WO2018220462A1 - Composition for adsorbing phosphorus and/or nitrogen from effluents or liquid waste, processes, products and uses - Google Patents
Composition for adsorbing phosphorus and/or nitrogen from effluents or liquid waste, processes, products and uses Download PDFInfo
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- WO2018220462A1 WO2018220462A1 PCT/IB2018/053426 IB2018053426W WO2018220462A1 WO 2018220462 A1 WO2018220462 A1 WO 2018220462A1 IB 2018053426 W IB2018053426 W IB 2018053426W WO 2018220462 A1 WO2018220462 A1 WO 2018220462A1
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- serpentinite
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- 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
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- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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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
Definitions
- the present invention is a composition for phosphorus and / or nitrogen adsorption of effluent or liquid waste comprising at least one support material, preferably serpentinite, vermiculite, charcoals (modified by oxidative or non-oxidative treatments) and / or phosphate-rich effluent treatment plant sludge; such support material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined. It also addresses the use of the composition, the process for preparing the composition, the process for producing soil conditioning and nutrient release additives, phosphorus and / or nitrogen recovery devices and the additives produced.
- Phosphorus (usually in the form of phosphate) and nitrogen (present in various forms, such as ammonium, nitrate and urea), present in industrial and domestic effluents and waste, are an environmental problem as they cause eutrophication of rivers and lakes when discarded.
- a phosphorus concentration from 0.03 mg / L is already sufficient to cause cyanobacterial blooms (WANG, R. et al. Flickering gives early warning signals of a critical transition to a eutrophic lake state. Nature, v. 492, No. 7429, pp. 419-422, 12/20/2014 print. ISSN 0028-0836).
- Nitrogen also contributes to eutrophication, but to a lesser extent, since phosphorus is a limiting element for flowering (ROWE, EC et al. Vegetation Type Affects the Relationship Between Soil Carbon and Nitrogen Leaching. Water, Air, and Soil Pollution, v. 177, no. 1, pp. 335-347, 2006 // 2006. ISSN 1573-2932.).
- phosphorus and nitrogen are extremely important nutrients for agriculture.
- Agriculture, the food and detergent industry are the main consumers of phosphorus (COOPER, J. et al., The Future Distribution and Production of Global Phosphate Rock Reserves. Resources, Conservation and Recycling, v. 57, p. 78-86,12,201.
- Phosphorus and / or nitrogen can be removed from effluents in two ways: biological or physicochemical.
- biological treatment organisms capable of absorbing nutrients in the form of phosphate / nitrates are used. After absorption, the generated sludge is removed and digested anaerobically, which causes the absorbed compounds to return to the aqueous phase. This nutrient-rich liquid returns to the beginning of treatment.
- the physicochemical treatment uses iron, aluminum, magnesium or calcium ions to precipitate phosphorus in the form of phosphate, which is removed together with the sludge.
- struvite ammonium phosphate and magnesium hexahydrate
- Struvite has a slow nutrient release rate, allowing lower frequency of fertilizer application (LUZ, E .; BASHAN, Y. Recent advances in removing phosphorus from wastewater and its future use as fertilizer (1997 “ 2003). V. 38 , p. 4222 "4246, 2004).
- Coals, vermiculite and serpentinites are commonly applied as additives for agriculture. Coals are very interesting both for their porous structures and high surface area, as well as their ability to increase soil organic matter content and cation exchange capacity, improving the efficiency of fertilizer use, promoting the development of beneficial microorganisms. plant growth, among other agronomically desirable characteristics (SANTALLA, M. et al. Effectiveness of wood ash containing charcoal as a fertilizer for a forest plantation in a temperate region. Plant and Soil, v. 346, no. 1, p. 63 -78,201 / 201 / 2011. ISSN 1573-5036).
- SANTALLA M. et al. Effectiveness of wood ash containing charcoal as a fertilizer for a forest plantation in a temperate region. Plant and Soil, v. 346, no. 1, p. 63 -78,201 / 201 / 2011. ISSN 1573-5036).
- Vermiculite is a mica-like mineral formed by hydration of certain basaltic minerals, with formula (MgFe, AI) 3 (AI, Si) 4O 10 (OH) 2 .4H 2 O. It has expansion capacity, when subjected to temperatures close to 900 ° C its volume may increase from 10 to 30 times. After this process gets the name of expanded vermiculite, where each flake trap air cells, giving the material insulating capacity. This expanded material, in addition to its insulating capabilities, is non-irritating to skin or lung, has low electrical conductivity, does not decompose and does not attract insects. Expanded vermiculite can absorb up to five times its mass in water, is a good lubricant and filter material.
- vermiculite in agriculture is wide due to its characteristics such as high cation exchange capacity, good water retention, low mass and chemical reactivity, absence of toxicity, thermal insulation and good particle size.
- it can be used in the production of agricultural substrates, in the cover of seeds and seedlings, as soil conditioner, nutrient and herbicide / insecticide / fungicide container, sandy soil water retainer, grassy field antifreeze agent, manufacturing load.
- pesticides and hydroponic agriculture WU, N. et al. Organic intercalation of structure modified vermiculite. Journal of Colloid and Interface Science, v. 457, p. 264-271, 11/1/2015. ISSN 0021 -9797
- Serpentinites comprise a class of ultrabasic magnesian metamorphic rocks composed mainly of calcium, magnesium and silicon oxides.
- Part of the serpentine mineralogical group are magnesium silicate materials derived from changes in the hydration of olivines, which may be in nature in the form of lizardite, antagonist or chrysotile.
- Serpentinite composition and arrangement vary from region to region due to metamorphism, which can shift silicate to carbonate phases (PEREIRA, D .; PEINADO, M. Serpentinite. Geology Today, v. 28, no. 4, p. 152- 156, 2012. ISSN 1365-2451).
- the serpentinite reserves are distributed in the following states: Bahia, Ceará, Goiás, Minas Gerais, Mato Grosso do Sul, Para, Paraiba, Paraná, Rio Grande do Sul, Sergipe and Sao Paulo.
