WO2021006737A1 - Récupération de phosphore - Google Patents

Récupération de phosphore Download PDF

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Publication number
WO2021006737A1
WO2021006737A1 PCT/NL2020/050454 NL2020050454W WO2021006737A1 WO 2021006737 A1 WO2021006737 A1 WO 2021006737A1 NL 2020050454 W NL2020050454 W NL 2020050454W WO 2021006737 A1 WO2021006737 A1 WO 2021006737A1
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WO
WIPO (PCT)
Prior art keywords
composition
phosphorous
paper ash
solution
aqueous solution
Prior art date
Application number
PCT/NL2020/050454
Other languages
English (en)
Inventor
Nicolaas Voogt
Original Assignee
Cdem B.V.
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 Cdem B.V. filed Critical Cdem B.V.
Publication of WO2021006737A1 publication Critical patent/WO2021006737A1/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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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

Definitions

  • the present invention is in the field of a method for recovery of phosphorous, in particular of phosphorous from a waste stream, and to a product obtained thereby.
  • the product is preferably in a form wherein phosphorous can be released to e.g. the soil and plants at a desired amount per interval of time .
  • Phosphorous is an element (P) that is used abundantly especially for growing crops, such as by adding fertilizer. To stress the significance of phosphorous it is noted that P fertilizer is essential for modern food production and is the limiting factor in crop yields. P is a critical global resource, as are water and energy resources. Phosphorus is considered essential for all living matter, including bacteria, plants and animals.
  • Phosphate rock used as a source for P in fertilizers, clearly is a non-renewable resource that are likely to be depleted in 50-100 years, so there is a need to reuse phosphorus. Production peak is expected in about twenty years' time. Unlike other natural resources phosphorus has no substitute in food production. In view of a growing food demand such is even more of a concern. It is also noted that mining (of phosphate) is an energy intensive and polluting activity. Such will become even worse as the quality of phosphate rock is declining ( [P2O5] in mined rock is decreasing and the concentration of associated heavy metals is increasing) . It is noted that in principle heave metals need to removed, if applied as fertilizer, which is at the least energy intensive. One may conclude based on the above that cheap fertilizer is an element of the past. Alternative strategies need to be developed, as is the case.
  • the present inventors have obtained a patent US10294167 (B2) for method for recovery of phosphorous, in particular of phosphorous from a waste stream, and a product obtained thereby.
  • the product is in a form wherein phosphorous can be released to, e.g., the soil and plants at a desired amount per interval of time, typically brushite.
  • US2013/0299420 Al recites a method for recovering phosphate from sewage treatment plants using multi-stage anaerobic digestion includes the treatment of organic acid digest with calcium hydroxide, calcium oxide, and similar compounds to raise pH to near neutral values and precipitate calcium phosphate compounds such as brushite and similar amorphous compounds.
  • the method includes the formation of calcium phosphates on weak-acid ion exchange columns and membranes in contact with organic acid digest.
  • the system includes removal of the calcium phosphate compounds formed by sedimentation, either static or against an upwelling flow, centrifugation, or filtration. Under ideal conditions and surplus of calcium 50-90% (15/17 or ⁇ 88%) of the phosphate may be captured, i.e. 10-40% remains in the sewage; these conditions are typically not reached, so incomplete capturing of phosphate occurs.
  • the present invention relates to a method for recovering phosphorous from an aqueous solution.
  • the present method uses a cheap composition that can be used abundantly. As a result the amount of phosphorous captured is effectively only limited by the amount of composition used; as the composition can be used abundantly practically all of the phosphorous can be captured, typically close to 100%.
