CN102553597A - Preparation method of supported Ni-B amorphous catalyst for selective hydrogenation - Google Patents
Preparation method of supported Ni-B amorphous catalyst for selective hydrogenation Download PDFInfo
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Abstract
The invention relates to a preparation method of a supported Ni-B amorphous catalyst for selective hydrogenation. Ultrasonic waves, spray drying and microwave radiation are respectively introduced into an impregnation-reduction method to prepare the supported Ni-B amorphous catalyst. In the impregnation, drying and roasting process, the invention enhances the dispersity of the Ni precursor in the support and the interaction with the support, greatly improves the catalytic performance of the supported Ni-B amorphous alloy catalyst in the TDA (tolylenediamine) synthesis process by DNT (dinitrotoluene) hydrogenation, greatly shortens the preparation period of the catalyst, and has wide industrial prospects.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, relate in particular to a kind of preparation method who is used to select hydrogenation carried non-crystal Ni-B alloy catalyst.
Background technology
Toluenediamine (TDA) has another name called diaminotoluene, in industry, has been widely used, and its topmost purposes is as production toluene di-isocyanate(TDI) (TDI), and TDI is one of important source material of producing polyurethane.Usually adopt dinitrotoluene (DNT) (DNT) to add the synthetic toluenediamine (TDA) (reaction equation-1) of hydrogenation under organic solvent and the catalyst existence outside in the industry.Because catalyst is one of core technology of DNT hydrogenation, in recent years, the research of the synthetic toluenediamine catalyst of DNT hydrogenation is become the focus of domestic and international research.
DNT+6H
2→TDA+4H
2O (1)
In existing DNT hydrogenation catalyst, noble metal catalysts such as load type palladium, platinum and rhodium have very high activity, but cost is high, and are easy to carbon distribution; Though the skeleton nickel low price in the preparation process, owing to use a large amount of caustic soda extracting aluminium, cause serious environmental to pollute, and there is safety problem in easy spontaneous combustion in air, is difficult to satisfy the requirement that serialization is produced.
Since nineteen eighty, amorphous alloy receives much concern as a kind of novel catalysis material.Wherein, Support type Ni-B amorphous alloy catalyst has embodied excellent hydrogenation activity and selectivity in the catalytic hydrogenation field; It is little to have overcome non-loading type Ni-B specific surface area of catalyst simultaneously, and the characteristics of poor heat stability are expected to replace traditional skeleton nickel and noble metal catalyst.Thereby the preparation and the application in the DNT hydrogenation reaction thereof of research support type Ni-B amorphous alloy catalyst have important practice significance.
Patent CN1850330A discloses carried non-crystal alloy catalyst of a kind of phenol catalytic hydrogenation preparing cyclohexanone and preparation method thereof, utilizes incipient impregnation KBH
4Reducing process prepares amorphous alloy catalyst.Preparation process comprises: with slaine precursor solution and hydrotalcite supports incipient impregnation; Dry; Roasting; Drip reducing agent KBH
4Solution reduces and washs.Prepare in the reaction of cyclohexanone at phenol hydrogenation, have higher activity and selectivity.
Patent CN1196975A discloses a kind of support type Ni-B amorphous alloy catalyst.It adopts porous material is catalyst carrier, preferred silica, and aluminium oxide or active carbon, reduction has prepared the Ni-B amorphous alloy catalyst with dipping through chemical reduction method.
Patent CN1850330A and CN1850330A adopt conventional immersion reduction method to prepare support type Ni-B amorphous alloy catalyst, though improved the hydrogenation performance of catalyst to a certain extent.But because at Ni precursor skewness in carrier, and with carrier interactions a little less than, in reduction process, the metal ion at carrier hole road junction preferentially is reduced, the amorphous alloy of formation can stop up the duct of carrier.Selfdecomposition can take place in unnecessary reducing agent, thereby has stoped the reduction that is deposited on carrier deep hole internal metal ion, causes active component content decline and radial distribution inhomogeneous.This method for preparing catalyst is because preparation process is many simultaneously, and the Preparation of Catalyst cycle is long, is unfavorable for the industrial applications of catalyst.
