KR20020070502A - Process for the Preparation of Substituted Formamides - Google Patents

Abstract

There is provided a process for preparing substituted formamide by oxidizing an amine in the presence of a catalyst.

Description

Process for the Preparation of Substituted Formamides

The preparation of substituted formamides from tertiary amines by liquid phase catalytic oxidation is described in US Pat. No. 4,543,424 and the literature cited therein.

U.S. Patent No. 3,483,210 describes the oxidation of methyl groups of tertiary N-methylamines in the liquid phase to formyl using oxygen at atmospheric pressure in the presence of a heterogeneous catalyst selected from platinum group transition metals.

Methylamine is prepared by the gas phase reaction of methanol and ammonia on an acidic catalyst such as silica-alumina. A representative molar ratio of amine prepared using this catalyst is CH ₃ NH ₂ : (CH ₃ ) ₂ NH: (CH ₃ ) ₃ N = 17: 21: 62 (equilibrium value). However, market demand is greatest for dimethylamine. One of the main uses of this amine is in the manufacture of solvents such as dimethylformamide. Typically, trimethylamine is reacted with additional methanol to produce higher amounts of commercially desirable dimethylamine. There is a need for an efficient process for using trimethylamine in the production of further dimethylamine or derivatives thereof, such as dimethylformamide.

The present invention relates to a process for producing substituted formamide by gas phase oxidation of the side chain of a tertiary amine in the presence of a catalyst.

Summary of the Invention

The present invention

(i) (a) Formula A _x Au _y M _{1- (x + y)} , wherein A is selected from the group consisting of Cu, Cr, Ru, Co, and combinations thereof, and M is Al, Mg, Nb , Si, Ti, Zr and combinations thereof, x is from 0.001 to 0.5, y is from 0 to 0.2) xerogel or aerogel; (b) a heteropolyacid selected from the group consisting of H ₄ PMo ₁₁ VO ₄₀ , H ₅ PMo ₁₀ V ₂ O ₄₀ , H ₆ PMo ₉ V ₃ O ₄₀ and H ₇ P ₂ Mo ₁₇ VO ₆₂ ; (c) H _{4+ (6-z)} PMo ₁₀ VEO ₄₀ , H _{5+ (6-z)} PMo ₉ V ₂ EO ₄₀ , H _{6+ (6-z)} PMo ₈ V ₃ EO ₄₀ and H _{7+ ( 6-z)} metal substituted heteropolyacids selected from the group consisting of P ₂ Mo ₁₆ VEO ₆₂ , wherein E is an element selected from the group consisting of Cu, Cr, Zn and Co, z is the valence of E; (d) Q _q H ₄ PMo ₁₁ VO ₄₀ , Q _q H ₅ PMo ₁₀ V ₂ O ₄₀ , Q _q H ₆ PMo ₉ V ₃ O ₄₀ , Q _q H ₇ P ₂ Mo ₁₇ VO ₆₂ , Q _q H _{4+ (6-z)} PMo ₁₀ VEO ₄₀ , Q _q H _{5+ (6-z)} PMo ₉ V ₂ EO ₄₀ , Q _q H _{6+ (6-z)} PMo ₈ V ₃ EO ₄₀ and Q _q H _{7+ ( 6-z)} P ₂ Mo ₁₆ VEO ₆₂ wherein Q is selected from the group consisting of Ag and Cs, where Q is Ag, q is from 0 to (number of hydrogen atoms) × 0.5, and when Q is Cs Is 0 to (number of hydrogen atoms) × 1) heteropolyacid salt selected from the group consisting of; (e) Formula Ru _r (HPA) _s M _1- (r + s), where r is 0.001 to 0.1, s is 0.001 to 0.05, HPA is a heteropolyacid and heteropolyacid salt of catalysts (b) and (d) X, or aerogel composite of M), M is selected from the group consisting of Al, Mg, Nb, Si, Ti, and Zr; And (f) Formula (Bi _t Co _u Ni _v ) _w Mo _1-w O _a , wherein t, u and v are each independently 0 to 1, t + u + v = 1, w is 0.01 to 0.75 And a is 1.125 to 4.875 in the presence of a catalyst selected from the group consisting of metal oxides, oxygen in the gaseous phase is represented by the formula CH ₃ NR ₂ , wherein R is C ₁ -C ₈ alkyl, phenyl, naphthyl and C ₁ -C ₄ alkyl substituted phenyl or mixtures thereof), and

ii) recovering N-substituted formamide of the formula HC (O) NR ₂

It describes a method for producing the substituted formamide comprising a.

Further, the formula A _x Au _y M _{1- (x + y)} , wherein A is selected from the group consisting of Cu, Cr, Ru, Co, and combinations thereof, and M is Al, Mg, Nb, Si, Ti , Zr and combinations thereof, x is from 0.001 to 0.5, y is from 0 to 0.2).

Further, the formula Ru _r (HPA) _s M _{1- (r + s)} , wherein r is from 0.001 to 0.1, s is from 0.001 to 0.05, HPA is selected from the group consisting of heteropolyacids and heteropolyacid salts, and M is Also described are compositions comprising xerogel or aerogel composites of Al, Mg, Nb, Si, Ti and Zr).

details

The tertiary amine starting material to be oxidized is of the formula CH ₃ NR ₂ , wherein R is selected from the group consisting of C ₁ -C ₈ alkyl, phenyl, naphthyl and C ₁ -C ₄ alkyl substituted phenyl or mixtures thereof. Anything that follows can be anything. The oxidation product may be any formamide corresponding to the formula HC (O) NR ₂ . Preference is given to oxidizing trimethylamine with dimethyl formamide.

The oxygen used in this process may be pure, mixed with inert gas, or air. Preference is given to using air.

