CN102500395A - TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application - Google Patents

TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application Download PDF

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CN102500395A
CN102500395A CN2011103348978A CN201110334897A CN102500395A CN 102500395 A CN102500395 A CN 102500395A CN 2011103348978 A CN2011103348978 A CN 2011103348978A CN 201110334897 A CN201110334897 A CN 201110334897A CN 102500395 A CN102500395 A CN 102500395A
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tio
catalyst
tio2
load
loaded
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CN102500395B (en
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张凤宝
彭文朝
张国亮
范晓彬
戈建华
段卫东
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Caike Huayu Chemical Co ltd
Tianjin University
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HEBEI HUA-CHEM DYE CHEMICAL Co Ltd
Tianjin University
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Abstract

The invention discloses a preparation method and application of a TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst. The TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst enables a commercialized TiO2 P25 nanometer particle to be a carrier, and Ni-Au-Pt nanometer composite metal with the quality to be 2.5-3.5% of the quality of TiO2 is loaded on the carrier, and the mole ratio of Ni: Au: Pt is 1: 0.2-0.4: 0.1-0.4. A preparation process comprises enabling mixed solution of Ni (NO3) 2, HAu Cl4 and H2PtCl6 to serve as a raw material, carrying out steeping, room-temperature aging, vacuum drying, high-temperature calcination and hydrogen reduction to mixed solution, and obtaining the TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst. The catalyst is used for a reaction of catalytic hydrogenation reduction of DNS sodium salt so as to prepare DSD acid. The preparation method and the application of the TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst have the advantages that the catalyst is simple in process during the preparation process, and industrialization is achieved easily. The obtained catalyst is used for the reduction preparation process of the DSD acid, and the catalysis performance is high.

