CN101346343A - Process for producing nitrogen-containing compounds - Google Patents
Process for producing nitrogen-containing compounds Download PDFInfo
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- CN101346343A CN101346343A CNA2006800494490A CN200680049449A CN101346343A CN 101346343 A CN101346343 A CN 101346343A CN A2006800494490 A CNA2006800494490 A CN A2006800494490A CN 200680049449 A CN200680049449 A CN 200680049449A CN 101346343 A CN101346343 A CN 101346343A
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Abstract
The present invention relates to a process for producing an aliphatic amine, comprising the step of contacting a linear or branched, or cyclic aliphatic alcohol having 6 to 22 carbon atoms with ammonia and hydrogen in the presence of a catalyst formed by supporting at least (A) a ruthenium component produced by hydrolysis of a ruthenium compound on a carrier, or by further supporting, in addition to the component (A), a specific second metal component or a specific third metal component on the carrier. According to the process of the present invention, an aliphatic primary amine can be produced from an aliphatic alcohol with a high catalytic activity and a high selectivity.
Description
Technical field
The present invention relates to make the method for nitrogenous compound, particularly make the method for fatty amine.
Background technology
Armeen is the important compound in family and the industrial application and has been used as the raw material of making tensio-active agent, fibre finish etc.
Armeen is by the whole bag of tricks manufacturing.As one of manufacture method, known have a method that aliphatic primary alcohol and ammonia and hydrogen are contacted in the presence of catalyzer.In this catalyzed reaction, nickel/copper-based catalysts or noble metal-based catalysts have been used.
As using the particularly method of ruthenium-based catalyst of noble metal-based catalysts, the method of being made amine by alcohol etc. is for example disclosed in the presence of catalyzer, this catalyzer is by the ruthenium of about 0.001 to 25 weight % is supported on (for example, referring to the JP 8-243392A) that forms on the such porous oxide of for example aluminum oxide, silicon oxide and silico-aluminate with for example rhodium of about 0 to 5 weight %, palladium, platinum, copper, silver and composition thereof such promotor.In addition, disclose and used by the cobalt of the ruthenium of about 0.001 to 25 weight % and about 0.1 to 6 weight % and/or nickel are supported on for example aluminum oxide with the accelerator that is made of various metals of about 0 to 10 weight % copper and about 0 to 5 weight %, on the such porous oxide of silicon-dioxide and silico-aluminate and the method for the catalyzer that forms (for example, referring to JP 10-174874A), and use by the ruthenium of about 0.001 to 25 weight % and cobalt and/or the nickel of about 6 to 50 weight % are supported on for example aluminum oxide with the copper of about 0 to 10 weight % and the accelerator that is made of various metals of about 0 to 5 weight %, on the such porous oxide of silicon-dioxide and silico-aluminate and the method (for example, referring to JP 10-174875A) of the catalyzer that forms.
In these technology, make catalyzer by pickling process, and with the catalyzer drying made, under 400 ℃, fired 4 hours, under 300 ℃, impose hydrogen reduction then and handled 20 hours.In addition, catalyzer does not show competent reactivity and selectivity.
Summary of the invention
Method of the present invention relates to:
(1) a kind of method of making fatty amine, comprise making straight or branched or the pure step that contacts with ammonia and hydrogen of annular aliphatic with 6 to 22 carbon atoms in the presence of catalyzer, this catalyzer forms by (A) ruthenium component of being made by the hydrolysis of ruthenium compound is supported on the carrier;
(2) a kind of method of making fatty amine, comprise and make straight or branched or the pure step that in the presence of catalyzer, contacts with ammonia and hydrogen of annular aliphatic with 6 to 22 carbon atoms, wherein this catalyzer by make (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten be supported on the carrier and form, described (A) ruthenium component and described (B) metal component hydrolysis of the compound by ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten are respectively made;
(3) a kind of method of making fatty amine, comprise the step that straight or branched with 6 to 22 carbon atoms or annular aliphatic alcohol and ammonia and hydrogen are contacted in the presence of catalyzer, wherein this catalyzer is supported on the carrier with (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium and forms by making at least a metal component of nickel and cobalt that is selected from of (A) ruthenium component, (B ').
Embodiment
The present invention relates to make with high catalytic activity and highly selective the method for fatty amine, particularly Armeen by fatty alcohol.
In the method for manufacturing fatty amine according to the present invention, use has the straight or branched of 6 to 22 carbon atoms or ring-type is saturated or unsaturated aliphatic is pure as raw material.
The example of available fatty alcohol comprises hexanol, isohexyl alcohol, octanol, isooctyl alcohol, 2-Ethylhexyl Alcohol, nonyl alcohol, isononyl alcohol, 3 among the present invention, 5,5-trimethyl hexanol, decyl alcohol, 3,7-dimethyl octanol, 2-propyl enanthol, as the dodecanol the lauryl alcohol, tetradecanol, cetyl alcohol, Stearyl alcohol, oleyl alcohol, behenyl alcohol, eicosanol (icosyl alcohols), Geraniol, cyclopentyl carbinol, cyclopentenyl methyl alcohol, hexahydrobenzyl alcohol and the cyclohexenyl methyl alcohol etc. as stearyl alcohol as the tetradecyl alcohol.
In the present invention, in above-mentioned fatty alcohol, preferably have the straight chain fatty alcohol of 6 to 22 carbon atoms, more preferably have the straight chain fatty alcohol of 8 to 22 carbon atoms.
