WO1992015528A1 - Procede destine a enlever et/ou a recuperer du mercure - Google Patents

Procede destine a enlever et/ou a recuperer du mercure Download PDF

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Publication number
WO1992015528A1
WO1992015528A1 PCT/AU1992/000091 AU9200091W WO9215528A1 WO 1992015528 A1 WO1992015528 A1 WO 1992015528A1 AU 9200091 W AU9200091 W AU 9200091W WO 9215528 A1 WO9215528 A1 WO 9215528A1
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WO
WIPO (PCT)
Prior art keywords
mercury
resin
trade mark
registered trade
anion exchange
Prior art date
Application number
PCT/AU1992/000091
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English (en)
Inventor
Robert James Eldridge
Norman Samuel Charles Becker
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
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 Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to JP4505890A priority Critical patent/JPH06504948A/ja
Publication of WO1992015528A1 publication Critical patent/WO1992015528A1/fr

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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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • 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
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/10—Regeneration or reactivation of ion-exchangers; Apparatus therefor of moving beds
    • B01J49/14—Regeneration or reactivation of ion-exchangers; Apparatus therefor of moving beds containing anionic exchangers
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • 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
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Definitions

  • the present invention relates to a method for removing and/or recovering mercury from natural water or wastewater.
  • Mercury is a potentially very toxic pollutant to the aqueous environment.
  • the levels of mercury in wastewater need to be considerably reduced prior to discharge. Typically mercury levels need to be reduced from mg/1 levels to low ppb levels, generally 10 to 200 ppb or less.
  • the usual procedure for treating mercury containing wastewater is to precipitate the mercury chemically.
  • the most common approach is to precipitate the mercury with sulphide. This step results in the formation of a sludge containing the sparingly soluble mercury sulphide along with other precipitated metals which can then be dumped as landfill.
  • This precipitation technique although effective for reducing mercury content of wastewater, has several disadvantages.
  • the mercury that is precipitated is not recoverable and the disposal of the sulphide sludge itself may pose significant environmental problems.
  • Mercury is commonly present in a wastewater as the complex anion (usually as the chloride) and so an ion exchange process needs to be developed around extracting mercury specifically as a complex anion. It is an object of the present invention to provide an ion exchange process in which the uptake of mercury is achieved by using anion exchange resins.
  • a method for removing and/or recovering mercury from natural water or wastewater contaminated with mercury characterized in that the method comprises the steps of:
  • the mercury may be optionally recovered from the eluate and the eluate may be optionally recycled as the eluant to step (b).
  • the recovered mercury may be optionally converted into metallic mercury or a desired mercury compound.
  • wastewater as used herein includes aqueous effluents and other wastewaters containing mercury which are discharged from industrial processes.
  • the mercury to be removed and/or recovered by the method of the invention is present in the natural water or wastewater as a complex anion.
  • the complex anion is (HgCl 4 ) 2 ".
  • the mercury is extracted using any suitable technique known per se for use in ion exchange processes, e.g. by passing the natural water or wastewater through a bed of settled anion exchange resin.
