WO2015181205A1 - Procédé pour l'élimination de phosphate dans des fractions d'eau - Google Patents

Procédé pour l'élimination de phosphate dans des fractions d'eau Download PDF

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WO2015181205A1
WO2015181205A1 PCT/EP2015/061647 EP2015061647W WO2015181205A1 WO 2015181205 A1 WO2015181205 A1 WO 2015181205A1 EP 2015061647 W EP2015061647 W EP 2015061647W WO 2015181205 A1 WO2015181205 A1 WO 2015181205A1
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Prior art keywords
phosphate
adsorbent
starch
water fraction
ppb
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Arie Cornelis Besemer
Vincenzo Roberto Calderone
Richard Johannes VAN DUIN
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BIAQUA BV
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BIAQUA BV
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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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • 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
    • B01J2220/46—Materials comprising a mixture of inorganic and 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/58—Use in a single column
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • C02F2101/105—Phosphorus 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 pertains to a method for removing phosphate from water fractions.
  • Phosphate is present in many water fractions, including waste water and water derived from water cleaning operations. As phosphate is an important nutrient for microorganisms, its presence may contribute to the growth of microorganisms.
  • a particular problem with bacterial growth is that even minor growth of microorganisms, a process which is sometimes also indicated as biofouling, may interfere with further
  • water streams are often subjected to treatment in membrane operations, e.g., membrane filtration or reverse osmosis.
  • membrane operations e.g., membrane filtration or reverse osmosis.
  • the occurrence of even minor amounts of biofouling in apparatus provided with a membrane will severely affect operation thereof.
  • WO90/05705 describes a method for the removal of phosphate from water wherein water is treated with an iron (II)
  • W02011 / 107524 also describes phosphate adsorption using ion exchange resin.
  • the resin can be regenerated using an alkaline solution of, e.g., NaOH or KOH .
  • W02011 / 107524 also describes phosphate adsorption using ion exchange resin.
  • the resin can be regenerated using an alkaline solution of, e.g., NaOH or KOH .
  • EP1764348 describes the use of thermophilic ferritin in the removal of phosphate from water fractions.
  • US2014/0138320 describes an agent for removing dissolved phosphorus compounds from water which comprises a biopolymer and at least one metal compound.
  • the biopolymer is selected from a large number of compounds, and so are the metal compounds.
  • the biopolymer is selected from alginate, kappa-carrageenan, xanthan, and gellan.
  • adsorption capacity of the materials described therein is between 1 and 12 mg P/g adsorbent.
  • US2014/0141243 describes a method for removing dissolved phosphorus from water comprising the steps of activating a cellulose material, coating the activated cellulose material with a biopolymer with an ionic character, coating the thus obtained materials with a water soluble polyvalent metal, and crosslinking the cellulose biopolymer material and the metal compound.
  • the biopolymer is selected from a large number of compounds, and so are the metal compounds. In the Examples, the biopolymer is selected from alginate, kappa-carrageenan, xanthan, and gellan.
  • the adsorption capacity of the materials described therein is of the order of 1 mg P/g adsorbent.
  • the present invention provides such a method.
  • the invention pertains to a method for removing phosphate from a phosphate-containing water fraction comprising the steps of contacting a phosphate-containing water fraction with an adsorbent, the adsorbent comprising a complex of Fe(III) and starch, and withdrawing an effluent water
  • the use of the specific adsorbent according to the invention has a number of advantages. In the first place, it was found that it makes it possible to obtain effluent water fractions with very low phosphate contents, as will be discussed in more detail below. Further, it has been found that the adsorbent has a high adsorption capacity, expressed in mg of phosphate per gram of adsorbent. This is important as it determines the size of the adsorption unit. Further, it has been found that the adsorbent used in the present invention can be regenerated in an efficient manner to allow re-use. Further, the adsorbent is based on a
  • EP2319804 US5,846,426, W02010 / 100112 , and EP1932808.
  • phosphate adsorption of phosphate from body fluids to reduce hyperphosphataemia cannot be compared to phosphate adsorption in water treatment.
  • phosphate In the first place, in water treatment, phosphate has to be reduced to very low levels, to prevent the growth of microorganisms as has been discussed above. In the human organism, phosphate removal to such low levels is not intended, and even undesirable.
