic species are Rh(III) species. Preferably the Rh(III) species are dispersed substantially uniformly throughout the calcium silicate host. Preferably the Rh(III) species are chemically bound or coordinated to the calcium silicate host, rather than simply being supported by the host. Preferably the amorphous calcium silicate has a microplate-like structure, the Rh(III) species being bound or coordinated to the surface(s) of the microplates, wherein preferably the dimensions of the microplates are substantially between 5-10 nanometres thick by 20-100 nanometres wide. Preferably the pH of the catalyst, or achieved in preparation of the catalyst, is substantially between pH=7 and pH=l 1. In one form the silicate host originates from geothermal, silica rich, aqueous systems. According to a second aspect of the invention there is provided a homogeneous catalyst for hydroformylation reactions substantially as herein described with reference to any one or more of the Examples and/or Figures. Further described herein is a matrix effective as, or providing a, hydroformylation catalyst, comprising or including: a) silicate, and b) a metal catalyst linked thereto, wherein : IPONZ 26 MAY 2003 50 88 44 5 i) the silicate is an amorphous silicate structure containing or linked by metal linker species, and ii) the metal catalyst is a transition metal ion suitable for use as a catalysing species in a hydroformylation process. Preferably the metal linker species is selected from a group II or transition metal ion with a valency of at least two; preferably the metal linker species is selected from the group comprising Ca2+, Mg2+, Cu2+, Zn2+, Al3+ and Sn2+; more preferably the metal linker species is Ca2+. More specifically, in a third aspect of the invention there is provided a matrix effective as, or providing a, hydroformylation catalyst, comprising or including: a) silicate, and b) a metal catalyst linked thereto, wherein: i) the silicate is a substantially amorphous calcium silicate structure, and ii) the metal catalyst is a transition metal ion suitable for use as a catalysing species in a hydroformylation process. Preferably the metal catalyst is an ion of a metal selected from the list consisting of: Co, Mo, V, Cr, Mn, Fe, Pt, Au, W, Ir, Re, Ru, Os, Ag, Pd and Rh. More preferably, the metal catalyst is an ion of a metal selected from the list consisting of: Co, Mo, V, Cr, Mn, Fe and Rh. In a further preferred embodiment, the metal catalyst is an ion of a metal selected from the list consisting of: Co, Os, Ru, Pd and Rh. Still more preferably the metal catalyst is rhodium ions, the rhodium ions existing as Rh(III) ions throughout the calcium silicate structure. Preferably the calcium silicate structure is porous in nature and wherein, relative to a non-porous structure, the porosity gives rise to: i) an increased number of chemical binding sites for the Rh(III) ions to the silicate host, and ii) increased access to and/or from the Rh(III) species (and pre-cursor species and/or products thereof) by reactants and/or products in a hydroformylation reaction. 50884^ Preferably the Rh(III) ions are dispersed substantially uniformly throughout the calcium silicate structure. Preferably the Rh(III) ions are chemically bound or coordinated to the calcium silicate structure, rather than being simply supported by the calcium silicate structure; more preferably the amorphous calcium silicate has a microplate-like structure, the Rh(III) ions being bound or otherwise coordinated to the surface(s) of the microplates. Preferably the dimensions of the microplates are substantially between 5-10 nanometres thick by 20-100 nanometres wide. According to a further aspect of the invention there is provided a matrix effective as, or providing a, hydroformylation catalyst substantially as herein described with reference to any one or more of the Examples and/or Figures. Also described herein is a method of preparing a homogeneous catalyst for hydroformylation reactions comprising or including the step of: A) contacting or mixing: ■ a solution containing silicate species, with ■ a source of metal catalyst species, being transition metal ions suitable for use as catalysing species in a hydroformylation process, such that the metal catalyst species bind with the silicate, and B) recovering the homogeneous catalyst as a solid phase product. Preferably precipitation is caused by contacting the solution containing the silicate species with a source of metal linker species, the metal linker species comprising cations of group II or transition metals, with a valency of at least two. Preferably the source of the metal linker species is a hydroxide of the metal linker. Preferably the metal linker species is selected from the group comprising: Ca2+, Mg2+, Cu , Zn , A1 and Sn ; more preferably the metal linker species is Ca . More specifically, in a further aspect of the invention there is provided a method of preparing a homogeneous catalyst for hydroformylation reactions comprising or including the step of: A) contacting or mixing: ■ a solution containing silicate species, with 508844 7 ■ a source of calcium cations, ■ a source of metal catalyst species, being transition metal ions suitable for use as catalysing species in a hydroformylation process, such that the metal catalyst species bind with the silicate, and B) recovering the homogeneous catalyst as a solid phase product. Preferably the solid phase product precipitates out of solution. Preferably the source of the metal catalyst species is mixed with the solution containing the silicate species before or during precipitation of the solid phase product. Preferably precipitation is caused by contacting the solution containing the silicate species with the source of calcium cations. Preferably the source of the calcium cations is calcium hydroxide. Preferably the solution containing the silicate species is, or originates from, geothermal, silica rich, aqueous systems. Preferably the metal catalyst species is an ion of a metal selected from the list of Co, Mo, V, Cr, Mn, Fe, Pt, Au, W, Ir, Re, Ru, Os, Ag, Pd and Rh. More preferably, the metal catalyst is an ion of a metal selected from the list consisting of: Co, Mo, V, Cr, Mn, Fe and Rh. In a further preferred embodiment, the metal catalyst is an ion of a metal selected from the list consisting of: Co, Os, Ru, Pd and Rh. Still more preferably the metal catalyst species is Rh(III) ions. Preferably the source of Rh(III) ions is water-soluble; more preferably the source of Rh(III) ions is selected from a polyethylene glycolate or a chloride hydrate. Preferably the solution containing silicate species (before, during or after contact with the source of metal catalyst species) is pH adjusted to increase binding of the metal catalyst species with the silicate. Preferably the pH is adjusted to be substantially between pH=6.0 and pH=12.5; more preferably the pH is adjusted to be substantially between pH=7.0 and pH=9.0. Preferably there is further the step of acid washing of the recovered solid product to remove surface bound calcium ions and/or facilitate a redistribution of the silicate material to increase the structural robustness and stability of the catalyst. Preferably the solution containing silicate species is sodium silicate, the source of the calcium cations is calcium hydroxide and the source of the metal catalyst species is rhodium polyethylene glycolate or rhodium trichloride hydrate. 