  • the anion exchange resins suitable for use in the present invention can be broadly classified into two types, namely, strong base and weak base exchange resins. Strong base resins comprise functional groups that are quaternary ammonium groups and remain ionised over all pH ranges, while weak base resins usually comprise primary, secondary or tertiary amines that are readily converted to their free base forms and hence lose their ion exchange properties above pH 7.
  • strong base anion exchange resins include those containing benzyltrimethyl ammonium functional groups, for example, Amberlite IRA 900,
  • Duolite A161, Diaion PA-318, Lewatit MP-500 and Dowex MSA-1 examples include those containing tertiary amine functional groups, for example, Amberlite IRA 93, Amberlyst A-21, Duolite A378, Diaion WA-30, Lewatit MP-62 and Dowex MWA- 1.
  • An example of a very weak base anion exchange resin is Reillex 425 which is composed of polyvinyl pyridine.
  • the anion exchange resin is a strong base as such resins exhibit much lower leakages of, and a higher capacity for, mercury. More preferably, the anion exchange resin contains benzyltrimethyl ammonium functional groups, such as, for example, Amberlite IRA900 which is capable of removing mercury from a complex acidic wastewater resulting in mercury leakages of less than 1%.
  • benzyltrimethyl ammonium functional groups such as, for example, Amberlite IRA900 which is capable of removing mercury from a complex acidic wastewater resulting in mercury leakages of less than 1%.
  • the adsorbed mercury may be removed from the loaded anion exchange resin by elution with a complexing agent that binds more strongly with mercury than the resin itself.
  • the complexing agent is selected from a sulphur containing inorganic anion, such as, for example, sulphide, sulphite or thiosulphite and an organic ligand containing one or more donor atoms selected from oxygen, nitrogen or sulphur, such as, for example, ethylenediamine, ethylenediaminetetracetic acid (EDTA), thiourea, methionine, thiazoleamine, diaminodiphenyl- sulphide or thioglycolic acid.
  • a complexing agent is selected from a sulphur containing inorganic anion, such as, for example, sulphide, sulphite or thiosulphite and an organic ligand containing one or more donor atoms selected from oxygen, nitrogen or sulphur, such
  • a particularly preferred complexing agent is ethylenediamine which can be used to successfully elute mercury from both strong and weak base resins.
  • ethylenediamine which can be used to successfully elute mercury from both strong and weak base resins.
  • 3-5 bed volumes of 1.5M ethylenediamine will achieve complete mercury elution. This is more efficient than a strong base resin where complete mercury elution occurs after 5-6 bed volumes.
  • the weak base resin With the weak base resin, a slow growing precipitate forms in eluate fractions containing high mercury concentrations following ethylenediamine elution.
  • Sodium sulphite may also be used to elute mercury from both strong and weak base resins. Although sodium sulphite is not as effective as ethylenediamine in eluting mercury from the resin, it is relatively cheap, easy to handle and readily available. In both strong and weak base resins, a slow growing precipitate forms in eluate fractions containing high mercury concentrations. Complete elution of mercury from a weak base resin with 1M sodium sulphite occurs within 7 bed volumes, while with the strong base resin complete elution occurs within 15 bed volumes. Sodium sulphide and EDTA can also elute mercury from both types of resins, but not as effectively as sodium sulphite or ethylenediamine.
  • a strong base anion exchange resin is used in combination with sodium sulphite as the complexing agent.
  • the mercury may be recovered from the eluate.
  • a precipitate forms, as in the case of ethylenediamine or sodium ⁇ sulphite elution, the mercury complex can be recovered directly.
  • the precipitates are generally slow forming and depend on the concentration of mercury in the eluate.
  • the precipitate can be isolated from the eluate after a time and the eluate can then be recycled back as eluant to step (b).
  • Thermogravimetric analysis indicates that the sulphite precipitate is a better candidate for thermal decomposition, than the ethylenediamine precipitate.
