WO2014012134A1 - Biosorbant pour l'élimination de métaux lourds - Google Patents

Biosorbant pour l'élimination de métaux lourds Download PDF

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Publication number
WO2014012134A1
WO2014012134A1 PCT/AU2013/000782 AU2013000782W WO2014012134A1 WO 2014012134 A1 WO2014012134 A1 WO 2014012134A1 AU 2013000782 W AU2013000782 W AU 2013000782W WO 2014012134 A1 WO2014012134 A1 WO 2014012134A1
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Prior art keywords
biosorbent
metal
contacting
metals
garden grass
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PCT/AU2013/000782
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English (en)
Inventor
Huu Hao Ngo
Wenshan Guo
Cong Liu
Original Assignee
University Of Technology, Sydney
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Priority claimed from AU2012903061A external-priority patent/AU2012903061A0/en
Application filed by University Of Technology, Sydney filed Critical University Of Technology, Sydney
Priority to CN201380049536.6A priority Critical patent/CN104661964B/zh
Publication of WO2014012134A1 publication Critical patent/WO2014012134A1/fr

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    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208—Tissues; Wipes; Patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9789—Magnoliopsida [dicotyledons]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9794—Liliopsida [monocotyledons]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/14—Preparations for removing make-up
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • 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 methods and processes for removing toxins and in particular metals and heavy metals from various sources including water and land. In certain embodiments this involves the use of biological materials to produce a biosorbent for such toxins, metals and heavy metals, e.g., copper, zinc and lead.
  • the biosorbent is preferably produced from waste agricultural materials.
  • the present invention also provides methods pre-treatment and regeneration of a biosorbent.
  • Biosorption is the uptake of metals/ substances by a biological means.
  • Biosorbents as applied herein, generally fall into several categories including bacteria, fungi, algae, industrial wastes, agricultural waste and/or other polysaccharide materials.
  • Agricultural waste or other biosorption processes which employ inexpensive dead biomass are particularly popular to sequester heavy metals from aqueous solutions, and are especially useful for the removal of trace amounts of heavy metals.
  • the major advantages of biosorption include its low cost, high efficiency of heavy metal removal from dilute solutions, cost-effective and simple regeneration of the biosorbent, the possibility of metal recovery, and the lack of nutrient requirements. Due to its excellent prospects, numerous materials have been studied for the development of cheaper and more effective biosorbents.
  • biosorbent processes are metal-specific.
  • the biosorbent is chosen and prepared specifically to absorb a particular metal. Methods and processes are generally needed for a multi-metal system and for multiple uses.
  • CN 101601991, to Hunan University discloses a biosorbent for removing lead ions in wastewater.
  • the biosorbent is granular and uses calcium alginate and gelatin as carriers in which grapefruit peel powder is embedded.
  • the biosorbent is added into wastewater for proceeding adsorption treatment for at least 30 minutes at normal temperature in which pH value is 3.5-7.0, which can basically remove lead ions in the wastewater.
  • US 2012/0024795 describes a biosorbent for removing cationic and/or anionic metals from aqueous solutions, and a process for the production of the biosorbent.
  • the biosorbent includes bacterial aggregates of Bacillus sp., treated with polyethyleneimine and glutaraldehyde. Removal or recovery of metals from wastewater using the biosorbent is also described.
  • a biosorbent comprising watermelon rind.
  • a biosorbent comprising sugarcane bagasse.
  • a biosorbent comprising garden grass.
  • a biosorbent comprising at least two components selected from the group consisting of: watermelon rind, sugarcane bagasse and garden grass.
  • the components are provided in quantities to synergistically enhance biosorptive activity.
  • the biosorbent comprises watermelon rind, sugarcane bagasse and garden grass.
  • these three constituents are provided in an approximate 1 : 1 : 1 ratio by mass.
  • the biosorbent is provided in a dry powdered form.
  • the biosorbent has a pH of about 6 to about 7; preferably about 6.5 to about 7; and most preferably about 6.8.
  • a method for removing toxins from a material comprising contacting said material with a biosorbent as defined according to the first through fourth aspects of the present invention.
  • the material is a fluid.
  • the material is an aqueous solution.
  • the biosorbent is provided in a dosage of between about 0.1 and 5.0 g/L.
