CN106732615A - A kind of preparation method of the Ni-based activated-carbon catalyst of Fe doping and its application in nitrocyclohexane hydrogenation reaction - Google Patents
A kind of preparation method of the Ni-based activated-carbon catalyst of Fe doping and its application in nitrocyclohexane hydrogenation reaction Download PDFInfo
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Abstract
Preparation method the invention provides a kind of Fe Ni-based activated-carbon catalysts of doping and its application in nitrocyclohexane hydrogenation reaction.The present invention is first acidified to activated carbon, then with it as carrier, while, then be applied to the gained Fe Ni-based activated-carbon catalysts of doping in nitrocyclohexane hydrogenation reaction by nickel-loaded and iron.The present invention is doped modified, low cost with Fe, pollutes small, and will not etching apparatus, active component is done using base metal nickel, activated carbon can be significantly reduced to this as carrier；Gained catalyst is used in nitrocyclohexane hydrogenation reaction, conversion ratio, the cyclohexanone oxime selectivity of nitrocyclohexane is improved under relatively mild reaction conditions, so as to realize inexpensive Catalyst Production high-quality cyclohexanone oxime.
Description
Technical field
The invention belongs to field of material preparation, more particularly to a kind of Fe adulterate Ni-based activated-carbon catalyst preparation method and
Its application in nitrocyclohexane hydrogenation reaction.
Background technology
Nitrocyclohexane hydrogenation mainly generates cyclohexanone oxime, and cyclohexanone oxime synthesis of caprolactam, caprolactam is important
One of Organic Chemicals, is mainly used to the fiber of synthetic nylon -6 and nylon-6 engineering plastics.Due to caprolactam have it is excellent
Heat endurance, high mechanical strength, chemical resistance and machinability, its range of application is quite extensive, is mainly used in vapour
The field such as car, medical equipment, ship, electric, articles for daily use.From the point of view of in the scope in the whole world, the consumption neck of caprolactam
Domain mainly includes fiber（Civilian silk, industrial yarn, carpet silk）, engineering plastics and food package film three major types.Additionally, caprolactam
Can be used for producing 6-aminocaprolc acid（Antiplatelet drug）, the high chemicals of the value such as Laurocapram.
Current synthesizing cyclohexane 1 ketoxime technique mainly has cyclohexanone-hydroxylamine assay, oximes method, hexamethylene photocatalysis nitrosation
Method, the cyclohexene method etc..Need to use during cyclohexanone-hydroxylamine assay cyclohexanone, and cyclohexane oxidation for cyclohexanone technology extremely
The present is difficult to popularization in the industrial production；PNC process for caprolactam need to carry out radioreaction with substantial amounts of ultraviolet light, and course of reaction consumes energy too
Greatly.And above-mentioned production process is both needed to consume oleum, thus there is different degrees of environmental pollution and generate low
The problems such as value accessory substance ammonium sulfate causes the wasting of resources.And the emerging environmental protection of nitrocyclohexane production line, environment friend
Good, process is simple.Therefore, it is key point to improve the yield of cyclohexanone oxime, reduces cost in this route.
Active metal is that the loaded catalyst of the VIIIth race's element in the periodic table of elements has preferable hydrogenation activity, quilt
It is widely used in nitrocyclohexane hydrogenation process.
University Of Xiangtan sieve and peace et al.（CN102125840A）It is carrier loaded VIIIth race's element to have invented with CNT
Catalyst and its hydrogenation application with alkali metal.There are problems that catalyst.
Liu Pingyue County of University Of Xiangtan et al.（CN104341318A）Invent and urged by carrier loaded VIIIth race's element of molecular sieve
The method for changing nitrocyclohexane hydrogenation.Be present the catalyst high cost when carried noble metal in the method, urged during load base metal
The low problem of agent activity.
In sum, current nitrocyclohexane hydrogenation technique has that catalyst high cost, environmental pollution are more serious etc. to ask
Topic, and yield can be caused too low when directly substituting noble metal with reduces cost with base metal again.
The content of the invention
For above-mentioned technical problem, the present invention provide the preparation method that a kind of Fe adulterates Ni-based activated-carbon catalyst and its
Application in nitrocyclohexane hydrogenation reaction.
The technical scheme is that：
A kind of preparation method of the Ni-based activated-carbon catalyst of Fe doping, comprises the following steps：
（1）By Ni (NO3 )2·6H2O、Fe(NO3)3·9H2O is first dissolved in water, then mixes with the activated carbon of acid activation, then
Impregnated 8 ~ 16 hours in 25 ~ 45 DEG C of stirrings；The activated carbon of acid activation, Ni (NO3 )2·6H2O、Fe(NO3)3·9H2The quality of O
Than being 1：0.5~1.5：0.05~0.22.
