Ammoximation method

FIELD: chemistry.

SUBSTANCE: invention relates to a redox ammoximation method, wherein a ketone or aldehyde reacts with ammonia and oxygen in the presence of a catalyst, where the catalyst is a redox catalyst based on aluminophosphate, having a qualitative general formula M1M2AlPO-5 (I), where M1 denotes at least one transition metal selected from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V) and Ru(III); M2 denotes a metal selected from Ge(IV), Sn(IV), Re(IV), V(IV) and mixtures thereof; M1 and M2 are different from each other; and a certain portion of phosphorus atoms in the structure of the type M1M2AlPO-5 is substituted with atoms of M2. Also disclosed is a redox ammoximation catalyst.

EFFECT: providing a selective ammoximation method.

11 cl, 5 tbl, 6 dwg, 16 ex

 

The present invention relates to a method of maximiliane using a redox catalyst containing lumotast, usually referred to as "AlPO" system.

Connection AlPO well known and known to their use as molecular sieves and as catalysts for various processes, for example, as described in US4567029. They are nanoporous solids with channels, penetrating all the material, giving this material a very large surface area that can be used for catalysis. The basic structure contains atoms of aluminum, phosphorus and oxygen, where some of the aluminum atoms substituted by one or more other atoms, to provide the desired catalytic activity.

J.M. Thomas & R. Raja, [Design of a "green" one-step catalytic production of ε-caprolactam (precursor of nylon-6), Proceedings Natl. Acad. USA, 102, 13732-13736 (2005)]; R. Raja, G. Sankar & J.M. Thomas, [Bifunctional molecular sieve catalysts for the bening ammoximation of cyclohexanone: One-step, solvent-free production of oxime and ε-caprolactam with a mixture of air and ammonia, J. Am. Chem. Soc. 123, 8153-8154 (2001)] and Nature (October 2005, Vol. 437; page 1243) describe the method of preparation of certain predecessors nylon, in particular ε-caprolactam, using such AlPO catalysts, in particular AlPO catalysts having at least two active site, one of which is a redox center, is usually based the m atoms With(III), Mn(III) or Fe(III), and the other is Pentecostal acid center, usually based on the atoms of Zn(II), Mg(II) or Co(II). In these structures, both metal replaces aluminum in the structure of AlPO. Two types of centers are well separated in the three-dimensional structure of AlPO and separately affect raw materials. As a result, it is possible to turn cyclohexanone raw materials in ε-caprolactam with an efficiency of over 70%, about 80%, at one stage, and not to use multi-stage procedure used in present - see Nature (op cit).

However, for commercial purposes 70% conversion is not appropriate, and therefore, although the reaction proposed in the above literature, it is very elegant and has considerable scientific interest, it currently has little commercial value.

In addition, there is a request to obtain compounds which can serve as intermediates for other useful products. These intermediate compounds include oximes, in particular cyclohexanone-oxime.

As described in international patent application number PCT/GB2008/002286, the present inventors unexpectedly discovered that modification of the catalyst used in the reaction described above, capable of performing maximiliane with the best output. The resulting oxime can then effectively be transformed using well-known reactions in W is being ε-caprolactam.

In particular, international patent application number PCT/GB2008/002286 describes how redox maximiliane, in which a ketone or aldehyde is reacted with ammonia and oxygen in the presence of a catalyst, where the catalyst is a redox catalyst based alumophosphate having at least two different redox catalytic center that contains atoms of different transition metals. The catalyst described in international patent application number PCT/GB2008/002286, has the overall quality of the formula (I) or (II):

M1M2AlPO (I)

or

M1M2SalPO (II)

where M1and M2differ from each other and each denotes a transition metal atom having a redox catalytic ability; and

some of the phosphorus atoms can be substituted by other equivalent atoms.

Although the catalysts described in international patent application number PCT/GB2008/002286 provide improved catalytic properties over known catalysts, for example, when performing reactions maximiliane, the present inventors prepared the new catalysts, which unexpectedly show superior catalytic properties or comparable catalytic properties compared with catalysts, description is nami in international patent application number PCT/GB2008/002286. Described here catalysts show high selectivity and conversion (% mol.) the cyclohexane oxime, when conducting maximilianii cyclohexanone with ammonia, using air as oxidant.

