US20040164028A1 - Bimetallic catalyst for the treatment of water containing nitrates - Google Patents

Bimetallic catalyst for the treatment of water containing nitrates Download PDF

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Publication number
US20040164028A1
US20040164028A1 US10/735,597 US73559703A US2004164028A1 US 20040164028 A1 US20040164028 A1 US 20040164028A1 US 73559703 A US73559703 A US 73559703A US 2004164028 A1 US2004164028 A1 US 2004164028A1
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US
United States
Prior art keywords
catalyst
noble metal
hydrotalcite
accordance
incorporated
Prior art date
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Abandoned
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US10/735,597
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English (en)
Inventor
Avelino Corma Canos
Antonio Palomares Gimeno
Jose Prato Moreno
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Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
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Assigned to UNIVERSIDAD POLITECNICA DE VALENCIA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS reassignment UNIVERSIDAD POLITECNICA DE VALENCIA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CORMA CANOS, AVELINO, PALOMARES GIMENO, ANTONIO EDUARDO, PRATO MORENO, JOSE GREGORIO
Publication of US20040164028A1 publication Critical patent/US20040164028A1/en
Priority to US12/195,401 priority Critical patent/US7857981B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/166—Nitrites
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Definitions

  • the present invention belongs to the field of catalysts, particularly that of bimetallic catalysts, useful in the purification of natural waters by means of catalytic elimination of nitrates and nitrites that are present.
  • Nitrates are stable ions highly soluble in water, which can be eliminated by physical/chemical treatments such as ion exchange, reverse osmosis and electrodialysis. Nevertheless, these techniques end up by generating a concentrated solution of these ions and it is therefore necessary to employ other techniques that are more respectful of the environment [A, Kapoor and T. Viraraghavan, J., Environ. Eng., 123 (4), 371 (1997)].
  • the present invention aims to overcome the drawbacks of conventional treatments of waters containing nitrates by means of a catalyst for the reduction of nitrates in waters in which it has been surprisingly seen that a support with an Mg/Al structure and especially with a hydrotalcite structure in the formulation of the overall catalyst produces a catalyst that is very active, selective and stable.
  • the present invention refers to a bimetallic catalyst for the treatment of waters containing nitrates, which comprises a support and at least one noble metal and at least one non-noble metal, characterized in that the support, in elemental and anhydrous form, has a composition corresponding to the formula:
  • X is at least one noble metal, preferably selected among Pd, Pt, Ru, Ir and Rh;
  • Y is at least one non-noble metal, preferably selected among Cu, Sn, Zn, In, Ni, Ag, Fe or Co,
  • Mg is magnesium
  • Al is aluminium.
  • Mg and Al preferably form a hydrotalcite structure.
  • the metals can have been incorporated into the hydrotalcite structure by impregnation or during the synthesis stage of the hydrotalcite.
  • non-noble metal or metals can have been incorporated into the hydrotalcite structure during the synthesis stage of the hydrotalcite, in which case the noble metal or metals have been incorporated by impregnation in a stage subsequent to the synthesis stage.
  • Mg and Al are present in the form of aluminium and magnesium oxides obtained from a precursor of hydrotalcite by calcination in air at temperatures between 350 and 800° C., for a period of between 1 and 20 hours.
  • at least one noble metal and at least one non-noble metal can have been incorporated into the structure of the hydrotalcite precursor during the synthesis stage of the hydrotalcite.
  • the non-noble metal or metals have been incorporated into the structure of the precursor during the synthesis stage of the hydrotalcite in order to form oxides of Mg/Al/non-noble metal, in which case the noble metal or metals have been incorporated by impregnation in a stage subsequent to the synthesis stage.
  • the catalyst of the present invention is useful for water treatment processes wherein the nitrates are eliminated in the liquid phase, and which consist of reducing the nitrates to nitrogen using a reducing agent, such as might be for example hydrogen, formic acid, hydrocarbons and combinations thereof.
  • a reducing agent such as might be for example hydrogen, formic acid, hydrocarbons and combinations thereof.
  • the hydrotalcite consists of a laminar structure that can be considered to derive from that of brucite, Mg(OH) 2 , wherein some of the magnesium atoms octahedrally coordinated by OH groups and which form an infinite two-dimensional lamina, have been replaced with trivalent metals (in this case, Al 3+ ), thereby generating an excess of positive charge in the lamina which has to be compensated with anions (normally, CO 3 2 ⁇ ) which are located in the interlaminar space.
  • the laminas are stacked one on top of another, giving rise to a laminar structure for these compounds.
  • Hydrotalcite can be prepared by, for example, co-precipitation of a solution containing the appropriate metals in the form of soluble salts, preferably aluminium nitrates and magnesium nitrate, with an alkaline solution formed by a mixture of hydroxides and alkaline carbonates, preferably NaOH and Na 2 CO 3 , in sufficient concentration for achieving total precipitation of the metals of the first solution.
