CN104557727B - A kind of method for preparing 5 aminobenzimidazole ketone - Google Patents
A kind of method for preparing 5 aminobenzimidazole ketone Download PDFInfo
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- CN104557727B CN104557727B CN201310515919.XA CN201310515919A CN104557727B CN 104557727 B CN104557727 B CN 104557727B CN 201310515919 A CN201310515919 A CN 201310515919A CN 104557727 B CN104557727 B CN 104557727B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
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Abstract
The invention provides a kind of method for preparing 5 aminobenzimidazole ketone, wherein, the method includes：In the presence of nickel base amorphous alloy catalyst, 5 nitrobenzimidazole ketone are contacted with hydrogen-containing gas, 5 aminobenzimidazole ketone are isolated from the mixture after contact.The method of the present invention, 5 nitrobenzimidazole ketone high conversion rates, 5 aminobenzimidazole ketone selectivity is high, the conversion ratio of 5 nitrobenzimidazole ketone can reach more than 99.5%, the selectivity of 5 aminobenzimidazole ketone is more than 98.0%, and environment-friendly, with good prospects for commercial application.
Description
Technical field
Method the present invention relates to prepare 5-Amino-2-benzimidazolinone, in particular to 5-Nitro-2-benzimidazolinone
It is raw material with hydrogen-containing gas, the side that hydrogenating reduction prepares 5-Amino-2-benzimidazolinone is carried out using nickel base amorphous alloy catalyst
Method.
Background technology
5-Amino-2-benzimidazolinone is the important intermediate of synthesizing benzimidazole ketone pigment, and benzimidazolone pigment is a kind of
Widely used azo-type top grade organic pigment.It is generally heterocyclic derivative as the molecular structure of chemistry of high-grade organic pigment,
The agent structure of benzimidazolone is azo, with preferable planes of molecules and molecular symmetry, can form intramolecular
Hydrogen bond, intermolecular hydrogen are good for, or are formed metal complex or increased relative molecular mass, to improve the performance of pigment.
Due to the presence of amino and carbonyl in 5-Amino-2-benzimidazolinone molecule, easily form intermolecular hydrogen and be good for so that
The pigment has excellent fast light, fastness to weathering, heat-resistant stability, resistance to migration and solvent resistance, and fastness to light is reachable
7-8 grades, heat resistance is more than 250 DEG C.Due to various superior performances so that it is more special that benzimidazolone pigment can meet
Application requirement, be such as used to paint industry manufacture car original finish paint, mending paint and metallic paint；For manufacture building coating and
Emulsion paint；For polyethylene, polyvinyl chloride, polystyrene and other need the coloring of polymer processed at high temperature；For
Colorings of fiber stoste such as polypropylene fibre, acrylic, viscose glue, modified viscose glue and for manufacturing senior outdoor advertising printing ink.
Generally, 5-Amino-2-benzimidazolinone is to be reduced through 5-Nitro-2-benzimidazolinone and prepared, and restoring method has iron powder also
Former, hydrazine hydrate reduction and catalytic hydrogenating reduction.
Iron powder used by iron powder reducing method is cheap, is the main method of industrial use at present, but but exists tight
The problem of environmental pollution of weight, produces substantial amounts of waste water and " iron cement " in process of production, and labour intensity is big, operating environment bar
Part is severe, it is difficult to realize continuous prodution.
Less, reaction condition is gentle, and reduction effect is good, and waste gas waste residue is not produced for the equipment investment of hydrazine hydrate reduction method, but
Small lot is only applicable to, and is not suitable for large-scale industrial production, and hydrazine hydrate toxicity is very big, to the body band of operator
Greatly injure.
Catalytic hydrogenating reduction method, with hydrogen as reducing agent, can carry out reaction orientation, not produce harmful pair due to hydrogenation method
Product, waste gas and waste liquid discharge is few, and strong acid, highly basic medium, high income advanced with technique, good product quality, environment are not related to
Friendly the advantages of.Catalyst for 5-Nitro-2-benzimidazolinone Hydrogenation for 5-Amino-2-benzimidazolinone many is with Raney Ni
It is main.