It is carrier with inorganic oxide and molecular sieve that CN1546229A has reported a kind of, and adopting metal A g, Pd and Fe etc. is derivant, obtains the preparation method of support type Ni-B amorphous alloy catalyst through electroless plating method.Ni-B accounts for the 5%-50% of catalyst quality, wherein Ni/B=70 in the gained catalyst: 30.Though this method has increased the decentralization of Ni-B at carrier surface to a certain extent; But in reduction process; Be reflected in the whole solution during reducing agent reducing metal ion and carry out; So amorphous alloy can not be deposited on the carrier fully, a part is assembled the back attached on the wall or be deposited on container bottom.
Summary of the invention
The purpose of this law invention provides a kind of Ni-B amorphous alloy and is uniformly dispersed at carrier surface, interacts by force with carrier, and shortens the preparation method of a kind of support type Ni-B amorphous alloy catalyst of manufacturing cycle greatly.
Prepare the problem in the process in order to overcome above-mentioned support type Ni-B amorphous alloy catalyst.The present invention is with ultrasonic wave; Spray-drying and microwave radiation are incorporated into the dipping that immersion reduction method prepares support type Ni-B amorphous alloy catalyst respectively; In dry and the roasting process, not only increased the Ni precursor in carrier decentralization and and carrier interactions, improved support type Ni-B amorphous alloy catalyst greatly and synthesized the catalytic performance among the TDA at the DNT hydrogenation; And shortened the Preparation of catalysts cycle greatly, have very big industrial prospect.
Technical scheme and concrete steps that the present invention adopts are:
(1) carrier preliminary treatment: with 80-150 purpose SiO
2, Al
2O
3Or absorbent charcoal carrier is at 80-120 ℃ of oven dry 1-3h, with the moisture evaporate to dryness in the carrier;
(2) dipping: the load capacity by Ni is 1-15wt%, and nickel chloride, nickel nitrate or nickel acetate are mixed with solution, puts into the carrier after the oven dry then, is the medium volume dipping of 30-100W ultrasonic wave 20-120min at power;
Can also pass through Mo at dipping process, Zr, Pd, Sn, the method for the soluble salt solution of auxiliary agents such as Pt and Ni solution hybrid infusion is introduced above-mentioned metal ion, and the introducing amount is the 0.1-30wt% of Ni content;
(3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 0.7-1.5MPa, EAT 220-250 ℃, leaving air temp 100-140 ℃;
(4) roasting: under 150-200 ℃ of temperature, roasting 20-100min obtains Ni at precursor under the microwave radiation condition that drying is good
2+/ carrier;
(5) reduction: in ice-water bath with the KBH of 0.5-2.5mol/L
4Solution, the NaOH solution through 2.0mol/L is with KBH
4Solution is adjusted to neutrality, presses KBH
4: the Ni mol ratio is 1-5, is added drop-wise to the Ni after the roasting with the speed of 3-10ml/min
2+In/the carrier, after dropwising, continue to be stirred to no bubble and produce and finish, be washed with distilled water to neutrality earlier, be kept in the ethanol with after the washing with alcohol three times again, make catalyst.
The present invention prepares the Application of Catalyst process conditions: reaction temperature 80-150 ℃, reaction pressure 0.5-2.5MPa makees solvent with methyl alcohol or ethanol, and the DNT initial concentration is 2-20wt%, and catalyst concn is 0.1-10wt%.
Advantage of the present invention is following:
The present invention has improved the decentralization of Ni precursor at carrier surface greatly through the ultrasonic wave infusion process, has shortened dip time greatly; It is dry to flood the suspension of accomplishing through spray-drying, has shortened drying time greatly; Through microwave the precursor of dried nickel-loaded is carried out roasting; Because the uniformity of heating using microwave; Overcome since conventional heating since heat the inhomogeneous Ni that causes carrier surface reunite problem; Increased the decentralization of Ni precursor in carrier greatly, strengthened greatly and carrier interactions, thereby the Ni-B alloy after the reduction can be dispersed in the carrier more uniformly.
