Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
  • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
  • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
  • C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
• • 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
  • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
  • C02F1/5209—Regulation methods for flocculation or 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
  • C02F2101/20—Heavy metals or heavy metal 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
  • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
• • 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
  • C02F2209/02—Temperature
• • 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
  • C02F2209/03—Pressure
• • 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
  • C02F2209/06—Controlling or monitoring parameters in water treatment pH
• • 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
  • C02F2209/40—Liquid flow rate

Definitions

• the present invention relates to the field of treatment of highly alkalinized effluents and loaded with metals, including alkaline earths with a view to neutralize them and significantly eliminate the metals present in the effluent.
• This problem is found particularly in the iron and steel industry, but other industries may be concerned and in particular we can cite the case of the treatment of water from the production of aluminum based on natural raw materials such as bauxite (called “sludge”). red ", very heavily loaded with aluminum, among others).
• the removal of aluminum can be achieved by adding CO2 to convert the solubilized aluminate in basic medium aluminum hydroxide AI (OH) 3 which, poorly soluble, will tend to precipitate.
• the pH of the effluent is reduced, or more exactly neutralized or partially neutralized and thus freed of aluminum, it will be purified.
• the working pH range for this operation is generally:
• the pH can not be too low ( ⁇ 5) because then the aluminum solubilizes in Al 3+ form.
• the particles formed are fairly strong and can lead, if they accumulate, clogging in the downstream portion of the injection site. • Finally, the various stages (injection / transfer of the gas and contact of the dissolved CO2 with the effluent containing the aluminates) are often carried out in the same zone, the same apparatus or piping, while the conditions required for each step are different. .
• the injection is alternatively directly carried out not in a basin but in line, in a pipe.
• the gaseous (or liquid) CO2 is injected, via a means that goes from the simplest (for example a simple opening pipe) to the most refined (many are the gas-liquid contactors commercially available to improve dissolution, such as static mixers, venturis or the like ).
• the particles are then formed directly in the flow, a flux that normally remains only to separate from the liquid (filtration, settling tank ).
• the direct addition of the acid (CO2) in a very basic water and highly charged with aluminate causes an instantaneous precipitation that is difficult to control.
• the acidification causes massive blockages very frequent, so frequent that:
• the transfer rate that is to say the dissolution of CO2
• this solution has the following disadvantage: water is consumed with an associated cost and an unfavorable environmental footprint because it increases the total liquid flow that must be treated on the decanter by diluting the effluent.
• the present invention seeks to propose a new solution for treating such effluents rich in aluminum, allowing the optimal implementation of CO2.
• the proposed solution according to the present invention is then based on the separation of the process into two distinct phases, into two distinct zones:
• the first phase during which we seek to achieve the generation of crystals in the form of aluminum hydroxide mainly.
• This zone “1" may be a basin, an area in which the highly alkaline and aluminum-rich effluent arrives (for example at a pH of the order of
• zone 1 the formation of the solid that can be incrustant takes place in zone 1 and so if the solid is incrustant at the time of its formation the problem appears in this first zone which must contain enough dissolved CO2 to "neutralize" the raw effluent incoming.
• a second phase in which one seeks to realize the injection and the maximized, maximized dissolution of the CO2 , by limiting very strongly, or even by canceling any phenomenon of precipitation, more exactly of generation of hydroxide crystals aluminum.
• the second zone which can be called “CO2 dissolution zone” can:
• zone 2 serves to dissolve the CO2 in a fluid flow that is pumped from zone 1 and that is returned to zone 1. This zone is calculated to dissolve enough CO2 to lower the pH of zone 1 of the arrival value of the alkaline effluent (for example 12.5) at the desired setpoint (for example 8).
• zone 2 there is no reduction of a strongly alkaline pH (such as 12.5) to a neutral or acidic value, but zone 1 fluid, thus close to neutral, is pumped for the first time. acidify even more. There is therefore no formation of solid in this zone 1 (or in an anecdotal manner) and thus the risk of clogging is eliminated or reduced very significantly.
• a strongly alkaline pH such as 12.5
• the pH of the pond / zone 1 is calculated by calculating for a given flow rate and a given initial pH, the amount of CO2 that must be dissolved in zone 2 (recirculation loop) to reach the desired pH in the zone 1, with obviously a margin of safety.
• the sizing is based on the combination of a gas-liquid ratio (generally between 0.1 and 5 Nm 3 of gas per m 3 of liquid, preferably 0.1 and 1 Nm 3 of gas per m 3 of liquid ), the pressure in this zone and a flow of effluent taken that will dissolve all the CO2 necessary to maintain the desired operating conditions, in particular the pH in the zone 1 in which the initial effluent arrives, in general continuously.
• a gas-liquid ratio generally between 0.1 and 5 Nm 3 of gas per m 3 of liquid, preferably 0.1 and 1 Nm 3 of gas per m 3 of liquid
• the solution will include, in particular, a pump, a gas-liquid contactor (a static mixer for example), a pipe of good size to remain in a turbulent regime and of sufficient length to guarantee the desired residence time (and therefore the contact time ), for example a contact time close to 10 seconds.
