EP1515914A1 - Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil - Google Patents

Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil

Info

Publication number
EP1515914A1
EP1515914A1 EP03727742A EP03727742A EP1515914A1 EP 1515914 A1 EP1515914 A1 EP 1515914A1 EP 03727742 A EP03727742 A EP 03727742A EP 03727742 A EP03727742 A EP 03727742A EP 1515914 A1 EP1515914 A1 EP 1515914A1
Authority
EP
European Patent Office
Prior art keywords
soil
water
oxidation method
wet oxidation
crude petroleum
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.)
Withdrawn
Application number
EP03727742A
Other languages
German (de)
French (fr)
Inventor
Markos Ninolakis
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.)
Ninolakis Markos
Original Assignee
Ninolakis Markos
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 Ninolakis Markos filed Critical Ninolakis Markos
Publication of EP1515914A1 publication Critical patent/EP1515914A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
    • 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
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/18—Removal of treatment agents after treatment
    • C02F2303/185—The treatment agent being halogen or a halogenated compound

Definitions

  • the invention refers to an electrochemical wet oxidation method for hydrocarbons deriving from the pumping of crude petroleum from sub-sea or terra firma sources, using a specific Electrode, whose anode is constructed of titanium or a titanium and palladium alloy.
  • Welded on the anode is a coating of platinum or iridium or palladium or rhodium or ruthenium or zirconium or alloys of the aforementioned, or alternatively two coatings, the first being of tantalum, or niobium or zirconium or alloys of the aforementioned and the second coating being of platinum or iridium or palladium or rhodium or ruthenium or Zirconium or alloys of the aforementioned, and the cathode is constructed of 316L steel and specific electrolysis conditions.
  • the invention is based on the method of wet oxidation for hydrocarbons mixed with water or soil containing hydrocarbons, from crude petroleum pumping units, that by mechanical means or ultrasounds pulverizes the soil to granulometric values under 75 micros, and by Electrolysis, with a specific electrode, during which the ratio of sodium chloride in the Water is from 2% to 4% in weight, the voltage of the direct electrical current ranges from 5 to 60 Volts, the intensity of the direct electrical current is from 50 to 900 Amp, the temperature of the liquids during electrolysis being from 4 to 50 degrees Celsius, and the pH value being from 4 to 8,5 units. Neutralization of the residual oxidants is achieved by acidic sodium sulfite or sulfur dioxide by using a Redox reactions calculator.
  • the system disposes a heat-exchanger (e) keeping the temperature during electrolysis below 60 degrees Celsius and specifically at 24 degrees Celsius.
  • PH is modulated to 4 by a pH calculator (f), and depending on the desired value, acid or base is added to the mixture from tanks (g), (h), through the dosage meter pumps (i), (j).
  • the Redox calculator (k) that adds acidic sodium sulfite obtained from tank (I).
  • EXAMPLE 2 (Drawing 2) 30 kg of muddy soil from crude petroleum pumping is pulverized by mechanical means, pulverize (a), until its granulometric value is ⁇ micros The pulverized soil is mixed in tank (b), whose active volume 150 liters with 100 liters of seawater containing 3,1% sodium chloride. An underwater recirculating pump 15m3 (c) has been placed in tank (b) leading the mixture soil-water-hydrocarbons to an electrolytic cell (d) whose anode is constructed of noble and strategic metals and whose cathode is constructed of steel 316L
  • the electrolytic cell (d) is supported by a direct current power supplier (e) voltage is regulated between 05 to 60 Volts and the intensity is between 0,5 to 900 Amp.
  • the mixture soil-water-hydrocarbons are electrolyzed at 24 volts voltage and intensity 180 amp for 20 minutes.
  • the system contains a heat exchanger (f) keeping the temperature during electrolysis below 60 degrees Celsius and specifically at 24 degrees Celsius.
  • PH is modulated to 8 through the pH calculator (g) that according to the desired value, adds acid or base from tanks (h),(i) through the dosage meter pumps (j) (k).
  • the Redox calculator (I) that adds acidic sodium sulfite obtained from tank (m).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Electrochemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Soil Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping, using a specific electrode, with regulated voltage and intensity of the direct electrical current, regulated content of sodium chloride in the water, regulated temperature of liquids during electrolysis, regulated pH value during electrolysis and neutralizing of residual oxidants with acidic sodium sulfite or sulfur dioxide, and pulverizing of soil and granulometry achieved by mechanical means or ultrasounds. This method succeeds in fully oxidizing the hydrocarbons mixed in the water and soil.