This reaction is typically carried out at a temperature of about 125 ° C to about 450 ° C, preferably about 150 ° C to about 275 ° C. The reaction pressure is typically from about 1 atmosphere (100 kPa) to about 10 atmospheres (1000 kPa).

Oxidation products are recovered from the product mixture by conventional techniques such as fractional distillation.

The catalyst described in the present invention can be prepared by various known methods such as impregnation, xerogel or aerogel formation, polyoxometallate formation by reflux and ion exchange, lyophilization, spray drying and spray calcination. In addition to catalyst powders, extrudates and pellets, monoliths can also be used provided they have sufficient porosity for use in the reactor.

Xerogels or aerogels used in the present invention comprise the active catalyst component (s) derived from one or more dissolved component (s) and comprise a matrix material derived from a solution of the matrix component (s). The matrix is the framework of oxides and oxyhydroxides derived from hydrolysis of alkoxides and condensation with other reagents. The framework typically comprises at least 30% by weight of the total catalyst composition. The matrix material may comprise magnesium, silicon, titanium, zirconium or aluminum, oxide / hydroxide xerogels or aerogels which together form from 30 mol% to 99.9 mol%, preferably 65 mol% to 85 mol% of the catalyst composition. It contains a mixture of.

In the present invention, one or more metal alkoxides (eg aluminum isopropoxide) may be used as starting material for gel preparation. Inorganic metal alkoxides used in the present invention may include any alkoxide containing an alkoxide group containing 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms, and preferably dissolved in a liquid reaction medium. Can be. Preference is given to C ₁ -C ₄ alkoxides such as aluminum isopropoxide, titanium isopropoxide and zirconium isopropoxide.

Commercially available alkoxides can be used. However, inorganic alkoxides can be prepared by other routes. Some examples include the direct reaction of an alcohol with zero valence metal in the presence of a catalyst. Many alkoxides can be formed by the reaction of metal halides with alcohols. Alkoxy derivatives can be synthesized by reacting alkoxides with alcohols in a ligand exchange reaction. Moreover, the direct reaction of metal dialkylamide and alcohol also forms an alkoxide derivative. Further examples are described in "Metal Alkoxides" by D.C. Bradley et al., Academic Press, (1978).

The first step in the synthesis of alcohols or gels containing alcohols involves first preparing a non-aqueous solution of alkoxides and other reagents and a separate solution containing a protic solvent such as water. When the alkoxide solution is mixed with a solution containing a protic solvent, the alkoxide polymerizes to form a gel.

The dissolution medium used in this process should generally be a solvent for the inorganic alkoxide or alkoxides used in the one-step synthesis and additional metal reagents and promoters added. The solubility of all components in their respective media (aqueous and non-aqueous) preferably produces highly dispersed materials. By using soluble reagents in this manner, the mixing and dispersion of active metals and promoter reagents can be close to the atomic level, reflecting in fact their dispersion in their respective solutions. The precursor gel prepared by this method will contain highly dispersed active metals and promoters. High dispersion results in the production of catalytic metal particles in the nanometer size range.

Notable is an embodiment where the catalytic metal component of the gel is dissolved in a separate protic solvent such as water and the solution of such catalytic metal compound (s) is mixed with the non-aqueous solution of the matrix component (s). Also noteworthy is an embodiment in which the catalytic metal component is dissolved in the same non-aqueous solution as the matrix component (s) and an aqueous replenishment solution is used.

Typically, the concentration of the amount of solvent used is related to the alkoxide content. Although an ethanol: total alkoxide molar ratio of 26.5: 1 may be used, the molar ratio of ethanol: total alkoxide may be about 5: 1 to 53: 1, or greater. If a large excess of alcohol is used, gelation will generally not occur immediately and some solvent evaporation will be required. At low solvent concentrations, heavier gels will be formed with such pore volume and surface area.

In the present invention, water and aqueous solutions are added dropwise to alcohol soluble alkoxides and other reagents to cause hydrolysis and condensation. Depending on the alkoxide system, it is possible to reach a gelling point which can be differentiated within minutes or hours. The molar ratio of the total water added (including water present in the aqueous solution) to the total Al, Mg, Nb, Si, Ti and Zr added will depend on the particular inorganic alkoxide to be reacted.

Generally, a water: alkoxide molar ratio of 0.1: 1 to 10: 1 is used. However, in the case of zirconium (alkoxide) ₄ and titanium (alkoxide) ₄ it is at 4: 1, in the case of Mg (alkoxide) ₂ at 2: 1 and in the case of Al (alkoxide) ₃ at 3: 1. , A ratio close to 5: 1 for Nb (alkoxide) ₅ and 4: 1 for Si (alkoxide) can be used. The amount of water used for the reaction is a calculated value for hydrolyzing the inorganic alkoxide in the reaction mixture. Use of a lower ratio than necessary to hydrolyze the alkoxide species results in partially hydrolyzed material, which in most cases reaches the gel point at a much slower rate depending on the aging process and the presence of atmospheric moisture.

The addition of acidic or basic reagents to the inorganic alkoxide medium can affect the kinetics of hydrolysis and condensation reactions, and the microstructure of the oxide / hydroxy matrix derived from alkoxide precursors that capture or incorporate soluble metals and promoter reagents. May affect In general, a pH of 1 to 12 may be used. A pH range of 1 to 6 is preferred.

After the alcohol formation reaction of the present invention, it may be necessary to complete the gelling process by slightly aging the gel. This ripening can take from one minute to several days. Generally, all alcohols are aged for at least several hours at room temperature in air.