Catalyst of the present invention has higher hydrogenation activity, especially has very high catalytic activity and selectivity in the reaction to DNT hydrogenation preparing TDA.
The specific embodiment
Make further detailed description through the specific embodiment specific embodiments of the invention below.
Embodiment 1
1) carrier preliminary treatment: with 5g 80-100 purpose SiO
2Carrier is at 80 ℃ of oven dry 1h.
2) dipping: with 0.405g NiCl
26H
2O is mixed with the 10ml aqueous solution, puts into the carrier after the oven dry then and carries out incipient impregnation at ultrasonic wave, and the load capacity of Ni is 2wt%, and dip time is 20min, and ultrasonic power is 30W.
3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 0.7MPa, 220 ℃ of EATs, 100 ℃ of leaving air temps.
4) roasting: at precursor under the microwave radiation condition that drying is good under 150 ℃ of temperature, roasting 20min.
5) reduction: in ice-water bath with the KBH of 2mol/L
4Solution, the NaOH solution through 2.0mol/L is with KBH
4Solution is adjusted to neutrality, is added drop-wise to the Ni after the roasting with the speed of 3ml/min
2+/ SiO
2In, KBH
4/ Ni=1 (mol ratio) after dropwising, continues to be stirred to no bubble and produces and finish, and is washed with distilled water to neutrality earlier, is kept in the ethanol with after the washing with alcohol three times again, and it is subsequent use to obtain catalyst.
Embodiment 2
1) carrier preliminary treatment: 5g 100-120 purpose absorbent charcoal carrier is dried 2h at 90 ℃.
2) dipping: with 0.848g C
4H
6NiO
44H
2O and 0.018g PdCl
2Be mixed with the mixed solution of 10ml, put into the carrier after the oven dry then and carry out incipient impregnation at ultrasonic wave, the load capacity of Ni is 4wt%, and the load capacity of Pd is 0.2wt%, and dip time is 40min, and ultrasonic power is 40W.
3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 1.0MPa, 230 ℃ of EATs, 100 ℃ of leaving air temps.
4) roasting: at precursor under the microwave radiation condition that drying is good under 170 ℃ of temperature, roasting 30min.
5) reduction: in ice-water bath with the KBH of 2mol/L
4Solution, the NaOH solution through 2.0mol/L is with KBH
4Solution is adjusted to neutrality, is added drop-wise to the Ni after the roasting with the speed of 4ml/min
2+In/the active carbon, KBH
4/ Ni=2 (mol ratio) after dropwising, continues to be stirred to no bubble and produces and finish, and is washed with distilled water to neutrality earlier, is kept in the ethanol with after the washing with alcohol three times again, and it is subsequent use to obtain catalyst.
Embodiment 3
1) carrier preliminary treatment: with 5g 100-120 purpose γ-Al
2O
3Carrier is at 100 ℃ of oven dry 3h.
2) dipping: with 3.04g NiCl
26H
2O and 0.29g ZrCl
4Be mixed with the 10ml mixed aqueous solution, put into the carrier after the oven dry then and carry out incipient impregnation at ultrasonic wave, the load capacity of Ni is 15wt%, and the load capacity of Zr is 2.5wt%, and dip time is 80min, and ultrasonic power is 60W.
3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 1.2MPa, 240 ℃ of EATs, 120 ℃ of leaving air temps.
4) roasting: at precursor under the microwave radiation condition that drying is good under 210 ℃ of temperature, roasting 40min.
5) reduction: in ice-water bath with the KBH of 2mol/L
4Solution, the NaOH solution through 2.0mol/L is with KBH
4Solution is adjusted to neutrality, is added drop-wise to the Ni after the roasting with the speed of 5ml/min
2+/ γ-Al
2O
3In, KBH
4/ Ni=4 (mol ratio) after dropwising, continues to be stirred to no bubble and produces and finish, and is washed with distilled water to neutrality earlier, is kept in the ethanol with after the washing with alcohol three times again, and it is subsequent use to obtain catalyst.