In the present invention, as catalyzer, use: (1) is supported on the catalyzer that forms on the carrier by making (A) ruthenium component of being made by the hydrolysis of ruthenium compound; (2) by make (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten (hereinafter referred do " second metal component (B)) be supported on the catalyzer that forms on the carrier, above-mentioned (A) ruthenium component and above-mentioned (B) metal component hydrolysis of the compound by ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten are respectively made; Perhaps (3) by make at least a metal component that is selected from nickel and cobalt of (A) ruthenium component, (B ') (hereinafter only be called " second metal component (B ')) and (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium (hereinafter only be called " the 3rd metal component (C)) be supported on the catalyzer that forms on the carrier (following only above-mentioned catalyzer (1) to (3) is referred to as " ruthenium-based catalyst " sometimes).In (3), the example of carrier comprises macromolecular compound, metal phosphate and porous oxide etc. at each above-mentioned catalyzer (1).The example of used above-mentioned porous oxide comprises aluminum oxide, zirconium white, titanium dioxide, silicon-dioxide, gac, silico-aluminate, diatomite, hydrotalcite-type compound (for example magnesium/aluminium base composite oxides), alkaline earth metal oxide and niobium oxides (niobia) among the present invention.The example of macromolecular compound comprises polystyrene, nylon and resin etc., and the example of metal phosphate comprises calcium phosphate and aluminum phosphate calcium etc.In these carriers, consider high catalytic activity and highly selective, preferably porous oxide, more preferably aluminum oxide, zirconium white, titanium dioxide and silico-aluminate, further preferably aluminum oxide and zirconium white.Especially, the catalyzer that uses zirconium white or titanium dioxide to make shows advantages of high catalytic activity, and the catalyzer that uses aluminum oxide or silico-aluminate to make show to primary amine than highly selective.
In the present invention, the carrier of above-mentioned macromolecular compound, metal phosphate, porous oxide and so on can use separately, or two or more are used in combination arbitrarily.
Among the present invention used ruthenium-based catalyst by make ruthenium component (A) separately, ruthenium component (A) and second metal component (B) the two or ruthenium component (A), second component (B ') and whole being supported on the above-mentioned carrier of the 3rd metal component (C) form.In above-mentioned catalyzer (1),, ruthenium component (A) is supported on the carrier by the hydrolysis ruthenium compound.In above-mentioned catalyzer (2),, ruthenium component (A) and second metal component (B) are supported on the carrier by hydrolysis ruthenium compound and at least a compound that is selected from the metal of nickel, cobalt and tungsten respectively.In above-mentioned catalyzer (3), by hydrolysis ruthenium compound, at least a compound and at least a compound that is selected from the metal of lanthanum, yttrium, magnesium and barium that is selected from the metal of nickel and cobalt respectively, ruthenium component (A), second metal component (B ') and the 3rd metal component (C) are supported on the carrier.
The method that supports these components is not particularly limited, comprises any usually optional currently known methods, for example pickling process, the precipitator method, ion exchange method and the method etc. of mixing.
As second metal component (B) that will be supported on the carrier, consider catalytic activity and the selectivity of improving the gained catalyzer, use the metal component that is selected from nickel, cobalt and tungsten.These second metal components can be separately or arbitrarily two or more in conjunction with supporting.As being supported on second metal component on the carrier (B '), consider catalytic activity and the selectivity of improving the gained catalyzer, use at least a metal component that is selected from nickel and cobalt.In these second metal components (B '), nickel component preferably.In addition, as the 3rd metal component (C) that will be supported on the carrier, consider the catalyzer that obtains to have both high catalytic activity and highly selective, use at least a metal component that is selected from lanthanum, yttrium, magnesium and barium, the preferred at least a metal component that is selected from lanthanum and magnesium.
Then, illustrate the method for making each ruthenium-based catalyst.
At first, above-mentioned catalyzer (1) can followingly be made: the carrier of porous oxide and so on is added in the medium of ion exchanged water and so on the preparation suspension liquid, in this suspension liquid, add then by ruthenium compound being dissolved in the solution of making in the aqueous medium of ion exchanged water and so on, if desired, when stirring, heat subsequently so that the suspension liquid temperature is controlled to be about 20 to 95 ℃, preferred 40 to 80 ℃.Except using respectively by being dissolved in the solution of making in the aqueous medium as the ruthenium compound in ruthenium component (A) source and the metallic compound of originating as second metal component (B), and by with ruthenium compound, be dissolved in the solution of making in the aqueous medium as the metallic compound in second metal component (B ') source with as the metallic compound in the 3rd metal component (C) source, above-mentioned catalyzer (2) and above-mentioned catalyzer (3) can be according to making with the used identical mode of the manufacturing of catalyzer (1).
The example of above-mentioned ruthenium compound comprises muriate, nitrate, formate, ammonium salt of ruthenium etc.As the metallic compound in second metal component (B) or (B ') source with comprise the muriate, nitrate, carbonate, vitriol, ammonium salt etc. of above-mentioned each component as the example of the metallic compound in the 3rd metal component (C) source.
Then, it is extremely about 4 to 12 with the pH value of regulating suspension liquid to add alkali in the suspension liquid that contains as each compound in the source of above-mentioned each metal component, and preferably approximately 6 to 11 can make each compound hydrolysis thus.Then, the gained reaction mixture is worn out so that each component is supported on the carrier of porous oxide and so on.Kind to above-mentioned alkali is not particularly limited.The example of available alkali comprises ammoniacal liquor and for example alkali-metal carbonate, oxyhydroxide etc. of sodium and potassium and so among the present invention.Be adjusted to aging required temperature and time from the pH value and be not particularly limited, as long as guarantee the abundant hydrolysis of ruthenium compound.
Then, by adding for example reductive agent of formaldehyde, hydrazine and sodium borohydride and so on therein, and as required with mixture heating up to about 20 to 95 ℃, preferred 60 to 95 ℃, handle thereby reaction mixture is imposed reduction.After this, the solid-liquid that the gained reaction soln is imposed filtration and so on separates, to obtain solid.With thus obtained solid water thorough washing, then at preferred 140 ℃ or drier under normal pressure or decompression under the low temperature.These reductive agents can use separately or two or more are used in combination arbitrarily.
Reductive agent can use with common about 1 to 50 mole of the metal component that always supports with respect to every mole, preferred 15 to 40 moles amount, each metal component that supports with effective reduction.
Allow reduction reaction to proceed to required degree as long as guarantee this time, just the above-mentioned reduction treatment time is not particularly limited.
Simultaneously, above-mentioned reduction is handled optional.After supporting each component on the carrier by hydrolysis, can water thorough washing, drying then by the solid that the solid-liquid separation circuit obtains.