  • a method of remediating land comprising contacting said land with a biosorbent as defined according to any one of the first through fourth aspects of the present invention.
  • a method of adsorbing metal from a material comprising one or more cycles of: a) contacting said material with a biosorbent as defined according to any one of the first through fourth aspects of the present invention; and desorbing said biosorbent.
  • the desorption step comprises contacting said biosorbent with a suitable eluant for a predetermined period.
  • the method comprises up to 10 cycles.
  • the method comprises up to 30- 40 cycles.
  • the desorption step comprises contacting said biosorbent with one or more eluants selected from the group consisting of: distilled water, tap water, Milli-Q water, NaOH, HN0 3 , HC1, H 2 S0 4 and CH 3 COOH.
  • the biosorbent prior to the contacting step, the biosorbent undergoes a pH pre-treatment to provide the biosorbent at a substantially neutral pH.
  • the biosorbent prior to the contacting step, undergoes a pre-treatment comprising contacting the biosorbent with NaOH for a predetermined period.
  • the biosorbent has a pH of between about 6 and 7. Most preferably, the biosorbent has a pH of about 6.8.
  • a method for adsorbing metals from a material comprising contacting said material with a biosorbent as defined according to any one of the first through fourth aspects of the present invention.
  • the metals comprise copper, zinc and lead, either alone or in combination.
  • the material is water or wastewater.
  • a cosmetic formulation for topical application comprising a biosorbent as defined according to any one of the first through fourth aspects of the present invention.
  • a method of removing heavy metals from a user's skin comprising administering to said user an effective amount of a biosorbent as defined according to any one of the first through fourth aspects of the present invention, or of a cosmetic formulation as defined according to the ninth aspect of the present invention.
  • any biosorbent or biosorbent-containing composition that contacts with a user's skin should ideally be substantially pH-neutral.
  • biosorption is a process whereby metals or other substances can be adsorbed using a biological substrate.
  • Agricultural waste in particular, is a large potential source of biosorbent as it currently has no prominent utilisation.
  • Watermelon rind (Citrullus lanatus, family Cucurbitaceae) is a common agricultural by-product and natural and rich source of non-essential amino acid citrulline containing abundant carboxyl and amino functional groups which have a remarkable capability of binding heavy metals from aqueous solutions. Studies have found that only half of a watermelon fruit is edible while the other half, consisting of about 30-35% rind and 15% peel goes to waste.
  • Bagasse is the fibrous matter that remains after sugarcane or sorghum stalks are crushed to extract their juice.
  • sugarcane bagasse As an effective biosorbent, however, it has generally been used in isolation, i.e., not in the synergistic combination proposed by the present invention.
  • Garden grass is self-explanatory; it is intended to encompass the clippings of any domestic lawn/parkland. Green grasses, rye grasses, etc., are all envisaged.
  • the present invention also provides a synergistic combination of various biosorbent materials which are suitable for multi-metal systems. Although it is not abundantly clear how this occurs, it appears that the combination of various biological materials in the inventive biosorbent has a synergistic effect in providing a greater number of functional groups than the cumulative number provided by each material. This synergistic effect, provides a "biosorptive capacity" which is several orders of magnitude greater than the individual components, or what would be expected by simple aggregation of these components.
  • biosorbents in the form of, simply, watermelon rind and garden grass. Again, the biosorption capabilities of these materials has to date, as far as the Applicant is aware, been unknown. As discussed below, watermelon rind is an inexpensive,
  • Figure 1 is a graph showing the effect of contact time of copper biosorption on a combined biosorbent in accordance with a preferred embodiment of the present invention.
  • Figure 2 is a graph showing the effect of pH on metal removal efficiency in a single metal solution using a biosorbent as indicated, i.e., dosage: 0.5 g; particle size ⁇ 150 ⁇ ; contact time: 10 h; initial metal concentration of Cu, Zn and Pb: 10 mg/L; 125 rpm; 20 °C; NaOH: 0.1 mol/L.
  • Figure 3 is a graph showing the effect of pH on metal removal efficiency in a multi-metal solution using a biosorbent in accordance with a preferred embodiment of the present invention, i.e., dosage: 0.5 g; particle size ⁇ 150 ⁇ ; contact time: 10 h; initial metal concentration of Cu, Zn and Pb: 10 mg/L; 125 rpm; 20 °C.
