The method of hydrogenation of nitrile

 

(57) Abstract:

The invention relates to an improved method for the hydrogenation of nitrile, for example NITRILES of General formula NC-R-CN where R means alkylenes group containing 1-12 carbon atoms, with hydrogen in the liquid phase in the presence of a catalyst selected among metal compounds containing one or more divalent metals selected from Nickel or cobalt, possibly in a reduced state, uniformly testirovanie phase containing one or more alloying trivalent metals selected from chromium, molybdenum, iron, manganese, titanium, vanadium, gallium, indium, bismuth, yttrium, cerium, lanthanum and other trivalent lanthanide in the form of oxides, the molar ratio of the alloying metal/ferrous metal 0,01 - 0,50 obtained by deposition of a mixture of the corresponding aqueous solutions of inorganic compounds of divalent metals and alloying metals and carbonate of an alkali metal with the formation of compounds having the structure of the family of layered double hydroxides type hydrotalcite General formula I [M(II)1-xM(III)x(HE2)]x+(Ax/n)nmH2Oh, where a is an inorganic anion, such is at, cuprate, gallate, the anion of heteroalicyclic, the anion of carboxylic acid, or a mixture of several of these anions, M(II) - Nickel or cobalt, M(III) corresponding to the above-mentioned trivalent metal, and x is a number from 0.01 to 0.33, n is the valence of the anion And m is a variable number of molecules, depending on the conditions obtaining with subsequent washing, drying, calcining, and restoring at least part of the divalent metal to the oxidation state 0. It is possible that in the specified catalyst up to 50% of the divalent metals are replaced with one or more metals selected from zinc, copper, silver, gold, ruthenium, platinum or palladium, and lepirudin metals can be replaced up to 50% aluminum oxide. The method enables selective and economical to carry out the hydrogenation process and to increase the validity of the catalyst. 7 C.p. f-crystals, 2 tab.

The present invention relates to a method for hydrogenation of nitrile with the help of metal compounds as catalysts.

Among the many metal compounds, especially used as catalysts in various chemical reactions, hydrogenation catalysts based on Nickel or cobalt are an important class. Such catalysts is the Oia many hydrogenation reactions.

Catalysts of this type are very efficient and have very wide applications, however, have some disadvantages and limitations in application.

From the very beginning of their obtaining is performed by etching using a strong base alloy based on Nickel or cobalt with a high aluminium content.

Such reception, therefore, inevitably leads to large quantities of liquid alkaline aqueous wastes containing aluminates, which should be processed.

Another limitation in the use of Nickel and cobalt of Renee because of their reduced form is pyrophoric; it must be handled with caution and it can only be used in protected form or in the form of a suspension in a liquid or solid protective shell. This makes it difficult to use in a fixed bed in an industrial scale.

Finally, see a gradual deactivation of the Nickel or cobalt of Renea, while effective method of regeneration is unknown. One hypothesis, which seems reasonable to explain this decontamination especially in an environment containing water, and, more SPE is which covers the active surface of the Nickel or cobalt.

To smooth some of the above-mentioned disadvantages of the catalysts of Renea was used another form of metal catalysts: metal is applied to the carrier. Thus, in European patent application 0566197 described hydrogenation catalysts based on Nickel and/or cobalt deposited(s) on solid media, such as aluminium silicate, aluminium oxide or silicon oxide, preferably with socialization, such as not sour salt or oxide of an alkaline or alkaline-earth metal.

In the catalysts of this type the uniform distribution of the active metal in the solid media is not always very high. In addition, the presence of the media in some cases may limit the activity of the catalyst and at least dilutes the active metal phase.

Thus, in European patent application 0566197 examples show that the concentration of active metal in the deposited catalyst does not exceed 20%, and often equal to 5%.

Finally, the method of applying an active metal by impregnation of the substrate may result in partial dissolution of the active metal in the reaction medium during use of the catalyst.

In the French patent application 2091785 described ka is the gear carrier, containing magnesium, Nickel, cobalt; divalent copper, zinc, manganese and/or iron and trivalent aluminum, chromium and/or iron. The ratio of divalent and trivalent metals in these catalysts is, in fact, 6 atoms of divalent metals on the two atoms of trivalent metals.

These catalysts contain mainly aluminum as a trivalent metal and magnesium, Nickel and cobalt, sometimes in combination with other metals, as divalent metals. They can be used for the dehydrogenation of secondary alcohols or monoolefins, isomerization reactions or dealkylation or for the hydrogenation of nitro compounds.

