Classifications

• • 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
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2415—Tubular reactors
• • 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
  • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
  • B01J3/008—Processes carried out under supercritical conditions
• • 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
  • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
  • B01J3/04—Pressure vessels, e.g. autoclaves
• • 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
  • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
• • 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
• • 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
• • 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
  • C02F11/086—Wet air oxidation in the supercritical state
• • 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
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2209/00—Controlling or monitoring parameters in water treatment
  • C02F2209/001—Upstream control, i.e. monitoring for predictive control
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2209/00—Controlling or monitoring parameters in water treatment
  • C02F2209/05—Conductivity or salinity
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2209/00—Controlling or monitoring parameters in water treatment
  • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2209/00—Controlling or monitoring parameters in water treatment
  • C02F2209/29—Chlorine compounds
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2301/00—General aspects of water treatment
  • C02F2301/06—Pressure conditions
  • C02F2301/066—Overpressure, high pressure
• • 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
  • C02F2303/08—Corrosion inhibition
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S210/00—Liquid purification or separation
  • Y10S210/902—Materials removed
  • Y10S210/908—Organic

Definitions

• the present invention relates to a hydrothermal oxidation process of waste contained in an aqueous effluent.
• the invention relates in particular to the treatment of aqueous effluents comprising organic waste and / or dissolved salts.
• WO 02/20414 A method of this type, which is particularly interesting, is described in WO 02/20414, which makes it possible to control the temperature rise produced during hydrothermal oxidation.
• the effluent is treated in a tubular reactor by introducing the oxidizing agent not all at once but progressively along the tubular reactor, into several injection points of more in addition downstream of the flow of the effluent, which makes it possible to progressively increase the temperature of the flow according to an increasing curve, from an initial non-supercritical temperature (for example of the order of ambient or higher) until at a supercritical temperature.
• This process called “by multi-injection of the oxidizing agent” makes it possible to carry out the oxidation in a controlled manner, avoiding a too intense production of energy which would otherwise damage the walls of the reactor, and nevertheless in an efficient manner, in particular account in view of the fact that the rise in temperature is continuous and strictly increasing (which, among other things, has the advantage of not inducing the sudden drops in temperature that can be observed with processes where the temperature is back-controlled by additions of refrigerants, which are suitable for inhibiting the oxidation reaction by quenching phenomena).
• An object of the present invention is thus to improve the process described in WO 02/20414, in particular so as to make it well adapted to an industrial implementation where the nature and the concentration of the effluents can vary to a very large extent at course of time.
• the present invention proposes to modify the process of WO 02/20414 by analyzing the quantity of compounds to be treated in the effluent to be treated, and possibly other parameters such as the concentration of halide ions or salts, and adjusting, if necessary, these parameters upstream of the hydrothermal treatment reactor prior to the multi-injection oxidation.
• the subject of the present invention is a process for the hydrothermal oxidation of organic compounds contained in an aqueous effluent, optionally with oxidizable inorganic compounds, in which the said aqueous effluent is injected into a tubular reactor where it is carried. effluent at supercritical pressure (i.e.
• composition and / or the concentration of the organic compounds and / or oxidizable inorganic compounds within the effluent to be treated varies with time, and in that, upstream of the tubular reactor where the oxidation is carried out the DTO of the effluent to be treated is measured and maintained, or adjusted if necessary, to a value of less than 250 g / l.
• the DTO of the effluent to be treated is measured, maintained or adjusted if necessary, to a value greater than 120 g / l and less than 250 g / l, prior to its injection into the tubular reactor.
• the DTO of the effluent to be treated is measured, maintained or adjusted if necessary to a value of between 130 and 240 g / l, preferably between 130 and 220 g / l, advantageously between 140 and 220 g / l, prior to its injection into the tubular reactor.
• DTO is meant here the total chemical oxygen demand of the effluent to be treated, expressed in mole / L, which corresponds to the total amount of oxygen (expressed in moles) required to carry out the complete oxidation of the compounds organic and inorganic oxidizable present within one liter of the effluent.
• This total chemical demand “DTO” takes into consideration all the oxidizable species present, namely both the organic compounds and, where appropriate, those of any oxidizable inorganic compounds. It differs from “COD” (chemical oxygen demand) which only takes into consideration organic species. DTO is equal to COD when oxidizable inorganic species are absent.
• the DTO of the effluent is preferably maintained or adjusted between 150 and 220 g / l before injection into the tubular reactor.
• the effluent to be treated contains oxidizable inorganic compounds (especially oxidizable metal compounds)
• the DTO of the effluent is maintained or adjusted between 150 and 200 g / L before injection into the tubular reactor.
• the control of the DTO of the effluent to be treated below 250 g / L before its introduction into the tubular oxidation reactor, as produced according to the invention, has, among other things, the advantage of inhibit an excessive rise in the operating temperature of the reactor, which could otherwise lead to damage. Therefore, the implementation of the invention translates into undeniable advantages in terms of safety and durability of the equipment and therefore the cost of maintenance and maintenance.