  • Figure 4 is an FTIR spectral analysis of a combined biosorbent in accordance with another embodiment of the present invention.
  • Figure 5 is an FTIR spectral analysis of a watermelon rind biosorbent in accordance with yet another embodiment of the present invention.
  • Figure 6 is an FTIR spectral analysis of sugar cane bagasse in accordance with yet another embodiment of the present invention.
  • Figure 7 is an FTIR spectral analysis of a garden grass biosorbent in accordance with yet another embodiment of the present invention.
  • Figure 8 is a graph showing the effect of pH on metal removal efficiency for copper, zinc and lead using watermelon rind as a biosorbent in a single metal solution.
  • Figure 9 is a graph showing the effect of pH on metal removal efficiency for copper, zinc and lead using watermelon rind as biosorbent in a multi-metal solution.
  • Figure 1 OA is a graph showing the effect of initial copper concentration and contact time using garden grass as a biosorbent.
  • Figure 10B is a graph showing the effect of pH on copper adsorption using garden grass as a biosorbent.
  • Figure IOC is a graph showing the effect of biosorbent dosage on copper removal, using garden grass as a biosorbent.
  • Figure 10D is a graph showing the effect of particle size of a biosorbent on the removal efficiency of copper using garden grass as a biosorbent.
  • Figure 11 A shows the effect of desorption/regeneration of a garden grass biosorbent using various eluants
  • Figure 1 IB is a graph showing the effects of desorption/adsorption cycles of copper using garden grass as a biosorbent.
  • biosorption is the uptake of metals or other substances by biological means.
  • the biosorbent is obtained from agricultural materials such as wastes which are comprised of lignin and celluloses major constituents. They may also include other polar functional groups of lignin which include alcohols, aldehydes, ketones, carboxylates, phenols and ethers. These functional groups have the ability to some extent to bind heavy metals by donation of an electron pair from these groups to form complexes with metal ion in solution.
  • biosorbents have included rubber wood dust, peanut shells, hazelnut husk, Ceiba pentandra hulls, banana peel, citrus peel, palm olive fruit shell, tree fern, Irish peat moss, cellulose pulp waste, wheat bran and micro algaes.
  • the present Inventors have found new and effective biosorbents which can be used either alone or in a synergistic combination.
  • Sugarcane bagasse and watermelon rind were collected from a local market while garden grass was collected from a recreational grass area. The collected biomass was washed with tap water and then rinsed with distilled water. Subsequently, the various components were dried, ground into powder and then mixed together in an approximate mass ratio of 1 : 1 : 1. Drying, as discussed below, was carried out in a laboratory- scale oven. The dried combined biosorbent was stocked in desiccator at room temperature (20 °C).
  • FIG. 1 is a graphical representation of removal efficiency versus time for copper adsorption. It can be seen from Figure 1 that at approximately two hours the biosorption process it close to its equilibrium since there is minimal increased removal after this point. Accordingly, it can be seen that an optimal contact time with the combined biosorbent may be four hours or less, preferably three hours, more preferably two hours or less. The most effective concentration appeared to be 25 mg/L. It should be recognised that this test was conducted with no pre-treatment applied to the combined biosorbent. Later processes included a NaOH pre-treatment step.
  • pre-treatment significantly improves the removal efficiency of metals.
  • the NaOH pre-treatment may increase the surface area of the combined biosorbent and thereby activate more suitable binding sides.
  • more functional groups i.e., OH "
  • more micro-precipitation/adsorption will occur on the binding sides so as to remove the target ion, e.g., metal, heavy metal, etc.
  • the negative charged surface can result in an attraction between the combined biosorbent and the target ion.
  • strong physical adsorption means more metal ions can be removed.
  • biosorbent dosages above 0.5 g work best for Cu.
  • the novel combined biosorbent is extremely efficient at removing Cu irrespective of the biosorbent dosage.
  • Even at the biosorbent dosage of 0.1 g Pb removal efficiency is over 97%.
  • Zn metal removal appears to increase in proportion to biosorbent dosage.