50 8 8 A 4 It is also preferred that the pH of the mixture be adjusted to achieve maximum binding of the catalyst metal into the matrix. A skilled worker will appreciate that the optimum pH adjustment is readily determinable by simple experimentation. If equimolar quantities of Ca2+ (1 mol of CaO to 1 mol of Si02) are added to the silicate solution at a pH of greater than about pH = 10, an amorphous calcium silicate is produced. Depending upon the exact method of preparation, the calcium silicate material typically has a high oil absorption of up to 200 - 400 g oil per 100 g silicate and a high surface of up to about 200 - 300 m2 g"1 [14]. Acid washing removes surface ■j, bound Ca ions and facilitates a redistribution of the silicate material to increase the structural robustness and stability of the compound. According to a further aspect of the invention there is provided a homogeneous catalyst for hydroformylation reactions as prepared by the above method. According to a further aspect of the invention there is provided a method of catalysing the hydroformylation of one or more olefins comprising or including the steps of: (a) Reacting one or more olefins with a CO/H2 gas in the presence of a homogeneous catalyst or matrix of the invention; (b) Separating the hydroformylation product(s) from the catalyst or matrix (or vice versa). Preferably the catalyst or matrix is separated by filtration. Preferably the product(s) are one or more of a liquid phase aldehyde, carboxylic acid or alcohol. According to a further aspect of the invention there is provided a product formed by the method of catalysing the hydroformylation of one or more olefins as described above. According to a further aspect of the invention there is provided a catalytic vessel for use in a hydroformylation reaction comprising or including: *0 88 4 4 ■ a chamber partially, substantially or entirely compared of, or supporting a homogenous catalyst or matrix of the invention. Preferably the vessel has at least two openings. Preferably the openings are an inlet and an outlet. Preferably at least one opening is covered by a liquid permeable barrier. Preferably one or both of the liquid permeable barriers is a porous barrier; more preferably one or both of the porous barriers is a ceramic porous barrier. According to a further aspect of the invention there is provided a continuous flow hydroformylation process comprising or including the steps of: i) continuously passing one or more olefins through a catalytic vessel of the invention, and ii) collecting a liquid containing the reaction products of the hydroformylation process. Preferably there is the further step of: iii) isolating products from the liquid containing the reaction products. According to a further aspect of the invention there is provided reaction products of a hydroformylation process produced according to the method described above. BRIEF DESCRIPTION OF THE FIGURES The invention will be more fully described below with reference to the accompanying figures in which: Figure 1 is a scanning electron microscope picture of a rhodium-containing calcium silicate, magnification 600:1. Figure 2 is an energy dispersive X-ray Spectrum of rhodium-containing calcium silicate. Figure 3a is a scatter plot for calcium, silicon and rhodium. Figure 3b is a magnification of rhodium rich regions of the matrix. The even distribution of pixels depicting the Si, Rh, and Ca elemental spatial elemental composition across the secondary electron image confirm the uniformity of composition of the particles. IPONZ 26 MAY 2003 5 0 8 8 4 4 10 Figure 4a is a further scatter plot for calcium, silicon and rhodium. Figure 4b is a magnification of regions of the matrix with equimolar parts of rhodium, calcium and silicon. The even distribution of pixels depicting the Si, Rh, and Ca elemental spatial elemental composition across the secondary electron image confirm the uniformity of composition of the particles. Figure 5 is an image of rhodium-containing calcium silicate derived from X-ray elemental mapping. The even distribution of pixels depicting the Si, Rh, and Ca elemental spatial elemental composition across the secondary electron image confirm the uniformity of composition of the particles. DETAILED DESCRIPTION OF THE INVENTION 1. Definitions Wherein this specification the following terms have been used, they have the following meanings: Linking/link: The linking metal cations (here (but not restricted to) Ca ions in the examples) link the silicate ions together under alkaline conditions to form the novel amorphous calcium silicate host structure into which the active catalytic metal entity can be incorporated 2. General We have surprisingly found that the use of rhodium-tri-polyethylene glycolate as the rhodium source with amorphous silicates form a novel homogeneous phase catalyst having improved performance over the prior art. Two important aspects of the novel catalyst are as follows: 2.1 Rhodium-Tri-Polyethylene Glycolate Bogdanovic et al (US 6,225,508- the whole of which is incorporated herein by way of reference) have disclosed the use Rhodium-Tri-Polyethylene Glycolate of a polyethylene glycol as a heterogeneous catalyst in water, polyethylene glycol or a mixture of the two as a solvent. Hydroformylation reactions are carried out under hydrogen or carbon monoxide, in water or polyethylene glycol, or a mixture of the IPONZ 26 MAY ?nm 50 8 B 4 4u two as a solvent. The reaction temperature is preferably between 50 -150C and at a pressure between 60-200 bar. As is disclosed in this publication, the rhodium tri (polyethylene glycolate) has the polyethylene glycol bound as a glycolate to the rhodium. 2.2 Amorphous Silica We have used, as the basis for our solid phase, homogeneous catalyst, the amorphous, metal rich silica products obtainable from aqueous solutions. A preferred means (but not necessarily the only means) of preparation and characterisation of these solids is disclosed by Johnston et al (in WO 00/786755 - the whole of which is incorporated herein by way of reference). 3 Preparation of the Novel Catalysts The invention will be illustrated below by way of examples. The examples provided are not intended to limit the invention. Rhodium polyethylene glycolate was synthesised from rhodium trichloride hydrate and polyethylene glycol 400 [5'6]. Characterisation: 'H NMR: 3.747 (-CH2OH, m), 3.510 (-0CH2CH20-H, t), 3.404 (-CH2OCH2CH2OCH2-, m), 1.917 (-CH2OH, t) ppm. IR (film): v = 3354 (st, br), 2056 (w, sh), 1989 (st, sh), 1734 (w, sh) cm"1. 3.1 General synthesis of a calcium silicate slurry[14] To a suspension of 2.313 g (31.2 mmol) of calcium hydroxide in 5 ml of water, 0.9 ml (1.81 g/cm3, 98 %, 16.3 mmol) sulphuric acid was added. The mixture was stirred for 30 minutes and then added to a solution of 6.52 g (23%, containing 25.0 mmol Si02) of sodium silicate in 40 ml water under vigorous stirring. It should be noted that the aqueous silicate solution may be obtained from artificial and geothermal methods as discussed in WO 00/786755. 