- rocking or remineralization rock dust is used to correct acidity and replenish soil nutrients.
- the water acts by slowly leaching nutrients from the rock, thus obtaining a natural soil conditioner with gradual release of nutrients.
- One of the advantages of this technique is the decrease in the consumption of industrial fertilizers (ANDEF - National Association of Plant Protection. Phytosanitary application technology manual. 2004).
- a problem with this technique is uncontrolled application, which can lead to nutritional imbalance and / or accumulation of heavy metals in the soil.
- the sludge produced by the phosphating industry has a very high phosphorus and urea adsorption capacity.
- immersion phosphating stands out.
- a residue called phosphate sludge or phosphate sludge is formed, formed from the reaction of Fe 3+ ions (originated by the oxidation of Fe 2+ ions present in solution) with phosphate ion (P0 4 3 ), forming , iron phosphate (FeP0 4 ).
- Characterization studies by Giffoni & Lange (2005) show that the main constituents of sludge are iron, zinc, nickel and sodium due to the attack on the metal surface and the acid mixture formation of the phosphating tank.
- Patent document CN102229506 entitled Ivlethod for recovering phosphorus and potassium from effluent and producing slow-release composite fertilizer of phosphorus and potassium, describes a method of recovering urine phosphorus by adding magnesium to precipitate struvite producing a slow release fertilizer. Formation of the desired composite is done by first analyzing the urine composition and then adding magnesium and phosphate salts to maintain some specific proportions of magnesium, potassium and phosphate in solution, following a pH adjustment of the solution. Under such established conditions and constant agitation, the desired salt precipitates as granules.
- the patent document CN 102167434, titled Ivlethod for recovering nitrogen and phosphorous from urine ⁇ discloses a method of separating sources of sewage and chemical method for treatment of urine recovery of nutrients, particularly nitrogen and phosphorus. Fresh urine is used to further measure the pH. The phosphorus and nitrogen concentration of the solution is adjusted by adding Na 2 HPO 4 and MgCl 2 at the required concentrations. In this process struvite is obtained, with phosphorus and nitrogen recovery of about 95%.
- This document differs from the present invention in that it does not use the proposed composition.
- Patent document JP201417739 entitled Hecovery phosphorus ⁇ describes a process of phosphorus recovery in effluents using a material made of a metal oxide capable of adsorbing the phosphorus contained in the solution.
- the desorption process is done by placing the material in an alkaline solution.
- a precipitation process is then made by adding calcium to the solution.
- Patent Document PI 0204877-9 Titled ⁇ Sanitary Granulate used in the treatment and handling of pet waste, and the process of preparing it, utilizes the functioning vermiculite. as a sponge for the retention of animal waste that will later be used directly in agriculture.
- the present invention proposes a composition for phosphorus and / or nitrogen adsorption of effluents or liquid waste, comprising at least one support material, preferably serpentinite, vermiculite, charcoals (modified by oxidative or non-oxidative treatments) and / or phosphate-rich effluent treatment plant sludge; such support material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined.
- This technology also addresses the use of the composition, the process for preparing the composition, the process for producing additives for soil conditioning and nutrient release, phosphorus and / or nitrogen recovery devices, the additives produced and their uses.
- the proposed composition allows phosphorus and nitrogen adsorption directly from the effluent and can subsequently be used as an agricultural input without the need for any treatment other than decontamination.
- Figure 1 depicts the phosphate adsorption isotherm using TEE sludge as adsorbent.
- the present invention is a phosphorus and / or nitrogen adsorption composition of effluent or liquid waste comprising at least one support material, preferably serpentinite, vermiculite, charcoals (modified by oxidative or non-oxidative treatments) and / or phosphate-rich effluent treatment plant sludge; such support material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined. It also addresses the use of the composition, the process for preparing the composition, the process for producing soil conditioning and nutrient release additives, phosphorus and / or nitrogen recovery devices and the additives produced.
- the proposed process for preparing the phosphorus and / or nitrogen adsorption composition of effluent or liquid waste comprises the following steps:
- The. Add the support material to an aqueous solution of 0.5 to 50% (w / w) Ca, Zn, Cu, Mn, Mo, B, Co and / or Ni salts / oxides;
- the support material should preferably be serpentinite, vermiculite, activated or non-activated charcoals (modified by oxidative treatments or not) and / or phosphate-rich effluent treatment plant sludge.
- Serpentinite Mg 3 Si 2 0 5 (OH) 4
- the particle vermiculite is preferably present from 0.3 "0.6 cm and approximate composition of (Al 0. 30 Fe 0 .o4 Ti 0 .63 Mg 2. 0 o) (Si 3. Al 2 i 0. 79) (OK (OH) 2 , Mg 0. 0 i 3 In. 02 K 0. i 0 (H 2 0) n).
- Activated or non-activated charcoals may undergo oxidative processes for the insertion of acidic groups on their surface by reaction with hot concentrated HN0 3 (80 to 100 ° C) for 5 to 30 minutes.
- the process for producing soil conditioning additives and nutrient release from effluent and / or liquid waste comprises the following steps:
- the effluent may be selected from the group comprising industrial effluent and / or domestic effluent free of heavy metals or toxic organic molecules and shall contain phosphate concentrations greater than 10 mg / l or 0.03 ppm.
- the liquid residues are preferably human or animal urine, free of heavy metals or toxic organic molecules, with phosphate concentrations between 100-1000 mg / l and urea on the order of 1-20 g / l, wherein the adsorbent material may be contained in a wrapper, such as sachets or cases.
- the decontamination of the adsorbent material can be carried out by using NaCIO, 0 3 , H 2 0 2 , artificial (Hg lamp) or natural (sun) UV light, combined or not.