CN1974559A discloses a kind of with skeleton nickel catalyzed 5-nitrobenzimidazole ketone reducing preparation 5- amino benzo miaows
The method of oxazolone, including by skeleton nickel and 5-Nitro-2-benzimidazolinone and absolute ethyl alcohol according to certain mass ratio, be added to anti-
In answering kettle, reaction condition：Temperature is 80-120 DEG C, pressure is 1.0-6.0MPa, and the reaction time is 4-15 hours, takes out filtrate,
After removing catalyst, filter cake vacuum drying is obtained 5-Amino-2-benzimidazolinone by filtrate decompression distillation and concentration, suction filtration.The present invention
Advantage be process is simple, operation is easy, low cost, and product yield is that 89.0-94.0%, purity are 97.0-99.8%, is produced
Raw " three wastes " are few, and the pollution to environment is small.
Fine chemistry industry（2007,24（8）：829~832）Using skeleton nickel reduction 5-Nitro-2-benzimidazolinone synthesis 5- amino
Benzimidazolone, catalyst amount is 1.3-1.4%, and reaction temperature is 90-95 DEG C, and reaction pressure is 2-3MPa, and the reaction time is
8-15h, reaction solution is that concentration is the ethanol solution of 120mL/mol5- nitrobenzimidazole ketone, with this understanding, product yield
It is 90%, mass fraction of product is more than 99%.
However, tradition Raney Ni are selectively poor, more accessory substance is produced, and easily inactivate, it is impossible to continuous behaviour
Make；The presence of accessory substance will influence directly using for 5-Amino-2-benzimidazolinone, need to increase multiple refined, separation processes to remove
These impurity, therefore increase industrial cost.How catalysis activity, extension catalyst life, popularization environment friend are improved
The commercial Application of good Catalytic Hydrogenation Techniques, is urgent problem.
The content of the invention
It is an object of the invention to provide it is a kind of clean, efficiently, catalyst activity is high and long service life, hydrogenation conversion
High, selectivity 5-Nitro-2-benzimidazolinone Hydrogenation high for 5-Amino-2-benzimidazolinone method.
To realize object defined above, the invention provides a kind of method for preparing 5-Amino-2-benzimidazolinone, wherein, the method
Including：In the presence of nickel base amorphous alloy catalyst, 5-Nitro-2-benzimidazolinone is contacted with hydrogen-containing gas, from after contact
5-Amino-2-benzimidazolinone is isolated in mixture.
The method of the present invention, 5-Nitro-2-benzimidazolinone high conversion rate, 5-Amino-2-benzimidazolinone selectivity is high, 5- nitros
The conversion ratio of benzimidazolone can reach more than 99.5%, and the selectivity of 5-Amino-2-benzimidazolinone is more than 98.0%, and
And it is environment-friendly, with good prospects for commercial application.