Object of the invention is to provide a method for hydrogenation of nitrile with hydrogen in the liquid phase in the presence of a catalyst, the distinguishing feature of which is the fact that the use of a catalyst selected from metal compounds containing one or more divalent metals selected from Nickel and cobalt, at least partially restored, uniformly texturename phase containing one or more alloying trivalent metals selected from chromium, molybdenum, gadow, in the form of oxides, in which the molar ratio of the alloying metal/ferrous metal is from 0.01 to 0.50, and prepared by precipitation of a mixture of the corresponding aqueous solutions of inorganic compounds of divalent metals and alloying metals and carbonate of an alkali metal with the formation of compounds having the structure of the family of layered double hydroxides type hydrotalcite General formula I

M(II)1-xM(III)x(OH)2Ix+(Ax/n)nm H2O,

where a is an inorganic anion such as carbonate, sulfate, nitrate, Iodate, halide, Vanadate, chromate, molybdate, aluminate, stannate, zincate, permanganate, cuprate, gallate, the anion of heteroalicyclic, the anion of carboxylic acid, or a mixture of several of these anions,

M(II) - Nickel or cobalt,

M(III) appropriate vysheukazannye trivalent metal,

x is a number from 0.01 to 0.33,

n is the valence of the anion AND,

m - variable number of molecules, depending on the conditions obtaining with subsequent washing, drying, calcining, and restoring at least part of the divalent metal to the oxidation state 0.

According to a preferred form of execution of the M(II) represents, at least partially, Ni or Co, M(III) is of organza, titanium, vanadium, gallium, indium, bismuth, yttrium, cerium, lanthanum and other trivalent lanthanides, And denotes the anion carbonate, nitrate, Vanadate, chromate, molybdate, aluminate, stannate, zincate, permanganate, cuprate, gallate, carboxylate or mixtures of several of these anions, and x denotes a number from 0,048 to 0.23.

According to another preferred form of execution the molar ratio of the alloying metal/ferrous metal is from 0.01 to 0.50.

In addition, from 0 to 50% of divalent metals, Nickel or cobalt substituted, mol for mol, one or more other metals selected from zinc, copper, silver, gold, ruthenium, platinum or palladium; from 0 to 50% of oxides of the alloying metals substituted, mol for mol, aluminum oxide.

It is preferred that the compounds having the structure belonging to the family of layered double hydroxides (LDH) type hydrotalcite, obtained by deposition of a mixture of aqueous solutions of inorganic compounds of divalent metals and alloying metals included in the above hydrotalcite, and carbonate, in particular, alkali metal, and calcining the connection type hydrotalcite at a temperature varying between 250 and 600o

The metal compounds according to the invention when used as catalysts, especially as hydrogenation catalysts, have the efficiency of the same order, which is obtained with Nickel or cobalt of Renea, without the above disadvantages, especially in regard to their deactivation and regeneration.

Finally, they may have a molar ratio between the contained metals in relatively wide ranges, which allows to adapt their structure to their subsequent use as catalysts.

More specifically, these metal compounds are compounds containing one or more divalent metals, at least partially restored, textured phase containing one or more alloying metals selected among chromium, molybdenum, iron, manganese, titanium, vanadium, gallium, indium, bismuth, yttrium, cerium, lanthanum and other trivalent lanthanides, in the form of oxides.

Metals in the form of oxides, in this text referred to as alloying metals, as they are necessary to tvtome, they give the system sufficient specific surface area.

Divalent metals, preferred are Nickel or cobalt.

Usually, at least 20% of the atoms are in a reduced state, that is in oxidation state 0. Preferably, at least 50% of the atoms of Nickel or cobalt was restored.

Divalent metals are in the form of particles having dimensions of from 1 to 20 nanometers. More specifically, the particle size of divalent metals is from 3 to 5 nanometers. These particle sizes are measured by the method of x-ray diraction processes.

Particles of divalent metal evenly textured with particles of at least one oxide of the alloying metal having a particle size of the same order as the particle size of the divalent metal.

The specific surface of the metal compounds according to the invention is usually from 20 to 150 m2/,

The molar ratio of the alloying metal/ferrous metal in the metal compounds according to the invention is usually from 0.01 to 0.50.

Preferably this molar ratio is from 0.05 to 0.30.

For the molar ratio of the alloying metal/ferrous metal defined before this, these other metals present in case of need, are considered as an integral part of the totality of divalent metals.

The oxides of the alloying metals can also be partially replaced by aluminum oxide. This aluminum oxide, based on the aluminum may be present in an amount of 0-50 mol. % relative to the total amount present of the alloying metals.

Alloying metals present in the form of oxides in the metal compounds according to the invention are usually in the oxidation state 3, but some of them can at least partially be present in the oxidation States 4 or 5.

Another object of the invention relates to precursors of the above metal compounds.

These precursors are metal compounds containing one or more divalent metals in the form of oxides, textured phase containing one or NEA, bismuth, yttrium, cerium, lanthanum and other trivalent lanthanides, in the form of oxides.

As indicated above, the metal compounds in which the divalent metal or divalent metals are at least partially restored, from 0 to 50 mol. % of oxides of the alloying metal may be replaced by aluminum oxide and from 0 to 50 mol. % oxide or oxides of divalent metals may be replaced by oxides of zinc, copper, silver, gold, ruthenium, platinum and/or palladium.

Oxides of divalent metals of these precursors, as well as oxides mostly metals, the ability to replace some of the divalent metals are easily recoverable. Predecessors allow you to get a metallic compound according to the invention by recovery at relatively moderate temperatures.

