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WO2000000285A1 - Elimination des flux de dechets et des produits de process industriels et catalyseurs utilises a cet effet - Google Patents

Elimination des flux de dechets et des produits de process industriels et catalyseurs utilises a cet effet Download PDF

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Publication number
WO2000000285A1
WO2000000285A1 PCT/AU1999/000513 AU9900513W WO0000285A1 WO 2000000285 A1 WO2000000285 A1 WO 2000000285A1 AU 9900513 W AU9900513 W AU 9900513W WO 0000285 A1 WO0000285 A1 WO 0000285A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
red mud
surfactant
liquor
catalytically active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU1999/000513
Other languages
English (en)
Inventor
Manh Hoang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commonwealth Scientific and Industrial Research Organization CSIRO
Original Assignee
Commonwealth Scientific and Industrial Research Organization CSIRO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commonwealth Scientific and Industrial Research Organization CSIRO filed Critical Commonwealth Scientific and Industrial Research Organization CSIRO
Priority to AU45904/99A priority Critical patent/AU758883B2/en
Publication of WO2000000285A1 publication Critical patent/WO2000000285A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C02F11/08—Wet air oxidation
    • 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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation

Definitions

  • This invention relates to catalysts and process for wet oxidation of organic substances present in industrial process and waste streams and other sources of wastes.
  • the present invention is particularly applicable to the wet oxidation of organic substances present in industrial process and waste streams including effluents from the pulp and paper, textile, dairy, wine, tannery, alumina refinery and other chemical and petrochemical industries.
  • organic substances in industrial process and waste streams can be a complex mixture of different compounds ranging from simple low molecular weight hydrocarbons such as alcohols, aldehydes, ketones, carboxyhc acids, low molecular weight fatty acids etc...to a very high molecular weight hydrocarbons such as fulvic and humic acids.
  • Organic substances in industrial waste effluents may contain nitrogen, chloride, and sulphur and some effluents contain process inorganic chemicals which need to be recycled, e.g. black liquor from Bayer process and pulp mill.
  • Activated sludge treatment is a widely used method for the treatment of various kinds of aqueous wastes because of its simplicity and low cost.
  • the microorganisms used for this process can only be effective for low organic content wastes.
  • wet oxidation (wet-air oxidation) is a process in which organic substances in aqueous streams are oxidized by strong oxidants.
  • both non-catalytic and catalytic wet oxidation can be used to convert organic substances into CO 2 and biodegradable low molecular substances, e.g. mono or dicarboxylic acids.
  • Catalytic wet oxidation is a promising alternative technique, which can operate at lower temperatures and pressures.
  • Catalytic wet oxidation can be carried out by means of homogeneous or heterogeneous catalysis.
  • homogeneous catalytic systems There are a number of homogeneous catalytic systems reported which effectively oxidise organic substances from aqueous streams. Examples of such catalytic systems are CuSO 4 and Cu(NO 2 ) 2 .
  • the need for down stream processing to remove the spent catalyst is a distinct disadvantage making homogeneous technology commercially infeasible.
  • Heterogeneous catalysis appears to be a better alternative.
  • the catalytic activity is attributable to surface oxygen available on the solid catalyst.
  • a good catalyst is characterised by high surface oxygen availability and fast oxygen transfer ability.
  • the present invention provides a catalytic system for the oxidation of organic substances present in process and waste streams.
  • the catalyst system comprises red mud, a waste from Bayer process for extraction of alumina from bauxite, as a catalyst support, and at least one catalytically active component selected from Ag, Mn, Cr, Ce, Zr, Ni, Pt, Ru, Cu, V and Co.
  • the said active components may be present in any form such as metallic, oxide, or carbonate and in any oxidation state.
  • the active components may be chemically bound to the support surface or present as separate crystalline phases.
  • the weight ratio of the active components to red mud as support catalyst may be in the range of approximately 0.01:99.99 to 99.9:0.01 but preferably in the range of 0.01:99.99 to 50:50.
  • the catalyst may contain one or more additional components, which alter its activity and selectivity. These additional components may be selected from oxides or carbonates of metal of groups LA , IIA, transition metals and lanthanides or mixtures thereof.
  • Red mud as hereinafter referenced, is a waste material remaining from the Bayer process for extraction of alumina from bauxite.
  • the exact composition of red mud varies depending on the bauxite used but it contains Al, Si, Fe as the major components.
  • the iron is usually present in red mud in the form of hematite, sideride and goethite.
  • the aluminum is usually present in the form of gibbsite, boehmite and sodalite.
  • the silicon is usually present in the form of quartz and sodalite.
  • the red mud also contains smaller amounts of Ti, K, Ca, Na, Mn, Mg, P, S, Mn, Mg, P, S, Cr, Ni, Co, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Ba, Pb, V, U, Th, Ag and significant amounts of residue caustic used in the Bayer process.
  • the red mud may be used as received from industry but is preferably pretreated by any known technique such as washing, drying, calcining, neutralizing, size reducing/uniforming or combination thereof.