508 2 Characterisation: IR (KBr) : v = 3418 (st, br), 2980 (w, sh), 2883 (w, sd), 1623 (m, sh), 1460 (m, br), 1388 (w, sd), 1154 (st, sh), 1094 (st, sh), 1017 (st, sd), 882 (m, sd), 802 (w, sh) 685 (st, sh), 598 (st, sh) cm"1. 'HNMR : 1.595 (s, H20), 1.293 (SiO H20), 0.879 (SiOH, m) ppm. 3.2 Rhodium-containing calcium silicate 1 Immediately after addition of the calcium suspension to the sodium silicate solution, 0.525 ml rhodium polyethylene glycolate solution (polyethylene glycol 400 containing 6.56 mg, 6.38 x 10~5 mol rhodium) was added to the calcium silicate slurry. The resulting slurry of rhodium-containing calcium silicate was stirred for 30 minutes, filtered and washed with 50 ml of water. The pale yellow filter cake was dried at 110 °C resulting in 3.88 g of 1. The filtrate was colourless and contained no detectable amount of rhodium. Water was removed from the filtrate, the residue dried at 110 °C and washed with alcohol. From the alcoholic solution 0.7 g of polyethylene glycol 400 was recovered. The pH before and after addition of the calcium mixture 9 1 was 11.2. The specific surface area was 109.9 m g" . The oil absorption was 157 g linseed oil per 100 g of 1. Characterisation: IR (KBr) : v = 3619 (w, sd), 3561 (w, sh), 3438 (st, br), 2931 (w, sh), 1630 (m, sh), 1447 (m, br), 1389 (w, sd), 1154 (st, sh), 1094 (st, sh), 1017 (st, sd), 882 (m, sd), 781 (w, sh) 669 (m, sh), 606 (m, sh) cm"1. !H NMR : 1.603 (s, H20), 1.303 (SiO H20), 0.892 (SiOH, m) ppm. 3.3 Synthesis of rhodium-containing calcium silicate 2 For the preparation of 2 1.050 ml (containing 13.1 mg, 1.28 x 10-4 mol rhodium) rhodium polyethylene glycolate solution was added to the slurry of calcium silicate immediately after the addition of the calcium mixture. A slurry of rhodium-containing calcium silicate resulted which was stirred for 30 minutes and then filtered. After washing and drying of the pale yellow filter cake at 110 °C, 3.89 g of 2 was isolated. No detectable amount of rhodium was found in the colourless filtrate. Water was removed from the filtrate, the white residue dried at 110 °C and washed with alcohol. From the alcoholic solution 1.4 g of polyethylene glycol 400 was able to be recovered. The pH before addition of the calcium mixture was 11.2. The pH after tPONZ 26 MAY . 50 88 4 4,, addition of the calcium and rhodium mixtures was 11.0. The specific surface area was 76.7 m2 g"1. The oil absorption was 128 g linseed oil per 100 g of 2. Characterisation: IR (KBr) : v = 3619 (m, sh), 3561 (m, sh), 3438 (st, br), 2931 (w, sh), 2873 (w, sd), 1624 (m, sh), 1459 (m, br), 1389 (w, sd), 1154 (st, sh), 1094 (st, sh), 1017 (st, sd), 882 (m, sd), 781 (w, sh) 669 (st, sh), 606 (st, sh) cm"1. *H NMR : 1.600 (s, H20), 1.288 (SiO H20), 0.916 (SiOH, m) ppm. 3.4 Synthesis of rhodium-containing calcium silicate 3 Similar to the preparation of 2 1.050 ml (containing 13.1 mg, 1.28 x 10-4 mol rhodium) rhodium polyethylene glycolate solution was added immediately. By gradual addition of sulphuric acid the pH of the resulting slurry of rhodium-containing calcium silicate was adjusted to 7.0. The reaction mixture was stirred for 30 minutes and then filtered. 3.60 g 3 in form of a slightly yellow filter cake was obtained after washing with 50 ml of water and drying at 110 °C. The filtrate was pale yellow in colour. After removal of water from the filtrate the red, solid residue was washed with ethanol. From the ethanolic solution 1.3 g of polyethylene glycol 400 was able to be recovered. The rest of the residue was dissolved in water and from the solution 4.3 mg (4.2 x 10"5 mol) of rhodium could be obtained. The pH before addition of the calcium mixture was 11.2. The pH after addition of the calcium and rhodium mixtures was 11.0. The end pH after pH adjustment was 7.0. The specific surface area was 89.2 m g"1. The oil absorption was 123 g linseed oil per 100 g of 3. Characterisation: IR (KBr) : v = 3619 (m, sh), 3561 (m, sh), 3430 (st, br), 2953 (w, sh), 2931 (w, sh), 2873 (w, sd), 1624 (m, sh), 1459 (m, br), 1389 (w, sd), 1154 (st, sh), 1094 (st, sh), 1017 (st, sd), 882 (m, sd), 800 (m, sh) 669 (st, sh), 606 (st, sh) cm"1. 'H NMR : 3.750 (-CH2OH, m), 3.530 (-0CH2CH20-H, t), 3.408 (-CH2OCH2CH2OCH2-, m), 1.890 (-CH2OH, t), 1.543 (s, H20), 1.255 (SiO H20), 0.879 (SiOH, m) ppm. 3.5 Synthesis of rhodium-containing calcium silicate 4 The preparation of 4 was carried out by rapidly adding 1.050 ml (containing 13.1 mg, 1.28 x 10"4 mol rhodium) rhodium polyethylene glycolate solution to the slurry of calcium silicate. The pH of the resulting slurry of rhodium-containing calcium silicate IPONZ 26 MAY 2003 14 was adjusted to 9.0 by addition of sulphuric acid. T itirred for 30 minutes and then filtered. The pale yellow filter cake was washed with 50 ml water and dried at 110 °C resulting in 3.80 g of 4. From the pale yellow filtrate water was removed and the yellow residue washed with alcohol. From the alcoholic solution 1.3 g of polyethylene glycol 400 was recovered. From an aqueous solution of the residue approximately 0.8 mg (7.8 x 10~6 mol) of rhodium was obtained. The pH before addition of the calcium mixture was 11.2. The pH after addition of the calcium and rhodium mixtures was 11.0. The end pH after pH adjustment was 9.0. The specific surface area was 108.6 m2 g"1. The oil absorption was 143 g linseed oil per 100 g of 4. Characterisation: IR (KBr) : v = 3621 (m, sh), 3561 (m, sh), 3440 (st, br), 2959 (w, sh), 2931 (w, sh), 2873 (w, sd), 1624 (m, sh), 1459 (m, br), 1389 (w, sd), 1154 (st, sh), 1094 (st, sh), 1017 (st, sd), 870 (m, sd), 799 (m, sh) 669 (st, sh), 606 (st, sh) cm"1. NMR : 3.750 (-CH2OH, m), 3.530 (-0CH2CH20-H, t), 3.407 (-CH2OCH2CH2OCH2-, m), 1.900, (-CH2OH, t), 1.576 (s, H20), 1. SiO H20), 0.870 (SiOH, m) ppm. 3.6 Synthesis of rhodium-containing calcium silicate 5 A solution of 33.7 mg (1.28 x 10"4 mol) rhodium trichloride hydrate in 0.5 ml water was added to the calcium silicate mixture immediately after addition of the calcium solution and the resulting slurry of rhodium-containing calcium silicate was stirred for 30 minutes and then filtered. The pale yellow filter cake was washed with 50 ml of water. After drying it at 110 °C a yield of 3.85 g of 5 was obtained. The colourless filtrate collected contained no detectable amount of rhodium. (16.0 + 0.4) mg of chloride was found via titration of the filtrate with silver nitrate. The pH before addition of the calcium mixture was 11.2. The pH after addition of the calcium and 2 1 rhodium mixtures was 10.6. The specific surface area was 69.6 m g" . The Oil absorption was 125 g linseed oil per 100 g of 5. Characterisation: IR (KBr) : v = 3625 (m, sh), 3561 (m, sh), 3440 (st, br), 2931 (w, sh), 2873 (w, sd), 1619 (m, sh), 1459 (m, br), 1391 (w, sd), 1154 (st, sh), 1094 (st, sh), 1017 (st, sd), 870 (m, sd), 783 (m, sh) cm"1. lH NMR : 1.545 (s, H20), 1.249 rSiO HoOY 0 863 fSiOH m) ppm. i'ELLECTUAL PROPERTY OFFICE OF N.Z . 