This recovery can be carried out by heating in a hydrogen atmosphere. Temperature recovery is preferably from 200 to 500oC.

Hydrogen can be used under pressure or by blowing.

The duration of the recovery can vary within very wide limits. For information, it is usually the status is particularly aluminum oxide, present in case of need, are not reversed in the above conditions, recovery of ferrous metals. Thus, the metal compounds according to the invention do not contain aluminium in oxidation state 0, in contrast to Nickel and cobalt of Renee.

The method of synthesis of precursors of the metal compounds according to the invention is to obtain compounds having the structure belonging to the family of layered double hydroxides (LDH) type hydrotalcite, and the subsequent firing of the above-mentioned compounds of the type hydrotalcite.

Hydrotalcite (or SDG), so named as a result of extensive interpretation of the names of natural compounds of Mg6Al2(OH)16CO34H2O, are compounds of General formula (I)

[M(II)1-xM(III)x(OH)2]x+(Ax/n)nmn20 (I)

where And denotes an inorganic anion such as carbonate, sulfate, nitrate, Iodate, halide, Vanadate, chromate, molybdate, aluminate, stannate, zincate, permanganate, cuprate, gallate, the anion of heteroalicyclic, the anion of carboxylic acid, or a mixture of several of these anions,

M(II) represents a divalent metal,

M(III) Ref is anion AND,

m denotes a variable number of molecules, depending on the method of preparation and drying conditions.

In the case of SDG, leading to the precursors of the metal compounds according to the invention, M(II) represents, at least partially, Ni and Co and M(III) represents at least one alloying metal in oxidation state 3, choose among chromium, molybdenum, iron, manganese, titanium, vanadium, gallium, indium, bismuth, yttrium, cerium, lanthanum and other trivalent lanthanides.

The preferred hydrotalcite formula (I) are those for which a denotes an anion: a carbonate, nitrate, Vanadate, chromate, molybdate, aluminate, stannate, zincate, permanganate, cuprate, gallate, the anion of carboxylic acid, or a mixture of several of these anions, and x denotes a number from 0,048 to 0.23.

Hydrotalcite formula (I) is obtained by precipitation of a mixture of aqueous solutions of inorganic compounds of divalent metals and alloying metals included in the above hydrotalcite, and especially carbonate of an alkali metal.

Compounds that can be used are water-soluble salts of various metals M(II) and M(III).

As examples and not limiting such Salta, the cobalt chloride, cobalt iodide, cobalt nitrate, cobalt sulphate, copper acetate, copper chloride, copper nitrate, copper sulfate, silver fluoride, silver nitrate, zinc acetate, zinc bromide, zinc chloride, zinc formate, zinc nitrate, zinc sulfate, chromium chloride, chromium sulfate, chromium bromide, iron bromide, iron chloride, iron formate, iron nitrate, iron oxalate, ferrous sulfate, titanium chloride, titanium bromide, gallium bromide, gallium chloride, gallium nitrate, gallium sulfate, bromide, indium chloride, India nitrate India, sulfate, indium, vanadium bromide, iodide, vanadium, underslept, cerium acetate, cerium bromide, cerium iodide, cerium nitrate, lanthanum acetate, lanthanum bromide, lanthanum iodide, lanthanum nitrate, the nitrate of bismuth, molybdenum nitrate, manganese nitrate.

The dissolution of these compounds and deposition of hydrotalcite formula (I) is carried out at a temperature equal to or below the 100oC.

Hydrotalcite formula (I), for which a denotes an anion other than carbonate, can be derived from hydrotalcite-carbonate obtained before that, through the exchange of carbonate anions to other anions in alkaline medium.

It is important to wash hydrotalcite to remove a large part of neozhidannyh inorganic cat is BNY, at least some of them, to promote the sintering of the particles of divalent metal, which leads to an increase of their size and specific surface reduction of the precursor and metal compounds that are derived from these hydrotalcites.

Thus obtained hydrotalcite dried, and then calcined to obtain the precursor of the metal compounds according to the invention.

This annealing carried out usually at a temperature of from 250 to 600oUsually with air blowing. The temperature of annealing pick up in a certain interval, depending on the nature of the alloying metals and the ratio of the alloying metal/ferrous metal.

The duration of calcination may vary within wide limits. For information, most often it is in the range from several minutes to 24 hours.

The metal compounds according to the invention defined before it can be used as catalysts in many reactions. Usually they can be used in reactions catalyzed by Nickel or cobalt of Renee.

Consequently, more specifically, they are hydrogenation catalysts. That is as NITRILES, imine, oximes, nitrogen-containing heterocycles, azo compounds, nitro compounds,

- carbonylic compounds, such as sugar,

- compounds with unsaturated carbon-carbon bond, such as ethylene compounds

- compounds with aromatic cycle, for example benzene or naphthalene compounds.

Among the substrates, the hydrogenation of which can be catalyzed by metal compounds according to the invention, are preferred NITRILES.

The metal compounds according to the invention can be used in the method of hydrogenation of aliphatic, cycloaliphatic, heterocyclic or aromatic mononitriles or dinitriles. Dinitrile represent a particularly interesting class of compounds in connection with the compounds to which they lead.

