GB2452259A - Method of catalysing a chemical reaction and preparation of the catalyst used therein - Google Patents

Method of catalysing a chemical reaction and preparation of the catalyst used therein Download PDF

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Publication number
GB2452259A
GB2452259A GB0716622A GB0716622A GB2452259A GB 2452259 A GB2452259 A GB 2452259A GB 0716622 A GB0716622 A GB 0716622A GB 0716622 A GB0716622 A GB 0716622A GB 2452259 A GB2452259 A GB 2452259A
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Prior art keywords
catalyst
metal cation
cation
examples
wool
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GB0716622A
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GB0716622D0 (en
GB2452259B (en
GB2452259B8 (en
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Katherine Huddersman
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De Montfort University
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De Montfort University
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Priority to GB0716622A priority Critical patent/GB2452259B8/en
Publication of GB0716622D0 publication Critical patent/GB0716622D0/en
Priority to ES08788424.3T priority patent/ES2613960T3/en
Priority to EP08788424.3A priority patent/EP2185271B1/en
Priority to PCT/GB2008/002864 priority patent/WO2009027649A2/en
Priority to PL08788424T priority patent/PL2185271T3/en
Priority to US12/675,054 priority patent/US8513303B2/en
Publication of GB2452259A publication Critical patent/GB2452259A/en
Publication of GB2452259B publication Critical patent/GB2452259B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B01J32/00—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

A method of catalysing a chemical reaction comprising the step of contacting one or more reactants with a catalyst, wherein the catalyst comprises a keratinous support and a first metal cation fixed to the keratinous support. The first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, under conditions for catalysis of the chemical reaction. Also disclosed is a method for preparing the catalyst, comprising treating the keratinous support with a hydrazine salt and a hydroxylamine salt in the presence of a base and treating the modified keratinous support with an aqueous solution comprising a salt of the first metal cation; a method for preparing the catalyst, comprising treating the keratinous support with a hydroxylamine salt, in the presence of a base and treating the modified keratinous support with an aqueous solution comprising a salt of a first metal cation and a salt of a second metal cation. Further disclosed, is the catalyst comprising a keratinous support, such as wool fibre and a first metal cation fixed to the keratinous support, such as wool fibre in an amount 0.03 or greater per gramme of the keratinous support.

Description

* 1 2452259 Catalyst The present invention relates to methods of catalysing a chemical reaction using a catalyst comprising a keratinous support (such as a wool fibre), to methods for preparing a catalyst comprising a keratinous support (such as a wool fibre) and to a catalyst comprising a keratinous support (such as a wool fibre). In particular, the present invention relates to methods of catalysis and to uses of catalysts comprising a keratinous support (such as a wool fibre) in the treatment of a waste stream.
The processes conducted in many industries, such as the chemical, pharmaceutical, petroleum chemical, photo-processing, pulp, leather, agro-chemical, furniture manufacturing and textile industries, produce waste streams that contain undesired compounds, for example that may be harmful to the environment. For example, waste streams that are produced in the textile industry (for example in dyeing and finishing processes) and that are produced in the pulp and leather industnes may contain undesired compounds such as sulfides. dyes, phenols, nonylphenols and other organic compounds. Waste streams that are produced in the photo-processing industry may contain undesired compounds such as amines, aminophenols, phenylenediamineS, triethanolamine, ethylenediaminetetraaCetic acid and other organic compounds. It is advantageous to treat these waste streams, so as to substantially remove the undesired compounds before further treatment and/or disposal or use.
Undesired organic compounds, such as those discussed above, may substantially be removed from waste streams by oxidative decomposition. This converts the undesired organic compound(s) into derivatives of these compounds which may then be more easily disposed of or, if appropriate, isolated and collected for use elsewhere.
The oxidative decomposition of an organic compound may be conducted by reaction with a transition metal cation and an oxidant, such as hydrogen peroxide or oxygen. This reaction is known as "Fentons chemistry (see, for example, Advanced Inorganic Chemistry, Cotton, Wilkinson, Murrillo and Bochmann, John Wiley and Sons, 1999, 6th edition, pages 458 and 459). Any transition metal cation that can easily undergo redox reaction to another oxidation state can participate in the Fentons chemistry reaction. For example, when the transition metal is iron, the iron cation Fe2 may react with hydrogen peroxide and be oxidised to form the Fe3 cation * 2 as well as a hydroxide anion and a hydroxyl radical. The hydroxyl radical can then act as an oxidising agent, for example to oxidise an organic compound. Non-transition metal cations cannot participate in the Fentons chemistry reaction because they have only one oxidation state.
The source of transition metal cations for use in such an oxidative decomposition reaction may be in the form of a homogeneous catalyst. The homogeneous catalyst typically comprises a transition metal salt or complex. The use of a homogeneous catalyst to treat waste streams has some disadvantages. For example, the homogeneous catalyst cannot be regenerated or recycled for further use. Additionally, the homogeneous catalyst introduces the transition metal(s) into the waste streams. This is undesirable because transition metals typically are toxic and potentially harmful to the environment. Thus, the transition metal(s) must be removed from the treated waste stream before further processing or disposal, which is costly, time consuming and difficult to perform.
In order to try to overcome the problems associated with homogeneous catalysts, heterogeneous catalysts were proposed. In use of a heterogeneous catalyst, only negligible amounts of metal are released into the waste stream and the catalyst can be regenerated or recycled for further use. However, reactions involving heterogeneous catalysts often are slow and difficult to regulate. This is because heterogeneous catalysts typically exist in a granulated form, which forms a packed bed or layer of the catalyst. This makes it difficult to pass a waste stream through the catalyst and limits access to the active sites of the catalyst.
Certain fibrous catalysts, which are catalysts comprised of polymer fibres to which catalytically active sites or centres are attached, have been suggested.
Fibrous catalysts have an increased exterior surface area compared to granulated heterogeneous catalysts, which typically improves access of the reactant substances to the catalyst active sites and improves the catalytic activity. The more accessible structure of the fibrous catalysts also typically makes it easier to pass a waste stream through the catalyst.
For example, GB-A-i,436,245 discloses catalysts for the oxidation of carbon monoxide and several processes for preparing the catalysts. The catalysts comprise * activated carbon fibres that carry active catalyst ingredients such as one or more of palladium, ruthenium, rhodium and platinum. GB-A-I,436,245 teaches that the S 3 activated carbon fibres may be made by subjecting carbon fibres to a known activation treatment and that the carbon fibres may be made by carbonising various fibres, including wool fibres.
Several catalysts are know that comprise polyacrylonitrile threads or fibres with metal cations fixed thereto. For example, RU-A-21 18908 discloses a textile fibrous bulked catalyst made in the form of a fabric including a carrier layer made from single filaments and modified ion-containing complex threads of polyacrylonitrile filaments including one or more ions of metal of variable valence.
GB-A-2,346,569 discloses methods for producing a fibrous catalyst. One method comprises the steps of treating a knitted fabric consisting of an inert filament and complex polyacrylonitrile threads with a hot alkaline solution of hydrazine hydrochloride and then with an aqueous transition metal salt solution. Another method comprises the steps of treating a fabric comprising polyacrylonitrile threads with an alkaline solution of a hydrazine salt, a hydroxylamine salt and sodium nitrite and then with a solution containing at least one transition metal salt.
V. V. lshtchenko et a/.(Applied Catalysis A: General 242 (2003), 123-137) discloses the preparation of a catalyst by impregnating a modified knitted mesh comprised of complex polyacrylonitnie threads and inert polypropylene support threads with a transition metal salt solution.
R. F. Vitkovskaya et a!. (Fibre Chemistry, 35(3) (2003), 202-207) discloses the preparation of a catalyst by treating modified complex polyacrylonitrile fibres with a concentrated solution of an iron salt.
RU-2266304 discloses catalysts for waste water and emission gas treatment.
The catalysts are prepared by treating a knitted fabric consisting of polyacrylonitrile monothreads and complex threads with a modifying solution of a chlorine-containing hydrazine salt and a chlorine-containing hydroxylamine salt and then with transition metal salts.
Co-pending International patent application number PCT/GB2007/00061 2 discloses the preparation of a catalyst by treating modified polyacrylonitrile fibres with an aqueous solution comprising a salt of a transition metal cation and a salt of a non-transition metal cation. S 4
Whilst the catalysts discussed above may be efficient at treating waste streams, there remains a need for alternative catalysts that are efficient in catalysis and that meet environmental and economical requirements.
The present invention provides a method of catalysing a chemical reaction, a method for preparing a catalyst and a catalyst comprising a keratinous support (such as a wool fibre). None of the prior art documents discussed above disclose a catalyst that comprises a keratinous support or wool fibre.
Wool is a well known and widely used material, for example in the manufacture of cloths, fabrics and carpets. It is known to use certain chemicals, such as hydroxylamine, as dye bath additives for example in the commercial dyeing of wool. Dye bath additives are believed to bind to reactive and unstable chemical groups in wool. For example it has been shown that amino acid residues in wool react with hydroxylamine so as to form pendant hydroxamic acid (i.e. -R-C(O)-NHOH, where R represents an organic residue) groups and that iron cations can complex to these groups (see, for example, WRONZ Technical Bulletin, S Simpson, Methods to reduce dye bath yellowing of wool, March 1997, WRONZ Report R213, W S Simpson, Reactions of Wool with Hydroxylamine, December 1997 and WRONZ Confidential Report, W S Simpson, Discolouration of Wool in Blank Dyebaths, January 1996). However, there has been no disclosure of the use of wool in catalysis.
According to one aspect of the present invention there is provided a method of catalysing a chemical reaction, wherein the method comprises the step of contacting one or more reactants with a catalyst, wherein the catalyst comprises a keratinous support and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, under conditions for catalysis of the chemical reaction.
According to another aspect of the present invention there is provided a method of catalysing a chemical reaction, wherein the method comprises the step of contacting one or more reactants with a catalyst, wherein the catalyst comprises a wool fibre and a first metal cation fixed to the wool fibre, which first metal cation is S 5.
selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt.
nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, under conditions for catalysis of the chemical reaction.
The method of the present invention of catalysing a chemical reaction, which uses a catalyst comprising a keratinous support (such as a wool fibre), provides very real advantages in use, for example in comparison to methods of the prior art that use alternative catalysts. For example, the catalysts comprising a keratinous support (such as a wool fibre) are economical and convenient to prepare, for example using starting materials that are readily available, cheap and safe to use.
The catalysts comprise materials that are available naturally, without substantial manufacturing and/or processing prior to their use in catalysis. Additionally, the used or spent catalysts are easily and conveniently disposed of. Furthermore, the catalysts are efficient in a range of chemical reactions, particularly in oxidation reactions, and can be used in a range of different conditions, such as at a range of different pHs (for example typically at a pH range of about 2 to 9.5). The catalysts also can be made into a range of forms suitable for being installed into different systems/devices.
The chemical reaction catalysed according to the method of the present invention may be any suitable chemical reaction. For example, the chemical reaction may be an oxidation reaction, for example in which one or more organic compounds is oxidised. The chemical reaction may alternatively be a hydrogenation reaction (for example when the first metal cation is a selected metal cation, such as a palladium cation).
The method of catalysing a chemical reaction includes the step of contacting the one or more reactants with the catalyst. The reactants and catalyst may be contacted in any suitable manner, for example by placing them in a suitable reaction vessel, preferably with agitation and/or stirring. Suitably, the catalyst may be contacted with the one or more reactants by means of a fluid medium. The fluid medium may be liquid or gaseous. The references herein to liquids include gels and pastes. The references herein to gases include vapours. As a person skilled in the art would appreciate, the fluid medium may comprise the one or more reactants and/or one or more additional solvents and/or carriers. * 6
When the chemical reaction is an oxidation reaction, the one or more reactants are suitably contacted with the catalyst in the presence of an oxidant. Any suitable oxidant may be used. Suitable oxidants include oxygen, ozone and peroxygen compounds (such as hydrogen peroxide). Typically, it is sufficient to conduct the chemical reaction in air, with the oxygen in the air acting as the oxidant.
The oxidant may be delivered using any suitable means. The particular means of delivering the oxidant will depend on the compound(s) being oxidised and the reaction conditions applied. For example, the oxidant may be delivered by bubbling air or oxygen into a reaction vessel containing the reactants and the catalyst.