• a gas-liquid contactor a static mixer for example
• a pipe of good size to remain in a turbulent regime and of sufficient length to guarantee the desired residence time (and therefore the contact time ), for example a contact time close to 10 seconds.
• the carbonated effluent can be returned to the first zone. It therefore contains substantially CO 2 in dissolved form, namely CO 2 and bicarbonate HCO3 and therefore hardly gas if the operating conditions have been met (transfer rate higher than 80% or even 90%). The operating conditions are thus maintained to guarantee these dissolved forms, namely in general a low pH (less than 8 to 9), preferably not falling below 5.
• Zone 1 must allow: - First of all, the most intimate mixture possible between the fresh incoming effluent (charged with aluminate) and the by-product stream which was carbonated in zone 2 and which is returned to zone 1 (charged with enough dissolved CO 2 , in HCO3 form and especially CO 2 , to guarantee the target pH of precipitation in zone 1). This will maximize the production of solids / precipitates. The mixture will then consist of liquid freed of a large part of its aluminum and solid particles.
• zone 1 is sized to ensure a desired target volume / pH pair.
• zones 1 and 2 will therefore consist for example of:
• zone 1 a tank which contains a stirred part allowing the good mixing of the liquid streams (fresh effluent to be treated and return from zone 2) and good precipitation (no strong shear by the agitator (s), sufficient residence time if it operates in "batch", semi-continuous or continuous ...), even a partial decantation (via a zone protected by a deflector for example) to be able to extract a part of the treated effluent in this tank and send it to zone 2 (recirculation pipe).
• the liquid and solid mixture can be decanted directly into the tank (“batch" operation on a stirred tank) or can be decanted downstream.
• zone 2 for example a recirculation loop mounted on the equipment of zone 1, namely a pump which sends the flow to a gas-liquid contactor (static mixer) which makes it possible to inject and to mix the gas-CO2 and the liquid to promote the dissolution of the CO2 and finally enough length of piping to guarantee a residence time sufficient to favor, here too, the dissolution before the return of the water thus carbonated in zone 1.
• gas-liquid contactor static mixer
• Its sizing is based essentially on the gas-liquid ratio, the quantity of CO2 necessary to precipitate what is wanted (almost all in general) the aluminum contained in the effluent to be treated fresh and the solubility of CO2 in the effluent.
• the total volume of zone 2 is therefore not critical here.
• the effluent arrives in the center of the neutralization basin where it ensures a good homogeneity, basin equipped with a stirring system, possibly supplemented by an additional agitator if what is already in place is not enough.
• the recirculation loop must therefore provide in dissolved form at least 18 kg / h of CO2.
• the temperature of the effluent being around 25 ° C, the solubility is of the order of 1, 4 kg CO2 / 1T1 3 to 1 bar abs.
• the enrichment flow must be close to 6.5 m 3 / h.
• the neutralized effluent with its solid exits the bottom (pumped) to be subsequently decanted (filtration).
• the gas-liquid mixture is then sent into a coil whose length ensures a sufficient contact time to maximize the amount of CO2 transferred into the stream.
• this flux acidified with pFb is returned to the basin where, as close as possible to the incoming flow at pHi, it will mix to guarantee the phh that prevails in the basin, phh optimum for the formation of crystals of aluminum hydroxide .
• the incoming effluent, at high pH (10-12), is mainly composed of dissolved aluminum in AI (OH) 4 form .
• CO2 It is almost impossible for CO2 to have a pH lower than 5-5.5 and to resolubilize the particles of aluminum hydroxide that have been formed.
• CO2 is a weak diacid whose first pKa does not allow to fall below about 5.
• the effluent, after being treated and thus rid of a large amount of dissolved aluminum, will be able to absorb CO 2 (part of the flux derived between zones 1 and 2). It is nevertheless preferred to work in the upper part of the targeted zone (rather to 8 than to 5) in order to have more dissolved CO 2 (better solubility of CO 2 at high pH than low because the hydrogen carbonate form HCO3 is favored rather than CO 2 free).
• FIG. 1 recognizes the following elements, already mentioned several times in the description above:
• a recirculation loop 10 constituting the zone 2 adapted to take (5) a portion of the medium present in the basin 1 through a pump 2, loop which receives a CO2 injection and which is provided with a coil whose length ensures sufficient contact time to maximize the amount of CO2 transferred to the flow;
• the flow thus treated is returned to the pond 1, thus contributing, by mixing the initial effluent (4) and the medium treated with CO 2 in the loop 10, to achieve the target pH prevailing in the basin 1;
• the basin is provided with means (6) for extracting the treated effluent.
• the precipitation zone 1 (reactor, decanter, etc.) must always be maintained at a pH lower than that of the incoming flow to be treated in order to allow the precipitation of aluminum in the form of aluminum hydroxide (around pH 8 per minute). example).
• the effluent to be treated arriving is then diluted in zone 1, which should lead to a slight increase in pH, which will in fact be offset by the injection of CO2 into zone 2, namely the recirculation loop.
• To guarantee a maximized CO2 transfer rate which results from the choice of operating conditions and technologies in the recirculation loop (turbulence). This will result in a consumption of the system's needs (no overconsumption).