The aim of the present invention is to address at least some of the problems and shortcomings of the prior art and to provide an effective and selective method of maximiliane.

In the first aspect of the present invention is provided by way redox maximiliane, in which a ketone or aldehyde is reacted with ammonia and oxygen in the presence of a catalyst, where:

a catalyst is a redox catalyst based alumophosphate with the qualitative General formula (I):

M1M2AlPO-5 (I)

where M1means, at least one atom of the transition metal having a redox catalytic ability;

M2means, at least one metal in oxidation state (IV);

M1and M2differ from each other; and some of the phosphorus atoms in the structure of type M1M2AlPO-5 substituted by atoms of M2.

In the second aspect of the present invention offers a redox catalyst based alumophosphate, have s qualitative General formula (I):

M1M2AlPO-5 (I)

where M1means, at least one atom of the transition metal having a redox catalytic ability;

M2means, at least one metal in oxidation state (IV);

M1and M2differ from each other; and some of the phosphorus atoms in the structure of type M1M2AlPO-5 substituted by atoms of M2.

The term "lumotast with the qualitative General formula (I): M1M2AlPO-5 (I)"used here, is used to describe bimetallicheskie-substituted aluminophosphate molekularbiologie catalyst. Alumophosphate formed of alternating tetrahedra AlO45-and RHO43-connected together by a bridge of the total oxygen. These elements are combined together, forming a multitude of secondary structural elements, which are joined together in different positions, forming the structure of the AlPO-5. Redox active centers are formed by substitution of (isomorphism) of small amounts of structural aluminum and phosphorus ions M1and M2. This simplified form is depicted in figure 1. By performing only the minimum isomorphous substitution (usually approximately 2% of the mass. up to 18% of the mass. or from about 2 to 10% of the mass. ions of aluminum and is roughly 2% of the mass. up to 18% of the mass. or from about 2 to 10% of the mass. ions of phosphorus) there are two types of active centers, which are usually well separated (usually isolated), and usually essentially evenly distributed on the structure of AlPO, forming thus two coexisting one heterogeneous catalyst. The metal-containing alumophosphate and methods for their preparation are known in the art, the details of which are given below. The terminology "M1M2AlPO" is well known in the art, see, for example, R. Raja, G. Sankar & J.M. Thomas, [Bifunctional molecular sieve catalysts for the bening ammoximation of cyclohexanone: One-step, solvent-free production of oxime and ε-caprolactam with a mixture of air and ammonia, J. Am. Chem. Soc. 123, 8153-8154 (2001)].

The expression "structure type "M1M2AlPO-5"is used here to describe the open structure of the aluminophosphate molecular sieves. Such structures are well known in the art.

The expression "portion of the phosphorus atoms in the structure of type M1M2AlPO-5 substituted by atoms of M2" is used here to describe the case when part of the phosphorus atoms in the formula (I) substituted by atoms of M2that leads to isomorphic substitution in the lattice AlPO. For example, some of the phosphorus atoms can be replaced by titanium atoms. Usually from 2 to 18 wt. -%, more preferably from 2 to 10% of the mass. ions of phosphorus are replaced by ions of M2.

The metal atom is redox capacity is defined here as the atom, where there is a change in the oxidation state of the metal atom during the catalytic process. For example, With(III), Mn(III), etc. are restored to the Co(II) and Mn(II) during the catalytic process. Without regard to any particular theory, it is believed that the change in the degree of oxidation leads to the formation of free radicals (initiation phase), which leads to a concomitant oxidation of the ketone into the oxime by free-radical route in the presence of oxygen.

Every aspect specified here can be combined with any other aspect or aspects, unless otherwise noted. In particular, any sign that is specified as preferred or advantageous may be combined with any other sign or signs, which is the preferred or preferential.