  • Mercury from the sulphite precipitate may also be converted to mercurous chloride which can be processed commercially into calomel or another mercury product by dissolving the precipitate in hydrochloric acid. The acid will destroy the sulphite and remove it from solution through the evolution of sulphur dioxide yielding a reasonably pure solution of mercuric chloride. Mercury can also be recovered by precipitation as Hg(I) or Hg(0) after the addition of a suitable reductant. There are many reagents capable of reducing Hg(II). One of the most common reagents used to reduce mercuric compounds is stannous chloride.
  • stannous chloride If the stannous chloride is added in excess, then the product will be Hg(0), but if not in excess, then Hg(I) will be precipitated. Ascorbic acid also reduces mercuric solutions and reduction has also been observed with hydrazine solution.
  • the mercury in the eluate may also be precipitated by reduction using electrolysis. It is also possible to recover dissolved mercury as the metal from both • ethylenediamine and sodium sulphite solutions, which are both decomposable by electrolysis.
  • mercury recovery isolation of the mercury ethylenediamine or mercury sulphite precipitates in the eluate with eluate recycling is the most preferred option.
  • Mercury can then be recovered from the precipitate by a variety of means depending on the desired mercuric compound.
  • each resin was first regenerated with NaOH, then converted to the chloride form with NaCl or HC1.
  • Hg uptake of Hg by each resin was tested by passing a Hg solution containing about 40 mg/1 Hg in H 2 S0 4 solution containing about 2000 mg/1 Cl (as NaCl) at pH 1.5 through a bed (3-5 ml wet settled resin (wsr)) of the resin.
  • Mercury was analysed by either flame atomic absorption spectrophotometry (AAS) in the case of high [Hg] (in excess of 20-50 mg/1) or by the cold vapour flameless AAS procedure using a home made set up for low level [Hg] .
  • AAS flame atomic absorption spectrophotometry
  • the distribution coefficients for the four anion exchangers were determined in the presence of 400 mg/1 Hg solution and 2000 mg/1 Cl plus S0 4 at pH 1.5. The resins were tested in the Cl form.
  • the strong base resin Amberlite IRA900 has also been tested for its ability to extract mercury from a wastewater obtained from a zinc refinery.
  • the wastewater was scrub tower effluent ex Al pellet column treatment.
  • This waste typically contains high levels of zinc and aluminium and lower levels of other metals including mercury in an acidic sulphuric acid medium containing a variety of other anions (pH 1.6). Some mercury was added to the waste to bring the total Hg concentration to 9.09 mg/1.
  • Anion exchangers can usually be regenerated by passing a strong solution of a salt containing an anion that in excess will displace other anions loaded on the resin.
  • a dilute alkali solution can be passed through the resin which results in the resin being converted to the free base form which effectively switches off the anion exchange resin.
  • Ethylenediamine can also elute Hg from a strong base resin.
  • a typical elution curve with Amberlite IRA900 resin and 1.5M ethylenediamine is shown in Figure 3.
  • the elution curve produced is broader than the weak base resin curve but is still quite acceptable. Once again, most of the Hg is removed from the resin after 5 B.V's.
  • the optimum ethylenediamine concentration for the removal of Hg from both the weak and strong base resins was determined. These experiments showed that 1M to 1.5M is the optimum ethylenediamine concentration to use for elution of Hg from these resins.
  • the weak base resin is particularly sensitive to changes in ethylenediamine concentration whilst the strong base resin performs equally as well with 1M ethylenediamine as with 2M.
  • Ethylenediaminetetraacetic acid was one reagent that was also found to elute Hg from a weak base resin. EDTA's mode of action is similar to that of ethylenediamine where a stable complex is formed between the Hg and the EDTA. Unfortunately, the concentration of EDTA required for efficient elution of Hg from the resin is quite high.