  • the present composition is preferably added as a suspension.
  • An important advantage is that the product has a dry solids content of above 25%; such a product is found to be dried easily with relatively cheap measures, such as a big bag sieve. In comparison, when using calcium hydroxide and/or calcium oxide a dry solids content of some 15% is reached, resulting in a product that is very difficult to dry, and therefore for practical reasons not considered.
  • the present method has been found to be insensitive to impurities, such as heavy metals and organic material.
  • the present method makes use of cheap reactants, such as CaO, sorosilicate clay, Ca(OH) , and CaC0 3 , which reactants are present as a mixture of ingredients; such is clearly different in chemical and physical aspects from a composition having a similar amount and/or ratio of chemical elements (e.g. Ca, C, 0, Al, Si) being present, as the person skilled in the art will appreciate.
  • Clay minerals are hydrous aluminium phyllosilicates , sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations; clays are considered to comprise SiCy units and AIO 4 units.
  • a CSH is not a clay nor does it resemble a clay.
  • the present method has been found to be robust, e.g. it can handle almost any aqueous solution, such as waste streams.
  • the present method can be performed at ambient temperature and pressure; hence besides reactants no reaction costs are involved.
  • the efficiency of the present process is more than sufficient, as all the phosphorous being present is typically captured and recovered.
  • the present method can be operated in a continuous or semi continuous mode, making it possible to process continuous flows without problem at a relatively constant output.
  • the process is also scalable, hence small and large volumes can be processed.
  • composition/g soluble P is added, such as 1-10 gr composition.
  • amount of composition is calculated based on an amount of CaO: 0.5-2 mole CaO/mole soluble P is added, which is typically close to 1 mole CaO per mole soluble P. It is therefore a surprise that the present composition comprising relatively low amounts of CaO (or for that matter Ca-compounds ) is still very capable of precipitating phosphorous (typically as CaPO-d . Such depends a bit on the characteristics of the aqueous solution.
  • the phosphorous settles easily and can then be recovered.
  • the present invention provides a solution to one or more of the above mentioned problems and overcomes drawbacks of the prior art.
  • the present invention relates to a method of recovering phosphorous from an aqueous solution comprising the steps of providing the aqueous solution comprising soluble phosphorous, adding the present composition, and recovering the phosphorous.
  • the mineral may comprise 33-66 wt% melilite, such as gehlenite, akermanite, and combinations thereof, preferably gehlenite.
  • Gehlenite and/or akermanite may be present in an amount of 5- 66 wt% each individually, preferably 10-50 wt%, such as 30-45 wt% .
  • the composition may comprise 50-70 wt% crystalline minerals, and 30-50 wt% amorphous components.
  • the composition may comprise per kg composition (after drying) 250-500 g Ca, preferably 300-450 g Ca, more preferably 330-420 g Ca, such as 350-400 g Ca.
  • the composition may comprise per kg composition (after drying) 2- 20 g Mg, preferably 3-15 g Mg, more preferably 4-410 g Mg, such as 5-8 g Mg.
  • the composition may comprise per kg composition (after drying) 0.2-5 g Na, preferably 0.5-4 g Na, more preferably 0.8-2 g Na, such as 1-1.6 g Na.
  • the composition may comprise per kg composition (after drying) 1-5 g S, preferably 1.5-4 g S, more preferably 2-3.5 g S, such as 2.5-3.0 g S .
  • the composition may comprise per kg composition (after drying) 30- 120 g Al, preferably 300-450 g Al, more preferably 330-420 g Al, such as 350-400 g Al .
  • the composition may comprise per kg composition (after drying) 2- 15 g Fe, preferably 3-12 g Fe, more preferably 5-10 g Fe, such as 7-9 g Fe .
  • the composition may comprise per kg composition (after drying) 0.1-3 g K, preferably 0.2-2g K, more preferably 0.3-1.5 g K, such as 0.5-1 g K.
  • the composition may comprise per kg composition (after drying) 0.1-3 g P, preferably 0.3-2 g P, more preferably 0.5-1.2 g P, such as 0.6-1.0 g P.
