Nickel hydrogenation catalyst and preparation method thereof

FIELD: chemistry.

SUBSTANCE: invention relates to catalytic chemistry - design of an efficient catalyst for hydrogenation of alkenes and a method of preparing said catalyst, which can be used in fine organic synthesis. Described is a catalyst for hydrogenation of unsaturated compounds - alkenes, obtained from a nickel compound and a reducing agent, where the catalyst is obtained using nickel bis-acetylacetonate as the starting nickel compound and lithium tetrahydroaluminate as the reducing agent and a modifying additive is also added - a proton-containing compound selected from a group comprising water, alcohol, phenol or acid, with the following ratio of components: nickel bis-acetylacetonate/lithium tetrahydroaluminate/proton-containing compound 1:2-50:1-34. The invention also describes a method of preparing the catalyst for hydrogenation of unsaturated compounds - alkenes, based on reducing a nickel (II) compound with lithium tetrahydroaluminate, in which the nickel (II) compound used is nickel bis-acetylacetonate, the reducing agent is lithium tetrahydroaluminate and a modifying additive is also added; where the said additive is a proton-containing compound - water, alcohol, phenol or acid; the catalyst is formed in a hydrogen current at temperature 20-35°C (293-308 K) for 5-30 minutes.

EFFECT: preparation of nickel-containing catalyst with high hydrogenation catalytic activity when carrying out the catalytic process in mild conditions (at room temperature and normal (atmospheric) hydrogen pressure or 1 excess atm).

2 cl, 16 ex, 3 tbl

 

The present invention relates to the field of catalytic chemistry - the development of effective Nickel hydrogenation catalysts and method of production thereof, which can be used in fine organic synthesis.

Known homogeneous catalyst for selective hydrogenation of cyclic polyene [Pat. Republique Franqalise No. 2.032.065 from 09.11.1970, 01J 11/00, SS 5/00] for example, hydrogenation cyclododecatriene to cyclododecene when the hydrogen pressure of 30 ATM and a temperature of 50-100°C on the basis of cobalt naphthenate and LiAlH(OR)3(R=tert-Bu).

The disadvantage of the catalyst are the counterpart of the hard conditions of the hydrogenation process - high hydrogen pressure (30 ATM) and, as a consequence, the need for a process of hydrogenation in an autoclave.

A known catalyst for the hydrogenation of alkenes (cyclopentadiene to cyclopentene; cyclooctadiene to cyclooctene) and ketones (acetophenone to methylphenylcarbinol) [Pat. Republique Franqalise No. 2.151.749 from 26.03.1973, SW 1/00, B01J 11/00] based on bis-acetylacetonate Nickel and complex hydride LiAlH4·3C4H8O (C4H8O - tetrahydrofuran) in benzene. The hydrogenation is carried out in an autoclave at a hydrogen pressure of 30 bar and a temperature of 27°C (300 K).

The disadvantage of the catalyst are the counterpart of the hard conditions of the hydrogenation process - high hydrogen pressure (30 ATM), and, as SL is stvie this, the need for a process of hydrogenation in an autoclave.

A known catalyst for the hydrogenation of alkenes [Takegama Century Yo, Ueno T., Fujii T. The Preparation of Heavy Metal Hydride and Its Catalytic Activity. VII. The Hydrogenation of Various Olefins with a Ferric Chloride-Lithium Aluminum Hydride or a Cobaltous Chloride-Lithium Aluminum Hydride Catalyst // Bull. Chem. Soc. Japan. - 1965. - Vol.38, No. 8. - PP. 1279-1285] on the basis of the chlorides of iron(III) or cobalt(II) and tetrahydroaluminate lithium for different ratios of the halide of the transition metal and LiAlH4(molar ratio MCl2/LiAlH4=1:0.8-1.43), which hydrasuit alkenes (styrene, inden, isoprene, cyclohexene) under mild conditions (temperature - 0°C, normal (atmospheric) pressure of hydrogen).