2 E MAY 2003 "CEIVF' 3.7 Synthesis of rhodium-containing calcium silicate 6 Similar to the preparation of 5 a solution of 33.7 mg (1.28 x 10-4 mol) rhodium trichloride hydrate in 0.5 ml water was added rapidly to the calcium silicate slurry and the pH was adjusted to 9.0 using sulphuric acid. The resulting rhodium-containing calcium silicate mixture was stirred for 30 minutes and then filtered. The pale yellow filter cake was washed with 50 ml of water and dried at 110 °C resulting in 3.82 g of 6. The filtrate was pale yellow coloured and contained approximately 0.5 mg (4.9 x 10"6 mol) of rhodium. (15.7 ± 0.4) mg of chloride was determined by titration of the filtrate with silver nitrate. The pH before addition of the calcium mixture was 11.2. The pH after addition of the calcium and rhodium mixtures was 10.6. The end pH 2 1 • after pH adjustment was 9.0. The specific surface area was 108.6 m g" . The oil absorption was 141 g linseed oil per 100 g of 6. Characterisation: IR (KBr): v = 3621 (m, sh), 3561 (m, sh), 3440 (st, br), 2930 (w, sh), 2873 (w, sd), 1624 (m, sh), 1445 (m, br), 1385 (w, sd), 1154 (st, sh), 1094 (st, sh), 1017 (st, sd), 870 (m, sd), 799 (m, sh) cm"1. 'H NMR : 1.605 (s, H20), 1.293 (SiO H20), 0.906 (SiOH, m) ppm. XRD (Kai wavelength : 1.54056 A; K^ wavelength : 1.54439 A; Kai/K„2 ratio 0.50000; Ka : 1.54056 A; Kp wavelength : 1.39222 A) : 6.02819 (55.86 %), 4.35711 (7.46 %), 3.47207 (58.17 %), 3.00823 (100.00 %), 2.80728 (80.90 %), 2.72261 (19.47 %), 2.34454 (13.00 %), 2.14243 (13.80 %), 1.90977 (10.99 %) 1.84801 (33.35 %), 1.73964 (5.05 %), 1.69496 (11.20 %), 1.35544 (0.87 %), 1.30201 (5.89%), 1.28662 (7.43 %). 4. Structural and Chemical Characterisation Scanning electron microscopy equipped with energy dispersive X-ray analysis has been used to study the structure and composition of these new rhodium-containing calcium silicates. Scanning electron microscopy shows a uniform porous bulk structure of the rhodium-containing calcium silicates (figure 1). Calcium sulfate impurities appear as small white spots. The presence of these impurities is confirmed by X-ray powder diffraction. 2 6 MAY 2003 50 88 A A The energy dispersive X-ray spectrum of the surface of a bulk particle is presented in figure 2. The spectrum shows the main components to be Si and Ca in essentially equal amounts, with a smaller quantity of S from the calcium sulfate impurity. The Rh content is very small and is only just above background. Precise analysis of Rh was carried out by a chemical method. Element distribution and correlation maps in the form of scatter plots for Ca, Si and Rh were calculated from the X-ray mapping data collected across a rhodium-containing calcium silicate particle (figures 3 and 4). As expected, this shows a strong correlation between Ca and Si. In these maps, points which are close to the apices of the triangle represent a phase with a significant enrichment in the particular element concerned. Points which group in the centre of the triangle represent particles with a uniform distribution of elements within it. The scatter plots essentially show this even distribution of the elements that suggest the particles essentially have a uniform composition. In particular no zones with high Rh content can be found on the particle surface as would be expected if the Rh was not evenly distributed within the particle structure (figures 3-5). The region of interest is magnified and the data presented as a pseudo compositional image in figure 8. The essentially uniform distribution of the Rh similarly shows that it is uniformly distributed through the particle and correlates with Ca and Si (figure 3 and 4). The infrared spectra of the rhodium-containing calcium silicates are similar to those of amorphous calcium silicates. This was expected due to the small amount of rhodium incorporated into the structure. However additional two weak signals at 3619 and 3561 cm"1 are present. These signals shift if the sample is treated with D20 to 2588 and 2543 cm"1 and can therefore be attributed to hydroxyl groups. For the preparation of the rhodium-containing calcium silicates (above), rhodium polyethylene glycolate (silicates 1, 2, 3 and 4) and rhodium trichloride hydrate (silicates 5 and 6), have been used. In the *H nuclear magnetic resonance ('H-NMR) spectra the expected signals for water and hydroxy groups are observed. The silicates 3 and 4 contain traces of polyethylene glycol. During the preparation of these two 508844 17 silicates and silicate 6 the pH of the reaction mixture was adjusted to pH = 7.0 for 3 and to pH = 9.0 for 4 and 6. As a consequence of the pH adjustment some of the rhodium was washed out of the silicate. It was recovered so the exact rhodium content of the silicate could be determined (Table 1). Additionally, the residual amounts of polyethylene glycol and chloride from the preparation were determined. The silicates 5 and 6 contain no residual chloride. The 'H-NMR spectra showed some polyethylene glycol residue in 3 and 4. For silicates where the pH was adjusted to pH = 9.0 (4 and 6), the specific surface area and oil absorption increased in comparison to the silicates prepared without pH adjustment (2 and 5) (Table 1). Further addition of acid led to a decrease of these values (3). Silicate 1 contains the smallest amount of rhodium. Table 1: Comparison of rhodium content, oil absorption and specific surface area. Silicate Rhodium Rhodium PH Oil absorptionc Specific surface content [mol retention adjustment [g oil. 100 g"1] area [m2 g"1] g-V [%]" 1 1.64 x 10"5 100 - 157 110 2 3.29 x 10'5 100 - 128 77 3 2.31 x 10-5 67 to pH 7.0 123 89 4 3.16 x 10-5 94 to pH 9.0 143 109 5 3.29 x 10"5 100 - 125 70 6 3.22 x 10"5 96 to pH 9.0 141 109 "Rhodium content: mol rhodium . g'1 rhodium-containing calcium silicate. bRhodium retention: percent rhodium incorporated into rhodium-containing calcium silicate. pH adjustment to pH = 9.0 resulted in a rhodium loss of an average of 5 %. cThe results of the oil absorption are subjective and can only be compared for one operator, they do not represent objective results. Thus, if equimolar quantities of Ca2+ (1 mol of CaO to 1 mol of SiC^) are added to the silicate solution at a pH of greater than about pH = 10, an amorphous calcium silicate is produced. Depending upon the exact method of preparation, the calcium silicate 50884^ l8 material typically has a high oil absorption of up to 200 - 400 g oil per 100 g silicate and a high surface of up to about 200 - 300 m2 g"1 [14]. 5 Catalytic hydroformylation of olefins using rhodium-containing calcium silicates 5.1 Catalysis test Hydroformylation reactions were carried out in a Parr Minireactor 4560 (300 ml) equipped with temperature, stirring and pressure control device. The consumption of carbon monoxide and hydrogen gas was monitored at constant pressure by the pressure drop from a gas reservoir. The pressure in the reservoir was recorded using a pressure transducer and recorder system. 