Title of Invention

A DEVICE FOR CHEMICAL OXYGEN DEMAND TREATMENT OF EFFLUENTS BY ANODIC OXIDATION

Abstract The invention relates to a device for Chemical Oxygen Demand (COD) treatment of effluents by anodic oxidation, comprising a first electrolyser having a first type of anode for oxygen evolution and at least one second electrolyser having a second type of anode for oxygen evolution with higher overvoltage than the first.
Full Text FIELD OF THE INVENTION
The present invention relates to a device for Chemical Oxygen Demand
treatment of effluents by anodic oxidation.
BACKGROUND OF THE INVENTION
The treatment of effluents very rich in COD (Chemical Oxygen Demand)
upstream the biologic purification units is quite challenging. For this reason, a
few electrochemical techniques of COD pre-treatment have been explored. COD
oxidation may be carried out by electrolysis on anodes characterized by high
oxygen evolution overvoltage or with similar specific electrocatalytic properties.
The tin and antimony oxide-coated electrodes are included among those, and
reference will be made in the following as a non-limiting example of high oxygen
overvoltage anodes. Such electrodes have been used in plain electrolysers.
Known in the art, for instance in perpendicular flow-type electrolysers. In such
electrolysers the solution to be treated passes alternatively through anodes and
cathodes consisting of meshes or sponges. The COD reduction of several
effluents by this technique was actually observed, nevertheless a very low faradic
yield is associated to such system, even though the COD reduction is as low as
about 50%.
Another kind of electrode having a higher oxygen overvoltage than the tin and

antimony oxide-coated anodes is known.,namely the boron-doped diamond
electrode (BDD), which consists of a layer of boron-doped diamond deposited on
a conductive support. The drawbacks of this type of electrode are twofold,
namely its cost and its relative brittleness requiring special and expensive
electrolysers for its utilization, on the other hand, its much higher potential under
oxygen evolution leads to much bigger COD reduction rates with better faradic
yields. It can be supposed that, due to the higher potential, a number of
molecules contributing to the COD are degraded by the dissociation of their
backbones.
DETAIL DESCRIPTION OF THE INVENTION
The invention consists of the simultaneous use in series or in parallel of at least
two types of electrode. The rationale is to utilize to a highest degree the handier
and less expensive elements, that is the tin and antimony oxide-based anodes or
other equivalent electrodes, installed in a conventional electrochemical plate or
tube reactor, and to a lesser extent the BDD electrode installed in its own
appropriate electrolyser to accomplish the part of reaction which cannot be
carried out on the tin and antimony oxide-based anodes or equivalent thereof.
Being the molecules making up the COD partially degraded by the BDD anode, it
becomes easier to complete their oxidation on the tin and antimony oxide-based
anode, as confirmed by the experimental observations. For each type of effluent,
it will be necessary to determine the most convenient apportionment of electrical
current between the two processes of oxidation on BDD and on the tin and
antimony oxide- based electrode. The ideal current apportionment is usually

comprised between 55:45 and 95:5, depending on the effluent type, such
apportionment may be obtained in a very simple manner by acting on the overall
anodic surface of each electrolyser (for instance by fixing the ratio between
overall anodic surface of tin and antimony oxide-based anode to BDD at a value
comprised between 5:45 and 95:5), but other solutions are also possible. For
plants having to treat several kinds of effluent, it is advisable that such
apportionment be adjustable by means of systems known in the art.
The tin and antimony oxide-based electrode may be constructed according to
various typologies, for example it may be obtained as a ceramic electrode, for
instance sintered from powders of two oxides optionally mixed to other
components, or it may consist of a metallic base, for instance of titanium or
other valve metal, coated with tin and antimony oxides optionally mixed to small
amounts of conductive elements (for example copper) or elements with
desirable electrochemical properties (for example iridium) in order to adjust its
potential. In principle, also anodes of titanium coated with oxygen-evolution
catalysts (for example iridium and tantalum oxide mixtures) might be used,
nevertheless the oxygen overvoltage turns out to be too low in this case and the
electrolyser coupling of the invention leads to less favourable results.
The results relative to the COD treatment of a typical degreasing bath are
reported hereafter. With electrodes coated with tin and antimony oxides installed
in a RETECĀ® -type electrolyser, the COD decreased by one half in the courts of
100 hours with an average faradic yield of about 7%. Once coupled the previous
electrolyser with a second electrolyser containing the BDD electrode,

setting 90% of the current on the RETEC(R) -electrolyser and 10% on the BDD-
equipped electrolyser, the destruction of 80% of the COD was achieved in the
course of about 10 hours with an average faradic yield higher than 24%. This
method thus permits a strong improvement in the rate of destroyed COD, with a
better faradic yield (lower electric energy costs), simultaneously limiting the
capital investment deriving from the use of BBDs restricting the application
thereof to a small percentage of the treatment.

