CN106540698A - A kind of preparation method of the loading type nickel-based catalyst of chloronitrobenzene selective hydrogenation synthesis chloro aminobenzen - Google Patents
A kind of preparation method of the loading type nickel-based catalyst of chloronitrobenzene selective hydrogenation synthesis chloro aminobenzen Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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Abstract
A kind of preparation method of the loading type nickel-based catalyst of chloronitrobenzene selective hydrogenation synthesis chloro aminobenzen, will be added in solvent with nickel salt after carrier calcination first and is mixed, and after the lower heating of stirring, Deca precipitant obtains suspension to pH=6～12；Filter after the suspension static burn in that step (1) is obtained, wash to filtrate in neutrality, after being dried, 2～6h of roasting at 200～800 DEG C, obtains catalyst precursor in atmosphere；Catalyst precursor is being passed through into H2With N2Under the conditions of gaseous mixture or H2Under the conditions of reduce, reduction temperature be 200～800 DEG C, the recovery time be 0.5～4h, obtain for chloronitrobenzene selective hydrogenation synthesize chloro aminobenzen it is nickel catalyst carried.The catalyst has low production cost, preparation process is simple, and short preparation period pollutes little, and the reactivity worth with good chloronitrobenzene hydrogenation synthesis chloro aminobenzen, and dechlorination is low.
Description
Technical field
The present invention relates to a kind of catalyst, and in particular to a kind of chloronitrobenzene selective hydrogenation synthesizes the negative of chloro aminobenzen
The preparation method of load type nickel-base catalyst, the catalyst are particularly well-suited to the reaction of chloronitrobenzene hydrogenation synthesis chloro aminobenzen.
Background technology
The hydrogenation products chloro aminobenzen of chloronitrobenzene is the important organic intermediate of a class, in medicine, pesticide, and dyestuff,
Occupy critical role in the synthesis of the fine chemical products such as pigment.The technique of commercial synthesis chloro aminobenzen is a lot, but most
Chloro aminobenzen is obtained via chloronitrobenzene reduction, and this causes chloronitrobenzene reduction to prepare chloro aminobenzen becomes a class weight
The organic synthesiss unit process wanted.At present, iron powder reducing, akali sulphide or hydrazine hydrate reduction, sulfonation ammonolysis are mainly adopted in industry
Chloro aminobenzen is synthesized by chloronitrobenzene with the several method such as liquid phase catalytic hydrogenation.Wherein, using iron powder, akali sulphide or hydrazine hydrate
Deng reduction reaction route there is many long flow path, the three wastes, poor product quality, severe operational environment the shortcomings of.Using sulfonation ammonolysis
Rule needs to add mercury salt targeting agent, also easily causes the pollution to environment.By contrast, liquid phase catalytic hydrogenation reducing process be compared with
For the green production process of cleaning, the application prospect with good sustainable development.
In the technical process that chloronitrobenzene liquid phase catalytic hydrogenation synthesizes chloro aminobenzen, not only need to ensure reactant tool
There is higher conversion ratio, while it is also noted that suppressing the generation of the side reaction such as dechlorination on phenyl ring, it is ensured that target product has higher
Selectivity, therefore design and prepare the key that a kind of suitable catalyst is hydrogenation reaction.At present, study and using more
Noble metal catalyst that hydrogenation catalyst is mainly loaded with inorganic carrier or macromolecular compound (J Mol Catal, 2009,
310:144-149；Catalysis Communications,2007,8:1999–2006；Journal of Catalysis,
2011,218:1-7 etc.) and amorphous alloy catalyst (Chin.J.Catal., 2012,33:1883–1888；
Chin.J.Catal.,2006,27(2):119-123 etc.), but as noble metal is easily inactivated, high cost, it is difficult to realize industry
Change.Although amorphous alloy catalyst is also needed with higher activity, its heat stability of new catalysis material a kind of
Further to improve.Supported non-precious metal catalyst such as load-type nickel, Co catalysts etc. have preferable catalysis activity, are urging
Change the aspects such as reformation, methanation and catalytic hydrogenation and all there is relatively broad application.
Patent of invention CN1762588A adopts Ni/SiO2,Ni/TiO2,Ni/ZrO2Catalyst, is 80 DEG C in reaction temperature,
During pressure 1.0Mpa, o-chloronitrobenzene conversion ratio is up to 99.9%, and o-chloraniline selectivity is up to 96.6～99.1%.
