• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for treating heavy metals in liquid effluents, said process comprising a physico-chemical step coupled to an ion exchange step.
    公开号:FR3022900A1
    申请号:FR1456150
    申请日:2014-06-30
    公开日:2016-01-01
    发明作者:Guy Vanderghote；Isabelle Baudin；Maite Brugioni；Jocelyn Leveque
    申请人:Suez Environnement SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a novel process for the treatment of liquid effluents loaded with metals, in particular salts-laden waters. Globally, wastewater treatment is the first public health issue. Wastewater is all the water loaded with various elements from the population but also commercial and industrial activities and which are likely to pollute the environment in which they will be dumped. This is why, in order to respect these different environments, treatments are carried out on these effluents before discharge to the natural environment or in a sanitation network. Among the elements to be addressed are heavy metals such as zinc, nickel, chromium, copper, thallium, arsenic, lead, mercury and cadmium which are important contaminants in ecosystems. and the food web. Many solutions have been made to treat heavy metals, in the form of various methods, all of which have drawbacks: physico-chemical processes induce, when high technical performance is desired, significant operating expenses (OPEX) related to at the cost of reagents. Moreover, these processes use sulfur-containing chemicals, such as sodium sulphide (Na2S) or tri-mercaptan, which have a negative impact on the environment and are not efficient in case of concentration peaks, the processes ion exchange systems that use chelating resins for the selective fixing of heavy metals also induce significant operating expenses (OPEX) related to the cost of regeneration of the resins or to their renewal, this cost being notoriously high in the case of treatment of effluents loaded with metals. In addition it is essential to manage the used resins which are considered as solid hazardous waste and to manage the eluates which are considered as dangerous liquids, the membrane techniques which implement membranes of ultrafiltration, nanofiltration or reverse osmosis which lead to significant operating expenses (OPEX) because the conversion rate is often less than 50% for effluents loaded with salts (management and removal of concentrates). Moreover, these techniques are unusable because of the rapid and irreversible clogging, when the waters are highly loaded with salts, in particular calcium and sulphate, and the techniques of evapo-concentration or evapo-crystallization induce expenditure of (OPEX) because of the energy required for evaporation and high CAPEX. In addition, there is a need to manage brines either by eliminating them or by enhancing them.
    [0002] Also, there is a need for a technique that allows both the optimization of OPEX, in particular by reducing the quantities of reagents used and that of technical performance, in particular: limitation / suppression of releases of hazardous substances (mercury , cadmium, lead, zinc, etc.), better purification efficiency, lower or even zero metal emission levels, control of emission peaks without overdosing of chemicals. However, the inventors realized that by coupling two methods, a physico-chemical method and an ion exchange method, it was possible to provide a metal treatment process on effluents loaded with salts which solves the problem. all the problems mentioned above. Thus, the subject of the present invention is a process for treating heavy metals present in liquid effluents, loaded with salts, in particular salts-laden water, said process comprising the following steps: a. treatment of the liquid effluent likely to contain heavy metals with a neutralizing agent selected from the group comprising in particular sodium hydroxide, milk of lime, milk of magnesia, at a pH of 5 to 6, b. coagulation of the effluent treated in step a), during which a dose of coagulant is injected into said effluent, c. precipitation of the mixture obtained in step b) with a neutralizing agent chosen from the group comprising, in particular, sodium hydroxide, milk of lime, milk of magnesia, at a pH of 9 to 10, d. flocculation of the mixture obtained during the coagulation step b) or of the mixture obtained during the treatment step with a neutralizing agent c), during which an injection of flocculant into said mixture is carried out, to agglomerate the particles suspended in the form of flocs, e. removing the flocs formed in step d) and recovering the liquid, f. treatment of the residual suspensions in step e) by filtration, g. contacting the liquid recovered in step f) with an ion exchange resin capable of adsorbing one or more heavy metals or put in successive contact with a plurality of ion exchange resins, each resin being capable of adsorbing one or more metals heavy, in order to reduce the concentration of heavy metals present in said liquid, h. recovery of the heavy metal free liquid. According to the invention, step a) can be carried out according to any technique known to those skilled in the art, in particular by mixing the slaked lime in the form of milk of lime with the effluent to be treated. The pH is adjusted by any known acid, especially 33% hydrochloric acid in a range of 5.5 to 8.5. According to the invention, the coagulation step b) can be carried out by addition of a coagulant. This step can be performed separately from step a) or simultaneously with step a). In both embodiments, the coagulated mixture is subjected to a flocculation step d). The precipitation step c) is optional, that is to say that step d) can be done directly after step b). At the end of step d), the floc is removed, for example by decantation (step e), according to techniques known to those skilled in the art and the decanted liquid is filtered, for example on a sand filter (step f). ) before being contacted with ion exchange resins (step g). The coagulation and flocculation steps are carried out by techniques known to those skilled in the art such as those described in the Water Technical Memo Tenth Edition Volume 1 Chapter 3 page 185 and following Editor Degrémont Suez). Coagulation consists in the addition of a coagulant such as, for example, trivalent cations, in particular iron or aluminum salts, allowing