  • the products are filtered and washed until the filtrate has a pH between 6.8 and 7.5. Finally, the product is calcined at a temperature above 300° C.
  • the noble metal preferably Pd, Pt, Ru, Ir or Rh, and the non-noble metal, preferably Cu, Sn, Zn, In, Ni, Fe, Ag or Co, are impregnated on a hydrotalcite base. These metals are incorporated by impregnation at a temperature between 10 and 100° C., and preferably between 15 and 80 ° C., on the hydrotalcite starting from an aqueous solution of a soluble salt which, when calcined, produces the corresponding oxide on the hydrotalcite.
  • the percentage of noble metal oxide with respect to the mixture obtained is between 0.1 and 30% by weight, preferably between 0.5 and 15% by weight.
  • the preferred percentage of non-noble metal lies in the range 0.05% to 10% by weight.
  • One or two metals can also be incorporated into the hydrotalcite by adding a soluble salt of the metal to the solution that contained the Mg and Al salts during the synthesis stage.
  • concentrations are adjusted in order to obtain the desired proportions of metals in the final catalyst.
  • a copper compound such as for example copper nitrate
  • the necessary amount of a copper compound is added to the solution of aluminium nitrate and magnesium nitrate in order to obtain the quantity of copper that is desired in the final product.
  • the synthesised hydrotalcite or preferably hydrotalcite synthesised at a temperature between 350 and 800° C. for a period of between 1 and 20 hours, or more preferably hydrotalcite calcined at between 400 and 600° C. for a period of between 1 and 12 hours, can be used as support.
  • the calcination is carried out in the presence of air and preferably in the absence of CO 2 .
  • the second metal can be incorporated by impregnation on the hydrotalcite structure or preferably on the structure resulting from calcining the synthesis hydrotalcite according to the calcination conditions stated above.
  • the resulting material can be used as a catalyst or preferably calcined according to the conditions described above before being used as a catalyst.
  • the material is suitable for the treatment of waters containing nitrates and nitrites, in particular for eliminating nitrates present in natural waters.
  • a reducing agent preferably hydrogen or a source of hydrogen, such as for example hydrocarbons dissolved in nitrogen
  • the catalyst reduces the nitrates to nitrogen, forming a minimum quantity of ammonia.
  • FIG. 1 shows the concentration of nitrates against reaction time in the catalysts of examples 1, 2 and 3, according to the reaction conditions described in example 4;
  • FIG. 2 shows the concentration of nitrites against reaction time in the catalysts of examples 1, 2 and 3, according to the reaction conditions described in example 4;
  • FIG. 3 shows the concentration of ammonium against reaction time in the catalysts of examples 1, 2 and 3, according to the reaction conditions described in example 4.
  • the precipitate is then left to age for 18 h at 80° C. and it is filtered and washed until the pH of the wash waters is 7.
  • the sample obtained is calcined at 750° C., with the BET area being 178 m 2 .g ⁇ 1 .
  • the necessary quantity of copper is then impregnated at pore volume in order to 1.5% by weight of copper.
  • the impregnated material is then dried and calcined at 500° C.
  • the necessary quantity of palladium is then impregnated at pore volume in order to 5% by weight of palladium. It is then dried and calcined at 500° C.
  • a catalyst is prepared starting from a solution (A): 1.2 M in Mg(II) and 0.3 M in Al (III), and an aqueous solution (B): 3.33 M of NaOH and 1 M of Na 2 CO 3 are prepared.
  • the precipitate is then left to age for 18 h at 80° C. and it is filtered and washed until the pH of the wash waters is 7.
  • the sample obtained is calcined at 750° C., with the BET area being 170 m 2 .g ⁇ 1 and the copper content being 1.5% weight.
  • the necessary quantity of palladium is then impregnated at pore volume in order to 5% by weight of palladium.
  • the impregnated material is dried and calcined at 500° C.
  • the catalyst of example 1 is used in order to evaluate its capacity for elimination of nitrates.
  • the material is first reduced in a flow of hydrogen at 500° C. for 2 hours and then hydrogenated in the liquid phase for 60 minutes at ambient temperature.
  • 0.8 g of catalyst is used in order to try to eliminate the nitrates present in 600 ml of a solution with a nitrates concentration of 90 mg/l.
  • the reaction is left to take place for 2 hours and the evolution of the concentration of nitrates, nitrites and NH 4 + during the reaction can be seen in FIGS. 2 and 3.
  • the catalyst of example 2 is used in order to evaluate its capacity for elimination of nitrates following the same process as that described in example 4 and with the results shown in FIGS. 1, 2 and 3 being observed.
  • the catalyst of example 3 is used in order to evaluate its capacity for elimination of nitrates following the same process as that described in example 4 and with the results obtained in FIGS. 1, 2 and 3 being observed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
US10/735,597 2001-06-15 2003-12-12 Bimetallic catalyst for the treatment of water containing nitrates Abandoned US20040164028A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/195,401 US7857981B2 (en) 2001-06-15 2008-08-20 Bimetallic catalyst for the treatment of water containing nitrates