  • the desorption characteristics and regeneration ability of the combined biosorbent was also investigated. After each desorption the biosorbent was contacted with a suitable eluant. Several eluants were used to test desorption characteristics, including tap water, Milli-Q water, distilled water, NaOH, HN0 3 , HC1, H 2 S0 4 , or CH 3 COOH.
  • Tables 9, 10 and 11 all relate to metal removal efficiency following ten rounds of adsorption and resorption with initial metal concentrations of copper, zinc and lead of 25, 50 and 100 mg/L, respectively. All other conditions were the same throughout these three experiments.
  • Table 13 shows the biosorptive capacity (in mg/g) of each of the three biosorbent constituents (banana peel, sugarcane bagasse and watermelon rind). The skilled addressee will note that the results for copper and zinc display marked synergy.
  • the Table provides comparative data of the biosorptive capacity of the combined biosorbent compared with other biosorbents. It can be seen that the novel combined biosorbent has a biosorptive capacity against conventional biosorbents such as banana peel and sugarcane bagasse, several orders of magnitude higher for all metal types shown.
  • the functional groups provided by the combined biosorbent do not result from the cumulative functional groups of the individual components. Rather, there appears to be a synergistic effect in the combining of these individual biosorbents to provide a biosorbent with a different functional group profile as well as a substantially enhanced biosorptive capacity over the individual biosorbents mentioned above. This appears to be a significant contributing factor to the functional capabilities of the inventive combined biosorbent having watermelon rind, sugar cane bagasse and garden grass in apparently synergistic quantities.
  • Watermelon rind was collected from a local market. The collected watermelon rind was washed with tap water and then rinsed with distilled water. Subsequently, watermelon rind was cut into small pieces, dried, and grounded into powder before its use in biosorption experiments. The drying experiments were carried out in a laboratory scale oven. Dried watermelon rind was stocked in a desiccator at room temperature (20 ⁇ 1 °C). All the chemicals used in this study were of analytical grade. Stock solutions of metal ions were prepared in Milli-Q water. During the biosorption experiments, stock solutions were diluted to the specified concentration. Watermelon rind was contacted with each solution at pH 6.48 ⁇ 0.1 (the approximate pH of tap water).
  • reaction mixture was agitated at 125 rpm on a shaker. Agitation contact time was kept for 10 h, which was sufficient to reach equilibrium. All the samples from the experiments were filtered through a 0.45 ⁇ nylon membrane filter and the filtrate was kept for analysis. Biosorption experiments were conducted in triplicate and average values were used for discussion. The whole experiment was conducted at ambient room temperature (20 ⁇ 1 °C).
  • the solution pH can play a critical role in biosorption. It can affect the solution chemistry of metals and the activity of the functional groups of the biosorbents and can even completely inactivate the activity of binding sites.
  • the speciation and biosorption availability can also be strongly affected by solution pH. Under the condition of higher solution pH, the solubility of metal complexes decreases, which may subsequently, lead to
  • FIG. 9 shows the effect of solution pH on removal efficiency using watermelon rind as a biosorbent in a multi metal solution. Again the dosage was 0.5 g with an initial metal concentration of 10 mg/L. Particle size was ⁇ 150 ⁇ with a contact time of 10 hours, agitation of 125 rpm at 20 °C.
  • Table 15 shows a comparison of removal efficiency of the three metals in a single-metal solution and a multi-metal solution using watermelon rind as a novel biosorbent.
  • the pH for this comparison was 6.48 with an initial concentration of 10 mg/L. Other test criteria were as indicated.
  • Desorption is an important part in the biosorption process for metal removal. As will be clear to persons skilled in the art, there is a need to desorb and recover the metal and thereby "regenerate" the biosorbent, at regular intervals. The efficiency of the regeneration of biosorbent after metal desorption also plays a vital role in the application of biosorption technology. Therefore, regeneration of biosorbents becomes significant. In large-scale applications, regeneration of the biosorbent has various benefits, such as keeping process costs down and recovering the metals extracted from the liquid phases. For this reason, environmentally-sensitive and inexpensive eluants become desirable to achieve non-destructive recovery so as to regenerate biosorbents for further reuse in multiple cycles.