the destabilization of the colloidal particles present in the water and the neutralization of all the electronegative charges of these substances. particles. During this step, the neutralized particles begin to agglomerate by mechanical agitation to form micro-flocs. These microflocs are too small to be eliminated, especially by decantation. Also the flocculation step is necessary to fatten these flocs. According to the invention, the liquid decanted (step e) and filtered (step f) can be brought into contact with a single resin capable of capturing several heavy metals or on a battery of resins each being capable of fixing one or more heavy metals . By way of example of a resin, mention may be made of the monosplus TP207, Amberlite IRC 748, lanxess monoplus TP 214 and Ambersep GT 74. At the end of step g), the heavy metal-free liquid is recovered which can therefore be be rejected in the natural environment or in a sanitation network. According to the invention, the process allows the treatment of heavy metals such as zinc, nickel, chromium, copper, thallium, arsenic, lead, mercury and cadmium which are present in water by precipitation (by neutralizing agent or insolubilizer) and adsorption on resin. According to the invention, it is possible to remove one or more of these metals depending on the type of resin used. The skilled person in the light of this general knowledge will know how to choose and combine the type of adequate resin. The process according to the invention is applicable to any liquid medium, in particular any aqueous effluent, in particular flue-cleaning effluents from incineration plants for non-hazardous waste or hazardous waste, plant leachate from storage of non-hazardous waste, effluent from surface treatment, mining effluents, coal-fired power plants or gas.
    [0003] The treatment method according to the invention makes it possible, at the end of the process, to obtain a concentration of each of the heavy metals of less than 0.01 mg / l. According to the invention, the process may further comprise, after step g), at least one step of eluting the resins to desorb the heavy metals fixed on said resins, the recovery of the eluates containing said heavy metals and at least a step of regenerating said resins for their subsequent use in a new cycle. The resins used to adsorb mercury are not regenerable due to the complexity of the regeneration method. These resins, such as used resins (resin having reduced efficiency after several cycles of production / regeneration) are eliminated in a conventional manner. The regeneration eluates of the resins comprising high concentrations of heavy metals can be subjected to a physico-chemical treatment (recycling upstream of the process). Indeed, the resins are a refining treatment (secondary treatment) and the physicochemical is a primary treatment suitable for the treatment of effluents concentrated in metals. According to the invention, the emission levels can be controlled by a tool for online and continuous monitoring of the metal content at the inlet and the outlet of the ion exchange resin treatment; depending on the metal leakage, it will be possible to know precisely the saturation state of the resin and to trigger if necessary the regeneration of the resins. - 6 - Still according to the invention, the exploitation can be optimized by setting up a control of the process in order to guarantee the emission levels (quality of the treated water) while optimizing / limiting the regenerations of the resins (and thus the OPEX of this station): - recovery and processing of the data of the analyzers then predictive calculation of the cycles remaining to satisfy the desired quality of water. - display the real-time count of the remaining cycle in order to regenerate only when the metal leaks on the resins do not satisfy the desired water quality.
    [0004] In order to better understand the method that is the subject of the present invention, an embodiment is described below. It remains understood that this is only an example having no limiting character. In the course of this description, reference is made to FIG. 1 of the accompanying drawings, which is a diagram illustrating the different steps of the method according to the invention. In this figure, the effluent to be treated is directed to a tank (1) provided with a stirrer in which lime and coagulant are also added while controlling the pH; the effluent thus treated is brought into a tank (2) and again treated with lime, at controlled pH, and then the mixture is fed from the tank (2) into a tank (3) in which a flocculant is added. After flocculation, the flocculated mixture is fed from the tank (3) into a lamellar decanter (4) and the floc is removed. The liquid decanted and filtered on a sand filter (R1) is then subjected to a passage over different resins (R2 = resin 1 and R3 = resin 2), each of these resins being able to adsorb one or more heavy metals that the it is desired to eliminate the effluent to be treated. After passing on these resins, the heavy metal-free liquid is released into the natural environment or into a sewerage system. The performance of the process according to the invention compared to those of the known processes of the prior art are summarized in Table 1 below. Table 1 METAL Concentration Final concentration continued Initial concentration in physic-final treatment following the chemical effluent alone (mg / 1) treatment according to the invention (mg / 1) Zinc and its 5 - 150 0.01 - 1,3 (4,5) <0,01 compounds Nickel and its 0,5 - 1 0,01 - 0,3 (0,3) <0,01 compounds Chrome and 0,5 - 2 0,01 - 0 , 1 (0,1) 0,005 - 0,05 its compounds Copper and its 1 - 10 0,01 - 0,4 (0,4) <0,005 compounds Thallium and 0,05 - 0,1 0,01 - 0, 05 (0,05) 0,01 - 0,05 its compounds Arsenic and its compounds 0,5 - 1 0,01 - 0,05 (0,05) 0,005 - 0,05 Lead and its 1 - 50 0,01 - 0.15 (1.25) <0.005 Mercury compounds and 0.5 - 0.001 - 0.04 (1.1) <0.0001 its cadmium compounds and 0.5 - 5 0.01 - 0.03 ( 0.2) 0.001 - 0.01 its compounds The process according to the invention has the following advantages: - an OPEX gain of 25 to 30% compared to the physico-chemical sector alone, - an environmental gain due to the decrease see the removal of sulfur products classically used for the precipitation of metals and - a technical gain related to the best abatement of metals.