With methanol as solvent, attapulgite is carrier to patent of invention CN101745382A, and Pt is active component in reaction temperature
Spend for 40～100 DEG C, 2～3Mpa of pressure obtains the selectivity of the conversion ratio and parachloroanilinum of parachloronitrobenzene and reaches 100%
Patent of invention CN101020136A reports the preparation method of nanometer carbon material supported metal catalyst and its in chlorine
Synthesize the application in chloro aminobenzen reaction for hydrogenation of chloronitrobenzene.In 140 DEG C of reaction temperature, pressure 2Mpa, response time 150min,
Up to 99%, the selectivity of o-chloraniline has reached 98% to the conversion ratio of o-chloronitrobenzene.
Carbon nanotube carried metal Pt and Pd catalyst is applied to chloronitrobenzene hydrogenation by patent of invention CN1506348A
In the reaction of synthesis chloro aminobenzen, at 80 DEG C, under the reaction condition of 1.0Mpa, dechlorination rate is less than 0.1%, and the yield of product exceedes
99%.Liu etc. is prepared for the Pt catalyst of PU loads and studies o-chloronitrobenzene hydrogenation reaction, is as a result displayed in PU/Pt catalysis
In agent, o-chloronitrobenzene can be converted at room temperature completely, and the selectivity of o-chloraniline has reached 99.5% (J Colloid
Interface Sci, 2014,424：44-48)
Some problems present in current these synthetic methods：Although the noble metal such as Pt, Pd hydrogenation activity is high, be conducive to chlorine
For nitrobenzene hydrogenation, but which is expensive, and the characteristic for being not easily recycled and being easy to inactivate is unfavorable for commercial Application, base metal
Catalyst has preferable catalysis activity, and cost is relatively low, with good industrial application value.
The content of the invention
It is an object of the invention to provide a kind of method is simple, the chloro of short preparation period and with low cost, excellent performance
The preparation method of the loading type nickel-based catalyst of Nitrobenzol selective hydrogenation synthesis chloro aminobenzen, process is simple, beneficial to industrialization.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of nickel catalyst carried preparation method for chloronitrobenzene selective hydrogenation, comprises the following steps：
(1) will be added in solvent with nickel salt after carrier calcination first and mix, stirring is lower heat after Deca precipitant to pH
=6～12, obtain suspension；
(2) filter after the suspension static burn in for obtaining step (1), wash to filtrate in neutrality, after being dried, in air
In at 200～800 DEG C 2～6h of roasting, obtain catalyst precursor；
(3) catalyst precursor is being passed through into H2With N2Under the conditions of gaseous mixture or H2Under the conditions of reduce, reduction temperature is 200
～800 DEG C, the recovery time is 0.5～4h, obtains synthesizing the load-type nickel of chloro aminobenzen for chloronitrobenzene selective hydrogenation
Catalyst.
The present invention is further improved by, and in the step (1), carrier is aluminium sesquioxide, titanium dioxide, titanium dioxide
One or more in zirconium, silicon dioxide, magnesium oxide, ferrum oxide；The nickel salt is nickel nitrate, nickel acetate, Nickel dichloride., nickel sulfate
In one or more；Solvent is deionized water, dehydrated alcohol, one or more in ethylene glycol.
The present invention is further improved by, and in the step (1), the sintering temperature of carrier is 200～800 DEG C, during roasting
Between be 2～6h.
The present invention is further improved by, and in the step (1), carrier and the amount ratio of the material of nickel salt are 10:1；Carrier
Ratio with solvent is 2g:(10～100) mL.
The present invention is further improved by, and the temperature of heating is 60～130 DEG C in the step (1), and the time is 10～
80min。
The present invention is further improved by, and in the step (1), precipitant is sodium carbonate liquor, sal volatile, hydrogen
One or more in sodium hydroxide solution, urea liquid, ammonia.
The present invention is further improved by, and the sodium carbonate liquor, sal volatile, sodium hydroxide solution, carbamide are molten
The concentration of liquid is 0.1～1mol/L, and the concentration of ammonia is 0.2～2mol/L.
The present invention is further improved by, and in the step (2), the temperature of static burn in is 25～100 DEG C, and the time is 2
～10h；Dry temperature is 60～120 DEG C, and drying time is 12～24h.