The disadvantage of the catalyst-analogue is low catalytic activity in the hydrogenation, which is not more than 0.2 mol of styrene/ g-at Fe·min at 0°C and atmospheric pressure of hydrogen.

The closest analogue is the catalyst for the hydrogenation of unsaturated compounds [Ashby Y.S., Lin, J.J. Selective reduction of alkenes and alkynes by the reagent lithium aluminum hydride-transition metal halide // J. Org. Chem. - 1978 - Vol.43, N 13. - PP.2567-2572] on the basis of the halides of the metals of the first transition series, including dichloride Nickel (TiCl3, FeCl3, FeCl2, CoCl2,NiCl2and LiAlH4that exhibits catalytic activity in the hydrogenation of various alkenes (styrene, octene-1, hexene-1, CIS-hexene-2, TRANS-hexene-2, cyclohex the Yong) and alkynes (phenylacetylene) under mild conditions: at room temperature and atmospheric pressure of hydrogen.

The disadvantage of the catalyst-analogue is low catalytic activity in the hydrogenation, which is less than 0.03 mol octene-1/ g-at Ni-min; 4.2·10-4mol of cyclohexene / g-at Ni-min at room temperature and atmospheric pressure of hydrogen.

A method of obtaining Nickel catalyst for hydrogenation [Angula I., Lok S.M., Norambuena V.F.Q., M. Lutz, A.L. Spek, E. Bouwman Homogeneous hydrogenation of 1-octene; effect ofanion, solvent and ligand on hydrogenation activity and selectivity values. Crystal structure of the catalyst precursor [Ni(o-MeO-dppp)(tfa)2] // J. Mol. Catal. A: Chem. - 2002. -V. 187. - P. 55-67] unsaturated hydrocarbons for use as precursors of phosphine complexes of Nickel(II) [Ni(o-MeO-dppp)(tfa)2], where o-MeO-dppp - 1.3-bis(di(o-methoxyphenyl)phosphino)propane; tfa - triptorelin. The method of producing catalytic hydrogenation is as follows. To a solution of the Nickel complex [Ni(o-MeO-dppp)(tfa)2] was added to the substrate (octene-1) and was stirred for 5 minutes Then the reaction mixture was transferred into an autoclave and created a hydrogen pressure of 50 bar. The hydrogenation was carried out at 50°C (333 K). The catalytic activity of the Nickel catalyst in the hydrogenation of octene-1 under these conditions amounted to 19.3 mol H2/g-at Ni-min, if the solvent was methanol, 31.5 mol H2/g-at Ni·min during the process in a mixture solvent: methanol-dichloromethane in a 1:1 ratio.

The disadvantage of this method of obtaining Nickel is th hydrogenation catalyst is a low catalytic activity of the obtained Nickel catalyst in harsh conditions - hydrogen pressure of 50 bar and a need for a process in the autoclave.

A method of obtaining Nickel catalyst for hydrogenation of unsaturated hydrocarbons [Brunet J.-J., Gallois Ph., P. Caubere Activation of Reducing Agents. Sodium Hydride Containing Complex Reducing Agents. 12. New Convenient, Hinghly Active and Selective Nickel Hydrogenation Catalysts. // J. Org. Chem. - 1980. - V. 45. - P.1937-1945] by restoring diacetate Nickel (Ni(OAc)2) comprehensive regenerating agent is sodium hydride (NaH) is a sodium alcoholate (RONa), where R=Et, Ph, f-Am, i-Pr, i-Bu, etc. a Method of producing catalytic hydrogenation is as follows. To the reaction system containing pre-washed in tetrahydrofuran (THF) sodium hydride suspension diacetate Nickel in THF, under nitrogen atmosphere at 45°C was bury, for example, a solution of isoamyl alcohol in THF and was stirred for 3 hours, the resulting suspension of the Nickel catalyst was tested in the hydrogenation of alkenes and alkynes. The catalytic activity obtained in this way Nickel catalyst in the hydrogenation of alkenes at 25°C (298 K) and atmospheric (normal) hydrogen pressure is 5.2 mol H2/g-at Ni·min in the hydrogenation of octene-1, 2.0 mol H2/g-at Ni·min in the hydrogenation of pentene - 1,3 .9 mol H2/g-at Ni·min in the hydrogenation of styrene.

