CN101346343B - Process for producing nitrogen-containing compounds - Google Patents
Process for producing nitrogen-containing compounds Download PDFInfo
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- CN101346343B CN101346343B CN2006800494490A CN200680049449A CN101346343B CN 101346343 B CN101346343 B CN 101346343B CN 2006800494490 A CN2006800494490 A CN 2006800494490A CN 200680049449 A CN200680049449 A CN 200680049449A CN 101346343 B CN101346343 B CN 101346343B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 through the whole bag of tricks manufacturing.As one of method of manufacture, 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 through 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 the for example rhodium of about 0 to 5 weight %, palladium, platinum, copper, silver and composition thereof such promotor.In addition; The method used through 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 the catalyzer that forms on the such porous oxide of for example aluminum oxide, silicon-dioxide and silico-aluminate with the accelerator that is made up of various metals of about 0 to 10 weight % copper and about 0 to 5 weight % is disclosed (for example; Referring to JP 10-174874A); And use through the cobalt of the ruthenium of about 0.001 to 25 weight % and about 6 to 50 weight % and/or nickel are supported on the method (for example, referring to JP 10-174875A) of the catalyzer that forms on the such porous oxide of for example aluminum oxide, silicon-dioxide and silico-aluminate with the accelerator that is made up of various metals of the copper of about 0 to 10 weight % and about 0 to 5 weight %.
In these technology, make catalyzer through pickling process, and the catalyzer of processing is dry, 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 in the presence of catalyzer, contacts with ammonia and hydrogen of annular aliphatic with 6 to 22 carbon atoms, this catalyzer forms through (A) ruthenium component of being processed 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 forms through (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten are supported on the carrier, and said (A) ruthenium component and said (B) metal component are processed through the hydrolysis of compound that ruthenium compound and at least a is selected from the metal of nickel, cobalt and tungsten respectively;
(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 through 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.
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 instance 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, like 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 VLTN 6 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 through making (A) ruthenium component of being processed by the hydrolysis of ruthenium compound; (2) through making (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 are processed through the hydrolysis of compound that ruthenium compound and at least a is selected from the metal of nickel, cobalt and tungsten respectively; Perhaps (3) through make at least a metal component that is selected from nickel and cobalt of (A) ruthenium component, (B ') (hereinafter only is 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 instance of carrier comprises macromolecular compound, metal phosphate and porous oxide etc. at each above-mentioned catalyzer (1).The instance of used above-mentioned porous oxide comprises aluminum oxide, zirconium white, titanium oxide, silicon-dioxide, gac, silico-aluminate, zeyssatite, hydrotalcite-type compound (for example magnesium/aluminium base composite oxides), alkaline earth metal oxide and niobium oxides (niobia) among the present invention.The instance of macromolecular compound comprises PS, nylon and resin etc., and the instance of metal phosphate comprises calcium phosphate and phosphagel phosphaljel calcium etc.In these carriers, consider high catalytic activity and highly selective, porous oxide preferably, more preferably aluminum oxide, zirconium white, titanium oxide and silico-aluminate, further preferably aluminum oxide and zirconium white.Especially, the catalyzer that uses zirconium white or titanium oxide to process shows advantages of high catalytic activity, and the catalyzer that uses aluminum oxide or silico-aluminate to process 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 through 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 through the hydrolysis ruthenium compound.In above-mentioned catalyzer (2),, ruthenium component (A) and second metal component (B) are supported on the carrier through 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); Through 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.
To the not special restriction of the method that supports these components, comprise any optional currently known methods, for example pickling process, the precipitator method, ion exchange method and the method etc. of mixing usually.
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 combinations support.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,, 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 as the 3rd metal component (C) that will be supported on the carrier.
Then, illustrate the method for making each ruthenium-based catalyst.
At first; Above-mentioned catalyzer (1) can be made as follows: 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 through ruthenium compound being dissolved in the solution of processing 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 through being dissolved in the solution of processing 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 through with ruthenium compound, be dissolved in the solution of processing 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) can be according to making with the used identical mode of the manufacturing of catalyzer (1) with above-mentioned catalyzer (3).
The instance of above-mentioned ruthenium compound comprises muriate, nitrate salt, formate, ammonium salt of ruthenium etc.The muriate, nitrate salt, carbonate, vitriol, ammonium salt etc. that comprise above-mentioned each component as the metallic compound in second metal component (B) or (B ') source with as the instance 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 in the suspension liquid that contains as each compound in the source of above-mentioned each metal component, to add alkali, 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.To the not special restriction of the kind of above-mentioned alkali.The instance of available alkali comprises ammoniacal liquor and the for example alkali-metal carbonate, oxyhydroxide etc. of sodium and potassium and so among the present invention.Be adjusted to the not special restriction of aging required temperature and time from the pH value, as long as guarantee the abundant hydrolysis of ruthenium compound.
