CN1524613A - High activity wet oxidation catalyst with carbon material as carrier and its preparation method - Google Patents
High activity wet oxidation catalyst with carbon material as carrier and its preparation method Download PDFInfo
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- CN1524613A CN1524613A CNA031173756A CN03117375A CN1524613A CN 1524613 A CN1524613 A CN 1524613A CN A031173756 A CNA031173756 A CN A031173756A CN 03117375 A CN03117375 A CN 03117375A CN 1524613 A CN1524613 A CN 1524613A
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Abstract
The invention provides a high-activity wet-oxidation catalyst using carbon as carrier as well as its preparing method. It contains one of the noble metals: Pt, Pd, Ru, Ir Rh and Au, uses carbon as carrier and has the weight percents of component: noble metal 0.25-0.5% and the rest carbon, where the carbon surface area is 80-1500 sq m/g. It can heighten dipersivity and utilization ratio of noble metal and at the same time has stronger ability to absorb organic matters and dissolved oxygen, very adaptive to catalysis and its content of noble metal is only 1/4-1/8 of Japanese similar catalysts and its catalyzing activity is 15-75% higher than the Japanese similar catalysts'. It can largely reduce processing cost and is an effective way to extend the application of wet catalytic oxidizing technique in processing waste water.
Description
Technical field
The present invention relates to a kind of is the catalytic wet oxidation Catalysts and its preparation method of active component with the noble metal, and this catalyst is specially adapted to handle the organic wastewater of high-concentration hardly-degradable.
Background technology
In the technology of handling high concentration hard-degraded organic waste water, that comparatively advanced is catalytic wet oxidation technology (CWOP).This technology is in the presence of catalyst, and bubbling air or oxygen, and under uniform temperature and pressure condition organic wastewater is carried out purified treatment make C, H in the waste water, O, N respectively with CO
2, H
2O and N
2Form discharging, and non-secondary pollution.The core of this technology is a catalyst.But present catalyst is mostly with TiO
2, ZrO
2Or porous metal materials such as their composite oxides or Langaloy are carrier, with iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten and at least a metallic compound insoluble or that be insoluble in water deposit on the above-mentioned carrier, as Chinese patent CN1121322A disclosed " method of wastewater treatment of use in waste water treatment catalyst and manufacture method thereof and this catalyst of use " and CN1084496A disclosed " containing high-enriched organics and ammonia trade effluent wet oxidation cleaning catalyst and preparation method ", they all will use more noble metal as active component, not only be difficult to reduce the cost of catalyst, and TiO
2, ZrO
2Deng carrier and noble metal coupling, its catalytic activity is unsatisfactory.Therefore, be necessary prior art is improved.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of active high, bullion content is low and be the wet oxidizing catalyst of carrier with the material with carbon element.
It is the preparation method of the wet oxidizing catalyst of carrier with the material with carbon element that another object of the present invention provides above-mentioned.
A further object of the present invention provides the preparation method of carrier one material with carbon element of above-mentioned wet oxidizing catalyst.
Wet oxidizing catalyst provided by the invention contains a kind of among precious metals pt, Pd, Ru, Ir, Rh, the Au, it is characterized in that it is carrier with carbon, the percentage by weight of its component is: noble metal 0.25-0.5%, all the other are carbon, and the surface area of carbon is a 80-1500 rice
2/ gram.
Provided by the invention is that the preparation method of the wet oxidizing catalyst of carrier is that to adopt the spraying infusion process be a kind of nitrate in the precious metals pt, Pd, Ru, Ir, Rh, Au of 10-20wt% or chloride solution with concentration under 90 ℃ of heating, the state that stirs spraying was flooded 1-2 hour with the material with carbon element, it is supported on the material with carbon element carrier, after treating the moisture evaporate to dryness, at 100 ℃ of following vibration drying 2-3 hours, use hydrogen reducing 3 hours down at 300-500 ℃ again, obtaining with the material with carbon element is the wet oxidizing catalyst of carrier.
Provided by the invention is that the preparation method of the wet oxidizing catalyst of carrier adopts the spraying infusion process that a kind of nitrate among precious metals pt, Pd, Ru, Ir, Rh, the Au or chloride solution are supported on the material with carbon element carrier with the material with carbon element, it is characterized in that the material with carbon element carrier adopts following process to make:
A, to select bamboo cheap and easy to get, coconut husk, coal for use be raw material, after one or more shapes in the section of being processed into, joint, piece, the sheet, at 100 ℃ of following vacuum drying 20-28 hours;
B, a kind of activator of putting into zinc chloride that concentration is 30-80wt%, potassium sulfide, phosphoric acid, potassium hydroxide soaked 1-2 days, at 100 ℃ of following vacuum drying 20-28 hours;
C, under nitrogen protection, carry out the roasting charing of three stages by following temperature and time: 250-350 ℃ roasting 2-3 hour; 450-500 ℃ roasting 2-4 hour; 650-750 ℃ roasting 3-5 hour;
Be washed with water to cleaning solution PH=6-7 after D, the cooling,, promptly get the material with carbon element carrier at 100 ℃ of following vacuum drying 20-28 hours.