The present invention is further improved by, and in the step (3), shielding gas is H2When, it is passed through H2Flow velocity be 10～
80mL/min；Shielding gas is H2With N2Gaseous mixture when, mixed gas flow velocity be 10～100mL/min, wherein H2Account for mixed gas
Volume ratio be 10～80%.
Prepared by the method nickel catalyst carried, can be used for the preparation of chloronitrobenzene class compound selective catalytic hydrogenation
Chloro aminobenzen, wherein：10%-40% of the consumption of catalyst for chloronitrobenzene compound quality, reacts by mass percentage
Pressure is 1～3MPa, and reaction temperature is 50～150 DEG C, 0.5～5h of response time.
Compared with prior art, the device have the advantages that：The present invention is adopted by adopting nickel salts for raw material
Precipitate prepared by deposition-precipitation method is changed into corresponding catalytic materials presoma Jing after filtration, dry, roasting, Jing after hydrogen reducing
Obtain for the nickel catalyst carried of chloronitrobenzene class compound selective catalytic hydrogenation, the catalyst has production cost
Low, preparation process is simple, short preparation period pollute little, and with good chloronitrobenzene hydrogenation synthesis chloro aminobenzen
Reactivity worth, dechlorination are low.Obtained in of the invention, catalyst is in use, be first passed through the load that hydrogen reducing obtains high dispersive
Type Raney nickel, is 1～3MPa then at pressure, and temperature is 0.5～5h of reaction under the conditions of 50～150 DEG C, obtains chloro aminobenzen, and
And the high conversion rate of chloronitrobenzene, up to 99.99%, chloro aminobenzen selectivity is up to 99.27%.The present invention adopts base metal
For raw material, cheap and easy to get, preparation method is simple, yield is big, overcomes the long flow path of traditional method presence, the three wastes are more, product matter
The problems such as measuring poor, severe operational environment, can cause chloronitrobenzene almost all to be converted into chloro under the conditions of relatively mild
Aniline.
Description of the drawings
Fig. 1 is the NiO/ γ-Al after 500 DEG C of roastings 4 hours2O3The SEM spectrum and TEM energy spectrum diagrams of catalyst precursor.Its
In, it is (a) SEM spectrum, is (b) TEM collection of illustrative plates.
Specific embodiment
With reference to embodiment, the invention will be further described, but it is not intended to limit protection scope of the present invention.
The present invention catalyst using deposition-precipitation method preparation, it is scrubbed and dry after, the Jing different temperatures in Muffle furnace
Roasting is obtained.
In the examples below that, conversion ratio and selectivity are defined by following formula.
Chloronitrobenzene conversion ratio (%)=100 × n chloronitrobenzenesfinal/ (n chloronitrobenzenesinitial- n chloro nitros
Benzenefinal)；
Chloro aminobenzen selectivity (%)=100 × n chloro aminobenzens/(n chloronitrobenzenesinitial- n chloronitrobenzenesfinal)；
Embodiment 1
For the nickel catalyst carried preparation method of chloronitrobenzene selective catalytic hydrogenation, comprise the following steps：
(1) first by γ-Al2O3The roasting 5h at 500 DEG C；
(2) γ-Al after 2g roastings are weighed2O3With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL second two
In alcohol, 90 DEG C under stirring, are warming up to, maintain 30min, the Na of 0.2mol/L is then added under stirring2CO3Aqueous solution is to pH
=9-10, obtains suspension.
Suspension filtered after static aging 2h at 25 DEG C, washed to filtrate in neutrality, 12h is dried at 120 DEG C, is ground
Honed 100 mesh sieve, obtains pressed powder；
(3) by the pressed powder for obtaining in air the roasting 4h at 400 DEG C, obtain catalyst precursor.
(4) the catalytic materials presoma of gained is placed in tubular heater, in the High Purity Hydrogen atmosphere that flow velocity is 20mL/min
Lower reduction, reduction temperature are 300 DEG C, and the recovery time is 1h, you can must be used for the load-type nickel of chloronitrobenzene selective hydrogenation
Catalysis, is labeled as Cat-1.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-1 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 2
Step (1)-(2) are with embodiment 1.
(3) by the pressed powder for obtaining at 500 DEG C roasting 4h, obtain catalytic materials presoma.