Embodiment 4
1) carrier preliminary treatment: with 5g 100-120 purpose γ-Al
2O
3Carrier is at 110 ℃ of oven dry 2h.
2) dipping: with 4.96g Ni (NO
3)
26H
2O and 0.43g MoCl
5Be mixed with the 10ml mixed aqueous solution, put into the carrier after the oven dry then and carry out incipient impregnation at ultrasonic wave, the load capacity of Ni is 20wt%, and the Mo load capacity is 100min for the 3wt% dip time, and ultrasonic power is 70W.
3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 1.3MPa, 250 ℃ of EATs, 120 ℃ of leaving air temps.
4) roasting: at precursor under the microwave radiation condition that drying is good under 230 ℃ of temperature, roasting 50min.
5) reduction: in ice-water bath with the KBH of 2mol/L
4Solution, the NaOH solution through 2.0mol/L is with KBH
4Solution is adjusted to neutrality, is added drop-wise to the Ni after the roasting with the speed of 5ml/min
2+/ γ-Al
2O
3In, KBH
4/ Ni=5 (mol ratio) after dropwising, continues to be stirred to no bubble and produces and finish, and is washed with distilled water to neutrality earlier, is kept in the ethanol with after the washing with alcohol three times again, and it is subsequent use to obtain catalyst.
Embodiment 5
1) carrier preliminary treatment: 5g 140-200 purpose absorbent charcoal carrier is dried 2h at 110 ℃.
2) dipping: with 1.215g NiCl
26H
2O and 0.14g PtCl
4Be mixed with the 10ml mixed aqueous solution and be mixed with the 10ml mixed aqueous solution, put into the carrier after the oven dry then and carry out incipient impregnation at ultrasonic wave, the load capacity of Ni is 6wt%, and the Pt load capacity is 1.6wt%, and dip time is 110min, and ultrasonic power is 60W.
3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 1.4MPa, 235 ℃ of EATs, 110 ℃ of leaving air temps.
4) roasting: at precursor under the microwave radiation condition that drying is good under 200 ℃ of temperature, roasting 60min.
5) reduction: in ice-water bath with the KBH of 2mol/L
4Solution, the NaOH solution through 2.0mol/L is with KBH
4Solution is adjusted to neutrality, is added drop-wise to the Ni after the roasting with the speed of 5ml/min
2+In/the active carbon, KBH
4/ Ni=4 (mol ratio) after dropwising, continues to be stirred to no bubble and produces and finish, and is washed with distilled water to neutrality earlier, is kept in the ethanol with after the washing with alcohol three times again, and it is subsequent use to obtain catalyst.
Embodiment 6
1) carrier preliminary treatment: with 5g 100-120 purpose SiO
2Carrier is at 110 ℃ of oven dry 2h.
2) dipping: with 1.215g NiCl
26H
2O and 0.085g SnCl
4Be mixed with the 10ml mixed aqueous solution and be mixed with the 10ml mixed aqueous solution, put into the carrier after the oven dry then and carry out incipient impregnation at ultrasonic wave, the load capacity of Ni is 6wt%, and the Sn load capacity is 60min for the 0.8wt% dip time, and ultrasonic power is 60W.
3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 1.2MPa, 230 ℃ of EATs, 100 ℃ of leaving air temps.
4) roasting: at precursor under the microwave radiation condition that drying is good under 200 ℃ of temperature, roasting 100min.
5) reduction: in ice-water bath with the KBH of 2mol/L
4Solution, the NaOH solution through 2.0mol/L is with KBH
4Solution is adjusted to neutrality, is added drop-wise to the Ni after the roasting with the speed of 5ml/min
2+/ SiO
2In, KBH
4/ Ni=4 (mol ratio) after dropwising, continues to be stirred to no bubble and produces and finish, and is washed with distilled water to neutrality earlier, is kept in the ethanol with after the washing with alcohol three times again, and it is subsequent use to obtain catalyst.