Without wanting to be bound by any particular theory, believe that the introduction of centers M2(preferably Ti(IV)in connection with the redox center (M1(in particular, From(III) and Mn(III)) leads to a tetrahedral active centers M2(preferably Ti(IV)). This is shown by studies on UV seemingly diffuse reflection. In contrast, in monometallic TiAlPO-5 catalysts characteristic broadening of the peak is observed at 230 nm. It is believed that this occurs because of the presence of tedionica titanium particles. It turns out that the presence of tetrahedral redox active centers M1very close to the tetrahedral M2(preferably Ti(IV)) has a synergistic effect on the catalytic activity and selectivity of the redox centers, leading to improved catalyst and improved method of maximiliane.

M1represents a transition metal atom having a redox catalytic ability. Preferably M1choose from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V), Ru(III) and mixtures thereof. In one embodiment, M1choose from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V), Ru(III). More preferably M1choose from Co(III), Mn(III), Fe(III) and mixtures thereof. Even more preferably M1choose from Co(III), Mn(III) and mixtures thereof.

M2represents at least one metal in oxidation state (IV). Preferably M2choose from, at least, Ge(IV), Sn(IV), the transition metal in oxidation state (IV) and mixtures thereof. For example, M2may be at least one transition metal in oxidation state (IV)selected from Ti(IV), Re(IV), V(IV) and mixtures thereof. Preferably M2choose from the Ge(IV), Sn(IV), Ti(IV), Re(IV), V(IV) and mixtures thereof. In one embodiment, M2choose from the Ge(IV), Sn(IV), Ti(IV), Re(IV) and V(IV). In another embodiment, Khujand the exercise of M 2choose from the Ge(IV), Sn(IV), Re(IV), V(IV) and mixtures thereof. More preferably M2choose from Ti(IV), V(IV) and mixtures thereof. Even more preferably M2is a Ti(IV).

In one embodiment, M2represents at least one transition metal in oxidation state (IV)other than Ti(IV).

In another embodiment, M1choose from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V), Ru(III) and mixtures thereof, and M2choose from, at least, Ge(IV), Sn(IV), the transition metal in oxidation state (IV) and mixtures thereof. Preferably M1choose from Co(III), Mn(III), Fe(III) and mixtures thereof, and M2choose from one of Ge(IV), Sn(IV), Ti(IV), Re(IV), V(IV) and mixtures thereof.

In another embodiment, M1choose from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V), Ru(III) and mixtures thereof, and M2choose from the at least one transition metal in oxidation state (IV) and mixtures thereof. Preferably M1choose from Co(III), Mn(III), Fe(III) and mixtures thereof, and M2selected from at least one of Ti(IV), Re(IV), V(IV) and mixtures thereof.

In an additional embodiment, M1choose from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V), Ru(III) and mixtures thereof, and M2choose from the Ge(IV), Sn(IV) and mixtures thereof. Preferably M1choose from Co(III), Mn(III), Fe(III) and mixtures thereof, and M2choose from the Ge(IV), Sn(IV) and mixtures thereof.

In a preferred embodiment, the catalysate is R is chosen from the Co IIITiIVAlPO, MnIIITiIVAlPO, FeIIITiIVAlPO, CrVITiIVAlPO, CuIIITiIVAlPO, VVTiIVAlPO and ENIIITiIVAlPO. More preferably the catalyst is chosen from the CoIIITiIVAlPO and MnIIITiIVAlPO.

In one embodiment, only one type of M1and one type of M2present in the catalyst. In another embodiment, at least two types of M1and one type of M2present in the catalyst. In another embodiment, at least one type of M1and two types of M2present in the catalyst. In yet another embodiment, at least two types of M1and at least two types of M2present in the catalyst.

Specific preferred examples of these catalysts are the CoIIITiIVAlPO-5 or MnIIITiIVAlPO-5. They are especially used in the processes of maximiliane and, more specifically, used in maximilianii cyclohexanone.

The catalyst of the present invention may include silicon (IV). Preferably Si(IV) replaces at least part of the phosphorus atoms in the structure of type M1M2AlPO-5. Thus, in one embodiment, the present invention redox catalyst based alumophosphate has as the percent of the General formula (II)

M1M2SiAlPO-5 (II)

where M1means, at least one atom of the transition metal having a redox catalytic ability;

M2means, at least one metal in oxidation state (IV);

M1and M2differ from each other; and some of the phosphorus atoms in the structure of type M1M2AlPO-5 substituted by atoms of M2.