In the present invention, above-mentioned washing step preferably proceeds to the degree that makes gained filtrate have 50 μ S/cm or littler specific conductivity, thereby prevents that counter ion from staying in the gained catalyzer.
In the present invention, when each metal component is supported on the carrier by the said hydrolyzed method, not necessarily need the operation of required operation of handling and so on as high-temperature firing such as common pickling process and the high temperature reduction processing under inert atmosphere etc., thereby obtain simple catalyzer manufacturing process.
Consider competent catalytic activity and selectivity and low cost, the ruthenium-based catalyst of making thus preferably contains by metal Ru based on about 0.1 to 25 quality % of the catalyzer total amount that comprises carrier, the more preferably ruthenium component (A) of 1 to 15 quality %.In addition, ruthenium-based catalyst preferably contains by the metal element and accounts for about 0.1 to 25 quality % of the catalyzer total amount that comprises carrier, more preferably second metal component (B) or (B ') of 0.2 to 15 quality %.In addition, ruthenium-based catalyst preferably contains by the metal element and accounts for about 0.01 to 10 quality % of the catalyzer total amount that comprises carrier, more preferably the 3rd metal component (C) of 0.05 to 5 quality %.
The content of ruthenium component (A) can be measured by the ICP emission spectrometry method after using monoammonium sulfate to melt this catalyzer in the catalyzer.Second metal component (B) or (B ') and the content of the 3rd metal component (C) also can pass through the ICP emission spectrometry method, after under the not siliceous situation of carrier catalyzer being imposed wet decomposition (using sulfuric acid/hydrogen peroxide) processing, measure, or after catalyzer is imposed the alkali fusion processing, measuring under the siliceous situation of carrier.
In the method for manufacturing fatty amine according to the present invention, will in the presence of the ruthenium-based catalyst of making thus, contact with hydrogen to make fatty amine as the fatty alcohol of raw material with ammonia, preferably make Armeen.
Catalyzed reaction can be carried out in intermittent type closed system or intermittent type flow system or in fixed bed flow system.The amount of catalyst system therefor becomes with the kind of used reactive system.In batch reaction system, consider to obtain good reactivity and selectivity that catalyzer is with preferred 0.1 to the 20 quality % of feedstock fat family alcohol, the more preferably amount use of 0.5 to 10 quality %.In addition, consider good transformation efficiency and selectivity and prevent catalyst deactivation that temperature of reaction is 120 to 280 ℃, preferred 180 to 250 ℃, reaction pressure be normal pressure to 40MPaG, preferred 0.5 to 30MPaG.
Consider the good conversion rate and to the good selectivity of primary amine, be generally 0.5 to 10, preferred 2 to 7 as the mol ratio (ammonia/fatty alcohol) of the ammonia and the fatty alcohol of raw material.Ammonia can separate interpolation with hydrogen, or can introduce with the form of the mixed gas of ammonia and hydrogen.
In the time of in being used in the intermittent type closed system, be preferably 0.01 to 3.0, more preferably 0.02 to 2.0 as the mol ratio (hydrogen/fatty alcohol) of the hydrogen and the fatty alcohol of initial charge.In the time of in being used in intermittent type flow system or fixed bed flow system, flowing through the hydrogen of this system and the mol ratio of fatty alcohol at first and be preferably 0.01 to 1.0, more preferably 0.02 to 0.8.But in any above-mentioned reaction method, the mol ratio in each reaction process not necessarily is confined to above-mentioned stated limit.
Manufacturing method according to the invention can be made fatty amine, particularly Armeen with high catalytic activity and highly selective by fatty alcohol.
With reference to the present invention of the following example more detailed description.But, be noted that these embodiment only are exemplary, rather than will limit the present invention.
Preparation example 1
Can divide 10.0 grams of packing in the flask can be available from the alumina powder " A-11 " of Sumitomo Chemical Co (SumitomoChemical Corp.) and 170 gramion exchanged waters to prepare suspension liquid, be dissolved in the solution of making in the 40 gramion exchanged waters to wherein adding then, then this suspension liquid be heated to 60 ℃ when stirring by hydration ruthenium chloride with 0.59 gram molecular weight 252.68.Thus obtained suspension liquid (under 60 ℃) was stirred 3 hours, splash into ammoniacal liquor as precipitation agent then therein so that suspension liquid pH value is adjusted to 11 so that its hydrolysis makes this suspension liquid wear out 2 hours down at 60 ℃ then.Then, this suspension liquid is mixed with 4.8 grams, 37 quality % formalin solutions, and be heated to 90 ℃, this moment was with suspension liquid reduction 1 hour.After this, filtering separation gained powder reaches 30 μ s/cm or littler with the ion-exchange water washing until the specific conductivity of filtrate, then dry under 13kPa pressure under 60 ℃, obtains about 10 grams, 2 quality % ruthenium/aluminium oxide catalyst A thus.
Preparation example 2
Repeat with preparation example 1 in identical operation, only be to use 1.47 gram hydration ruthenium chlorides, obtain about 10 thus and restrain 5 quality % ruthenium/aluminium oxide catalyst B.
Preparation example 3
Repeat with preparation example 1 in identical operation, only being to use can be available from (the Dai-Ichi Kigenso Kagaku Kogyo Co. of the first rare element chemistry Industrial Co., Ltd, Ltd.) Zirconium oxide powder " RC-100 " replaces alumina powder, obtains ruthenium/zirconia catalyst C of about 10 grams, 2 quality % thus.
Preparation example 4
Repeat with preparation example 1 in identical operation, only being to use can be available from Sakai KagakuKogyo Co., the titania powder of Ltd. " SSP-25 " replaces alumina powder, obtains the about 10 ruthenium/titanium deoxide catalyst D that restrain 2 quality % thus.
Preparation example 5
Repeat with preparation example 2 in identical operation, only be to use and can replace alumina powder available from the synthetic zeolite powder " CP814E " of Zeolyst Inc., obtain the about 10 ruthenium/zeolite catalyst E that restrain 5 quality % thus.