The oxidant may, for example, be a peroxygen compound. Examples of suitable peroxygen compounds include hydrogen peroxide, hydrogen peroxide liberating compounds, hydrogen peroxide generating compounds, organic and inorganic peroxyacids and salts thereof, and mixtures thereof. For example, hydrogen peroxide liberating compounds include alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide and inorganic persalt bleaching compounds such as the alkali metal perborate, percarbonates1 perphosphates and persulfates. Organic peroxyacids include compounds containing one or more peroxycarboxyl groups (i.e. -C(O)-O-OH), such as peracetic add, performic acid and perpropionic acid. Further suitable oxidants include peroxyheptanoic acid, peroxynonanoic acid, perlaunc acid, monopergiutaric acid, dipergiutaric acid, succinylperoxide, derivatives of perbenzoic acid, magnesium salts of peroxyphthalate, peracid powders (for example made in situ by adding water to mixtures of organic acid reservoirs to hydrogen peroxide reservoirs such as sodium peroxide, benzoyl peroxide, t-butyl hydroperoxide) permanganates such as potassium permanganate. calcium peroxide and monoperoxy-sulfuric acid, and mixtures thereof.
Preferably, the chemical reaction catalysed by the method of the present invention is a chemical reaction conducted in a waste stream, for example to treat the waste stream so as to oxidise undesired organic compounds present in the waste stream. Such oxidation of the undesired organic compounds typically results in their decomposition and conversion into derivatives that may be disposed of or, if appropriate, isolated and collected for further use. Thus, the method of catalysing a chemical reaction may comprise the step of contacting one or more reactants in a waste stream with the catalyst. In other words, in such a method, the one or more reactants may represent one or more undesired organic compounds that it is desired S 7 to decompose and convert into derivatives. The one or more undesired organic compounds are typically contacted with the catalyst in the presence of an oxidant.
Thus, the present invention further provides a method of treating a waste stream by catalysing a chemical reaction, wherein the method comprises the step of contacting one or more reactants in the waste stream with a catalyst, wherein the catalyst comprises a keratinous support and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, under conditions for catalysis of the chemical reaction.
The present invention further provides a method of treating a waste stream by catalysing a chemical reaction, wherein the method comprises the step of contacting one or more reactants in the waste stream with a catalyst, wherein the catalyst comprises a wool fibre and a first metal cation fixed to the wool fibre, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, under conditions for catalysis of the chemical reaction.
A wide variety of waste streams comprising virtually any undesired organic compound(s) may be contacted with the catalyst according to the method of catalysing a chemical reaction of the present invention. In other words, the chemical reaction catalysed may comprise the oxidative decomposition of virtually any undesired organic compound(s). For example, the waste stream may originate from any suitable industry, including from the chemical, pharmaceutical, petroleum chemical, textile, pulp, leather, agro-chemical, furniture manufacturing and photo-processing industries, and may comprise virtually any undesired organic compound(s). In particular, the waste stream to be treated may contain one or more undesired organic compounds, for example the waste stream may contain one or more undesired phenol compounds and originate from an industry such as the paper or chemical industries. The waste stream to be treated may contain one or more undesired organic compounds, for example one or more undesired hormones.
As discussed above, the references to a chemical reaction conducted in a waste stream so as to treat the waste stream are intended to refer to the conversion of an undesired, potentially harmful, "waste" compound contained in the waste stream into a new derivative that typically is at least less harmful and/or easier to dispose of. In some cases, the new derivative formed may be useful in another process and/or application and may be isolated and/or collected, for further use.
When this is not the case, the new derivative that is formed typically will be collected and/or disposed of in any suitable manner. As discussed above, the conversion of the undesired "waste" compound into a new derivative typically is by the oxidative decomposition of that compound.
Examples of undesired, organic waste compounds that may be oxidised in the chemical reaction include one or more organic compounds selected from sulfides, thiols, dyes, phenols (including bisphenols, nonyiphenols and aminophenols), amines, phenylenediamines, triethanol amine, ethylenediamine and tetraacetic acid (for example one or more organic compounds selected from sulfides, dyes, phenols, nonyiphenols, aminophenols, amines, phenylenediamines, triethanol amine, ethylenediamine and tetraacetic acid, especially one or more organic compounds selected from phenols, nonylphenols and/or aminophenols).
The chemical reaction catalysed by the method of the present invention may not proceed to 100% reaction. For example, when the chemical reaction is an oxidation reaction, the catalysed chemical reaction may not convert 100% of the organic compound(s) (for example the undesired "waste" compound(s) in a waste stream) into the new derivative(s). As the skilled person would appreciate, the percentage conversion will depend on a number of factors, including the particular catalyst selected and the chemical reaction being conducted, which may depend on the composition of a waste stream being treated. It is expected that the oxidation reaction and catalysts of the present invention will generally convert from about 50% to about 100% by weight of the organic compound(s) (for example the undesired "waste" compound(s) in a waste stream) into the new derivative(s).
The method of catalysing a chemical reaction is conducted under conditions suitable for the catalysis of the chemical reaction. As the skilled person would appreciate, the particular conditions used will depend on a number of factors, including the particular chemical reaction being conducted and the particular catalyst used. Typically, a preferred pH is in the range of from 2 to 9.5. S 9
The one or more reactants are typically in the form of a fluid, which may be liquid or gaseous. For example, the one or more reactants may be provided in a waste stream, which waste stream is in the form of a fluid, which may be liquid or gaseous. In one aspect, the one or more reactants are provided in a waste stream which is in the liquid phase. For example, the liquid waste stream may be aqueous or organic based.
The waste stream may originate from any relevant process or industry, for example the waste stream may originate from the chemical, pharmaceutical, petroleum chemical, agro-chemical, textile, pulp, leather, furniture manufacturing or photo-processing industry, particularly from the textile, pulp or photo-processing industry.
Examples of dyes that may be oxidised in the catalytic method of the present invention include anthraquinone dyes, such as Acid Blue 45 and Natural Red 4, and azo dyes, such as Cetacid red 4G.
Examples of phenol compounds that may be oxidised in the catalytic method of the present invention include phenol, nonyipheriol (for example 4-nonyiphenol), as well as bisphenols (for example bisphenol A).
Examples of sulfide compounds that may be oxidised in the catalytic method of the present invention include dialkylsulfides (for example diethylsulfide).
Examples of thiol compounds that may be oxidised in the catalytic method of the present invention include alkyithiols (for example butylmercaptan).
An example of a hormone that may be oxidised in the catalytic method of the present invention is estrone (El).
The method of the present invention of catalysing a chemical reaction comprises the step of contacting one or more reactants with a catalyst. The catalyst comprises a keratinous support and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof. * 10
The first metal cations are all cations of transition metals. It is believed that the first metal cation forms a complex with reactive groups on the keratinous support, i.e. so as to fix the first metal cation to the keratinous support.
As the skilled person would appreciate, the particular first metal cation(s) used depends on the chemical reaction being catalysed, for example on the composition of a waste stream being treated, and on the reaction/treatment conditions applied.
In one aspect of the invention, the first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof. In another aspect of the invention, the first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper cation, and mixtures thereof. In another aspect of the invention, the first metal cation is selected from a titanium, chromium, manganese, iron, cobalt, nickel and copper cation (particularly a chromium, manganese, iron, cobalt, nickel and copper cation), and mixtures thereof. In yet another aspect of the invention, the first metal cation is selected from an iron (for example Fe2 or Fe3) and copper (for example Cu2) cation, and mixtures thereof. In yet another aspect, the first metal cation is an iron cation (for example Fe2 or Fe3, especially Fe3). Iron cations are advantageous because iron is non-toxic and is easily disposed of after use.
In one aspect of the invention, the catalyst may further comprise one or more additional metal cations fixed to the keratinous support in addition to the first metal cation. Such an additional metal cation may be selected from a zinc or aluminium cation, and mixtures thereof.
Keratinous supports include supports derived from animal fleeces, such as wool, mohair, camel hair and so on, as well as supports derived from animal nail and/or hoof. The keratinous support may be in any suitable form, such as in the form of fibres and/or flakes.
In one aspect of the present invention, the keratinous support is wool (for example a wool fibre). As the skilled person would appreciate, wool is a fibrous material derived from the fleece or hair of animals, principally sheep. Wool fibres are C 11 in the form of monofilaments. A wool fibre may be bound, felted or spun into a yarn or thread, which yarn or thread may then be formed into a fabric or cloth, for example by knitting, weaving, sewing and/or needle punching. Thus a wool fibre of the catalyst of the present invention may take any suitable form, for example a wool fibre may be in the form of a yarn or thread and/or of a fabric or cloth. As the skilled person would appreciate, a plurality of wool fibres may be formed into a yam or thread and a plurality of such yarns or threads may be formed into any such fabric or * cloth. Any such fabric or cloth may additionally comprise an additional non-wool fibre, yarn and/or thread (such as polypropylene), which may for example be included by knitting, weaving, sewing and/or needle punching the non-wool fibre along with the wool yarn or thread.
The keratinous support may be provided on a suitable carrier, such as a carrier comprised of an inert mesh (for example comprised of an inert metal and/or an inert plastics material such as nylon, polypropylene and/or polyester).
Wool fibres from any source may be used in the catalysts of the present invention. For example, suitable wools include commercially available wools, such as wools from the Woolmark company and from the Thomas Chadwick and Sons company. Specific examples of wools that may be used include processed top wool (such as WOOLMARK 2pm mean fibre diameter wool), top wool (such as supplied by DEFRA) and wools provided by Thomas Chadwick and Sons, such as Dark Grey Herdwick, Swaledale, Crosses and Blackface. The wool fibre may be a scoured wool fibre.
The method of catalysing a chemical reaction may further comprise the step of preparing the catalyst, i.e. for use in the catalytic method. The catalyst may be prepared by any suitable method and the method of preparation of the catalyst typically comprises the step of fixing the first metal cation to a keratinous support (such as a wool fibre), which keratinous support (such as a wool fibre) may optionally have been modified prior to impregnation with the first metal cation. Suitable methods of preparing the catalyst include (but are not limited to) those methods discussed herein. If appropriate, the catalyst may be prepared and used in the method of catalysing a chemical reaction in situ.
The present invention further provides a method for preparing a catalyst, the method comprising the steps of: * 12 (i-a) treating a keratinous support (such as a wool fibre) with a hydrazine salt and a hydroxylamine salt in the presence of a base to provide a modified keratinous support (such as a modified wool fibre); and (u-a) treating the modified keratinous support (such as a modified wool fibre) with an aqueous solution comprising a salt of a first metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof.
The present invention further provides a method for preparing a catalyst, the method comprising the steps of: (i-b) treating a keratinous support (such as a wool fibre) with a hydrazine salt in the presence of a base to provide a modified keratinous support (such as a modified wool fibre); and (u-b) treating the modified keratinous support (such as a modified wool fibre) with an aqueous solution comprising a salt of a first metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof.
The present invention further provides a method for preparing a catalyst, the method comprising the steps of: (i-c) treating a keratinous support (such as a wool fibre) with an aqueous solution of a hydroxylamine salt in the presence of a base to provide a modified keratinous support (such as a modified wool fibre), wherein the concentration of the hydroxylamine salt in the aqueous solution is in the range of from 14 to 70 g/l; and (u-c) treating the modified keratinous support (such as a modified wool fibre) with an aqueous solution comprising a salt of a first metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof.
In the steps (ia), (u-b) and/or (u-c) above, the aqueous solution may further comprise a salt of a second metal cation, which second metal cation is selected from C 13 lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminium, gallium, indium, thallium, tin, lead, antimony and bismuth, and mixtures thereof.
The present invention further provides a method for preparing a catalyst, the method comprising the steps of: (i-d) treating a keratinous support (such as a wool fibre) with a hydroxylamine salt in the presence of a base to provide a modified keratinous support (such as a modified wool fibre); and (ii-d) treating the modified keratinous support (such as a modified wool fibre) with an aqueous solution comprising a salt of a first metal cation and a salt of a second metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, and which second metal cation is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminium, gallium, indium, thallium, tin, lead, antimony and bismuth, and mixtures thereof.
In steps (i-a), (i-b), (i-c) and (i-d) of the methods of the present invention for preparing a catalyst, the keratinous support (such as a wool fibre) is modified". The steps (i-a), (i-b), (i-c) and (i-d) are referred to hereinafter as the modification step(s)".
It is believed that, in the modification step, reactive groups on the keratinous support (such as a wool fibre) react with hydroxylamine salts and/or hydrazine salts to form groups (such as hydroxamic groups) that may complex with first metal cations (and possibly with second metal cations) as defined herein.