Solvent removal from the alcohol can be accomplished in several ways. Removal by vacuum drying or by heating in air forms xerogels. Aerogels of the material can typically be formed by placing in a pressurization system such as an autoclave. The solvent containing gels produced in the present invention are placed in an autoclave whereby the supercritical fluid flows through the gel material until the solvent is no longer extracted by the supercritical fluid, thereby allowing it to be in contact with fluids above the critical temperature and pressure. When performing such extraction to produce airgel materials, various fluids may be used at their critical temperatures and pressures. Examples of such fluids suitable for this method are Freon® fluorochloromethane (eg Freon® 11 (CCl ₃ F), Freon® 12 (CCl ₂ F ₂ ) or Freon ( Fluorochlorocarbon, ammonia, and carbon dioxide, as represented by 114 (CClF ₂ CClF ₂ )). Typically, the extraction fluid is a gas at atmospheric conditions, so that drying can avoid void collapse due to capillary forces at the liquid / solid interface. In most cases, the resulting material has a higher surface area than the material dried in non-supercritical conditions.

The xerogels and aerogels thus prepared can be said to be precursor salts dispersed in an oxide or oxyhydroxide matrix. The maximum theoretical value of hydroxyl content corresponds to the valence of the central metal atom. In addition, the H ₂ O: alkoxide molar ratio can affect the final xerogel stoichiometry, so there will be residual -OR groups in the unmatured gel. However, the reaction with atmospheric moisture in the course of subsequent polymerization and dehydration will convert them to the corresponding -OH and -O groups. Aging, even under inert conditions, can achieve condensation of —OH through subsequent crosslinking and polymerization, ie gel formation, to remove H ₂ O. In part, the degree of crosslinking and conversion of —OH is represented by variable stoichiometry of the hydroxyl content shown in the formula. Examples are AlO _1.5-z (OH) _2z , where z is a variable and is 1.5 (for all hydroxyl) to 0 (for all oxide).

In another embodiment of the invention, one or more inorganic metal colloids can be used as starting material for gel preparation. These colloids include colloidal alumina sol, colloidal zirconia sol, colloidal titania sol, mixed oxide colloidal sol, colloidal silica sol, ternary or more oxide sol and mixtures thereof. Some of these colloidal sols are commercially available. There are also several methods for producing colloids as described in "Inorganic Colloid Chemistry", Volumes 1, 2 and 3, J. Wiley and Sons, Inc., 1935. Colloidal formation includes nucleation and growth, or subdivision or dispersion processes. For example, hydrous titanium dioxide sol can be prepared by adding ammonia hydroxide to a solution of tetravalent titanium salt and then peptising (redispersing) with dilute alkali. Zirconium oxide sol can be prepared by dialysis of sodium oxychloride. The preparation of other sols is also described in these documents.

Commercially available alkoxides such as tetraethylorthosilicate and organic titanate esters (sold under the trade name " Tyzor " by the DuPont Company) can be used. In addition, inorganic alkoxides can be prepared by various routes. Examples include the direct reaction of metals with zero valence and alcohols in the presence of a suitable catalyst and the reaction of metal halides with alcohols. Alkoxy derivatives can be synthesized by reacting alkoxides with alcohols by ligand exchange reactions. Direct reaction of metal dialkylamides with alcohols also forms alkoxide derivatives. Further examples are given in D.C. Bradley et al., Metal Alkoxides (Academic Press, 1978).

In a preferred embodiment of the process of the invention, a colloidal sol or aquasol in preformed water is used. Aquasol consists of colloidal particles having a particle size in the range of 2 to 50 nm. In general, smaller primary particle sizes (2-5 nm) are preferred. Preformed colloids contain from 10 to 35% by weight colloidal oxide or other material, depending on the stabilization method. In general, after addition of the active metal component (as catalyst or promoter, in the case of partial oxidation), the final unstable colloid may have about 1 to 35% by weight solids, preferably about 1 to 20% by weight solids. .

Colloidal oxides or mixtures thereof become unstable by acid or base addition or by solvent removal (both of which change pH) during the soluble salt addition of primary and promoter cationic species. If the particles are in sufficiently intimate contact when unstable, polymerization and crosslinking reactions may occur between surface functional groups such as surface hydroxyls. In one embodiment of the present invention, colloids, which are originally stable heterogeneous dispersions of oxides and other species in a solvent, are destabilized to produce colloidal gels. In some cases, destabilization is caused by the addition of soluble salts, such as chlorides or nitrates, or solvent removal, which change the pH and ionic strength of the colloidal suspension with acid or base addition. Generally, pH changes occur with the addition of soluble salts. In general, this is preferred over solvent removal. Generally, a pH range of about 0 to about 12 can be used to destabilize the colloid, but very large extremes can cause aggregation and precipitation. For this reason, in general, a pH range of about 2 to 8 is preferred.

The medium used in this method is typically aqueous, but non-aqueous colloids may also be used. The additional metal or inorganic reagents used (ie, salts or promoters of Cr) should be soluble in the appropriate aqueous and non-aqueous media.

Aerogels or xerogels can be prepared by achieving solvent removal from the gel by several methods as described above.

Heteropolyacid (HPA) catalysts (catalysts (b), (c) and (d)) of the present invention are typically produced by an aqueous method. Appropriate amounts of reagents, in amounts calculated to give the vanadium-promoted heteropolyacid substituted with the desired transition metal, are mixed in water and heated to elevated temperature. Suitable temperature is reflux temperature (100 ° C.) and suitable time is overnight. However, if time / temperature is sufficient to dissolve all reagents to form a clear, usually highly colored solution, time and temperature are not critical. In some cases, the reaction is completed within 2 hours at reflux temperature, and in some cases a longer time is required.

Preferably, the reaction is carried out in an air atmosphere. Inert atmospheres may also be used. This method is usually carried out at normal pressure, but elevated or reduced pressure may also be used. Agitation is not required, but is usually provided to aid in heat transfer.

Commercially available reagents are used for HPA preparation. The purity of the reagents should be known so that the gross amount required can be calculated. The amount of reagent used should be within ± 5%, preferably within ± 2% of the stoichiometrically indicated amount.