5.2 Hydroformylation reactions For a typical experiment the formation of the catalyst was carried out by charging the reaction vessel with 270 mg of a rhodium-containing calcium silicate either as a dry powder or dispersed in 20 ml toluene, and the reaction gas (H2 / CO, 7 MPa). Under stirring the autoclave was heated to 80 °C for 1 hour. Then the olefin (20.0 ml) and n-nonane (1.00 ml, 0.718 g / cm , 5.60 mmol) as internal standard were added. The reaction mixture was stirred (1000 rpm) for 5 h at 80 °C and the consumption of reaction gas was recorded. Catalytic reactions were terminated by depressurization after cooling in a water bath. The catalyst was filtered off and the product phase was analysed. 5.3 Results & Discussion The new rhodium-containing calcium silicates show a very high activity in the hydroformylation of olefins. As they are a solid, they can be separated from the product phase by simple filtration and be reused several times without any evidence of degradation (Table 2). This simple application provides the opportunity of using the new rhodium-containing calcium silicate catalysts in a continuous process where the catalyst is contained between two layers of porous ceramic and the reactants enter at one end and the product leaves at the other end. The porous nature of the new rhodium-containing calcium silicates is essential to this type of application. 50 88 A ^ » Table 2: Example for the hydroformylation of hex-l-ene using fresh and recycled rhodium-containing calcium silicate. Silicate Rhodium concentration [mol x 10"6 (ppm)]c Conversion [mmol (%)]d Selectivity Iso/ne TOF [mol mol"1 h"1]f 5a 8.88 (27.9) 135 (75.1) 0.57 3040 5 recycled b 0.82 (2.6) 13 (7.0) 0.55 3050 Conditions: Reaction temperature 80 °C; 20 ml (0.72 g cm"1, 171 mmol) hex-l-ene; 7 MPa hydrogen : carbon monoxide (1 : 1); 2 ml n-nonane internal standard; 20 ml toluene; 270 mg silicate; 5 h. bConditions: Reaction temperature 80 °C; 20 ml (0.72 g cm"1, 171 mmol) hex-l-ene; 7 MPa hydrogen : carbon monoxide (1 : 1); 2 ml n-nonane internal standard; 25 mg silicate recycled froma; 5 h. cRhodium concentration of the reaction mixture in mol and ppm dPercent conversion - mmol products per mmol olefin; material balance 99 %: loss of olefin occurs during charging and depressurization of the autoclave. Selectivity of branched aldehydes + non-volatile products per linear aldehydes; 5 % of non-volatile products were found. fTurnover frequency - mol aldehyde per mol rhodium per hour. Because of the small amounts of catalyst used in this laboratory scale development, the recovery of the pure catalyst by filtration was somewhat difficult. This would not be the case for a larger or industrial scale operation. Toluene was therefore added to improve product separation and filtration of the small amounts of catalyst used. The results for the hydroformylation of hex-l-ene with the rhodium-containing calcium silicates show a correlation between the specific surface area and the activity (expressed as turnover frequency (TOF) in mol aldehyde per mol rhodium per hour) (Table 3). Although the differences in activity and properties of the rhodium-containing calcium silicates are significant, the overall conversion is very similar for all the new rhodium-containing calcium silicates tested. This divergence between conversion and activity is due to the absorption of the olefins into the pores and desorption of the products being the limiting step of the process. A comparatively high amount of non-volatile products was found in all catalytic tests. These are probably oxidation products that are formed due to the relatively high number of hydroxy groups in the silicates. '£0E^LOFP,gERTV 2 6 MAY 2003 5 0 8 B 4 A 20 A comparison for the hydroformylation of hex-l-ene using rhodium-containing calcium silicate or rhodium polyethylene glycolate is shown in Table 3. Rhodium polyethylene glycolate is applied as a phase transfer catalyst with the hydroformylation reaction occurring at the phase boundary between aqueous and substrate phase. Rhodium-containing calcium silicate performs in the direct comparison of the hydroformylation results better than rhodium polyethylene glycolate. It is 3.5 to 7.5 times more active and shows a higher selectivity towards the linear aldehydes. The amount of rhodium sufficient to provide nearly complete conversion is by a factor of 4 to 8 less for the application of rhodium-containing calcium silicate. For the hydroformylation with rhodium polyethylene glycolate a phosphine had to be added to minimise the loss of catalytic material. This was not necessary for rhodium-containing calcium silicate because the silicate is insoluble in the product. In case of rhodium polyethylene glycolate the product has to be separated from the aqueous catalyst phase in a phase separator. For the silicate catalyst easier filtration can be applied. Table 3: Hydroformylation of hex-l-ene using rhodium-containing calcium silicates. a Silicate Rhodium concentration [mol x 10"6 (ppm)]b Specific surface area [mlg1] Conversion [mmol (%)]0 Selectivity isoln d TOF [mol mol"1 h"1]e 1 4.43 (13.9) 109.9 135 (75.1) 0.59 6096 2 8.88 (27.9) 76.7 130 (72.5) 0.58 2926 3 6.24 (19.6) 89.2 150 (83.1) 0.67 4810 4 8.53 (26.8) 108.6 144 (80.3) 0.57 3375 5 8.88 (27.9) 69.6 135 (75.1) 0.57 3040 6 8.69 (27.3) 108.6 153 (84.8) 0.51 3519 Rh- PEGf 31.7(86.0) - 162(95.0) 1.08 833 ,ELkf9™AL PROPERTY OFFICE OF ISI.Z 2 6 MAY 2003 "CEIvr 5 0 B 8 4 4 2i Conditions: Reaction temperature 80 °C; 20 ml (0.72 g cm'1, 171 mmol) hex-l-ene; 7 MPa hydrogen : carbon monoxide (1 : 1); 2 ml n-nonane internal standard; 20 ml toluene; 270 mg silicate; 5 h. bRhodium concentration of the reaction mixture in mol and ppm. cPercent conversion - mmol products per mmol olefin; material balance 99 %: loss of olefin occurs during charging and depressurization of the autoclave. dSelectivity of branched aldehydes + non-volatile products per linear aldehydes; for the silicates 2 to 6 up to 5 % for 1 up to 3 % of non-volatile products were found. eTurnover frequency - mol aldehyde per mol rhodium per hour. For Comparison: Rh-PEG: Rhodium polyethylene glycolate dissolved in excess polyethylene glycol was applied as a phase transfer catalyst in the hydroformylation of hex-l-ene. Conditions: Reaction temperature 100 °C; 20 ml (0.72 g cm'1, 171 mmol) hex-l-ene; 20 ml water; 10 MPa hydrogen : carbon monoxide (1 : 1); 2 ml n-nonane internal standard; 0.25 ml polyethylene glycol containing the catalyst; 5 h. 4 equivalents of tris(3-sulfonatophenyl-phosphine) were added to prevent catalyst leaching. The specific surface area was not determined because the catalyst could not be isolated. 15'6] A comparison for the hydroformylation of hex-l-ene with and without addition of toluene shows that the toluene has no influence on the activity and selectivity of the process (Table 4). However, the amount of non-volatile products is reduced substantially for the solvent free conversion, which is a very significant attribute for these new rhodium-containing calcium silicates. Although the amount of rhodium in the catalyst varies significantly, the extent of conversion achieved with the different rhodium-containing calcium silicates is comparatively similar. This is due to the reaction being diffusion controlled. As the actual catalytic process is very fast, the rate of absorption of olefins into the silicates and the rate of desorption of the aldehydes limit the activity. Therefore the pore size of the rhodium-containing calcium silicates has probably a more significant effect on the turnover frequency than does the actual rhodium content. 