Compared with prior art, 5-Nitro-2-benzimidazolinone Hydrogenation of the invention for 5-Amino-2-benzimidazolinone method
Have a clear superiority：Product can be easily separated with catalyst system, and good product purity, target product selectivity is high.And catalyst
Can apply mechanically and reclaim and use, reduce product cost, and the method for the present invention does not produce harmful side product, it is waste gas, useless
Liquid discharge capacity is few, environment-friendly.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of method for preparing 5-Amino-2-benzimidazolinone, wherein, the method includes：Nickel-base amorphous
In the presence of alloy catalyst, by 5-Nitro-2-benzimidazolinoneConnect with hydrogen-containing gas
Touch, 5-Amino-2-benzimidazolinone is isolated from the mixture after contact
The method for preparing 5-Amino-2-benzimidazolinone of the invention, preferably described nickel base amorphous alloy catalyst is
Amorphous Ni-Al-M catalyst, M is other metallic elements.So can further improve turning for 5-Nitro-2-benzimidazolinone
The selectivity of rate and 5-Amino-2-benzimidazolinone.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the hydrogen-containing gas can be the gas containing hydrogen
Body or other hydrogeneous gases, for the present invention, preferably described hydrogen-containing gas are hydrogen.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, preferably on the basis of total catalyst weight, Ni, Al
Weight ratio and M between is 1-200:0.5-30:1, preferably 5-60:1-10:1.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, preferably described M is selected from I B races, II B races, III B
One or more in VIII race's metal of race, IV B races, VI B races, VII B races and non-nickel, specifically the M be selected from titanium, cobalt, molybdenum,
One or more in cerium, zirconium, chromium, manganese, iron, platinum, copper, ruthenium and palladium.So can further improve 5-Nitro-2-benzimidazolinone
Conversion ratio and 5-Amino-2-benzimidazolinone selectivity.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, preferably described M is titanium.So can further carry
The conversion ratio of 5-Nitro-2-benzimidazolinone high and the selectivity of 5-Amino-2-benzimidazolinone.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the preparation of the nickel base amorphous alloy catalyst
Method can be the customary preparation methods of this area, can use any one existing side for preparing amorphous alloy catalyst
It is prepared by method.For the present invention, preferably described nickel base amorphous alloy catalyst can be prepared as follows：By nickel, aluminium and
Metal M and the alloy heating melting of aluminium composition, are solidified fused mass with the cooldown rate of >=1000 DEG C/S, afterwards, use aqueous slkali
Alloy to solidifying is stripped dealuminzation.Wherein, on the basis of catalyst weight, the consumption of each component and the extracting make finally
Weight ratio in catalyst between Ni, Al and M is 1-200:0.5-30:1, preferably 5-60:1-10:1.Meanwhile, according to amorphous
The usual requirement that state alloy catalyst is used, after alkali density dealuminzation, also uses the step of distilling water washing including catalyst, passes through
The cleaning solution of the washing control discharge is washed with ethanol and preserved in ethanol afterwards to neutrality.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, when the M is titanium, preferably described Ni-based amorphous
State alloy catalyst is prepared as follows：Ni-Al amorphous alloys are contacted with the solution of titanium-containing compound.Can so carry
The activity of high catalyst.
In the present invention, the Ni-Al amorphous alloys are by by Ni-Al alloy moltens and then chilling, then using alkali density
Ni-Al amorphous alloys remove the aluminium in alloy, obtain the amorphous state Ni-Al alloy catalysts of chilling.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, preferably by Ni-Al amorphous alloys and containing titanizing
The condition of polymer solution contact includes：Temperature is 20-100 DEG C, preferably 30-80 DEG C.The activity of catalyst can so be improved.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, more preferably by Ni-Al amorphous alloys and titaniferous
The condition of compound solution contact also includes：The time of contact is 5-120min, preferably 20-100min.Can so improve and urge
The activity of agent.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, more preferably by Ni-Al amorphous alloys and titaniferous
The condition of compound solution contact also includes：Titanium tetrachloride is 0.001-1 with the weight ratio of Ni-Al amorphous alloys:1, preferably
It is 0.002-2:1, more preferably 0.01-0.5:1.The activity of catalyst can so be improved.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, more preferably by Ni-Al amorphous alloys and titaniferous
The condition of the solution contact of compound also includes：The concentration of titanium-containing compound is 10-30 weight % in titanium-containing compound solution, excellent