WE CLAIM
1. Device for COD treatment of an effluent by anodic oxidation, comprising a first
electrolyser equipped with a first type of anode for oxygen evolution connected in
series or in parallel and coupled to at least one second electrolyser equipped with a
second type of anode for oxygen evolution, said second type of anode being a
boron-doped diamond anode and having higher overvoltage for oxygen evolution
than said first type of anode.
2. The device as claimed in claim 1, wherein said at least one second electrolyser has
an overall anodic surface lower than said first electrolyser.
3. The device as claimed in any one of the previous claims, wherein said first type of
anode for oxygen evolution of said first electrolyser comprises tin and antimony
oxides.
4. The device as claimed in claim 2, wherein the ratio between the active surface of
said first electrolyser and the active surface of said at least one second electrolyser
is comprised between 55:45 and 95:5.

5. The device as claimed in any one of the previous claims, wherein the ratio between
the electrical current supplied to a said first and to said at least one second
electrolyser is adjustable.
6. An effluent COD treatment process comprising carrying out an anodic oxidation
process in the device of any one of the previous claims.
7. The process as claimed in claim 6, wherein the ratio between the electrical current
supplied to a said first and to said at least one second electrolyser is comprised
between 55:45 and 95:5.


The invention relates to a device for Chemical Oxygen Demand (COD) treatment
of effluents by anodic oxidation, comprising a first electrolyser having a first type
of anode for oxygen evolution and at least one second electrolyser having a
second type of anode for oxygen evolution with higher overvoltage than the first.

Documents:

01286-kolnp-2007-abstract.pdf

01286-kolnp-2007-claims.pdf

01286-kolnp-2007-correspondence others 1.1.pdf

01286-kolnp-2007-correspondence others 1.2.pdf

01286-kolnp-2007-correspondence others 1.3.pdf

01286-kolnp-2007-correspondence others.pdf

01286-kolnp-2007-description complete.pdf

01286-kolnp-2007-form 1.pdf

01286-kolnp-2007-form 18.pdf

01286-kolnp-2007-form 2.pdf

01286-kolnp-2007-form 3.pdf

01286-kolnp-2007-form 5.pdf

01286-kolnp-2007-gpa.pdf

01286-kolnp-2007-international publication.pdf

01286-kolnp-2007-international search report.pdf

01286-kolnp-2007-pct request.pdf

1286-KOLNP-2007-(11-11-2011)-AMANDED CLAIMS.pdf

1286-KOLNP-2007-(11-11-2011)-CORRESPONDENCE.pdf

1286-KOLNP-2007-ABSTRACT 1.1.pdf

1286-KOLNP-2007-AMANDED CLAIMS.pdf

1286-KOLNP-2007-CORRESPONDENCE.pdf

1286-KOLNP-2007-DESCRIPTION (COMPLETE) 1.1.pdf

1286-KOLNP-2007-EXAMINATION REPORT REPLY RECIEVED.pdf

1286-KOLNP-2007-EXAMINATION REPORT.pdf

1286-KOLNP-2007-FORM 1-1.1.pdf

1286-KOLNP-2007-FORM 18.pdf

1286-KOLNP-2007-FORM 2-1.1.pdf

1286-KOLNP-2007-FORM 26.pdf

1286-KOLNP-2007-FORM 3--1.2.pdf

1286-KOLNP-2007-FORM 3-1.1.pdf

1286-KOLNP-2007-FORM 5-1.1.pdf

1286-KOLNP-2007-FORM 5-1.2.pdf

1286-KOLNP-2007-GRANTED-ABSTRACT.pdf

1286-KOLNP-2007-GRANTED-CLAIMS.pdf

1286-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

1286-KOLNP-2007-GRANTED-FORM 1.pdf

1286-KOLNP-2007-GRANTED-FORM 2.pdf

1286-KOLNP-2007-GRANTED-SPECIFICATION.pdf

1286-KOLNP-2007-OTHERS 1.1.pdf

1286-KOLNP-2007-OTHERS-1.2.pdf

1286-KOLNP-2007-PETITION UNDER RULE 137.pdf

1286-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

1286-KOLNP-2007-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf


Patent Number 251479
Indian Patent Application Number 1286/KOLNP/2007
PG Journal Number 12/2012
Publication Date 23-Mar-2012
Grant Date 20-Mar-2012
Date of Filing 12-Apr-2007
Name of Patentee INDUSTRIE DE NORA S.P.A.
Applicant Address VIA BISTOLFI 35 20134 MILAN
Inventors:
# Inventor's Name Inventor's Address
1 YVES LUCIEN PELLET 1090 ROUTE DE BELLEVUE F-01280 PREVESSIN-MOENS
2 PAOLO ROSSI VIA FRATELLI BANDIERA 52 I-20047 BRUGHERIO (MI)
3 DIDIER CARLE GASTON GRANGE 16 RUE ARCHIMBAUD F-42170 SAINT JUST SAINT RAMBERT
PCT International Classification Number C02F 1/467
PCT International Application Number PCT/EP2005/011197
PCT International Filing date 2005-10-18
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 MI 2004A001974 2004-10-18 Italy