The product is isolated by evaporation of the reaction mixture until it is dried. This is a known method and typically can be done using a vacuum to speed up the process. The isolated product can be used on its own or, if specific equipment is used for subsequent use of the HPA, the product HPA can be processed or prepared into particles of various sizes and shapes before use. That is, the product can be ground, pelletized, briquette, flattened, or otherwise shaped as required for use in a particular equipment.

Alternatives to the preparation process include preparing an ammonium salt of the desired HPA followed by heat treatment to remove ammonia. Another alternative is to generate the desired acid form of HPA using ion exchange.

Xerogel or aerogel complexes of heteropolyacids and suitable sol gel derived materials can also be used in the present invention, which are described in the catalyst (e) section in the Summary of the Invention. This complex can be synthesized by adding a water soluble heteropoly acid to the alkoxide solution during the alkoxide hydrolysis, or to the aquasol before or during the destabilization of the aquasol to prepare a gel material. During this addition, other inorganic reagents (eg Ru as cationic species which can function as counterions for heteropoly acids) can be added.

Lyophilization processes can be used for several catalyst compositions (eg, as described in the catalyst (f) section of the Summary of the Invention), which allows the catalyst precursor to be frozen in water or rapidly (in less than one minute). It is useful if it can be dissolved in other solvents. The precursor salt is dissolved in an appropriate amount of solvent to form a solution or fine colloid. The solution is then rapidly cooled and frozen by immersion in a suitable medium such as liquid nitrogen. If the solution is frozen quickly, the salts and other ingredients will be intimately mixed and will not be separated to a significant extent. The frozen solids are transferred to a freeze drying chamber. The solution is evacuated and kept frozen while removing water vapor.

The spray drying process uses a solution, colloid or slurry containing the catalyst precursor or catalyst compound described in the catalysts (a), (b), (c), (d), (e) and (f) in the summary section of the invention. It involves doing. The technique involves atomizing these liquids (usually aqueous, but not exclusively) with a spray, and evaporating moisture by contacting the spray with a dry medium (usually hot air). Is done. Drying of the spray liquid proceeds until the moisture content of the dried particles reaches the desired amount, and the product is recovered by suitable separation techniques (usually cyclone separation is used). A detailed description of the spray drying method can be found in the Spray Drying Handbook, 4th edition by K Masters (Longman Scientific and Technical, John Wiley and Sons, NY) c. 1985].

Spray calcining involves the use of solutions or colloids, but generally involves drying and firing (at high temperatures) in one process step to produce a catalyst powder.

In the experiment described in the present invention, a 2-section Virtis lyophilization unit was used. A freezing shelf was used to prevent frozen solids from thawing in the exhaust. All percentages in the following examples are by weight unless otherwise indicated.

General Procedure for Catalyst Testing

In a representative test, a 6.4 mm (1/4 ") stainless steel reactor was placed in a defined volume (0.625 ml) of catalyst (with silica wool used to hold it in place) and the initial reaction temperature under nitrogen ( 175 ° C.) The gas supply system was configured to deliver a mixture of 1.5% trimethylamine / 20% oxygen / 78.5% nitrogen to the reactor at a constant flow rate of 20.9 cc / min at 1 atmosphere. Unreacted feed gas samples were taken to confirm the gas composition Gas mixture analysis was performed by GC Hewlett-Packard Model 5890 Gas Chromatography Unit including two detectors (flame ionization detector and thermal conductivity detector) The effluent gas was analyzed using (1) 3.05 m (10 ') x 3.2 mm (1/8 ") stainless steel 60/80 mesh (0.25 / 0.18 mm) Molecular Sieve 13X columns (Used for H ₂ O, N ₂ and CO separation) and 0.61 m (2 ') × 3.2 mm (1/8 ") stainless steel 80/100 mesh (0.18 / 0.15 mm) Haysep R (registered trademark) ) (Copolymer of divinylbenzene and N-vinyl-2-pyrrolidone) column (used to separate H ₂ O, CO ₂ and butane), and (2) 20 m × 0.53 mm DBI (dimethylpolysiloxane) A capillary column (used for organic separation) was included Helium was used as the carrier gas for all columns The analysis by the two column system was performed simultaneously using separate samples taken from two 500 μl sample loops. Valve opening and closing schemes were used to ensure that each sample was properly analyzed, and the GC was programmed to adjust the column temperature so that the entire analysis could be completed within 15.45 minutes.

Response factors for some compounds were determined using two methods: (1) syringe injection of gas or liquid or (2) sample loop injection of gas.

After feed gas analysis, the reacted gas samples were taken at each of three or four temperatures (175 ° C., 225 ° C., 275 ° C. and again 175 ° C.) and analyzed as described above. The test was terminated by taking the final feed gas sample for analysis. The data was then collected and calculated to determine the conversion of trimethylamine and the selectivity for dimethylformamide and monomethylformamide.

The catalyst test results are shown in Tables 1-5 below.

legend

T: Temperature CT: Contact time

TMA: (CH ₃ ) ₃ NDMF: (CH ₃ ) ₂ NCHO

MMF: CH ₃ NHCHO

Example 1

47.33 mL of a 0.349M solution of magnesium methoxide in ethanol was added together with 21.776 mL of a 0.02M solution of AuCl ₃ in ethanol with gentle swirling in a 150 mL Petri dish. In the second step, 0.87 mL (0.5 M) of aqueous chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ) was slowly added. The gel point was reached and the material aged for at least 24 hours before use. After drying at 120 ° C. under vacuum for 5 hours, the material was calcined at 250 ° C. in air for 1 hour. The calcined powder was pelleted at 20,000 psig (138 mPa) and granulated with a -40, +60 mesh (-0.42, +0.25 mm) screen before use. The nominal metal composition of the catalyst was Au _0.025 Cr _0.025 Mg _0.95 .