（2）By step（1）Gained suspension is placed in drying box 100 ~ 130 DEG C of dryings 10 ~ 20 hours, after then drying
Decorating film mortar grind into fine powder, be put into roasting reduction in tube furnace, obtain Fe and adulterate Ni-based activated-carbon catalyst.
Further, the method for activated carbon acid activation is：1 is pressed in activated carbon：15 ~ 25 solid-liquid mass ratio, adds dense
Nitric acid, is soaked 8 ~ 16 hours, suspension suction filtration under normal temperature, is washed with distilled water to neutrality, and 80 ~ 120 DEG C of dryings are obtained for 10 ~ 15 hours
To the activated carbon of acid activation.
Further, the method for roasting reduction is：First paragraph is under nitrogen protection with the heating rate of 4 ~ 8 DEG C/min from room
Temperature is warming up to 200 ~ 400 DEG C, and second segment nitrogen protects lower 200 ~ 400 DEG C of constant temperature calcinings 1 ~ 4 hour, the 3rd section of 200 ~ 400 DEG C of perseverances
Warm hydrogen reducing 1 ~ 3 hour, after be down to room temperature under nitrogen protection.
Application of the above-mentioned Fe Ni-based activated-carbon catalysts of doping in nitrocyclohexane hydrogenation reaction, including following step
Suddenly：
The Fe Ni-based activated-carbon catalysts of doping of nitrocyclohexane and its quality 5 ~ 30% are added in autoclave, while plus
Enter the ethylenediamine of 8 ~ 14 times of nitrocyclohexane quality, be put into magneton, sealing autoclave replaces air 3 ~ 5 times in kettle, very with hydrogen
Kettle is evacuated to vacuum by empty pump, and then reactor is placed in oil bath, and control pressure is 0.2 ~ 0.5MPa, 40 ~ 80 DEG C of reactions 6 ~ 12
Hour.
The beneficial effects of the present invention are：
（1）The present invention is doped modified, low cost with Fe, pollutes small, and will not etching apparatus, labored using base metal nickel
Property component, activated carbon can be significantly reduced to this as carrier.
（2）Gained catalyst of the invention is used in nitrocyclohexane hydrogenation reaction, carries under relatively mild reaction conditions
The conversion ratio of nitrocyclohexane high, cyclohexanone oxime selectivity, so as to realize inexpensive Catalyst Production high-quality cyclohexanone oxime.
Brief description of the drawings
Fig. 1 is the preparation technology FB(flow block) of the Ni-based activated-carbon catalyst of Fe doping of the invention.
Specific embodiment
The present invention is described in further details with reference to embodiment, but the present invention is not limited thereto.
Embodiment 1
10g merchandise active carbons are weighed, is placed in single-necked flask, according to 1：20 solid-liquid mass ratio, adds concentrated nitric acid, is soaked under normal temperature
Bubble 12h, suspension suction filtration is washed with distilled water to neutrality, and 100 DEG C dry the activated carbon after 12h is activated.Weigh above-mentioned pre-
Activated carbon 1g after treatment is placed in single-necked flask, weighs 1.13gNi (NO3 )2·6H2O, 0.0734gFe (NO3)3·9H2O,
After distilling water dissolves with 34g, solution is added in the single-necked flask equipped with activated carbon, adds magnetite, is impregnated in being stirred at 30 DEG C
10h.Suspension after stirring is placed in beaker and is put into 12 hours of 110 DEG C of dryings in drying box, by dried decorating film
Mortar grind into fine powder is used, roasting reduction in tube furnace is put into, first paragraph is carried out with 5 DEG C/Min for 30-350 DEG C under nitrogen protection
The intensification of heating rate, 350-350 DEG C of second segment carries out 4 hours of nitrogen protective roast, and the 3rd section 350-350 DEG C carries out hydrogen
Reduction 3 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition：1%Fe-20%Ni/AC.
Embodiment 2
The 1%Fe-20%Ni/AC catalyst for weighing the gained of 0.12g embodiments 1 is placed in pyroreaction kettle 50mL liners, adds 0
.5g nitrocyclohexane, 5 .2g ethylenediamines, are put into magneton, and sealing autoclave replaces air 4 times in kettle with hydrogen, and vavuum pump will
Kettle is evacuated to vacuum, and then reactor is placed in oil bath.After 60 DEG C of reaction temperatures of setting are raised to, pressurized with hydrogen to 0 is passed through
.3 MPa, opens magnetic agitation, and reaction timing starts.After reaction 8 hours, reaction mixture is filtered, each material in filtrate
Content gas chromatographic analysis.The conversion ratio of nitrocyclohexane is 87.55%, and the selectivity of cyclohexanone oxime is 83.09%.