- the invention also relates to a device for phosphorus and / or nitrogen adsorption of effluents or liquid waste and production of soil conditioning and nutrient release additives, comprising the phosphorus and / or nitrogen adsorption composition defined in
- the present invention is contained in a casing, such as sachets or cases, which allows effluent or liquid waste to pass through and retains the composition for reuse.
- Shells shall have sufficient mechanical and chemical resistance not to degrade and / or rupture when in contact with effluent / liquid waste. Provided that the permeability and resistance characteristics (both chemical and mechanical) are observed, the malleability of the enclosures will depend on their use.
- the present technology addresses the additive for soil conditioning and nutrient release obtained by the proposed process.
- the proposed composition may be used for phosphorus and / or nitrogen adsorption for treatment of phosphorus and / or nitrogen rich industrial and / or domestic effluents; or for the production of additives for soil conditioning and nutrient release.
- the material may also be used as a bed for poultry tailings storage bed.
- poultry manure comes into contact with the composition of the present invention and the nutrients from such manure are adsorbed / retained on the material, which may later be used as an additive for soil conditioning and nutrient release.
- the phosphorus and / or nitrogen adsorption composition of effluent and / or liquid waste comprises at least one support material selected from the serpentinite, vermiculite, charcoal and phosphate-rich effluent treatment plant sludge group; the support materials being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined.
- Equation (1) 3Ca 2+ (aq) + ⁇ 0 4 3 " ⁇ 3 ⁇ ) 3 ⁇ 4 Ca 3 (P0 4 ) 2 (s) .
- vermiculite For preparation of the composition using vermiculite as a support material, previously expanded commercial vermiculite was used.
- the vermiculite used had particles between 0.3 " 0.6 cm and approximate composition of (Al 0. 3 o Ti 0. 0 4 Fe 0. 6 3 Mg 2. 00 ) (Si 3. 2 i Al 0. 79 ) (O 10 ( OH) 2 , Mg 0. at 0 i 3. O.10 2 0 (H 2 0) n).
- impregnations were carried out, whether or not combined, in concentrations ranging from 0.5 to 50% (w / w) Ca, Zn, Cu, Mn, Mo, B, Co and Ni
- the salts / oxides of the metals were solubilized in water, the vermiculite was added to the suspension and the system was kept under heating and stirring to dryness. After this step, the material was bake for 3 hours at 300 ° C, 500 ° C and 700 ° C. Another procedure used was impregnation without further calcination.
- Serpentinite rock samples of the general formula Mg 3 Si 2 0 5 (OH) 4 were extracted in a mine and had Mg and Fe contents of 12-17% m / m and 2-3% m / m, respectively. .
- Serpentinite powder was used, with particle size ranging from 1 to 5 mm.
- Serpentinite samples were sprayed and retained on 200 mesh sieves.
- the composition containing the serpentinite as support was prepared in the same manner as with vermiculite. The metal ions were dispersed in water, the serpentinite was added and the system was left under heating and stirring until complete drying.
- the materials were calcined for 3 hours at temperatures of 300 ° C, 500 ° C and 700 ° C. These materials can be prepared without the impregnation step, with only calcination for three hours at 500 ° C, 700 ° C and 900 ° C for powdered material and calcination at 700 ° C for three hours for material with particle size ranging from 1 to 5 mm.
- Activated or not activated charcoals are subjected or not to oxidative processes for insertion of acidic groups on their surface by reaction with hot concentrated HN0 3 (80 to 100 ° C) for 5 to 30 minutes.
- the metal impregnation step Ca 2+ , Zn 2+ , Cu 2+ , Mn x + , Mo 6+ , B + , Co 2+ and ⁇ , are carried out at concentrations between 0.5 " 50% (The activated carbon used in this example was produced from coconut shell and activated using water vapor at 800 ° C, with a surface area between 600-800 m 2 / g and ash content of the order of 5%.
- the base material was calcined, accompanied by surface calcium impregnation with CaO (lime) or CaCl 2 in aqueous medium. with constant heating and stirring for water evaporation and calcium impregnation on the material surface.
- ETE automobile effluent treatment plant
- Equation (2) P0 4 3 " + 12Mo0 4 2" + 27H + "H 3 P0 4 (Mo0 3 ) i 2 + 12H 2 0
- Equation (3) H 3 P0 4 (Mo0 3) + C 12 H 8 0 6 6 "molybdenum blue
- compositions for use in chemical toilets and in the form of urinal cases.
- the sachet and case should allow liquid waste to pass through and prevent solid material from entering. In addition, they must retain the composition and allow its recovery to prepare additives for soil conditioning and nutrient release.
- Capture assays were performed using a standard mass of 80 mg of the material synthesized in 40 mL of the standard phosphate solution, where the material remains in contact with the solution for about 8 hours, with constant stirring at 100 to 180 rpm. All initial standard solutions had an initial concentration of 300 mg / L, with percentage removals calculated from this concentration.
- WWTP sludge from metal surface treatment processes may have a high phosphorus content as well as its capture materials due to the metal surface process used in the metallurgical industry, called diphosphating. This consists in creating on the metallic surface, after the removal of impurities, phosphate crystals of the metal, converting it from metallic to non-metallic. As a result, phosphating improves paint adhesion and makes the metal surface up to 700 times stronger.
- the adsorption isotherm was made by repeating the material mass and volume, 200 mg and 20 mL, respectively, with the gradual increase of phosphorus concentration in the medium. The material was in contact with the solution for about 8 hours to ensure phosphorus adsorption and desorption equilibrium on its surface.
- Solubility in citric acid simulates nutrient availability when associated with roots with mycorrhizae, ie, in this condition the available phosphorus is absorbed by the plant, obtaining greater use of it, so this feature is extremely favorable for fertilizer production.
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Abstract
The present invention relates to a composition for adsorbing phosphorus and/or nitrogen from effluents or liquid waste, comprising at least one supporting material, preferably serpentinite, vermiculite, plant charcoals (optionally modified by oxidative treatment) and/or sludge from phosphate-rich effluent treatment plants, said supporting material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and/or nickel, and calcinated. The present invention also relates to use of the composition, the process for preparing the composition, the process for producing additives for conditioning soil and releasing nutrients, devices for recovering phosphorus and/or nitrogen and the additives produced.