7ELLECTUAL PROPERTY OFFICE OF N.Z 2 6 MAY 2003 •"CEIVE 5 0 8 8 4 422 Table 4: Comparison of the hydroformylation of hex-l-ene using rhodium-containing calcium silicate 3 without solvent and dispersed in toluene. Silicate Rhodium concentration [mol x 10"6 (ppm)]c Conversion [mmol (%)]d Selectivity Iso/n e TOF [mol mol"1 h"1]f 3 (dispersed in toluene)a 6.24(19.6) 150 (83.1) 0.67 4810 3 (without solvent)b 4.85 (32.6) 112(65.5) 0.68 4618 Conditions: Reaction temperature 80 °C; 20 ml (0.72 g cm"1, 171 mmol) hex-l-ene; 7 MPa hydrogen : carbon monoxide (1 : 1); 2 ml n-nonane internal standard; 20 ml toluene; 270 mg silicate; 5 h. bConditions: Reaction temperature 80 °C; 20 ml (0.72 g cm'1, 171 mmol) hex-l-ene; 7 MPa hydrogen : carbon monoxide (1 : 1); 2 ml n-nonane internal standard; 210 mg silicate; 5 h. °Rhodium concentration of the reaction mixture in mol and ppm dPercent conversion - mmol products per mmol olefin; material balance 99 %: loss of olefin occurs during charging and depressurization of the autoclave. Selectivity of branched aldehydes + non-volatile products per linear aldehydes; for the hydroformylation with toluene 5 % and for the hydroformylation without a solvent 2 % of nonvolatile products were found. f Turnover frequency - mol aldehyde per mol rhodium per hour. The loss of the catalyst into the product phase was also tested. A detectable amount of rhodium was found in the product phase for the silicates 2 and 5 only. This may be due to the fact that silicate 1 contains less rhodium and therefore the amount of rhodium in the product phase was below detection level. For silicates 3, 4 and 6, any loosely bound rhodium was washed out of the particles during the pH adjustment and hence only strongly bound rhodium remained in the catalyst. A study of the rhodium-containing calcium silicates after the hydroformylation revealed no changes in their properties. This suggests that if carbonyl species are formed during the reaction they are not stable enough to be detected. For the hydroformylation of oct-l-ene, similar results to these for hex-l-ene were obtained (conversion 104 mmol (76.1 %); 8.6 % non-volatile products; iso/n /ELLECTUAL PROPERTY OFFICE OF N.Z 2 6 MAY 2003 "rnciwc * 508844 2j selectivity 0.63; TOF 2529 mol product per mol rhodium per hour). The amount of non-volatile products formed was doubled. 6. General Experimental Comments/Notes Reactions and measurements were carried out in air and unless otherwise stated at room temperature. Synthesis gas, 99.90 % H2 : CO, 1:1, was obtained from Gerling. The solvents used were distilled prior to use. NMR spectra were measured using a Varian Inova 300 MHz spectrometer at room temperature. Tetramethylsilane was used as an external standard for 'h NMR. The key to NMR data is : s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet. Infrared spectra were recorded on Bio-Rad FTS-7 and Perkin Elmer System 2000 NIR FT-Raman spectrometers. The samples were prepared either as KBr pellets (KBr) or as film between KBr plates (film). The key to IR data is : st, strong; m, medium; w, weak; br, broad; sh, sharp; sd, shoulder. Scanning electron micrographs were recorded using a Philips SEM 505 scanning electron microscope with the samples being carbon or gold coated prior to measurements. Copper was used as standard for Energy Dispersive X-ray Analysis (EDS) and X-ray maps obtained using the Philips SEM 505 scanning electron microscope. The amount of rhodium not incorporated into the silicate structure was analysed gravimetrically as the trichloride [15]. The results are recorded in mg of rhodium. The quantitative analysis of the reactant and hydroformylation products was determined via a HP 6890 Series GC gas chromatograph equipped with a HP-5 column 30 m x 0.32 mm x 0.25 (am and FID detector, using internal standards. The carrier gas was helium. The specific surface area was determined using a Micrometrics Flowsorb II 2300 by measurement of desorption of 30 % nitrogen and 70 % helium at 21°C and 1 atm. The oil absorptions were measured using linseed oil spatula rubout method. The X-ray powder diffraction patterns were measured on a Philips PW 3710 mpd controlled diffractometer. 7. Summary Rhodium-containing calcium silicates are stable and highly active in the hydroformylation of olefins. The rhodium is an integral part of the structure and is evenly distributed on the surface of these porous silicates. By pH-adjustment to a lower more neutral or slightly alkaline pH value, the structural integrity of the silicates can be increased with no subsequent loss of catalytic material into the IPONZ 26 MAY 2003 24 4 product phase being detectable for these catalytic mate^IsMheSmodTum-containing calcium silicates can be separated by simple filtration from the product phase. As the substrate or reactant is absorbed into the solid catalytic material where it is converted solvents are redundant. Therefore the rhodium-containing calcium silicates offer the opportunity for using the catalyst in a continuous hydroformylation process. The present invention also provides a novel method for the synthesis of a transition metal-containing silicate matrix, with rhodium as the metal in the form of a rhodium-containing calcium silicate, for catalysts in the hydroformylation of olefins. As clearly distinct from the existing systems where the solid phase is used as a simple carrier, the rhodium in the new rhodium-containing calcium silicate described herein is integral to the silicate structure, forming a stable compound with unique properties and high catalytic activity. The method leaves the polar phase redundant via the application of a novel solid phase catalyst. Although the examples described deal with rhodium as the catalytic metal it is known by skilled workers in the art that a number of other metals catalyse, or have the ability to catalyse hydroformylation reactions and the scope of this invention includes those metals. In particular Co, Mo, V, Cr., Mn and Fe are included. I ! 2 6 MAY 2003 .ELLECTUAL PROPERTY OFFICE OF N.Z CEIVF 508844 References [1] B. Cornils, W. A. Herrmann, R. W. Eckl, J. Molec. Catal. A: Chemical 1997, 116, 27. [2] W. A. Herrmann, C. W. Kohlpainter, Angew. Chem. 1993, 105, 1588; Angew. Chem. Int. Ed. Engl. 1993, 32, 1524. [3] Edit. B. Cornils, W. A. Herrmann, Applied Homogeneous Catalysis with Organometallic Compounds, VCH Weinheim, New York, Basel, Tokyo 1996. [4] Edit. B. Cornils, W. A. Herrmann, Aqueous-Phase Organometallic Catalysis, VCH Weinheim 1998. [5] U. Ritter, T Borrmann, S. Bogdanovic, H. W. Roesky, Hoechst AG, Patent 1997, US 6,225,508. [6] T. Borrmann, H. W. Roesky, U.Ritter, J. Molec Catal A: Chemical 2000, 153, 31. [7] N. Takahashi, M. Kobayashi, J. Catal. 1984, 85, 89. [8] Edit. P. A. Jacobs, N. I. Jaeger, P. Jiru, G. Schulz-Eklov, Studies in Surface Science and Catalysis: Metal Microstructures in Zeolites, Elsevier Amsterdam 1982,12. [9] E. Rode, M. E. Davis, B. E. Hanson, J. Chem. Commun. 1985, 1477.

