CN1031663A - Aminating reaction catalyst - Google Patents

Aminating reaction catalyst Download PDF

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CN1031663A
CN1031663A CN 87105833 CN87105833A CN1031663A CN 1031663 A CN1031663 A CN 1031663A CN 87105833 CN87105833 CN 87105833 CN 87105833 A CN87105833 A CN 87105833A CN 1031663 A CN1031663 A CN 1031663A
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catalyst
reaction
carrier
selectivity
atomic ratio
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CN1010284B (en
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刘君佐
吴葆珠
陈亚军
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Sinopec Research Institute of Petroleum Processing
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Abstract

With Al 2O 3Be the aminating reaction catalyst of its Main Ingredients and Appearance, the first is by δ-or θ-or (δ+θ)-Al of arbitrary proportion 2O 3Load Ni, Cu, Cr and/or Re isoreactivity component are formed, wherein Al 2O 3Be 65～90%, the atomic ratio of all the other each active components is: Ni: Cu=1: 0.2～0.8, and Ni: Cr=1: 0.0～0.5, Ni: Re=1: 0.001～0.01; It two is the compound of Ni, the Cu, Cr, Ti and the Al that are made by the precipitation method, wherein Al 2O 3Be 63～32%, the atomic ratio of all the other each active components is: Ni: Cu=1: 1.0～2.0, and Ni: Cr=1: 0.1～0.5, Ni: Ti=1: 1.0～2.0.This catalyst can be used for all kinds of aminating reactions, is suitable for producing morpholine, N-alkyl morpholine, fatty amine and N heterocyclic compound especially.

Description

Aminating reaction catalyst
The present invention relates to aminating reaction catalyst, or rather, the present invention relates to Al 2O 3And the aminating reaction catalyst of the metal of from Ni, Cu, Cr, Ti and Re, selecting more than three kinds or three kinds or its oxide or their mixture composition.
In the organic chemistry industry, often use the compound of hydroxyl, as aliphatic monobasic alcohol or dihydroxylic alcohols, wherein particularly diethylene glycol (DEG) (DEG) or two alkylidene glycol (DAG) or derivatives thereofs carry out ammonification and produce compounds such as fatty amine, morpholine, N-alkyl morpholine to obtain class important chemical raw material and a product.Chang Yong this class catalyst had in the past:
(1) Cu, Ni, Cr, Co, Mg, Mn, Pd, Pt, Rh, the oxide of these metals or its mixture (USP.3,151,112);
（2）60-85%Ni、14-37%Cu、1-5%Cr（Mol.）〔USP.3，152，998;USP.4，508，896〕;
（3）0.2-5%Ru（wt.）/Al 2O 3〔USP.3，155，357〕;
(4) Raney Ni type catalyst (special public clear 46-32188 ,-32189; The spy opens clear 50-99987; The spy opens clear 55-31781 ,-31782; DE2,613,344);
(5) 50-90%Ni, 9-45%Cu, 1-5%MoO 3(special public clear 47-41908);
(6) 40-65%Ni, 15-40Cu, 1-10%Cr, 3-20%Al 2O 3(Mol.) (special public clear 49-32699);
（7）25-55%NiO、15-40%CuO、0.7-7%Cr 2O 3、20-40%TiO 2（Wt）〔SU.968，029〕;
（8）Ni，Co，Cr/γ-Al 2O 3〔EP.0，036，331〕;
(9) CoO-CuO-Th or CoO-CuO-Ce (USP.4,532,324);
（10）Cu-Ni-Co/Al 2O 3〔DE3，125，662〕。
; these known catalysts ubiquity active metallic contents are too high; easily efflorescence is separated at the ammonia of diethylene glycol (DEG) and can be made defectives such as intermediate diglycolamine (DGA) growing amount is excessive in the cyclisation reaction, needs improvements in addition at aspects such as stability, active, selectivity and intensity.So from the viewpoint of commercial Application, it is well-content still can not to say so.