Then, through adding the for example reductive agent of formaldehyde, hydrazine and Peng Qinghuana 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 preferred 140 ℃ or more under the low temperature in normal pressure or decompression drying down.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 to the not special restriction of above-mentioned reduction treatment time.
Simultaneously, above-mentioned reduction is handled optional.After supporting each component on the carrier through hydrolysis, can water thorough washing, drying then through 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 filtrating 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 through the said hydrolyzed method; Not necessarily need the operation of required operation of handling and so on like 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 processing 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 through the ICP emission spectrometry method after using this catalyzer of monoammonium sulfate fusing 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 processing 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.
More describe the present invention in detail with reference to the following example.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 processing in the 40 gramion exchanged waters to wherein adding then, then this suspension liquid be heated to 60 ℃ when stirring through 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 IX water washing until the specific conductivity of filtrating, then dry under 13kPa pressure under 60 ℃, obtains about 10 grams, 2 quality % ruthenium/aluminium oxide catalyst A thus.
Preparation example 2
Identical operation in repetition and the preparation example 1 only is to use 1.47 gram hydration ruthenium chlorides, obtains about 10 grams, 5 quality % ruthenium/aluminium oxide catalyst B thus.
Preparation example 3
Identical operation in repetition and the preparation example 1; 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
Identical operation in repetition and the preparation example 1, only being to use can be available from Sakai KagakuKogyo Co., and the titania powder of Ltd. " SSP-25 " replaces alumina powder, obtains ruthenium/titanium deoxide catalyst D of about 10 grams, 2 quality % thus.
Preparation example 5
Identical operation in repetition and the preparation example 2 only is to use and can replaces alumina powder available from the synthetic zeolite powder " CP814E " of Zeolyst Inc., obtain ruthenium/zeolite catalyst E of about 10 grams, 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 under 400 ℃, fires 4 hours, obtains ruthenium/aluminium oxide catalyst F of about 6 grams, 2 quality % thus.
Embodiment 1
150 gram (0.55 mole) VLTN 6s and 3 of in 500 milliliters of electromagnetic induction rotation stir-type autoclaves, packing into restrain the catalyst A of in preparation example 1, processing (for 2.0 quality % of raw alcohol); 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 amount more pure than initial feed of the alcohol that consumes in the reaction process, 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 catalyzer (B), (C), (D) that processes in the preparation example 2,3,4 and 5 respectively and (E) replace catalyzer (A), and supply the hydrogen of additional quantity so that the initial peak pressure that under 220 ℃ of temperature of reaction, records 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 processing 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 VLTN 6s and use 69 to restrain the ammonia of (4.06 moles), thereby react 11 hours.The initial peak pressure that under 220 ℃ of temperature of reaction, records 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 laurylamine, 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
In separable flask, packing 10.0 grams 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 processing in the 40 gramion exchanged waters to the hydration ruthenium chloride and the 0.18 gram six hydration nickel sulfate that wherein add through 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 IX water washing until the specific conductivity of filtrating,, 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
Identical operation in repetition and the preparation example 6 only is to use 0.59 gram hydration ruthenium chloride and 0.16 gram cobalt chloride hexahydrate, and use ammoniacal liquor obtains 2 quality % rutheniums/0.4 quality % cobalt catalyst H that about 10 gram zirconium whites support thus as precipitation agent.
Preparation example 8
In separable flask, packing 10.0 grams 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 processing in the 40 gramion exchanged waters to wherein adding then, then this suspension liquid be heated to 60 ℃ when stirring through 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 through 0.64 gram ammonium metawolframate is dissolved in the solution processed 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 IX water washing until the specific conductivity of filtrating,, 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
In separable flask, packing 10.0 grams 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 processing in the 40 gramion exchanged waters to the hydration ruthenium chloride and the 0.72 gram six hydration nickel sulfate that wherein add through 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 IX water washing until the specific conductivity of filtrating, 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
Identical operation in repetition and the preparation example 6 only is to use 10.0 grams to obtain 2 quality % rutheniums/0.4 quality % nickel catalyzator K that about 10 gram aluminum oxide support thus available from the alumina powder " A-11 " of Sumitomo Chemical Co.
Preparation example 11
In separable flask, packing 10.0 grams 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 processing in the 40 gramion exchanged waters to the hydration ruthenium chloride and the 0.72 gram six hydration nickel sulfate that wherein add through 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 IX water washing until the specific conductivity of filtrating; 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 under 400 ℃, fires 4 hours.Then, thus obtained year ruthenium Zirconium oxide powder is immersed in through 0.12 gram Nickelous nitrate hexahydrate is dissolved in the solution of processing 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 under 400 ℃, fires 4 hours, obtains 2 quality % rutheniums/0.4 quality % nickel catalyzator M that about 6 gram zirconium whites support thus.
