CN105032433A - Preparation method of adipic dinitrile hydrogenation catalyst utilizing TiO2 nano tube as carrier - Google Patents
Preparation method of adipic dinitrile hydrogenation catalyst utilizing TiO2 nano tube as carrier Download PDFInfo
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Abstract
The invention provides a preparation method of an adipic dinitrile hydrogenation catalyst utilizing a TiO2 nano tube as a carrier. The preparation method comprises the following steps: preparing a TiO2 nano tube, namely weighing anatase TiO2 particles, dissolving the anatase TiO2 particles in a NaOH solution, then adding chromic nitrate, stirring, transferring a mixed liquor to a hydrothermal reaction kettle for reaction, cooling after reaction is over, filtering, washing until the solution is neutral, soaking the obtained solid with an HCl aqueous solution, filtering, washing until the solution is neutral, finally drying in a baking oven, and calcinating, thereby preparing the TiO2 nano tube; adding the carrier into an aqueous solution of nickel nitrate and potassium nitrate, stirring uniformly, standing for ageing, drying a dip compound in the baking oven, calcinating the dried sample in a muffle furnace so as to obtain a catalyst precursor; and reducing the catalyst precursor, thereby obtaining the catalyst. The catalyst provided by the invention is relatively high in mechanical strength, easy for separation, free from a great amount of alkali liquor in a reaction process and capable of reducing the environmental pollution.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind of catalyst, a kind of with TiO specifically
2nanotube is the preparation method of the adipic dinitrile hydrogenation catalyst of carrier.
Background technology
Adipic dinitrile hydrogenation is the committed step of butylene Hydrogenation caprolactam, and adipic dinitrile hydrogenation product hexamethylene diamine is a kind of important organic intermediate, and application is wide.Adipic dinitrile hydrogenation core technology is monopolized by trans-corporation, and is domesticly still in the starting stage to its research, so have very large research space to the research of this technique.
For probing into of adipic dinitrile hydrogenation reaction, be mainly divided into two large classes: gas phase hydrogenation method and By Liquid-phase Hydrogenation Process.For adiponitrile liquid-phase hydrogenatin reaction, study mainly with the process route centered by coproduction hexamethylene diamine and ACN.With RaneyCo or RaneyNi for catalyst choice catalytic hydrogenation liquid phase adiponitrile, alkaline assistant auxiliary under, present the selective of good catalytic activity and high object product.The RaneyNi catalyst of doping Cr and Fe, under the condition of 353K, 6.89MPa, the conversion ratio of adiponitrile reaches 90%, the selective of ACN reaches 82%.But, the easy spontaneous combustion of RaneyNi catalyst, low, the difficult separation of mechanical strength, and need in course of reaction to add a large amount of ammonia to suppress the generation of secondary amine and tertiary amine, three-protection design and equipment cost expense increase, and economic benefit has to be hoisted.Adiponitrile gas phase hydrogenation achieves certain breakthrough, after continuous service 216h, adiponitrile conversion ratio reaches 70%, the selective of ACN reach 80%, but topmost shortcoming, for consuming amounts of hydrogen too large (cost is high), reaction temperature too high (energy consumption is high), catalyst life short (cost is high), causes gas phase hydrogenation complex manufacturing and has higher production cost.Therefore, develop a kind of alkali free environment, good mechanical property, selective hydrogenation behavior is good, reaction condition is gentle liquid phase adipic dinitrile hydrogenation catalyst have important application prospect and theory value.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of with TiO
2nanotube is the preparation method of the adipic dinitrile hydrogenation catalyst of carrier, and described is this with TiO
2it is short that nanotube is that the preparation method of the adipic dinitrile hydrogenation catalyst of carrier solves adipic dinitrile hydrogenation catalyst life of the prior art, the technical problem that production cost is high, energy consumption is high.