Description
COMPOSIÇÃO PARA ADSORÇÃO DE FÓSFORO E/OU NITROGÉNIO DE EFLUENTES OU RESÍDUOS LÍQUIDOS, PROCESSOS, PRODUTOS COMPOSITION FOR Phosphorus and / or Nitrogen Adsorption of Effluents or Liquid Waste, Processes, Products
E USOS_ AND USES_
[001 ] A presente invenção trata de uma composição para adsorção de fósforo e/ou nitrogénio de efluentes ou resíduos líquidos, compreendendo pelo menos um material de suporte, preferencialmente serpentinito, vermiculita, carvões vegetais (modificados por tratamentos oxidativos ou não) e/ou lodo de estação de tratamento de efluentes ricos em fosfato; sendo tal material de suporte impregnado com cálcio, zinco, cobre, manganês, molibdênio, boro, cobalto e/ou níquel; e calcinado. Trata também do uso da composição, do processo para preparação da composição, do processo para produção de aditivos para condicionamento de solo e liberação de nutrientes, de dispositivos para recuperação de fósforo e/ou nitrogénio e dos aditivos produzidos. [001] The present invention is a composition for phosphorus and / or nitrogen adsorption of effluent or liquid waste comprising at least one support material, preferably serpentinite, vermiculite, charcoals (modified by oxidative or non-oxidative treatments) and / or phosphate-rich effluent treatment plant sludge; such support material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined. It also addresses the use of the composition, the process for preparing the composition, the process for producing soil conditioning and nutrient release additives, phosphorus and / or nitrogen recovery devices and the additives produced.
[002] O fósforo (normalmente na forma de fosfato) e o nitrogénio (presente em diversas formas, como amónio, nitrato e ureia), presentes em efluentes e rejeitos industriais e domésticos, são um problema ambiental por causarem eutrofização de rios e lagos quando descartados. Uma concentração de fósforo a partir de 0,03 mg/L já é suficiente para causar florações de cianobactérias (WANG, R. et al. Flickering gives early warning signals of a criticai transition to a eutrophic lake state. Nature, v. 492, n. 7429, p. 419-422, 12/20/print 2012. ISSN 0028-0836). O nitrogénio também contribui para a eutrofização, porém em menor escala, uma vez que o fósforo é elemento limitante para a ocorrência das florações (ROWE, E. C. et al. Vegetation Type Affects the Relationship Between Soil Carbon to Nitrogen Ratio and Nitrogen Leaching. Water, Air, and Soil Pollution, v. 177, n. 1 , p. 335-347, 2006// 2006. ISSN 1573-2932.). Por outro lado, o fósforo e o nitrogénio são nutrientes extremamente importantes para a agricultura.
[003] A agricultura, a indústria de alimentos e de detergentes são os principais consumidores de fósforo (COOPER, J. et al. The future distribution and production of global phosphate rock reserves. Resources, Conservation and Recycling, v. 57, p. 78-86, 12// 201 1 . ISSN 0921 -3449.). A agricultura é responsável por aproximadamente 85% do consumo mundial de fósforo (AHMAD, M.; CHAUDHRY, M. G.; CHAUDHRY, G. M. Some non-price explanatory variables in fertiliser demand: the case of irrigated Pakistan. Pakistan Development Review, v. 39, p. 477+, 2000 Winter// 2000. ISSN 00309729.). Phosphorus (usually in the form of phosphate) and nitrogen (present in various forms, such as ammonium, nitrate and urea), present in industrial and domestic effluents and waste, are an environmental problem as they cause eutrophication of rivers and lakes when discarded. A phosphorus concentration from 0.03 mg / L is already sufficient to cause cyanobacterial blooms (WANG, R. et al. Flickering gives early warning signals of a critical transition to a eutrophic lake state. Nature, v. 492, No. 7429, pp. 419-422, 12/20/2014 print. ISSN 0028-0836). Nitrogen also contributes to eutrophication, but to a lesser extent, since phosphorus is a limiting element for flowering (ROWE, EC et al. Vegetation Type Affects the Relationship Between Soil Carbon and Nitrogen Leaching. Water, Air, and Soil Pollution, v. 177, no. 1, pp. 335-347, 2006 // 2006. ISSN 1573-2932.). On the other hand, phosphorus and nitrogen are extremely important nutrients for agriculture. [003] Agriculture, the food and detergent industry are the main consumers of phosphorus (COOPER, J. et al., The Future Distribution and Production of Global Phosphate Rock Reserves. Resources, Conservation and Recycling, v. 57, p. 78-86,12,201. ISSN 0921-3449.). Agriculture accounts for approximately 85% of world phosphorus consumption (AHMAD, M .; CHAUDHRY, MG; CHAUDHRY, GM. Some non-price explanatory variables in fertilizer demand: The case of irrigated Pakistan. Pakistan Development Review, v. 39, 477+, 2000 Winter // 2000. ISSN 00309729.).
[004] No Brasil, o agronegócio é um dos setores mais importantes para a economia, representando 1/3 da riqueza do país. Mesmo sendo um dos maiores produtores mundiais de alimentos, grande parte dos solos brasileiros são pobres em macronutrientes, o que demanda um grande uso de fertilizantes fosfatados. Porém, a produção de fertilizantes não acompanha a produção de alimentos agrícolas. Assim, o país é o 4° maior importador de fertilizantes e o 2° de fertilizantes fosfatados (ANDEF - Associação Nacional de Defesa Vegetal. Manual de tecnologia de aplicação de produtos fitossanitários, 2004). [004] In Brazil, agribusiness is one of the most important sectors for the economy, representing 1/3 of the country's wealth. Even being one of the world's largest food producers, most Brazilian soils are poor in macronutrients, which requires a large use of phosphate fertilizers. However, fertilizer production does not keep up with agricultural food production. Thus, the country is the 4th largest importer of fertilizers and the 2nd of phosphate fertilizers (ANDEF - National Plant Protection Association. Phytosanitary Application Technology Manual, 2004).