Elect 20 weight % as.So can further improve the activity of the catalyst for preparing.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, more preferably by Ni-Al amorphous alloys and titaniferous
The condition of compound solution contact also includes：The consumption of titanium-containing compound solution did not had the Ni-Al amorphous alloys at least, excellent
It is 1-10 with the volume ratio of the Ni-Al amorphous alloys to select titanium-containing compound solution:1.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the optional scope of the species of the titanium-containing compound
Wider, inorganic titanium-containing compound or organic titanium-containing compound may be incorporated for the present invention, preferably described containing titanizing for the present invention
Compound is one or more in titanium tetrachloride, tetraethyl titanate and butyl titanate.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the preferably solvent in titanium-containing compound solution are water
And/or alcohol, it is of the invention it is a kind of preferred embodiment, when titanium-containing compound is titanium tetrachloride, titanium-containing compound it is molten
Solvent in liquid is water；When titanium-containing compound is tetraethyl titanate and/or butyl titanate, the solvent in the solution of titanium-containing compound is
Alcohol.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, preferably described alcohol is the alcohol of C1-C10, more preferably
It is the alcohol of C1-C5, more preferably one or more in methyl alcohol, ethanol and isopropanol, particularly preferably ethanol and/or different
Propyl alcohol.So can further improve the activity of catalyst.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the condition of preferably described contact includes：Temperature is
50-250 DEG C, preferably 70-160 DEG C.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the condition of preferably described contact also includes：Contact
Pressure be 0.1-15MPa, most preferably preferably 0.3-8.0MPa, 2-5MPa.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the condition of preferably described contact also includes：Catalysis
Agent concentration is 0.01-20 weight %.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the condition of preferably described contact also includes：Stop
Time is 1-500min, preferably 60-300min.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, preferably described contact is carried out in the presence of solvent,
So can further improve the mixability between each reactant in reaction system, enhanced dispersion and more easily to reaction
Severe degree be adjusted.Under preferable case, the solvent is selected from the fatty alcohol with 1-2 carbon atom and individual with 4-6
One or more in the aliphatic hydrocarbon of carbon atom, preferably methyl alcohol and/or ethanol.
The method for preparing 5-Amino-2-benzimidazolinone of the invention, the consumption of the solvent is not particularly limited, can
Think conventional selection.Usually, the solvent and the mass ratio of 5-Nitro-2-benzimidazolinone are 0.5-10:1, preferably 1-6:1.
In the present invention, the contact can be carried out in existing various reactors, shape of the present invention to the reactor
Formula has no particular limits, wherein, the example of the reactor is included but is not limited to：Fixed bed reactors, paste state bed reactor,
Tank reactor and fluidized-bed reactor, preferably tank reactor or fluidized-bed reactor.Wherein, the fluidized-bed reactor
Can be plunger flow reactor, bubbling style reactor or magnetically stabilized bed reactor etc..The tank reactor can be batch still
Formula reactor.
In the present invention, paste state bed reactor refers to well known to those of ordinary skill in the art to hang solid particle catalyst
Float over the reaction vessel in reaction liquid material, such as mechanical stirring kettle, Gas Stirring kettle and make solid catalysis by liquid flowing
Agent is suspended in the liquid phase suspension bed reactor in reaction vessel, and paste state bed reactor can be single reactor, or two
To the reactor of multiple serial or parallel connections.
The invention will be further described for following examples, but and is not so limited the scope of the present invention.
In following examples and comparative example, if not otherwise specified, used reagent is commercially available reagent.
In following examples and comparative example, if not otherwise specified, pressure is gauge pressure.
In following examples and comparative example, the composition of the liquid phase mixture obtained using liquid chromatography for measuring reaction is led to
Overcorrect normalization method is quantified, and sample is analyzed using liquid chromatography：
HPLC chromatogram condition is as follows：
Chromatographic column：ODS-2C18（150mm×4.6mm）；
Mobile phase：10mmol ammonium acetate solutions：Methyl alcohol=60:40；
Column temperature：35℃
Wavelength：240nm
Sample size：5uL
The conversion ratio of 5-Nitro-2-benzimidazolinone and the selectivity of 5-Amino-2-benzimidazolinone are calculated using below equation.