When a hydrazine salt is used in the modification step of the methods for preparing a catalyst of the present invention, as the skilled person would appreciate, any suitable hydrazine salt may be used. For example, suitable hydrazine salts include hydrazine dihydrochlonde, hydrazine monohydrochloride, hydrazine hydrate, hydrazine monohydrobromide, hydrazine acetate, hydrazine sulfate and dihydrazine sulfate, and mixtures thereof (particularly hydrazine dihydrochloride, hydrazine sulfate and dihydrazine sulfate). Salts of hydrazines containing from one to four substituents may be used, which substituents may be the same or different and selected from (1-4C)alkyl, aryl (such as phenyl) and (1-4C)alkanoyl and which C 14 substituents may be further substituted for example by one or more further substituents which may be the same or different selected from halogeno, nitro and hydroxyl. As the skilled person would appreciate, one or more hydrazine salts may be used in the modification step, as appropriate.
When a hydroxylamine salt is used in the modification step of the methods for preparing a catalyst of the present invention, as the skilled person would appreciate, any suitable hydroxylamine salt may be used. For example, suitable hydroxylamine salts include hydroxylamine monohydrochioride, hydroxylamine sulfate and hydroxylamine phosphate, and mixtures thereof (particularly hydroxylamine monohydrochioride or hydroxylamine sulfate). Salts of hydroxylamines containing one or two substituents may be used, which substituents may be the same or different and selected from (1-4C)atkyl, aryl (such as phenyl) and (1-4C)alkanoyl and which substituents may be further substituted for example by one or more further substituents which may be the same or different selected from halogeno, nitro and hydroxyl. As the skilled person would appreciate, one or more hydroxylamine salts may be used in the modification step, as appropriate.
In the modification step of the methods of the present invention, the keratinous support typically is treated with a hydrazine salt and/or a hydroxylamine salt in a suitable solvent (for example as a solution of a hydrazine salt and/or a * hydroxylamine salt in a suitable solvent) and in the presence of a suitable base. The keratinous support may be treated with a hydrazine salt and a hydroxylamine salt in a suitable solvent (for example as a solution of a hydrazine salt and a hydroxylamine salt in a suitable solvent) and in the presence of a suitable base. Typically, a suitable solvent is an aqueous solvent, such as water. Thus, typically an aqueous solution of a hydrazine salt and/or a hydroxylamine salt is used. The concentration of the hydrazine salt (when present) used in the modification step may be in the range of from 10 to 50 gIl, particularly in the range of from 20 to 40 g/l, more particularly about g/l. The concentration of the hydroxylamine salt (when present) used in the modification step may be in the range of from 14 to 70 g/l, particularly in the range of from 30 to 55 g/l, more particularly about 42 g/l.
When the keratinous support is treated with a solution of a hydrazine salt and a hydroxylamine salt in the modification step, the hydrazine salt and hydroxylamine salt may be present in a molar ratio in the range of from about 1:1 to about 1:3, preferably of about 1:2. * 15
Typically in the modification step, the weight ratio of wool to total hydrazine salt and/or hydroxylamine salt may be in the range of from about 1:8 to 1:0.5, preferably in the range of from about 1:6 to about 1:2, more preferably in the range of from about 1:4 to about 1:2, even more preferably of about 1:2.7.
Any suitable base may be used in the modification step of the methods for preparing a catalyst of the present invention. For example, a suitable base may be selected from sodium hydroxide, potassium hydroxide and sodium carbonate (particularly sodium hydroxide). The base is used in the modification step to maintain a suitable pH, i.e. at which modification of the keratinous support may occur. A suitable pH is, for example, a pH in the range of from 4 to 9.5, particularly a pH in the range of from 6 to 8 and more particularly a pH of about 7.
The modification step may conveniently be conducted at a temperature of greater than room temperature (for example at a temperature of greater than about 25°C), particularly at a temperature in the range of from 60 to 180°C, more particularly at a temperature in the range of from 100 to 105°C, for example at a temperature of about 100 to 101 CC.
As the skilled person would appreciate, the time taken for the modification step depends on the particular keratinous support and/or reagents used. However, a typical treatment time is from about 30 minutes to 3 hours, suitably about 2 hours.
In the steps (il-a), (u-b), (u-c) and (ii-d) of the methods for preparing a catalyst of the present invention, the modified keratinous support (i.e. as prepared in corresponding modification steps (i-a), (i-b), (i-c) and (i-d)) is treated with an aqueous solution so as to provide the catalyst. The aqueous solution typically is an aqueous metal salt solution, i.e. comprising a first metal cation as defined herein. The steps (u-a), (u-b), (il-c) and (ii-d) are referred to hereinafter as the "impregnation step(s)".
The aqueous solution comprises a salt of a first metal cation as defined herein. As the skilled person would appreciate, the aqueous solution may, in one aspect, comprise only one salt of a first metal cation. However, in another aspect, the aqueous solution may comprise more than one salt of a first metal cation. In other words, the aqueous metal salt solution may comprise a mixture of first metal salts. g 16
In one aspect, the first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof.
In another aspect of the invention, the first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper cation, and mixtures thereof. In another aspect of the invention, the first metal cation is selected from a titanium, chromium, manganese, iron, cobalt, nickel and copper cation (particularly a chromium, manganese, iron, cobalt, nickel and copper cation), and mixtures thereof. In yet another aspect of the invention, the first metal cation is selected from an iron (for example Fe2 or Fe3) and copper (for example Cu2) cation, and mixtures thereof. In yet another aspect, the first metal cation is an iron cation (for example Fe2 or Fe3, especially Fe3).
As the skilled person would appreciate, the salts of the first metal cation(s) may comprise any suitable anion. Suitable anions include, for example, chlorides, iodides, bromides, fluorides, sulfates, carboxylates, thiosulfates, thiocyanates, perchiorates, nitrates and nitrites, particularly chlorides, sulfates, nitrates and nitrites, more particularly chlorides and sulfates, even more particularly chlorides. Suitable first metal cations are as discussed above. Examples of suitable first metal salts include FeCI3.6H20, FeSO4.xH2O (wherein x is 1, 4, 5 or 7), Fe2(S04)3.H20, CuCI2.2H20 and CuSO4.5H20 (especially FeCI3.6H20 and Fe2(S04)3.H20).
In the impregnation step, the aqueous solution may comprise a salt of a first metal cation and a salt of a second metal cation, which first and second metal cations are as defined herein. The aqueous solution may comprise only one salt of a second metal cation or may comprise a mixture of second metal salts. As the skilled person would appreciate, the second metal cations are cations of the metals belonging to Groups 1, 2, 12, 13, 14 and 15 as set out in the Periodic Table of Elements (according to established IUPAC nomenclature). It is believed that the second metal cation salts act as facilitators to increase the fixing of the first metal cation to the keratinous support.
In one aspect of the present invention, the second metal cation is selected from lithium, sodium, potassium, magnesium, calcium, zinc and aluminium, and mixtures thereof. In another aspect of the present invention, the second metal cation is selected from lithium, sodium, potassium, magnesium, calcium and zinc, and * 17 mixtures thereof. in another aspect, the second metal cation is selected from a lithium, magnesium, calcium and zinc cation, and mixtures thereof. In yet another aspect of the invention, the second metal cation is selected from a lithium and calcium cation, and mixtures thereof. In yet another aspect of the invention, the second metal cation is selected from a sodium, potassium and calcium cation, and mixtures thereof. In yet another aspect of the invention, the second metal cation is a calcium cation. In yet another aspect of the invention, the second metal cation is a sodium cation.
As the skilled person would appreciate, the salts of the second metal cation(s) may comprise any suitable anion. Suitable anions include, for example, chlorides, iodides, bromides, fluorides, sulfates, carboxylates, thiosulfates, thiocyanates, perchiorates, nitrates and nitrites, particularly chlorides, sulfates, nitrates and nitrites, more particularly chlorides, nitrates and sulfates, even more particularly nitrates and sulfates. Suitable second metal cations are as discussed above. Examples of suitable second metal salts include Ca(N03)2.4H20, Mg(N03)2.6H20, Li2SO4.H20, ZnSO4.7H20, NaCl and Na2SO4 (especially Ca(N03)2.4H20 and Li2SO4.H20).
The total metal cation concentration in the aqueous solution may be in the range of from 0.05 gIL to 500 gIL, such as in the range of from 5 gIL to 100 g/L.
In the aqueous solution, the molar ratio of the first metal salt to the second metal salt (when present) may be in the range of from 1:1(0 1:12, particularly in the range of from 1:2 to 1:6, more particularly in the range of from 1:3 to 1:6.
The impregnation step may conveniently be conducted at a temperature in the range of from about 5 to 80°C, preferably at ambient temperature, i.e. a temperature in the range of from 10 to 30°C, particularly in the range of from 20 to 30°C, for example about 25°C.
The impregnation step may conveniently be conducted at any suitable pH, for example at a pH in the range of from 1 to 7, particularly at a pH in the range of from 2 to 3.
Typically, the keratinous support is washed between each of the modification and impregnation steps of the methods of the present invention for preparing the catalyst. For example, the keratinous support may be washed with water, for example with distilled water. The washing step substantially removes residual reagents present from the previous reaction step(s).
Typically, after the impregnation step the catalyst is dried before use. The catalyst may be dried using any conventional means, for example at temperatures Up to 125°C.
The keratinous support used in the methods of the present invention for preparing a catalyst may be in any suitable form, for example as discussed above.
The method of the invention for preparing the catalyst may further comprise the step of forming a fabric or cloth from a keratinous material, such as a wool fibre. Any suitable method may be used to form the fabric or cloth, for example wool fibre(s) may be bound, felled and/or spun into a yam or thread, which may then be formed into a fabric or cloth, for example by knitting, weaving, sewing and/or needle punching. Any such fabric or cloth may include a non-wool fibre and/or an inert carrier, as discussed above.
A wool fibre used in the method for preparing the catalyst may be commercially available and may be purchased as pre-scoured wool fibre.
The methods of the invention for preparing the catalyst may further comprise a pre-treatment step, for example in which the keratinous support is pre-treated prior to the modification step. The pre-treatment step may comprise the step of scouring of the keratinous material (such as a wool fibre), for example to reduce or remove contaminants on the keratinous material (such as a wool fibre), especially hydrophobic contaminants such as lipids, oils, grease and/or wax. The use of a scoured keratinous material (such as a scoured wool fibre) in the methods for preparing the catalyst may provide materials (such as wool fibres) having fewer contaminants (especially hydrophobic contaminants) thereon and therefore it is believed that the use of a scoured wool fibre may promote the efficient modification and impregnation of the fibre, as discussed herein.
The pre-treatment step (when conducted) may comprise contacting a wool fibre with water (such as distilled water) and/or contacting a wool fibre with water (such as distilled water) in the presence of a suitable surfactant, such as a non-ionic surfactant. Suitable non-ionic surfactants include alkyl phenol ethoxylates and fatty alcohol ethoxylates. In any pre-treatment step, the wool fibre may additionally or alternatively be contacted with a builder such as soda ash (sodium carbonate), sodium chloride and/or sodium sulfate. It is believed that contacting with such builders may allow for shorter contacting times to achieve the reduction or removal of contaminants from the wool fibre. The wool fibre may be dried by any conventional means prior to the modification step. The pre-treatment step may be conducted at any suitable temperature, for example at a temperature in the range of from 40 to 80°C, especially in the range of from 50 to 70°C, more especially at about 60°C.
According to another aspect of the present invention there is provided a catalyst obtainable by the methods of the present invention for preparing the catalyst.
According to yet another aspect of the present invention there is provided a catalyst obtained by the methods of the present invention for preparing the catalyst.
According to yet another aspect of the invention, there is provided a catalyst comprising a keratinous support and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof and wherein the first metal cation is present in an amount of 0. 03 mmol or greater per gram of keratinous support. For example, the first metal cation may be present in an amount of from 0.03 to 1.0 mmol per gram of keratinous support, such as in an amount of from 0.03 to 0.5 mmol per gram of keratinous support, more particularly of from 0.03 to 0.1 mmol per gram of keratinous support, even more particularly of from 0.07 to 0.1 mmol per gram of keratinous support. In the catalyst, the keratinous support and first metal cation are as defined above.
According to yet another aspect of the invention, there is provided a catalyst comprising a wool fibre and a first metal cation fixed to the wool fibre, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof and wherein the first metal cation is present in an amount of 0.03 mmol or greater per gram of wool fibre. For example, the first metal cation may be present in an amount of from 0.03 to 1.0 mmol per gram of wool fibre, such as in an amount of from 0.03 to 0.5 mmol per gram of wool fibre, more particularly of from 0.03 to 0.1 mmol per gram of wool fibre, even more particularly of from 0.07 to 0.1 mmol per gram of wool fibre.