These dinitrile are, more specifically, but not limited to, nitrile substrates of formula (II)

NC-R-CN (II)

in which R denotes alkylenes or alkenylamine group, linear or branched, containing from 1 to 12 carbon atoms, or Allenova, or Aracinovo, or oralgenital group, substituted or unsubstituted.

Predpochtitel is certain, containing from 1 to 6 carbon atoms.

As examples of such dinitriles can be called especially dinitrile adipic acid, dinitrile methylglutaric acid, dinitrile adelantarnos acid, dinitrile dimethylethanol acid, dinitrile malonic acid, dinitrile succinic acid and dinitrile glutaric acid and mixtures thereof, especially mixtures of dinitrile adipic acid, dinitrile methylglutaric acid, dinitrile adelantarnos acid, which receive the same method of synthesis of dinitrile adipic acid.

Preferably the reaction of hydrogenation of NITRILES is carried out in the presence of a strong base. This strong base is preferably choose among the following compounds: LiOH, NaOH, KOH, RbOH, CsOH and mixtures thereof.

Actually, for a reasonable compromise property is the price most often used are NaOH and KOH, although RbOH and CsOH give even better results.

The reaction medium hydrogenation preferably is a liquid. It contains at least one solvent capable of dissolving GearWay nitrile substrate as the reaction proceeds best when the above-mentioned substrate is in solution.

According to and the water. Water is generally present in a quantity less than or equal to 50%, mainly less than or equal to 20 wt. % relative to the total weight of the reaction medium. Even more preferably the water content in the reaction medium is enclosed between 0.1 and 15 wt. % relative to the total weight of the components of the above-mentioned environment.

In addition to the water or instead of water can be provided, at least one other solvent, type of alcohol and/or amide. The most suitable alcohols are, for example, methanol, ethanol, propanol, isopropanol, butanol, glycols, such as ethylene glycol and/or propylene glycol, polyhydric alcohols and/or mixtures of the aforementioned compounds.

When the solvent is an amide, it could be, for example, N-medierranean or dimethylacetamide.

When used with water, the solvent, preferably an alcohol, is from 1 to 1000% relative to the weight of water, preferably from 2 to 300%.

In accordance with another preferred feature of the hydrogenation in the reaction medium is injected diamine, which is formed in the reaction. We are talking about, for example, hexamethylenediamine were when the nitrile substrate is dinitrile of adipine between 50 and 99 wt. % relative to the total amount of solvent contained in the above-mentioned reaction medium, and even more preferably it lies between 60 and 99 wt. %.

The hydrogenation in the liquid phase can be carried out in an intermittent mode (bath) on one nitrile or, if necessary, with additives other liquid compounds, such as diamine, which is formed in the reaction, and/or the solvent or solvents.

Equally it can be carried out with the continuous introduction of the nitrile substrate.

When operating with nitrile and one or more solvents and/or diamine, the introduction of the nitrile substrate, such as dinitrile adipic acid, in a reaction medium exercise, maintaining a concentration of between 0.001 and 30 wt. % relative to the total weight of the liquid reaction medium, preferably between 0.1 and 20 wt. %.

The amount of base in the reaction medium varies depending on the nature of the reaction medium.

In those cases, when the reaction medium contains only water and consider amine as a liquid solvent, the amount of base favorably greater than or equal to 0.1 mol/kg of catalyst, preferably the conclusion is In the case when the reaction medium contains water and alcohol and/or amide, the amount of the base is greater than or equal to 0.05 mol/kg of catalyst, preferably it lies between 0.1 and 10.0 mol/kg and even more preferably between 1.0 and 8.0 mol/kg

The amount of catalyst is not critical, since according to the form of the method it can be present in an amount that is many times greater than the number gidrirovannogo substrate, especially when it is continuously injected into the reaction medium containing the catalyst. For information, the catalyst may be from 0.1 to 100 wt. % relative to the liquid reaction medium and, most often, from 1 to 50%.

Deciding the issue of the composition of the reaction medium and the choice of catalyst, start mixing these two elements, then heated the mixture to the reaction temperature, which is lower than or equal to 150oWith, preferably lower than or equal to 120oWith and even more preferably lower than or equal to 100oC.

Specifically, this temperature lies between room temperature (approximately 20 theoC) and 100oC.

Previously, simultaneously or after heating the reaction chamber is filled with hydrogen at an appropriate pressure, i.e., at the D. the conditions and catalyst.

For discontinuous method of carrying out the reaction it may vary from several minutes to several hours.

In the continuous method of carrying out the reaction, which is quite suitable for this type of reactions, duration, obviously, is not a fixed parameter.

It is necessary to note that the specialist can change the chronology of the stages of method respectively operating conditions. The procedure given above is only the preferred form of the method of hydrogenation, but is not restrictive.

Other conditions that control the hydrogenation of (continuous or intermittent way), belong to the traditional technical devices in and of themselves known.