• control of the DTO in the abovementioned ranges allows an optimal treatment of the waste to be treated, the DTO being sufficiently weak to allow an effective and total or substantially total oxidation of the species to be treated (oxidizable organic and / or inorganic compounds ).
• control of the DTO above 120 g / mol makes it possible to induce in the tubular oxidation reactor a operating temperature sufficient not to consume the oxidizing agent unnecessarily.
• the implementation of the conditions of the present invention allows a particularly advantageous optimization of the safety, efficiency and costs of the waste treatment facility and its maintenance.
• the measurement of the DTO of the effluent and, if necessary, the modification of this DTO can be carried out according to any means known per se.
• the measurement of the DTO can in particular be carried out using a conventional DTO-meter or DCO-meter, for example of the type described in standards NFEN1484, IS08254, EPA4151. It is particularly possible to use DCO / DTO analyzers of the type marketed by ANAEL.
• the modulation of the DTO can be obtained:
• DTO measured upstream of the reactor is too low: by concentration, for example by addition of organic and / or inorganic waste or a more concentrated effluent in the effluent to be treated.
• a device for analyzing and preparing the effluent to be treated which typically comprises, upstream to downstream:
• an analysis zone (and possibly a storage zone) for the effluent to be treated, provided with means for analyzing the DTO of the effluent;
• an adjustment zone of the DTO provided with means for feeding the medium contained in the analysis zone, and means for diluting or concentrating the medium contained in the adjustment zone (typically, this zone of adjustment is a tank equipped with means for supplying water (for dilution) or waste or concentrated effluent (for concentration); and
• the method of the invention may have at least one of the additional characteristics described below:
• the halogen concentration in the effluent to be treated is measured and maintained, or adjusted if necessary, to a lower value. at 2 g / L and preferably less than 1 g / L.
• the limitation of the halogen content makes it possible, inter alia, to inhibit the deterioration of the reactor by corrosion, which, again, results in advantages in terms of safety and cost reduction.
• the measurement of the halogen concentration can typically be carried out according to the IS09562 standard for the halogen dosing of absorbable organic compounds (AOX) and by inductively coupled plasma mass spectroscopy (ICP-MS) analysis. Adjustment of the concentration may be carried out by diluting the effluent (by addition of water or other more diluted effluent).
• AOX absorbable organic compounds
• ICP-MS inductively coupled plasma mass spectroscopy
• the concentration of salts in the effluent to be treated is measured and maintained, or adjusted if necessary, at a value of less than 10 g / l and preferably less than 5 g / l.
• the measurement of the salt concentration can typically be carried out by measuring the ionic conductivity of the medium. Adjustment of the concentration can be done by diluting the effluent (again, by adding water or other more diluted effluent).
• the process of the invention is well adapted to the treatment of most aqueous effluents, in particular urban sludge and effluents from the basic and processing industries, particularly effluents from the agri-food, paper, chemical and pharmaceutical industries, refining, oil, mechanical, metallurgical, aeronautical and nuclear industries.
• Embodiments 1 and 2 correspond to the implementation according to the invention and the following two are provided for comparison.
• the waste treated is a waste product from the chemical industry containing only compounds based on the elements C, H and O (a mixture comprising essentially alkanes alcohols and organic acids of the fatty acid type).
• an aqueous medium was made whose DTO was controlled and regulated upstream of the oxidation reactor, in order to obtain at the reactor inlet a value of DTO called "initial DTO" whose values are given below.
• the mixture was preheated at the reactor inlet and then injected into the reactor where multiple oxygen injection was performed at three points further downstream.
• the first injection raises the medium to a temperature T1, the second to a temperature T2 and the third to a temperature T3, according to an increasing temperature profile (without ever decreasing temperature).
• the DTO of the flow at the outlet of the reactor called “final DTO" was measured.
• T3 530 ° C According to this illustrative embodiment of the present invention, effective waste conversion is achieved with a final DTO of 10 mg / L, with control of temperature rise.
• the final DTO is 25 g / 1 + - 5g / l, which is too high, and does not allow sufficient treatment of the waste. (DTO of rejection too high).
• the final DTO is 65 g / l + - 5g / l, which is too high.
• the embodiment at a DTO of 250 g / L also corresponds to a limit at which the temperature becomes too high, inducing a risk of deterioration of the reactor.
• Treated waste is a waste from a distillery made up of alcoholic drifts and drifts of sugars mainly. From this waste, an aqueous medium was made whose DTO was controlled and regulated upstream of the oxidation reactor, in order to obtain at the reactor inlet a value of DTO called "initial DTO" whose value is given below.
• the mixture was preheated at the reactor inlet and then injected into the reactor where multiple oxygen injection was performed at three points further downstream. The first injection raises the medium to a temperature T1, the second at a temperature T2 and the third at a temperature T3, according to an increasing temperature profile (without ever decreasing temperature).
• the DTO of the flow at the outlet of the reactor called “final DTO", was measured.
• Initial DTO 220 g / 1

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Hydrology & Water Resources (AREA)
• Engineering & Computer Science (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Treatment Of Water By Oxidation Or Reduction (AREA)
• Treatment Of Sludge (AREA)

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• 2011
  • 2011-01-12 FR FR1150247A patent/FR2970247B1/fr not_active Expired - Fee Related
• 2012
  • 2012-01-09 CA CA2824476A patent/CA2824476A1/fr not_active Abandoned
  • 2012-01-09 WO PCT/EP2012/050248 patent/WO2012095391A1/fr active Application Filing
  • 2012-01-09 EP EP12700069.3A patent/EP2663533A1/fr not_active Withdrawn
  • 2012-01-09 KR KR1020137019599A patent/KR20140020854A/ko not_active Application Discontinuation
  • 2012-01-09 BR BR112013017895A patent/BR112013017895A2/pt not_active IP Right Cessation
  • 2012-01-09 CN CN201280012717.7A patent/CN103459330B/zh not_active Expired - Fee Related
  • 2012-01-09 US US13/979,224 patent/US9073769B2/en not_active Expired - Fee Related
  • 2012-01-09 MX MX2013008155A patent/MX336168B/es unknown
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