[10] B. E. Hanson, M. E. Davis, D. Taylor, Inorg. Chem. 1984, 23, 52.

[11] M. E. Davis, E. Rode, D. Taylor, B. E. Hanson, J. Catal. 1984, 86, 67.

[12] E. Rode, M. E. Davis, B. E. Hanson, J.Chem. Soc. Chem. Commun. 1985, 716.

[13] Seminar at Degussa, Frankfurt 1999.

[14] R. T. Harper, J. H. Johnston, N. Wiseman, Tasman Pulp & Paper Co., Limited, Geochemistry Research Limited 1997, US 5,595,717.

[15] GMELIN Handbuch der Anorganischen Chemie, 8 edn., Verlag Chemie 1938, Vol. Rh. 'S^L0FPRN0iER^ 2 6 MAY 2003 . ICEIVF- 1 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 50 88 A A 26 WHAT WE CLAIM IS:

1. A homogeneous catalyst for hydroformylation reactions comprising or including: a) a substantially amorphous calcium silicate host, and b) a plurality of metal cationic species capable of catalysing a hydroformylation reaction, coordinated or bound to the host.

2. A catalyst as claimed in Claim 1 wherein the calcium silicate host is porous in nature and wherein, relative to a non-porous host, the porosity gives rise to: i) an increased number of chemical binding sites for the metal cationic species to the calcium silicate host, and ii) increased access to and/or from the metal cationic species (and pre-cursor species and/or products thereof) by reactants in a hydroformylation reaction.

3. A catalyst as claimed in Claim 2 wherein the metal cationic species are Rh(III) species.

4. A catalyst as claimed in Claim 3 wherein the Rh(III) species are dispersed substantially uniformly throughout the calcium silicate host.

5. A catalyst as claimed in Claim 4 wherein the Rh(III) species are chemically bound or coordinated to the calcium silicate host, rather than simply being supported by the host.

6. A catalyst as claimed in Claim 4 or 5 wherein the calcium silicate host has a microplate-like structure, the Rh(III) species being bound or coordinated to the surface(s) of the microplates.

7. A catalyst as claimed in Claim 6 wherein the dimensions of the microplates are substantially between 5-10 nanometres thick by 20-100 nanometres wide. •euktual property OFFICE OF N.Z 2 6 MAY 2003 ~QE!VF 508844 27

8. A catalyst as claimed in Claim 7 wherein the pH of the catalyst, or achieved in the preparation of the catalyst, is substantially between pH=7 and pH=l 1.

9. A catalyst as claimed in Claim 8 wherein the calcium silicate host originates from geothermal, silica rich, aqueous systems.

10. A homogeneous catalyst for hydroformylation reactions substantially as herein described with reference to any one or more of the Examples and/or Figures.

11. A matrix effective as, or providing, a hydroformylation catalyst, comprising or including: a) silicate, and b) a metal catalyst linked thereto, wherein: i) the silicate is a substantially amorphous calcium silicate structure, and ii) the metal catalyst is a transition metal ion suitable for use as a catalysing species in a hydroformylation process.

12. A matrix as claimed in Claim 11 wherein the metal catalyst is an ion of a metal selected from the list consisting of: Co, Mo, V, Cr, Mn, Fe, Pt, Au, W, Ir, Re, Ru, Os, Ag, Pd and Rh.

13. A matrix as claimed in Claim 12 wherein the metal catalyst is an ion of a metal selected from the list consisting of: Co, Mo, V, Cr, Mn, Fe and Rh.