The catalytic activity obtained in this way Nickel catalyst in hydrogenation and is of kinow at 25°C (298 K) and atmospheric (normal) hydrogen pressure in the hydrogenation of phenylacetylene is 2.0 mol H 2/g-at Ni·min at 90%selectivity to styrene; hydrogenation hexyne-2 catalytic activity is 3.3 mol H2/g-at Ni·min at 96%selectivity for CIS-hexene-2.

The disadvantage of this method of obtaining a Nickel hydrogenation catalyst is a low catalytic activity of the obtained Nickel catalyst.

The closest known solution of an analogous problem to the technical essence and the achieved effect is a method of obtaining a Nickel catalyst for hydrogenation [Ashby E.G., Lin, J.J. Selective reduction of alkenes and alkynes by the reagent lithium aluminum hydride-transition metal halide // J. Org. Chem. - 1978 - Vol.43, N 13. - PP.2567-2572] by the interaction of Nickel dichloride with tetrahydroaluminate lithium in the presence of substrate. To this flask was placed a metal halide, tetrahydrofuran in a stream of nitrogen was added the substrate (alkene). To pre-cooled mixture of dry ice-acetone reaction system was added LiAlH4, the molar ratio of the components: NiCl2/LiAlH4/substrate=1:1-10:4-20. After 10 min the temperature was raised to room temperature and was the process of hydrogenation.

The disadvantage of this method is the low activity of the resulting catalyst in the hydrogenation of alkenes at room temperature and atmospheric pressure of hydrogen.

The present invention laid the solution recip is of Nickel-containing hydrogenation catalyst, who would have high catalytic activity, could carry out the catalytic hydrogenation process under mild conditions (at room temperature and normal (atmospheric) pressure).

According to the invention this task is solved in that the hydrogenation catalyst containing a compound of Nickel (II), a reducing agent and a modifying additive, as a starting compound of Nickel using bis-acetylacetonate Nickel, as a reductant - tetrahydroaluminate lithium, as well as modifying additives - protonotaries connection with the following molar ratio of reagents: Ni(acac)2/ LiAlH4/ protonotaries connection=1:2-50:1-34. As protonotaries of the connections are water, alcohols, phenol, acid.

In the method of producing catalytic hydrogenation, based on the interaction of compounds of Nickel(II) with tetrahydroaluminate lithium at the optimum temperature of formation of the catalyst 20-35°C (293-308 K) and the optimal time of formation of the catalyst 5-30 min, use a modifier additive, which is used protonotaries connection-modifying additive is introduced after the stage of interaction of bis-acetylacetonate, Nickel(II) with tetrahydroaluminate lithium.

The applicant has not identified the sources containing information about technical solutions, identifying the data present invention, that allows to make a conclusion about its compliance with the criterion of "novelty".

A distinctive feature of the present invention is the use of the modifying additive - protonotaries connections, which use water, alcohols, phenol, acid, and introducing it into the reaction system after the stage of interaction of Ni(acac)2with tetrahydroaluminate lithium.

The applicant has not found any sources of information containing data about the impact of an alleged distinguishing signs on achieved as a result of their implementation of the technical result. This, according to the applicant demonstrates compliance with this technical solution, the criterion of "inventive step".

The proposed method is efficient Nickel catalyst for hydrogenation of unsaturated compounds (alkenes) is as follows.

To a solution of becausethat Nickel in benzene, placed in a thermostatted vessel type "duck"at room temperature in a stream of hydrogen added sequentially alkene, a solution of tetrahydroaluminate lithium in tetrahydrofuran (THF); this forms a brown solution. The reaction mixture is optionally stirred at a temperature of 20-35°C (293-308) within 5-30 minutes Then the reaction mixture is injected aliquot protonotaries connection and use is gidrirovanii.