Description

TiO 2Load Ni-Au-Pt nano composite catalyst and preparation method and application
Technical field
The present invention relates to a kind of TiO 2Load Ni-Au-Pt nano composite Preparation of catalysts methods and applications belong to Ni-Au-Pt nanometer alloy catalyst and application technology.
Background technology
Metal oxide supported metal nanoparticle catalyst is applied in the various chemical syntheses owing to its good selectivity more and more.Utilize transition metal oxide as carrier, various metal nanoparticles or multiple metal nanoparticle mixture are loaded on oxide surface and the catalyst processed has good catalytic activity.Spain scientist Corma etc. and have proved that they have good selectivity to the reduction of the nitroaromatic that contains reducibility groups such as carbon-carbon double bond, aldehyde radical, itrile group in the hydrogenating reduction that has been applied in the compound that contains nitro of gold nano grain as the catalyst success that will load in 2008 on titanium dioxide and the tri-iron tetroxide.Started the research boom of people thus to a loaded catalyst new round.Wherein, TiO 2Nano catalyst (the Au/TiO of load 2) because its good catalytic activity and selectivity form the focus into people's research, and be successfully applied in a plurality of reduction reactions.Existing patent generally is the single loaded catalyst of preparation; Yet; Because the price of gold is higher, is unfavorable for the industrialization of this catalyst, and the catalytic activity of gold is not high; Reaction time is often longer, thereby and gold nano grain in use can assemble gradually and reduce this activity of such catalysts and selectivity.
DSD Acid in English 4,4 '-Diaminostilbene-2, 2'-disulfonic? Acid abbreviation, the Chinese called 4,4' - diamino-2, 2'- disulfonic acid, also known as acid stilbene's .DSD acid is a kind of important intermediate of making fluorescer, brightening agent, mothproofing agent, and content was about 100,000 tons in global year.DSD acid by 4,4 '-dinitro talan-2,2 '-sodium salt of disulfonic acid (DNS) is through also original preparation, the traditional reduction method adopts iron powder reducing, needs to add a large amount of additives, labour intensity is big, and environmental pollution is serious.
Summary of the invention
The object of the present invention is to provide a kind of TiO 2Load Ni-Au-Pt nano composite Catalysts and its preparation method and application, the TiO that this method makes 2Load Ni-Au-Pt nanometer alloy catalyst is used for preparing DSD acid process by DNS sodium salt hydro-reduction, and selectivity is high, and this method for preparing catalyst process is simple.
The present invention realizes through following technical scheme, a kind of TiO 2Load Ni-Au-Pt nano composite catalyst, this catalyst is with business-like TiO 2The P25 nano particle is a carrier, it is characterized in that, at TiO 2Load quality is TiO on the carrier 22.5~3.5% Ni-Au-Pt nano composite of quality, wherein the mol ratio of Ni: Au: Pt is 1: 0.2~0.4: 0.1~0.4.
Above-mentioned TiO 2Load Ni-Au-Pt nano composite Preparation of catalysts method is characterized in that comprising following process:
Adopt infusion process, at first by Ni: the mol ratio of Au: Pt be 1: 0.2~0.4: 0.1~0.4 and the gross mass of three kind of metal account for carrier TiO 22.5~3.5% of quality is with Ni (NO 3) 2, HAuCl 4And H 2PtCl 6Three kinds of precursor mixing also are dissolved in the deionized water, in solution, add the business-like TiO of carrier 2P25; In 25~30 ℃ of condition held of temperature ageing, 10~15h; Behind vacuum drying 2~3h under 100~120 ℃ of conditions of temperature, put it into again in the Muffle furnace then, rise to 500~600 ℃ of temperature calcining 2~3h down with the heating rate of 2 ℃/min; After the cooling, with the gained solid in 200~220 ℃ of temperature down with the H of 100mL/min 2: N 2Mixed airflow reduction 1.5~2.5h of=1: 3~4 makes TiO 2Load Ni-Au-Pt nano composite catalyst.
The above-mentioned catalyst or the catalyst applications of method for preparing are used for the reaction that the catalytic hydrogenation reducing DNS sodium salt prepares DSD acid, and used reducing agent is a hydrogen; The reduction process cleaning; Environmentally friendly, selectivity and productive rate are all very high, and catalyst can reuse.
The invention has the advantages that the Preparation of catalysts process adopts the most frequently used infusion process, the preparation process is simple, is easy to realize industrialization.Carrier TiO 2P25 is a kind of business-like nano particle, wide material sources.And be metal Ni by the main body of carried metal, low price.The adding of Au element makes the generation of accessory substance such as no azanol in the course of reaction, and the adding of Pt element has improved catalyst activity, has accelerated reaction speed, reduces production costs effectively.This catalyst is in the process of reduction preparation DSD acid, and catalyst amount is few, need not to add in addition additive, and selectivity and productive rate are all high, and the use of hydrogen makes course of reaction not have discarded object basically and generates cleaning.Catalyst can recycle.
The specific embodiment
Embodiment 1
With 0.105g Ni (NO 3) 2, 0.012g HAuCl 44H 2O, 0.008g H 2PtCl 66H 2O (mol ratio is 7: 2: 1) mixes and is dissolved in the 1mL deionized water.Add 1.0g TiO then 2The P25 solid in 25 ℃ of condition held of temperature ageing 12h, behind vacuum drying 5h under 100 ℃ of conditions of temperature, is put into Muffle furnace with the gained solid then, calcines 3h after rising to 550 ℃ with the heating rate of 2 ℃/min, utilizes the H of 100mL/min then 2With N 2Mixed airflow reductase 12 h (H under 200 ℃ of conditions 2: N 2=1: 3), can make final carrier nanometer catalyst.
Embodiment 2
With 0.091g Ni (NO 3) 2, 0.012g HAuCl 44H 2O, 0.017g H 2PtCl 66H 2O (mol ratio is 6: 2: 2) mixes and is dissolved in the 1mL deionized water.Add 1.0g TiO then 2The P25 solid in 25 ℃ of condition held ageing 12h, behind vacuum drying 5h under 100 ℃ of conditions, is put into Muffle furnace with the gained solid then, calcines 3h after rising to 570 ℃ with the heating rate of 3 ℃/min, utilizes the H of 100mL/min then 2With N 2Mixed airflow reductase 12 h (H under 200 ℃ of conditions 2: N 2=1: 3), can make final carrier nanometer catalyst.
Embodiment 3
With 0.091g Ni (NO 3) 2, 0.009g HAuCl 44H 2O, 0.017g H 2PtCl 66H 2O (mol ratio is 6: 1.5: 2) mixes and is dissolved in the 1mL deionized water.Add 1.0g TiO then 2The P25 solid in 25 ℃ of condition held ageing 12h, behind vacuum drying 5h under 100 ℃ of conditions, is put into Muffle furnace with the gained solid then, calcines 3h after rising to 550 ℃ with the heating rate of 2 ℃/min, utilizes the H of 100mL/min then 2With N 2Mixed airflow reductase 12 h (H under 200 ℃ of conditions 2: N 2=1: 3), can make final carrier nanometer catalyst.
Embodiment 4
With 0.091g Ni (NO 3) 2, 0.009g HAuCl 44H 2O, 0.013g H 2PtCl 66H 2O (mol ratio is 6: 2: 1.5) mixes and is dissolved in the 1mL deionized water.Add 1.0g TiO then 2The P25 solid in 25 ℃ of condition held ageing 12h, behind vacuum drying 5h under 100 ℃ of conditions, is put into Muffle furnace with the gained solid then, calcines 3h after rising to 600 ℃ with the heating rate of 2 ℃/min, utilizes the H of 100mL/min then 2With N 2Mixed airflow reductase 12 h (H under 200 ℃ of conditions 2: N 2=1: 3), can make final carrier nanometer catalyst.