In the catalyst, the wool fibre and first metal cation are as defined above.
According to another aspect of the present invention there is provided a catalyst system or kit for providing a catalyst, the catalyst system or kit comprising: (i) a keratinous support (such as a wool fibre); (ii) a hydrazine salt and/or a hydroxylamine salt; (iii) a base; and (iv) a salt of a first metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, indium, platinum and gold cation, and mixtures thereof.
The catalyst system or kit may further comprise (v) a salt of a second metal cation, which second metal cation is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminium, gallium, indium, thallium, tin, lead, antimony and bismuth, and mixtures thereof.
In the catalyst system or kit, the keratinous support, hydrazine salt, hydroxylamine salt, base, salt of a first metal cation and salt of a second metal cation (when present) are as defined above.
The catalyst system or kit includes those components that are required to prepare a catalyst. The catalyst may be prepared using any suitable method, for example using a method for preparing a catalyst as hereinbefore defined. The base typically is selected so as to provide the desired pH during the preparation of the catalyst, as necessary. The catalyst system or kit may further comprise instructions for preparing the catalyst and/or for the use of the catalyst in a chemical reaction (such as the use in the treatment of a waste stream).
The catalyst system or kit may be used to prepare a catalyst for use in any suitable chemical reaction, such as those chemical reactions discussed above.
According to another aspect of the present invention, there is provided the use of a catalyst as herein defined, for the catalysis of a chemical reaction. For example, there is provided the use of a catalyst comprising a keratinous support (such as a wool fibre) and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, for the catalysis of a chemical reaction.
According to another aspect of the present invention, there is provided the use of a catalyst as herein defined in the treatment of a waste stream. For example.
there is provided the use of a catalyst comprising a keratinous support (such as a wool fibre) and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, in the treatment of a waste stream by the catalysis of a chemical reaction.
In the above mentioned uses of a catalyst, the keratinous support and first metal cation are as defined above.
The uses of the aforementioned catalysts may be conducted in relation to any suitable chemical reaction as discussed above, for example to catalyse an oxidation reaction, especially the oxidation of one or more organic compounds as discussed herein. Thus, the catalysts may be used in the presence of a suitable oxidant, as described above. The uses may be conducted under any suitable conditions, as described above.
Typically, the waste stream is in the form of a fluid, which may be liquid or gaseous. In one aspect of the invention, the waste stream is in the liquid phase. For example, the liquid waste stream may be aqueous or organic based.
The waste stream may originate from any relevant process or industry, for example the waste stream may originate from the chemical, pharmaceutical, petroleum chemical, agro-chemical, textile, pulp, leather, furniture manufacturing or photo-processing industry, particularly from the textile, pulp or photo-processing industry.
References herein to a wool fibre are intended to relate to one or more wool fibres, in any suitable form as discussed above.
The invention will now be illustrated by the following non-limiting examples in which, unless stated otherwise: (a) temperatures are given in degrees Celsius (°C); (b) operations were conducted at room or ambient temperature, that is a temperature in the range of from 18 to 25C; (c) chemical symbols have their usual meanings; and (d) SI symbols and units are used.
PreDaration of the Catalvsi Catalysts were prepared from wool fibres using the steps set out below and according to the parameters shown in Table 1.
The catalyst preparation steps include an optional pre-treatment step, in which wool fibres are pre-treated by scouring. Following the optional pre-treatment step, an optional modification step is conducted, followed by an impregnation step, as set out below.
Optional Pre-treatment Step -Scouring An optional pre-treatment step, in which wool fibres are pre-treated by scouring, may be included in the catalyst preparation. Where pre-treatment by scouring of the wool fibres was conducted (i.e. prior to the modification and/or impregnation steps), it was performed as follows: (a) Wool fibres (2g) were treated with distilled water (200ml) for 10 minutes at 60°C. Any excess water was rung out (by hand) after treatment.
(b) The wool fibres from (a) were treated in the presence of non-ionic UPL (United Phosphorous Ltd) surfactant (2g11) (supplied by Drummond Parkiand) in water for 15 minutes at 60°C. Excess solution was again rung out (by hand) after treatment.
(c) The wool fibres from (b) were treated in the presence of UPL surfactant (lg/l) in water for 15 minutes at 60°C. After treatment, excess solution was run off. The wool was then washed with distilled water, dried and air conditioned.
In all stages (a) to (c) above, the liquor to wool ratio (mI:g) was 100:1. All treatments were carried out in a continuous mechanical shaking bath.
Optional Modification Step A wool sample (3.lg, in the form of wool fibres) was suspended in a modification solution according to the parameters shown in Table I below.
The modification solutions used were as follows: 1. Aqueous hydroxylamine solution: 200m1 containing 42g/I of hydroxylamine monohydrochioride (NH2OH. HCI); 2. Aqueous hydrazine and hydroxylamine solution: 1 OOml of 3OgIl hydrazine dihydrochionde (N2H4.2HCI) and lOOml of 42g/l hydroxylamine monohydrochioride (NH2OH.HCI).
3. Aqueous hydrazine solution: 200m1 containing 3OgIl of hydrazifle dihydrochioride (N2H4.2HCI).
Each modification solution was adjusted to pH 7 or 9.5 by addition of sodium hydroxide pellets prior to contacting the modification solution with the wool fibres.
The wool samples were then left in the modification solution and heated at a temperature of from 100 to 101°C for 2 hours. Each sample was then allowed to cool to a temperature at which it could be handled and washed thoroughly with double distilled water (approximately 3 litres). The sample was then left to dry in a desiccator at room temperature for 24 hours.
Wool Impregnation with First Metal Salt Wool fibres (ig, optionally pre-treated and/or modified as described above) were placed in a sealed vial containing ferric chloride hexahydrate, FeCI3.6H20 (0.IM Fe3 solution, 50m1 at pH = 1.72) or salts solution (100 ml) containing FeCl3.6H20 and either Ca(N03)2.4H20 or Li2SO4.H20. The sealed vial was attached to a rotator for continuous shaking at room temperature for 24 hours. Once complete, the wool was removed from the solution and thoroughly washed with double distilled water. The sample was then left to dry in a desiccator at room temperature for 24 hours.
The total amount of first metal cation (i.e. Fe3') adsorbed onto the wool was determined by atomic adsorption spectroscopy, as follows: (i) Calibration Method: Standard solutions (1, 2, 3, 4 and 5ppm) of Fe3' were prepared and analysed using atomic adsorption spectroscopy to produce a calibration graph with respect to concentration. Each solution was analysed i n triplicate.
(ii) Total iron determination for each wool sample: Impregnated wool (O.lg) containing Fe3' cations was weighed out and then heated in hydrochloric acid (2M, 25m1) to remove the iron cations from the fibers.
The solution was filtered and the fibers washed with double distilled water. The filtrate and washings were collected and placed in a volumetric flask (5Oml). Double distilled water was used to dilute the solution up to 5Oml. The samples were then analysed in triplicate using atomic adsorption spectroscopy. This process was then repeated again for each sample to produce an average.
Table I -Technical Parameters for Preparation of Catalysts Modification Step Impregnation Step Example Scouring? Hydrazine Ilydroxylamine pH Temp Duration impregnating Solution Duration Iron Concentration concentration (hours) (hours) content (gil) (g/l) _____________ of Metal concentration catalyst Cation(s) (M) (mmoiig 1 Yes 30 42 7.0 100 2 Fe3 0.1 24 0.044 2 Yes 30 42 7.0 100 2 Fe 0.1 24 0.044 3 Yes 30 42 7.0 100 2 Fe44 0.1 24 0.044 4 Yes 0 42 7.0 100 2 Fe 0.1 24 0. 076 Yes 0 42 7.0 100 2 Fe 0.1 24 0.076 U' 6 Yes 0 42 7.0 100 2 Fe 0.1 24 0. 076 7 Yes 0 0 ---Fe 0.1 24 0.007 8 Yes 0 0 ---Fe 0.1 24 0.007 9 No 0 0 ---Fe 0.1 24 0.024 No 0 0 ---Fe 0.1 24 0.024 11 Yes 0 0 ---Fe4 0.1 24 0.007 12 Yes 30 0 9.5 100 2 Fe 0.1 24 0.088 13 Yes 0 42 9.5 100 2 Fe4 0.1 24 0.060 14 Yes 30 42 9.5 100 2 Fe4 0.1 24 0.088 Yes 30 42 7.0 100 2 Fe 0.1 24 0.037 16 Yes 30 42 7.0 100 2 Fe 0.1 24 0.037 17 Yes 30 42 7.0 100 2 Fe' 0.1 24 0.037 18 Yes 0 42 7.0 100 2 Fe 0.1 24 0.076 19 Yes 0 42 7.0 100 2 F&4 0.1 24 0.076 Yes 0 42 7.0 100 2 Fe 0.1 24 0.076 21 Yes 0 0 ---Fe 0.1 24 0.007 22 Yes 0 0 ---Fe 0.1 24 0.007 23 No 0 0 ---Fe4 0.1 24 0.009 24 No 0 0 ---Fe4 0.1 24 0.009 Yes* 30 42 7.0 100 2 Fe 0.1 24 0.040 26 Yes* 30 42 7.0 100 2 Fe 0.1 24 0.040 27 Yes* 30 42 7.0 100 2 Fe 0.1 24 0.040 28 Yes* 0 42 7.0 100 2 Fe 0.1 24 0.055 29 Yes* 0 42 7.0 100 2 Fe 0.1 24 0. 055 Yes* 0 42 7.0 100 2 F?' 0.1 24 0.055 31 Yes* 0 0 ---F?' 0.1 24 0.020 32 Yes 0 0 ---F?' 0.1 24 0.020 33 No 0 0 ---F?' 0.1 24 0.036 34 No 0 0 --- F?' 0.1 24 0.036 Yes 30 42 7.0 100 2 F?' 0.1 24 0.059 36 Yes 30 42 7.0 100 2 Fe" 0.1 24 0.059 37 Yes 0 42 7.0 100 2 F?' 0.1 24 0.076 38 Yes 0 42 7.0 100 2 Fe3 0.1 24 0.076 39 Yes 0 0 ---F?' 0.1 24 0.047 Yes 0 0 ---Fe' 0.1 24 0.047 41 Yes' 30 42 7.0 100 2 Fed' 0.1 24 0.055 42 Yes' 30 42 7.0 100 2 Fed' 0.1 24 0.055 42 Yes' 0 42 7.0 100 2 Fe 0.1 24 0.107 44 Yes' 0 42 7.0 100 2 Fe' 0.1 24 0.107 Yes' 0 0 ---Fe 0.1 24 0.024 46 Yes' 0 0 ---Fe 0.1 24 0.024 47 No 0 0 ---Fe 0.1 24 0.030 48 No 0 0 ---Fe 0.1 24 0.030 49 Yes 30 42 7.0 100 2 Fe3 0.1 24 0.098 Yes 30 42 7.0 100 2 Fe 0.1 24 0.098 51 Yes 0 42 7.0 100 2 Fed' 0.1 24 0.074 52 Yes 0 42 7.0 100 2 Fed' 0.1 24 0.074 53 Yes 0 0 ---Fe 0.1 24 0.016 54 Yes 0 0 ---Fe3' 0.1 24 0.016 Yes 0 42 7.0 100 2 F&4 0.1 24 0.077 56 Yes 0 42 7.0 100 2 Fe 0.1 24 0.077 57 Yes 0 42 7.0 100 2 Fe 0.1 24 0.074 58 Yes 0 42 7.0 100 2 F?' 0.1 24 0.074 59 Yes 0 42 7.0 100 -2 F?' 0.1 24 0.060 Yes 0 42 7.0 100 2 Fe3' 0.1 24 0.060 61 Yes 0 42 7.0 100 2 F?' 0.1 24 0.101 62 Yes 0 42 7.0 100 2 Fe3' 0.1 24 0.101 63 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A (control) 64 Yes 30 42 7.0 100 2 N/A N/A N/A 0.000 (control) Yes 0 42 7.0 100 2 N/A N/A N/A 0.000 (control) 66 Yes 0 0 N/A N/A N/A N/A N/A N/A 0.000 (control) 67 Yes 30 42 7.0 100 2 N/A N/A N/A 0.000 (control) 68 Yes 0 42 7.0 100 2 N/A N/A N/A 0.000 (control) 69 Yes 0 0 N/A N/A N/A N/A N/A N/A 0.000 (control) Yes* 30 42 7.0 100 2 N/A N/A N/A 0.000 (control) 71 Yes* 0 42 7.0 100 2 N/A N/A N/A 0.000 (control) _________ 72 Yes* 0 0 N/A N/A N/A N/A N/A N/A 0.000 (control) ________ _________ ____________ ________ _________ 73 Yes 30 42 7.0 100 2 N/A N/A N/A 0.000 (cofltrol) _________ _____________ ________ _________ 74 Yes* 0 42 7.0 100 2 N/A N/A N/A 0.000 (control) ______ ________ __________ _____________ ________ _________ Yes 30 42 7.0 100 2 N/A N/A N/A 0.000 (control) 76 Yes* 0 42 7.0 100 2 N/A N/A N/A 0. 000 (control) 77 Yes 0 42 7.0 100 2 Fe 0.1 24 0.088 78 Yes 0 42 7.0 100 2 Fe4 0.1 24 0.074 79 Yes 0 42 7.0 100 2 Fe4 0.1 24 0.081 Yes 0 42 7.0 100 2 Fe/ 0.039/0.095 24 0.080 2+ Ca 81 Yes* 0 42 7.0 100 2 Fe/Li 0.064/0.116 24 0.079 82 Yes* 0 42 70 100 2 Fe/ Li 0.064/0.116 24 0.079 83 Yes* 0 42 7.0 100 2 Fe/ 0.028/0.095 24 0.080 Ca2 S 30 Column 2 in Table 1 indicates whether or not the catalyst preparation included a pre-treatment scouring step. Where "Yes" is indicated, the pre-treatment scouring step was conducted as described above (referred to herein as laboratory scoured" wool). Where uyes*n is indicated, the pre-treatment scouring step was conducted by the wool manufacturer prior to purchase of the wool, by the mill scouring method known in the art.