  • the water stream to be treated with the process according to the invention is a phosphate-containing water stream.
  • the water stream has a phosphate content of at least 10 ppb, in particular at least 20 ppb, more in particular at least 50 ppb, still more in particular at least 100 ppb.
  • the maximum for phosphate content is not critical. A suitable maximum value may be at most 50000 ppb (50 ppm) . In one embodiment, the phosphate content may be at most 2000 ppb, specifically at most 1000 ppb, more specifically below 500 ppb .
  • phosphate encompasses organic and inorganic phosphates, including orthophosphate and polyphosphate.
  • the phosphate content can be determined using the phosphate-molybdenum method, which is well known in the art.
  • Other parameters of the water fraction to be treated with the process according to the invention are generally not
  • the water fraction to be treated will generally have a pH around 7, e.g. in the range of 6 to 7.5.
  • the water fraction to be treated may have a variable salt content. Its conductivity is generally in the range of 20-100 mS/m, in particular in the range of 40-70 mS/m.
  • the water fraction to be treated may, e.g., have a nitrate content in the range of 0.1 to 50 mg N/1, in particular 1-20 mg N/1.
  • the water fraction to be treated may originate from various sources. In one embodiment it is derived from a waste water treatment plant.
  • the water fraction can be subjected to conventional pretreatment steps to remove contaminants.
  • Suitable pretreatment steps include filtration and ultrafiltration.
  • the adsorbent used in the present invention comprises a complex of Fe(III) and starch.
  • Starch or amylum is a carbohydrate consisting of a large number of glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants as an energy store. It is contained in large amounts in plants like potatoes, wheat, maize (corn), rice, and cassava.
  • Starch The starch industry extracts and refines starches from seeds, roots and tubers, by wet grinding, washing, sieving and drying. Starch can be hydrolyzed into simpler carbohydrates by acids, various enzymes, or a combination of the two. The resulting fragments are known as dextrins. Starch is
  • oxidised starch is used. It has been found that, as compared to unoxidised starch, oxidised starch may result in an adsorbent with a higher phosphate adsorption capacity in mg/g.
  • oxidised starch is used with a carboxylate content of at least 200 peq/g (microequivalent carboxylate per gram) . It is preferred for the carboxylate content to be higher, e.g. at least 300 peq/g, in particular at least 400 peq/g, as a higher carboxylate content makes for increased phosphate adsorption. As a maximum for the carboxylate content, a value of at most 2000 peq/g may be mentioned, more in particular a value of at most 1000 peq/g.
  • the carboxylate content may be determined by methods known in the art, e.g., by conductometric titration or FTIR (Fourier Transform Infrared spectroscopy) . Oxidised starch is known in the art, and commercially
  • oxidising agents like hydrogen peroxide or other peroxide compounds, nitrogen tetroxide, whether gaseous or in solution such as phosphoric acid solution, periodate, leading to the corresponding dialdehyde derivative, followed by oxidation to the dicarboxy starch with sodium chlorite, optionally in the presence of hydrogen peroxide,
  • hypochlorite, hypobromite, or hypoiodite compounds organic oxidising agents like TEMPO ( ( 2 , 2 , 6 , 6-tetramethylpiperidin-l- yl ) oxidanyl ) , or 4-hydroxy-TEMPO, and combinations thereof. Suitable combinations are reaction with hypochlorite, hypobromite, or hypoiodite, or other oxidising compound in the presence of TEMPO.
  • TEMPO ( 2 , 2 , 6 , 6-tetramethylpiperidin-l- yl ) oxidanyl )
  • 4-hydroxy-TEMPO 2-hydroxy-TEMPO
  • oxidising agent is also possible. Methods for manufacturing oxidised starch require no further elucidation here. JP57- 130545 describes oxidising starch with periodate and using the resulting product as urea adsorbing compound in a blood perfusion method.
  • the oxidised starch e.g., has a degree of oxidation between 1 and 30%. If the degree of oxidation is below 1 wt . % the advantageous effect of using oxidised starch may not be obtained. If the degree of oxidation is above 30 wt.%, the integrity of the starch may be affected. It may be preferred for the oxidised starch, if used, to have a degree of
  • the complex of Fe(III) and starch generally has an Fe(III) content of at least 1 wt.%, expressed as metallic iron, per gram of starch. If the Fe(III) content is too low, the adsorption capacity of the adsorbent will be insufficient. It may be preferred for the Fe(III) content to be at least 5 wt.%, expressed as metallic iron per gram of starch, more in particular at least 10 wt.% expressed as metallic iron per gram of starch.