Thanks to all helpful to the regulations mentioned above, the metal compounds according to the invention allow gidrirovanii nitrile substrates in amines selectively, rapidly, conveniently and economically.

Hydrogenation of dinitrile adipic acid hexamethylenediamine were particularly important, because it gidrirovannoe derived is one of the main monomers for obtaining, polyamide-6,6.

Hydrogenation of dinitriles equal treatment of adipic acid, to obtain the nitrile aminocaproic acid. This is the last connection by ciclismo hydrolysis, can be easily converted into caprolactam, which is the original product of another large-scale industrial synthesis of polyamide, such as polyamide-6.

The invention is illustrated by the following examples of the preparation of the metal compounds according to the invention and their use in hydrogenation dinitrile adipic acid hexamethylenediamine were.

EXAMPLES

Examples of obtaining metal compounds according to the invention

Example 1.

Prepare 200 ml of an aqueous solution containing 0.3 mole of Ni and CR in the form of their nitrate Ni(NO3)26H20 and SG(NO3)38H2Oh, when this molar ratio Ni/Cr is equal to 3.

Prepare 200 ml of an aqueous solution B containing 0.4 mole of sodium carbonate.

The solution And within a few minutes evenly poured into solution B with stirring, with both solution have a temperature of 80oC.

Observe the formation of a homogeneous sediment. The mixture was kept at 80oWith stirring for approximately 20 minutes.

The precipitate is filtered and washed it on the filter 1500 ml in the Asses; get a green powder formula Ni6Cr2(OH)16CO34H2O.

This compound is then calcined in a ventilated oven for 3 hours at 300oC. Thus remove hemosorption water and CO2. The metal precursor compounds according to the invention represents a very poorly crystalline mixed oxide of Ni and Cr.

Then, the precursor to recover hydrogen at 350oWith over 29 hours. Get metal compound according to the invention consisting of Ni in the oxidation States 0 and chromium oxide (molar ratio Ni/Cr=3); this connection is a black powder with a specific surface area of 70 m2/g: link ().

Examples 2-4.

Repeat example 1, selecting appropriate amount of nitrate Ni and nitrate SG thus, to obtain the molar ratio Ni/Cr equal to 5 (example 2), 10 ( example 3) and 20 ( example 4).

After the different stages of the synthesis described in example 1, receive three of the following metal compounds according to the invention:

connection (6): black powder consisting of Ni and oxide SG with a molar ratio of Ni/Cr=5, having a specific surface 103 m2/g;

2/g;

connection (g): black powder consisting of Ni and oxide SG with a molar ratio of Ni/Cr=20, having a specific surface area of 30 m2/,

Examples 5-10.

Following the procedure described in example 1 to a solution And add the amount of copper nitrate Cu(NO3)26N2On or zinc nitrate Zn(NO3)26N20, necessary to obtain a molar ratio of Ni/Cu equal to 5, 10 or 20 or molar ratio Ni/Zn equal to 5, 10 or 20. The molar ratio of Ni+Cu/Cr or Ni+Zn/Cr equal to 5 for all examples.

After the different stages of the synthesis described in example 1, get six of the following metal compounds according to the invention:

connection (e): black powder consisting of Ni, si and oxide SG with a molar ratio of Ni/Cu= 5 and the molar ratio of Ni+Cu/Cr=5, having a specific surface area of 85 m2/g;

connection (s): black powder consisting of Ni, si and oxide SG with a molar ratio of Ni/Cu= 10 and the molar ratio of Ni+Cu/Cr=5, having a specific surface area of 75 m2/g;

connection (W): black powder consisting of Ni, si and oxide SG with a molar ratio of Ni/Cu= 20 and the molar ratio of Ni+Cu/Cr=5, having a specific surface area of 70 m2/g;

connection (s): black powder, network 95 m2/g;

connection (s): black powder consisting of Ni, Zn and oxide SG with a molar ratio of Ni/Zn= 10 and the molar ratio of Ni+Zn/Cr=5, having a specific surface area of 87 m2/g;

connection (to): black powder consisting of Ni, Zn and oxide SG with a molar ratio of Ni/Zn= 20 and the molar ratio of Ni+Zn/Cr=5, having a specific surface area of 82 m2/,

Examples 11 and 12.

Following the procedure described in example 1 to prepare a solution with quantities of Nickel nitrate Ni(NO3)26H2Oh and cerium nitrate CE(NO3)36N2On or nitrate of Nickel, chromium nitrate CR(NO3)38H2Oh and nitrate of cerium required to obtain a molar ratio of Ni/Ce equal to 5, or a molar ratio of Ni/Cr+Ce equal to 4.

After the different stages of the synthesis described in example 1, receive two of the following metal compounds according to the invention:

connection (l): black powder consisting of Ni and oxide SG with a molar ratio of Ni/Cr=5, having a specific surface area of 100 m2/g;

connection (m): black powder consisting of Ni, CE oxide and oxide SG with a molar ratio of Ni/Ce+Cr= 4 and the molar ratio of CR/CE=5, having a specific surface area of 90 m2/,

Examples aimery 13-22 and comparative experiment 1.