In recent years, once disclose, in the autoclave reaction of intermittently operated, can use at γ-or α-Al 2O 3On be loaded with the catalyst of components such as Ni, Re with DEG and NH 3Make morpholine (MOR), wherein, with respect to the Ni content of vehicle weight be: 2～20%.Other component content and reaction result are as follows:
(11) Ni-Cu-Cr-Re/ α-Al 2O 3(spy opens clear 58-225078):
Ni: Cu=1: the 0.4-0.02(atomic ratio)
Ni: Cr=1: the 0.5-0.05(atomic ratio)
Ni: Re=1: the 0.3-0.01(atomic ratio)
DEG conversion ratio: 58-60%
MOR selectivity: 32-35%
DGA selectivity: 51-55%
(12) Ni-Cr-Re/ α-Al 2O 3(spy opens clear 59-4444):
Ni: Cr=1: the 0.5-0.05(atomic ratio)
Ni: Re=1: the 0.3-0.01(atomic ratio)
DEG conversion ratio: 70-79%
MOR selectivity: 40-50%
DGA selectivity: 36-47%
(13) γ-Al of Ni-Re/＞900 ℃ roasting 2O 3(spy opens clear 59-19543):
Ni: Re=1: the 0.12-0.05(atomic ratio)
DEG conversion ratio: 88-92%
MOR selectivity: 58-63%
DGA selectivity: 24-31%
(14) Ni-Re-Er/ γ-Al 2O 3(spy opens clear 59-115746):
ZrO 2: 1-20wt%(is with respect to γ-Al 2O 3)
Ni: Re=1: the 0.01-0.3(atomic ratio)
DEG conversion ratio: 75-79%
MOR selectivity: 43-48%
DGA selectivity: 37-44%
This class catalyst is at 200kg/cm 2(1.96 * 10 7Pa) pressure operation down, though have mechanical strength and stability preferably, still showing on active and selectivity needs improvements, in reactor product, there are a large amount of accessory substances to generate, and raw material availability, generally below 85%, this certainly will make production efficiency reduce in commercial Application.
In addition, general by DEG and NH 3Make in the method for morpholine, reactor product except contain＞20%(mol) intermediate products DGA, also contain the ethers impurity of 1-2% usually, for example: glycol monoethyl ether (HOCH 2CH 2OCH 3).Because the boiling point of this impurity and MOR is very approaching, so, be difficult for from the morpholine product, being removed.Because it is a short stopping agent when the synthetic rubber emulsion polymerization, so such morpholine product will be not suitable for using as emulsifying agent.
The objective of the invention is to obtain a kind of improved aminating reaction catalyst, to overcome the above-mentioned shortcoming of existing catalyst.
Another object of the present invention is to be used for aminating reaction with having the catalyst that improves performance, improves process, improves process efficiency, reduces production costs.
Catalyst of the present invention has following characteristics:
With Al 2O 3Be carrier, in the aminating reaction catalyst that metallic element such as load Ni, Cu, Cr, Re or its oxide are formed, said carrier is δ-Al 2O 3Or θ-Al 2O 3Or both are to be obtained 750～920 ℃ of following roastings 2～8 hours by boehmite with the mixture that arbitrary proportion is formed, and carrier shared percentage by weight in catalyst is 65～90, and all the other are active component.Each active component is respectively the atomic ratio of Ni: Ni: Cu=1: 0.2～0.8, and Ni: Cr=1: 0.0～0.5, Ni: Re=1: 0.001～0.01.The specific area of alumina support is 50～200m 2/ g, preferably 80～170m 2/ g.Pore volume is 0.2～1.0ml/g, preferably 0.3～0.5ml/g.The load of active component can be undertaken by the mode that branch soaks or soaks altogether, and dipping solution can be selected the aqueous solution of corresponding salt for use, any in alcoholic solution or the ketone solution.
Another program of catalyst of the present invention is: the amination catalyst that the composite oxides of Ni, Cu, Cr, Ti and the Al that is made by the precipitation method are formed.Al wherein 2O 3Weight ratio in catalyst is 63～32%, and all the other components are 37～68%, are respectively according to the atomic ratio with Ni: Ni: Cu=1: 1.0～2.0, and Ni: Cr=1: 0.1～0.5, Ni: Ti=1: 1.0～2.0.Its preparation method be nitrate (as Ni, Cu, Cr) with said components and sulfate (as Ti) according to the method for knowing with Na 2CO 3Precipitate, under 120～380 ℃, carry out drying, roasting then.Behind the crushing screening, add with commercially available SB-aluminium hydrate powder that water is kneaded, extrusion molding, again in 60～120 ℃ dry down, 480 ℃ down activation form, through X-ray diffractometer Fixed, Al 2O 3Be γ-crystalline phase.