Embodiment 7
150 gram (0.55 mole) VLTN 6s and 3 of in 500 milliliters of electromagnetic induction rotation stir-type autoclaves, packing into restrain the catalyzer G (for 2.0 quality % of raw alcohol) that in preparation example 6, processes; 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) processed in the preparation example 7 and 8 and (I) replacement catalyzer (G) respectively, and supply the hydrogen of additional quantity so that the initial peak pressure that under 220 ℃ of temperature of reaction, records 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; 6 restraints of just packing into are equipped with the catalyzer of processing in the example 9 (J) (4.0 quality % of raw alcohol) and replace catalyzer (G), and the hydrogen of supply additional quantity is so that the initial peak pressure that under 220 ℃ of temperature of reaction, records 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; 3 restraints of just packing into are equipped with the catalyzer of processing in the example 11 (L) (2.0 quality % of raw alcohol) and replace catalyzer (G), and the hydrogen of supply additional quantity is so that the initial peak pressure that under 220 ℃ of temperature of reaction, records 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 processing in the comparative preparation example 2 (G).Reaction was carried out 6 hours, and the initial peak pressure that under 220 ℃ of temperature of reaction, records 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 VLTN 6s and use 69 to restrain (4.06 moles) ammonia, reacted thus 9 hours.The initial peak pressure that under 220 ℃ of temperature of reaction, records 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 laurylamine, and the amount of the dilaurylamine of processing is 8.9%, and the amount of other by product that generates is 0.6%.
Embodiment 13
150 gram (0.55 mole) VLTN 6s and 3 of in 500 milliliters of electromagnetic induction rotation stir-type autoclaves, packing into restrain the catalyzer G (for 2.0 quality % of raw alcohol) that in preparation example 6, processes, and when stirring (1000rpm), in nitrogen atmosphere (0MPaG), autoclave contents are heated to 220 ℃ then.Then, ammonia and hydrogen respectively with 19.1 grams (1.1 moles)/hour with 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 laurylamine, and the amount of the dilaurylamine of processing 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 processing 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 laurylamine, and the amount of the dilaurylamine of processing is 7.3%, and the amount of other by product that generates is 2.2%.
Preparation example 12
In separable flask, packing 10.0 grams 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 processing in the 40 gramion exchanged waters to the hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and the 0.04 gram Lanthanum trinitrate that wherein add through 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 IX water washing until the specific conductivity of filtrating,, 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
Identical operation in repetition and the preparation example 12 only is to use 0.29 gram hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and 0.04 to restrain magnesium chloride, obtains 1 quality % ruthenium/1.6 quality % nickel/0.1 weight % Mg catalyst O that about 10 gram zirconium whites support thus.
Preparation example 14
Identical operation in repetition and the preparation example 12 only is to use 0.29 gram hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and 0.04 to restrain Yttrium trinitrate, obtains 1 quality % ruthenium/1.6 quality % nickel/0.1 weight % yttrium catalyst P that about 10 gram zirconium whites support thus.
Preparation example 15
Identical operation in repetition and the preparation example 12 only is to use 0.29 gram hydration ruthenium chloride, 0.72 gram six hydration nickel sulfate and 0.02 to restrain nitrate of baryta, obtains 1 quality % ruthenium/1.6 quality % nickel/0.1 weight % titanate catalyst Q that about 10 gram zirconium whites support thus.
Simultaneously, in above-mentioned preparation example and comparative preparation example, through following ICP emission spectrometry method mensuration based on the component (A) in each catalyzer of catalyzer total amount, (B), (B ') and content (C).
The measurement of each component concentration:
The following ruthenium components contents of measuring.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 through ICP emmission spectrometric analysis device.In addition, measure nickel component and barium components contents as follows.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 with gained solution repeated heating 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 through ICP emmission spectrometric analysis device.
Embodiment 15
150 gram (0.55 mole) VLTN 6s and 3 of in 500 milliliters of electromagnetic induction rotation stir-type autoclaves, packing into restrain the catalyzer of in preparation example 12, processing (N) (for 2.0 quality % of raw alcohol); 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 processing in the preparation example 13 (O) to replace catalyzer (N), and supply the hydrogen of additional quantity so that the initial peak pressure that under 220 ℃ of temperature of reaction, 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 6 and restrain be equipped with the catalyzer (P) processed in the example 14 and 15 and (Q) (4 quality % of raw alcohol) replacement catalyzer (N), and supply the hydrogen of additional quantity so that the initial peak pressure that under 220 ℃ of temperature of reaction, 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 VLTN 6s and use 69 to restrain (4.06 moles) ammonia, reacted thus 9 hours.The initial peak pressure that under 220 ℃ of temperature of reaction, records 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 laurylamine, 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
According to the method for the invention, can make fatty amine, particularly armeen with high catalytic activity and highly selective by fatty alcohol.The gained fatty amine is the important compound in family and the industrial application and for example is suitable as the raw material of making tensio-active agent, fibre finish etc.