  • the invention provides a method of preparing a catalyst comprising the steps of: grinding a red mud slurry to achieve a reduction in the particle size and a more uniform particle size distribution, adding solutions containing ions of at least one catalytically active component selected from Ag, Mn, Cr, Ce, Zr, Ni, Pt, Ru, Cu, V and Co, increasing the pH of the mixture of catalyst support and ions of at least one catalytically active component to co-precipitate the hydroxides or carbonates of the at least one catalytically active component onto the catalyst support, separating the precipitate from the solution, washing and drying the precipitate, and heating the precipitate to a temperature sufficient to activate the catalyst.
  • at least one catalytically active component selected from Ag, Mn, Cr, Ce, Zr, Ni, Pt, Ru, Cu, V and Co
  • a process for improving the sodium recovery and/or silicon removal from a Bayer black liquor including the steps of contacting the catalyst of the invention with a Bayer black liquor in the presence of an oxidising agent and then separating the catalyst from the effluent stream.
  • a novel catalyst system for the wet oxidation of organic substances present in industrial process and waste streams which comprises catalytic active components selected from Ag, Mn, Cr, Ce, Zr, Ni, Pt, Ru, Cu, V and Co supported on a readily abundant red mud, a solid waste from Bayer process for extraction of alumina from bauxite.
  • Red mud received from industry may be as a dry solid or as slurry containing 10-90% solids.
  • Red mud may be subjected to a size reducing/uniforming process such as milling using high-speed stirring and sintered ceramic as the milling media.
  • Other types of grinding may be used provided the primary objective of the grinding is to reduce the larger particles which may be found in the red mud slurry to a particle size less than 10 microns thereby providing a more uniform particle size in the slurry.
  • a solution containing ions of at least one catalytically active component selected from the group of Ag, Mn, Cr, Ce, Zr, Ni, Pt, Ru, Cu, V, Co or mixtures thereof is then prepared and added to the red mud slurry while milling is continued.
  • the solution of active components may be prepared from any suitable source including the chloride, sulphate or nitrate of the metals or carboxyhc acid anions containing sources of the metals such as acetates or the like.
  • the solution may also contain ions of a secondary catalytic component, which affect the activity or selectivity of the main catalytic component. These secondary catalytic components may be selected from the groups IA, IIA, transition metals and lanthanide or mixtures thereof.
  • a caustic solution prepared from the hydroxide or carbonate of sodium is then added to the red mud-catalyst mixture while the milling is continued to co-precipitate hydroxides or carbonates of the catalytically active components from the solution onto the red mud catalyst support.
  • the resulting catalyst is then separated from the liquid phase, washed, dried and calcined at a suitable temperature.
  • the prepared catalyst system is then used to catalyse the wet oxidation of organic substances including chlorine-, sulphur- and nitrogen-containing hydrocarbons to less harmful products as well as affecting the colour and odour removal.
  • the catalyst system and process described in the present invention may also be used as a means of process improvement such as oxidation of the sulphide containing green liquor in pulp and paper industry, improvement of sodium recovery and removal of silicon content in Bayer black liquor as consequences of organic substance destruction.
  • the process of the present invention may be carried out in the presence of oxygen or oxygen-containing gases or any other oxidants such as ozone and hydrogen peroxide, and in any suitable reactor.
  • Additives such as surfactants may be added to enhance the reaction rate.
  • the surfactant may be selected from amines or sodium salts of alkyl sulphonates or alkyl sulphates or any suitable commercial surfactant.
  • the weight ratio of the surfactant to liquor may be in the range of approximately 0.01 :99.99 to 99.99:0.01 but preferably in the range of approximately 0.01:99.99 to 10:90.
  • Example 3 l.l t%Ag 2 O and 4.7wt%Cr 2 O 3 supported on red mud
  • the testing procedure in example 17 was followed except that the catalyst prepared in example 4 was used.
  • the Na 2 CO 3 content in the treated liquor increased to 90.5g/L and the SiO content decreased to 173g/L. This represents a 195% increase in the soda content and a 74% decrease in silica content.
  • Examples 16 and 17 show the effectiveness of the catalyst described in the present invention for increasing the sodium recovery and for reducing the silicon content in the Bayer process.
  • Example 16 also shows that a high proportion of the COD reduction occurs upon initial exposure of the catalyst and support to the effluent to be treated.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un système catalytique d'oxydation par voie humide. Ce système comporte au moins un composant catalytiquement actif qui est choisi parmi les Ag, Mn, Cr, Ce, Zr, Ni, Pt, Ru, Cu, V et Co et qui est supporté sur des boues rouges qui sont un résidu du procédé bayer. Ce catalyseur convient à l'oxydation par voie humide de substances organiques présentes dans les flux de déchets et les produits de process industriels.
PCT/AU1999/000513 1998-06-26 1999-06-25 Elimination des flux de dechets et des produits de process industriels et catalyseurs utilises a cet effet Ceased WO2000000285A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU45904/99A AU758883B2 (en) 1998-06-26 1999-06-25 Catalysts and processes for treatment of industrial process and waste streams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPP4369A AUPP436998A0 (en) 1998-06-26 1998-06-26 A method and catalyst for treatment of waste water
AUPP4369 1998-06-26