[005] O fósforo e/ou nitrogénio podem ser removidos de efluentes de duas maneiras: biológica ou físico-química. No tratamento biológico são utilizados organismos capazes de absorver nutrientes na forma de fosfato/nitratos. Após a absorção, o lodo gerado é retirado e digerido anaerobicamente, o que faz com que os compostos absorvidos retornem para a fase aquosa. Esse líquido rico em nutrientes retorna para o início do tratamento. O tratamento físico-químico utiliza íons de ferro, alumínio, magnésio ou cálcio para precipitar fósforo na forma de fosfato, que é retirado juntamente com o lodo. Phosphorus and / or nitrogen can be removed from effluents in two ways: biological or physicochemical. In biological treatment organisms capable of absorbing nutrients in the form of phosphate / nitrates are used. After absorption, the generated sludge is removed and digested anaerobically, which causes the absorbed compounds to return to the aqueous phase. This nutrient-rich liquid returns to the beginning of treatment. The physicochemical treatment uses iron, aluminum, magnesium or calcium ions to precipitate phosphorus in the form of phosphate, which is removed together with the sludge.
[006] Outra maneira de retirar fósforo de efluentes é a precipitação de estruvita (fosfato de amónia e magnésio hexahidratado), que pode ser
utilizada na fabricação de fertilizantes. A estruvita apresenta uma taxa de liberação de nutrientes lenta, permitindo menor frequência de aplicação do fertilizante (LUZ, E.; BASHAN, Y. Recent advances in removing phosphorus from wastewater and its future use as fertilizer ( 1997 " 2003 ). v. 38, p. 4222"4246, 2004). Another way of removing phosphorus from effluents is precipitation of struvite (ammonium phosphate and magnesium hexahydrate), which can be used in the manufacture of fertilizers. Struvite has a slow nutrient release rate, allowing lower frequency of fertilizer application (LUZ, E .; BASHAN, Y. Recent advances in removing phosphorus from wastewater and its future use as fertilizer (1997 " 2003). V. 38 , p. 4222 "4246, 2004).
[007] Carvões, vermiculita e serpentinitos são comumente aplicados como aditivos para agricultura. Os carvões são muito interessantes tanto pelas suas estruturas porosas e elevada área superficial, quanto pela sua capacidade em aumentar os teores de matéria orgânica e capacidade de troca de cátions do solo, melhorando a eficiência no uso de fertilizantes, promovendo o desenvolvimento de microrganismos benéficos ao crescimento vegetal, entre outras características agronomicamente desejáveis (SANTALLA, M. et al. Effectiveness of wood ash contai ning charcoal as a fertilizer for a forest plantation in a temperate region. Plant and Soil, v. 346, n. 1 , p. 63-78, 201 1// 201 1 . ISSN 1573-5036). A possibilidade de se usar o carvão como condicionador de solos surgiu ao se observar certas características químicas das Terras Pretas de índio amazônicas (solos de baixa fertilidade, como os Latossolos da Amazónia, podem ser transformados em solos férteis, não apenas pela adição de fontes minerais de nutrientes, mas pela adição de compostos orgânicos estáveis na forma de carvão). A remoção de amónia em efluentes utilizando carvões tem sido estudada por vários grupos de pesquisa (GLASER, B. ; BIRK, J. J. State of the scientific knowledge on properties and génesis of Anthropogenic Dark Earths in Central Amazónia (terra preta de índio). Geochimica et Cosmochimica Acta, v. 82, p. 39-51 , 4/1/ 2012. ISSN 0016- 7037; ASADA, T. et al. Ammonia Adsorption on Bamboo Charcoal with Acid Treatment. Journal of Health Science, v. 52, n. 5, p. 585-589, 2006). Coals, vermiculite and serpentinites are commonly applied as additives for agriculture. Coals are very interesting both for their porous structures and high surface area, as well as their ability to increase soil organic matter content and cation exchange capacity, improving the efficiency of fertilizer use, promoting the development of beneficial microorganisms. plant growth, among other agronomically desirable characteristics (SANTALLA, M. et al. Effectiveness of wood ash containing charcoal as a fertilizer for a forest plantation in a temperate region. Plant and Soil, v. 346, no. 1, p. 63 -78,201 / 201 / 2011. ISSN 1573-5036). The possibility of using coal as a soil conditioner arose from observing certain chemical characteristics of the Amazonian Indian Black Earths (low fertility soils such as Amazonian Oxisols) can be transformed into fertile soils, not only by the addition of mineral sources. nutrients, but by the addition of stable organic compounds in the form of coal). The removal of ammonia in effluents using charcoals has been studied by several research groups (GLASER, B.; BIRK, JJ. Geochimica et al. Cosmochimica Acta, v. 82, pp. 39-51, 4/1 / 2012. ISSN 0016-7037; ASADA, T. et al., Ammonia Adsorption on Bamboo Charcoal with Acid Treatment, Journal of Health Science, v. 52, no. 5, pp 585-589, 2006).