  • An elution curve for Amberlite IRA93 weak base resin using IM Na 4 EDTA (the tetra sodium salt of EDTA is the only salt that will completely dissolve at this concentration, and even at IM the solution is quite syrupy) at pH 12.7 is shown in Figure 6. The elution curve obtained is very broad with complete elution of Hg not occurring until about 18 B.V's. of eluant has been passed through the column.
  • Na 2 S will also elute Hg from a weak base resin.
  • An elution of Amberlite IRA93 with 0.5M Na 2 S at pH 7 was performed. Initially, as expected the elution produced a black precipitate (HgS) which passed through the column with the effluent. After about a further 30 minutes collection time the black precipitate completely dissolved as more Na 2 S was run through the column. The mercury remained in solution under alkaline conditions, but when acid was added the black precipitate reformed (with the evolution of H 2 S). Also when the solution was diluted with distilled water (10:1) the precipitate again reformed. HgS is soluble in concentrated (0.5M is concentrated) alkaline sodium sulphide solutions.
  • Hg can be recovered directly from either ethylenediamine (weak base resin only) or Na 2 S0 3 eluates as the precipitate that forms in high [Hg] fractions of the eluate.
  • the precipitates are generally slow forming (several hours is required for maximum formation depending on the concentration of Hg in the eluate) .
  • the precipitate can be isolated from the eluate after a time and the eluate can then be recycled back as eluant for the next regeneration of loaded resin.
  • Table 9 shows that a precipitate was observed to form in the eluate when the [Hg] was above about 6000 mg/1. The result also indicates that the eluate could be recycled back as regenerant after a small charge with some fresh Na 2 S0 3 and still elute most of the Hg from the resin. After collection of precipitated Hg complex, the regeneration effluent could also be recycled.
  • the Hg from the precipitate could be obtained by breaking the precipitate down thermally.
  • Thermogravimetric analysis (TGA) of Na 2 Hg(S0 3 ) 2 precipitate indicates that at 150°C the precipitate loses 30% of its weight and up to 60% at 220°C leaving a grey residue. Hg was probably lost as elemental Hg(vap) to the atmosphere, and could be collected by condensation.
  • the Hg-ethylenediamine precipitate was more resistant to thermal decomposition, losing only 30% of its weight at 280°C. This result indicates that the sulphite precipitate would be a good candidate for thermal decomposition, but not the ethylenediamine precipitate.
  • the mercury in the eluate could be precipitated by reduction using electrolysis.
  • Some electrolysis trials were carried out on Hg-ethylenediamine and Hg-sulphite solutions using a variable voltage/current DC power supply connected to two strips of platinum foil about 1cm in width (the electrodes). The electrodes were dipped into a beaker containing about 30ml of the solution to be tested and a suitable constant voltage and current were applied.
  • Electrolysis of a 1.5M ethylenediamine solution containing 28,300 mg/1 Hg and IM NaCl was carried out at 5V and 200 mA for 40 minutes.
  • a colourless gas was evolved at the cathode (and possibly also at the anode) along with the deposition of mercury metal (which coated the cathode after a time and began to drop off in globules).
  • the voltage dropped slowly with time.
  • analysis of the solution [Hg] showed a 75% drop in solution [Hg] .
  • the pH of the solution had also dropped from 12.0 to 11.1 and a distinctive ammonia smell indicating decomposition of ethylenediamine was observed.
  • Electrolysis of a IM Na 2 S0 3 solution resulted in the formation of a colourless odourless gas at the cathode.
  • S0 4 2 " was probably produced at the anode.
  • Electrolysis of a filtered (to remove Na 2 Hg(S0 3 ) 2 complex precipitate) Hg-S0 3 2 " solution at 4-5V and 200 mA resulted in evolution of a colourless odourless gas at the cathode along with formation of a black precipitate in the beaker followed by coating of the cathode with mercury metal.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