Catalyst of the present invention can be widely used in all kinds of aminating reactions, being suitable for especially with hydroxy-containing compounds such as fatty alcohol, diethylene glycol (DEG) (DEG), two alkylidene glycol (DAG) is that raw material is made in the reaction of fatty amine, morpholine, N-alkyl morpholine, and this series products can be represented with following general formula:
Figure 871058332_IMG3
In the formula, R 1, R 2, R 3Can be identical or different, each represents the alkyl of H or 1-4C atom.R 4Represent the alkyl, aryl, cycloalkyl of H or replacement or unsubstituted 1-7C atom, saturated heterocyclic radical or acyl group etc.R 5Can be alkyl, aryl, cycloalkyl or the acyl group of replacement or unsubstituted 1-18C atom.
In addition, also to can be used for the aliphatic dihydric alcohol be that raw material is produced five yuan or hexa-atomic saturated N heterocyclic compound such as piperazine, piperidines etc. to catalyst of the present invention.
The method of producing above-claimed cpd with catalyst of the present invention is:
5 * 10 5～6 * 10 6Pa(preferably 1.5～4.5 * 10 6Pa) under the pressure and the inherent H of 160～300 ℃ of temperature ranges 2With under any existence in the aforementioned catalyst raw material (as DEG or DAG) and liquefied ammonia are added from the top of fixed-bed catalytic reactor continuously, keeping liquid charging air speed is 0.2～2.5hr -1, H 2And the ratio of raw material is 1～10: between 1, the ratio of ammonia and raw material is 1.5～8: between 1, make morpholinium compound or other ammonolysis reaction product according to the trickle bed reactive mode.
The distinguishing feature of catalyst of the present invention is to have excellent mechanical intensity and stability.It is containing liquid NH 3, DEG adds in the autoclave of water, water generation reaction and hydrogen, in pressure＞5.9 * 10 6Pa(60Kg/cm 2), temperature: 200-220 ℃, and under mixing speed: 200-400 rev/min, turned round 5 hours at every turn, replace virgin material then, after successive reaction 20 stills, powder phenomenon-tion does not take place in the catalyst that the draws off particle that still is kept perfectly.In continuous fixed bed reactor, the accumulative total charging did not also find that catalyst granules has any damage more than 1300 hours.
Another distinguishing feature of catalyst of the present invention is to have advantages of high catalytic activity.For example, it can make DEG be bordering on aminating reaction takes place fully (near 100%), thereby can boost productivity significantly.
The distinguishing feature of catalyst of the present invention is to have good selectivity.For example, it can make the DEG of conversion only generate purpose product MOR basically, and the growing amount of other impurity can be reduced to 2%(mol) about, the DEG utilization rate is up to 98%(mol), thereby the product separation is carried out easily.
A distinguishing feature again of catalyst of the present invention is to have advantages of higher stability, i.e. Chang service life.As in the manufacturing of morpholine, use catalyst of the present invention, under the situation that needn't adopt the special reproduction technology, the accumulative total charging is more than 1300 hours, DEG conversion ratio and MOR once through yield can remain on 98%(mol respectively) and 94% above and constant, and still have sizable operation potentiality.
Adopt catalyst of the present invention, carry out aminating reaction,, make the selectivity of conversion of raw material and product obtain very big improvement because catalyst performance is good.Thereby can improve product yield, improve the efficient of production process, reduce production costs.
Below be the embodiment of catalyst of the present invention and application thereof.Having enumerated in the example with DEG is raw material, carries out the result that ammonia is separated cyclisation reaction (aminating reaction a kind of) in the presence of catalyst of the present invention, but catalyst of the present invention has more than and limits the use of in this class reaction.