  • the composition may comprise per kg composition (after drying) 10- 3 —10 g organic matter, preferably 2*10 -3 -1 g, more preferably 4*10 3 -0.1 g, such as 6*10 -3 -0.01 g.
  • the composition may comprise per kg composition (after drying) 350-700 g 0 preferably 400-600 g 0, more preferably 450-550 g 0, such as 480-520 g 0.
  • the composition may be a paper ash, preferably paper ash incinerated at a temperature of above 700 °C in a fluid bed, during a period of at least 2 minutes. Regardless of how the ash is formed, the ash may be humidified such that it is prevented from forming, or persisting as, airborne dust particles. This allows the composition to be handled, transported, stored and used in the method according to the invention more safely.
  • the composition may thus more specifically be a humidified paper ash.
  • ash formed by the previously mentioned incineration is humidified, directly, subsequent its formation. Given the above it is thus an option that paper ash, used in the method according to the invention, comprises 20-45% water, preferably 25-40% water.
  • the ash becomes sticky.
  • the ash itself albeit humidified is non-reactive with Calcium hydroxide during handling, storage and transport due to an absence of metakaolin therein.
  • Said calcium hydroxide may also originate from the paper ash itself.
  • the paper ash is prevented from decaying by way of its own constituents reacting with amongst themselves during storage or handling.
  • the method may further comprise the step of collecting the phosphorous onto the paper ash, namely onto particulates of the paper ash.
  • the mixed composition is a paper ash that takes the form of a particulate, such as a fine powder or dust. It is thus appreciated that the particulate is chemically reflective of the mixed composition.
  • the step of recovering the phosphorous would in this example comprise precipitating the paper ash together with the thereon collected phosphorous and recovering said precipitated paper ash.
  • the manner in which phosphorous is collected onto the paper ash particulate is by means of crystallization. That is to say the phosphate collects onto the paper ash in the form of a calcium phosphate crystals.
  • the ash particles may end up forming ooid grains, in which each ash particle of the particulate is a crystallization nucleus surrounded by calcium phosphate.
  • the humidification of the paper ash may, also separate from this example, occur after the precipitation, and optionally after the recovery thereof. This also prevents any fine grain structures from becoming airborne which increases handling safety of the material.
  • Steering a ratio between crystallization nuclei, such as the particulates of the paper ash, and calcium hydroxide can be effected through the adding of Ca(OH)2, such as during the method step in which the phosphorous is collected on the paper ash. This allows a precipitation rate and the collection rate to be optimized, such as for time. It shall be understood that the paper ash has a twofold purpose. Namely collecting the phosphor, and precipitating the phosphor, such as in an oxidized form together with calcium.
  • the aqueous solution is an acidic solution, the acid aqueous solution having a pH of 1-6, and wherein the pH may be increased to 5.5-8 by adding the composition.
  • the aqueous solution may be selected from waste water, treated waste water, sludge, organic acid digest solution, acid digest solution, animal manure, such as pig manure, cow manure, and combinations thereof.
  • the solution may comprise 0.01-6 wt . % precipitated solids.
  • the solution may comprise impurities, such as heavy metals, organic matter, and humus.
  • an amount of soluble phosphorous present in the aqueous solution may be in a range of 10 -2 -50 g/1, preferably 0.1-10 g/1, such as 0.5-5 g/1.
  • the recovered phosphorous and sludge may be dewatered, such as in a big bag sieve, preferably to a water content of ⁇ 50%, such as ⁇ 25%.
  • the composition may comprise 2-20% CaO, preferably 3-15% CaO, more preferably 4-10% CaO, such as 5-7% CaO, and/or 40-55% aluminosilicate, such as 42-50 %, and/or 2-8% CaO3 ⁇ 4, such as 3-7 %, and/or 2-8% CaC0 3 , such as 3-7 %, and/or 0.2-2% S1O2, such as 0.4-1.4 % .