    权利要求:
    Claims (6)
    [0001]
    REVENDICATIONS1. Process for the treatment of heavy metals present in liquid effluents charged with metals, in particular salts-laden waters, said process comprising the following steps: a. treatment of the liquid effluent likely to contain heavy metals with a neutralizing agent selected from the group comprising in particular sodium hydroxide, milk of lime, milk of magnesia, at a pH of 5 to 6, b. coagulation of the effluent treated in step a), c. precipitation of the mixture obtained in step b) with a neutralizing agent chosen from the group comprising, in particular, sodium hydroxide, milk of lime, milk of magnesia, at a pH of 9 to 10, d. flocculation of the mixture obtained during the coagulation step b) or the mixture obtained during the treatment step with a neutralizing agent c), e. removing the flocs formed in step d) and recovering the liquid, f. treatment of residual suspensions in step e) by filtration, g. contacting the liquid recovered in step f) with an ion exchange resin capable of adsorbing one or more heavy metals or put in successive contact with a plurality of ion exchange resins, each resin being capable of adsorbing one or more metals heavy, in order to reduce the concentration of heavy metals present in said liquid, h. recovery of the heavy metal free liquid.
    [0002]
    2. Process according to claim 1 characterized in that the heavy metals are selected from the group consisting of zinc, nickel, chromium, copper, thallium, arsenic, lead, mercury and cadmium.
    [0003]
    3. Treatment process according to any one of the preceding claims characterized in that the concentration of each of the heavy metals at the end of the process is less than 0.01 mg / l.
    [0004]
    4. Treatment process according to claim 1 characterized in that it further comprises after step g), at least one step of eluting the resins to recover said adsorbed heavy metals and at least one step of regenerating said resins.
    [0005]
    5. Treatment process according to claim 1 characterized in that the online and continuous monitoring of the metal leak on the ion exchange resin stage allows to know the saturation state of the resin and to trigger if necessary the regeneration of the resins.
    [0006]
    6. Treatment process according to claim 5 characterized in that the leakage of metals on the ion exchange resin stage is the subject of a predictive calculation to know the duration of the remaining cycle before a new regeneration.
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    同族专利:
    公开号 | 公开日
    HK1232206A1|2018-01-05|
    CN106458673A|2017-02-22|
    EP3160912A1|2017-05-03|
    FR3022900B1|2016-10-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0341792A1|1988-05-12|1989-11-15|Krupp Stahl Aktiengesellschaft|Process for treating spent pickling bath solutions|WO2017084643A2|2017-03-09|2017-05-26|Heraeus Deutschland GmbH & Co. KG|Process for the treatment of wastewater|US6103092A|1998-10-23|2000-08-15|General Electric Company|Method for reducing metal ion concentration in brine solution|CN108264164A|2018-01-15|2018-07-10|湖南永清环保研究院有限责任公司|A kind of nickel-containing wastewater treatment technology|
    CN108285239A|2018-04-11|2018-07-17|攀钢集团攀枝花钢铁研究院有限公司|A kind of process for treating waste liquor and system|
    CN109607854A|2018-12-14|2019-04-12|四川农业大学|A kind of high-content heavy metal ion underwater prevention method|
    CN110776184A|2019-11-07|2020-02-11|广东先导稀材股份有限公司|Advanced treatment method of thallium-containing wastewater|
    法律状态:
    2015-03-11| PLFP| Fee payment|Year of fee payment: 2 |
    2016-01-01| PLSC| Search report ready|Effective date: 20160101 |
    2016-06-13| PLFP| Fee payment|Year of fee payment: 3 |
    2017-06-13| PLFP| Fee payment|Year of fee payment: 4 |
    2018-05-29| PLFP| Fee payment|Year of fee payment: 5 |
    2020-06-25| PLFP| Fee payment|Year of fee payment: 7 |
    2021-06-25| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1456150A|FR3022900B1|2014-06-30|2014-06-30|PROCESS FOR TREATING SALTWATER SALT WATER|FR1456150A| FR3022900B1|2014-06-30|2014-06-30|PROCESS FOR TREATING SALTWATER SALT WATER|
    CN201580035400.9A| CN106458673A|2014-06-30|2015-06-30|Method for treating salty water|
    EP15751077.7A| EP3160912A1|2014-06-30|2015-06-30|Method for treating salty water|
    HK17105715.4A| HK1232206A1|2014-06-30|2017-06-09|Method for treating salty water|
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