Links to M1and M2described herein in relation to formula (I)also apply to M1and M2in the formula (II).

Metal-containing aluminophosphate catalysts and methods for their preparation are known in the art. Catalysts containing one redox catalytic center, described for example in US-A-4567029, "Catalytically active centres in porous oxides: design and performance of highly selective new catalysts", J.M. Thomas and R. Raja, Chem. Comm., 2001, 675-787 and Design of a "green" one-step catalytic production of ε-caprolactam (precursor of nylon-6)", J.M. Thomas and R. Raja, PNAS, Vol 102/39), 13732-13736. Catalysts with two metal centers can be prepared in a similar manner. Catalysts with three metal centers can also be prepared in a similar manner, see, e.g., Catal. Lett.99, 2005, 231 by Zhou et al.

In General the procedure is as follows: source of phosphorus (usually 85% N3RHO4and the required amount of distilled demonsbane the H 2On the first mix, for example, with gentle stirring (400 rpm), for example, using a mechanical stirrer in lined with Teflon autoclave. To this mixture add the source of aluminum (usually Al(OH)3), preferably slowly. The two sources of redox metals (M1and M2) is dissolved in water and then added, preferably slowly, to a previously prepared mixture of Al-H3RHO4(preferably with stirring). Appropriate (depending on the desired type of structure) matrix (represented by the structure of the agent) is then introduced dropwise with vigorous stirring (for example, at 1700 rpm), and the gel can withstand, for example, for about 1-2 hours at 298 K. This gel is then heated in order to synthesize the desired type of structure, for example, it can be sealed in lined with Teflon autoclave of stainless steel and heated to the desired temperature under autogenous pressure for the required amount of time. The solid product is isolated, preferably by filtration or by centrifugation (after crystallization), washed with a large quantity of distilled deionized water and dried under vacuum (90-120°C). Thus prepared, the product is calcined, for example, at 550°C, first in nitrogen for 4 hours and then in a dry kislorod for 16 hours before use as a catalyst.

The phase purity, structural integrity and the crystallinity of the final catalyst can be proved by using a combination of powder x-ray diffraction analysis (PCA)spectroscopy x-ray absorption (XAS) and electron tomography high resolution. The exact stoichiometry (with an error of about ± 3·10-3) can be determined by analysis with induction-coupled plasma (ICP) (metal).

The present invention will now be described additionally, only as an example, with reference to the following drawings, where:

Figure 1 is a schematic representation of the centers of substitution.

Figures 2 and 3 show x-ray diffraction patterns of the two metals embedded in AlPO-5.

Figure 4 shows the image of scanning electron microscopy CoMnAlPO-5.

Figure 5 shows an image of scanning electron microscopy CoTiAlPO-5.

Figure 6 shows the image of scanning electron microscopy MnTiAlPO-5.

In the method of the present invention, the ketone or aldehyde is reacted with ammonia and oxygen. The ketone or aldehyde may be any ketone or aldehyde, for example, With3-C20ketone or2-C20aldehyde, and may be linear, branched or cyclic. Preferred ketones are cyclic ketones, for example, With -C12cyclic ketones, where C6and C12ketones are the most preferred. Cyclohexanone is especially preferred ketone. Preferred aldehydes include cyclic or aromatic ring, particularly a ring With a6. The preferred aldehyde is benzaldehyde. The ketone or aldehyde may be unsubstituted or substituted, for example, With1-C4alkyl or alkenylphenol group, HE or halogen. The ammonia can be in the form of a gas or dissolved in a solvent such as water. For commercial applications, it is preferably in the form of gas. In other applications it may be preferable that he was in the form of aqueous ammonium hydroxide. No additional solvent other than water present in aqueous ammonium hydroxide, is generally not required but may be used if desirable. If additional solvent is used, it preferably is inert. Oxygen provide in the form of a gas, for example, in the form of O2or air.

The reaction product is typically a reaction corresponding to the original ketone or aldehyde. Thus, for example, the present invention can be used to maximiliane of cyclohexanone to cyclohexanone oxime, which is a precursor for ε-kaprol the Tama, and the ε-caprolactam is an important precursor for nylon-6, for which there is a large and growing market, and therefore this reaction is particularly preferred. It can also be used to maximiliane benzaldehyde in the reaction of benzaldehyde. In the reaction of cyclohexanone or benzaldehyde reacts with ammonia, preferably in gaseous form for commercial applications, however, it may be in the form of aqueous ammonium hydroxide) and oxygen (which may be provided in the form of pure oxygen or air) in the presence of this catalyst.