  • the Fe(III) content will be at most 90 wt.%, expressed as metallic iron, per gram of starch. When more iron is present, the accessibility of the additional iron will be limited, and it will therefore only have a limited contribution to the phosphate removal. More specifically, the Fe(III) content may be at most 60 wt.%, more in particular at most 50 wt.%, expressed as iron per gram of starch.
  • Fe(III) contents e.g., at most 50 wt.%, more in particular at most 30 wt.%, in some embodiments at most 20 wt.%. In one embodiment of the
  • the particle size is at least 100 microns, as discussed in more detail below, it may be particularly preferred for the Fe(III) content to be in the range of 1-30 wt.%, in particular 5-20 wt .
  • the complex of Fe(III) and starch can be obtained by
  • starch may be contacted with an aqueous solution of an Fe(III) salt, e.g., a
  • the starch onto which iron (III) has been adsorbed can be removed from the aqueous solution, and dried if so desired.
  • Suitable bases include, e.g., sodium carbonate, sodium hydroxide, potassium
  • optionally oxidised starch is prepared as follows: starch, optionally oxidised starch, is contacted with an aqueous suspension comprising one or more
  • the aqueous suspension comprising one or more Fe ( III ) oxide, Fe ( III ) hydroxide, and Fe(III) oxyhydroxide, can suitably be obtained by adding a water soluble inorganic base, in solid form, or in the form of an aqueous solution, to a solution of an inorganic Fe(III) salt, e.g., a sulphate, nitrate, or chloride salt. In this way, a suspension will be obtained wherein the Fe(III)
  • (hydr) oxide compounds have a relatively small particle size, which makes for a high dispersion of the Fe(III) (hydr) oxide compounds on the (oxidised) starch.
  • inorganic base is, e.g., selected from one or more of sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, NH3, and NH40H.
  • This method may be particularly suitable for (oxidised) starch with a particle size below 100 microns to ensure a good Fe(III) distribution.
  • a complex of Fe(III) and starch is prepared as follows: (oxidised) starch is contacted simultaneously with an aqueous solution of an inorganic Fe(III) salt, e.g., a sulphate, nitrate, or chloride salt, and an aqueous
  • a water soluble inorganic base e.g., selected from one or more of sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, and NH40H, followed by removal of water.
  • a water soluble inorganic base e.g., selected from one or more of sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, and NH40H
  • one or more Fe ( III ) oxide, Fe ( III ) hydroxide, and Fe(III) oxyhydroxide are formed in the presence of the (oxidised) starch. This may lead to an improved distribution of the Fe(III) (hydr) oxide compound on the (oxidised) starch. This method may also be particularly suitable for (oxidised) starch with a particle size below 100 microns to ensure a good Fe(III) distribution.
  • a complex of Fe(III) and starch, optionally oxidised starch is
  • (oxidised) starch is contacted with an aqueous solution of an inorganic Fe(III) salt, e.g., a sulphate, nitrate, or chloride salt.
  • an inorganic Fe(III) salt e.g., a sulphate, nitrate, or chloride salt.
  • excess water is removed, e.g., by filtration.
  • the resulting Fe ( I I I ) -containing starch is dried. Then, in a second step, the Fe ( I I I ) -containing starch is contacted with an aqueous solution of a water soluble
  • inorganic base e.g., selected from one or more of sodium carbonate, sodium hydroxide, potassium carbonate, and
  • one or more Fe ( III ) oxide, Fe ( III ) hydroxide, and Fe(III) oxyhydroxide are formed after the Fe(III) salt has been adsorbed onto the starch. This may lead to an improved distribution of the Fe(III) (hydr) oxide compound on the starch, especially, where the starch has a particle size of at least 100 microns. It can of course also be applied on starch with a smaller particle size.
  • oxidised starch e.g., by one of the methods discussed above, and then provide the
  • iron(III) iron(III) .