(4) the catalytic materials presoma of gained is placed in tubular heater, in the High Purity Hydrogen atmosphere that flow velocity is 20mL/min
Lower reduction, reduction temperature are 300 DEG C, and the recovery time is 1h, you can must be used for the load-type nickel of chloronitrobenzene selective hydrogenation
Catalyst, is labeled as Cat-2.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-2 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Fig. 1 (a) for 500 DEG C of roastings 4 hours after (i.e. embodiment 2) NiO/ γ-Al2O3The SEM figures of catalyst precursor
Spectrum.The SEM figures of observation sample, it can be seen that NiO particles are highly dispersed at the γ-Al of lamellar2O3On carrier.
Fig. 1 (b) for 500 DEG C of roastings 4 hours after (i.e. embodiment 2) NiO/ γ-Al2O3The TEM figures of catalyst precursor
Spectrum.By the TEM figures for observing sample, it can be seen that NiO/ γ-Al2O3Catalyst precursor granule spherical in shape, well dispersed, nothing
It is obvious to obtain agglomeration.
Embodiment 3
Step (1)-(2) are with embodiment 1.
(3) by the pressed powder for obtaining at 600 DEG C roasting 4h, obtain catalytic materials presoma.
(4) the catalytic materials presoma of gained is placed in tubular heater, in the High Purity Hydrogen atmosphere that flow velocity is 20mL/min
Lower reduction, reduction temperature are 300 DEG C, and the recovery time is 1h, you can must be used for the load-type nickel of chloronitrobenzene selective hydrogenation
Catalyst, is labeled as Cat-3.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-3 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 4
Step (1)-(3) are with embodiment 2.
(4) the catalytic materials presoma of gained is placed in tubular heater, in the High Purity Hydrogen atmosphere that flow velocity is 20mL/min
Lower reduction, reduction temperature are 200 DEG C, and the recovery time is 1h, you can must be used for the load-type nickel of chloronitrobenzene selective hydrogenation
Catalyst, is labeled as Cat-4.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-4 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 5
Step (1)-(3) are with embodiment 2.
(4) the catalytic materials presoma of gained is placed in tubular heater, in the High Purity Hydrogen atmosphere that flow velocity is 20mL/min
Lower reduction, reduction temperature are 400 DEG C, and the recovery time is 1h, you can must be used for the load-type nickel of chloronitrobenzene selective hydrogenation
Catalyst, is labeled as Cat-5.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-5 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 6
Step (1)-(3) are with embodiment 2.
(4) the catalytic materials presoma of gained is placed in tubular heater, in the High Purity Hydrogen atmosphere that flow velocity is 20mL/min
Lower reduction, reduction temperature are 500 DEG C, and the recovery time is 1h, you can must be used for the load-type nickel of chloronitrobenzene selective hydrogenation
Catalyst, is labeled as Cat-6.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-6 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 7
Step (1) is with embodiment 2.
(2) γ-Al after 2g roastings are weighed2O3With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL second two
In alcohol, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=7-
8, obtain suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.
To filter after suspension static aging 2h, wash to filtrate in neutrality, 12h is dried at 120 DEG C, it is ground
100 mesh sieves, obtain pressed powder；
Step (3) and (4) are with embodiment 2；Catalyst is labeled as Cat-7.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-7 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 8
Step (1) is with embodiment 2.
(2) γ-Al after 2g roastings are weighed2O3With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL second two
In alcohol, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=8-
9, obtain suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.
To filter after suspension static aging 2h, wash to filtrate in neutrality, 12h is dried at 120 DEG C, it is ground
100 mesh sieves, obtain pressed powder；
Step (3) and (4) are with embodiment 2；Catalyst is labeled as Cat-8.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-8 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 9
Step (1) is with embodiment 2.
(2) γ-Al after 2g roastings are weighed2O3With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL second two
In alcohol, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=
10-11, obtains suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.
To filter after suspension static aging 2h, wash to filtrate in neutrality, 12h is dried at 120 DEG C, it is ground
100 mesh sieves, obtain pressed powder；
Step (3) and (4) are with embodiment 2；Catalyst is labeled as Cat-9.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-9 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 10
Step (1) is with embodiment 1.
(2) γ-Al after 2g roastings are weighed2O3With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 100mL second two
In alcohol, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=9-
10, obtain suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.To filter after suspension static aging 2h, wash
Wash to filtrate in neutrality, 12h is dried at 120 DEG C, ground 100 mesh sieve obtains pressed powder；
Step (3) and (4) are with embodiment 1；Catalyst is labeled as Cat-10.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-10 catalyst, the anhydrous second of 20mL are pressed in 100 DEG C, hydrogen
Under conditions of alcohol, after reaction 120min, o-chloraniline is obtained.Reaction result is as shown in table 1.