Publications (1)

Publication Number Publication Date
WO2000000285A1 true WO2000000285A1 (fr) 2000-01-06

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WO (1) WO2000000285A1 (fr)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008006384A3 (fr) * 2006-07-14 2008-09-04 Scf Technologies As Méthode et dispositif de production de bio-éthanol et d'autres produits de fermentation
WO2010105305A1 (fr) * 2009-03-20 2010-09-23 Very Small Particle Company Pty Ltd Elimination d'impuretés organiques des liqueurs du procédé bayer
CN103521164A (zh) * 2013-10-18 2014-01-22 东南大学 一种烟气脱汞脱硫脱硝吸附剂及其制备方法
CN104971726A (zh) * 2015-05-18 2015-10-14 深圳职业技术学院 用于难降解有机物催化氧化的催化剂及其制备方法与应用方法
WO2015170265A1 (fr) * 2014-05-08 2015-11-12 Hindustan Petroleum Corporation Ltd. Élimination des sulfures présents dans un flux caustique usé par passage sur des catalyseurs actifs en phase solide
CN106315818A (zh) * 2016-09-23 2017-01-11 郑州航空工业管理学院 V2O5/CeO2纳米复合材料在降解含头孢氨苄废水中的应用
CN106881019A (zh) * 2017-02-23 2017-06-23 中国矿业大学 一种利用赤泥和活性炭热活化制备脱硫剂的方法
CN110639546A (zh) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 有机胺工业废水湿式氧化催化剂及工业废水处理中的应用
CN111450841A (zh) * 2020-05-22 2020-07-28 福州大学 一种利用赤泥制备的还原法同时脱硫脱硝催化剂及其制备方法
CN112191248A (zh) * 2020-08-07 2021-01-08 光大水务科技发展（南京）有限公司 一种含固废免烧型污水臭氧氧化处理用催化剂及其制备方法
US11059030B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for bi-reforming processes
US11059720B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst carrier for dry reforming processes
US11066299B1 (en) 2020-01-28 2021-07-20 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for steam reforming processes
WO2021154864A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Compositions catalytiques ayant une acidité améliorée pour des procédés de reformage à sec
WO2021154795A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Support de catalyseur pour procédés de bi-reformage
WO2021154756A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de reformage à sec
CN113457691A (zh) * 2021-07-16 2021-10-01 南京工业大学 一种金银合金纳米花水处理催化剂及其制备方法和应用
US11242246B2 (en) 2020-01-28 2022-02-08 Saudi Arabian Oil Company Catalyst carrier for autothermal reforming processes
US11242245B2 (en) 2020-01-28 2022-02-08 Saudi Arabian Oil Company Catalyst carrier for steam reforming processes
US11286160B2 (en) 2020-01-28 2022-03-29 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for autothermal reforming processes
US11338270B2 (en) 2020-01-28 2022-05-24 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for autothermal reforming processes
US11365120B2 (en) 2020-01-28 2022-06-21 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for steam reforming processes
US11396006B2 (en) 2020-01-28 2022-07-26 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for bi-reforming processes
CN115072658A (zh) * 2022-06-27 2022-09-20 南京师范大学 一种用于甲烷化学链蒸汽重整的改性赤泥载氧体制备方法

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CN111974395B (zh) * 2020-09-25 2023-07-25 郑州大学 一种赤泥基非均相催化剂及制备方法、污染物降解方法