This reaction will take place in a wide range of temperatures and pressures, and the exact temperature and pressure are not critical to the present invention. However, the authors usually prefer to conduct the reaction under heating, for example at a temperature in the range from 40 to 200°C., preferably from 50 to 150°C., more preferably from 50 to 90°C. is Preferably used pressure, for example, from 0.5 MPa [5 bar] up to 10 MPa [100 bar], more preferably from 1 to 5 MPa, and most preferably from 3 [30 bar] up to 3.5 MPa [35 bar].

The resulting oxime can turn into other compounds, for example, lactam. A suitable method using a Beckmann rearrangement described in PNAS 102 (39) 13732-13736.

The oxime can turn into ε-caprolactam is using known methods. One such known method described in K Wessermel and H. J. Arpe, Industrial Organic Chemistry 1978, p255.

The method of the present invention ensures oxime with an unexpectedly high rate of conversion and good selectivity. The data in table 1 from J. Am. Chem. Soc. 2001, 123, 8153-4 show the magnitude of the conversion of 6 hours up to 20%. In the method according to the present invention is achieved, the conversion value of at least 40%, preferably at least 50% or at least 60%, as described in the following examples.

In one aspect of the present invention offers a redox catalyst based alumophosphate with the qualitative General formula (I):

M1M2AlPO-5 (I)

where M1means, at least one atom of the transition metal having a redox catalytic ability;

M2means, at least one metal in oxidation state (IV);

M1and M2differ from each other; and some of the phosphorus atoms in the structure of type M1M2AlPO-5 substituted by atoms of M2.

M1represents at least one transition metal atom having a redox catalytic ability. Preferably M1choose from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V), Ru(III) and mixtures thereof. In one embodiment, M1 choose from one of the Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V) and Ru(III). More preferably M1choose from Co(III), Mn(III), Fe(III) and mixtures thereof. Even more preferably M1choose from Co(III), Mn(III) and mixtures thereof.

M2represents at least one metal in oxidation state (IV). Preferably M2selected from at least one of Ge(IV), Sn(IV), the transition metal in oxidation state (IV) and mixtures thereof. For example, M2may be at least one transition metal in oxidation state (IV)selected from Ti(IV), Re(IV), V(IV) and mixtures thereof. Preferably, M2choose from the Ge(IV), Sn(IV), Ti(IV), Re(IV), V(IV) and mixtures thereof. In one embodiment, M2choose from the Ge(IV), Sn(IV), Ti(IV), Re(IV) and V(IV). You can choose M2of Ge(IV), Sn(IV), Re(IV), V(IV) and mixtures thereof. More preferably M2choose from Ti(IV), V(IV) and mixtures thereof. Even more preferably M2is a Ti(IV).

In a preferred embodiment, the catalyst is chosen from the CoIIITiIVAlPO, MnIIITiIVAlPO, FeIIITiIVAlPO, CrVITiIVAlPO, CuIIITiIVAlPO, VVTiIVAlPO and ENIIITiIVAlPO. More preferably the catalyst is chosen from the CoIIITiIVAlPO and MnIIITiIVAlPO.

The present invention will be further illustrated with reference to the following, non-limiting example is.

Patterns AlPO-5 was synthesized using N-methyldicyclohexylamine (MDCA) as specifying the structure of the agent (ZSA). The desired lattice reached, starting with the exact composition of the gel hydrothermal synthesis, i.e. the exact proportion of aluminum, phosphorus, metal, ZSA and water. General procedure for the synthesis is given below with the specific reaction conditions for each sample.