The present invention compared with prior art has following advantage and effect:
1, carbon carrier has higher specific surface area and flourishing pore structure, can improve the dispersiveness and the utilization rate of noble metal, it has stronger adsorption capacity to organic matter and dissolved oxygen simultaneously, 200-300 ℃ of temperature, under the 3-15Mpa pressure, its absorption affinity is well suited for catalytic action, carbon carrier can with precious metals pt, Pd, Ru, Ir, Rh, Au isoreactivity deposits yields concerted catalysis effect, thereby can obtain better catalytic activity;
2, bullion content only is the 1/4-1/8 of Japanese similar catalyst, and under situations such as same treatment condition, identical simulated wastewater, same catalyst consumption, the catalytic activity of the present invention's catalyst (CODcr clearance) exceeds 15-75% than Japanese similar catalyst;
3, the carbon carrier raw material is easy to get, and good and cheap, and its cost is far below other carrier.
4, the carbon carrier processing method is simple, and saves the bonding forming operation in the conventional preparing carriers.
5, this catalyst can reduce the processing cost of high concentration hard-degraded organic waste water greatly, for the catalytic wet oxidation technology finds effective way applying aspect the wastewater treatment.
The catalytically active assessment of the present invention and Japanese similar catalyst:
Stir 800 rev/mins brute force, in the autoclave of intermittent duty, carry out the catalytic wet oxidation reaction with simulated wastewater,, calculate the percentage that COD reduces by analyzing the COD data before and after the operation.
The composition of simulated wastewater: ammonium sulfate is equivalent to NH
3-N6000mg/L, succinic acid is equivalent to COD7000mg/L.
Reaction unit: autoclave, its technical conditions:
Reactor volume 250mL, simulated wastewater amount 80mL, pH value 11,250 ℃ of initial temperatures, 275 ℃ ± 5 ℃ of temperature controls, air ratio 1: 1, mixing speed 800rpm, 30 minutes reaction time, initial pressure 4.3Mpa.See Table 1.
The specific embodiment
Embodiment 1
A, to select hard, fine and close, growth period bamboo more than a year for use be raw material, is processed into required section or joint, 100 ℃ of following vacuum drying 20 hours;
B, to put into concentration be that the zinc chloride activation agent of 50wt% was soaked 1 day, 100 ℃ of following vacuum drying 24 hours;
C, under nitrogen protection, carry out the roasting charing of three stages: 250 ℃ of roastings 3 hours by following temperature and time; 450 ℃ of roastings 4 hours; 650 ℃ of roastings 5 hours;
Be washed with water to cleaning solution PH=6-7 after D, the cooling,, promptly get the material with carbon element carrier 100 ℃ of following vacuum drying 20 hours;
E, to adopt the spraying infusion process be that nitrate solution spraying under 90 ℃ of heating, the state that stirs of the precious metals pt of 10wt% was flooded 1 hour with concentration, and it is supported on the material with carbon element carrier;
F, treat the moisture evaporate to dryness after, 100 ℃ of following vibration dryings 2 hours, again 300 ℃ down with hydrogen reducings 3 hours, obtaining with the material with carbon element is the wet oxidizing catalyst of carrier, its composition is:
Precious metals pt 0.25%, carbon 99.75%, and the surface area of carbon is 80 meters
2/ gram.
Embodiment 2
A, to select discarded coconut husk for use be raw material, is processed into required or sheet, 100 ℃ of following vacuum drying 28 hours:
B, to put into concentration be that the potassium hydroxide activator of 30wt% soaked 2 days, 100 ℃ of following vacuum drying 28 hours;
C, under nitrogen protection, carry out the roasting charing of three stages: 350 ℃ of roastings 1 hour by following temperature and time; 500 ℃ of roastings 2 hours; 750 ℃ of roastings 3 hours;
Be washed with water to cleaning solution PH=6-7 after D, the cooling, promptly got carbon carrier in 28 hours 100 ℃ of following vacuum drying;
E, to adopt the spraying infusion process be that chloride solution spraying under 90 ℃ of heating, the state that stirs of the noble metal Rh of 20wt% was flooded 1-2 hour with concentration, and it is supported on the material with carbon element carrier;
F, treat the moisture evaporate to dryness after, 100 ℃ of following vibration dryings 3 hours, again 500 ℃ down with hydrogen reducings 3 hours, be able to the wet oxidizing catalyst that carbon is carrier, its composition is:
Noble metal Rh 0.29%, carbon 99.71%, and the surface area of carbon is 1400 meters
2/ gram.