The invention provides a kind of with TiO
2nanotube is the preparation method of the adipic dinitrile hydrogenation catalyst of carrier, comprises the following steps:
1) a preparation TiO
2the step of nanotube, takes anatase TiO
2particle, by anatase TiO
2grain dissolution is in NaOH solution, and described NaOH solution concentration is 1 ~ 20mol/L, described anatase TiO
2the mass volume ratio of particle and NaOH solution is 1g:20 ~ 50ml, add chromic nitrate again, the mass percent concentration of the chromic nitrate added in above-mentioned solution is 0 ~ 2%, stir 8 ~ 15 hours, mixed liquor is transferred in hydrothermal reaction kettle, 20 ~ 50h is reacted at 150 DEG C, after reaction terminates, cooling, filters, and spend deionized water to neutral, the solids obtained is placed in the HCl aqueous solution of PH=1 ~ 2, filters after soaking 3 ~ 24h, wash to neutral, be finally placed in the baking oven inner drying 1 ~ 4h of 80 ~ 100 DEG C, 400 ~ 500 DEG C of roasting 1 ~ 3h, obtained TiO
2nanotube;
2) step adopting equi-volume impregnating to prepare nickel-base catalyst, by above-mentioned carrier TiO
2nanotube joins in the aqueous solution of nickel nitrate and potassium nitrate, and in the above-mentioned aqueous solution, the mass percent concentration of nickel nitrate is 20 ~ 30%, and the mass percent concentration of potassium nitrate is 0.05 ~ 0.2%, carrier TiO
2the mass volume ratio of nanotube and the above-mentioned aqueous solution is 1g:20 ~ 50ml, after stirring, leaves standstill aging 1 ~ 4h, dip compound is placed in the baking oven of 100 ~ 140 DEG C, drying, by dried sample roasting 1 ~ 3h in 400 ~ 500 DEG C of Muffle furnaces, obtains catalyst precursor;
3) by catalyst precursor compressing tablet, pulverize, be screened to 20-40 order, then use H
2/ N
2mixing reducing gases at 400 ~ 500 DEG C, reduce 1 ~ 4h, obtain catalyst.
Further, described H
2/ N
2mixing reducing gases in, H
2volume ratio be 10 ~ 90%, mixing reducing gases specific gas flow rate 5 ~ 20ml/min.
Further, the chromic nitrate added mass percent concentration is in the solution 0 or 0.2% or 0.8% or 2%.
Further, in catalyst, the weight ratio of nickel, potassium is 25:0.1.
The present invention is a kind of loading type nickel-based catalyst, from water heat transfer TiO
2nanotube sets out, with the TiO of sodium or chromium modification
2nanotube is carrier, at TiO
2add the chromium source of different amount in nanotube preparation process, post processing pickling time difference makes residual sodium amount different, with above-mentioned titanium dioxide for carrier prepares nickel-base catalyst presoma, after hydrogen reducing, obtains loading type nickel-based catalyst.
Mix chromium in catalyst to be conducive to improving the selective of primary amine, for containing 0.8wt%Cr
3+catalyst, adiponitrile conversion ratio reaches 83.5%, and hexamethylene diamine and the selective of ACN are respectively 30% and 66.4%; The optionally raising that sodium is conducive to adiponitrile conversion ratio and primary amine is mixed in catalyst, when being 20h for pickling time, sodium content is the catalyst of 0.67wt.%, the conversion ratio of adiponitrile can reach 92%, and hexamethylene diamine and the selective of ACN can reach 36.3% and 59.2% respectively.
The present invention compares Raney's nickel catalyst, need not add a large amount of alkali lye and suppress cyclisation, make reaction trend towards environmental friendliness in course of reaction.Loading type nickel-based catalyst mechanical strength prepared by the present invention is larger, easily separated, in course of reaction without the need to adding a large amount of alkali lye, reduce the pollution to environment, and substantially increase operability.Technological operation of the present invention is simple, cost is low, easy industrialization, and the three wastes few, easily process, there is good application prospect.
Detailed description of the invention
The present invention realizes in the following ways, describe in detail, but following embodiment is not limitation of the invention below in conjunction with embodiment.
The preparation of embodiment 1 catalyst
1) the anatase TiO of 1g is got
2particle, in 30mlNaOH (10M) solution, adds 0-0.154g chromic nitrate (mixing chromium amount is 0,0.2wt.%, 0.6wt.%, 0.8wt.%, 2wt.%), room temperature for overnight; Mixed liquor is transferred to and has in teflon-lined 100ml hydrothermal reaction kettle, at 150 DEG C, react 48h; After reaction terminates, be cooled to room temperature, filter, and spend deionized water to neutral; The solids obtained is placed in the HCl aqueous solution of PH=1.5, soaks 24h (20h, 3h) and filter afterwards, wash to neutrality; Finally be placed in the baking oven inner drying 3h of 100 DEG C, 450 DEG C of roasting 2h, obtained TiO
2nanotube.
2) adopt equi-volume impregnating to prepare nickel-base catalyst: to be joined by 1g carrier (Ni load capacity is 25wt.%, K load capacity is 0.1wt.%) in the aqueous solution of nickel nitrate and potassium nitrate, after stirring, leave standstill aging 3h; Dip compound is placed in 120 DEG C of baking ovens, dried overnight; Dried sample roasting 2h in 450 DEG C of Muffle furnaces is obtained catalyst precursor.