Example 2

Follow the same procedure as described in Example 1 except that the reagent was used as follows: 68.19 ml of 0.05 M solution of aluminum isopropoxide in ethanol, 1.740 ml of 0.02 M solution of AuCl ₃ in ethanol and chromium hydroxide 0.07 mL (0.5 M) of aqueous acetate solution (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ). The nominal metal composition of the catalyst was Au _0.01 Cr _0.01 Mg _0.98 .

Example 3

Follow the same procedure as described in Example 1 except that the reagents were used as follows: 0.317 ml of a 0.6 vol% solution of tetraethyl orthosilicate in ethanol, 22.436 ml of a 0.02M solution of AuCl ₃ in ethanol, magnesium methoxide in ethanol 46.349 mL of 0.349 M solution of seeds and 0.897 mL (0.5 M) of an aqueous solution of chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ). The nominal metal composition of the catalyst was Au _0.025 Mg _0.9025 Cr _0.015 Si _0.0475 .

Example 4

Follow the same procedure as described in Example 1 except that the reagents were used as follows: 69.821 ml of a 0.5 M solution of aluminum isopropoxide in ethanol and an aqueous solution of chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ) 0.179 mL (0.5 M). The nominal metal composition of the catalyst was Cr _0.025 Al _0.975 .

Example 5

The same procedure as described in Example 1 was followed except that the reagents and stoichiometry were adjusted. 0.9579 g of AuCl ₃ was dissolved in 50 mL of ethanol, which was added to 24.51 g of aluminum isopropoxide dissolved in 2500 mL of isopropanol. Dissolution was performed in an inert atmosphere drying box. Aqueous chromium solution was prepared by dissolving 0.6351 g of chromium hydroxide acetate in 1 ml of water and then diluting the solution with 10 ml of ethanol. The nominal metal composition of the catalyst was Au _0.025 Al _0.95 Cr _0.025 .

Example 6

Follow the same procedure as described in Example 1 except that the reagent was used as follows: 64.842 ml of 0.05M solution of aluminum isopropoxide in ethanol, 4.49 ml of 0.02M solution of AuCl ₃ in ethanol, magnesium methoxide in ethanol 0.488 ml of a 0.349 M solution of seeds and 0.180 ml (0.5 M) of an aqueous solution of chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ). The nominal metal composition of the catalyst was Au _0.075 Cr _0.025 Al _0.9025 Mg _0.0475 .

Example 7

Follow the same procedure as described in Example 1 except that the reagent was used as follows: 64.842 ml of 0.05M solution of aluminum isopropoxide in ethanol, 4.518 ml solution of 0.02M solution of AuCl ₃ in ethanol, tetraethyl in ethanol 0.064 mL of a 0.6 vol% solution of orthosilicate and an aqueous solution of chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ) 0.181 mL (0.5 M). The nominal metal composition of the catalyst was Au _0.025 Cr _0.025 Al _0.9025 Si _0.0475 .

Example 8

Follow the same procedure as described in Example 1 except that the reagent was used as follows: 51.21 ml of 0.05 M solution of aluminum isopropoxide in ethanol, 10.107 ml of 0.02 M solution of AuCl ₃ in ethanol, tetraethyl in ethanol 0.952 ml of a 0.6 vol% solution of orthosilicate, 7.326 ml of a 0.349 M solution of magnesium methoxide in ethanol and 0.404 ml (0.5 M) of an aqueous solution of chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ). The nominal metal composition of the catalyst was Au _0.025 Cr _0.025 Mg _0.32 Al _0.32 Si _0.32 .

Example 9

Follow the same procedure as described in Example 1 except that reagents were used as follows: 49.396 mL of 0.02M solution of AuCl ₃ in ethanol, 13.25 mL of 0.6 vol% solution of tetraethylorthosilicate in ethanol, magnesium methoxide in ethanol 5.371 mL of a 0.349 M solution of seeds and 1.976 mL (0.5 M) of an aqueous solution of chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ ). The nominal metal composition of the catalyst was Au _0.025 Cr _0.025 Si _0.9025 Mg _0.0475 .

Example 10

To a 3L round bottom flask with addition funnel, mechanical stirrer and reflux cooler was added 1000 ml of water, 122.4 g of MoO ₃ and 4.6 g of vanadium pentoxide. The slurry was refluxed. Then 11.5 g of aqueous phosphoric acid solution was slowly added over 20 minutes until the desired stoichiometry was achieved. After about 3 hours, an orangeish red solution formed. Typically, reflux was continued for 16 hours (overnight). The sample was dried at 120 ° C. for about 12 hours in nitrogen. The catalyst composition was H ₇ P ₂ Mo ₁₇ VO ₆₂ .

Example 11

The same procedure as described in Example 10 was used. To a 3L round bottom flask with addition funnel, mechanical stirrer and reflux cooler was added 1000 ml of water, 100.2 g of MoO ₃ , 6.33 g of vanadium pentoxide and 5.5 g of CuO. The slurry was refluxed. Subsequently, 8.1 g of aqueous phosphoric acid solution was slowly added over 20 minutes until the desired stoichiometry was achieved. After about 3 hours, an orangeish red solution formed. Typically, reflux was continued for 16 hours (overnight). The sample was dried at 120 ° C. for about 12 hours in nitrogen. The catalyst composition was H _p PMo ₁₀ CuVO ₄₀ , where p is 8 and 9.

Example 12

The same procedure was used as described in Example 11 using the following reagents: 1000 ml of water, 100.2 g of MoO ₃ , 6.3 g of vanadium pentoxide, 1.1 g of CuO, 27.8 g of Cr (NO ₃ ) ₃ .9H ₂ O and phosphoric acid 8.0 g of aqueous solution. The catalyst composition was Cu _0.2 H _n PMo ₁₀ VCrO ₄₀ , where n is 3.6 and 3.8.