Embodiment 11
Step (1) is with embodiment 2.
(2) γ-Al after 2g roastings are weighed2O3With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL second two
In alcohol, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=9-
10, obtain suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.To filter after suspension static aging 2h, wash
Wash to filtrate in neutrality, 24h is dried at 120 DEG C, ground 100 mesh sieve obtains pressed powder；
Step (3) (4) is with embodiment 2；Catalyst is labeled as Cat-11.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-11 catalyst, the anhydrous second of 20mL are pressed in 100 DEG C, hydrogen
Under conditions of alcohol, after reaction 120min, o-chloraniline is obtained.Reaction result is as shown in table 1.
Embodiment 12
Step (1)-(4) are with embodiment 2.
That is the application of catalyst is evaluated to above-mentioned catalyst：
3.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-2 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 13
Step (1)-(4) are with embodiment 2.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-2 catalyst, 20mL dehydrated alcohol are pressed in 80 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 14
Step (1)-(4) are with embodiment 2.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-2 catalyst, 20mL dehydrated alcohol are pressed in 120 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 15
Step (1)-(4) are with embodiment 2.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-2 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 60min, obtain o-chloraniline.Reaction result is as shown in table 1.
Embodiment 16
Step (1) is with embodiment 2.
(2) weigh the TiO after 2g roastings2With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL ethylene glycol
In, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=9-
10, obtain suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.
To filter after suspension static aging 2h, wash to filtrate in neutrality, 12h is dried at 120 DEG C, it is ground
100 mesh sieves, obtain pressed powder；
Step (3) and (4) are with embodiment 2；Catalyst is labeled as Cat-12.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-12 catalyst, the anhydrous second of 20mL are pressed in 100 DEG C, hydrogen
Under conditions of alcohol, after reaction 120min, o-chloraniline is obtained.Reaction result is as shown in table 1.
Embodiment 17
Step (1) is with embodiment 2.
(2) weigh the SiO after 2g roastings2With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL ethylene glycol
In, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=9-
10, obtain suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.
To filter after suspension static aging 2h, wash to filtrate in neutrality, 12h is dried at 120 DEG C, it is ground
100 mesh sieves, obtain pressed powder；
Step (3) and (4) are with embodiment 2；Catalyst is labeled as Cat-13.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-13 catalyst, the anhydrous second of 20mL are pressed in 100 DEG C, hydrogen
Under conditions of alcohol, after reaction 120min, o-chloraniline is obtained.Reaction result is as shown in table 1.
Embodiment 18
Step (1) is with embodiment 2.
(2) weigh the ZrO after 2g roastings2With 0.9908g nickel nitrates (Ni (NO3)2·6H2O) it is added to 50mL ethylene glycol
In, stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is to pH=9-
10, obtain suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.
To filter after suspension static aging 2h, wash to filtrate in neutrality, 12h is dried at 120 DEG C, it is ground
100 mesh sieves, obtain pressed powder；
Step (3) and (4) are with embodiment 2；Catalyst is labeled as Cat-14.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.2000g Cat-14 catalyst, the anhydrous second of 20mL are pressed in 100 DEG C, hydrogen
Under conditions of alcohol, after reaction 120min, o-chloraniline is obtained.Reaction result is as shown in table 1.
Embodiment 19
Step (1) is with embodiment 2.
(2) MgO the and 0.9908g nickel nitrates (Ni (NO after 2g roastings are weighed3)2·6H2O) it is added in 50mL ethylene glycol,
Stirring is warming up to 90 DEG C, maintains 30min, the Na of 0.2mol/L is added dropwise under stirring2CO3Aqueous solution is obtained to pH=9-10
To suspension；Wherein, Na2CO3The rate of addition of aqueous solution is 5mL/min.
To filter after suspension static aging 2h, wash to filtrate in neutrality, 12h is dried at 120 DEG C, it is ground
100 mesh sieves, obtain pressed powder；
Step (3) and (4) are with embodiment 2；Catalyst is labeled as Cat-15.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g o-chloronitrobenzene, 0.4000g Cat-15 catalyst, the anhydrous second of 20mL are pressed in 100 DEG C, hydrogen
Under conditions of alcohol, after reaction 120min, o-chloraniline is obtained.Reaction result is as shown in table 1.