Examples 1 to 10 and Control Examples 64 to 66 use WOOLMARK top wool.
Examples 11 to 24 and Control Examples 67 to 69 use DEFRA top wool. The term "top wool" is a recognised term within the art and as the skilled person would appreciate refers to main wool fleece, not including fleece from underneath the sheep (for example from the stomach/belly area). All other wools were provided by Thomas Chadwick and Sons, being Dark Grey Herdwick (Examples 25 to 40 and Control Examples 70 to 72), Swaledale (Examples 41 to 54 and Control Examples 73 to 76), Crosses (Examples 55 to 58 and Examples 77 to 83), Halfbreds (Examples 59 and 60) and Blackface (Examples 61 and 62). No wool was used in Control Example 63.
Test for Iron Removal Degree For each catalyst prepared, a test was conducted to determine how strongly the iron was fixed on the wool (prior to catalysis).
Iron fixing strength is evaluated using a strong complexing agent, such as disodium-ethyl enediamine tetraacetic acid (disodium-EDTA). The disodium-EDTA complexes with Fe3 ions at pH 5 and results in the removal of the Fe3 ions from the wool into solution if they are not strongly fixed.
Wool fibers (0.19) containing the metal cation were thoroughly ground and left in contact with aqueous disodium-EDTA solution (0.5M, 5ml) for 24 hours. An aliquot of the wool-EDIA solution (imI) was diluted with distilled water and made up to the mark in a volumetric flask (5Oml). The total iron content of the solution was determined in triplicate directly using atomic adsorption spectroscopy. S 31
Examples I to 62 and 83 and Control Examples 63 to 76 -Determination of Activity of the Catalyst In Examples 1 to 10 and 15 to 62 and Control Examples 63 to 76, the activity of the catalyst was determined in relation to the decomposition (by oxidation) of phenol.
In Examples 11 to 14, the activity of the catalyst was determined in relation to the decomposition (by oxidation) of the dye, Acid Blue 45.
In Example 83, the activity of the catalyst was determined in relation to the decomposition (by oxidation) of Estrone (El) in a static reactor.
In Examples I to 62 and 83 and Control Examples 63 to 76, the catalysts were evaluated in a static reactor.
Phenol Decomposition Examples 1 to 10 and 15 to 62 and Control Examples 63 to 76 were conducted as follows: As the feed solution for the determination of catalyst activity by phenol decomposition, an aqueous solution of phenol (50m1, 24ppm) was provided and adjusted to pH 3 by adding dilute (0.OIM) hydrochloric acid. 5 ml of an aqueous stock solution of H202 (500ppm) was added to give a resultant H202 concentration of about 45ppm and a resultant phenol concentration of about 22ppm.
Various concentrations of aqueous phenol solutions were prepared (5, 10, 15, 20, 25 and 3oppm) and analysed by HPLC to prepare a calibration graph. A standard C-18 (250 x 4.6mm) packed column was used as the stationary phase. The mobile phase was a mixture of water (10% v/v) and acetonitrile (90% v/v) at a flow rate of 1 mI/mm. The column elute was passed through a UV detector (Helios Gamma UVNIS spectrophotometer supplied by Thermo Scientific) set at 254nm.
Sample volumes of 2Opl were injected onto the column. Samples were analysed in triplicate. S 32
For the catalysis, feed solution (50m1) was placed in a Dreschel bottle and a zero reading taken for analysis, this became the t = 0 minutes reading (i.e. before exposure to the catalyst). The catalyst (0.6g) was then added to the feed solution and the vessel stoppered allowing air to flow through. Samples of the treated feed solution were collected at ten minute intervals for a total of 2 hours. Once complete, the catalyst was removed and rinsed with double distilled water to remove any traces of hydrogen peroxide.
Each sample collected was analysed by HPLC for residual phenol content, using the same column as for the calibration step discussed above. The mobile phase was a mixture of water (40% v/v) and methanol (60% v/v) at a flow rate of 1 mi/mm. UV detection and volume of sample injection were as for the calibration step discussed above.
A control solution (feed (phenol) solution+H202+bubbled air, but no catalyst) was used to evaluate the hydrogen peroxide contribution to catalysis using the same setup (Example 63). Wool samples with no Fe3 impregnation were evaluated in the same manner (Examples 64 to 76).
Acid Blue 45 DecomDosition Examples 11 to 14 were conducted as follows: The catalysis was conducted as described above for Examples 1 to 10 and to 62 and Control Examples 63 to 76. except that the samples were analysed by UVNIS spectrophotometry. The UVNIS Spectrophotometer used was the Helios Gamma supplied by Thermo Scientific at A = 594nm.
The feed solution comprised the dye Acid Blue 45 (50 ml. 10 ppm) was adjusted to pH 3 with dilute hydrochloric acid (2M). H202 (5 ml) was added from a stock solution (500ppm), to provide a resultant concentration of H202 was about 45ppm. The resultant initial acid blue 45 concentration was about 9.lppm.
Estrone (E1 Decomposition Example 83 was conducted as follows: S 33 The catalysis was conducted as described above for Examples 1 to 10 and to 62 and Control Examples 63 to 76, except that each sample collected at the end of experiment was analysed for residual estrone (El) content using an ELISA kit in accordance with the standard technique for El analysis (Method A) described in the Users Guide (Estrone (El) ELISA KIT (Microplate). User's Guide, Japan EnviroChemicals, Ltd) and based on measuring the absorbance of the samples at 450nm at ambient temperature using MULTISKAN EX (Thermo, Electron Corporation) equipment.
The feed solution had a volume of 1 OOml and comprised an aqueous estrone (El) solution (lOOmI, 1 pg/I)and H202(57ppm). 0.2g of catalyst was used and air was passed through the solution at a rate of Il/minute; duration of treatment was 2 hours at room temperature.
Comments on Examples I to 62 and 83 and Control Examples 63 to 76 Example I below relates to the catalytic process (i.e. phenol decomposition) conducted as described above using the catalyst as prepared in Example 1, as shown in Table I. The same numbering applies to all other Examples and Control
Examples.
References to three cycles of catalysis mean that a catalyst is contacted with a first feed solution for the specified time of oxidation, removed from the first feed solution, contacted with a second fresh feed solution for the specified time of oxidation, removed from the second feed solution and contacted with a third fresh feed solution for the specified time of oxidation. In other words, the catalyst undergoes three cycles of catalysis by contacting with three fresh feed solutions.
References herein to Examples la-ic relate to the three cycles of catalysis that is conducted with the catalyst of Example 1 (as shown in Table 1) and similarly with the other Examples and Control Examples where reference is made to examples a-c.
Examples I to 3
Examples 1 a-Ic illustrate the catalytic activity over three cycles for laboratory scoured WOOLMARK wool modified with a mixture of hydrazine and hydroxylamine followed by impregnation with Fe3 cations as described in Table 1 above. Examples 2a-3c illustrate the outcome of batch-to-batch reproducibility studies over three cycles (each using a fresh feed solution) used in Examples la-Ic using the catalysts as prepared in Examples 2 and 3 described as prepared in Table 1 above.
All catalytic activity evaluations contained hydrogen peroxide (5Oppm) in the feed.
Examples 4 to 6
Examples 4a-4c illustrate the catalytic activity over three cycles for laboratory scoured WOOLMARK wool modified with hydroxylamine followed by impregnation with Fe3 cations. Examples 5a-6c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 4a-4c.
Examples 7 and 8
Examples 7a-7c illustrate the catalytic activity over three cycles for laboratory scoured WOOLMARK wool impregnated with Fe3 cations. Examples 8a-8c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 7a-7c.
Examples 9 and 10
Examples 9a-9c illustrate the catalytic activity over three cycles for non-scoured WOOLMARK wool impregnated with Fe3 cations. Examples lOa-lOc illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 9a-9c.
Example 11
Examples 11 a-i I c illustrate the catalytic activity of laboratory scoured and Fe3 cation impregnated DEFRA wool modified against Acid Blue 45 over three cycles.
Example 12
Examples 1 2a-1 2c demonstrate the catalytic activity of laboratory scoured DEFRA wool modified at pH 9.5 with hydrazine followed by impregnation with Fe3 cations against Acid Blue 45 over three cycles.
Example 13
Examples 1 3a-1 3c demonstrate the catalytic activity of laboratory scoured DEFRA wool modified at pH 9.5 with hydroxylamine followed by impregnation with Fe3 cations against Acid Blue 45 over three cycles.
Example 14
Examples 14a-14c demonstrate the catalytic activity of laboratory scoured * DEFRA wool modified at pH 9.5.
Examples 15 to 17
Examples 1 5a-1 5c illustrate the catalytic activity over three cycles for laboratory scoured DEFRA wool modified with a mixture of hydrazine and hydroxylamine followed by impregnation with Fe34. cations as described in Table I above. Examples 16a-17c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 15a-15c.
Examples 18 to 20
Examples 18a-18c illustrate the catalytic activity over three cycles for laboratory scoured DEFRA wool modified with hydroxylamine followed by impregnation with Fe34 cations. Examples I 9c-20c illustrate the outcome of batch-to- * batch reproducibility studies over three cycles for the same sample used in Examples 18a-18c.
Examples 21 and 22
Examples 21a-21c illustrate the catalytic activity over three cycles for laboratory scoured DEFRA wool impregnated with Fe3 cations. Examples 22a-22c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 21 a-21c.
Examples 23 and 24
Examples 23a-23c illustrate the catalytic activity over three cycles for non-scoured DEFRA wool impregnated with Fe3 cations. Examples 24a-24c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 23a-23c.
Examples 25 to 27
Examples 25a-25c illustrate the catalytic activity over three cycles for mill scoured Dark Grey Herdwick wool modified with a mixture of hydrazine and hydroxylamine followed by impregnation with Fe3 cations as described in Table I above. Examples 26a-27c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 25a-25c.
Examples 28 to 30
Examples 28a-28c illustrate the catalytic activity over three cycles for mill scoured Dark Grey Herdwick wool modified with hydroxylamine followed by impregnation with Fe3 cations. Examples 29a-30c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 29a-29c.
Examples 31 and 32
Examples 31 and 32 illustrate the catalytic activity over one cycle for two batches of mill scoured Dark Grey Herdwick wool impregnated with Fe3 cations.
Examples 33 and 34
Examples 33 and 34 illustrate the catalytic activity over one cycle for two batches of non-scoured Dark Grey Herdwick wool impregnated with Fe3 cations. S 37
Examples 35 and 36
Examples 35a-35c illustrate the catalytic activity over three cycles for laboratory scoured Dark Grey Herdwick wool modified with a mixture of hydrazine and hydroxylamine followed by impregnation with Fe3 cations as described in Table 1 above. Examples 36a-36c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 35a-35c.