Experimental procedure

Aluminum hydroxide (~0,053 mol) and phosphoric acid (0,098 mol) were combined in a PTFE beaker with 20 ml of water and left to mix for 20 minutes, obtaining a homogeneous mixture. For bimetallic AlPO, two metal precursor was dissolved in two separate glasses and left under stirring before being added dropwise simultaneously to the aluminum/phosphate mixture. The obtained gel was left for 30 minutes for homogenization, and then was added dropwise specifies the structure of the agent with the remainder water, and left for 1 hour under vigorous stirring. This gel was then divided into three lined with Teflon autoclave and was led at 140-200°C for 2 hours (for grill AFI).

After crystallization, the sample was cooled and washed with water before calcination at 550°C in a stream of air for 8 hours. The resulting sample is then stored in nitrogen, to minimize the recovery of the metal C is ntrol in the lattice AlPO, specific reaction conditions are listed in table 1.

Table 1
The list of conditions for the synthesis of samples of pure phase
MAlPOThe composition of the gel usedThe ZSAandThe content of theb(%atom)Timewith(watch)Rated
Comparative exampleCoAlPO-50,96Al:1,5P:0,8R:40H2OThe teae42200
Comparative exampleCoAlPO-50,96Al:1,5P:0,8R:40H2OMDCAf42200
Comparative exampleMnAlPO-50,96Al:1,5P:0,8R:40H2OThe tea42,45150
Comparative exampleMnAlPO-50,96Al:1,5P:0,8R:40H2OMDCA42150
Comparative exampleTiAlPO-50,96Al:1,5P:0,8R:40H2OThe tea25180
Comparative exampleTiAlPO-50,96Al:1,5P:0,8R:50H2OMDCA42180
Comparative exampleCoMnAlPO-50,96Al:1,5P:0,8R:40H2OThe tea63170
Comparative exampleCoMnAlPO-50,94Al:1P:0,75R:20H2OMDCA62-24180
Comparative exampleCoMnAlPO-5 0,94Al:1,5P:0,8R:50H2OMDCA122180
Comparative exampleCoMnAlPO-50,94Al:1,5P:0,8R:50H2OMDCA182180
Example 1 catalystCoTiAlPO-50,94Al:1,5P:0,8R:50H2OMDCA62170
Example 2 catalystCoTiAlPO-50,94Al:1,5P:0,8R:50H2OMDCA122180
Example 3 catalystCoTiAlPO-50,94Al:1,5P:0,8R:50H2OMDCA182180

Example 4 catalystMnTiALPO-50,4Al:1,5P:0,8R:40H 2OMDCA62180
Example 5 catalystMnTiALPO-50,94Al:1,5P:0,8R:50H2OMDCA122200
Example 6 catalystMnTiALPO-50,94Al:1,5P:0,8R:50H2OMDCA182200
andSpecifies the structure of the agent,bThe full amount of the metal added to the original gel,withThe time of crystallization,dThe temperature of crystallization,ethe triethylamine,fN-methyldicyclohexylamine

Table 2
ICP analysis
% atom (gel)% mass. from ICPwt. -%(calc)theory% messersmith % atom(calc)from ICP
AlPO-5CoMnTiCoMnTiCoMnTiCoMnTiCoMnTi
CoMn110,430,390,480,440,050,050,870,89
CoMn331,481,321,421,33-0,1 0,012,982,99
CoMn662,592,852,812,620,220,235,526,5
CoMn993,75of 3.464,163,880,410,428,079,15
CoTi110,470,390,480,390,0100,970,99
CoTi331,351,291,431,160,08-0,12,833,32
CoTi662,39 2,242,832,30,440,065,085,85
CoTi993,613,14,193,410,580,317,768,2
MnTi11 0,410,390,450,390,0400,910,99
MnTi331,731,321,331,16-0,4-0,24,493,39
MnTi662,082,482,642,30,56-0,2of 5.46,44
MnTi 993,173,433,923,420,75-08,329