Prepare embodiment 1
1.5kg nickel and 1.5kg aluminium are added in graphite crucible, it is heated to melting in coreless induction furnace, then this melts
Melt liquid to be sprayed onto from crucible nozzle on the copper roller that a rotating speed is 600 revs/min, cooling water is led in copper roller, aluminium alloy is with 1000 DEG C/s
Cooling velocity quickly thrown away along copper roller tangent line after cooling, form flakey band, flakey band is ground to particle diameter
It is less than 70 microns, obtains foundry alloy.50g foundry alloys are slowly added into and fill 500 grams of 20wt% sodium hydrate aqueous solutions
In there-necked flask, it is that 80 DEG C and constant temperature are stirred 1 hour to control its temperature.After stopping heating and stirring, liquid is filtered off, with 100 DEG C
Distillation water washing to pH value is 10；
It is 20% that the 20.0g Ni-Al alloys of above-mentioned preparation are added into 30mL titanium tetrachlorides concentration at 50 DEG C（Weight）'s
Stirred in titanium tetrachloride aqueous solution, after reaction 60min, it is 7 or so to be washed with distilled water to pH value, and catalyst composition is shown in Table 1.
Prepare embodiment 2
1.5kg nickel and 1.5kg aluminium are added in graphite crucible, it is heated to melting in coreless induction furnace, then this melts
Melt liquid to be sprayed onto from crucible nozzle on the copper roller that a rotating speed is 1000 revs/min, cooling water is led in copper roller, aluminium alloy is with 1000 DEG C/s
Cooling velocity quickly thrown away along copper roller tangent line after cooling, form flakey band, flakey band is ground to particle diameter
It is less than 70 microns, obtains foundry alloy.50g foundry alloys are slowly added into and fill 500 grams of 20wt% sodium hydrate aqueous solutions
In there-necked flask, it is that 80 DEG C and constant temperature are stirred 1 hour to control its temperature.After stopping heating and stirring, liquid is filtered off, with 100 DEG C
Distillation water washing to pH value is 10；
At 50 DEG C, 25mL titanium tetrachlorides are added in the 20.0g Ni-Al alloys in the state of stirring to above-mentioned preparation
Concentration is 20%（Weight）Titanium tetrachloride aqueous solution in stir, after reaction 60min, be washed with distilled water to pH value for 7 or so.
Catalyst composition is shown in Table 1.
Prepare embodiment 3
1.5kg nickel and 1.5kg aluminium are added in graphite crucible, it is heated to melting in coreless induction furnace, then this melts
Melt liquid to be sprayed onto from crucible nozzle on the copper roller that a rotating speed is 800 revs/min, cooling water is led in copper roller, aluminium alloy is with 1000 DEG C/s
Cooling velocity quickly thrown away along copper roller tangent line after cooling, form flakey band, flakey band is ground to particle diameter
It is less than 70 microns, obtains foundry alloy.50g foundry alloys are slowly added into and fill 500 grams of 20wt% sodium hydrate aqueous solutions
In there-necked flask, it is that 80 DEG C and constant temperature are stirred 1 hour to control its temperature.After stopping heating and stirring, liquid is filtered off, with 100 DEG C
Distillation water washing to pH value is 10；
It is 20% that the 20.0g Ni-Al alloys of above-mentioned preparation are added into 60mL titanium tetrachlorides concentration at 50 DEG C（Weight）Water
Stirred in solution, after reaction 60min, it is 7 or so to be washed with distilled water to pH value.Catalyst composition is shown in Table 1.