Embodiment 1
Specific surface 149m 2/ g, pore volume 0.42ml/g(BET method) φ 1.5mm strip θ-Al 2O 3(behind the commercially available SB-aluminium hydrate powder extruded moulding, at 120 ℃ of dry 4hr, 900 ℃ of roasting 4hr form.Crystalline phase is measured with x-ray diffractometer) 17 grams, with 19.5 gram Ni(NO 3) 26H 2O, 3.8 gram Cu(NO 3) 23H 2O and 6.6 gram Cr(NO 3) 39H 2The saturated solution dipping of O in ethanol.Surplus liquid is soaked in elimination, at 60 ℃, and 2hr; 120 ℃, 4hr; 300 ℃ after the 2hr drying, is the 0.2ml perrhenic acid (HReO of 38mgRe/ml with concentration again 4) with the solution (with the catalyst equal-volume) of water dipping.Surplus liquid is soaked in elimination, at 60 ℃, and 4hr; 120 ℃, after the 4hr drying, obtain finished catalyst A.The chemical composition that plasma emission spectroscopy is measured is: Al 2O 3: the NiO(weight ratio)=12.5: 1.Activity component metal gram atom ratio is:
Ni∶Cu＝1∶0.26
Ni∶Cr＝1∶0.32
Ni∶Re＝1∶0.0023
The ammonia of DEG is separated the cyclisation test and is carried out on common continuous-flow fixed-bed catalytic reactor.At internal diameter 8mm, length 350mm, in the tubular reactor of making by stainless steel, the 4.8ml(3.6 that packs into gram) granularity is 20-40 purpose catalyst A.At 300 ℃, be 3-5 * 10 with pressure 5Pa, flow velocity are the H of 83ml/min 2Behind the air-flow reduction 3hr, regulating hydrogen pressure is 3 * 10 6Pa, reaction temperature is 220 ℃.Then, at DEG: H 2(mol ratio)=1: 8 time, according to volume space velocity DEG=0.4hr -1And DEG: NH 3(mol ratio)=1: 10, add DEG and liquid NH with pump from reactor head 3Reactor product is with being filled with the gas chromatograph of Porapak P post with flame ionization detection.
Result of the test is shown in table 1.Tables of data reveals high DEG conversion ratio and MOR selectivity, and the MOR once through yield is up to 97%(mol).
Embodiment 2
Catalyst B is 210 ℃ except not containing Cr component and reaction temperature, and it is identical with embodiment 1 that preparation method and ammonia are separated the cyclisation test method.Catalyst consists of: Al 2O 3: the NiO(weight ratio)=7.7: 1, activity component metal gram atom ratio is:
Ni∶Cu＝1∶0.61
Ni∶Re＝1∶0.0045
Result of the test is shown in table 1 equally.Data demonstrate high DEG activity of conversion and DEG utilization rate.But the cyclisation selectivity is low slightly, and except that the product of production are the MOR, the intermediate products DGA(DGA selectivity that also generates some is about 11%mol).
Embodiment 3
The method for making of catalyst C is 97.3 gram Ni(NO 3) 26H 2O, 121.5 gram Cu(NO 3) 23H 2O, 36.9 gram Cr(NO 3) 39H 2O and 84.1 gram Ti(SO 4) 2Be dissolved in 3 liters 50 ℃ the warm water, with Na 2CO 310H 2The O precipitation is until solution P H≈ 8.Filter, wash, carry out repeatedly six times.Behind 120 ℃ and 380 ℃ of dryings, each 4hr of roasting, pulverize, sieve.Take by weighing 23 gram dry glue powders and 29 and restrain commercially available SB-aluminium hydrate powder and add water and knead evenly, be squeezed into φ 1.5mm strip.Again through 60 ℃, 3hr; 90 ℃, 3hr; 120 ℃, 3hr is dry and at 480 ℃ of activation 8.5hr, gained finished catalyst Al 2O 3Be γ-phase, it consists of: Al 2O 3: NiO=3.5: the 1(weight ratio), the metal gram atom ratio of active component is:
Ni∶Cu＝1∶1.58
Ni∶Cr＝1∶0.30
Ni∶Ti＝1∶1.18
DEG ammonia is separated the cyclisation test method, and except that reaction temperature is 235 ℃, all the other are identical with embodiment 1.The result also is shown in Table 1.Data demonstrate high MOR selectivity and DEG selectivity and DEG utilization rate, but DEG activity of conversion low slightly (the DEG conversion ratio is about 83%).
Embodiment 4
The method for making of catalyst D is: specific surface 159m 2/ g, the spherical (δ+θ)-Al of the φ 1.5mm of pore volume 1.0ml/g 2O 3(the spherical aluminium hydroxide of aluminium sol method by Research Institute of Petro-Chemical Engineering's preparation forms at 870 ℃ of roasting 4hr) 8.3 grams are with 3.9 gram Ni(NO 3) 26H 2O, 1.2 gram Cu(NO 3) 23H 2O, 1.6 gram Cr(NO 3) 39H 2O and 0.16ml HReO 4The solution impregnation that (concentration is 38mgRe/ml) become with 6ml water.At 60 ℃, 3hr; 120 ℃, the 3hr drying, and behind 400 ℃ of activation 4hr, the consisting of of gained finished catalyst: Al 2O 3: the NiO(weight ratio)=7.4: 1; The metal gram atom ratio of active component is:
Ni∶Cu＝1∶0.36
Ni∶Cr＝1∶0.27
Ni∶Re＝1∶0.0011
It is identical with embodiment 1 that DEG ammonia is separated the cyclisation test method.Reaction result also provides in table 1.Data show, change Al 2O 3Carrier precursor and crystalline phase, and utilize water logging, and do not have the method for soaking altogether of soaking surplus liquid, can reach the effect identical with catalyst A.