Comparative preparation example 1
On ceramic disc, 0.26 gram ruthenium trichloride is dissolved in the 5.8 gramion exchanged waters, and 6 grams can be immersed in the gained solution available from the alumina powder " A-11 " of Sumitomo Chemical Co, and it was at room temperature placed 2 hours.Then, the gained suspension liquid is heated to 65 ℃ and dewater simultaneously at blended, then under 120 ℃ under normal pressure dry one day one night.With the gained dried powder with 3Nm
3Temperature rise rate with 5 ℃/minute under the airflow of the speed charging of/h is heated to 400 ℃, and fires under 400 ℃ 4 hours, obtains ruthenium/aluminium oxide catalyst F of about 6 grams, 2 quality % thus.
Embodiment 1
The catalyst A (for 2.0 quality % of raw alcohol) that 150 gram (0.55 mole) stearyl alcohol of packing in 500 milliliters of electromagnetic induction rotation stirring-type autoclaves and 3 grams are made in preparation example 1, in autoclave, pack into then 47 the gram (2.76 moles) ammonia, and further to wherein being pressed into 0.17 moles of hydrogen so that the integral pressure in the autoclave that at room temperature records reaches 2.8MPaG.Then, when stirring (1000rpm), autoclave contents is heated to 220 ℃ temperature of reaction.Under 220 ℃, the initial peak pressure in the autoclave is 16MPaG.In autoclave, infeed hydrogen continuously so that integral pressure wherein remains on the constant pressure of 16MPaG, simultaneously, make the autoclave contents interreaction.The gained reaction product is filtered therefrom to remove catalyzer, carry out vapor-phase chromatography then and form, measure the transformation efficiency of raw alcohol thus, the amount of the by product of the selection rate of stearylamine and generation to analyze it." alcohol transformation efficiency " used herein is meant the amount of the amount of the alcohol that consumes in the reaction process than initial feed alcohol, and " to the selection rate of stearylamine " is meant as the amount of the stearylamine of the reaction product amount (this definition is equally applicable to description subsequently) than the alcohol that consumes in the reaction process.The result is presented in the table 1.
Embodiment 2～5
Repeat with embodiment 1 in identical operation, just use the catalyzer (B) made in preparation example 2,3,4 and 5, (C), (D) respectively and (E) replace catalyzer (A), and the hydrogen of supply additional quantity is so that the initial peak pressure that records under 220 ℃ of temperature of reaction remains on the steady state value shown in the table 1.According to embodiment 1 in identical mode analyze the gained reaction product.The result is presented in the table 1.
Table 1-1
| Catalyzer | Initial peak pressure (MPaG) | Reaction times (h) | |
| Embodiment 1 | A | 16 | 6.0 |
| Embodiment 2 | B | 16 | 6.0 |
| Embodiment 3 | C | 16 | 6.0 |
| Embodiment 4 | D | 16 | 6.0 |
| Embodiment 5 | E | 16 | 4.0 |
Table 1-2
Comparative example 1
Repeat with embodiment 1 in identical operation, only be to use catalyzer (F) the replacement catalyzer of making in the comparative preparation example 1 (A).More specifically, be under the condition of 16MPaG at the initial peak pressure that records under 220 ℃, reacted 6 hours.According to embodiment 1 in identical mode analyze the gained reaction product.The result confirms that the transformation efficiency of raw alcohol is 54.9%.
Embodiment 6
Repeat with embodiment 3 in identical operation, only be to use 150 gram (0.81 mole) lauryl alcohols to replace stearyl alcohol and use 69 to restrain the ammonia of (4.06 moles), thereby react 11 hours.The initial peak pressure that records under 220 ℃ of temperature of reaction is 21MPaG.According to embodiment 1 in identical mode analyze the gained reaction product.The result confirms that the transformation efficiency of raw alcohol is 96.3%, is 74.9% to the selection rate of lauryl amine, and the amount of the dilaurylamine of generation is 12.3%, and the amount of other by product that produces is 10.9%.
Preparation example 6
Packing 10.0 grams in separable flask into can be available from the Zirconium oxide powder " RC-100 " of the first rare element chemistry Industrial Co., Ltd and 170 gramion exchanged waters to prepare suspension liquid, be dissolved in the solution of making in the 40 gramion exchanged waters to the hydration ruthenium chloride and the 0.18 gram six hydration nickel sulfate that wherein add by with 0.59 gram molecular weight 252.68 then, then this suspension liquid be heated to 60 ℃ when stirring.Thus obtained suspension liquid (under 60 ℃) was stirred 10 hours, splash into aqueous sodium carbonate as precipitation agent then therein so that suspension liquid pH value is adjusted to 11 so that its hydrolysis makes this suspension liquid wear out 2 hours down at 60 ℃ then.Then, this suspension liquid is mixed with 4.8 grams, 37 quality % formalin solutions, and be heated to 90 ℃, this moment was with suspension liquid reduction 1 hour.After this, filtering separation gained powder, reach 30 μ s/cm or littler with the ion-exchange water washing until the specific conductivity of filtrate,, obtain 2 quality % rutheniums/0.4 quality % nickel catalyzator G that about 10 gram zirconium whites support thus then dry under 13kPa pressure under 60 ℃.
Preparation example 7
Repeat with preparation example 6 in identical operation, only be to use 0.59 gram hydration ruthenium chloride and 0.16 gram cobalt chloride hexahydrate, and use ammoniacal liquor as precipitation agent, obtain about 10 thus and restrain 2 quality % rutheniums/0.4 quality % cobalt catalyst H that zirconium whites support.