Experience as catalysts for various metal compounds obtained before this.

Test hydrogenation allows in certain strictly defined conditions to compare the activity and selectivity of the metal compounds of different compositions.

The device used consists of a stainless steel autoclave, in which carry out the reaction, the above-mentioned autoclave equipped with a steel vial for filling that can withstand the pressure, inlet for hydrogen or inert gas, self-regulating heating system and devices for measurement and control of pressure and temperature, a magnetic core rotating at a speed of 1500 revolutions per minute, and an outlet for gases.

In the autoclave download metal compound according to the invention (0.2 g Ni) and either (1) 40 g of ethanol and 1.6 g of water (examples 13-16 and comparative experiment 1) or (2) 0.3 ml of ethanol, 38 g of diamine, 4 g of distilled water (examples 17-22) and the hydroxide of alkaline metal (sodium hydroxide, unless otherwise specified) at the rate of 2 mol/kg Ni metal compounds. The homogenized mixture and cover it with argon. Then rinsed with nitrogen, then with hydrogen. Finally, heated to the selected temperature (80is Mulu to fill and three times rinsed it with hydrogen. The injection box ABOVE is carried out for 1 hour.

As a comparison, conducting experience in the same conditions as in examples 13-16, with the solvent environment (1), using Nickel of Renee containing 4.5% of CR and having a specific surface area of 70 m2/g (molar ratio Ni/Cr of about 20). This Nickel of Renee contains about 7 wt. % metal A1 with respect to Ni.

At the end of the reaction the temperature and pressure of the leave until the consumption of hydrogen. The amount of the product of hydrogenation determined chromatographically in the vapor phase. Thus determine the selectivity (s) are received various side products.

Quantitatively determine the following by-products:

GM: hexamethylenimine,

AMCA: aminoethylethanolamine,

N-AGMD: N - ethylhexylamine,

DCG: diaminocyclohexane CIS and TRANS,

OSH: bis(hexamethylenediamine).

Selectivity for GMI in percent is given by the ratio: 100 - sum of selectively by-products. In fact, as the GMI is a large part of the reaction solvent, it cannot be directly quantified with high accuracy. On the contrary, it is checked that the by-products identified VNOM formed by-product in relation to developed ABOVE. All of the examples and comparative experiments, the degree of transformation ABOVE (as well as the degree of conversion of the intermediate nitrile aminocaproic acid) is equal to 100%. For convenience, the selectivity is expressed in micromol by-product per mole turned OVER. Table 1 below lists the reference used metal compound, the divalent nature and alloying metals which it is formed, the molar ratio of these metals, the selectivity for GMI and certain by-products.

Examples 23 and 24.

Repeat examples 17-22 hydrogenation OVER in the same operating conditions and with the solvent medium (2), using as a catalyst a metal compound (l) and (m).

Get the results collected in table 2.

Comparative experience 2.

Obtaining metal compounds not included in the invention: Ni/Al2O3.

Following the procedure described in example 1 to prepare a solution with quantities of Nickel nitrate Ni(NO3)26H2O and aluminum nitrate Al(NO3)38H2O required to obtain a molar ratio of Ni/Al equal to 3.

After the different stages of the synthesis, opisi of Ni and Al oxide with a molar ratio of Ni/Al = 3, having a specific surface area of 150 m2/,

Comparative experience 3.

The use of metal compounds (b) as a hydrogenation catalyst.

Repeat examples 13-16 hydrogenation OVER in the same operating conditions and with the solvent environment (1), using as a catalyst a metal compound (b).

Get the following results,%:

WITH GMI - 81,3

WITH GMS - 154000

WITH AMCA - 0

N-AGMD - 2500

WITH DCG - 420

WITH OSH - 15300

With AKA*, CVA* - 15000

(*) AKA - aminocaproic acid amide; CVA - amide cyanovalerianic acid.

Comparative experience 4.

Aging of the catalyst in hydrogenation reactions. A series of hydrogenation reactions OVER perform in the operating conditions described for examples 13-22 environment (2), but injective 10 g OVER an hour, with one hand, with the compound (g) according to the invention (Ni/Cr = 20) and, on the other hand, with Nickel of Renea used in comparative experiment 1 (Ni/Cr = 20).

For each hydrogenation measure end time To1, i.e. the time during which continues the absorption of hydrogen after the termination of the injection box ABOVE.

With each of the two catalysts perform vtoro the tats:

example 25:To1=15 minutes (With the GMD=99%)

To=16 minutes,

- comparative experience 4:To1=17 minutes (With the GMD=98,7%)

To=99 minutes.

See rapid deactivation of the catalyst of Raney, whereas the catalyst according to the invention retains a constant activity.