Table 1(1)
Catalyst Reaction temperature, ℃ DEG conversion ratio ［ 2 ］, mol% MOR selectivity ［ 3 ］, mlo% DGA selectivity ［ 4 ］ mol% DEG utilization rate ［ 5 ］, mol% MOR once through yield ［ 6 ］, mol%
A B C D 220 210 235 220 110 99.38 82.79 98.52 96.89 86.66 95.44 96.99 1.86 10.92 1.0 2.0 98.75 97.58 96.44 98.99 96.89 86.12 79.01 95.55
(1) data are the mean value of six sub-sampling analysis results during reaction;
(2) DEG conversion ratio (mol%)
=(mole number that DEG consumes)/(DEG charging mole number) * 100%
(3) MOR selectivity (mol%)
=(mole number that MOR generates)/(the total mole number of DEG converted product) * 100%
(4) DGA selectivity (mol%)
=(mole number that DGA generates)/(the total mole number of DEG converted product) * 100%
(5) DEG utilization rate (mol%)
=MOR selectivity+DGA selectivity
(6) MOR once through yield (mol%)
=DEG conversion ratio * MOR selectivity
Embodiment 5
Catalyst B and the 200 gram DEGs of 20 grams behind 300 ℃ of reduction 4hr, 193 gram deionized waters join in the stainless steel electromagnetic agitation of the 1l autoclave, use H 2After the displacement, add 48 gram liquid NH 3Again with hydrogen be pressurized to～3 * 10 5Pa is warming up to 200 ℃ of reaction 4hr.Catalyst composition, reaction condition and ammonia are separated the cyclisation result of the test and are shown in Table 2.
Comparative example 1
Specific area 1m 2/ g, diameter 2mm, the sheet α of long 4mm-Al 2O 350ml is with containing 16.15 gram Ni(NO 3) 26H 2O, 0.67 gram Cu(NO 3) 23H 2O, 4.45 gram Cr(NO 3) 39H 2O and 0.74 gram perrhenic acid amine (NH 4ReO 4) aqueous solution 17ml dipping.Afterwards, at 100 ℃ of dry 1hr, at H 2In the atmosphere in 300 ℃ of reductase 12 hr.
Above-mentioned catalyst 15ml and 150 gram DEG are joined in the stainless steel electromagnetic agitation of the 0.5l autoclave.Use H 2After the displacement, add 120 gram NH 3, use H again 2Be pressurized to 2.65 * 10 6Pa is warming up to 240 ℃ of reaction 2hr.
About catalyst composition, reaction condition, the reaction result that reaches according to the reaction solution analytical calculation also is shown in Table 2.
Comparative example 2
Remove that to contain Ni on the catalyst is 8.4wt%, Ni: Cu=1: 0.1, Ni: Cr=1: 0.3 and Ni: Re=1: outside 0.10, all the other are all identical with comparative example 2.Reaction condition and result are shown in Table 3 equally.
Table 2
Figure 871058332_IMG4
Embodiment 6
From specific surface 120m 2/ g, φ 1.5 spherical δ-Al of pore volume 0.79ml/g 2O 3(being formed at 770 ℃ of roasting 4hr by oil three factories industrial alucol method aluminium hydroxide) sets out, and according to the catalyst E of embodiment 4 methods preparation, its chemical composition is:
Al 2O 3∶NiO＝3.5∶1
Ni∶Cu＝1∶0.23
Ni∶Cr＝1∶0.14
Ni∶Re＝1∶0.004
The materialization data of carrier and catalyst are shown in table 3.
Table 3
According to embodiment 1 described method, catalyst E is in reaction pressure 2.94 * 10 6Pa, temperature 210-230 ℃, volume space velocity DEG=0.45hr -1, DEG: H 2=1: 6.2 and DEG: NH 3Carry out ammonia under=1: 6.7 the condition and separate cyclisation reaction test 1300hr, up to the reaction later stage, data are stabilized in following level respectively.