Embodiment 3
The 1%Fe-20%Ni/AC catalyst for weighing the gained of 0.12g embodiments 1 is placed in pyroreaction kettle 50mL liners, adds 0
.5g nitrocyclohexane, 5 .2g ethylenediamines, are put into magneton, and sealing autoclave replaces air 4 times in kettle with hydrogen, and vavuum pump will
Kettle is evacuated to vacuum, and then reactor is placed in oil bath.After 50 DEG C of reaction temperatures of setting are raised to, pressurized with hydrogen to 0 is passed through
.3 MPa, opens magnetic agitation, and reaction timing starts.After reaction 8 hours, reaction mixture is filtered, each material in filtrate
Content gas chromatographic analysis.The conversion ratio of nitrocyclohexane is 75 .63%, and the selectivity of cyclohexanone oxime is 81 .21%.
Embodiment 4
The 1%Fe-20%Ni/AC catalyst for weighing the gained of 0.12g embodiments 1 is placed in pyroreaction kettle 50mL liners, adds 0
.5g nitrocyclohexane, 5 .2g ethylenediamines, are put into magneton, and sealing autoclave replaces air 4 times in kettle with hydrogen, and vavuum pump will
Kettle is evacuated to vacuum, and then reactor is placed in oil bath.After 60 DEG C of reaction temperatures of setting are raised to, pressurized with hydrogen to 0 is passed through
.4MPa, magnetic agitation is opened, reaction timing starts.After reaction 8 hours, reaction mixture is filtered, each material contains in filtrate
Amount gas chromatographic analysis.The conversion ratio of nitrocyclohexane is 91 .63%, and the selectivity of cyclohexanone oxime is 71 .21%.
Embodiment 5
The 1%Fe-20%Ni/AC catalyst for weighing the gained of 0.12g embodiments 1 is placed in pyroreaction kettle 50mL liners, adds 0
.5g nitrocyclohexane, 5 .2g ethylenediamines, are put into magneton, and sealing autoclave replaces air 4 times in kettle with hydrogen, and vavuum pump will
Kettle is evacuated to vacuum, and then reactor is placed in oil bath.After 60 DEG C of reaction temperatures of setting are raised to, pressurized with hydrogen to 0 is passed through
.3 MPa, opens magnetic agitation, and reaction timing starts.After reaction 7 hours, reaction mixture is filtered, each material in filtrate
Content gas chromatographic analysis.The conversion ratio of nitrocyclohexane is 82 .73%, and the selectivity of cyclohexanone oxime is 77.41%.
Comparative example 1
To catalyst mix Fe to be modified, it is specific as follows：
10g merchandise active carbons are weighed, is placed in single-necked flask, according to 1：20 solid-liquid mass ratio, adds concentrated nitric acid, is soaked under normal temperature
Bubble 12h, suspension suction filtration is washed with distilled water to neutrality, and 100 DEG C dry the activated carbon after 12h is activated.Weigh above-mentioned pre-
Activated carbon 1g after treatment is placed in single-necked flask, weighs 1.13gNi (NO3 )2·6H2O, it is molten after distilling water dissolves with 34g
Liquid is added in the single-necked flask equipped with activated carbon, adds magnetite, and 10h is impregnated in being stirred at 30 DEG C.By the suspension after stirring
It is placed in beaker and is put into 12 hours of 110 DEG C of dryings in drying box, dried decorating film mortar grind into fine powder is put into
Roasting reduction in tube furnace, first paragraph is carried out with the intensification of 5 DEG C/Min heating rates, second segment for 30-350 DEG C under nitrogen protection
350-350 DEG C is carried out 4 hours of nitrogen protective roast, and the 3rd section 350-350 DEG C carries out 3 hours of hydrogen reducing, after in nitrogen
The lower cooling of protection.Obtain catalyst composition：20%Ni/AC.
The 20%Ni/AC catalyst for weighing the gained of 0.12g comparative examples 1 is placed in pyroreaction kettle 50mL liners, adds 0
.5g nitrocyclohexane, 5 .2g ethylenediamines, are put into magneton, and sealing autoclave replaces air 4 times in kettle with hydrogen, and vavuum pump will
Kettle is evacuated to vacuum, and then reactor is placed in oil bath.After 60 DEG C of reaction temperatures of setting are raised to, pressurized with hydrogen to 0 is passed through
.3 MPa, opens magnetic agitation, and reaction timing starts.After reaction 8 hours, reaction mixture is filtered, each material in filtrate
Content gas chromatographic analysis.The conversion ratio of nitrocyclohexane is 46.78%, and the selectivity of cyclohexanone oxime is 52.20%.