Example 13

The same procedure as described in Example 11 was used with the following reagents: 1000 ml of water, 100.2 g of MoO ₃ , 6.3 g of vanadium pentoxide, 9.5 g of ZnCl ₂ and 8.01 g of aqueous phosphoric acid solution. The catalyst composition was H ₈ PMo ₁₀ VZnO ₄₀ .

Example 14

H ₄ PMo ₁₁ VO ₄₀ was prepared using the procedure described in US Pat. No. 4,192,951. 48.75 g of dibasic sodium phosphate (Na ₂ HPO ₄ .7H ₂ O) was dissolved in 100 ml of refluxed H ₂ O. A second solution containing 22.17 g of sodium metavanadate (NaVO ₃ ) in 150 mL of H ₂ O was prepared. A third solution containing 411.98 g of sodium molybdate (Na ₂ MoO ₄ .2H ₂ O) in 500 mL of H ₂ O was prepared. The three solutions were then combined with 205.4 mL of sulfuric acid (H ₂ SO ₄ ). The combined solution was then added to a 250 mL separatory funnel. Diethyl ether was added to give the appropriate heteropoly etherate, which was then removed and dried to separate the heteropoly acid by yielding the free acid. Heteropoly acid was dissolved in water. Silver carbonate was added to produce an appropriate stoichiometric heteropolyacid. This material was evaporated to dryness before use. The catalyst composition was H ₂ Ag ₂ PMo ₁₁ VO ₄₀ .

Example 15

The same procedure as described in Example 10 was used. To a 5 L three-necked round bottom flask (equipped with a heating mantle for reflux) was added 440.9 g of molybdenum oxide (MoO ₃ ), 25.3 g of vanadium oxide (V ₂ O ₅ ) and 4000 mL of water. After reflux, 32.0 g of 85% by weight phosphoric acid were added. After about 16 hours of reflux, a reddish brown solution formed. This material was evaporated to dryness to produce free acid. Heteropoly acid was dissolved in water. Silver carbonate was added to produce an appropriate stoichiometric heteropolyacid. This material was evaporated to dryness before use. The catalyst composition was H ₃ AgPMo ₁₁ VO ₄₀ .

Example 16

The same procedure as described in Example 10 was used with the following reagents: 1000 ml of water, 9.0 g of MoO ₃ , 1.27 g of vanadium pentoxide, 0.55 g of CuO and 1.6 g of aqueous phosphoric acid solution. The catalyst composition was H _m PMo ₉ V ₂ CuO ₄₀ (m is 9 and 10).

Example 17

The same procedure as described in Example 10 was used with the following reagents: 1000 ml of water, 100.2 g of MoO _3, 6.33 g of vanadium pentoxide, 17.9 g of cobalt 2,4-pentanedionate and 8.01 g of aqueous solution of phosphoric acid. The catalyst composition was H ₈ PMo ₁₀ VCoO ₄₀ .

Example 18

Heteropolyacid "H ₄ PMo ₁₁ VO ₄₀ " was prepared as follows: 440.9 g of molybdenum oxide (MoO ₃ ), vanadium oxide (V ₂ O) in a 5 L three-necked round bottom flask (equipped with a heating mantle for reflux). ₅ ) 25.3 g and 4000 ml of water were added. After reflux, 32.0 g of 85% by weight phosphoric acid was added. After about 16 hours of reflux, a reddish brown solution formed. This material was evaporated to dryness to produce free acid. A portion (4.453 g) of this material was dissolved in water. 1.63 g of Cs ₂ CO ₃ was added to form the final stoichiometry. This material was dried. The catalyst composition was Cs ₄ PMo ₁₁ VO ₄ .

Example 19

An airgel composite of heteropolyacid H ₄ PMo ₁₁ VO ₄₀ was prepared. In an inert atmosphere dry box was added 183.794 g of titanium n-butoxide with 206.45 mL of ethanol to a 1.5 L resin kettle. A second solution containing 6.23 g of ruthenium trichloride in 38.91 mL of water, 4.634 mL of glacial acetic acid, 3.618 mL of nitric acid and 206.45 mL of ethanol was prepared in a dropping funnel and prepared with H ₄ PMo ₁₁ VO ₄₀ prepared as described in Example 18. 53.437 g were dissolved in water and then added to the alkoxide solution. In this case, the alcohol: metal molar ratio was 26.5: 1. During this addition the 1.5 L resin kettle was in a nitrogen purge and the solution was gently stirred. Gel material was produced, which was aged for 24 hours at room temperature and pelletized at 20,000 psig (138 mPa) before granulation to a -40, + 60 mesh (-0.42, + 0.25 mm) screen. The nominal catalyst composition was Ru _0.05 (H ₄ PMo ₁₁ VO ₄₀ ) _0.05 (TiO ₂ ) _0.9 .

Example 20

The same procedure as described in Example 19 was followed except that the reagents and stoichiometry were adjusted as indicated below. In this preparation, no heteropolyacid was added. 176.882 g of zirconium isopropoxide was dissolved using 412.5 mL of ethanol in an inert atmosphere dry box (under nitrogen). This was added to a 1.5 L resin kettle. In a second dropping funnel, a solution containing 412.5 ml of ethanol dissolved 6.223 g of RuCl _{3 and} 53.438 g of H ₄ PMo ₁₁ VO ₄₀ in another aqueous solution (38.913 ml of H ₂ O containing 3.619 ml of HNO _{3 and} 4.635 ml of acetic acid). To the zirconium isopropoxide solution. The H ₂ O: alkoxide ratio was 4: 1. During the addition, the resin kettle was blanketed with nitrogen and the solution was stirred during the addition. The nominal catalyst composition was Ru _0.05 (H ₄ PMo ₁₁ VO ₄₀ ) _0.05 (ZrO ₂ ) _0.9 .