DEG conversion ratio (mol%):＞99%
MOR selectivity (mol%):＞94%
DGA selectivity (mol%) :～2%
DEG utilization rate (mol%):＞96%
Embodiment 7
According to embodiment 6 methods, from specific surface 149m 2/ g, φ 1.2mm cloverleaf pattern strip δ-Al of pore volume 0.44ml/g 2O 3The catalyst F that sets out and prepare, other chemical composition is: Al 2O 3: NiO=5.6: 1
Ni∶Cu＝1∶0.35
Ni∶Cr＝1∶0.30
Ni∶Re＝1∶0.0044
The materialization data of carrier and catalyst are shown in table 4.
Table 4
Except the mixture with DEG and ethanol (EtOH) replaces simple DEG as the reaction feed, the synthetic test of N-ethylmorpholine (EtMOR) carries out in the presence of catalyst F according to the method that embodiment 1 is narrated.Remaining reaction condition and show table 5 according to the result of the test of gas-chromatography calculated by peak area.
Table 5
*With respect to the DEG that has transformed.
Embodiment 8
Except the mixture that replaces DEG and ethanol with the mixture (molecular proportion is 1: 1) of DEG and n-butanol (n-BuOH) as reaction feed, and H 2: DEG=94: 1, NH 3: DEG=1.9: outside 1, all the other are identical with embodiment 7.Product based on the gas-chromatography peak area distributes as shown in table 6.
Table 6
Figure 871058332_IMG8
Result of calculation based on the DEG converted product is as follows:
DEG conversion ratio: 97.31%
BuMOR selectivity: 63.96%
MOR selectivity: 19.27%
DGA selectivity: 9.05%
DEG utilization rate: 92.28%
N-butylamine (n-BuNH based on residue n-BuOH 2) production rate is: 90.72%

Claims (8)

1, a kind of by Al 2O 3Aminating reaction catalyst for metals such as carrier loaded Ni, Cu, Cr, Re or its oxide are formed is characterized in that said carrier is σ-Al 2O 3Or Q-Al 2O 3Or both are to be got in 750～920 ℃ of roastings 2～8 hours by boehmite with the mixture that arbitrary proportion is formed, and carrier shared percentage by weight in catalyst is 65～90, and all the other are active constituent; Each active component consumption is respectively with the atomic ratio measuring to Ni: Ni: Cu=1: 0.2～0.8, and Ni: Cr=1: 0.0～0.5, Ni: Re=1: 0.001～0.01.
2, according to the said catalyst of claim 1, the specific area of its alumina support is 50～200m 2/ g, pore volume are 0.2～1.0ml/g.
3, according to the said catalyst of claim 1, the specific area that it is characterized in that said aluminium oxide is 80～170m 2/ g, pore volume are 0.3～0.5ml/g.
4, a kind of with Al 2O 3It is characterized in that it being the composite oxides of Ni, the Cu, Cr, Ti and the Al that make by the precipitation method, wherein Al for the amination catalyst of its main component 2O 3Be γ-phase, the percentage by weight in catalyst is 63～32, and all the other components are 37～68, are respectively according to the atomic ratio with Ni: Ni: Cu=1: 1.0～2.0, and Ni: Cr=1: 0.1～0.5, Ni: Ti=1: 1.0～2.0.
5, according to each said catalyst in the claim 1,2,3 or 4, it is characterized in that can be used for making the reaction of general formula for a class morpholinium compound of (I), in the formula, R 1, R 2And R 3Can be identical or different, can be the alkyl of H or 1-4C atom, R 4Can be alkyl, aryl or the cycloalkyl of H or 1～7C atom.
Figure 871058332_IMG1
6, it is characterized in that can be used for fatty amine R according to each said catalyst in the claim 1,2,3 or 4 5NH 2Manufacturing.
7, according to each said catalyst in the claim 1,2,3 or 4, can be applied to HO(CH 2) nOH(n 〉=4) reaction of making saturated N heterocyclic compound for raw material.
8, by according to claim 1,2 or 3 said catalyst, be characterised in that its active component is to load on Al with the aqueous solution of corresponding salt or any mode that serves as stain liquid soaks or soaks altogether by branch in alcoholic solution or the ketone solution 2O 3On the carrier.
CN 87105833 1987-08-29 1987-08-29 Catalyst for ammoniation Expired CN1010284B (en)

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EP0737514A1 (en) * 1993-12-22 1996-10-16 Union Carbide Chemicals & Plastics Technology Corporation Reductive amination catalysts comprising at least one reduction amination metal on a transitional alumina carrier
US5750790A (en) * 1993-12-22 1998-05-12 Union Carbide Chemicals & Plastics Technology Corporation Reductive amination catalysts
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