Prepare embodiment 4
1.5kg nickel and 1.5kg aluminium are added in graphite crucible, it is heated to melting in coreless induction furnace, then will be molten
Melt liquid and pour into natural cooling in graphite crucible, it is less than 70 microns to particle diameter that bulk alloy is ground, obtains foundry alloy.Will
50g foundry alloys are slowly added into filling the there-necked flask that 500 grams of concentration are 20wt% sodium hydrate aqueous solutions, control its temperature to be
80 DEG C and constant temperature are stirred 1 hour.After stopping heating and stirring, liquid is filtered off, be 10 with 100 DEG C of distillation water washings to pH value；
It is 20% that the 20.0g Ni-Al alloys of above-mentioned preparation are added into 60mL titanium tetrachlorides concentration at normal temperatures（Weight）Four
Stirred in the aqueous solution of titanium chloride, after reaction 60min, it is 7 or so to be washed with distilled water to pH value.Catalyst composition is shown in Table 1.
Prepare embodiment 5
By 1.5kg nickel, 1.0kg aluminium and 1kg Ti10Al90Alloy is added in graphite crucible, and it is heated in coreless induction furnace
To melting, then the fused solution is sprayed onto on the copper roller that rotating speed is 1000/ point from crucible nozzle, and cooling water, alloy are led in copper roller
Liquid forms flakey band to be thrown away along copper roller tangent line after the cooling velocity of 1000 DEG C/s quickly cooling, and flakey band is through grinding
Particle diameter is milled to for less than 70 microns, foundry alloy is obtained.50g foundry alloys are slowly added into and fill 500 grams of concentration for 20 weights
Measure in the there-necked flask of % sodium hydrate aqueous solutions, it is that 80 DEG C and constant temperature are stirred 1 hour to control its temperature.Stop heating and stir
Afterwards, liquid is filtered off, is 7 with 100 DEG C of distillation water washings to pH value, obtain Ni-Al-Ti amorphous alloys, composition is shown in Table 1.
Prepare embodiment 6
1.5kg nickel, 1.0kg aluminium, 0.05kgFe and 0.1kg Cr are added in graphite crucible, it is added in coreless induction furnace
To melting, then the fused solution is sprayed onto on the copper roller that rotating speed is 1000 revs/min heat from crucible nozzle, and cooling water is led in copper roller,
Aluminium alloy forms flakey band, flakey band to be thrown away along copper roller tangent line after the cooling velocity of 1000 DEG C/s quickly cooling
Ground is less than 70 microns to particle diameter, obtains foundry alloy.50g foundry alloys are slowly added into and are filled 500 grams of concentration and is
In the there-necked flask of 20 weight % sodium hydrate aqueous solutions, it is that 80 DEG C and constant temperature are stirred 1 hour to control its temperature.Stop heating and stir
After mixing, liquid is filtered off, be 7 with 100 DEG C of distillation water washings to pH value, obtain Ni-Al-Fe-Cr amorphous alloys, composition is shown in Table
1。
Prepare embodiment 7
By 1.5kg nickel, 1.0kg aluminium and 1kg Mo10Al90Alloy is added in graphite crucible, and it is heated in coreless induction furnace
To melting, then the fused solution is sprayed onto on the copper roller that rotating speed is 1000 revs/min from crucible nozzle, and cooling water is led in copper roller, is closed
Golden liquid forms flakey band, flakey band warp to be thrown away along copper roller tangent line after the cooling velocity of 1000 DEG C/s quickly cooling
Particle diameter is ground to for less than 70 microns, foundry alloy is obtained.It is 20 50g foundry alloys to be slowly added into and fills 500 grams of concentration
In the there-necked flask of weight % sodium hydrate aqueous solutions, it is that 80 DEG C and constant temperature are stirred 1 hour to control its temperature.Stop heating and stir
Afterwards, liquid is filtered off, is 7 with 100 DEG C of distillation water washings to pH value, obtain Ni-Al-Mo amorphous alloys, composition is shown in Table 1.
