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 PDFInfo
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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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- Prior art keywords
- tio
- catalyst
- tio2
- load
- loaded
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 10
- 239000002184 metal Substances 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000002131 composite material Substances 0.000 title abstract 6
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 239000002114 nanocomposite Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- -1 DNS sodium salt Chemical class 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 abstract 1
- 229910010445 TiO2 P25 Inorganic materials 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000010931 gold Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- Catalysts (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110334897 CN102500395B (en) | 2011-10-31 | 2011-10-31 | TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110334897 CN102500395B (en) | 2011-10-31 | 2011-10-31 | TiO2-loaded Ni-Au-Pt nanometer composite metal catalyst and preparation method and application |
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| Publication Number | Publication Date |
|---|---|
| CN102500395A true CN102500395A (en) | 2012-06-20 |
| CN102500395B CN102500395B (en) | 2013-11-06 |
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ID=46212562
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
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Cited By (4)
| 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)
| 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 |
-
2011
- 2011-10-31 CN CN 201110334897 patent/CN102500395B/en active Active
Patent Citations (1)
| 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)
| Title |
|---|
| 王珏等: "DNS加氢还原制备DSD酸", 《化学工业与工程》 * |
Cited By (7)
| 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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| Publication number | Publication date |
|---|---|
| CN102500395B (en) | 2013-11-06 |
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