Embodiment 3
A, to select commercially available activated carbon for use be carrier, and adopting the spraying infusion process is that chloride solution spraying under 90 ℃ of heating, the state that stirs of the noble metal Ru of 15wt% was flooded 2 hours with concentration, and it is supported on the material with carbon element carrier;
B, treat the moisture evaporate to dryness after, 100 ℃ of following vibration dryings 2 hours, again 400 ℃ down with hydrogen reducings 3 hours, be able to the wet oxidizing catalyst that carbon is carrier, its composition is:
Noble metal Ru 0.5%, carbon 95.5%, and the surface area of carbon is 840 meters
2/ gram.
Table 1, the catalytic activity of the present invention and Japanese similar catalyst (CODcr clearance) contrast
| Carrier/raw material | Catalyst numbering/catalyst amount | Bullion content (%) | Catalytic activity (COD CrClearance %) | Remarks |
| TiO 2 | CAT (Japan)/8g | ?2.00 | ?80.30 | |
| TiO 2 | CAT (Japan)/4g | ?2.00 | ?53.00 | |
| ZT1/ bamboo 1 | ?CatZ1/4g | ?0.50 | ?88.20 | 98N/ |
| ZT2/ bamboo 2 | ?CatZ2/4g | ?0.50 | ?85.0 | 118N/ |
| ZT3/ bamboo 3 | ?CatZ3/4g | ?0.50 | ?91.30 | |
| The ZT4/ coconut husk | ?CatZ4/4g | ?0.50 | ?89.73 | |
| The ZT5/ coconut husk | ?CatZ5/4g | ?0.50 | ?84.98 | |
| ZT6/ bamboo 5 | ?CatZ6/4g | ?0.50 | ?85.15 | |
| ZT7/ bamboo 6 | ?CatZ7/4g | ?0.50 | ?83.42 | |
| The ZT8/ coconut husk | ?CatZ8/4g | ?0.50 | ?86.48 | |
| ZT9/ bamboo 7 | ?CatZ9/4g | ?0.50 | ?84.92 | |
| ZT10/ bamboo 8 | ?CatZ10/4g | ?0.50 | ?87.19 | |
| ZT11/ bamboo 9 | ?CatZ11/4g | ?0.50 | ?77.90 | |
| Industrial activited carbon 1/ coal | ?Catm1/4g | ?0.50 | ?74.14 | 184N/ |
| Industrial activited carbon 2/ coal | ?Catm2/4g | ?0.50 | ?73.21 | 84N/ |
| Industrial activited carbon 3/ coal | ?Catm3/48 | ?0.50 | ?81.05 |
Claims (3)
1, a kind of is the high activity wet oxidizing catalyst of carrier with the material with carbon element, contain a kind of among precious metals pt, Pd, Ru, Ir, Rh, the Au, it is characterized in that it is carrier with the material with carbon element, the percentage by weight of its component is: noble metal 0.25-0.5%, all the other are carbon, and the surface area of carbon is a 80-1500 rice
2/ gram.
2, a kind of is the preparation method of the wet oxidizing catalyst of carrier with the material with carbon element, to it is characterized in that adopting the spraying infusion process be a kind of nitrate in the precious metals pt, Pd, Ru, Ir, Rh, Au of 10-20wt% or chloride solution with concentration under 90 ℃ of heating, the state that stirs, and spraying was flooded 1-2 hour, it is supported on the material with carbon element carrier, after treating the moisture evaporate to dryness, at 100 ℃ of following vibration drying 2-3 hours, use hydrogen reducing 3 hours down at 300-500 ℃ again, obtaining with the material with carbon element is the wet oxidizing catalyst of carrier.