Example 21

The same procedure as described in Example 20 was followed except that the reagents and stoichiometry were adjusted as indicated below. 344 mL of ethanol was used to dissolve 143.195 g of niobium ethoxide. An aqueous solution was prepared by dissolving 5.186 g of RuCl _{3 and} 44.532 g of H ₄ PMo ₁₁ VO _{40 in} 40.534 mL of H ₂ O containing 3.77 mL of HNO ₃ , 4.828 mL of acetic acid and 344 mL of ethanol. The water: alkoxide ratio was 5: 1. The nominal catalyst composition was Ru _0.05 (H ₄ PMo ₁₁ VO ₄₀ ) _0.05 (NbO _2.5 ) _0.9 .

In Examples 22-28, l is> 0 and 1.

Example 22

The same procedure as described in Example 20 was used, except that the reagents and stoichiometry were adjusted as indicated below. 163.373 g of Ti-n-butoxide was dissolved in 371.21 ml of ethanol. An aqueous solution of chromium hydroxide acetate was prepared by dissolving 24.1332 g of chromium hydroxide acetate in 35.489 mL of H ₂ O and 8.24 mL of glacial acetic acid. The H ₂ O: alkoxide ratio was 4: 1. The nominal catalyst composition was Cr _0.2 (TiO _2-l (OH) _2l ) _0.8 .

Example 23

The same procedure as described in Example 20 was used, except that the reagents and stoichiometry were adjusted as indicated below. 163.373 g of tetraethylorthosilicate was dissolved in 371.21 mL of ethanol. An aqueous solution of chromium hydroxide acetate was prepared by dissolving 24.1332 g of chromium hydroxide acetate in 34.589 mL of H ₂ O. The H ₂ O: alkoxide ratio was 4: 1. The nominal catalyst composition was Cr _0.2 (SiO _2-l (OH) _2l ) _0.8 .

Example 24

The same procedure as described in Example 20 was used, except that the reagents and stoichiometry were adjusted as indicated below. 74.9988 g of tetraethylorthosilicate was dissolved in 278.4 ml of ethanol. An aqueous solution consisting of 24.1332 g of chromium hydroxide acetate, 15.5807 g of CoCl ₂ , 51.884 mL of H ₂ O and 278.41 mL of ethanol was used. The H ₂ O: alkoxide ratio was greater than 4: 1. The nominal catalyst composition was Cr _0.2 Co _0.2 (SiO _2-l (OH) _2l ) _0.6 .

Example 25

The same procedure as described in Example 20 was used, except that the reagents and stoichiometry were adjusted as indicated below. 118.75 g of tetraethylorthosilicate was dissolved in 435.84 ml of ethanol. An aqueous solution consisting of 6.282 g of ruthenium chloride, 41.07 mL of H ₂ O, and 3435.84 mL of ethanol was used as well as 3.82 mL of HNO ₃ and 4.89 mL of glacial acetic acid. The H ₂ O: alkoxide ratio was 4: 1. The nominal catalyst composition was Ru _0.05 (SiO _2-l (OH) _2l ) _0.95 .

Example 26

Using the same procedure as described in Example 20, except that the reagents and stoichiometry used were adjusted as follows. 151.11 g of niobium ethoxide was dissolved in 363.20 mL of ethanol. An aqueous solution consisting of 5.1858 g of ruthenium chloride in 3.979 mL HNO _{3 and} 5.096 mL glacial acetic acid as well as 42.786 mL H ₂ O and 363.20 mL ethanol was used. The H ₂ O: alkoxide ratio was 5: 1. The nominal catalyst composition was Ru _0.05 (NbO _2.5-l (OH) _2l ) _0.95 .

Example 27

Using the same procedure as described in Example 20, except that the reagents and stoichiometry used were adjusted as follows. 194.01 g of titanium n-butoxide was dissolved in 435.84 mL of ethanol. An aqueous solution consisting of 6.2223 g ruthenium chloride in 3.82 mL HNO ₃ and 4.89 mL glacial acetic acid as well as 41.08 mL H ₂ O and 45.843 mL ethanol was used. The H ₂ O: alkoxide ratio was 4: 1. The nominal catalyst composition was Ru _0.05 (TiO _2-l (OH) _2l ) _0.95 .

Example 28

Using the same procedure as described in Example 20, except that the reagents and stoichiometry used were adjusted as follows. 186.709 g of zirconium n-propoxide (70% by weight in propanol) was dissolved in 435.84 mL of ethanol. An aqueous solution consisting of 6.2229 g of ruthenium chloride in 3.82 mL HNO ₃ and 4.89 mL glacial acetic acid as well as 41.075 mL H ₂ O and 435.84 mL ethanol was used. The H ₂ O: alkoxide ratio was 4: 1. Nominal catalyst composition was Ru _0.05 (ZrO _2-l (OH) _2l ) _0.95

Example 29

An acrylonitrile catalyst (catalyst 41/49) commercially available from Standard Oil Company (Ohio) was used.

Example 30

1.714 ml of an aqueous 1.75 M ammonium molybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O) solution in 0.5 M bismuth nitrate solution (Bi (NO ₃ ) _{3 in} 1 M nitric acid) Prepared by dissolving 9H ₂ O), mixed with 32.0 ml, 0.5 ml of 1.0 M aqueous nickel chloride solution (NiCl ₂ · 6H ₂ O), and 0.5 ml of 1.0 M aqueous solution of cobalt nitrate (Co (NO ₃ ) ₂ · yH ₂ O) It was. The entire mixture was rapidly frozen with liquid nitrogen in a two-section Virtis Freezemobile and Unitop drying unit for at least 24 hours and dried in vacuo; The dryer rack was frozen to about −10 ° C. during the evacuation. The final dried material was calcined at 400 ° C. for 5 hours in air. The calcined powder was pelleted at 20,000 psig (138 mPa) prior to use and granulated with -40, +60 mesh (-0.42, +0.25 mm) screen. The nominal catalyst composition was Mo _0.375 Bi _0.5 Ni _0.063 Co _0.063 O _l .