Examples 37 and 38
Examples 37a-37c illustrate the catalytic activity over three cycles for laboratory scoured Dark Grey Herdwick wool modified with hydroxylamine followed by impregnation with Fe3 cations. Examples 38a-38c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in
Examples 37a-37c.
Examples 39 and 40
Examples 39 and 40 illustrate the catalytic activity over one cycle for two batches of laboratory scoured Dark Grey Herdwick wool impregnated with Fe3 cations.
Examples 41 and 42
Examples 41a-41c illustrate the catalytic activity over three cycles for mill scoured Swaledale wool modified with a mixture of hydrazine and hydroxylamine followed by impregnation with Fe3 cations as described in Table 1 above. Examples 42a-42c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 41a-41c.
Examples 43 and 44
Examples 43a-43c illustrate the catalytic activity over three cycles for mill scoured Swaledale wool modified with hydroxylamine followed by impregnation with Fe3 cations. Examples 44a-44c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 43a-43c.
Examples 45 and 46
Examples 45 and 46 illustrate the catalytic activity over one cycle for two batches of mill scoured Swaledale wool impregnated with Fe3 cationS.
Examples 47 and 48
Examples 47 and 48 illustrate the catalytic activity over one cycle for two batches of non-scoured Swaledale wool impregnated with Fe3 cations.
Examples 49 and 50
Examples 49a-49c illustrate the catalytic activity over three cycles for laboratory scoured Swaledale wool modified with a mixture of hydrazine and hydroxylamine followed by impregnation with Fe3 cations as described in Table I above. Examples 50a-50c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 49a-49c.
Examples 51 and 52
Examples 51a-51c illustrate the catalytic activity over three cycles for laboratory scoured Swaledale wool modified with hydroxylamine followed by impregnation with Fe3 cations. Examples 52a-52c illustrate the outcome of batch-to-batch reproducibility studies over three cydes for the same sample used in Examples 51a-51c.
Examples 53 and 54
Examples 53 and 54 illustrate the catalytic activity over one cycle for two batches of laboratory scoured Swaledale wool impregnated with Fe3 cations.
Examples 55 ancI56
Examples 55a-55c illustrate the catalytic activity over three cycles for mill scoured Crosses wool modified with hydroxylamine followed by impregnation with Fe3 cations. Examples 56a-56c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 55a-55c.
Examples 57 and 58
Examples 57a-57c illustrate the catalytic activity over three cycles for laboratory scoured Crosses wool modified with hydroxylamine followed by impregnation with Fe3 cations. Examples 58a-58c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 57a-57c.
Examples 59 and 60
Examples 59a-59c illustrate the catalytic activity over three cycles for laboratory scoured Halfbreds wool modified with hydroxylamine followed by impregnation with Fe3' cations. Examples 60a-60c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 59a-59c.
Examples 61 and 62
Examples 61a-61c illustrate the catalytic activity over three cycles for laboratory scoured Blackface wool modified with hydroxylamine followed by impregnation with Fe3' cations. Examples 62a-62c illustrate the outcome of batch-to-batch reproducibility studies over three cycles for the same sample used in Examples 61a-61c.
Control Example 63
This is a control experiment where no wool catalyst is present. It is to assess the amount of phenol decomposition achieved using hydrogen peroxide only.
Control Example 64
This is a WOOLMARK control sample. The wool underwent modification with a mixture of hydrazine and hydroxylamine as described in Table 1 above but was not subjected to impregnation with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 65
This is a WOOLMARK control sample. The wool was modified with hydroxylamine only and was not impregnated with Fe34 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 66
This is a WOOLMARK control sample. The wool was subjected to laboratory scouring. No modification or impregnation with Fe34 cations was performed. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 67
This is a DEFRA control sample. The wool was modified with 50% hydrazine and 50% hydroxylamine. No impregnation with Fe34 cations was performed. Phenol catalysis was performed using the control in ordei to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 68
This is a DEFRA control sample. The wool was modified with hydroxylamine only and was not impregnated with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 69
This is a DEFRA control sample. The wool was subjected to laboratory scouring only. No modification or impregnation with Fe3 cations was performed.
Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 70
This is a Dark Grey Herdwick control sample. The wool was modified with a mixture of hydrazine and hydroxylamine as described in Table I above. The wool was not impregnated with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 71
This is a Dark Grey Herdwick control sample. The wool was modified with hydroxylamine only and was not impregnated with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 72
This is a Dark Grey Herdwick control sample. The wool was supplied pre-scoured by Thomas Chadwick & Sons. No other treatment was performed. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 73
This is a Swaledale control sample. The wool was modified with a mixture of hydrazine and hydroxylamine as described in Table I above. There was no impregnation with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 74
This is a Swaledale control sample. The wool was modified with hydroxylamine only. There was no impregnation with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 75
This is a Swaledale control sample. The wool was supplied as scoured by Thomas Chadwick & Sons. The scoured wool was modified with a mixture of hydrazine and hydroxylamine as described in Table 1 above. There was no impregnation with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Control Example 76
This is a Swaledale control sample. The wool was supplied as scoured from Thomas Chadwick & Sons. The wool was modified with hydroxylamine only and there was no impregnation with Fe3 cations. Phenol catalysis was performed using the control in order to evaluate what contribution modified wool had on catalysis prior to iron loading.
Example 83
Example 83 demonstrates the catalytic actMty of mill scoured CROSSES wool modified at pH 7 with hydroxylamine only followed by impregnation with Fe3 and Ca2 cations against Estrone (El). This example was conducted over a single cycle only.
Table 2 contains the results for the catalysts of Examples I to 62 and 83 and Control Examples 63 to 76 evaluated in a static reactor. S 43
Table 2-Catalytic Activity Results obtained by Static Reactor Catalysis Iron Removal mass Initial degree after lsolution Time of concentration Conversion Catalytic Example EDTA solution volume oxidation of substrate degree process treatment ratio (mm) (mgll) (%) (%) (modulus) (kg/rn3) _________ ________
Example -Phenol
0.002 0.012 60 22 99 Ia Oxidation
Example Phenol
N/A 0.012 60 22 98 lb Oxidation
Example Phenol
N/A 0.012 60 22 98 Ic Oxidation
Example Phenol
0.002 0.012 60 22 99 2a Oxidation
Example -Phenol
N/A 0.012 60 22 98 2b Oxidation
Example Phenol
N/A 0.012 60 22 98 2c Oxidation
Example Phenol
0.002 0.012 60 22 99 3a Oxidation
Example Phenol
N/A 0.012 60 22 81 3b Oxidation
Example Phenol
N/A 0.012 60 22 98 3c Oxidation
Example Phenol
N.D. 0.012 60 22 99 4a Oxidation
Example -Phenol
N/A 0.012 60 22 100 4b Oxidation
Example -Phenol
N/A 0.012 60 22 100 4c Oxidation
Example -Phenol
N.D. 0.012 60 22 100 5a Oxidation
Example Phenol
N/A 0.012 60 22 100 5b Oxidation
Example Phenol
N/A 0.012 60 22 100 5c Oxidation
Example Phenol
N.D. 0.012 60 22 99 6a Oxi dation * 44
Example Phenol
N/A 0.012 60 22 100 6b Oxidation
Example Phenol
N/A 0.012 60 22 100 6c Oxidation
Example Phenol
0.010 0.012 60 22 99 7a Oxidation
Example Phenol
N/A 0.012 60 22 100 7b Oxidation
Example Phenol
N/A 0.012 60 22 100 7c Oxidation
Example Phenol
0.010 0.012 60 22 56 8a Oxidation
Example Phenol
N/A 0.012 60 22 52 8b Oxidation
Example Phenol
N/A 0.012 60 22 60 8c Oxidation
Example Phenol
0.008 0.012 60 22 36 9a Oxidation
Example Phenol
N/A 0.012 60 22 49 9b Oxidation
Example Phenol
N/A 0.012 60 22 48 9c Oxidation
Example Phenol
0.008 0.012 60 22 31 I Oa Oxidation
Example Phenol
N/A 0.012 60 22 49 lOb Oxidation
Example Phenol
N/A 0.012 60 22 49 lOc Oxidation Acid Blue
Example
0.011 45 0.012 30 9.1 86 ha Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 53 lib Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 2 lic Oxidation Acid Blue Exam pie 0.002 45 0.012 30 9.1 100 1 2a Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 100 1 2b Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 100 I 2c Oxidation Acid Blue
Example
N.D. 45 0.012 30 9.1 85 1 3a Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 81 1 3b Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 95 I 3c Oxidation Acid Blue
Example
0.001 45 0.012 30 9.1 100 I 4a Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 100 1 4b Oxidation Acid Blue
Example
N/A 45 0.012 30 9.1 100 I 4c Oxidation
Example Phenol
0.001 0.012 60 22 93 I 5a Oxidation
Example Phenol
N/A 0.012 60 22 93 I 5b Oxidation
Example Phenol
N/A 0.012 60 22 93 1 5c Oxidation
Example Phenol
0.001 0.012 60 22 93 16a Oxidation
Example Phenol
N/A 0.012 60 22 93 I 6b Oxidation
Example Phenol
N/A 0.012 60 22 94 I 6c Oxidation
S
Example Phenol
0.001 0.012 60 22 93 1 7a Oxidation
Example Phenol
NIA 0.012 60 22 93 1 7b Oxidation
Example Phenol
N/A 0.012 60 22 94 1 7c Oxidation
Example Phenol
N.D. 0.012 60 22 99 18a Oxidation
Example Phenol
N/A 0.012 60 22 99 1 8b Oxidation
Example Phenol
N/A 0.012 60 22 99 I 8c Oxidation
Example Phenol
N.D. 0.012 60 22 99 I 9a Oxidation
Example Phenol
N/A 0.012 60 22 99 I 9b Oxidation
Example Phenol
N/A 0.012 60 22 99 19c Oxidation
Example Phenol
N.D. 0.012 60 22 99 20a Oxidation
Example Phenol
N/A 0.012 60 22 99 20b Oxidation
Example Phenol
N/A 0.012 60 22 99 20c Oxidation
Example Phenol
0.011 0.012 60 22 54 21 a Oxidation
Example Phenol
N/A 0.012 60 22 47 21 b Oxidation
Example Phenol
N/A 0.012 60 22 50 21 c Oxidation
Example Phenol
0.011 0.012 60 22 53 22a Oxidation
Example Phenol
N/A 0.012 60 22 56 22b Oxidation
Example Phenol
N/A 0.012 60 22 51 22c Oxidation
Example Phenol
0.102 0.012 60 22 48 23a Oxidation * 47
Example Phenol
N/A 0.012 60 22 47 23b Oxidation
Example Phenol
N/A 0.012 60 22 45 23c Oxidation
Example Phenol
0.102 0.012 60 22 50 24a Oxidation
Example Phenol
N/A 0.012 60 22 50 24b Oxidation
Example Phenol
N/A 0.012 60 22 45 24c Oxidation
Example Phenol
0.002 0.012 60 22 100 25a Oxidation
Example Phenol
N/A 0.012 60 22 100 25b Oxidation
Example Phenol
N/A 0.012 60 22 100 25c Oxidation
Example Phenol
0.002 0.012 60 22 100 26a Oxidation
Example Phenol
N/A 0.012 60 22 100 26b Oxidation
Example Phenol
N/A 0.012 60 22 100 26c Oxidation
Example Phenol
0.002 0.012 60 22 100 27a Oxidation
Example Phenol
N/A 0.012 60 22 100 271, Oxidation
Example Phenol
N/A 0.012 60 22 100 27c Oxidation
Example Phenol
N.D. 0.012 60 22 26 28a Oxidation
Example Phenol
N/A 0.012 60 22 23 28b Oxidation
Example Phenol
N/A 0.012 60 22 24 28c Oxidation
Example Phenol