The selective data of the conversion ratio and o-chloraniline of 1 o-chloronitrobenzene of table
As it can be seen from table 1 when sintering temperature, reduction temperature, the pH value of solution in catalyst preparation process, reaction
The change of temperature, pressure, time etc. has significantly impact to reaction result, additionally, different carriers can also affect catalyst
Activity, wherein, catalyst performance prepared by embodiment 2 is best.Therefore, catalyst obtained in the present invention is used under appropriate conditions
There is preferable activity and selectivity in the hydrogenation reaction of o-chloronitrobenzene.
Embodiment 20
Step (1)-(4) are with embodiment 2.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g m-chloro-nitrobenzene, 0.4000g Cat-2 catalyst, 20mL dehydrated alcohol are pressed in 120 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain m-chloroaniline.Reaction result is as shown in table 2.
Embodiment 21
Step (1)-(4) are with embodiment 2.
That is the application of catalyst is evaluated to above-mentioned catalyst：
2.0Mpa, 1.0000g parachloronitrobenzene, 0.4000g Cat-2 catalyst, 20mL dehydrated alcohol are pressed in 100 DEG C, hydrogen
Under conditions of, after reaction 120min, obtain parachloroanilinum.Reaction result is as shown in table 2.
The selective data of the conversion ratio and chloro aminobenzen of 2 chloronitrobenzene of table
X=m-and p-.
From table 2 it can be seen that catalyst prepared by the embodiment of the present invention 2 is anti-in m-chloro-nitrobenzene and parachloronitrobenzene hydrogenation
Equally there is in answering preferable activity and selectivity.
Embodiment 22
(1) first by carrier at 200 DEG C roasting 6h, then the carrier after roasting and nickel salt are added in solvent and are mixed
Close, 60 DEG C are heated under stirring, continue stirring 80min after at 60 DEG C with the speed Deca precipitant of 2mL/min to pH=6,
Obtain suspension；Wherein, carrier and the amount ratio of the material of nickel salt are 10:1, the ratio of carrier and solvent is 2g:10mL；Carrier is oxygen
Change ferrum, nickel salt is the mixture of nickel acetate and Nickel dichloride. arbitrary proportion, and solvent is deionized water and dehydrated alcohol arbitrary proportion
Mixture, sodium carbonate liquor of the precipitant for 0.1mol/L.
(2) suspension for obtaining step (1) is being filtered after static burn in 10h at 25 DEG C, is being washed to filtrate in neutrality, 60
After 24h is dried at DEG C, the roasting 4h at 200 DEG C, obtains catalyst precursor in atmosphere；
(3) catalyst precursor is being passed through into the H that flow velocity is 10～80mL/min2Under the conditions of reduce, reduction temperature is 200
DEG C, the recovery time is 2h, obtains synthesizing the nickel catalyst carried of chloro aminobenzen for chloronitrobenzene selective hydrogenation.
Embodiment 23
(1) first by carrier at 800 DEG C roasting 2h, then the carrier after roasting and nickel salt are added in solvent and are mixed
Close, under stirring, be heated to 100 DEG C, with the speed Deca precipitant of 3mL/min to pH=at 100 DEG C after continuation stirring 40min
10, obtain suspension；Wherein, carrier and the amount ratio of the material of nickel salt are 10:1, the ratio of carrier and solvent is 2g:100mL；Carrier
For the mixture of aluminium sesquioxide, titanium dioxide and zirconium dioxide arbitrary proportion, nickel salt is any ratio of Nickel dichloride. and nickel sulfate
The mixture of example, solvent are the mixture of dehydrated alcohol and ethylene glycol arbitrary proportion, and precipitant is the ammonia spirit of 0.2mol/L.
(2) suspension for obtaining step (1) is being filtered after static burn in 5h at 50 DEG C, is being washed to filtrate in neutrality, 120
After 12h is dried at DEG C, the roasting 2h at 500 DEG C, obtains catalyst precursor in atmosphere；
(3) catalyst precursor is being passed through into the H that flow velocity is 80mL/min2Under the conditions of reduce, reduction temperature be 500 DEG C,
Recovery time is 1h, obtains synthesizing the nickel catalyst carried of chloro aminobenzen for chloronitrobenzene selective hydrogenation.