Optimal conditions for the formation of the catalyst: the ratio of bis-acetylacetonate Nickel: tetrahydroaluminate lithium ≥20 (table 1); the ratio of protonotaries connection:tetrahydroaluminate lithium depends on the nature of ROH (table 2); the greatest promoting effect of n-C4H9OH (table 2); the concentration of Ni(acac)2- 3.57 mmol/l (table 3).

Thus obtained catalyst allows gidrirovanii at a temperature of 35°C (308 K) styrene with activity 94 mol H2·(g-at Ni·min)-1when used as protonotaries water connections (table 2); activity 168 mol H2·(g-at Ni·min)-1when used as protonotaries connection ethanol (table 2); activity 220 mol H2·(g-at Ni·min)-1when used as protonotaries connection n-butanol (table 2); with an activity of 90 mol H2·(g-at Ni·min)-1when used as protonotaries connection ISO-butanol (table 2); with an activity of 70 mol H2·(g-at Ni·min)-1when used as protonotaries connection tert-butanol (table 2); activity 192 mol H2·(g-at Ni·min)-1when used as protonotaries connection n-pentanol (table 2); with an activity of 37 mol H2·(g-at Ni·min)-1when used as protonotaries the th phenolic compounds (table 2); activity 82 mol H2·(g-at Ni·min)-1when used as protonotaries connection acetic acid (table 2).

Its advantage in comparison with the prototype is the higher specific catalytic activity in the hydrogenation of alkenes under mild conditions, with a temperature of 35°C (308 K) and hydrogen pressure of 1 barg. ATM, which surpasses the prototype in the hydrogenation of terminal connections in 500-6500 time.

Example 1: To a solution of 0,01267 g (5·10-5mol) of Ni(acac)2in 10 ml of benzene, placed in otakuminopera, the hydrogen-filled vessel type "duck", sequentially add 1 ml of styrene (8.7·10-3mol), 2 ml of a solution of LiAlH4, (2.5·10-4mol) in tetrahydrofuran and stirred the reaction mixture for 20 min at 35°C and hydrogen pressure 1 (excess air). Hydrogenation of styrene does not occur. To the resulting brown "solution" was added 1 ml of ethanol. The resulting solution of the catalyst is not active in the hydrogenation of styrene (table 1).

Example 2: To a solution of 0,01267 g (5·10-5mol) of Ni(acac)2in 10 ml of benzene, placed in otakuminopera, the hydrogen-filled vessel type "duck", sequentially add 1 ml of styrene (8.7·10-3mol), 2 ml of a solution of LiAlH4, (5·10-4mol) in tetrahydrofuran and stirred the reaction mixture for 20 min at 35°C. the hydrogen pressure 1 (excess air). Hydrogenation of styrene does not occur. To the resulting brown "solution" was added 1 ml of ethanol. The hydrogenation is carried out at intensive stirring, precluding the flow of process in the diffusion region. Control over the course of the process perform volumetric and GLC (a chromatograph Chrom-5, DIP, phase - carbowax-20M, the column length is 3.6 m, the temperature of thermostat 100°C). The catalyst activity is 88 mol H2·(g-at Ni·min)-1that is, the quantitative conversion of styrene to ethylbenzene (table 1).

Examples 3-5: the Method is carried out as in example 2. These examples illustrate the effect of the ratio of LiAlH4/Ni on the activity of the hydrogenation of styrene. The procedure for conducting experiments similar to example 2.

Examples 6-11: these examples illustrate the effect of the nature protonotaries compound and its concentration on the activity of the hydrogenation of styrene (table 2). The procedure for conducting experiments similar to example 1-5.

Examples 12-16: these examples illustrate the effect of the concentration of bis-acetylacetonate Nickel on the activity of the hydrogenation of styrene (table 3). The procedure for conducting experiments similar to example 2.