Claims (18)
1. a method of making fatty amine is characterized in that,
Comprise making 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, this catalyzer is to form through being supported on the carrier by (A) ruthenium component that the hydrolysis of ruthenium compound is processed.
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 is to form on the carrier through (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten are supported on, said (A) ruthenium component and said (B) metal component respectively by ruthenium compound and at least a be selected from nickel, cobalt and tungsten metal compound hydrolysis and process.
3. 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 is through 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
Said catalyzer is as the ruthenium compound in component (A) source, process as the metallic compound in component (B ') source with as the metallic compound in component (C) source and with each metal component deposition through hydrolysis.
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 each described method of claim 1 to 4, it is characterized in that,
Said carrier is at least a compound that is selected from macromolecular compound, metal phosphate and porous oxide.
6. method according to claim 5 is characterized in that,
Said carrier is a porous oxide.
7. method according to claim 6 is characterized in that,
Said porous oxide is at least a oxide compound that is selected from aluminum oxide, zirconium white, titanium oxide, silico-aluminate, zeyssatite, hydrotalcite-type compound, alkaline earth metal oxide and niobium oxides.
8. according to claim 2 or 3 described methods, 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.
9. according to each described method of claim 1 to 3, 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.
10. according to each described method of claim 1 to 3, it is characterized in that,
With the catalyzer that uses therein 140 ℃ or low temperature drying down more.
11. each the described method according to claim 1 to 3 is characterized in that,
In the presence of at least a reductive agent that is selected from formaldehyde, hydrazine and Peng Qinghuana, the catalyzer of processing being imposed reduction handles.
12. each the described method according to claim 1 to 3 is characterized in that,
The catalyzed reaction of fatty alcohol and ammonia and hydrogen is carried out under 120～280 ℃ temperature.
13. each the described method according to claim 1 to 3 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).
14. each the described method according to claim 1 to 3 is characterized in that,
Amount with based on 0.1～20 quality % of fatty alcohol is used said catalyzer.
15. each the described method according to claim 1 to 3 is characterized in that,
Fatty amine is an armeen.
16. the purposes of a catalyzer in the method for making fatty amine is characterized in that,
Said catalyzer is to form through the ruthenium component of being processed by the hydrolysis of ruthenium compound (A) is supported on the carrier, and the method for said 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.
17. the purposes of a catalyzer in the method for making fatty amine is characterized in that,
Said catalyzer is to form through (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten are supported on the carrier; Said (A) ruthenium component and said (B) metal component are processed through the hydrolysis of compound that ruthenium compound and at least a is selected from the metal of nickel, cobalt and tungsten respectively, and the method for said manufacturing fatty amine is through making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia.
18. the purposes of a catalyzer in the method for making fatty amine is characterized in that,
Said catalyzer is through making at least a metal component of nickel and cobalt that is selected from of (A) ruthenium component, (B ') be supported on the carrier with (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium and form; The method of said manufacturing fatty amine is through making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia
Said catalyzer is as the ruthenium compound in component (A) source, process as the metallic compound in component (B ') source with as the metallic compound in component (C) source and with each metal component deposition through hydrolysis.
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| JP2005379660A JP4972315B2 (en) | 2005-12-28 | 2005-12-28 | Method for producing nitrogen-containing compound |
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| JP4892329B2 (en) | 2006-12-15 | 2012-03-07 | 花王株式会社 | Method for producing nitrogen-containing compound |
| WO2010032770A1 (en) * | 2008-09-19 | 2010-03-25 | 昭和電工株式会社 | Catalyst used in an alcohol hydride transfer reaction, manufacturing method therefor, and method for manufacturing a 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 |
| WO2017152413A1 (en) * | 2016-03-11 | 2017-09-14 | Rhodia Operations | Production of amines utilizing zeolite catalysts |
| CN111116377B (en) * | 2019-12-16 | 2021-03-30 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine |
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| GB1176337A (en) * | 1965-12-23 | 1970-01-01 | Du Pont | Producing Amines by Catalytic Hydrogenation over supported Ruthenium Catalyst |
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| 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 |
| EP1718596B1 (en) * | 2004-02-17 | 2014-08-27 | ExxonMobil Research and Engineering Company | Catalytic preparation of severely sterically hindered amino-ether alcohols using a metal loaded catalyst |
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| Elizarova, G. L.等.Synthesis of cobalt(III), manganese(III), ruthenium(IV) immobilized hydroxides and its catalytic properties in the reaction of water oxidation..《Chemical Abstracts Service》.1990, * |
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