Embodiment 24
(1) first by carrier at 400 DEG C roasting 4h, then the carrier after roasting and nickel salt are added in solvent and are mixed
Close, under stirring, be heated to 130 DEG C, with the speed Deca precipitant of 5mL/min to pH=at 130 DEG C after continuation stirring 10min
12, obtain suspension；Wherein, carrier and the amount ratio of the material of nickel salt are 10:1, the ratio of carrier and solvent is 2g:50mL；Carrier
For the mixture of aluminium sesquioxide, titanium dioxide and zirconium dioxide arbitrary proportion, nickel salt is that Nickel dichloride., nickel nitrate and nickel acetate are appointed
The mixture of meaning ratio, solvent are dehydrated alcohol, and precipitant is the ammonia spirit of 2mol/L.
(2) suspension for obtaining step (1) is in neutrality filtering after static burn in 2h at 100 DEG C, washing to filtrate,
After 18h is dried at 100 DEG C, the roasting 4h at 500 DEG C, obtains catalyst precursor in atmosphere；
(3) catalyst precursor is being passed through into H2With N2Gaseous mixture (H2With N2Volume ratio is 1:2) reduce under conditions of,
Reduction temperature is 800 DEG C, and the recovery time is 0.5h, obtains synthesizing the load of chloro aminobenzen for chloronitrobenzene selective hydrogenation
Type Raney nickel.
Claims (9)
1. a kind of chloronitrobenzene selective hydrogenation synthesizes the preparation method of the loading type nickel-based catalyst of chloro aminobenzen, its feature
It is to comprise the following steps：
(1) will be added in solvent with nickel salt after carrier calcination first and mix, stirring is lower heat after Deca precipitant to pH=6～
12, obtain suspension；
(2) filter after the suspension static burn in for obtaining step (1), wash to filtrate in neutrality, be dried after, in atmosphere in
At 200～800 DEG C, 2～6h of roasting, obtains catalyst precursor；
(3) catalyst precursor is being passed through into H2With N2Under the conditions of gaseous mixture or H2Under the conditions of reduce, reduction temperature be 200～800
DEG C, the recovery time is 0.5～4h, obtains synthesizing the load-type nickel catalysis of chloro aminobenzen for chloronitrobenzene selective hydrogenation
Agent.
2. a kind of chloronitrobenzene selective hydrogenation according to claim 1 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that carrier is aluminium sesquioxide, titanium dioxide, zirconium dioxide, dioxy in the step (1)
One or more in SiClx, magnesium oxide, ferrum oxide；The nickel salt be nickel nitrate, nickel acetate, Nickel dichloride., in nickel sulfate one
Plant or several；Solvent is deionized water, dehydrated alcohol, one or more in ethylene glycol.
3. a kind of chloronitrobenzene selective hydrogenation according to claim 1 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that in the step (1) sintering temperature of carrier be 200～800 DEG C, roasting time be 2～
6h。
4. a kind of chloronitrobenzene selective hydrogenation according to claim 1 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that carrier and the amount ratio of the material of nickel salt are 10 in the step (1):1；Carrier and solvent
Ratio be 2g:(10～100) mL.
5. a kind of chloronitrobenzene selective hydrogenation according to claim 1 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that the temperature of heating is 60～130 DEG C in the step (1), the time is 10～80min.
6. a kind of chloronitrobenzene selective hydrogenation according to claim 1 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that precipitant is that sodium carbonate liquor, sal volatile, sodium hydroxide are molten in the step (1)
One or more in liquid, urea liquid, ammonia.
7. a kind of chloronitrobenzene selective hydrogenation according to claim 6 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that the sodium carbonate liquor, sal volatile, sodium hydroxide solution, the concentration of urea liquid
0.1～1mol/L is, the concentration of ammonia is 0.2～2mol/L.
8. a kind of chloronitrobenzene selective hydrogenation according to claim 1 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that the temperature of static burn in is 25～100 DEG C in the step (2), the time is 2～10h；
Dry temperature is 60～120 DEG C, and drying time is 12～24h.
9. a kind of chloronitrobenzene selective hydrogenation according to claim 1 synthesizes the loading type nickel-based catalysis of chloro aminobenzen
The preparation method of agent, it is characterised in that shielding gas is H in the step (3)2When, it is passed through H2Flow velocity be 10～80mL/min；
Shielding gas is H2With N2Gaseous mixture when, mixed gas flow velocity be 10～100mL/min, wherein H2Account for the volume ratio of mixed gas
For 10～80%.
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| CN113135825B (en) * | 2021-04-23 | 2022-04-08 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and hybrid nano-structure nickel catalyst thereof |
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