  • Other methods are also possible. For example, it is possible to first add the iron to the starch, and then carry out the oxidation step. This is less preferred,
  • the adsorbent used in the present invention may comprise additional components to the complex of Fe(III) and starch.
  • additional components are bonding agents.
  • the adsorbent prefferably be made up for at least 50 wt . % of the complex of Fe(III) and starch, in particular for at least 70 wt.%, more in particular for at least 80 wt.%, in some embodiments for at least 90 wt.%.
  • the reason for this preference is that the complex of Fe(III) and starch is responsible for the phosphate adsorption.
  • the presence of other components will increase the volume of the adsorbent without contributing to the phosphate adsorption. Therefore, the amount of other components is preferably limited.
  • the particle size of the adsorbent used in the present invention can vary within wide ranges, e.g., in the range of 10 microns to 5 mm.
  • the particle size of the adsorbent is at least 100 microns, in particular at least 200 microns, especially where the material will be used in an adsorption column, as this minimum particle size will result in an improved performance of this embodiment.
  • the maximum particle size preferably is at most 4 mm, in particular at most 2 mm. A particle size range of 0.2-2 mm is considered preferred.
  • particle size refers to the Dv50, which is the median
  • the adsorbent used in the present invention preferably has a phosphate adsorption capacity of at least 15 mg/g. Higher values, e.g., at least 30 mg/g, in particular at least 40 mg/g are considered preferred. As a general attainable maximum a value of 300 mg/g may be mentioned.
  • the phosphate containing water fraction is contacted with the adsorbent.
  • Contacting conditions are not critical, and encompass a contacting temperature of 0-100°C, in particular 1-50°C, more in particular 1-30°C.
  • the pressure may vary between wide ranges, e.g. from 0.1 to 10 bar. Atmospheric pressure is generally suitable. Where a column is used, a velocity of
  • 0.1-100 m/hour is generally suitable.
  • An effluent water fraction is withdrawn from the adsorbent.
  • the phosphate content of the effluent water fraction is lower than the phosphate content of the starting phosphate- containing water fraction.
  • the phosphate content of the effluent water fraction is less than 50% of the phosphate content of the starting phosphate-containing water fraction, in
  • the phosphate content of the effluent water fraction is reduced to a value of less than 100 ppb, in particular less than 50 ppb, more in particular less than 20 ppb, or even less than 10 ppb.
  • a process wherein the phosphate content of the effluent water fraction is below 10 ppb is of particular interest, especially, but not limited to, the situation where the effluent water fraction is to be provided to a reverse osmosis process, as will be discussed in more detail below.
  • the phosphate content of the effluent water fraction is determined by the phosphate content of the starting water fraction, the carboxylate and iron content of the adsorbent, the space velocity, and the amount of adsorbent. It is within the scope of the skilled person to select these parameters so that an effluent with the desired phosphate content is obtained .
  • the effluent water fraction can be processed as desired.
  • the effluent water fraction is provided to a reverse osmosis step, where the effluent water fraction is treated to form a purified effluent water fraction and a contaminant fraction.
  • the reverse osmosis step effects contaminant removal, in particular salt removal.
  • the adsorbent When the adsorbent has become saturated with phosphate, as can be seen from an increase in phosphate content of the effluent water fraction, the adsorbent can be regenerated if so desired.
  • the present invention also pertains to a method as described above wherein the adsorbent is periodically
  • the adsorbent can be regenerated by contacting it with an alkaline aqueous regeneration solution, more specifically an aqueous solution with a pH above 11.5.
  • the pH preferably is above 12. In general, the pH will not be above 14.
  • alkaline compound in the aqueous alkaline solution is not critical. Alkali metal hydroxides are generally preferred for reasons of availability, cost, and safety. The use of sodium hydroxide and/or potassium
  • hydroxide is considered preferred.
  • a solution comprising both an alkali metal hydroxide and a dissolved inorganic salt, in particular an alkali metal salt, e.g., NaCl or KC1.
  • an alkali metal salt e.g., NaCl or KC1.
  • a salt concentration of 0.05 to 1 M/l may be mentioned as suitable.
  • regeneration solution can be carried out using methods known in the art. Regeneration will be complete when the phosphate content of the regeneration solution does not further increase .