Preparation example 8
Packing 10.0 grams in separable flask into can be available from the Zirconium oxide powder " RC-100 " of the first rare element chemistry Industrial Co., Ltd and 170 gramion exchanged waters to prepare suspension liquid, be dissolved in the solution of making in the 40 gramion exchanged waters to wherein adding then, then this suspension liquid be heated to 60 ℃ when stirring by hydration ruthenium chloride with 0.59 gram molecular weight 252.68.Thus obtained suspension liquid (under 60 ℃) was stirred 10 hours, splash into therein then by 0.64 gram ammonium metawolframate is dissolved in the solution made in the 20 gramion exchanged waters and ammoniacal liquor so that suspension liquid pH value is adjusted to 11 so that its hydrolysis makes this suspension liquid wear out 2 hours down at 60 ℃ then.Then, this suspension liquid is mixed with 4.8 grams, 37 quality % formalin solutions, and be heated to 90 ℃, suspension liquid was reduced 1 hour at 90 ℃.After this, filtering separation gained powder, reach 30 μ s/cm or littler with the ion-exchange water washing until the specific conductivity of filtrate,, obtain 2 quality % rutheniums/0.4 quality % tungsten catalyst I that about 10 gram zirconium whites support thus then dry under 13kPa pressure under 60 ℃.
Preparation example 9
Packing 10.0 grams in separable flask into can be available from the Zirconium oxide powder " RC-100 " of the first rare element chemistry Industrial Co., Ltd and 170 gramion exchanged waters to prepare suspension liquid, be dissolved in the solution of making in the 40 gramion exchanged waters to the hydration ruthenium chloride and the 0.72 gram six hydration nickel sulfate that wherein add by with 0.29 gram molecular weight 252.68 then, then this suspension liquid be heated to 60 ℃ when stirring.Thus obtained suspension liquid (under 60 ℃) was stirred 10 hours, splash into ammoniacal liquor as precipitation agent then therein so that suspension liquid pH value is adjusted to 11 so that its hydrolysis makes this suspension liquid wear out 2 hours down at 60 ℃ then.Then, this suspension liquid is mixed with 3.2 grams, 37 quality % formalin solutions, and be heated to 90 ℃, under this temperature, suspension liquid was reduced 1 hour.After this, filtering separation gained powder reaches 30 μ s/cm or littler with the ion-exchange water washing until the specific conductivity of filtrate, then dry under normal pressure under 120 ℃, obtains 1 quality % ruthenium/1.6 quality % nickel catalyzator J that about 10 gram zirconium whites support thus.
Preparation example 10
Repeat with preparation example 6 in identical operation, only be to use 10.0 grams to obtain about 10 thus and to restrain 2 quality % rutheniums/0.4 quality % nickel catalyzator K that aluminum oxide support available from the alumina powder " A-11 " of Sumitomo Chemical Co.
Preparation example 11
Packing 10.0 grams in separable flask into can be available from the Zirconium oxide powder " RC-100 " of the first rare element chemistry Industrial Co., Ltd and 170 gramion exchanged waters to prepare suspension liquid, be dissolved in the solution of making in the 40 gramion exchanged waters to the hydration ruthenium chloride and the 0.72 gram six hydration nickel sulfate that wherein add by with 0.29 gram molecular weight 252.68 then, then this suspension liquid be heated to 60 ℃ when stirring.Thus obtained suspension liquid (under 60 ℃) was stirred 10 hours, splash into 10% aqueous sodium hydroxide solution as precipitation agent then therein so that suspension liquid pH value is adjusted to 11 so that its hydrolysis makes this suspension liquid wear out 2 hours down at 60 ℃ then.Then, after cooling, filtering separation gained powder reaches 30 μ s/cm or littler with the ion-exchange water washing until the specific conductivity of filtrate, dry under normal pressure under 120 ℃, obtain 1 quality % ruthenium/1.6 quality % nickel catalyzator L that about 10 gram zirconium whites support thus then.
Comparative preparation example 2
On ceramic disc, 0.26 gram ruthenium trichloride is dissolved in the 7.5 gramion exchanged waters, then 6 grams can be immersed in the gained solution available from the Zirconium oxide powder " RC-100 " of the first rare element chemistry Industrial Co., Ltd, and it was at room temperature placed 2 hours.Then the gained suspension liquid is heated to 65 ℃ and dewater simultaneously at blended, then under 120 ℃ under normal pressure dry one day one night.With the gained dried powder with 3Nm
3Temperature rise rate with 5 ℃/minute under the airflow of the speed charging of/h is heated to 400 ℃, and fires under 400 ℃ 4 hours.Then, thus obtained year ruthenium Zirconium oxide powder is immersed in by 0.12 gram Nickelous nitrate hexahydrate is dissolved in the solution of making in the 7.4 gramion exchanged waters, it was at room temperature placed 2 hours.Then, the gained suspension liquid is heated to 65 ℃ and dewater simultaneously at blended, then under 120 ℃ under normal pressure dry one day one night.With the gained dried powder with 3Nm
3Temperature rise rate with 5 ℃/minute under the airflow of the speed charging of/h is heated to 400 ℃, and fires under 400 ℃ 4 hours, obtains 2 quality % rutheniums/0.4 quality % nickel catalyzator M that about 6 gram zirconium whites support thus.
Embodiment 7
The catalyzer G (for 2.0 quality % of raw alcohol) that 150 gram (0.55 mole) stearyl alcohol of packing in 500 milliliters of electromagnetic induction rotation stirring-type autoclaves and 3 grams are made in preparation example 6, in autoclave, pack into then 47 the gram (2.76 moles) ammonia, and further to wherein being pressed into 0.17 moles of hydrogen so that the integral pressure in the autoclave that at room temperature records reaches 2.3MPaG.Then, when stirring (1000rpm), autoclave contents is heated to 220 ℃ temperature of reaction.Under 220 ℃, the initial peak pressure in the autoclave is 16MPaG.In autoclave, infeed hydrogen continuously so that integral pressure wherein remains on the constant pressure of 16MPaG, simultaneously, make the autoclave contents interreaction.The gained reaction product is filtered therefrom to remove catalyzer, carry out vapor-phase chromatography then to analyze its composition.The result is presented in the table 2.
Embodiment 8 and 9
Repeat with embodiment 7 in identical operation, just use the catalyzer (H) made in preparation example 7 and 8 respectively and (I) replace catalyzer (G), and the hydrogen of supply additional quantity is so that the initial peak pressure that records under 220 ℃ of temperature of reaction remains on the steady state value shown in the table 2.According to embodiment 7 in identical mode analyze the gained reaction product.The result is presented in the table 2.