  • composition/g soluble P may be added, preferably 10-80 g composition/g soluble P, more preferably 12-70 g composition/g soluble P, even more preferably 15-60 g composition/g soluble P, such as 30-40 g.
  • the present method is for forming a calcium phosphate mineral, wherein the mineral precipitates, and wherein preferably the precipitate is centrifuge, and/or the precipitate is recovered, and optionally dried.
  • the pH may be increased to 5-8, preferably to 5.5-7.5, more prefer ably to 6-7, such as by adding the present composition, or by adding a further base in typically relatively low amounts.
  • the sorosillicate mineral, CaC0 3 , and CaO3 ⁇ 4 may be homogeneously distributed, that is on a nanoscale level the composition is substantially homogeneous. That is particle sizes and composition per unit volume or unit surface varies over a narrow distribution. Such a composition provides the present results.
  • the composition may have a BET surface area of 5-100 m 2 /gr, such as 10-30 m 2 /gr.
  • a material with such a high BET-surface is considered advantageous as described throughout the application.
  • the present composition preferably has a particle size distribution (laser granulometric, ISO13320 (2009), e.g. Malvern, Mastersizer 3000) of 90% smaller than 50 pm, 80% smaller than 30 pm, 50% smaller than 10 pm, and 30% smaller than 3 pm.
  • the solution is an acidic solution, the acid aqueous solution having a pH of 1-6, wherein the pH is increased to 5.5-8 by adding the composition.
  • the solution is a basic solution.
  • an amount of soluble phosphorous present is in a range of 1-50 ppm (mg/1) . In a further example an amount of soluble phosphorous present is in a range of 100-1000 ppm (mg/1) . In a further example an amount of soluble phosphorous present is in a range of 10-250 g/1.
  • the present method is capable of reducing losses in (very) low soluble P concentration solutions to less than 20% and typically less than 10%; hence it is still worthwhile to strip such solutions from small amounts of phosphorous being present therein.
  • the present method is capable of reducing losses in (very) high soluble P concentration solutions to less than 1%; such is in view of the prior art a major step forward. In an example the present method may be performed more than once, especially for relatively high concentration solutions, e.g. first recovering almost all of the phosphorous, and then recovering a majority of what is left in the first step. As such losses can be reduced to less than 0.2%.
  • the clay preferably has a cationic exchange capacity of 2- 200 meq/100 grams clay at a pH of 7, more preferably 5-150 meq/100 grams, even more preferably 10-120 meq/100 grams. It has been found that clays having a relatively higher CEC perform better in terms of relevant characteristics for the present invention.
  • the aqueous solution may be treated further.
  • an organic acid digest may be treated for phosphorus recovery before it is added to a thermophilic or mesophilic digester.
  • Such treatment may relate to additional screening, floatation, sedimentation, filtration, or centrifugation of large particles in the digest before phosphate removal from the remaining liquid portion.
  • a resulting calcium phosphate product may be collected by sedimentation (either static sedimentation in a settling tank or sedimentation in an upwelling flow as in a fluidized bed reactor), filtration, or centrifugation.
  • the processed organic digest may be sent to the thermophilic digester for methanogenesis .
  • an organic acid digest either with or without particle removal may be applied to an ion exchange column loaded with e.g.
  • the water content of sludge was relatively low (or vice versa the dry solids content was rather high, >25%, after centrifugation) . When adding enough composition all the P was captured and could be recovered.
  • the present composition performed on a dose-response relation much better than the magnesium hydroxide and similar to the calcium hydroxide.
  • the present composition provides a better separation of the phosphate-containing calcium sludge than calcium hydroxide .
  • TopCrete® typically comprises 20-30 wt% CaO (and even more (35-45%) CaCCh) .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)