14. A matrix as claimed in Claim 12 wherein the metal catalyst is an ion of a metal selected from the list consisting of: Co, Os, Ru, Pd and Rh.

15. A matrix as claimed in any one of Claims 11 to 14 wherein the metal catalyst is rhodium ions, the rhodium ions existing as Rh(III) ions throughout the calcium silicate structure. 5088H

16. A matrix as claimed in Claim 15 wherein the calcium silicate structure is porous in nature and wherein, relative to a non-porous structure, the porosity gives rise to: i) an increased number of chemical binding sites for the Rh(III) ions to the calcium silicate structure, and ii) increased access to and/or from the Rh(III) ions (and pre-cursor species and/or products thereof) by reactants and/or products in a hydroformylation reaction.

17. A matrix as claimed in Claim 16 wherein the Rh(III) ions are dispersed substantially uniformly throughout the calcium silicate structure.

18. A matrix as claimed in Claim 17 wherein the Rh(III) ions are chemically bound or coordinated to the calcium silicate structure, rather than being simply supported by the calcium silicate structure.

19. A matrix as claimed in Claim 17 or 18 wherein the amorphous calcium silicate has a microplate-like structure, the Rh(III) ions being bound or coordinated to the surface(s) of the microplates.

20. A matrix as claimed in Claim 19 wherein the dimensions of the microplates are substantially between 5-10 nanometres thick by 20-100 nanometres wide.

21. A matrix effective as, or providing, a hydroformylation catalyst substantially as herein described with reference to any one or more of the Examples and/or Figures.

22. A method of preparing a homogeneous catalyst for hydroformylation reactions comprising or including the steps of: A) contacting or mixing: ■ a solution containing silicate species, with ■ a source of calcium cations, ■ a source of metal catalyst species, being transition metal ions suitable for use as catalysing species in a hydroformylation process, such that the metal catalyst species bind with the silicate, and . ELLECTUAL PROPERTY OFFICE OF N.Z 2 6 MAY 2003 "OEIVF 508844 29 B) recovering the homogeneous catalyst as a solid phase product.

23. A method as claimed in Claim 22 wherein the solid phase product precipitates out of solution.

24. A method as claimed in Claim 23 wherein the source of the metal catalyst species is mixed with the solution containing the silicate species before or during precipitation of the solid phase product.

25. A method as claimed in Claim 24 wherein precipitation is caused by contacting the solution containing the silicate species with the source of calcium cations.

26. A method as claimed in Claim 25 wherein the source of the calcium cations is calcium hydroxide.

27. A method as claimed in Claim 26 wherein the solution containing the silicate species is, or originates from, geothermal, silica rich, aqueous systems.

28. A method as claimed in any one of Claims 22 to 27 wherein the metal catalyst species is an ion of a metal selected from the list consisting of: Co, Mo, V, Cr, Mn, Fe, Pt, Au, W, Ir, Re, Ru, Os, Ag, Pd and Rh.

29. A method as claimed in Claim 28 wherein the metal catalyst species is an ion of a metal selected from the list consisting of: Co, Mo, V, Cr, Mn, Fe and Rh.

30. A method as claimed in Claim 28 wherein the metal catalyst species is an ion of a metal selected from the list consisting of: Co, Os, Ru, Pd and Rh.

31. A method as claimed in any one of Claims 22 to 30 wherein the metal catalyst species is Rh(III) ions. 50 88 44 30

32. A method as claimed in Claim 31 wherein the source of the Rh(III) ions is water-soluble.

33. A method as claimed in Claim 32 wherein the source of the Rh(III) ions is selected from a polyethylene glycolate or a chloride hydrate.

34. A method as claimed in any one of Claims 22 to 33 wherein the solution containing silicate species (before, during or after contact with the source of metal catalyst species) is pH adjusted to increase binding of the metal catalyst species with the silicate.

35. A method as claimed in Claim 34 wherein the pH is adjusted to be substantially between pH=6.0 and pH=12.5.

36. A method as claimed in Claim 35 wherein the pH is adjusted to be substantially between pH=7.0 and pH=9.0.

37. A method as claimed in Claim 36 wherein there is further the step of acid washing of the recovered solid phase product to remove surface bound calcium ions and/or facilitate a redistribution of the silicate material to increase the structural robustness and stability of the catalyst.

38. A method as claimed in any one of Claims 22 to 37 wherein the solution containing silicate species is sodium silicate, the source of calcium cations is calcium hydroxide and the source of the metal catalyst species is rhodium polyethylene glycolate or rhodium trichloride hydrate.

39. A homogeneous catalyst for hydroformylation reactions as prepared by the method of any one of Claims 22 to 38.

40. A method of catalysing the hydroformylation of one or more olefins comprising or including the steps of: ELLECTUAL PROPERTY OFFICE OF N1 2 6 MAY 2003 "OEIVF 5 4 4 31 a) Reacting one or more olefins with a CO/H2 gas in the presence of a homogeneous catalyst or matrix as claimed in any one of claims 1 to 19 or 35; b) Separating the hydroformylation product(s) from the catalyst or matrix (or vice versa).

41. A method as claimed in Claim 40 wherein the catalyst or matrix is separated by filtration.

42. A method as claimed in Claim 41 wherein the product(s) are one or more of a liquid phase aldehyde, carboxylic acid or alcohol.

43. A product formed by the method of catalysing the hydroformylation of one or more olefins as claimed in any one of Claims 40 to 42.

44. A catalytic vessel for use in a hydroformylation reaction comprising or including: ■ a chamber partially, substantially or entirely composed of, or supporting a homogenous catalyst or matrix as claimed in any one of Claims 1 to 21 or 39.

45. A catalytic vessel as claimed in Claim 44 wherein the vessel has at least two openings.

46. A catalytic vessel as claimed in Claim 45 wherein the openings are an inlet and an outlet.

47. A catalytic vessel as claimed in Claim 46 wherein at least one opening is covered by a liquid permeable barrier.

48. A catalytic vessel as claimed in Claim 47 wherein one or both of the liquid permeable barriers is a porous barrier.

49. A catalytic vessel as claimed in Claim 48 wherein one or both of the porous barriers is a ceramic porous barrier. ELLECTUAL PR0PERT\ OFFICE OF N.Z 2 6 MAY 2003 'OEIVF 508844 32

50. A continuous flow hydroformylation process comprising or including the steps of: i) continuously passing one or more olefins through a catalytic vessel as claimed in any one of Claims 44 to 49, and ii) collecting a liquid containing the reaction products of the hydroformylation process.

51. A process as claimed in Claim 50 wherein there is the further step of: iii) isolating products from the liquid containing the reaction products.

52. Reaction products of a hydroformylation process produced according to the method of any one of Claims 50 or 51. </div>