Embodiment 10
Repeat with embodiment 7 in identical operation, the catalyzer of making in the 6 gram preparation examples 9 of just packing into (J) (4.0 quality % of raw alcohol) replaces catalyzer (G), and the hydrogen of supply additional quantity is so that the initial peak pressure that records under 220 ℃ of temperature of reaction remains on the steady state value shown in the table 2.According to embodiment 7 in identical mode analyze the gained reaction product.The result is presented in the table 2.
Embodiment 11
Repeat with embodiment 7 in identical operation, the catalyzer of making in the 3 gram preparation examples 11 of just packing into (L) (2.0 quality % of raw alcohol) replaces catalyzer (G), and the hydrogen of supply additional quantity is so that the initial peak pressure that records under 220 ℃ of temperature of reaction remains on the steady state value shown in the table 2.According to embodiment 7 in identical mode analyze the gained reaction product.The result is presented in the table 2.
Table 2-1
| Catalyzer | Initial peak pressure (MPaG) | Reaction times (h) | |
| Embodiment 7 | G | 16 | 6.0 |
| Embodiment 8 | H | 16 | 6.0 |
| Embodiment 9 | I | 16 | 6.0 |
| Embodiment 10 | J | 15 | 4.0 |
| Embodiment 11 | L | 16 | 4.0 |
Table 2-2
Comparative example 2
Repeat with embodiment 7 in identical operation, only be to use catalyzer (M) the replacement catalyzer of making in the comparative preparation example 2 (G).Reaction was carried out 6 hours, and the initial peak pressure that records under 220 ℃ of temperature of reaction is 16MPaG.According to embodiment 7 in identical mode analyze the gained reaction product.The result confirms that the transformation efficiency of raw alcohol is 12.7%.
Embodiment 12
Repeat with embodiment 7 in identical operation, only be to use 150 gram (0.81 mole) lauryl alcohols to replace stearyl alcohol and use 69 to restrain (4.06 moles) ammonia, reacted thus 9 hours.The initial peak pressure that records under 220 ℃ of temperature of reaction is 21MPaG.According to embodiment 7 in identical mode analyze the gained reaction product.The result confirms that the transformation efficiency of raw alcohol is 97.9%, is 90.4% to the selection rate of lauryl amine, and the amount of the dilaurylamine of making is 8.9%, and the amount of other by product that generates is 0.6%.
Embodiment 13
The catalyzer G (for 2.0 quality % of raw alcohol) that 150 gram (0.55 mole) stearyl alcohol of packing in 500 milliliters of electromagnetic induction rotation stirring-type autoclaves and 3 grams are made in preparation example 6 is heated to 220 ℃ with autoclave contents then in nitrogen atmosphere (0MPaG) when stirring (1000rpm).Then, ammonia and hydrogen respectively with 19.1 grams (1.1 moles)/hour and 2.6 liters (0.12 mole)/hour data rate stream cross autoclave so that when reaction pressure remains on the steady state value of 2.0MPaG, react and carried out 3 hours.The gained reaction product is filtered therefrom to remove catalyzer, carry out vapor-phase chromatography then to analyze its composition.The result confirms that the transformation efficiency of raw alcohol is 96.0%, is 78.1% to the selection rate of lauryl amine, and the amount of the dilaurylamine of making is 13.4%, and the amount of other by product that generates is 7.6%.
Embodiment 14
Repeat with embodiment 13 in identical operation, only be to use the catalyzer of making in the preparation example 10 (K) to replace catalyzer (G), make ammonia and hydrogen respectively with 13.1 the gram (0.77 mole)/hour and 4.3 liters (0.19 mole)/hour data rate stream cross autoclave, reacted thus 6 hours.According to embodiment 7 in identical mode analyze the gained reaction product.The result confirms that the transformation efficiency of raw alcohol is 65.5%, is 85.5% to the selection rate of lauryl amine, and the amount of the dilaurylamine of making is 7.3%, and the amount of other by product that generates is 2.2%.
Preparation example 12
Packing 10.0 grams in separable flask into can be available from the Zirconium oxide powder " RC-100 " of the first rare element chemistry Industrial Co., Ltd and 170 gramion exchanged waters to prepare suspension liquid, be dissolved in the solution of making in the 40 gramion exchanged waters to the hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and the 0.04 gram lanthanum nitrate that wherein add by with 0.29 gram molecular weight 252.68 then, then this suspension liquid be heated to 60 ℃ when stirring.Thus obtained suspension liquid (under 60 ℃) was stirred 10 hours, splash into ammoniacal liquor as precipitation agent then therein so that suspension liquid pH value is adjusted to 11 so that its hydrolysis makes this suspension liquid wear out 2 hours down at 60 ℃ then.Then, this suspension liquid and 3.2 grams, 37 quality % formalin solutions are mixed and be heated to 90 ℃, under this temperature, suspension liquid was reduced 1 hour.After this, filtering separation gained powder, reach 30 μ s/cm or littler with the ion-exchange water washing until the specific conductivity of filtrate,, obtain 1 quality % ruthenium/1.6 quality % nickel/0.1 quality % lanthanum catalyst N that about 10 gram zirconium whites support thus then dry under 13kPa pressure under 60 ℃.
Preparation example 13
Repeat with preparation example 12 in identical operation, only be to use 0.29 gram hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and 0.04 gram magnesium chloride, obtain about 10 thus and restrain 1 quality % ruthenium/1.6 quality % nickel/0.1 weight % Mg catalyst O that zirconium whites support.
Preparation example 14
Repeat with preparation example 12 in identical operation, only be to use 0.29 gram hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and 0.04 gram Yttrium trinitrate, obtain about 10 thus and restrain 1 quality % ruthenium/1.6 quality % nickel/0.1 weight % yttrium catalyst P that zirconium whites support.
Preparation example 15
Repeat with preparation example 12 in identical operation, only be to use 0.29 gram hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and 0.02 gram nitrate of baryta, obtain about 10 thus and restrain 1 quality % ruthenium/1.6 quality % nickel/0.1 weight % titanate catalyst Q that zirconium whites support.