Table 1
The influence of the ratio of LiAlH4/Ni and the efficiency of the hydrogenation of styrene in the system Ni(acac) 2+n LiAlH4+C2H5OH
CNi=3.57 mmol/l, [substrate]/Ni=174, solvent - benzene - THF, the amount of solvent=12 ml; volume of ethanol to 1 ml; T=35°C, PH2=2 ATM
no experience12345
[LiAlH4]/[Ni(acac)2]510203050
Activity W, mol H2·(d-al Ni-min)-1088168168164

7
Table 2
The influence of nature protonotaries compounds on the activity of the hydrogenation of styrene in the system Ni(acac)2+20 LiAlH4+n ROH
CNi=3.85 mmol/l, [substrate]/Ni=174, solvent - benzene - THF, the amount of solvent=12 ml; T=35°C, PH22=ATM
no experience6891011
[ROH]/[LiAlH4]12481134
ROHActivity W, mol H2·(g-at Ni·min)-1
H2O69949476--
C2H5OH47123119164-168
N-C4H9OH100151220131131-
tert-C4H9OH3538704549 -
ISO-C4H9HE4190904949
n-C5H11HE82192123123151-
C6H5OH----37
CH3COOH820.20.6000

Table 3
The effect of the concentration of bis-acetylacetonate Nickel on the activity of the hydrogenation of styrene in the system Ni(acac)2+n LiAlH4+h-C4H9OH
vsubstrate=8.7·10-3mol, solvent - benzene - TG is, the volume of solvent=12 ml; volume of n-C4H9OH=0.37 ml; T=35°C, PH2=2 ATM
no experience1213141516
[LiAlH4]/[Ni(acac)2]25102050
the concentration of Ni(acac)2mmol/lActivity W, mol H2·(g-at Ni·min)-1
0.71000020
3.570088168168
7.1403578112-
14.2815285956 -

Effect : the creation of a Nickel-containing catalyst with high catalytic activity in the hydrogenation when carrying out a catalytic process under mild conditions (at room temperature and normal (atmospheric) pressure of hydrogen or 1 wt. ATM).

1. The catalyst for hydrogenation of unsaturated compounds alkenes obtained from a compound of Nickel and a reducing agent, characterized in that the catalyst is obtained using as a starting compound of Nickel bis-acetylacetonate Nickel, reductant - tetrahydroaluminate lithium and impose additional modifier additive - protonotaries a compound selected from the group comprising water, alcohols, phenol or acid, in the following ratio of components: bis-acetylacetonate Nickel / tetrahydroaluminate lithium / protonotaries connection=1:2-50:1-34.

2. The method of producing catalyst for the hydrogenation of unsaturated compounds, alkenes, based on the reconnection of Nickel (II) tetrahydroaluminate lithium, characterized in that compounds of Nickel (II) use bis-acetylacetonate Nickel, reductant - tetrahydroaluminate lithium and impose additional modifying additive, which is used protonotaries connection - water, alcohols, phenol or acid; formation can produce the RA carried out in a current of hydrogen at a temperature of 20-35°C (293-308) within 5-30 minutes



 

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18 cl, 1 tbl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalytic chemistry, namely to catalysts of deep oxidation of hydrocarbons and CO to carbon dioxide and water, and to method of its production. Invention covers the method of producing thermally stable catalyst of complete oxidation of hydrocarbons and carbon monoxide based of tin dioxide of common formula MeO·xSnO2, if Me = Zn2+; Cu2+; Mn2+; Co2+; Ni2+; Pb2+; Cd2+ or Me2O3•xSnO2, if Me2= Fe3+; Ce3+; La3+; Cr3+, where x=1-5 for divalent metals, and x=2-10 for trivalent metals. Note here that catalyst is produced by introducing in α-Sn(OH)4 of readily degradable metal salts, i.e. nitrates, acetates, or by co-precipitation of the solution containing SnCl4 and salt of Me -nitrates, chlorides, acetates, sulphates, by ammonium or alkaline solution.

EFFECT: higher activity of catalyst at increased temperatures.