• Zone 2 only serves to dissolve the CO2 in a water flow (effluent) pumped from zone 1 and return to zone 1. This zone is calculated to dissolve enough CO2 to lowering the pH of zone 1 of the arrival value of the alkaline effluent example 12.5 to the example set point 8. It is also possible to use this zone to supply a portion of the CO2 in the form of gas (fine bubbles) from zone 1 to 2.
• zone 2 there is no reduction of a strongly alkaline pH (12.5) to a neutral or acidic value, but the effluent from zone 1 is pumped, thus neutral or acid, to acidify it further. more. So there is no solid formation in this zone 1 (or anecdotally) and thus reduces the risk of clogging. It is even possible if even more CO2 is injected and this zone is further acidified, the aluminum solids formed at neutral pH are dissolved and the zone 1 can be decoloured even if in theory it is not necessary.
• the amount of dissolved CO2 available in zone 1 is 0.5 to 3 times greater, preferably between 1 and 1.5 times greater than the need necessary for the precipitation of the incoming effluent.
• the effluent entering zone 1 is very alkaline (thus pH 1 and high dissolved aluminum concentration). This is where he will be put in contact with the effluent, the pH was lowered to 3 rd pH containing dissolved CO2 necessary from zone 2 (pH 2 low since the effluent will contain at least all the CO2 necessary for the precipitation). In contact with the two, the dissolved CO2 will neutralize the alkalis of the incoming effluent and thus reduce the pH to allow precipitation and thus rid the effluent of its dissolved aluminum. The resulting pH pH 3 will be between the two previous pHs, adjusted to promote precipitation.
• a control-regulation system could adjust the amount of CO2 to the amount of alkali (which will have to lower the pH of the precipitation zone 1) but this is still difficult.
• the quantities involved size of zone 1 can induce a slow evolution of the operating parameters: with a sudden and strong influx of alkali, the pH of zone 1 will only move slowly if it is of significant size. (and therefore with a significant residence time).
• the amount of CO2 will not respond immediately or even too late, which can cause a rapid and strong undesirable precipitation in zone 2, a phenomenon that must be absolutely avoided at the risk of stopping everything by a clogging too massive.
• the approach of the present invention is therefore to keep a larger quantity than required by the effluent entering free CO2, dissolved and available in zone 1 where precipitation takes place.
• this supplement of dissolved CO2 compared to the quantity of CO2 necessary for the precipitation (thus stoichiometric) will allow to "neutralize” this supplement in a given time. This will avoid in any state The reason is to send dissolved aluminum or alkali to Zone 2 and allow time for the control system to adjust the amount of CO2 to be injected to compensate for this supplement.
• the basin (or zone 1) measures 55 m 3 , it will contain only 1 kg of free CO2, therefore available to compensate for excessively sudden excess of alkalinity. This would compensate for one minute the arrival of effluent, in case of stopping the injection of CO2 for example, or to compensate for a rise in the amount of alkali (for example, 1 kg / min of need at 1, 5 for example). In the latter case, in 40 seconds, the free CO2 will be consumed and the pH will then go up, the reactor or zone 1 will no longer precipitate all the incoming alkali and all the process will destabilize. Eventually, dissolved alkali will enter Zone 2, which could lead to precipitation and clogging. It is therefore preferred to increase the volume of zone 1 so as to have more free CO2 available to "erase” or neutralize the fluctuations or disturbances of the incoming effluent, among others.
• zone 1 the determination of zone 1 is carried out so that this zone contains at least 1.5 times to 3 times the amount of CO2 necessary to neutralize the alkali that arrive every minute in the zone and thus allow the precipitation of almost all of the aluminum (its oxides) in this zone 1.
• the amount of free CO2 in the area can be increased beyond 3, but not exceeding 10 or 15 for economic reasons.
• the free CO2 is 18 g / m 3 for a target pH of 8 and 57 g / m 3 for a set pH of 7.5
• Volume of zone 1 amount of CO2 in kg that has been determined / concentration of free CO2 at the target pH.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Engineering & Computer Science (AREA)
• Hydrology & Water Resources (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Geology (AREA)
• Inorganic Chemistry (AREA)
• Treating Waste Gases (AREA)
• Removal Of Specific Substances (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

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• 2018
  • 2018-06-05 FR FR1854871A patent/FR3081859B1/fr active Active
• 2019
  • 2019-05-29 EP EP19737173.5A patent/EP3802439A1/fr active Pending
  • 2019-05-29 CA CA3101245A patent/CA3101245A1/fr active Pending
  • 2019-05-29 WO PCT/FR2019/051272 patent/WO2019234327A1/fr unknown
  • 2019-05-29 BR BR112020024516-0A patent/BR112020024516A2/pt unknown
  • 2019-05-29 CN CN201980040700.4A patent/CN112334415B/zh active Active
  • 2019-05-29 US US16/972,474 patent/US20210163307A1/en active Pending
  • 2019-05-29 AU AU2019282381A patent/AU2019282381A1/en active Pending
  • 2019-05-29 JP JP2020564714A patent/JP2021526449A/ja active Pending

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