Simultaneously, in above-mentioned preparation example and comparative preparation example, measure based on the component (A) in each catalyzer of catalyzer total amount, (B), (B ') and content (C) by following ICP emission spectrometry method.
The measurement of each component concentration:
Following measurement ruthenium components contents.That is, monoammonium sulfate is added in the sample (catalyzer) so that the monoammonium sulfate consumption is tens of times of catalyst sample consumption, with the fusing under heating of gained mixture.With the cooling of gained melt, under heating, be dissolved in the pure water then, measure wherein ruthenium components contents by ICP emmission spectrometric analysis device.In addition, following measurement nickel component and barium components contents.That is, sulfuric acid is added in the sample (catalyzer), and with the gained mixture heating up.In addition, in mixture, add the hydrogen peroxide and the nitric acid of appropriate amount, and gained solution is heated repeatedly until producing clear solution.With the cooling of gained clear solution, mix with pure water then, measure wherein nickel component and barium component content separately by ICP emmission spectrometric analysis device.
Embodiment 15
The catalyzer (N) (for 2.0 quality % of raw alcohol) that 150 gram (0.55 mole) stearyl alcohol of packing in 500 milliliters of electromagnetic induction rotation stirring-type autoclaves and 3 grams are made in preparation example 12, in autoclave, pack into then 47 the gram (2.76 moles) ammonia, and further to wherein being pressed into 0.17 moles of hydrogen so that the integral pressure in the autoclave that at room temperature records reaches 2.3MPaG.Then, when stirring (1000rpm), autoclave contents is heated to 220 ℃ temperature of reaction.Under 220 ℃, the initial peak pressure in the autoclave is 16MPaG.In autoclave, infeed hydrogen continuously so that integral pressure wherein when remaining on the constant pressure of 16MPaG, makes the autoclave contents interreaction.The gained reaction product is filtered therefrom to remove catalyzer, carry out vapor-phase chromatography then to analyze its composition.The result is presented in the table 3.
Embodiment 16
Repeat with embodiment 15 in identical operation, only be to use the catalyzer of making in the preparation example 13 (O) to replace catalyzer (N), and supply the hydrogen of additional quantity under 220 ℃ of temperature of reaction so that the initial peak pressure that records remains on the steady state value shown in the table 3.According to embodiment 15 in identical mode analyze the gained reaction product.The result is presented in the table 3.
Embodiment 17 and 18
Repeat with embodiment 15 in identical operation, just be respectively charged into catalyzer (P) that 6 grams make in the preparation examples 14 and 15 and (Q) (4 quality % of raw alcohol) replace catalyzer (N), and supply the hydrogen of additional quantity under 220 ℃ of temperature of reaction so that the initial peak pressure that records remains on the steady state value shown in the table 3.According to embodiment 15 in identical mode analyze the gained reaction product.The result is presented in the table 3.
Table 3-1
| Catalyzer | Initial peak pressure (MPaG) | Reaction times (h) | |
| Embodiment 15 | N | 17 | 6.0 |
| Embodiment 16 | O | 17 | 7.0 |
| Embodiment 17 | P | 17 | 3.0 |
| Embodiment 18 | Q | 16 | 3.0 |
Table 3-2
Embodiment 19
Repeat with embodiment 15 in identical operation, only be to use 150 gram (0.81 mole) lauryl alcohols to replace stearyl alcohol and use 69 to restrain (4.06 moles) ammonia, reacted thus 9 hours.The initial peak pressure that records under 220 ℃ of temperature of reaction is 21MPaG.According to embodiment 15 in identical mode analyze the gained reaction product.The result confirms that the transformation efficiency of raw alcohol is 96.3%, is 90.9% to the selection rate of lauryl amine, and the amount of the dilaurylamine of generation is 8.2%, and the amount of other by product that generates is 0.6%.
Industrial applicability
The method according to this invention can be made aliphatic amine, particularly Armeen with high catalytic activity and high selectivity by aliphatic alcohol. The gained aliphatic amine be in family and the industrial application important compound and such as the raw material that is suitable as manufacturing table surface-active agent, fibre finish etc.
Claims (22)
1. a method of making fatty amine is characterized in that,
Comprise making straight or branched or the pure step that contacts with ammonia and hydrogen of annular aliphatic with 6 to 22 carbon atoms in the presence of catalyzer, this catalyzer is to form by being supported on the carrier by (A) ruthenium component that the hydrolysis of ruthenium compound is made.
2. a method of making fatty amine is characterized in that,
Comprise and make straight or branched or the pure step that in the presence of catalyzer, contacts with ammonia and hydrogen of annular aliphatic with 6 to 22 carbon atoms, wherein this catalyzer be by with (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten be supported on and form on the carrier, described (A) ruthenium component and described (B) metal component are made by the hydrolysis of the compound of ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten respectively.
3. a method of making fatty amine is characterized in that,
Comprise the step that straight or branched with 6 to 22 carbon atoms or annular aliphatic alcohol and ammonia and hydrogen are contacted in the presence of catalyzer, wherein this catalyzer is by at least a metal component of nickel and cobalt that is selected from of (A) ruthenium component, (B ') is supported on the carrier with (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium and forms.
4. method according to claim 3 is characterized in that,
The content of at least a metal component (C) that is selected from lanthanum, yttrium, magnesium and barium in catalyzer is counted 0.01 to 10 quality % based on the catalyzer total amount by the metal element.
5. according to claim 3 or 4 described methods, it is characterized in that,
Described catalyzer is as the ruthenium compound in component (A) source, make as the metallic compound in component (B ') source with as the metallic compound in component (C) source and with each metal component precipitation by hydrolysis.
6. according to each described method of claim 1 to 5, it is characterized in that,
Described carrier is at least a compound that is selected from macromolecular compound, metal phosphate and porous oxide.
7. method according to claim 6 is characterized in that,
Described carrier is a porous oxide.
8. method according to claim 7 is characterized in that,
Described porous oxide is at least a oxide compound that is selected from aluminum oxide, zirconium white, titanium oxide, silico-aluminate, diatomite, hydrotalcite-type compound, alkaline earth metal oxide and niobium oxides.