21 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: this invention relates to heterogeneous catalysis, namely to catalyst and method of purifying butenes of butadiene admixtures. This invention covers the catalyst intended for purifying butenes of harmful admixtures of diene hydrocarbons by selective hydrogenation that contains filamentous carbon bound with nickel alloy and carrier, i.e. aluminium oxide. It differs from known compositions in that it contains filamentous carbon bound with particles of nickel alloy with indium as a promoting addition with its content in (Ni-In)/C catalyst makes 35-80 wt % with nickel-to-indium atomic fraction ratio making 19 to 52. Content of (Ni-In)/C in catalyst makes 96 - 97 wt %, the rest making aluminium oxide. Invention covers also the method of preparing the catalyst intended for purifying butenes of harmful admixtures of diene hydrocarbons by selective hydrogenation that consists in mechanical activation of the mix of nickel oxide, aluminium hydroxide and compound containing promoting additive in centrifugal planetary mill, reducing and cocking up in methane at not less than 550°C and atmospheric pressure. It differs from known methods in that indium acetate is used as promoting additive to produce catalyst that filamentous carbon bound with particles of nickel alloy with indium as a promoting addition with its content in (Ni-In)/C catalyst makes 35-80 wt % with nickel-to-indium atomic fraction ratio making 19 to 52. Content of (Ni-In)/C in catalyst makes 96 - 97 wt %, the rest making aluminium oxide. This invention covers the catalyst intended for purifying butenes of harmful admixtures of diene hydrocarbons by selective hydrogenation in the presence of above described catalyst.

EFFECT: selective hydrogenation of butadiene to butenes at lower hydrogenation of butenes to butane.

5 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a combustion catalyst for combustion and removal of carbon-bearing material, to a method of preparing said catalyst, to a catalyst support and preparation method thereof. The method of preparing the carbon-bearing material combustion catalyst involves steps for mixing, drying and burning. At the mixing step, zeolite, except sodalite, and an alkali metal source and/or alkali-earth metal source are mixed in a polar solvent such as water or another in a defined ratio. At the drying step after mixing, the liquid mixture is heated with evaporation of water in order to obtain a solid substance. At the burning step, the substance is burnt at temperature of 600°C or higher to obtain a carbon-bearing material combustion catalyst. The invention describes a method of preparing a support for the carbon-bearing material combustion catalyst on a ceramic substrate, whereby the catalyst support is designed for combustion of carbon-bearing material contained in exhaust gas of an internal combustion engine, involving attaching the combustion catalyst made using the described method onto a ceramic substrate and a catalyst support made using this method.

EFFECT: stable combustion and removal of carbon-bearing material at low temperature for a long period of time.

17 cl, 6 ex, 2 av ex, 19 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for combustion of carbon-bearing material contained in exhaust gas of an internal combustion engine, to a method of preparing said catalyst, as well as a support for said catalyst and method of preparing said support. The invention describes a method of preparing a carbon-bearing material combustion catalyst which is attached to a ceramic substrate, involving mixing aluminium silicate having atomic equivalent ratio Si/Al≥1 and an alkali and/or alkali-earth metal source in a polar solvent such as water or another, drying the liquid mixture to obtain a solid substance and burning it at temperature of 600°C or higher. The aluminium silicate is sodalite. Alternatively, the carbon-bearing material combustion catalyst is prepared through a sequence of steps for mixing, drying and burning, whereby the method involves burning sodalite at temperature of 600°C or higher. A catalyst prepared using the method given above is described. Described also is a method of preparing a catalyst support involving a step for attaching the combustion catalyst to a ceramic substrate, and a catalyst support made using said method.

EFFECT: stable combustion and removal of carbon-bearing material at low temperature for a long period of time.

26 cl, 3 ex, 1 av ex, 27 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetylene through oxidative pyrolysis of methane in the presence of oxygen and a catalyst, characterised by that the catalyst is heated to 700-1200°C by passing electrical current through it. The catalyst used is a fechral alloy which is thermally treated on air at temperature 900-1100°C. The ratio of methane to oxygen is varied in the range of 5:1-15:1.

EFFECT: high output and selectivity of the process.

2 cl, 17 ex, 1 tbl, 1 dwg

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