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US8784513B2 (en) 2006-07-14 2014-07-22 Altaca Insaat Ve Dis Ticaret A.S. Method and apparatus for production of bio-ethanol and other fermentation products
WO2008006384A3 (fr) * 2006-07-14 2008-09-04 Scf Technologies As Méthode et dispositif de production de bio-éthanol et d'autres produits de fermentation
WO2010105305A1 (fr) * 2009-03-20 2010-09-23 Very Small Particle Company Pty Ltd Elimination d'impuretés organiques des liqueurs du procédé bayer
CN102361820A (zh) * 2009-03-20 2012-02-22 极小颗粒有限公司 从拜耳溶液中除去有机杂质
CN103521164A (zh) * 2013-10-18 2014-01-22 东南大学 一种烟气脱汞脱硫脱硝吸附剂及其制备方法
CN103521164B (zh) * 2013-10-18 2015-07-15 东南大学 一种烟气脱汞脱硫脱硝吸附剂及其制备方法
US10800691B2 (en) 2014-05-08 2020-10-13 Hindustan Petroleum Corporation Ltd. Removal of sulfides in spent caustic stream over active solid phase catalysts
WO2015170265A1 (fr) * 2014-05-08 2015-11-12 Hindustan Petroleum Corporation Ltd. Élimination des sulfures présents dans un flux caustique usé par passage sur des catalyseurs actifs en phase solide
CN104971726A (zh) * 2015-05-18 2015-10-14 深圳职业技术学院 用于难降解有机物催化氧化的催化剂及其制备方法与应用方法
CN106315818A (zh) * 2016-09-23 2017-01-11 郑州航空工业管理学院 V2O5/CeO2纳米复合材料在降解含头孢氨苄废水中的应用
CN106881019A (zh) * 2017-02-23 2017-06-23 中国矿业大学 一种利用赤泥和活性炭热活化制备脱硫剂的方法
CN110639546A (zh) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 有机胺工业废水湿式氧化催化剂及工业废水处理中的应用
CN110639546B (zh) * 2018-06-27 2022-12-09 中国石油化工股份有限公司 有机胺工业废水湿式氧化催化剂及工业废水处理中的应用
US11066299B1 (en) 2020-01-28 2021-07-20 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for steam reforming processes
US11247898B2 (en) 2020-01-28 2022-02-15 Saudi Arabian Oil Company Catalyst carrier for bi-reforming processes
US11059720B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst carrier for dry reforming processes
US11498053B2 (en) 2020-01-28 2022-11-15 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for dry reforming processes
WO2021154864A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Compositions catalytiques ayant une acidité améliorée pour des procédés de reformage à sec
WO2021154795A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Support de catalyseur pour procédés de bi-reformage
WO2021154756A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de reformage à sec
WO2021154867A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Compositions de catalyseur ayant une acidité améliorée pour des procédés de reformage à la vapeur
US11478777B2 (en) 2020-01-28 2022-10-25 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for dry reforming processes
US11242246B2 (en) 2020-01-28 2022-02-08 Saudi Arabian Oil Company Catalyst carrier for autothermal reforming processes
US11242245B2 (en) 2020-01-28 2022-02-08 Saudi Arabian Oil Company Catalyst carrier for steam reforming processes
US11059030B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for bi-reforming processes
US11286160B2 (en) 2020-01-28 2022-03-29 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for autothermal reforming processes
US11396006B2 (en) 2020-01-28 2022-07-26 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for bi-reforming processes
US11338270B2 (en) 2020-01-28 2022-05-24 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for autothermal reforming processes
US11365120B2 (en) 2020-01-28 2022-06-21 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for steam reforming processes
CN111450841A (zh) * 2020-05-22 2020-07-28 福州大学 一种利用赤泥制备的还原法同时脱硫脱硝催化剂及其制备方法
CN112191248A (zh) * 2020-08-07 2021-01-08 光大水务科技发展（南京）有限公司 一种含固废免烧型污水臭氧氧化处理用催化剂及其制备方法
CN113457691B (zh) * 2021-07-16 2022-04-29 南京工业大学 一种金银合金纳米花水处理催化剂及其制备方法和应用
CN113457691A (zh) * 2021-07-16 2021-10-01 南京工业大学 一种金银合金纳米花水处理催化剂及其制备方法和应用
CN115072658A (zh) * 2022-06-27 2022-09-20 南京师范大学 一种用于甲烷化学链蒸汽重整的改性赤泥载氧体制备方法

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