  • an appropriate eluant should met several requirements, such as yielding the metals in a concentrated form, no physical changes or damage to the biosorbent, and restoring the biosorbent close to the original condition for effective reuse with preferably undiminished metal uptake.
  • Pore properties of various biosorbents e.g., raw biosorbent, biosorbent after sorption process, and biosorbent after NaOH desorption process
  • the garden grass was collected from Oswald Street Reserve, Campsie, New South Wales, Australia after mowing. It was combined of three types of grasses.
  • the names of grasses were Kikuyu grass (Pennisetum clandestinum), Kangaroo grass (Themeda australis) and weeping grass (Microlaena stipoides) and in an attempt to make it user-friendly the grasses were not separated.
  • Foreign matter was removed from the garden grass and washed with tap water and distilled water to remove dirt.
  • the washed garden grass was kept in air to remove water from surface and then dried in oven at 105 °C for 24 h.
  • the dried garden grass was grounded into powder and kept in air-tight bottle for later use.
  • a stock solution (1000 mg/L) of Cu was prepared using copper sulfate pentahydrate (CuS0 4 .5H 2 0) in Milli-Q water.
  • the working solution was prepared by diluting this stock solution with distilled water
  • the effects of pH, garden grass doses, particle size, initial metal concentration (e.g., copper), contact time and temperature on metal adsorption were studied.
  • the effect of initial copper concentration and contact time were conducted in 100 mL water with 10, 50 and 100 mg/L copper and 0.5 g garden grass for 7 hours at room temperature and non-adjusted pH.
  • the pH experiment was done in 100 mL water with 0.5 g garden grass and the pH ranges were 2 to 8.
  • Dosage effects were performed in 100 mL water with 0.05, 0.1, 0.5, 1 and 2 g of garden grass and with 1, 2.5, 5, 10 and 15 mg/L copper concentration.
  • the effect of particle sizes were conducted in 100 mL water with 1-500 mg/L copper concentration and particle sizes were >75 ⁇ , 75 ⁇ and 150 ⁇ .
  • the temperature effects experiment was conducted at 20, 30, 40, 50 and 70 °C with 0.5 g garden grass.
  • the actual amount of copper adsorbed per unit mass of garden grass increased with the increase in copper concentration from 10 mg/L to 100 mg/L in the test water.
  • unit adsorption of copper on garden grass increased from 14.06 to 137.12 mg/g.
  • Maximum amount of copper was adsorbed within 400 min (6 hours) and equilibrium time for adsorption of copper onto garden grass was around 6 hours.
  • the pH of a solution affects surface charge of adsorbent and degree of ionisation and speciation of adsorbent.
  • metal adsorption is dependent on pH condition of water.
  • the effect of pH on the garden grass as a biosorbent for copper adsorption is exemplified in Figure 10B.
  • the highest value of copper removal was achieved at a pH of around 6.0.
  • the dominant species of copper was free Cu 2+ ion which mainly involved in adsorption process. Further adsorption test beyond this pH were hampered due to owing immediate precipitation of copper hydroxide.
  • Figure IOC Effect of garden grass doses on copper adsorption are shown in Figure IOC. These were conducted at initial copper of 1, 2.5, 5, 10 and 15 mg/L, while the garden grass doses was varied from 0.5, 1, 2, 5, 10 and 20 g/L. The results indicate that the removal of copper rapidly increases with the increase in doses up to 5 g/L and thereafter remained unchanged. At equilibrium, removal increased from 50 to 84% for an increase in dose from 0.5 to 5 g/L. The increase in copper removal is expected to be due to the increase in the available adsorption surfaces and sites. Maximum copper removal was found from 0.5 g/L garden grass dosage and 10 mg/L copper
  • Copper adsorption capacities at three particle sizes of garden grass are shown in Figure 10D.
  • the monolayer adsorption capacity (q m ) of copper increased as the particle size of the garden grass decreased.
  • Langmuir isotherm parameters q m and K for each of the three particle sizes were calculated and are listed in Table 19. It is noteworthy that q m for each particle size, increased from 6.064 to 11.173 mg/g with decreasing of particle size from 150 to ⁇ 75 ⁇ . This may be due to the larger specific surface area available for adsorption with smaller particles at a constant mass of garden grass during the process.