3, a kind of is the preparation method of the wet oxidizing catalyst of carrier with the material with carbon element, it adopts the spraying infusion process that a kind of nitrate among precious metals pt, Pd, Ru, Ir, Rh, the Au or chloride solution are supported on the material with carbon element carrier, it is characterized in that the material with carbon element carrier adopts following process to make:
A, to select bamboo cheap and easy to get, coconut husk, coal for use be raw material, after one or more shapes in the section of being processed into, joint, piece, the sheet, at 100 ℃ of following vacuum drying 20-28 hours;
B, a kind of activator of putting into zinc chloride that concentration is 30-80wt%, potassium sulfide, phosphoric acid, potassium hydroxide soaked 1-2 days, at 100 ℃ of following vacuum drying 20-28 hours;
C, under nitrogen protection, carry out the roasting charing of three stages by following temperature and time: 250-350 ℃ roasting 2-3 hour; 450-500 ℃ roasting 2-4 hour; 650-750 ℃ roasting 3-5 hour;
Be washed with water to cleaning solution PH=6-7 after D, the cooling,, promptly get the material with carbon element carrier at 100 ℃ of following vacuum drying 20-28 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031173756A CN1524613A (en) | 2003-02-27 | 2003-02-27 | High activity wet oxidation catalyst with carbon material as carrier and its preparation method |
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|---|---|---|---|
| CNA031173756A CN1524613A (en) | 2003-02-27 | 2003-02-27 | High activity wet oxidation catalyst with carbon material as carrier and its preparation method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007093081A1 (en) * | 2006-02-16 | 2007-08-23 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | Catalyst and process for syngas conversion |
| CN101485987B (en) * | 2009-02-25 | 2011-08-10 | 北京林业大学 | Catalyst for normal temperature and pressure catalysis wet-type oxidation technology and preparation method |
| CN102451712A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Bimetallic catalyst for treating industrial wastewater and preparation method thereof |
| CN102451713A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst for treating industrial wastewater, and preparation method thereof |
| CN102921406A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Active carbon catalyst and preparation method and application thereof |
| CN103263933A (en) * | 2013-06-07 | 2013-08-28 | 郑州源泽水处理设备有限公司 | Noble metal-doped active carbon catalyst |
| CN104084217A (en) * | 2014-07-17 | 2014-10-08 | 厦门大学 | Catalyst for wet oxidation during catalysis of ammonia-nitrogen wastewater and preparation method of catalyst |
| CN104667921A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Method for preparing noble metal catalyst for catalytic wet oxidation |
| CN105854900A (en) * | 2016-04-27 | 2016-08-17 | 厦门大学 | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof |
| CN108654601A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院城市环境研究所 | Photic thermal drivers Pt-CNTs catalytic purifications VOCs |
| CN111372679A (en) * | 2017-11-02 | 2020-07-03 | 南洋理工大学 | Bimetallic composite catalyst for catalytic oxidation of organic pollutants |
-
2003
- 2003-02-27 CN CNA031173756A patent/CN1524613A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007093081A1 (en) * | 2006-02-16 | 2007-08-23 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | Catalyst and process for syngas conversion |
| CN101485987B (en) * | 2009-02-25 | 2011-08-10 | 北京林业大学 | Catalyst for normal temperature and pressure catalysis wet-type oxidation technology and preparation method |
| CN102451712B (en) * | 2010-10-15 | 2014-04-02 | 中国石油化工股份有限公司 | Bimetallic catalyst for treating industrial wastewater and preparation method thereof |
| CN102451713A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst for treating industrial wastewater, and preparation method thereof |
| CN102451712A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Bimetallic catalyst for treating industrial wastewater and preparation method thereof |
| CN102451713B (en) * | 2010-10-15 | 2014-04-02 | 中国石油化工股份有限公司 | Catalyst for treating industrial wastewater, and preparation method thereof |
| CN102921406A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Active carbon catalyst and preparation method and application thereof |
| CN103263933A (en) * | 2013-06-07 | 2013-08-28 | 郑州源泽水处理设备有限公司 | Noble metal-doped active carbon catalyst |
| CN104667921A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Method for preparing noble metal catalyst for catalytic wet oxidation |
| CN104667921B (en) * | 2013-11-29 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of preparation method of noble metal catalyst for CWO |
| CN104084217A (en) * | 2014-07-17 | 2014-10-08 | 厦门大学 | Catalyst for wet oxidation during catalysis of ammonia-nitrogen wastewater and preparation method of catalyst |
| CN104084217B (en) * | 2014-07-17 | 2017-03-08 | 厦门大学 | Catalyst that a kind of ammonia nitrogen waste water CWO is processed and preparation method thereof |
| CN105854900A (en) * | 2016-04-27 | 2016-08-17 | 厦门大学 | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof |
| CN108654601A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院城市环境研究所 | Photic thermal drivers Pt-CNTs catalytic purifications VOCs |
| CN111372679A (en) * | 2017-11-02 | 2020-07-03 | 南洋理工大学 | Bimetallic composite catalyst for catalytic oxidation of organic pollutants |
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