Description

ELECTROCHEMICAL WET OXIDATION METHOD FOR HYDROCARBONS MIXED WITH WATER OR WITH SOIL
TECHNICAL SPECIFICATIONS The invention refers to an electrochemical wet oxidation method for hydrocarbons deriving from the pumping of crude petroleum from sub-sea or terra firma sources, using a specific Electrode, whose anode is constructed of titanium or a titanium and palladium alloy. Welded on the anode is a coating of platinum or iridium or palladium or rhodium or ruthenium or zirconium or alloys of the aforementioned, or alternatively two coatings, the first being of tantalum, or niobium or zirconium or alloys of the aforementioned and the second coating being of platinum or iridium or palladium or rhodium or ruthenium or Zirconium or alloys of the aforementioned, and the cathode is constructed of 316L steel and specific electrolysis conditions.
PREVIOUS TECHNIQUE LEVEL
Up to now, the management of hydrocarbon contaminated water (both sea and non-sea Water), stops at centrifuging using centrifugal devices for liquids, which however are not able to collect all the hydrocarbons. As a result, their concentration in the water is over 20 ppm causing enormous environmental destruction, especially if this contamination is Continuous as is the case in platforms where the pumping of petroleum takes place and the only involve its collection in special storage tanks.
THE INVENTION'S ADVANTAGES
The electrochemical method, with the specific electrode, due to the production of strong oxidants as H2, Cl2. CIO2, O3, O2, H2O2, [OH], [CLOH] [O] during electrolysis, succeeds in Fully oxidizing the hydrocarbons is extremely quick and can be applied to massive Fluxions.
DESCRIPTION The invention is based on the method of wet oxidation for hydrocarbons mixed with water or soil containing hydrocarbons, from crude petroleum pumping units, that by mechanical means or ultrasounds pulverizes the soil to granulometric values under 75 micros, and by Electrolysis, with a specific electrode, during which the ratio of sodium chloride in the Water is from 2% to 4% in weight, the voltage of the direct electrical current ranges from 5 to 60 Volts, the intensity of the direct electrical current is from 50 to 900 Amp, the temperature of the liquids during electrolysis being from 4 to 50 degrees Celsius, and the pH value being from 4 to 8,5 units. Neutralization of the residual oxidants is achieved by acidic sodium sulfite or sulfur dioxide by using a Redox reactions calculator.
EXAMPLE 1 (Drawing 1)
100 liters of seawater containing 3,1% sodium chloride and hydrocarbons (80ppm concentration) is led to a tank whose active volume is 150 litters (a). An underwater recirculating pump 15m3 (b) has been placed in tank (a) leading the mixture water- hydrocarbons to an electrolytic cell (c) whose anode is constructed of noble and strategic The electrolytic cell (c) is supported by a direct current power supplier (d), the voltage is regulated between 05 to 60 Volts and the intensity is between 0,5 to 900 Amp. The mixture water-hydrocarbons is electrolyzed with a voltage of 20 volts and intensity 150 amp for 5 minutes. The system disposes a heat-exchanger (e) keeping the temperature during electrolysis below 60 degrees Celsius and specifically at 24 degrees Celsius. PH is modulated to 4 by a pH calculator (f), and depending on the desired value, acid or base is added to the mixture from tanks (g), (h), through the dosage meter pumps (i), (j). At the end of the electrolysis the residual oxidants are neutralized by the Redox calculator (k) that adds acidic sodium sulfite obtained from tank (I).
EXAMPLE 2 (Drawing 2) 30 kg of muddy soil from crude petroleum pumping is pulverized by mechanical means, pulverize (a), until its granulometric value is δmicros The pulverized soil is mixed in tank (b), whose active volume 150 liters with 100 liters of seawater containing 3,1% sodium chloride. An underwater recirculating pump 15m3 (c) has been placed in tank (b) leading the mixture soil-water-hydrocarbons to an electrolytic cell (d) whose anode is constructed of noble and strategic metals and whose cathode is constructed of steel 316L
The electrolytic cell (d) is supported by a direct current power supplier (e) voltage is regulated between 05 to 60 Volts and the intensity is between 0,5 to 900 Amp. The mixture soil-water-hydrocarbons are electrolyzed at 24 volts voltage and intensity 180 amp for 20 minutes. The system contains a heat exchanger (f) keeping the temperature during electrolysis below 60 degrees Celsius and specifically at 24 degrees Celsius. PH is modulated to 8 through the pH calculator (g) that according to the desired value, adds acid or base from tanks (h),(i) through the dosage meter pumps (j) (k). At the end of the electrolysis, residual oxidants are neutralized by the Redox calculator (I) that adds acidic sodium sulfite obtained from tank (m).