3) catalyst precursor through compressing tablet, pulverize, be screened to 20-40 order, for subsequent use.By catalyst precursor 10vol.%H
2/ N
2mixing reducing gases reductase 12 h at 450 DEG C, obtain catalyst, be placed in absolute ethyl alcohol (or vacuum) and save backup.
Embodiment 2
The catalyst (0Cr) obtained that 1g adiponitrile, 15g absolute ethyl alcohol and 0.6g catalyst precursor reduced joins in 100mL reactor, sealed reactor, to replace in still air 3-5 time, put into heating jacket with hydrogen (0.2-0.4MPa).Treat that temperature in the kettle rises to 75 DEG C, hydrogen is added to 2MPa, open magnetic stirring apparatus, reaction starts timing.After reaction 3h, cooling, isolated by filtration, gets liquid-like analysis, the results are shown in Table 1.
Embodiment 3
The catalyst (0.2wt.%Cr) obtained that 1g adiponitrile, 15g absolute ethyl alcohol and 0.6g catalyst precursor reduced joins in 100mL autoclave, sealed reactor, to replace in still air 3-5 time with hydrogen (0.2-0.4MPa), put into heating jacket.Treat that temperature in the kettle rises to 75 DEG C, hydrogen is added to 2MPa, open magnetic stirring apparatus, reaction starts timing.After reaction 3h, cooling, isolated by filtration, gets liquid-like analysis, the results are shown in Table 1.
Embodiment 4
The catalyst (0.8wt.%Cr) obtained that 1g adiponitrile, 15g absolute ethyl alcohol and 0.6g catalyst precursor reduced joins in 100mL autoclave, sealed reactor, to replace in still air 3-5 time with hydrogen (0.2-0.4MPa), put into heating jacket.Treat that temperature in the kettle rises to 75 DEG C, hydrogen is added to 2MPa, open magnetic stirring apparatus, reaction starts timing.After reaction 3h, cooling, isolated by filtration, gets liquid-like analysis, the results are shown in Table 1.
Embodiment 5
The catalyst (2wt.%Cr) obtained that 1g adiponitrile, 15g absolute ethyl alcohol and 0.6g catalyst precursor reduced joins in 100mL autoclave, sealed reactor, to replace in still air 3-5 time with hydrogen (0.2-0.4MPa), put into heating jacket.Treat that temperature in the kettle rises to 75 DEG C, hydrogen is added to 2MPa, open magnetic stirring apparatus, reaction starts timing.After reaction 3h, cooling, isolated by filtration, gets liquid-like analysis, the results are shown in Table 1.
Embodiment 6
1g adiponitrile, 15g absolute ethyl alcohol and 0.6g catalyst precursor are reduced catalyst (the pickling 3h obtained, sodium residual quantity is 1.38wt.%) join in 100mL autoclave, sealed reactor, to replace in still air 3-5 time with hydrogen (0.2-0.4MPa), put into heating jacket.Treat that temperature in the kettle rises to 75 DEG C, hydrogen is added to 2MPa, open magnetic stirring apparatus, reaction starts timing.After reaction 3h, cooling, isolated by filtration, gets liquid-like analysis, the results are shown in Table 1.
Embodiment 7
1g adiponitrile, 15g absolute ethyl alcohol and 0.6g catalyst precursor are reduced catalyst (the pickling 20h obtained, sodium residual quantity is 0.67wt.%) join in 100mL autoclave, sealed reactor, to replace in still air 3-5 time with hydrogen (0.2-0.4MPa), puts into heating jacket.Treat that temperature in the kettle rises to 75 DEG C, hydrogen is added to 2MPa, open magnetic stirring apparatus, reaction starts timing.After reaction 3h, cooling, isolated by filtration, gets liquid-like analysis, the results are shown in Table 1.
Embodiment 8
1g adiponitrile, 15g absolute ethyl alcohol and 0.6g catalyst precursor are reduced the catalyst obtained (with TiO
2nano particle is the catalyst of carrier) join in 100mL autoclave, sealed reactor, to replace in still air 3-5 time with hydrogen (0.2-0.4MPa), puts into heating jacket.Treat that temperature in the kettle rises to 75 DEG C, hydrogen is added to 2MPa, open magnetic stirring apparatus, reaction starts timing.After reaction 3h, cooling, isolated by filtration, gets liquid-like analysis, the results are shown in Table 1.