  • the specific surface areas of the garden grass biosorbent was calculated; the results are presented in Table 20.
  • the maximum specific surface area of garden grass was 167.36 m 2 /g for ⁇ 75 ⁇ particle size which is higher than BET surface area ⁇ see, Table 19).
  • Tests were also conducted to determine the desorption characteristics and regeneration ability of the garden grass.
  • Eight types of eluants including 0.1 N H 2 SO 4 , 0.1 N HC1, 0.1 N HNO 3 acids were used as eluant for copper desorption from garden grass.
  • Figure 11 A adsorption of copper onto garden grass is easily regenerated by a small amount of 0.1 N H 2 SO 4 .
  • the results showed that the removal percentage of 95% of copper was realised with 0.1 N H 2 SO 4 from Cu-loaded 0.5 g garden grass.
  • the adsorption and desorption cycles were repeated five times. Although adsorption and desorption efficiency for the regenerated garden grass decreased gradually ⁇ see, Figure 1 IB), the regenerated garden grass could still be used five times with minor deviation of efficiency.
  • bioadsorbent depends on a number of factors including the higher metal adsorption capacity, specific surface area, user friendly, nature of the material availability and environmental friendliness uses.
  • comparative adsorption capacities of garden grass and other adsorbents, including activated carbon produced from agricultural wastes (as calculated from the Langmuir isotherm model) for copper are compared in Table 19. It can be seen from these results that the proposed biosorbent from garden grass adsorbs copper from water more than any of the other biosorbents obtained from agricultural wastes and activated carbons. It is also noted that such a biosorbent from garden grass has a higher specific surface area and is arguably more environmentally-friendly due to its non-adjusted pH. Table 20
  • garden grass is a robust reusable and stable biosorbent for metal such as copper and there removal from various materials including water.
  • the present invention is not limited to remediating wastewater and the like; it also finds potential application in the field of cosmetics.
  • Many makeups contain undesirable levels of heavy metals that are coated onto a user's skin (in particular, a user's face), absorb into the user's skin - and may subsequently remain in the skin when the makeup is removed either by washing or wiping.
  • the present invention thereby has real potential when incorporated into a cosmetic product, such as a moisturising emollient base, when formulated within a cosmetic "mask” - or even when applied directly to a user's skin.
  • a cosmetic "wipe” comprising one or more of the biosorbents described in relation to the present invention.
  • the constituent/s of the inventive biosorbent - namely, watermelon rind, garden grass and sugarcane bagasse are appealingly “natural” and “organic” to consumers.

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Abstract

L'invention concerne un biosorbant comprenant de l'écorce de pastèque, de la bagasse de canne à sucre et/ou de l'herbe de jardin. De préférence, les trois sont présents en quantités synergiques. L'invention concerne également des procédés d'élimination de toxines d'un matériau, de dépollution d'une terre et d'adsorption d'un ou de plusieurs métaux à partir d'une matière telle que l'eau usée.
PCT/AU2013/000782 2012-07-18 2013-07-15 Biosorbant pour l'élimination de métaux lourds WO2014012134A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106215882A (zh) * 2016-09-08 2016-12-14 河海大学 一种用于处理染料废水的西瓜皮吸附剂的制备方法
EP3266748A1 (fr) 2016-07-06 2018-01-10 Clariant International Ltd Matériaux d'adsorption à base de lignine à faible coût pour le traitement de l'eau
CN109384277A (zh) * 2018-11-07 2019-02-26 环境保护部华南环境科学研究所 综合去除电镀废水中重金属的复合处理剂
CN109721213A (zh) * 2019-01-31 2019-05-07 环境保护部华南环境科学研究所 用于处理重金属废水的多级人工湿地***
CN109721151A (zh) * 2019-01-31 2019-05-07 环境保护部华南环境科学研究所 用于处理重金属废水的人工湿地用复合填料
CN109847714A (zh) * 2019-04-04 2019-06-07 岭南师范学院 一种甘蔗渣微球的制备方法
CN112568060A (zh) * 2020-12-07 2021-03-30 江西省农业生态与资源保护站 一种无公害富硒双孢蘑菇的培养料及栽培方法

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* Cited by examiner, † Cited by third party
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US673815A (en) * 1900-12-31 1901-05-07 Peerless Machinery Co Eyeleting-machine.