Prepare embodiment 8
1.5kg nickel, 1.0kg aluminium and 0.04kg iron are added in graphite crucible, it are heated to melting in coreless induction furnace,
Then the fused solution is sprayed onto on the copper roller that rotating speed is 1000 revs/min from crucible nozzle, in copper roller lead to cooling water, aluminium alloy with
The cooling velocity of 1000 DEG C/s throws away after quickly cooling down along copper roller tangent line, forms flakey band, and flakey band is ground extremely
Particle diameter is less than 70 microns, obtains foundry alloy.50g foundry alloys are slowly added into and fill 500 grams of concentration for 20 weight %
Sodium hydrate aqueous solution there-necked flask in, control its temperature to be stirred 1 hours for 80 DEG C and constant temperature.After stopping heating and stirring,
Liquid is filtered off, is 7 with 100 DEG C of distillation water washings to pH value, obtain Ni-Al-Fe amorphous alloys, composition is shown in Table 1.
Table 1
| Prepare embodiment | Catalyst constitutes * |
| 1 | |
| 2 | |
| 3 | |
| 4 | |
| 5 | |
| 6 | |
| 7 | |
| 8 |
* subscript represents the weight percentage of metal.
Embodiment 1-8
In 500mL autoclaves, 60g5- nitrobenzimidazole ketone, 300mL absolute ethyl alcohols, 2g amorphous alloy nickels are added
Catalyst（From the catalyst for preparing embodiment 1-8）, sealing autoclave, with 1MPa hydrogen replace three times, be then charged with hydrogen
Gas makes hydrogen pressure（Hydrogen Vapor Pressure）To 2.0Ma.Under 600rpm stirrings, in 4h is reacted at 90 DEG C, catalyst is isolated in release, is used
Liquid chromatograph assay products, reaction result is shown in Table 2.
Table 2
| Embodiment | Catalyst source | Conversion ratio, % | Selectivity, % |
| 1 | Prepare embodiment 1 | 100 | 99.4 |
| 2 | Prepare embodiment 2 | 100 | 99.2 |
| 3 | Prepare embodiment 3 | 100 | 99.1 |
| 4 | Prepare embodiment 4 | 98.2 | 97.3 |
| 5 | Prepare embodiment 5 | 100 | 98.9 |
| 6 | Prepare embodiment 6 | 95.4 | 96.5 |
| 7 | Prepare embodiment 7 | 94.5 | 94.3 |
| 8 | Prepare embodiment 8 | 95.3 | 95.4 |
Embodiment 9
In 500mL autoclaves, 60g5- nitrobenzimidazole ketone, 300mL absolute ethyl alcohols, 2g amorphous alloy nickels are added
Catalyst, catalyst composition is Ni84Ti5.7Al10.3（It is prepared by the method according to embodiment 5 is prepared）, sealing autoclave uses 1MPa
Hydrogen is replaced three times, and being then charged with hydrogen makes hydrogen be depressed into 4.0Ma.Under 600rpm stirrings, in 3h is reacted at 90 DEG C, release is separated
Go out catalyst, using liquid chromatograph assay products, reaction result is shown in Table 3.
Embodiment 10
In 500mL autoclaves, 60g5- nitrobenzimidazole ketone, 300mL absolute ethyl alcohols, 2g amorphous alloy nickels are added
Catalyst, catalyst composition is Ni84Ti5.7Al10.3（It is prepared by the method according to embodiment 5 is prepared）, sealing autoclave uses 1MPa
Hydrogen is replaced three times, and being then charged with hydrogen makes hydrogen be depressed into 2.0Ma.Under 600rpm stirrings, in 3h is reacted at 110 DEG C, release divides
Catalyst is separated out, using liquid chromatograph assay products, reaction result is shown in Table 3.
Embodiment 11
In 500mL autoclaves, 60g5- nitrobenzimidazole ketone, 300mL absolute ethyl alcohols, 2g amorphous alloy nickels are added
Catalyst, catalyst composition is Ni84Ti5.7Al10.3（It is prepared by the method according to embodiment 5 is prepared）And sealing autoclave, use 1MPa
Hydrogen is replaced three times, and being then charged with hydrogen makes hydrogen be depressed into 2.0Ma.Under 600rpm stirrings, in 3h is reacted at 160 DEG C, release divides
Catalyst is separated out, using liquid chromatograph assay products, reaction result is shown in Table 3.