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ES200101471 2001-06-15
ES200101471A ES2186547B1 (es) 2001-06-15 2001-06-15 Un catalizador bimetalico para el tratamiento de aguas que contienen nitratos.
PCT/ES2002/000296 WO2002102507A1 (es) 2001-06-15 2002-06-14 Un catalizador bimetalico para el tratamiento de aguas que contienen nitratos

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PCT/ES2002/000296 Continuation WO2002102507A1 (es) 2001-06-15 2002-06-14 Un catalizador bimetalico para el tratamiento de aguas que contienen nitratos

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EP (1) EP1466664B1 (es)
JP (1) JP2004528982A (es)
AT (1) ATE374076T1 (es)
DE (1) DE60222700T2 (es)
DK (1) DK1466664T3 (es)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030176275A1 (en) * 2000-06-13 2003-09-18 Volker Fraaije Catalytic solid supported on calcined hydrotalcite for olefinic polymerisation
CN100412001C (zh) * 2006-10-09 2008-08-20 北京理工大学 一种可再生循环使用的酸性废水处理剂
EP2130583A1 (en) * 2007-03-09 2009-12-09 Daicel Chemical Industries, Ltd. Method for producing carbonyl compound
EP2579984A1 (en) * 2010-06-14 2013-04-17 SK Innovation Co., Ltd. Catalyst for aqueous phase reforming of biomass-derived polyols and preparation method thereof

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JP4502877B2 (ja) * 2005-05-11 2010-07-14 株式会社神戸製鋼所 硝酸還元触媒組成物およびそれを用いた硝酸溶液処理方法
JP5137083B2 (ja) * 2009-07-27 2013-02-06 独立行政法人日本原子力研究開発機構 硝酸イオンの還元分解用触媒
US9248436B2 (en) * 2010-08-26 2016-02-02 Basf Se Highly active shift catalysts
CN103570114B (zh) * 2013-10-24 2015-03-25 上海大学 一种还原处理水中硝酸盐的方法
CN104944499A (zh) * 2015-05-25 2015-09-30 常州大学 一种处理皮革废水中高浓度氨氮的方法
CN108191029A (zh) * 2017-06-05 2018-06-22 湖南迪亚环境工程有限公司 一种化学去除亚硝酸盐的装置和方法
CN109095586A (zh) * 2018-08-08 2018-12-28 中国科学院南京土壤研究所 一种含铜混合金属氧化物/过硫酸钠体系及其应用
US11964884B2 (en) 2020-03-06 2024-04-23 Iowa State University Research Foundation, Inc. System and method for removing nitrate from water

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030176275A1 (en) * 2000-06-13 2003-09-18 Volker Fraaije Catalytic solid supported on calcined hydrotalcite for olefinic polymerisation
US7094724B2 (en) * 2000-06-13 2006-08-22 Bassell Polyelefine Gmbh Catalytic solid supported on calcined hydrotalcite for olefinic polymerisation
CN100412001C (zh) * 2006-10-09 2008-08-20 北京理工大学 一种可再生循环使用的酸性废水处理剂
EP2130583A1 (en) * 2007-03-09 2009-12-09 Daicel Chemical Industries, Ltd. Method for producing carbonyl compound
EP2130583A4 (en) * 2007-03-09 2012-07-18 Daicel Chem PROCESS FOR PREPARING A CARBONYL COMPOUND
EP2579984A1 (en) * 2010-06-14 2013-04-17 SK Innovation Co., Ltd. Catalyst for aqueous phase reforming of biomass-derived polyols and preparation method thereof
EP2579984A4 (en) * 2010-06-14 2014-02-26 Sk Innovation Co Ltd CATALYST FOR WATER PHASE REFORMATION OF BIOMASS POLYOLS AND METHOD OF MANUFACTURING THEREOF
US9095844B2 (en) 2010-06-14 2015-08-04 Sk Innovation Co., Ltd. Catalyst for aqueous phase reforming of biomass-derived polyols and preparation method thereof

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US20080302736A1 (en) 2008-12-11
WO2002102507A1 (es) 2002-12-27
EP1466664B1 (en) 2007-09-26
PT1466664E (pt) 2007-12-27
EP1466664A1 (en) 2004-10-13
JP2004528982A (ja) 2004-09-24
ES2186547B1 (es) 2004-08-01
ES2294139T3 (es) 2008-04-01
DE60222700T2 (de) 2008-07-17
US7857981B2 (en) 2010-12-28
ES2186547A1 (es) 2003-05-01
ATE374076T1 (de) 2007-10-15
DK1466664T3 (da) 2008-01-14
DE60222700D1 (de) 2007-11-08

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