Claims

1. Electrochemical wet oxidation method for hydrocarbons mixed with water or with Soil from crude petroleum pumping, with regulated voltage and direct current intensity, regulated content of sodium chloride in the water, regulated temperature of liquids during electrolysis, regulated pH value during electrolysis, neutralization of residual Oxidants with acidic sodium sulfite or sulfur dioxide, soil pulverizing and granulometry of latter by mechanical means or ultrasounds, using a specific efectrode, whose anode is constructed of titanium or a titanium and palladium alloy, welded on which, is a coating of platinum or iridium or palladium or rhodium or ruthenium or zirconium or alloys of the aforementioned or two coatings, the first of which is of Tantalum, niobium or zirconium or alloys of the aforementioned and the second is of Platinum or iridium or palladium or rhodium or ruthenium or zirconium or alloys of the aforementioned, and whose cathode is of 316L steel.
2. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, from crude petroleum pumping as in claim 1 , where the voltage of the direct electrical current ranges from 5 to 60 volts.
3. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as is claim 1 , where the intensity of the direct electrical current ranges from 50 to 900 amp.
4. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as in claim 1, where the content of sodium chloride in the water during electrolysis is between 2-4% w/w.
5. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as in claim 1, where the temperature during electrolysis is from 4 to 50 degrees Celsius
6. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as in claim 1 , where the pH value during electrolysis is from 4 to 8,5 units.
7. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as in claim 1, where the neutralizing of residual oxidants is achieved by acidic sodium sulfite.
8. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as in claim 1 , where the neutralizing of residual oxidants is achieved by sulfur dioxide.
9. Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as is claim 1, where the granulometric value of the pulverized by mechanical means soil is less than 75 micros.
10. Electrochemical wet oxidation method of hydrocarbons mixed with water or with soil, deriving from crude petroleum pumping as is claim 1, where the granulometric value of the pulverized by ultrasounds soil is less than 75 micros.
EP03727742A 2002-06-05 2003-06-05 Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil Withdrawn EP1515914A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GR2002100267 2002-06-05
GR20020100267A GR1004116B (en) 2002-06-05 2002-06-05 Electrochemical sewage wet oxidation method.
PCT/GR2003/000020 WO2003104152A1 (en) 2002-06-05 2003-06-05 Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil

Publications (1)

Publication Number Publication Date
EP1515914A1 true EP1515914A1 (en) 2005-03-23

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EP03727742A Withdrawn EP1515914A1 (en) 2002-06-05 2003-06-05 Electrochemical wet oxidation method for hydrocarbons mixed with water or with soil

Country Status (5)

Country Link
EP (1) EP1515914A1 (en)
AU (1) AU2003232943A1 (en)
GR (1) GR1004116B (en)
NO (1) NO20040673D0 (en)
WO (1) WO2003104152A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0604544D0 (en) * 2006-03-07 2006-04-19 Enviromental Processes Ltd Water Treatment
BRPI0814904A2 (en) * 2007-08-23 2015-02-03 Dow Global Technologies Inc PROCESS TO REDUCE ORGANIC CONTENT OF A PICKLE SOLUTION
FR2966820B1 (en) * 2010-11-03 2015-04-03 Spcm Sa PROCESS FOR TREATING PRODUCTION WATER PRODUCED FROM A PROCESS FOR ASSISTED RECOVERY OF PETROLEUM USING POLYMERS
AU2012318934B2 (en) 2011-10-07 2017-07-27 Robert Brian Dopp Electrochemical digestion of organic molecules

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT333674B (en) * 1975-02-18 1976-12-10 Voest Ag METHOD AND DEVICE FOR PURIFYING WASTE WATER BY ELECTROLYSIS
SU842036A1 (en) * 1978-05-26 1981-06-30 Московский Завод Автотракторногоэлектрооборудования Атэ-1 Method of automatic control of waste water electrochemical purification process
US4236992A (en) * 1979-08-06 1980-12-02 Themy Constantinos D High voltage electrolytic cell
SU1433905A1 (en) * 1986-07-11 1988-10-30 Одесский Инженерно-Строительный Институт Method of treating waste water
DE8809526U1 (en) * 1988-07-26 1988-12-15 Neuheiten-Gesellschaft mbH, 4300 Essen Device for the separation and selective degradation of ionic and non-ionic components from aqueous and non-aqueous solutions
GR1004008B (en) * 2000-07-13 2002-10-02 Environmental Focus International Bv (Efi) Method and metals for the construction of electrode anode for the electrolysis of liquid effluents
GR1004007B (en) * 2001-03-13 2002-09-27 Environmental Focus International Bv (Efi) Electrochemical method for the liquid oxidation of polychloro-bibhenyls
GR1004118B (en) * 2001-10-11 2003-01-21 Μαρκος Νινολακης Electrochemical sewage wet oxidation method.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03104152A1 *

Also Published As

Publication number Publication date
WO2003104152A1 (en) 2003-12-18
GR1004116B (en) 2003-01-21
AU2003232943A1 (en) 2003-12-22
NO20040673D0 (en) 2004-02-02

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