  • the adsorbent is contacted with a neutralizing solution between the step of withdrawing the alkaline aqueous regeneration solution from the adsorbent, and the step of resuming the provision of phosphate-containing water fraction to the regenerated adsorbent, the adsorbent is contacted with a neutralizing solution .
  • a suitable neutralising solution is, e.g., a slightly acidic solution with a pH in the range of 4-6.
  • Example 2 preparation of adsorbent using iron ( I I I ) chloride and sodium carbonate The samples obtained in Example 1 were loaded with Iron (III) to form adsorbents in accordance with the following
  • Example 3 Preparation of adsorbent using iron (III) chloride and ammonium hydroxide
  • FeCl3 (40% wt3, d: 1.26 g/ml) was diluted to 12.5ml using demiwater. While stirring, the solution was adjusted to pH 7.0 by dropwise addition of NaOH (5M) . To this solution, lOg of starch sample was added while stirring. The suspension was allowed to rest for 1 hour and the supernatant was decanted. The slurry was centrifuged at lOOOOrpm for 10 minutes, after which the supernatant was decanted. The material was washed with demiwater and centrifuged again. The final supernatant is decanted.
  • NaOH NaOH
  • the resulting material had an iron(III) content of 10% wt.%, expressed as metallic iron per gram of starch.
  • Example 5 Performance of samples in phosphate removal from phosphate-containing water fractions - static conditions
  • the phosphate adsorption capacity for the various samples described in Example 2 was determined as follows: 1 g of the iron (III) on starch material obtained as described in Example 2 was brought in a 30 ml column. Through the column 250 ml of a phosphate solution (0.47 g/L) was recirculated (5 ml/min) for a period of 18 hours at room temperature.
  • Lewatit® FO 36 is a weakly basic macroporous monodisperse polystyrene-based ion exchange resin for the selective adsorption of oxoanions, which is doped with a nano-scaled film of iron oxide covering the inner surfaces of the pores of the polymer bead.
  • the indication -1 refers to the unoxidised sample.
  • the indications -2 and -3 refer to oxidized versions of the corresponding -1 version.
  • Table 2 Phosphate adsorbing capacity of iron (III) starch complexes
  • oxidized starch shows a higher phosphate adsorption capacity as compared to the unoxidised starting material.
  • a comparison between potato-1 and potato-3 shows the same trend to a larger extent.
  • oxidized starch has an adsorption capacity which is higher than that of the unoxidised starting material. For dextrin this effect is not shown.
  • Example 6 Phosphate uptake by starch and Lewatit® F036 - dynamic conditions
  • suspension samples were taken at 2, 5, 15, 30, 60, 90, and 120 minutes. Immediately after sampling, the sample was filtrated over a 0.2 mm cellulose acetate filter to remove present adsorbent. The phosphate concentration was determined using the phosphate molybdenum test. The rate of phosphate adsorption onto the adsorbent is calculated from the decrease in phosphate concentration in the solution.
  • Table 3 Rate of phosphate adsorption of iron (III) loaded starch and Lewatit FO 36. Initial phosphate concentration is
  • the material according to the invention shows the same kinetic profile as the standard Lewatit® FO 36, showing that the material according to the invention is suitable for commercial operation.
  • the adsorbent of the present invention is derived from a renewable resource, and is biodegradable, both of which do not apply to Lewatit® FO 36. Additionally the adsorbent of the present invention is more attractive from a commercial point of view than Lewatit® FO 36.
  • Example 7 Performance of samples in phosphate removal from phosphate-containing water fractions - batch equilibrium test
  • the dynamic phosphate adsorption capacity for the samples obtained with Example 3 was determined as follows: 0.5g of iron (III) on starch material obtained as described in Example 3 was brought in 2-7L of a phosphate solution (10.08 g/L) . The phosphate solution was stirred continuously for a period of 24 hours at room temperature.
  • Lewatit® FO 36 (Lanxess) was also determined.
  • Lewatit® FO 36 is a weakly basic macroporous monodisperse polystyrene-based ion exchange resin for the selective adsorption of oxoanions, which is doped with a nanoscaled film of iron oxide covering the inner surfaces of the pores of the polymer.
  • the conditions of the batch equilibrium test are further specified in table 4.