[008] A vermiculita é um mineral semelhante à mica, formado por hidratação de certos minerais basálticos, com fórmula
(MgFe,AI)3(AI,Si)4O10(OH)2.4H2O. Possui capacidade de expansão, quando submetida a temperaturas próximas a 900°C seu volume pode aumentar de 10 a 30 vezes. Após esse processo ganha o nome de vermiculita expandida, onde cada floco aprisiona células de ar, conferindo capacidade isolante ao material. Esse material expandido, além das capacidades isolantes, não é irritante à pele ou pulmão, apresenta baixa condutividade elétrica, não se decompõe e não atrai insetos. A vermiculita expandida pode absorver até cinco vezes sua massa em água, é um bom lubrificante e material filtrante. A aplicação da vermiculita na agricultura é ampla, devido às suas características como elevada capacidade de troca catiônica, boa retenção de água, baixa massa e reatividade química, ausência de toxicidade, isolamento térmico e boa granulometria. Assim, pode ser utilizado na produção de substratos agrícolas, na cobertura de sementes e mudas, como condicionador de solos, contentor de nutrientes e herbicidas/inseticidas/fungicidas, retentor de água em solos arenosos, agente anti adensante em campos gramados, carga na fabricação de defensivos agrícolas e agricultura hidropônica (WU, N. et al. Organic intercalation of structure modified vermiculite. Journal of Colloid and Interface Science, v. 457, p. 264-271 , 1 1 /1 / 2015. ISSN 0021 -9797). Vermiculite is a mica-like mineral formed by hydration of certain basaltic minerals, with formula (MgFe, AI) 3 (AI, Si) 4O 10 (OH) 2 .4H 2 O. It has expansion capacity, when subjected to temperatures close to 900 ° C its volume may increase from 10 to 30 times. After this process gets the name of expanded vermiculite, where each flake trap air cells, giving the material insulating capacity. This expanded material, in addition to its insulating capabilities, is non-irritating to skin or lung, has low electrical conductivity, does not decompose and does not attract insects. Expanded vermiculite can absorb up to five times its mass in water, is a good lubricant and filter material. The application of vermiculite in agriculture is wide due to its characteristics such as high cation exchange capacity, good water retention, low mass and chemical reactivity, absence of toxicity, thermal insulation and good particle size. Thus, it can be used in the production of agricultural substrates, in the cover of seeds and seedlings, as soil conditioner, nutrient and herbicide / insecticide / fungicide container, sandy soil water retainer, grassy field antifreeze agent, manufacturing load. of pesticides and hydroponic agriculture (WU, N. et al. Organic intercalation of structure modified vermiculite. Journal of Colloid and Interface Science, v. 457, p. 264-271, 11/1/2015. ISSN 0021 -9797) .
[009] Os serpentinitos abrangem uma classe de rochas metamórficas magnesianas ultrabásicas, compostas, principalmente, por óxidos de cálcio, magnésio e silício. Fazem parte do grupo mineralógico das serpentinas, materiais de silicato de magnésio originados de alterações na hidratação de olivinas, que podem estar na natureza na forma de lizardita, antagorita ou crisotila. A composição e arranjo do serpentinito variam de uma região para outra devido ao metamorfismo, que pode deslocar fases silicáticas para carbonáticas (PEREIRA, D.; PEINADO, M. Serpentinite. Geology Today, v. 28, n. 4, p. 152-156, 2012. ISSN 1365-2451 ). No Brasil, as reservas de serpentinito estão distribuídas nos seguintes estados: Bahia, Ceará, Goiás,
Minas Gerais, Mato Grosso do Sul, Pará, Paraíba, Paraná, Rio Grande do Sul, Sergipe e São Paulo. A utilização de rochas na agricultura é denominada de rochagem ou remineralização. Nessa técnica, o pó da rocha é utilizado para corrigir acidez e repor nutrientes do solo. A água atua lixiviando lentamente nutrientes da rocha e, assim, obtém-se um condicionador de solos natural com liberação gradual de nutrientes. Uma das vantagens dessa técnica é a diminuição do consumo de fertilizantes industriais (ANDEF - Associação Nacional de Defesa Vegetal. Manual de tecnologia de aplicação de produtos fitossanitários. 2004). Um problema dessa técnica é a aplicação descontrolada, que pode gerar um desequilíbrio nutricional e/ou acúmulo de metais pesados no solo. Serpentinites comprise a class of ultrabasic magnesian metamorphic rocks composed mainly of calcium, magnesium and silicon oxides. Part of the serpentine mineralogical group are magnesium silicate materials derived from changes in the hydration of olivines, which may be in nature in the form of lizardite, antagonist or chrysotile. Serpentinite composition and arrangement vary from region to region due to metamorphism, which can shift silicate to carbonate phases (PEREIRA, D .; PEINADO, M. Serpentinite. Geology Today, v. 28, no. 4, p. 152- 156, 2012. ISSN 1365-2451). In Brazil, the serpentinite reserves are distributed in the following states: Bahia, Ceará, Goiás, Minas Gerais, Mato Grosso do Sul, Para, Paraiba, Paraná, Rio Grande do Sul, Sergipe and Sao Paulo. The use of rocks in agriculture is called rocking or remineralization. In this technique, rock dust is used to correct acidity and replenish soil nutrients. The water acts by slowly leaching nutrients from the rock, thus obtaining a natural soil conditioner with gradual release of nutrients. One of the advantages of this technique is the decrease in the consumption of industrial fertilizers (ANDEF - National Association of Plant Protection. Phytosanitary application technology manual. 2004). A problem with this technique is uncontrolled application, which can lead to nutritional imbalance and / or accumulation of heavy metals in the soil.
[010] O lodo produzido pela indústria de fosfatização tem uma capacidade de adsorção de fósforo e ureia muito elevada. Dentre os processos de preparação de superfícies metálicas usados na indústria metalúrgica, destaca-se a fosfatização por imersão. Durante esse procedimento é originado um resíduo denominado lama de fosfato ou borra de fosfato, formado a partir da reação dos íons Fe3+ (originados pela oxidação dos íons Fe2+ presentes em solução) com o íon fosfato (P04 3 ), formando, o fosfato de ferro (FeP04). Estudos de caracterização realizados por Giffoni & Lange (2005) demonstram que os principais constituintes da borra são ferro, zinco, níquel e sódio em função do ataque na superfície metálica e da constituição da mistura ácida do tanque de fosfatização. [010] The sludge produced by the phosphating industry has a very high phosphorus and urea adsorption capacity. Among the metal surface preparation processes used in the metallurgical industry, immersion phosphating stands out. During this procedure a residue called phosphate sludge or phosphate sludge is formed, formed from the reaction of Fe 3+ ions (originated by the oxidation of Fe 2+ ions present in solution) with phosphate ion (P0 4 3 ), forming , iron phosphate (FeP0 4 ). Characterization studies by Giffoni & Lange (2005) show that the main constituents of sludge are iron, zinc, nickel and sodium due to the attack on the metal surface and the acid mixture formation of the phosphating tank.