Claims (8)
1. a kind of Fe adulterates the preparation method of Ni-based activated-carbon catalyst, it is characterised in that comprise the following steps：
（1）By Ni (NO3 )2·6H2O、Fe(NO3)3·9H2O is first dissolved in water, then mixes with the activated carbon of acid activation, stirring
Under the conditions of impregnate；
（2）By step（1）Gained suspension is placed in drying box and dries, and then dried decorating film is smashed with mortar
Shape, is put into roasting reduction in tube furnace, obtains the Fe Ni-based activated-carbon catalysts of doping.
2. Fe according to claim 1 adulterates the preparation method of Ni-based activated-carbon catalyst, it is characterised in that acid activation
Activated carbon, Ni (NO3 )2·6H2O、Fe(NO3)3·9H2The mass ratio of O is 1：0.5~1.5：0.05~0.22.
3. Fe according to claim 1 and 2 adulterates the preparation method of Ni-based activated-carbon catalyst, it is characterised in that dipping
Temperature is 25 ~ 45 DEG C.
4. Fe according to claim 1 and 2 adulterates the preparation method of Ni-based activated-carbon catalyst, it is characterised in that dipping
Time is 8 ~ 16 hours.
5. Fe according to claim 1 and 2 adulterates the preparation method of Ni-based activated-carbon catalyst, it is characterised in that activity
The method of charcoal acid activation is：1 is pressed in activated carbon：15 ~ 25 solid-liquid mass ratio, adds concentrated nitric acid, 8 ~ 16 is soaked under normal temperature small
When, suspension suction filtration is washed with distilled water to neutrality, and 80 ~ 120 DEG C of dryings obtain the activated carbon of acid activation for 10 ~ 15 hours.
6. Fe according to claim 1 and 2 adulterates the preparation method of Ni-based activated-carbon catalyst, it is characterised in that roasting
The method of reduction is：First paragraph under nitrogen protection with the heating rate of 4 ~ 8 DEG C/min from room temperature to 200 ~ 400 DEG C,
Two sections of nitrogen protect lower 200 ~ 400 DEG C of constant temperature calcinings 1 ~ 4 hour, the 3rd section of 200 ~ 400 DEG C of constant temperature hydrogen reducing 1 ~ 3 hour, after
Room temperature is down under nitrogen protection.
7. Fe according to claim 1 and 2 adulterates the preparation method of Ni-based activated-carbon catalyst, it is characterised in that dry
Temperature is 100 ~ 130 DEG C, and drying time is 10 ~ 20 hours.
8. the Fe described in any one of claim 1 to 7 adulterates Ni-based activated-carbon catalyst in nitrocyclohexane hydrogenation reaction
Using comprising the following steps：
The Fe Ni-based activated-carbon catalysts of doping of nitrocyclohexane and its quality 5 ~ 30% are added in autoclave, while plus
Enter the ethylenediamine of 8 ~ 14 times of nitrocyclohexane quality, be put into magneton, sealing autoclave replaces air 3 ~ 5 times in kettle, very with hydrogen
Kettle is evacuated to vacuum by empty pump, and then reactor is placed in oil bath, and control pressure is 0.2 ~ 0.5MPa, 40 ~ 80 DEG C of reactions 6 ~ 12
Hour.
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| CN107469825A (en) * | 2017-08-25 | 2017-12-15 | 湘潭大学 | A kind of preparation method and application of the nickel-based multimetallic catalyst of the carbon nanotube loaded bimetallic copper magnesium codope of oxidation modification |
| CN109160887A (en) * | 2018-07-31 | 2019-01-08 | 湖南科技学院 | A kind of method that catalytic transfer hydrogenation nitrocyclohexane prepares cyclohexanone oxime |
| CN111137891A (en) * | 2020-01-10 | 2020-05-12 | 齐鲁工业大学 | Preparation method of nickel-doped magnetic carbon and application of nickel-doped magnetic carbon in hydrogen production by dark fermentation |
| CN111530465A (en) * | 2020-05-26 | 2020-08-14 | 湘潭大学 | Preparation method of supported cigarette end porous carbon material catalyst and application of supported cigarette end porous carbon material catalyst in nitrocyclohexane hydrogenation reaction |
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| CN107469825A (en) * | 2017-08-25 | 2017-12-15 | 湘潭大学 | A kind of preparation method and application of the nickel-based multimetallic catalyst of the carbon nanotube loaded bimetallic copper magnesium codope of oxidation modification |
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| CN111530465A (en) * | 2020-05-26 | 2020-08-14 | 湘潭大学 | Preparation method of supported cigarette end porous carbon material catalyst and application of supported cigarette end porous carbon material catalyst in nitrocyclohexane hydrogenation reaction |
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Application publication date: 20170531 |