1. The method of hydrogenation of the nitrile with hydrogen in the liquid phase in the presence of a catalyst, characterized in that the used catalyst selected among metal compounds containing one or more divalent metals selected from Nickel and cobalt, at least partially restored, uniformly texturename phase containing one or more alloying trivalent metals selected from chromium, molybdenum, iron, manganese, titanium, vanadium, gallium, indium, bismuth, yttrium, cerium, lanthanum and other trivalent lanthanides, in the form of oxides, in which the molar ratio of the alloying metal/ferrous metal is from 0.01 to 0.50, and prepared by precipitation of a mixture of the corresponding aqueous solutions of inorganic compounds of divalent metals and alloying metals and carbonate of an alkali metal, to obtain the compounds having the structure of the family of layered double hydroxides type>/BR>where a is an inorganic anion such as carbonate, sulfate, nitrate, Iodate, halide, Vanadate, chromate, molybdate, aluminate, stannate, zincate, permanganate, cuprate, gallate, the anion of heteroalicyclic, the anion of carboxylic acid, or a mixture of several of these anions;

M(II) - Nickel or cobalt;

M(III) corresponding to the above-mentioned trivalent metal;

x is a number from 0.01 to 0.33;

n is the valence of the anion;

m - variable number of molecules, depending on the conditions obtaining with subsequent washing, drying, calcining, and restoring at least part of the divalent metal to the oxidation state 0.

2. The method according to p. 1, wherein M(II) represents, at least partially, Ni or Co, M(III) represents at least alloying metal in oxidation state 3, selected from chromium, molybdenum, iron, manganese, titanium, vanadium, gallium, indium, bismuth, yttrium, cerium, lanthanum and other trivalent lanthanides, And denotes the anion carbonate, nitrate, Vanadate, chromate, molybdate, aluminate, stannate, zincate, permanganate, cuprate, gallate, the carboxylate or a mixture of several of these anions, and x denotes a number from 0,048 to 0.23.

3. The method according to any of paragraphs. 1 and 2, characterized in that Thu is made of PP. 1-3, characterized in that the 0-50% of divalent metals, Nickel or cobalt substituted mol per mol of one or more other metals selected from zinc, copper, silver, gold, ruthenium, platinum or palladium.

5. The method according to any of paragraphs. 1-4, characterized in that the 0-50% of oxides of the alloying metals substituted mol per mol of aluminum oxide.

6. The method according to any of paragraphs. 1-5, characterized in that the compounds having the structure belonging to the family of layered double hydroxides (LDH) type hydrotalcite, obtained by deposition of a mixture of aqueous solutions of inorganic compounds of divalent metals and alloying metals included in the above hydrotalcite, and carbonate, in particular, alkali metal and calcining the connection type hydrotalcite at a temperature varying between 250 and 600oC.

7. The method according to any of the Il PP. 1-6, characterized in that the nitrile selected from aliphatic NITRILES.

8. The method according to p. 7, wherein the nitrile is selected from NITRILES of General formula II

NC-R-CN,

where R means alkylenes group containing 1-12 carbon atoms.

 

Same patents:

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FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention relates to methods for preparing carbon monoxide-conversion catalysts used in production of hydrogen, nitrogen-hydrogen mixture, and other hydrogen-containing gases. According to first option, active catalyst component, i.e. iron compound, is precipitated from solution with precipitation reagent, whereupon precipitate is separated from mother liquor and washed to form catalyst mass, which is molded and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. According to second option, iron compound is first mixed with promoting additives and cations of promoting additives are precipitated jointly with iron cations, resulting precipitate is separated from mother liquor, washed and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. As iron compound in the first and second options, ferrous and ferric sulfates and, as precipitation reagent, carbonate salts or corresponding hydroxides are utilized. Promoting additives are selected from Cu, Mn, and Al or, in the second option, their mixture.

EFFECT: reduced content of sulfur in finished catalyst at the same catalyst activity.

3 cl, 1 tbl, 12 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention, in particular, relates to catalyst based on synthetic mesoporous crystalline materials and provides hydrocarbon conversion catalyst composed of: group VIII metal/SO42-/ZrO2-EOx, where E represents element of the group III or IV of Mendeleev's periodic table, x = 1.5 or 2, content of SO42- is 0.1 to 10% by weight, ZrO2/EOx molar ratio is 1:(0.1-1.0), which has porous crystalline structure with specific surface 300-800 m2/g and summary pore volume 0.3-0.8 cm3/g. Preparation method comprises precipitation of zirconium compounds, in particular zirconium hydroxide or zirconyl, under hydrothermal conditions in presence of surfactant to form mesoporous phase, which is stabilized with stabilizing agents: group III and IV elements. When stabilization is achieved, if necessary, acidity is adjusted and group VIII metal is added.

EFFECT: increased specific surface area and heat resistance at simplified technology.