[01 1 ] O documento de patente CN102229506, intitulado Ivlethod for recovering phosphorus and potassium from urine effluent and producing slow-release composite fertilizer of phosphorus and potassium, descreve um método de recuperação de fósforo da urina pela adição de magnésio para precipitar a estruvita produzindo um fertilizante de lenta liberação. A formação do compósito desejado é feita primeiro analisando a composição da urina e então adicionando sais de magnésio e fosfato para manter
algumas proporções específicas de magnésio, potássio e fosfato em solução, seguindo de um ajuste de pH da solução. Com tais condições estabelecidas e agitação constante, precipita-se o sal desejado, na forma de grânulos. [01 1] Patent document CN102229506, entitled Ivlethod for recovering phosphorus and potassium from effluent and producing slow-release composite fertilizer of phosphorus and potassium, describes a method of recovering urine phosphorus by adding magnesium to precipitate struvite producing a slow release fertilizer. Formation of the desired composite is done by first analyzing the urine composition and then adding magnesium and phosphate salts to maintain some specific proportions of magnesium, potassium and phosphate in solution, following a pH adjustment of the solution. Under such established conditions and constant agitation, the desired salt precipitates as granules.
[012] O documento de patente CN 102167434, intitulado Ivlethod for recovering nitrogen and phosphorous from urine^ descreve um método de separação de fontes de esgoto e método químico para tratamento de urina com recuperação de nutrientes, particularmente nitrogénio e fósforo. Utiliza- se urina fresca para posteriormente medir o pH. Ajusta-se a concentração de fósforo e nitrogénio da solução adicionando-se Na2HP04 e MgCI2 nas concentrações necessárias. Obtêm-se neste processo a estruvita, com recuperação de fósforo e nitrogénio de cerca de 95%. Esse documento se difere da presente invenção, por não utilizar a composição proposta. [012] The patent document CN 102167434, titled Ivlethod for recovering nitrogen and phosphorous from urine ^ discloses a method of separating sources of sewage and chemical method for treatment of urine recovery of nutrients, particularly nitrogen and phosphorus. Fresh urine is used to further measure the pH. The phosphorus and nitrogen concentration of the solution is adjusted by adding Na 2 HPO 4 and MgCl 2 at the required concentrations. In this process struvite is obtained, with phosphorus and nitrogen recovery of about 95%. This document differs from the present invention in that it does not use the proposed composition.
[013] O documento de patente JP201417739, intitulado Hecovery phosphorus^ descreve um processo de recuperação de fósforo em efluentes utilizando um material feito de um óxido de um metal capaz de adsorver o fósforo contido na solução. O processo de dessorção é feito ao colocar o material em uma solução alcalina. É feito então um processo de precipitação, através da adição de cálcio à solução. [013] Patent document JP201417739, entitled Hecovery phosphorus ^ describes a process of phosphorus recovery in effluents using a material made of a metal oxide capable of adsorbing the phosphorus contained in the solution. The desorption process is done by placing the material in an alkaline solution. A precipitation process is then made by adding calcium to the solution.
[014] O documento de patente US20030196965, intitulado rocess for recovery of nutrients from wastewater^ descreve um processo de recuperação de fósforo de efluentes, envolvendo conversão do fósforo em sal usando cloreto de magnésio e pH entre 8,4 e 10,7 que leva a precipitação de estruvita. Descreve também o uso desse sal como fertilizante. [014] US20030196965, entitled Rocess for Recovery of Nutrients from Wastewater ^ describes a waste phosphorus recovery process involving conversion of phosphorus to salt using magnesium chloride at pH 8.4 to 10.7 which takes precipitation of struvite. It also describes the use of this salt as fertilizer.
[015] O documento de patente PI 0204877-9, Intitulado ^Granulado sanitário usado no tratamento e manejo de dejetos de animais domésticos, e processo de preparação do mesmo, utiliza a vermiculita que funciona
como uma esponja para a retenção de dejetos animais que posteriormente será utilizado diretamente na agricultura. [015] Patent Document PI 0204877-9, Titled ^ Sanitary Granulate used in the treatment and handling of pet waste, and the process of preparing it, utilizes the functioning vermiculite. as a sponge for the retention of animal waste that will later be used directly in agriculture.
[016] No estado da técnica não foi descrita uma composição que permite a adsorção de fósforo e nitrogénio diretamente do efluente e que pode ser posteriormente utilizada como um insumo agrícola, sem a necessidade de qualquer tratamento que não seja a descontaminação. [016] In the prior art no composition has been described that allows phosphorus and nitrogen adsorption directly from the effluent and which can subsequently be used as an agricultural input without the need for any treatment other than decontamination.
[017] Já a presente invenção propõe uma composição para adsorção de fósforo e/ou nitrogénio de efluentes ou resíduos líquidos, compreendendo pelo menos um material de suporte, preferencialmente serpentinito, vermiculita, carvões vegetais (modificados por tratamentos oxidativos ou não) e/ou lodo de estação de tratamento de efluentes ricos em fosfato; sendo tal material de suporte impregnado com cálcio, zinco, cobre, manganês, molibdênio, boro, cobalto e/ou níquel; e calcinado. Esta tecnologia trata também do uso da composição, do processo para preparação da composição, do processo para produção de aditivos para condicionamento de solo e liberação de nutrientes, de dispositivos para recuperação de fósforo e/ou nitrogénio, dos aditivos produzidos e seus usos. Already the present invention proposes a composition for phosphorus and / or nitrogen adsorption of effluents or liquid waste, comprising at least one support material, preferably serpentinite, vermiculite, charcoals (modified by oxidative or non-oxidative treatments) and / or phosphate-rich effluent treatment plant sludge; such support material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined. This technology also addresses the use of the composition, the process for preparing the composition, the process for producing additives for soil conditioning and nutrient release, phosphorus and / or nitrogen recovery devices, the additives produced and their uses.