Claims (12)

(i) (a) Formula A _x Au _y M _{1- (x + y)} , wherein A is selected from the group consisting of Cu, Cr, Ru, Co, and combinations thereof, and M is Al, Mg, Nb , Si, Ti, Zr and combinations thereof, x is from 0.001 to 0.5, y is from 0 to 0.2) xerogel or aerogel; (b) a heteropolyacid selected from the group consisting of H ₄ PMo ₁₁ VO ₄₀ , H ₅ PMo ₁₀ V ₂ O ₄₀ , H ₆ PMo ₉ V ₃ O ₄₀ and H ₇ P ₂ Mo ₁₇ VO ₆₂ ; (c) H _{4+ (6-z)} PMo ₁₀ VEO ₄₀ , H _{5+ (6-z)} PMo ₉ V ₂ EO ₄₀ , H _{6+ (6-z)} PMo ₈ V ₃ EO ₄₀ and H _{7+ ( 6-z)} metal substituted heteropolyacids selected from the group consisting of P ₂ Mo ₁₆ VEO ₆₂ , wherein E is an element selected from the group consisting of Cu, Cr, Zn and Co, z is the valence of E; (d) Q _q H ₄ PMo ₁₁ VO ₄₀ , Q _q H ₅ PMo ₁₀ V ₂ O ₄₀ , Q _q H ₆ PMo ₉ V ₃ O ₄₀ , Q _q H ₇ P ₂ Mo ₁₇ VO ₆₂ , Q _q H _{4+ (6-z)} PMo ₁₀ VEO ₄₀ , Q _q H _{5+ (6-z)} PMo ₉ V ₂ EO ₄₀ , Q _q H _{6+ (6-z)} PMo ₈ V ₃ EO ₄₀ and Q _q H _{7+ ( 6-z)} P ₂ Mo ₁₆ VEO ₆₂ wherein Q is selected from the group consisting of Ag and Cs, where Q is Ag, q is from 0 to (number of hydrogen atoms) × 0.5, and when Q is Cs Is 0 to (number of hydrogen atoms) × 1) heteropolyacid salt selected from the group consisting of; (e) the formula Ru _r (HPA) _s M _{1- (r + s)} , wherein r is 0.001 to 0.1, s is 0.001 to 0.05, and HPA is a heteropolyacid and heteropolyacid salt of (b) and (d) X), or aerogel complex of M), wherein M is selected from the group consisting of Al, Mg, Nb, Si, Ti, and Zr; And (f) Formula (Bi _t Co _u Ni _v ) _w Mo _1-w O _a , wherein t, u and v are each independently 0 to 1, t + u + v = 1, w is 0.01 to 0.75 And a is 1.125 to 4.875 in the presence of a catalyst selected from the group consisting of metal oxides, oxygen in the gaseous phase is represented by the formula CH ₃ NR ₂ , wherein R is C ₁ -C ₈ alkyl, phenyl, naphthyl and C ₁ -C ₄ alkyl substituted phenyl or mixtures thereof), and ii) recovering the substituted formamide Method for producing the substituted formamide comprising a. The method of claim 1 wherein said substituted formamide is an N-substituted formamide of formula HC (O) NR ₂ . The method of claim 1, wherein the oxygen is selected from the group consisting of substantially pure oxygen, air, and oxygen mixed with an inert gas. The method of claim 1 wherein said contacting is performed at a temperature of about 125 ° C. to about 450 ° C. and at a pressure of about 1 atmosphere to about 10 atmospheres. The method of claim 4, wherein the temperature is about 150 ° C. to about 275 ° C. 6. The process according to any one of claims 1 to 4, wherein the substituted formamide is recovered by fractional distillation. The method of claim 1, wherein the xerogel or aerogel of (a) or (e) is prepared from a metal oxide selected from the group consisting of aluminum isopropoxide, titanium isopropoxide and zirconium isopropoxide. Way. The method of claim 1, wherein the xerogel or aerogel of (a) or (e) is alumina sol, colloidal zirconia sol, colloidal titania sol, mixed oxide colloidal sol, colloidal silica sol, ternary or more oxide sol And inorganic metal colloids selected from the group consisting of a mixture thereof. The method of claim 8, wherein the xerogel or aerogel of claim 1 is prepared from a preformed aquasol. Formula A _x Au _y M _{1- (x + y)} , wherein A is selected from the group consisting of Cu, Cr, Ru, Co, and combinations thereof, and M is Al, Mg, Nb, Si, Ti, Zr And combinations thereof, wherein x is from 0.001 to 0.5 and y is from 0 to 0.2). Formula Ru _r (HPA) _s M _{1- (r + s)} wherein r is 0.001 to 0.1, s is 0.001 to 0.05, HPA is selected from the group consisting of heteropolyacids and heteropolyacid salts, M is Al, Composition comprising a xerogel or aerogel composite of Mg, Nb, Si, Ti, and Zr). The method of claim 11, wherein the heteropolyacid and heteropolyacid salt are H ₄ PMo ₁₁ VO ₄₀ , H ₅ PMo ₁₀ V ₂ O ₄₀ , H ₆ PMo ₉ V ₃ O ₄₀ , H ₇ P ₂ Mo ₁₇ VO _62m , and H _{4+ (6-z)} PMo ₁₀ VEO ₄₀ , H _{5+ (6-z)} PMo ₉ V ₂ EO ₄₀ , H _{6+ (6-z)} PMo ₈ V ₃ EO ₄₀ and H _{7+ (6-z)} P ₂ Mo ₁₆ VEO ₆₂ , wherein E is an element selected from the group consisting of Cu, Cr, Zn and Co, and z is the valence of E.