  • the comparative Lewatit product according to the invention is also more environmentally attractive than the comparative Lewatit product as it is based on a biodegradable and renewable material. It is further more attractive from an economic point of view as it is less expensive.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

L'invention concerne un procédé d'élimination de phosphate dans une fraction d'eau contenant du phosphate, comprenant les étapes consistant à mettre en contact une fraction d'eau contenant du phosphate avec un adsorbant, l'adsorbant comprenant un complexe de Fe(III) et d'amidon et l'extraction d'un effluent de fraction d'eau à partir de l'adsorbant. Il a été découvert que l'utilisation de cet adsorbant spécifique permet d'obtenir des effluents de fractions d'eau ayant de très faibles teneurs en phosphate. En outre, il a été découvert que l'adsorbant a une capacité d'adsorption élevée, exprimée en mg de phosphate par gramme d'adsorbant. L'adsorbant peut être régénéré de manière efficace pour permettre une réutilisation. Il est basé sur un matériau dégradable, d'origine biologique.
PCT/EP2015/061647 2014-05-28 2015-05-27 Procédé pour l'élimination de phosphate dans des fractions d'eau Ceased WO2015181205A1 (fr)

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CN109126733A (zh) * 2018-09-29 2019-01-04 哈尔滨工业大学（深圳） 一种用于吸附污染物的改性陶粒组合填料的制备方法
CN110813246A (zh) * 2019-10-22 2020-02-21 浙江大学 一种纳米孔淀粉基吸附剂及其制备方法
WO2021077290A1 (fr) * 2019-10-22 2021-04-29 浙江大学 Adsorbant à base d'amidon nanoporeux et son procédé de préparation

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JPS57130545A (en) 1981-02-04 1982-08-13 Agency Of Ind Science & Technol Urea adsorbing agent
WO1990005705A1 (fr) 1988-11-14 1990-05-31 Nkt A/S Procede permettant d'enlever le phosphate de l'eau et systeme pour realiser ce procede
US5846426A (en) 1992-11-24 1998-12-08 B. Braun Melsungen Ag Process for the selective elimination of inorganic phosphate from liquids by means of adsorbent materials modified with polynuclear metal oxyhydroxiders and production of the adsorbent materials
US6174442B1 (en) 1995-12-19 2001-01-16 Vifor (International) Ag Adsorbent for phosphate from an aqueous medium, production and use of said adsorbent
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EP1764348A1 (fr) 2005-09-16 2007-03-21 Technische Universiteit Delft Matériaux et méthode pour éliminer des oxo-anions et des cations métalliques d'un liquide
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WO2010100112A1 (fr) 2009-03-02 2010-09-10 Vifor (International) Ag Adsorbant de phosphate
WO2011107524A1 (fr) 2010-03-02 2011-09-09 Philip Patrick Peter O'brien Améliorations dans et concernant un ensemble de traitement d'effluents
US20140138320A1 (en) 2012-11-20 2014-05-22 Zachodniopomorski Uniwersytet Technologiczny W Szczecinie Agent for removing phosphorus compounds from water
US20140141243A1 (en) 2012-11-20 2014-05-22 Zachodniopomorski Uniwersytet Technologiczny W Szczecinie Method of producing agent for removing dissolved phosphorus compounds from water and agent for removing dissolved phosphorus compounds from water

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109126733A (zh) * 2018-09-29 2019-01-04 哈尔滨工业大学（深圳） 一种用于吸附污染物的改性陶粒组合填料的制备方法
CN109126733B (zh) * 2018-09-29 2021-01-29 哈尔滨工业大学（深圳） 一种用于吸附污染物的改性陶粒组合填料的制备方法
CN110813246A (zh) * 2019-10-22 2020-02-21 浙江大学 一种纳米孔淀粉基吸附剂及其制备方法
WO2021077290A1 (fr) * 2019-10-22 2021-04-29 浙江大学 Adsorbant à base d'amidon nanoporeux et son procédé de préparation
JP2022500226A (ja) * 2019-10-22 2022-01-04 ヂェァジァン ユニバーシティZhejiang University ナノポア澱粉基吸着剤及びその製造方法
JP7005052B2 (ja) 2019-10-22 2022-02-04 ヂェァジァン ユニバーシティ ナノポア澱粉基吸着剤及びその製造方法

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