Procédé destiné à enlever et/ou à récupérer du mercure dans des eaux naturelles ou des eaux usées contaminées par du mercure, consistant (a) à extraire le mercure des eaux naturelles ou des eaux usées par adsorption sur une résine à échange d'anions et (b) à éliminer le mercure adsorbé par la résine à échange d'anions chargée en l'éluant avec un agent complexant sélectionné à partir d'un anion inorganique contenant du soufre et d'un ligand organique contenant un ou plusieurs atomes donneurs choisis parmi l'oxygène, l'azote et le soufre.
PCT/AU1992/000091 1991-03-01 1992-03-02 Procede destine a enlever et/ou a recuperer du mercure WO1992015528A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4505890A JPH06504948A (ja) 1991-03-01 1992-03-02 水銀の除去および／または回収法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPK4870 1991-03-01
AUPK487091 1991-03-01

Publications (1)

Publication Number Publication Date
WO1992015528A1 true WO1992015528A1 (fr) 1992-09-17

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PCT/AU1992/000091 WO1992015528A1 (fr) 1991-03-01 1992-03-02 Procede destine a enlever et/ou a recuperer du mercure

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EP (1) EP0573525A1 (fr)
JP (1) JPH06504948A (fr)
WO (1) WO1992015528A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014002131A (ja) * 2012-05-21 2014-01-09 Central Research Institute Of Electric Power Industry 水銀分析前処理方法、水銀分析前処理装置、水銀分析方法、水銀分析装置、及び水銀脱離溶液
CN116037168A (zh) * 2022-11-16 2023-05-02 安徽华塑股份有限公司 一种基于阴离子树脂吸收的氯化汞触媒循环生产方法
CN116607010A (zh) * 2023-07-19 2023-08-18 长沙华时捷环保科技发展股份有限公司 一种从含铅溶液中脱除与回收铅的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5114704B2 (ja) * 2006-04-27 2013-01-09 国立大学法人富山大学 金属の分離方法、および金属の回収方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2336762A (en) * 1961-10-23 1961-04-23 Diamond Alkali Company Chemical process
US3085859A (en) * 1960-09-01 1963-04-16 Dow Chemical Co Mercury recovery and removal
GB1379990A (en) * 1971-03-03 1975-01-08 Bayer Ag Process for removing mercury from aqueous liquids
DD260917A1 (de) * 1987-06-19 1988-10-12 Inst Energetik Verfahren zur quecksilbergewinnung aus waessrigen loesungen
US4909944A (en) * 1988-08-26 1990-03-20 The United States Of America As Represented By The United States Department Of Energy Removal of metal ions from aqueous solution

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085859A (en) * 1960-09-01 1963-04-16 Dow Chemical Co Mercury recovery and removal
AU2336762A (en) * 1961-10-23 1961-04-23 Diamond Alkali Company Chemical process
GB1379990A (en) * 1971-03-03 1975-01-08 Bayer Ag Process for removing mercury from aqueous liquids
DD260917A1 (de) * 1987-06-19 1988-10-12 Inst Energetik Verfahren zur quecksilbergewinnung aus waessrigen loesungen
US4909944A (en) * 1988-08-26 1990-03-20 The United States Of America As Represented By The United States Department Of Energy Removal of metal ions from aqueous solution

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 102, No. 20, 20 May 1985, (Columbus, Ohio, USA), Abstract No. 172029, "Mercury removal from water", MAKAREWICZ, M A; HANCHER, C W; MEREDITH, P F (Oak Ridge Y-12 Plant, TN, USA) Report 1984, Y/DZ-110). Order No. DE 85000383 (Eng). *
CHEMICAL ABSTRACTS, Volume 111, No. 6, 7 August 1989, (Columbus, Ohio, USA), Abstract No. 44719, "Mercury pollution Control by porous condensate anion exchanger", TIPNIS, UK; DASARE B D, Indian J Environ Prot 1988 8(12), 914-18, (Eng). *
Indian J Technol, 1986, 24(3), 127-9, PALL, G; DASARE, B D; "Uptake of mercury by porous condensate anion exchangers". *
See also references of EP0573525A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014002131A (ja) * 2012-05-21 2014-01-09 Central Research Institute Of Electric Power Industry 水銀分析前処理方法、水銀分析前処理装置、水銀分析方法、水銀分析装置、及び水銀脱離溶液
CN116037168A (zh) * 2022-11-16 2023-05-02 安徽华塑股份有限公司 一种基于阴离子树脂吸收的氯化汞触媒循环生产方法
CN116607010A (zh) * 2023-07-19 2023-08-18 长沙华时捷环保科技发展股份有限公司 一种从含铅溶液中脱除与回收铅的方法
CN116607010B (zh) * 2023-07-19 2023-10-17 长沙华时捷环保科技发展股份有限公司 一种从含铅溶液中脱除与回收铅的方法

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EP0573525A1 (fr) 1993-12-15
EP0573525A4 (fr) 1994-04-06
JPH06504948A (ja) 1994-06-09

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