GB1445754A (en) * 1972-11-20 1976-08-11 Elepon Kakoki Co Method of adsorbing heavy metal ions
JP2001276804A (ja) * 2000-03-31 2001-10-09 Taiheiyo Cement Corp ＰＣＢｓ及び／又はダイオキシン類含有土壌の植物による浄化方法
RU2221639C1 (ru) * 2002-12-23 2004-01-20 ГУ Волгоградский научно-исследовательский технологический институт мясомолочного скотоводства и переработки продукции животноводства РАСХН Способ получения сорбентов на растительной основе
CN101204415A (zh) * 2006-12-20 2008-06-25 天津市中宝制药有限公司 治疗中暑的贴剂
CN102464376A (zh) * 2011-10-20 2012-05-23 常州亚环环保科技有限公司 一种利用生物废渣基处理含铅废水的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6738815B1 (en) * 1998-07-01 2004-05-18 Telcordia Technologies, Inc. Systems and methods for utilizing a communications network for providing mobile users access to legacy systems
US7481934B2 (en) * 2006-01-20 2009-01-27 Renewable Fibers, Llc Methods for treatment of wastewater with powdered natural lignocellulosic material
CN100546564C (zh) * 2006-07-04 2009-10-07 何成钧 中药瓜果美容敷面膏及制备方法
CN101336874A (zh) * 2008-08-18 2009-01-07 贝侬生化（苏州工业园区）有限公司 果皮中水溶性活性提取物及制备方法和用途
JP2011016731A (ja) * 2009-07-07 2011-01-27 Kamiyama Biken:Kk 化粧料および化粧料組成液、化粧料の製造方法および化粧料組成液の製造方法
CN102363121B (zh) * 2011-05-16 2013-10-09 浙江海洋学院 一种脱除水产调味品中重金属铬的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US673815A (en) * 1900-12-31 1901-05-07 Peerless Machinery Co Eyeleting-machine.
GB1445754A (en) * 1972-11-20 1976-08-11 Elepon Kakoki Co Method of adsorbing heavy metal ions
JP2001276804A (ja) * 2000-03-31 2001-10-09 Taiheiyo Cement Corp ＰＣＢｓ及び／又はダイオキシン類含有土壌の植物による浄化方法
RU2221639C1 (ru) * 2002-12-23 2004-01-20 ГУ Волгоградский научно-исследовательский технологический институт мясомолочного скотоводства и переработки продукции животноводства РАСХН Способ получения сорбентов на растительной основе
CN101204415A (zh) * 2006-12-20 2008-06-25 天津市中宝制药有限公司 治疗中暑的贴剂
CN102464376A (zh) * 2011-10-20 2012-05-23 常州亚环环保科技有限公司 一种利用生物废渣基处理含铅废水的方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3266748A1 (fr) 2016-07-06 2018-01-10 Clariant International Ltd Matériaux d'adsorption à base de lignine à faible coût pour le traitement de l'eau
WO2018007150A1 (fr) 2016-07-06 2018-01-11 Clariant International Ltd Matériaux d'adsorption à base de lignine à faible coût pour le traitement de l'eau
CN106215882A (zh) * 2016-09-08 2016-12-14 河海大学 一种用于处理染料废水的西瓜皮吸附剂的制备方法
CN106215882B (zh) * 2016-09-08 2018-12-14 河海大学 一种用于处理染料废水的西瓜皮吸附剂的制备方法
CN109384277A (zh) * 2018-11-07 2019-02-26 环境保护部华南环境科学研究所 综合去除电镀废水中重金属的复合处理剂
CN109721213A (zh) * 2019-01-31 2019-05-07 环境保护部华南环境科学研究所 用于处理重金属废水的多级人工湿地***
CN109721151A (zh) * 2019-01-31 2019-05-07 环境保护部华南环境科学研究所 用于处理重金属废水的人工湿地用复合填料
CN109847714A (zh) * 2019-04-04 2019-06-07 岭南师范学院 一种甘蔗渣微球的制备方法
CN112568060A (zh) * 2020-12-07 2021-03-30 江西省农业生态与资源保护站 一种无公害富硒双孢蘑菇的培养料及栽培方法

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