200
Table 3
ICP analysis
MAlPOThe composition of the gel usedThe ZSAandThe content of theb(%atom)ICP content (%mass)Timewith(watch)Rated
CoAlPO-50,96Al:1,5P:0,8R:40H2OThe teae41,92200
CoAlPO-50,96Al:1,5P:0,8R:40H2OMDCAf41,92
MnAlPO-50,96Al:1,5P:0,8R:40H2OThe tea41,82,45150
MnAlPO-50,96Al:1,5P:0,8R:40H2OMDCA41,92150
TiAlPO-50,96Al:1,5P:0,8R:40H2OThe tea22,05180
TiAlPO-50,96Al:1,5P:0,8R:50H2OMDCA42,22180
CoMnAlPO-50,96Al:1,5P:0,8R:40H2OThe tea62,93170
CoMnAlPO-50,94Al:1P:0,75R:20H2OMDCA6 2,82-24180
CoMnAlPO-50,94Al:1,5P:0,8R:50H2OMDCA12of 5.42180
CoMnAlPO-50,94Al:1,5P:0,8R:50H2OMDCA187,22180
CoTiAlPO-50,94Al:1,5P:0,8R:50H2OMDCA62,62170
CoTiAlPO-50,94Al:1,5P:0,8R:50H2OMDCA124,62180
CoTiAlPO-50,94Al:1,5P:0,8R:50H2OMDCA186,72180
MnTiALPO-50,94Al:1,5P:0,8R:40H2O MDCA63,02180
MnTiALPO-50,94Al:1,5P:0,8R:50H2OMDCA124,52200
MnTiALPO-50,94Al:1,5P:0,8R:50H2OMDCA186,62200

Performed the characterization of all samples. The annealing was performed using a tubular furnace thermal design Lenton (serial No. 3/01/714). Powder x-ray diffraction analysis of all samples was performed in Souhampton diffractometer Siemens D5000, using Cu Kαlradiation, λ=1,54056 E. Additional powder x-ray diffraction analysis was carried out in UOP LLC (a Honeywell Group)using a Scintag XDS 2000 with Cu tube. UV-visible diffuse reflection andin situFT-IR was obtained in cooperation with the University of Turin, Italy. UV-visible UP was obtained using UV-Vis-NIR spectrometer Perkin-Elmer Lambda 900 DR software WinLab900, whereas FT-IR were obtained on Bruker IFS88 with a resolution of 4 cm-1. For these tests, the sample was placed under vacuum (5·10- mbar) to slow heating up to 550°C. the Vacuum was removed and added oxygen (130 mbar) at night in preparation for UV-visible BEFORE or FT-IR analysis. Gaseous ammonia was added stepwise from 2 mbar to 50 mbar, and FT-IR analysis was carried out at each stage. Scanning electron microscopy was performed using a microscope JSM5610, with carbon coating during preparation of the sample. The main results of EXAFS/XANES performed in Grenoble in collaboration with the University of Turin.

Catalytic procedures and analysis

The catalysis was carried out at high pressure in the reactor of 0.1 liter Parr 4590, lined with a mixture of RAILS and PTFE, and with the controller Parr 4843, whereas the catalytic data obtained using a gas chromatograph Varian Star 3400CX with a flame-ionization detector (PID). This method used the initial column temperature 80°C aging time of 7 minutes, the final temperature of the column 220°C With aging time of 10 minutes and a temperature rise of 3 degrees per minute.

Used two columns - column 1, using custom made methylsiloxane HP1 (30 m × 0.32 mm × 1 μm film thickness)was used for reactions maximiliane. Column 2, using cross-linked polyethylene glycol HP-Innowax HP1 (30 m × 0.53 mm × 1 μm film thickness)was used for the oxidation of cyclohexane and cyclohexanol. In each case, the injector was set at 220°C With D. what tectorum at 300°C.

All samples listed in table 1, was synthesized and tested using powder x-ray diffraction analysis. Some of the x-ray diffraction patterns shown in figure 2 and 3. CelRef used for the analysis of these spectra and determination of hkl values of these peaks.

Scanning electron microscopy (SEM) was used to obtain a more detailed analysis of the synthesized samples. Reports Hsu and Balkus presents the SEM analysis of structures AFI showing spherical particles, similar to those seen in figures 4-6. The samples on which they reported, was a pure AlPO-5, while SAM analysis CoTiAlPO-5, CoMnAlPO-5 and MnTiAlPO-5 is in good agreement and indicates particles with similar morphology. The three images shown in figures 4-6, provide examples of images with high, medium and low magnification, made for each sample, and indicate the structure of the AlPO-5. In addition, shown in the following image (and a number of other selected images also show a constant size and shape of the particles throughout the sample without indications to other products (for example, TiO2). Measurement of particle size was performed and resulted in table 4, they vary markedly from sample to sample, some of the messages showed AFI particles in the range of 10-60 μm. Visible here are the changes likely to occur because of the different conditions is of NASA or embedded metal.