N.D. 0.012 60 22 31 29a Oxidation
Example Phenol
N/A 0.012 60 22 33 29b Oxidation * 48
Example Phenol
N/A 0.012 60 22 28 29c Oxidation
Example Phenol
N.D. 0.012 60 22 26 30a Oxidation
Example Phenol
N/A 0.012 60 22 31 30b Oxidation
Example Phenol
N/A 0.012 60 22 23 30c Oxidation
Example Phenol
0.101 0.012 60 22 34 31 Oxidation
Example Phenol
0.101 0.012 60 22 30 32 Oxidation
Example Phenol
0.110 0.012 60 22 33 33 Oxidation
Example Phenol
0.110 0.012 60 22 38 34 Oxidation
Example Phenol
0.001 0.012 60 22 26 35a Oxidation
Example Phenol
N/A 0.012 60 22 29 35b Oxidation
Example Phenol
N/A 0.012 60 22 85 35c Oxidation
* Example Phenol
0.001 0.012 60 22 100 36a Oxidation
Example Phenol
N/A 0.012 60 22 100 36b Oxidation
Example Phenol
N/A 0.012 60 22 100 36c Oxidation
Example Phenol
N.D. 0.012 60 22 100 37a Oxidation
Example Phenol
N/A 0.012 60 22 100 37b Oxidation Exam pie Phenol N/A 0.012 60 22 85 37c Oxidation
Example Phenol
N.D. 0.012 60 22 100 38a Oxidation
Example Phenol
N/A 0.012 60 22 100 38b Oxidation
Example Phenol
N/A 0.012 60 22 100 38c Oxidation
Example Phenol
0.102 0.012 60 22 69 39 Oxidation
Example Phenol
0.102 0.012 60 22 100 Oxidation
Example Phenol
0.001 0.012 60 22 40 41 a Oxidation
Example Phenol
N/A 0.012 60 22 76 41 b Oxidation
Example Phenol
N/A 0.012 60 22 90 41c Oxidation
Example Phenol
0.001 0.012 60 22 45 42a Oxidation
Example Phenol
N/A 0.012 60 22 73 42b Oxidation
Example Phenol
N/A 0.012 60 22 85 42c Oxidation
Example Phenol
N.D. 0.012 60 22 21 43a Oxidation
Example Phenol
N/A 0.012 -60 22 96 43b Oxidation
Example Phenol
N/A 0.012 60 22 100 43c Oxidation
Example Phenol
N.D. 0.012 60 22 29 44a Oxidation
Example Phenol
N/A 0.012 60 22 89 44b Oxidation
Example Phenol
N/A 0.012 60 22 100 44c Oxidation
Example Phenol
0.101 0.012 60 22 63 Oxidation
Example Phenol
0.101 0.012 60 22 45 46 Oxidation Example Phenol -_________ 0.100 0.012 60 22 24 47 Oxidation
Example Phenol
0.100 0.012 60 22 46 48 Oxidation
Example Phenol
0.002 0.012 60 22 27 49a Oxidation
Example Phenol
N/A 0.012 60 22 53 49b Oxidation
Example Phenol
N/A 0.012 60 22 34 49c Oxidation
Example Phenol
0.002 0.012 60 22 29 50a Oxidation
Example Phenol
N/A 0.012 60 22 53 SOb Oxidation
Example Phenol
N/A 0.012 60 22 36 50c Oxidation
Example Phenol
N.D. 0.012 60 22 30 51 a Oxidation
Example Phenol
N/A 0.012 60 22 40 51 b Oxidation
Example Phenol
N/A 0.012 60 22 37 51 c Oxidation
Example Phenol
N.D. 0.012 60 22 46 52a Oxidation
Example Phenol
N/A 0.012 60 22 43 52b Oxidation
Example Phenol
N/A 0.012 60 22 39 52c Oxidation
Example Phenol
0.110 0.012 60 22 31 53 Oxidation
Example Phenol
0.110 0.012 60 22 25 54 Oxidation
Example Phenol
N.D. 0.012 60 22 65 55a Oxidation
Example Phenol
N/A 0.012 60 22 83 55b Oxidation
Example Phenol
N/A 0.012 60 22 98 55c Oxidation
Example Phenol
N.D. 0.012 60 22 62 56a Oxidation
Example Phenol
N/A 0.012 60 22 87 56b Oxidation
Example Phenol
N/A 0.012 60 22 100 56c Oxidation
Example Phenol
N.D. 0.012 60 22 28 57a Oxidation
Example Phenol
N/A 0.012 60 22 89 57b Oxidation
Example Phenol
N/A 0.012 60 22 98 57c Oxidation
Example Phenol
N.D. 0.012 60 22 25 58a Oxidation
Example Phenol
N/A 0.012 60 22 89 58b Oxidation
Example Phenol
N/A 0.012 60 22 98 58c Oxidation
Example Phenol
N.D. 0.012 60 22 11 59a Oxidation
Example Phenol
N/A 0.012 60 22 16 59b Oxidation
Example Phenol
N/A 0.012 60 22 82 59c Oxidation
Example Phenol
N.D. 0.012 60 22 14 60a Oxidation
Example Phenol
N/A 0.012 60 22 11 60b Oxidation
Example Phenol
N/A 0.012 60 22 84 60c Oxidation
Example Phenol
N.D. 0.012 60 22 43 61 a Oxidation
Example Phenol
N/A 0.012 60 22 53 61 b Oxidation
Example Phenol
N/A 0.012 60 22 83 61 c Oxidation
Example Phenol
N.D. 0.012 60 22 42 62a Oxidation
Example Phenol
N/A 0.012 60 22 49 62b Oxidation
Example Phenol 82
N/A 0.012 60 22 62c Oxidation
S
Control Phenol N/A 60 22 26 Example N/A Oxidation 63 _________ Control Phenol 0.012 60 22 21 Example N/A Oxidation 64 ________ Control Phenol 0.012 60 22 22 Example N/A Oxidation
_________
Control Phenol 0.012 60 22 23 Example N/A Oxidation 66 _________ Control Phenol 22 22 0.012 60 Example N/A Oxidation 67 _________ Control Phenol 22 23 0.012 60 Example N/A Oxidation 68 _________ Control Phenol 22 23 0.012 60 Example N/A Oxidation Control Phenol 0.012 60 22 25 Example N/A Oxidation
__________
Control Phenol 22 23 0.012 60 Example N/A Oxidation Control Phenol 22 24 0.012 60 Example N/A Oxidation 72 __________ Control Phenol 22 6 0.012 60 Example N/A Oxidation Control Phenol 0.012 60 22 32 Example N/A Oxidation Control Phenol 0.012 60 22 11 Example N/A Oxidation Control Phenol Example N/A 0.012 60 22 8 Oxidation 76 __________
Example Estrone
N/A N/A 120 lx 10 58 83 Oxidation N/A = data not available N.D = not detected Discussion of Results -Examples I to 62 and 83 and Control Examples 63 to Examples I to 10 and Control Examples 64 to 66 Examples 1 to 10 and Control Examples 64 to 66 all relate to catalysts made from WOOLMARK wool.
Catalysts comprising wool that was modified with a mixture of hydrazine and hydroxylamine and impregnated with Fe3 cations (Examples I to 3) had similar conversions of phenol (98 to 99%) as catalysts comprising wool modified with hydroxylamine only and impregnated with Fe3 cations (99 to 100%) (Examples 4 to 6).
A difference between the catalysts of Examples I to 3 and Examples 4 to 6 was the iron content of the catalyst and the extent of iron removal from the catalyst by EDTA. The catalysts of Examples 1 to 3, modified with a mixture of hydrazine and hydroxylamine, had an iron content of 0.044 mmol/g wool and the catalysts of Examples 4 to 6, modified with hydroxylamine only, had an iron content of 0.076 mmol/g wool. In the catalysts of Examples I to 3 0.002% of iron was removed, whereas for the catalysts of Examples 4 to 6 iron could not be detected in solution after exposure to EDTA and hence was not removed. Without wishing to be bound by any theory, it is believed that the higher iron loading and retention for the catalysts of Examples 4 to 6 potentially may produce a more efficient catalyst with respect to phenol conversion and catalyst lifetime.
In the catalysts of Examples 7 and 8 (with scouring) and 9 and 10 (without scouring), where there was no modification of the wool prior to impregnation with Fe3 cations, the iron content was reduced and the iron removal was increased, compared to the catalysts of Examples 1 to 6 with a modification step. Typically, the catalysts of Examples 7 to 10 also provided reduced conversions of phenol compared to Examples 1 to 6.
A comparison of the catalyst of Control Example 64 with the catalysts of Examples 1 to 3, of the catalyst of Control Example 65 with the catalysts of Examples 4 to 6 and of the catalyst of Control Example 66 with the catalysts of Examples 7 and 8 shows that without the presence of the active catalyst site (i.e. Fe3) the conversion degree of phenol is minimal. Thus impregnation with first metal ions (i.e. Fe3) is necessary in order to optimise the catalyst performance.
Examples 11 to 14
Examples 11 to 14 all relate to catalysts made from DEFRA wool.
Catalysts comprising wool that was modified with a mixture of hydrazine and hydroxylamine (Example 14), with hydroxyfamine only (Example 13) and with hydrazine only (Example 12), and impregnated with Fe3 cations had improved conversions of Acid Blue 45 compared to a catalyst comprising wool that was impregnated with Fe3 cations but not modified (Example 11).
The catalysts of Examples 12 to 14 had a higher iron loading and retention than the catalyst of Example 11.
Examples 15 to 24 and Control Examples 67 to 69 Examples 15 to 24 and Control Examples 67 to 69 all relate to catalysts made from DEFRA wool.
Catalysts comprising wool that was modified with a mixture of hydrazine and hydroxytamine and impregnated with Fe3 cations (Examples 15 to 17) and modified with hydroxylamine only and impregnated with Fe3 cations (Examples 18 to 20) had improved conversions of phenol compared to catalysts impregnated with Fe3 cations where the wool was not modified (Examples 21 and 22).
A difference between Examples 15 to 17 and 18 to 20 was the iron content of the catalyst and the extent of iron removal from the catalyst by EDTA. The catalysts S 55 of Examples 15 to 17, modified with a mixture of hydrazine and hydroxylamine, had an iron content of 0.037 mmol/g wool and the catalysts of Examples 18 to 20, modified with hydroxylamine only, had an iron content of 0.076 mmol/g wool. In the catalysts of Examples 15 to 17 0.001% of iron was removed, whereas for the catalysts of Examples 18 to 20 iron could not be detected in solution after exposure to EDTA and hence was not removed. Without wishing to be bound by any theory, it is believed that the higher iron loading and retention for the catalysts of Examples 18 to 20 potentially may produce a more efficient catalyst with respect to phenol conversion and catalyst lifetime.
In the catalysts of Examples 21 and 22 (with scouring) and 23 and 24 (without scouring), where there was no modification of the wool prior to impregnation with Fe3 cations, the iron content was reduced and the iron removal was increased, compared to the catalysts of Examples 15 to 20 with a modification step. Typically, Examples 21 to 24 also provided reduced conversions of phenol compared to
Examples 15 to 20.
A comparison of the catalyst of Control Example 67 with the catalysts of Examples 15 to 17, of the catalyst of Control Example 68 with the catalysts of Examples 18 to 20 and of the catalyst of Control Example 69 with the catalysts of Examples 21 and 22 shows that without the presence of the active catalyst site (i.e. Fe3) the conversion degree of phenol is minimal. Thus impregnation with first metal ions (i.e. Fe3) is necessary in order to optimise the catalyst performance.
Examples 25 to 40 and Control Examples 70 to 72 Examples 25 to 40 and Control Examples 70 to 72 all relate to catalysts made from Herdwick wool.
Catalysts comprising wool that was modified, with a mixture of hydrazine and hydroxylamine (Examples 25 to 27, 35 and 36) and with hydroxylamine only (Examples 28 to 30, 37 and 38), and impregnated with Fe3 cations had improved conversions of phenol compared to the catalyst comprising wool that was impregnated with Fe3 cations but not modified (Examples 31, 32, 39 and 40).
A comparison of the catalyst of Control Example 70 with the catalysts of Examples 35 and 36, of the catalyst of Control Example 71 with the catalysts of * 56 Examples 37 and 38 and of the catalyst of Control Example 72 with the catalysts of Examples 39 and 40 shows that without the presence of the active catalyst site (i.e. Fe3) the conversion degree of phenol is minimal. Thus impregnation with first metal cations (i.e. Fe3) is necessary in order to optimise the catalyst perlomiance.
Examples 41 to 54
Examples 41 to 54 all relate to catalysts made from Swaledale wool.
Catalysts comprising wool that was modified, with a mixture of hydrazine and hydroxylamine (Examples 41, 42, 49 and 50) and with hydroxylamine only (Examples 43, 44, 51 and 52), and impregnated with Fe3 cations generally had improved conversions of phenol compared to the catalyst comprising wool that was impregnated with Fe3 cations but not modified (Examples 45, 46, 53 and 54).
The catalysts of Examples 41 to 43 and 51 to 54 to 14 had a higher iron loading and retention than the catalyst of Examples 45 to 48, 53 and 54.