9. according to each described method of claim 2 to 8, it is characterized in that,
The content of component in catalyzer (B) or component (B ') is counted 0.1 to 25 quality % based on the catalyzer total amount by the metal element.
10. according to each described method of claim 1 to 9, it is characterized in that,
The content of the ruthenium component (A) in catalyzer is counted 0.1 to 25 quality % based on the catalyzer total amount by metal Ru.
11. each the described method according to claim 1 to 10 is characterized in that,
With the catalyzer that uses therein at 140 ℃ or drier under the low temperature.
12. each the described method according to claim 1 to 11 is characterized in that,
In the presence of at least a reductive agent that is selected from formaldehyde, hydrazine and sodium borohydride the catalyzer of making being imposed reduction handles.
13. each the described method according to claim 1 to 12 is characterized in that,
The catalyzed reaction of fatty alcohol and ammonia and hydrogen is carried out under 120～280 ℃ temperature.
14. each the described method according to claim 1 to 13 is characterized in that,
The catalyzed reaction of fatty alcohol and ammonia and hydrogen is to carry out under 0.5～10 the condition in the mol ratio that makes ammonia and fatty alcohol (ammonia/fatty alcohol).
15. each the described method according to claim 1 to 14 is characterized in that,
Use described catalyzer with amount based on 0.1～20 quality % of fatty alcohol.
16. each the described method according to claim 1 to 15 is characterized in that,
Fatty amine is an Armeen.
17. a catalyzer is characterized in that,
Be used for by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia, described catalyzer comprises carrier and is supported on the ruthenium component (A) that the hydrolysis of passing through ruthenium compound on the carrier is made.
18. a catalyzer is characterized in that,
Be used for by making fatty alcohol contact the method for making fatty amine with hydrogen with ammonia with 6 to 22 carbon atoms, described catalyzer comprises carrier, (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten, and described (A) ruthenium component and described (B) metal component hydrolysis of the compound by ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten are respectively made and be supported on the carrier.
19. a catalyzer is characterized in that,
Be used for by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia, described catalyzer comprises carrier and is supported at least a metal component of nickel and cobalt and (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium of being selected from of (A) ruthenium component on the carrier, (B ').
20. the purposes of a catalyzer in the method for making fatty amine is characterized in that,
Described catalyzer is to form by the ruthenium component of being made by the hydrolysis of ruthenium compound (A) is supported on the carrier, and the method for described manufacturing fatty amine is to make the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia.
21. the purposes of a catalyzer in the method for making fatty amine is characterized in that,
Described catalyzer be by make (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten be supported on the carrier and form, described (A) ruthenium component and described (B) metal component hydrolysis of the compound by ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten are respectively made, and the method for described manufacturing fatty amine is by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia.
22. the purposes of a catalyzer in the method for making fatty amine is characterized in that,
Described catalyzer be by make (A) ruthenium component, (B ') at least a be selected from the metal component of nickel and cobalt and (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium be supported on the carrier and form, the method for described manufacturing fatty amine is by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia.
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| JP2005379652A JP4972314B2 (en) | 2005-12-28 | 2005-12-28 | Method for producing nitrogen-containing compound |
| JP2005379655 | 2005-12-28 | ||
| JP2005379660A JP4972315B2 (en) | 2005-12-28 | 2005-12-28 | Method for producing nitrogen-containing compound |
| JP379655/2005 | 2005-12-28 | ||
| JP379660/2005 | 2005-12-28 | ||
| JP379652/2005 | 2005-12-28 | ||
| PCT/JP2006/326164 WO2007077903A2 (en) | 2005-12-28 | 2006-12-21 | Process for producing nitrogen-containing compounds |
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| CN109476581A (en) * | 2016-03-11 | 2019-03-15 | 罗地亚经营管理公司 | Amine is produced using zeolite catalyst |
| CN111116377A (en) * | 2019-12-16 | 2020-05-08 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine |
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| JP4972315B2 (en) * | 2005-12-28 | 2012-07-11 | 花王株式会社 | Method for producing nitrogen-containing compound |
| JP4892329B2 (en) | 2006-12-15 | 2012-03-07 | 花王株式会社 | Method for producing nitrogen-containing compound |
| JP5469607B2 (en) * | 2008-09-19 | 2014-04-16 | 昭和電工株式会社 | Catalyst used for hydrogen transfer reaction of alcohol, process for producing the same, and process for producing carbonyl group-containing compound |
| JP5599570B2 (en) * | 2009-02-10 | 2014-10-01 | 国立大学法人 香川大学 | Method for producing aryl derivative using heterogeneous catalyst |
| BR112013016515B1 (en) | 2010-12-27 | 2019-02-05 | Kao Corporation | process for tertiary amine production |
| US20230278947A1 (en) | 2020-09-25 | 2023-09-07 | Kao Corporation | Method for producing tertiary amine composition |
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| CH485646A (en) * | 1965-12-23 | 1970-02-15 | Du Pont | Process for the catalytic hydrogenation of nitrogen-containing compounds |
| JPH061758A (en) * | 1992-06-17 | 1994-01-11 | Idemitsu Petrochem Co Ltd | Production of amino compound |
| DE19507007A1 (en) * | 1995-02-28 | 1996-08-29 | Basf Ag | Catalysts for the amination of alcohols, ketones and aldehydes |
| JP4582992B2 (en) * | 2002-07-09 | 2010-11-17 | 旭化成ケミカルズ株式会社 | Method for producing alicyclic amine compound |
| WO2005082834A1 (en) * | 2004-02-17 | 2005-09-09 | Exxonmobil Research And Engineering Company | Catalytic preparation of severely sterically hindered amino-ether alcohols using a metal loaded catalyst |
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| CN109476581A (en) * | 2016-03-11 | 2019-03-15 | 罗地亚经营管理公司 | Amine is produced using zeolite catalyst |
| CN111116377A (en) * | 2019-12-16 | 2020-05-08 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine |
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| JP2007176891A (en) | 2007-07-12 |
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