Table 4
The particle size obtained using SAM
Calcined structureThe average particle size
CoMnAlPO-540 microns
CoTiAlPO-533 microns
MnTiAlPO-525 microns

Data on the composition of the gel maximiliane

Below is data about the composition of the gel maximiliane

Maximilianii cyclohexanone

The catalyst (1 g) was added into the reaction tank 10 g (0,101 mol) of cyclohexanone before sealing and blown with nitrogen at 30 bar for 20 minutes. The pressure dropped and added to 23.8 g (0,204 mol) of ammonium hydroxide (30% in water) with a syringe, and then added 30 bar air. The reaction vessel was heated to 60°C. under stirring at 830 rpm, samples were taken every 20 minutes. The samples were centrifuged, and then 0.2 µl was injected into the gas chromatograph.

Catalytic results

Catalytic tests were performed with the calcined samples, demonstrating maximilianii cyclohexanone. They re ulitity shown in table 5 below.

Cyclohexanone was converted into cyclohexanone oxime using ammonia and air in the reactor under pressure Parr. Initial results show good conversion and selectivity to oxime with CoMnAlPo-5 and CoTiAlPo-5. CoTiAlPo-5 gives the best selectivity, more than 85% in the reaction, and also gives the best speed (100-150).

1. The way redox maximiliane, in which a ketone or aldehyde reacts with ammonia and oxygen in the presence of a catalyst, where:
a catalyst is a redox catalyst based alumophosphate with the qualitative General formula (I):

where M1means, at least one transition metal selected from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V) and Ru(III);
M2means metal selected from Ge(IV), Sn(IV), Re(IV), V(IV) and mixtures thereof;
M1and M2differ from each other; and some of the phosphorus atoms in the structure of type M1M2AlPO-5 substituted by atoms of M2.

2. The method according to claim 1, where M1selected from Co (III), Mn(III) and Fe(III).

3. The method according to claim 1 or 2, where the ammonia is in the form of aqueous ammonium hydroxide.

4. The method according to claim 1 or 2, which is performed at a temperature of from 40 to 200°C.

5. The method according to claim 4, which is performed at a temperature of from 50 to 90°C.

6. The method according to claim 1 or 2, which done the Ute at a pressure of 0.5 MPa [5 bar] up to 10 MPa [100 bar].

7. The method according to claim 1, where the source material is a ketone.

8. The method according to claim 1, where the reaction product is a reaction.

9. The method of claim 8, where the cyclohexanone seem cyclohexanone.

10. The method according to claim 8 or 9, where the oxime converted into ε-caprolactam.

11. The catalyst redox maximiliane based alumophosphate with the qualitative General formula (I):

where M1means, at least one transition metal selected from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V) and Ru(III);
M2means metal selected from Ge(IV), Sn(IV), Re(IV), V(IV) and mixtures thereof;
M1and M2differ from each other; and some of the phosphorus atoms in the structure of type M1M2AlPO-5 substituted by atoms of M2.



 

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35 cl, 16 sch, 13 tbl, 43 ex

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The invention relates to new unsaturated derivatives of hydroximino acid formula

< / BR>
where R1means phenyl, optionally substituted by 1-3 substituents selected from the group comprising FROM1-2alkoxygroup, halogen, or represents a 6-membered unsaturated heterocyclic group containing one nitrogen atom as a heteroatom, and R2means hydrogen or R1together with R2form5-7-cycloalkyl group, Y represents hydrogen, a hydroxy-group,3-22-alkanoyloxy, X means halogen, a hydroxy-group or amino group, R3represents a group of formula-NR4R5where R4and R5mean independently from each other hydrogen, C1-5is an alkyl group, or R4and R5form with the adjacent nitrogen atom a 5 - or 6-membered saturated heterocyclic group which may contain an oxygen atom and may be condensed with a benzene ring, in addition, its geometrical and/or optical isomers and/or pharmaceutically acceptable acid salt additive
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