9 cl, 2 dwg, 2 tbl, 6 ex

FIELD: chemical industry; methods of production of zirconium oxides

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of obtaining of zirconium oxide for production of the catalytic agents used, for example, in the reactions of the organic synthesis. The invention presents the method of obtaining of zirconium oxide for production of the catalytic agents, which includes the operations of dissolution of the zirconium salt in water, treatment of the solution with the alkaline reactant, settling of the metals hydroxides, filtration, separation of the mother-liquor from the settlings, the settlings water flushing, its drying, calcination and granulation and-or granulation by molding. At that dissolution of the source zirconium chloride and-or zirconium oxychloride is conducted in the sodium chloride solution with concentration of 200-250 g/dc3 till reaching of the concentration of zirconium of 20-120 g/dc3. Settling of zirconium oxyhydrate is conducted by the adding the initial chloride solution in the solution of the sodium hydroxide with concentration of 20-80 g/dm3 up to reaching the suspension pH equilibrium value - 5-8. Then the suspension is filtered up to the zirconium oxyhydrate pasta residual humidity of 40-80 %. The mother chloride solution is separated from the settlings of zirconium oxyhydrate and again use it for dissolution of the next batch of zirconium chloride and-or zirconium oxychloride. The settlings of zirconium oxyhydrate are subjected to drying at 80-100°C within 2-6 hours, then the dry settlings are suspended in the water at the ratio of liquid to solid L:S = (5-10 :1, the suspension is filtered, the sediment on the filter is flushed by water, the chlorides are wash off up to the residual concentration of ions of chlorine in the flush waters of 0.1-0.5 g/dm3, divided into 2 parts, one of which in amount of 60-80 % is subjected to drying and calcinations at the temperatures of 300-600°C, and other part in amount of 20-40 % is mixed with the calcined part of the settlings and subjected to granulation by extrusion at simultaneous heating and dehydration of the damp mixture of zirconium oxide and zirconium oxyhydrate with production of the target product. The technical result of the invention is improvement of quality of the produced zirconium oxide for production of the catalytic agents due to provision of the opportunity to use ZrO2 for the subsequent production of the various catalytic agents of the wide range of application and thereby improving the consumer properties of the produced production.

EFFECT: the invention ensures improvement of the quality of the produced zirconium oxide for production of the catalytic agents with improved consumer properties.

1 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: chemical industry; materials and the methods for the catalyst carrier manufacture.

SUBSTANCE: the invention is pertaining to the new mixed oxides produced from ceric oxide and zirconium oxide, which can used as the catalyzers or the catalyzers carriers for purification of the combustion engine exhaust gases. The mixed oxide possesses the polyphase cubical form of the crystallization and oxygenous capacity of at least 260/ micromoles of O2 /g of the sample and the speed of the oxygen extraction of more than 1.0 mg-O2/m2-minute, which are measured after combustion within 4 hours at the temperature of 1000°C. The invention also presents the substrate with the cover containing the indicated mixed oxide. The method of production of the polycrystallic particles of the indicated mixed ceric-zirconium oxide includes the following stages: i) production of the solution of the mixed salt which are containing, at least, one salt of cerium and, at least, one salt of zirconium in the concentration, sufficient for formation of the polycrystallic particles of the corresponding dry product on the basis of the mixed oxide. At that the indicated particles have the cerium-oxide component and zirconium-oxide component, in which these components are distributed inside the subcrystalline structure of the particles in such a manner, that each crystallite in the particle consists of a set of the adjacent one to another domains, in which the atomic ratios of Ce:Zr which are inherited by the adjacent to each other domains, are characterized by the degree of the non-uniformity with respect to each other and determined by means of the method of the X-ray dissipation the small angles and expressed by the normalized intensity of the dissipation I(Q) within the limits from approximately 47 up to approximately 119 at vector of dissipation Q, equal to 0.10 A-1; ii) treatment of the solution of the mixed salt produced in compliance with the stage (i),with the help of the base with formation of sediment; iii) treatment of the sediment produced in compliance with the stage (ii),using the oxidative agent in amount, sufficient for oxidizing Ce+3 up to Ce+4; iv) washing and drying of the residue produced in compliance with the stage (iii); and v) calcination of the dry sediment produced in compliance with the stage (iv),as the result there are produced polycrystallic particles of the oxide of ceric and zirconium in the form of the mixed oxide with the above indicated characteristics. The technical result is the produced mixed oxide possesses both the high oxygenous capacitance, and the heightened speed of the oxygen return in the conditions of the high temperatures.

EFFECT: the invention ensures production of the mixed oxide manufactured from ceric oxide and zirconium oxide and possessing the high oxygenous capacitance and the heightened speed of the oxygen return in the conditions of the high temperatures.

68 cl, 21 ex, 2 dwg

FIELD: production of catalytic compositions.

SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.

EFFECT: enhanced efficiency.

29 cl, 8 ex

FIELD: redox reaction catalysts.

SUBSTANCE: invention relates to methods for preparing vanadium-titanium oxide catalysts for redox reactions, e.g. for industrial processes of production of phthalic anhydride via oxidation of o-xylene, selective reduction nitrogen oxides, and detoxification of organochlorine compounds. Method of invention comprises following stages: providing titanyl sulfate solution; adding ammonia and then vanadium peroxide solution to titanyl sulfate solution or adding to the same vanadyl sulfate or oxalate and then ammonia solution; optionally ageing suspension resulting after mixing of solutions; filtration; and calcinations at 450°C.

EFFECT: increased heat resistance of active chlorobenzene oxidation catalyst and reduced catalyst preparation time (10-12 h instead 72 h as in a known method).

1 tbl, 3 ex

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