Abstract

La présente invention concerne un procédé de récupération de phosphore, en particulier de phosphore issu d'un flux de déchets, et un produit obtenu par ce procédé. Le produit est de préférence sous une forme dans laquelle le phosphore peut être fourni, par exemple, au sol et aux plantes dans une quantité souhaitée par intervalle de temps.
PCT/NL2020/050454 2019-07-10 2020-07-10 Récupération de phosphore WO2021006737A1 (fr)

Applications Claiming Priority (2)

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NL2023467 2019-07-10
NL2023467A NL2023467B1 (en) 2019-07-10 2019-07-10 Recovery of phosphorous

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113200580A (zh) * 2021-03-29 2021-08-03 江苏省中国科学院植物研究所 一种基于生物质电厂灰的水体磷去除材料及其制备方法和应用

Citations (5)

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Publication number Priority date Publication date Assignee Title
EP2511243A1 (fr) 2011-04-12 2012-10-17 Karlsruher Institut für Technologie Installation et procédé de récupération de phosphore à partir d'eaux usées
US20130299420A1 (en) 2009-05-07 2013-11-14 Phillip Barak Phosphate recovery from acid phase anaerobic digesters
CN105236874A (zh) * 2015-08-21 2016-01-13 南京理工大学 一种具有供碱释钙能力的多功能陶粒、制备方法及其应用
US10294167B2 (en) 2014-07-24 2019-05-21 Cdem B.V. Recovery of phosphorous
WO2019113135A1 (fr) * 2017-12-04 2019-06-13 Gmt Ip, Llc Traitement de flux de déchets post-industriels et post-consommation et préparation de produits post-industriels et post-consommation à partir de ceux-ci

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Publication number Priority date Publication date Assignee Title
US20130299420A1 (en) 2009-05-07 2013-11-14 Phillip Barak Phosphate recovery from acid phase anaerobic digesters
EP2511243A1 (fr) 2011-04-12 2012-10-17 Karlsruher Institut für Technologie Installation et procédé de récupération de phosphore à partir d'eaux usées
US10294167B2 (en) 2014-07-24 2019-05-21 Cdem B.V. Recovery of phosphorous
CN105236874A (zh) * 2015-08-21 2016-01-13 南京理工大学 一种具有供碱释钙能力的多功能陶粒、制备方法及其应用
WO2019113135A1 (fr) * 2017-12-04 2019-06-13 Gmt Ip, Llc Traitement de flux de déchets post-industriels et post-consommation et préparation de produits post-industriels et post-consommation à partir de ceux-ci

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EHBRECHT ET AL., 2ND EUROPEAN SUSTAINABLE PHOSPHORUS CONFERENCE, 5 March 2015 (2015-03-05)
KAASIK ET AL: "Hydrated calcareous oil-shale ash as potential filter media for phosphorus removal in constructed wetlands", WATER RESEARCH, ELSEVIER, AMSTERDAM, NL, vol. 42, no. 4-5, 1 February 2008 (2008-02-01), pages 1315 - 1323, XP022482417, ISSN: 0043-1354, DOI: 10.1016/J.WATRES.2007.10.002 *
SARTORIUS ET AL.: "Phosphorus Recovery from Wastewater - State-of-the-Art and Future Potential", INT. CONFERENCE NUTRIENT RECOVERY AND MANAGEMENT, 2011
UTE BERG ET AL.: "Calcium silicate hydrate triggered phosphorous recovery - an efficient way to tap the potential of waste- and process waters as a key resource", INTERNET CITATION, 1 January 2006 (2006-01-01), pages 1747 - 1765, XP002680540, DOI: 10.2175/193864706783750150
WAJIMA T ET AL: "Removal behavior of phosphate from aqueous solution by calcined paper sludge", COLLOIDS AND SURFACES A: PHYSIOCHEMICAL AND ENGINEERING ASPECTS, ELSEVIER, AMSTERDAM, NL, vol. 435, 7 January 2013 (2013-01-07), pages 132 - 138, XP028694575, ISSN: 0927-7757, DOI: 10.1016/J.COLSURFA.2012.12.054 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113200580A (zh) * 2021-03-29 2021-08-03 江苏省中国科学院植物研究所 一种基于生物质电厂灰的水体磷去除材料及其制备方法和应用
CN113200580B (zh) * 2021-03-29 2023-08-18 江苏省中国科学院植物研究所 一种基于生物质电厂灰的水体磷去除材料及其制备方法和应用

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