Claims (3)

1. TiO 2Load Ni-Au-Pt nano composite catalyst, this catalyst is with business-like TiO 2The P25 nano particle is a carrier, it is characterized in that, at TiO 2Load quality is TiO on the carrier 22.5~3.5% Ni-Au-Pt nano composite of quality, wherein the mol ratio of Ni: Au: Pt is 1: 0.2~0.4: 0.1~0.4.
2. one kind prepares by the described TiO of claim 1 2Load Ni-Au-Pt nano composite catalyst method is characterized in that comprising following process:
Adopt infusion process, at first by Ni: the mol ratio of Au: Pt be 1: 0.2~0.4: 0.1~0.4 and the gross mass of three kind of metal account for carrier TiO 22.5~3.5% of quality is with Ni (NO 3) 2, HAuCl 4And H 2PtCl 6Three kinds of precursor mixing also are dissolved in the deionized water, in solution, add the business-like TiO of carrier 2P25; In 25~30 ℃ of condition held of temperature ageing, 10~15h; Behind vacuum drying 2~3h under 100~120 ℃ of conditions of temperature, put it into again in the Muffle furnace then, rise to 500~600 ℃ of temperature calcining 2~3h down with the heating rate of 2 ℃/min; After the cooling, with the gained solid in 200~220 ℃ of temperature down with the H of 100mL/min 2: N 2Mixed airflow reduction 1.5~2.5h of=1: 3~4 makes TiO 2Load Ni-Au-Pt nano composite catalyst.
3. press the described TiO of claim 1 for one kind 2Load Ni-Au-Pt nano composite catalyst or the TiO that makes by the described method of claim 2 2Load Ni-Au-Pt nano composite Application of Catalyst, be used for catalytic reduction 4,4 '-dinitro talan-2,2 '-sodium salt of disulfonic acid preparation 4,4 '-diaminobenzil-2,2 '-disulfonic acid.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103301853A (en) * 2013-06-20 2013-09-18 武汉大学 Gold catalyst removing carbon monoxide, formaldehyde and ethylene and preparation and application
CN108017565A (en) * 2017-12-22 2018-05-11 江苏淮河化工有限公司 Hydrogenating reduction method prepares DSD acid
US20190111415A1 (en) * 2017-10-12 2019-04-18 Korea Institute Of Science And Technology Immiscible composite catalyst for synthesis of hydrogen peroxide and methods for synthesizing of hydrogen peroxide using the same
CN114011430A (en) * 2021-12-10 2022-02-08 山西晋光化工有限公司 Catalyst for synthesizing DSD acid and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206175A (en) * 2011-04-18 2011-10-05 河北华戈染料化学股份有限公司 Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206175A (en) * 2011-04-18 2011-10-05 河北华戈染料化学股份有限公司 Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王珏等: "DNS加氢还原制备DSD酸", 《化学工业与工程》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103301853A (en) * 2013-06-20 2013-09-18 武汉大学 Gold catalyst removing carbon monoxide, formaldehyde and ethylene and preparation and application
CN103301853B (en) * 2013-06-20 2015-11-18 武汉大学 A kind of Au catalyst and preparation and application of removing carbon monoxide, formaldehyde and ethene
US20190111415A1 (en) * 2017-10-12 2019-04-18 Korea Institute Of Science And Technology Immiscible composite catalyst for synthesis of hydrogen peroxide and methods for synthesizing of hydrogen peroxide using the same
US10888843B2 (en) * 2017-10-12 2021-01-12 Korea Institute Of Science And Technology Immiscible composite catalyst for synthesis of hydrogen peroxide and methods for synthesizing of hydrogen peroxide using the same
CN108017565A (en) * 2017-12-22 2018-05-11 江苏淮河化工有限公司 Hydrogenating reduction method prepares DSD acid
CN114011430A (en) * 2021-12-10 2022-02-08 山西晋光化工有限公司 Catalyst for synthesizing DSD acid and preparation method and application thereof
CN114011430B (en) * 2021-12-10 2024-04-02 山西晋光化工有限公司 Catalyst for synthesizing DSD acid and preparation method and application thereof

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