Example 83
Example 83 relates to a catalyst made from CROSSES wool, modified with hydroxylamine only and impregnated with Fe3 and Ca2 cations. The catalyst was effective in the oxidative decomposition of Estrone.
Summary
The catalysts comprising a wool fibre and an iron cation fixed to the wool fibre were all catalytically active in Examples 1 to 62. It is believed that the Control Examples that use a wool fibre to which no iron cation is fixed apparently show some conversion due to possible sorption of hydrogen peroxide and/or chemical reaction of hydrogen peroxide with the wool. However, it is clear that the wool fibre with an iron cation fixed thereto acts as an efficient catalyst in the oxidation reactions shown above.
In general, catalysts prepared from wools that were modified prior to impregnation, especially wools modified with hydroxylamine only, have higher iron contents and higher phenol conversions. Additionally, modified wool samples appear * 57 to allow iron to be fixed more strongly to the wool (as the iron removal by EDTA is lower than for unmodified samples). In general, for catalysts made from wools that were modified, good batch-to-batch reproducibility was achieved.
Additionally, for catalysts where the wool was not modified prior to impregnation, it was generally observed that iron content was lower, with the amount of iron removed by EDTA greater. Typically, phenol conversions were lower than those obtained using modified wool, but these catalysts still showed improved phenol conversions over wool containing no iron cations.
Examples 77 to 82
Examples 77 to 82 relate to the evaluation of the catalysts for catalytic activity using a dynamic flow reactor. In these Examples, the wool was modified with hydroxylamine prior to impregnation with iron cations. All catalytic activity evaluations contained hydrogen peroxide (5Oppm) in the feed.
In Examples 77 to 82, the activity of the catalyst was determined in relation to the decomposition (by oxidation) of phenol.
In Examples 77 to 82, the catalysts were evaluated in a dynamic reactor.
Phenol Decomposition Examples 77 to 82 were conducted as follows: Catalyst (2g) was placed in a reactor and air was bubbled through at a rate of ml min1 as measured and controlled by a flow meter. A continuous flow of aqueous phenol solution (24ppm) containing hydrogen peroxide (5Oppm) was pumped through the reactor at a flow of 2 ml min1. The retention time within the reactor was 30 minutes. Samples were taken from the reactor outlet at regular time intervals and analysed for phenol by HPLC (using a Waters 510 HPLC pump). A standard C-18 (250 x 4.6mm) packed column was used for the stationary phase.
The mobile phase was a mixture of methanol (40%) and double distilled water (60%) with a flow of 1 ml min1. Sample volumes of 2Opl were injected and detected using UV (using a Philips PYE UNICAM PU 4025 UV Detector at Amax 254nm). The sample times were 5, 15, 30, 90, 120, 150, 180, 210, 240 and 300 minutes and then every 60 minutes until deactivation occurred and no further decrease in phenol concentration was observed (catalyst no longer active). Multiple samples from the same production batch were evaluated where deemed necessary.
The data collected in each dynamic study was used to calculate the following values: * The yield degree (a) of the substance (the substance being phenol in
Examples 77 to 82)
* The mass (M) of the substance decomposed (the substance being phenol in
Examples 77 to 82)
* The turn-over frequency (TOF) The yield degree of the substance (a) was calculated using the following equation:
S Co
where: S = Area above the dynamic curve calculated by the total area minus the area below the curve obtained by integration using a suitable computer program, in these examples using the computer program Origin (see Figure 1 relating to
Example 78)
= ratio between concentration of the substance in solution at time t (Ce) and initial concentration (C0) t duration of the process (minutes) The total area in Figure 1 is 2520 (Xmax X Yma*) and the area below the curve obtained through integration is 589.35, therefore in this case S 2520 -589.35.
Mass of the substance decomposed (by oxidation) M (mg) on the catalyst during the dynamic process was calculated as follows: M = a x Q x � x C0 where: a = the yield degree of the substance (calculated as set out above) Q = flow rate (mI/mm), which was 2 mI/mm for all experiments t = duration of the process (minutes) C0 = initial concentration of the substance in solution Turn-Over Frequency (TOE) is expressed as follows and relates the amount of phenol decomposed to the active sites on the catalyst: TOF = [Phenol] [Fe] x [Wool] x t where: [Phenolj = amount of phenol decomposed (mmol) (Fe] = concentration of iron (mmol / g wool) [Wool] = amount of wool. support (g), which was 2g in all cases.
Table 3 shows the results obtained for the dynamic evaluation. It is desirable to achieve the highest possible catalysts lifetime and/or the highest possible TOF.
Example 77
In Example 77, the catalyst used was Crosses wool that was laboratory scoured, modified with hydroxylamine and impregnated with Fe3 catioris.
Examples 78 and 79
In Examples 78 and 79, the catalysts used were Crosses wool that was mill scoured, modified with hydroxylamine and impregnated with Fe3 cations. Example 78 was from one batch of catalyst prepared and Example 79 from another to investigate reproducibility. S 60
Example 80
In Example 80, the catalyst used was Crosses wool that was mill scoured, modified with hydroxylamine and impregnated with Fe3 and Ca2 cations.
Examples 81 and 82
In Examples 81 and 82, the catalysts used were Crosses wool that was mill scoured, modified with hydroxylamine and impregnated with Fe3 and Li cations.
Two batches were again investigated for reproducibility.
Table 3 contains the results for the wool catalysts of Examples 77 to 82 evaluated in the dynamic reactor.
Table 3-Catalytic Activity Results for Examples 77 to 82 Reactor Retention Feed Catalyst Phenol TOF Catalytic.3 Example volume time concentration lifetime decomposed (x 10) process.
(ml) (mm) (mgIl) (hours) (mg) (mm)
Example Phenol
30 24 42 99.915 2.4018 77 Oxidation ________
Example Phenol
30 24 42 99.930 2.8544 78 Oxidation _______
Example Phenol
30 24 42 103.065 2.6789 79 Oxidation ________
Example Phenol
30 24 49 132.289 2.9730 Oxidation ________
Example Phenol
30 24 60 154.565 2.8835 81 Oxidation ________
Example Phenol
30 24 60 158.006 2.9477 82 Oxidation As shown in Table 3, the catalysts of Examples 77 to 79 had similar catalytic activity, with a lifetime of 42 hours. The lifetime and TOF was improved using an impregnation solution of Fe3/Ca2 or Fe3/Li (see Examples 80 to 82). Example 80 showed that using Fe3/Ca2 the lifetime was increased to 49 hours and the TOE increased to 2.9730 x i0 min1. Using Fe3/Li, the lifetime was improved to 60 * 61 hours with consequently more phenol decomposed, however TOF remained at about 2.9100 x i0 min' (Examples 81 and 82). * 62

Claims (28)

  1. Claims 1. A method of catalysing a chemical reaction, wherein the method comprises the step of contacting one or more reactants with a catalyst, wherein the catalyst comprises a keratinous support and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, under conditions for catalysis of the chemical reaction.
  2. 2. A method according to claim 1, wherein the chemical reaction is an oxidation reaction.
  3. 3. A method according to claim I or 2, wherein the one or more reactants are contacted with the catalyst in the presence of an oxidant.
  4. 4. A method according to any one or more of claims I to 3, wherein the one or more reactants are included in a waste stream.
  5. 5. A method according to any one or more of claims 1 to 4, wherein the first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper cation, and mixtures thereof.
  6. 6. A method according to claim 5, wherein the first metal cation is an iron cation.
  7. 7. A method according to any one of claims I to 6, further comprising the step of preparing the catalyst.
  8. 8. A method for preparing a catalyst, the method comprising the steps of: (i-a) treating a keratinous support with a hydrazine salt and a hydroxylamine salt in the presence of a base to provide a modified keratinous support; and (il-a) treating the modified keratinous support with an aqueous solution comprising a salt of a first metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, * 63 palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof.
  9. 9. A method for preparing a catalyst, the method comprising the steps of: (i-b) treating a keratinous support with a hydrazine salt in the presence of a base to provide a modified keratinous support; and (u-b) treating the modified keratinous support with an aqueous solution comprising a salt of a first metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof.
  10. 10. A method for preparing a catalyst, the method comprising the steps of: (i-c) treating a keratinous support with an aqueous solution of a hydroxylamine salt in the presence of a base to provide a modified keratinous support, wherein the concentration of the hydroxylamine salt in the aqueous solution is in the range of from 14 to 70 g/l; and (li-c) treating the modified keratinous support with an aqueous solution comprising a salt of a first metal cation, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof.
  11. 11. The method according to any one or more of claims 8 to 10, wherein the aqueous solution in step (u-a), (li-b) or (u-c) further comprises a salt of a second metal cation, which second metal cation is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminium, gallium, indium, thallium, tin, lead, antimony and bismuth, and * mixtures thereof.
  12. 12. A method for preparing a catalyst, the method comprising the steps of: (i-d) treating a keratinous support with a hydroxylamine salt in the presence of a base to provide a modified keratinous support; and (ii-d) treating the modified keratinous support with an aqueous solution comprising a salt of a first metal cation and a salt of a second metal cation, which first * 64 metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold cation, and mixtures thereof, and which second metal cation is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminium, gallium, indium, thallium, tin, lead, antimony and bismuth, and mixtures thereof.
  13. 13. A method according to any one or more of claims 8, 9 and 11, wherein the hydrazine salt is selected from hydrazine dihydrochloride, hydrazine monohydrochioride, hydrazine hydrate, hydrazine monohydrobromide, hydrazine acetate and hydrazine sulfate, and mixtures thereof.
  14. 14. A method according to any one or more of claims 8 and 10 to 13, wherein the hydroxylamine salt is selected from hydroxylamine monohydrochloride, hydroxylamine sulfate and hydroxylamine phosphate, and mixtures thereof.
  15. 15. A method according to any one or more of claims 8 to 14, wherein step (i-a), (i-b), (i-c) or (i-d) is conducted at a pH in the range of from 4 to 9.5.
  16. 16. A method according to any one or more of claims 8 to 15, wherein the base is selected from sodium hydroxide, potassium hydroxide and sodium carbonate, and mixtures thereof.
  17. 17. A method according to any one or more of claims 8 to 16, wherein the first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper cation, and mixtures thereof.
  18. 18. A method according to claim 17, wherein the first metal cation is an iron cation.
  19. 19. A method according to any one or more of claims 11 to 18, wherein the second metal cation is selected from a lithium, sodium, potassium, magnesium, calcium, zinc and aluminium cation, and mixtures thereof.
  20. 20. A method according to any one or more of claims 8 to 19, further comprising a pre-treatment step comprising scouring the keratinous support.
  21. 21. A method according to claim 7, wherein the catalyst is prepared according to the method of any one or more of claims 8 to 20.
  22. 22. A method according to any one or more of claims 1 to 21, wherein the keratinous support is a wool fibre.
  23. 23. A catalyst obtainable by a method according to any one or more of claims 8 to 22.
  24. 24. A catalyst comprising a keratinous support and a first metal cation fixed to the keratinous support, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, indium, platinum and gold cation, and mixtures thereof and wherein the first metal cation is present in an amount of from 0.03 mmol or greater per gram of keratinous support.
  25. 25. A catalyst comprising a wool fibre and a first metal cation fixed to the wool fibre, which first metal cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rheniumi, osmium, iridium, platinum and gold cation, and mixtures thereof and wherein the first metal cation is present in an amount of from 0.03 mmol or greater per gram of wool fibre.
  26. 26. A catalyst according to claim 24 or 25, wherein the first meta' cation is selected from a scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper cation, and mixtures thereof.
  27. 27. A catalyst according to claim 26, wherein the first metal cation is an iron cation.
  28. 28. A method or catalyst generally as herein described.
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GB2346569A (en) * 1998-12-30 2000-08-16 Univ Montfort Method for the production of fibrous catalysts
CN1788847A (en) * 2004-12-15 2006-06-21 中国科学院物理研究所 Carbon wool ball carried type catalyst and its preparation method and uses

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EP3521319B1 (en) * 2016-09-27 2024-01-10 National Institute of Advanced Industrial Science And Technology Method for liberating sugar chain from glycoprotein
CN108636430A (en) * 2018-04-20 2018-10-12 华东理工大学 A kind of preparation method and applications of the basic zirconium phosphate heterogeneous catalyst of vanadium modification
CN108636430B (en) * 2018-04-20 2020-10-13 华东理工大学 Preparation method and application of vanadium-modified zirconium phosphate heterogeneous catalyst

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