Embodiment 12
In 500mL autoclaves, 60g5- nitrobenzimidazole ketone, 300mL hexamethylenes, 2g amorphous alloy nickels is added to urge
Agent, catalyst composition is Ni84Ti5.7Al10.3（It is prepared by the method according to embodiment 5 is prepared）And sealing autoclave, use 1MPa hydrogen
Gas is replaced three times, and being then charged with hydrogen makes hydrogen be depressed into 2.0Ma.Under 600rpm stirrings, in 4h is reacted at 160 DEG C, release is separated
Go out catalyst, using liquid chromatograph assay products, reaction result is shown in Table 3.
Table 3
| Embodiment | Conversion ratio, % | Selectivity, % |
| 9 | 100 | 99.2 |
| 10 | 100 | 99.1 |
| 11 | 100 | 93.2 |
| 12 | 93.2 | 93.1 |
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to demetalization scope of the invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (8)
1. a kind of method for preparing 5-Amino-2-benzimidazolinone, it is characterised in that the method includes：Urged in nickel base amorphous alloy
In the presence of agent, 5-Nitro-2-benzimidazolinone is contacted with hydrogen-containing gas, 5- aminobenzenes are isolated from the mixture after contact
And imidazolone；
Wherein, the nickel base amorphous alloy catalyst is amorphous Ni-Al-M catalyst；
The M is titanium, and the nickel base amorphous alloy catalyst is prepared as follows：By Ni-Al amorphous alloys and titaniferous
Compound solution is contacted.
2. method according to claim 1, wherein, on the basis of total catalyst weight, the weight ratio between Ni, Al and M
It is 1-200:0.5-30:1.
3. method according to claim 1, wherein, the titanium-containing compound is titanium tetrachloride, tetraethyl titanate and metatitanic acid fourth
One or more in ester, the solvent in titanium-containing compound solution is alcohol and/or water.
4. method according to claim 1, wherein, the bar that Ni-Al amorphous alloys are contacted with titanium-containing compound solution
Part includes：Temperature is 20-100 DEG C, and the time is 5-120min, and titanium-containing compound is with the weight ratio of Ni-Al amorphous alloys
0.001-1:1；The consumption of titanium-containing compound solution did not had the Ni-Al amorphous alloys at least, contained in titanium-containing compound solution
The concentration of titanium compound is 10-30 weight %.
5. method according to claim 3, wherein, when titanium-containing compound is titanium tetrachloride, in the solution of titanium-containing compound
Solvent be water；When titanium-containing compound is tetraethyl titanate and/or butyl titanate, the solvent in the solution of titanium-containing compound is ethanol
With/isopropanol.
6. method according to claim 1, wherein, the condition bag that 5-Nitro-2-benzimidazolinone is contacted with hydrogen-containing gas
Include：Temperature is 50-250 DEG C, and Hydrogen Vapor Pressure is 0.1-15MPa, and catalyst concn is 0.01-20 weight %, and the residence time is 1-
500min。
7. method according to claim 1, wherein, it is described that 5-Nitro-2-benzimidazolinone is contacted in solvent with hydrogen-containing gas
In the presence of carry out, the mass ratio of the solvent and 5-Nitro-2-benzimidazolinone is 0.5-10:1.
8. method according to claim 7, wherein, the solvent is selected from the fatty alcohol with 1-2 carbon atom and has
One or more in the 4-6 aliphatic hydrocarbon of carbon atom.
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| Ni-Zr-Al基非晶态合金催化剂的苯加氢催化性能;张国胜等;《催化学报》;20001231;第21卷(第1期);第67-70页 * |
| 以骨架镍为催化剂由5-硝基苯并咪唑酮制备5-氨基苯并咪唑酮;谭川江等;《精细化工》;20071231;第24卷(第8期);第829-832页 * |
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