Catalyst adipic dinitrile hydrogenation evaluation result prepared by the different case study on implementation of table 1
A. with TiO
2the sample that nano particle (5-10nm) is carrier.
Claims (4)
1. one kind with TiO
2nanotube is the preparation method of the adipic dinitrile hydrogenation catalyst of carrier, it is characterized in that comprising the following steps:
1) a preparation TiO
2the step of nanotube, takes anatase TiO
2particle, by anatase TiO
2grain dissolution is in NaOH solution, and described NaOH solution concentration is 1 ~ 20mol/L, described anatase TiO
2the mass volume ratio of particle and NaOH solution is 1g:20 ~ 50ml, add chromic nitrate again, the mass percent concentration of the chromic nitrate added in above-mentioned solution is 0 ~ 2%, stir 8 ~ 15 hours, mixed liquor is transferred in hydrothermal reaction kettle, 20 ~ 50h is reacted at 150 DEG C, after reaction terminates, cooling, filters, and spend deionized water to neutral, the solids obtained is placed in the HCl aqueous solution of PH=1 ~ 2, filters after soaking 3 ~ 24h, wash to neutral, be finally placed in the baking oven inner drying 1 ~ 4h of 80 ~ 100 DEG C, 400 ~ 500 DEG C of roasting 1 ~ 3h, obtained TiO
2nanotube;
2) step adopting equi-volume impregnating to prepare nickel-base catalyst, by above-mentioned carrier TiO
2nanotube joins in the aqueous solution of nickel nitrate and potassium nitrate, and in the above-mentioned aqueous solution, the mass percent concentration of nickel nitrate is 20 ~ 30%, and the mass percent concentration of potassium nitrate is 0.05 ~ 0.2%, carrier TiO
2the mass volume ratio of nanotube and the above-mentioned aqueous solution is 1g:20 ~ 50ml, after stirring, leaves standstill aging 1 ~ 4h, dip compound is placed in the baking oven of 100 ~ 140 DEG C, drying, by dried sample roasting 1 ~ 3h in 400 ~ 500 DEG C of Muffle furnaces, obtains catalyst precursor;
3) by catalyst precursor compressing tablet, pulverize, be screened to 20-40 order, then use H
2/ N
2mixing reducing gases at 400 ~ 500 DEG C, reduce 1 ~ 4h, obtain catalyst.
2. one according to claim 1 is with TiO
2nanotube is the preparation method of the adipic dinitrile hydrogenation catalyst of carrier, it is characterized in that: described H
2/ N
2mixing reducing gases in, H
2volume ratio be 10 ~ 90%, mixing reducing gases specific gas flow rate 5 ~ 20ml/min.
3. one according to claim 1 is with TiO
2nanotube is the preparation method of the adipic dinitrile hydrogenation catalyst of carrier, it is characterized in that: the chromic nitrate added mass percent concentration is in the solution 0% or 0.2% or 0.8% or 2%.
4. one according to claim 1 is with TiO
2nanotube is the preparation method of the adipic dinitrile hydrogenation catalyst of carrier, it is characterized in that: in catalyst, the weight ratio of nickel, potassium is 25:0.1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN107486208A (en) * | 2017-08-25 | 2017-12-19 | 湘潭大学 | A kind of preparation method and application of carbon nanotube loaded quaternary amorphous nickel-base catalyst |
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| CN104001516A (en) * | 2014-05-29 | 2014-08-27 | 中国天辰工程有限公司 | Preparation method of catalyst for synthesizing hexanediamine by carrying out hydrogenation on hexane dinitrile |
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Patent Citations (2)
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| US20110313187A1 (en) * | 2009-02-09 | 2011-12-22 | Christof Wilhelm Wigbers | Method for improving the catalytic activity of monolithic catalysts |
| CN104001516A (en) * | 2014-05-29 | 2014-08-27 | 中国天辰工程有限公司 | Preparation method of catalyst for synthesizing hexanediamine by carrying out hydrogenation on hexane dinitrile |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107486208A (en) * | 2017-08-25 | 2017-12-19 | 湘潭大学 | A kind of preparation method and application of carbon nanotube loaded quaternary amorphous nickel-base catalyst |
| CN107486208B (en) * | 2017-08-25 | 2020-05-05 | 湘潭大学 | Preparation method and application of carbon nanotube-loaded quaternary amorphous nickel-based catalyst |
| CN107469825B (en) * | 2017-08-25 | 2022-12-20 | 湘潭大学 | Preparation method and application of oxidation-modified carbon nanotube-loaded bimetallic copper-magnesium co-doped nickel-based multi-metal catalyst |
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