Each catalyst activity rating result in the reaction of the synthetic TDA of catalysis DNT hydrogenation sees attached list 1:
Subordinate list 1
Claims (2)
1. a preparation method who is used to select hydrogenation support type Ni-B amorphous catalyst is characterized in that comprising the steps:
(1) carrier preliminary treatment: with 80-150 purpose SiO
2, Al
2O
3Or absorbent charcoal carrier is at 80-120 ℃ of oven dry 1-3h, with the moisture evaporate to dryness in the carrier;
(2) dipping: the load capacity by Ni is 1-15wt%, and nickel chloride, nickel nitrate or nickel acetate are mixed with solution, puts into the carrier after the oven dry then, is the medium volume dipping of 30-100W ultrasonic wave 20-120min at power;
(3) drying: will flood the suspension of accomplishing through spray-drying and carry out drying, spray-dired operating condition is: air intake pressure 0.7-1.5MPa, EAT 220-250 ℃, leaving air temp 100-140 ℃;
(4) roasting: under 150-200 ℃ of temperature, roasting 20-100min obtains Ni at precursor under the microwave radiation condition that drying is good
2+/ carrier;
(5) reduction: with the KBH4 solution of 0.5-2.5mol/L, the NaOH solution through 2.0mol/L is with KBH in ice-water bath
4Solution is adjusted to neutrality, presses KBH
4: the Ni mol ratio is 1-5, is added drop-wise to the Ni after the roasting with the speed of 3-10ml/min
2+In/the carrier, after dropwising, continue to be stirred to no bubble and produce and finish, be washed with distilled water to neutrality earlier, be kept in the ethanol with after the washing with alcohol three times again, make catalyst.
2. a kind of preparation method who is used to select hydrogenation support type Ni-B amorphous catalyst as claimed in claim 1; It is characterized in that at dipping process also with the soluble salt solution and the Ni solution hybrid infusion of Mo, Zr, Pd, Sn or Pt auxiliary agent; Its metal ion is introduced carrier, and the introducing amount is the 0.1-30wt% of Ni content.
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Cited By (7)
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CN103952719A (en) * | 2014-03-28 | 2014-07-30 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
CN105032429A (en) * | 2015-07-28 | 2015-11-11 | 湖北荆楚理工科技开发有限公司 | Benzoic acid hydrogenation catalyst prepared through micro-wave heating and preparation method |
CN105272863A (en) * | 2014-06-11 | 2016-01-27 | 宁夏明盛染化有限公司 | Preparation method for p-anisidine |
CN105983409A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院大连化学物理研究所 | Nickel-based amorphous hollow microsphere alloy catalyst, and preparation method and application thereof |
CN106967365A (en) * | 2017-04-25 | 2017-07-21 | 昆明理工大学 | A kind of method that abjection combined chloride prepares low-chlorine bleach lac |
CN107008444A (en) * | 2017-04-25 | 2017-08-04 | 昆明理工大学 | A kind of Pd Ni/ γ Al2O3‑SiO2Complex carrier bimetallic catalyst and preparation method thereof |
CN109718779A (en) * | 2018-12-26 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of ball-type skeleton Ni hydrogenation catalyst and its preparation method and application |
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CN103952719A (en) * | 2014-03-28 | 2014-07-30 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
CN105272863A (en) * | 2014-06-11 | 2016-01-27 | 宁夏明盛染化有限公司 | Preparation method for p-anisidine |
CN105983409A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院大连化学物理研究所 | Nickel-based amorphous hollow microsphere alloy catalyst, and preparation method and application thereof |
CN105032429A (en) * | 2015-07-28 | 2015-11-11 | 湖北荆楚理工科技开发有限公司 | Benzoic acid hydrogenation catalyst prepared through micro-wave heating and preparation method |
CN106967365A (en) * | 2017-04-25 | 2017-07-21 | 昆明理工大学 | A kind of method that abjection combined chloride prepares low-chlorine bleach lac |
CN107008444A (en) * | 2017-04-25 | 2017-08-04 | 昆明理工大学 | A kind of Pd Ni/ γ Al2O3‑SiO2Complex carrier bimetallic catalyst and preparation method thereof |
CN109718779A (en) * | 2018-12-26 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of ball-type skeleton Ni hydrogenation catalyst and its preparation method and application |
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