[018] A composição proposta permite a adsorção de fósforo e nitrogénio diretamente do efluente e pode ser posteriormente utilizada como um insumo agrícola, sem a necessidade de qualquer tratamento que não seja a descontaminação. [018] The proposed composition allows phosphorus and nitrogen adsorption directly from the effluent and can subsequently be used as an agricultural input without the need for any treatment other than decontamination.
[019] Os resultados obtidos nos ensaios classificam o resíduo como Classe II " A (não perigoso e não inerte). O ensaio de lixiviação não apresentou qualquer resultado acima dos limites estabelecidos, descartando, portanto, a classificação do resíduo como perigoso (Classe I) (GIFFIONI & LANGE, 2005).
BREVE DESCRIÇÃO DAS FIGURAS [019] The results obtained in the tests classify the waste as Class II " A (non-hazardous and non-inert). The leaching test did not yield any result above the established limits, thus discarding the classification of the waste as hazardous (Class I ) (GIFFIONI & LANGE, 2005). BRIEF DESCRIPTION OF THE FIGURES
[020] A figura 1 representa a isoterma de adsorção de fosfato utilizando lodo de ETE como adsorvente. Figure 1 depicts the phosphate adsorption isotherm using TEE sludge as adsorbent.
DESCRIÇÃO DETALHADA DA TECNOLOGIA DETAILED DESCRIPTION OF TECHNOLOGY
[021 ] A presente invenção trata de uma composição para adsorção de fósforo e/ou nitrogénio de efluentes ou resíduos líquidos, compreendendo pelo menos um material de suporte, preferencialmente serpentinito, vermiculita, carvões vegetais (modificados por tratamentos oxidativos ou não) e/ou lodo de estação de tratamento de efluentes ricos em fosfato; sendo tal material de suporte impregnado com cálcio, zinco, cobre, manganês, molibdênio, boro, cobalto e/ou níquel; e calcinado. Trata também do uso da composição, do processo para preparação da composição, do processo para produção de aditivos para condicionamento de solo e liberação de nutrientes, de dispositivos para recuperação de fósforo e/ou nitrogénio e dos aditivos produzidos. [021] The present invention is a phosphorus and / or nitrogen adsorption composition of effluent or liquid waste comprising at least one support material, preferably serpentinite, vermiculite, charcoals (modified by oxidative or non-oxidative treatments) and / or phosphate-rich effluent treatment plant sludge; such support material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined. It also addresses the use of the composition, the process for preparing the composition, the process for producing soil conditioning and nutrient release additives, phosphorus and / or nitrogen recovery devices and the additives produced.
[022] O processo proposto para preparo da composição para adsorção de fósforo e/ou nitrogénio de efluentes ou resíduos líquidos compreende as seguintes etapas: [022] The proposed process for preparing the phosphorus and / or nitrogen adsorption composition of effluent or liquid waste comprises the following steps:
a. Adicionar o material suporte a uma solução aquosa 0,5 a 50% (m/m) de sais/óxidos de Ca, Zn, Cu, Mn, Mo, B, Co e/ou Ni; The. Add the support material to an aqueous solution of 0.5 to 50% (w / w) Ca, Zn, Cu, Mn, Mo, B, Co and / or Ni salts / oxides;
b. Manter o sistema sob aquecimento entre 90 e 1 10°C e agitação até secagem total; B. Keep the system under heating at 90 to 110 ° C and stirring until completely dry;
c. Calcinar o material impregnado obtido em (b) a temperaturas entre 100 e 900°C, por 2 a 5 horas. ç. Calcine the impregnated material obtained in (b) at temperatures between 100 and 900 ° C for 2 to 5 hours.
[023] Na etapa a_ o material de suporte, deve ser, preferencialmente, serpentinito, vermiculita, carvões vegetais ativados ou não (modificados por tratamentos oxidativos ou não) e/ou lodo de estação de tratamento de efluentes ricos em fosfato.
[024] O serpentinito (Mg3SÍ205(OH)4) deve ser preferencialmente em pó, com granulometria entre 1 e 5 mm. [023] In step a, the support material should preferably be serpentinite, vermiculite, activated or non-activated charcoals (modified by oxidative treatments or not) and / or phosphate-rich effluent treatment plant sludge. Serpentinite (Mg 3 Si 2 0 5 (OH) 4) should preferably be powder, with a particle size between 1 and 5 mm.
[025] A vermiculita deve apresentar preferencialmente partículas entre 0.3" 0.6 cm e composição aproximada de (Al0.30 Ti0.o4 Fe0.63 Mg2.0o) (Si3.2i Al0.79) (OK, (OH)2 Mg0. i 3 Na0.02 K0. i 0 ( H20)n). [025] The particle vermiculite is preferably present from 0.3 "0.6 cm and approximate composition of (Al 0. 30 Fe 0 .o4 Ti 0 .63 Mg 2. 0 o) (Si 3. Al 2 i 0. 79) (OK (OH) 2 , Mg 0. 0 i 3 In. 02 K 0. i 0 (H 2 0) n).
[026] Os carvões vegetais, ativados ou não, podem ser submetidos a processos oxidativos para inserção de grupos ácidos em sua superfície, através da reação com HN03 concentrado a quente (80 a 100°C) por 5 a 30 minutos. [026] Activated or non-activated charcoals may undergo oxidative processes for the insertion of acidic groups on their surface by reaction with hot concentrated HN0 3 (80 to 100 ° C) for 5 to 30 minutes.
[027] O processo para produção de aditivos para condicionamento de solo e liberação de nutrientes a partir de efluentes e/ou resíduos líquidos compreende as seguintes etapas: [027] The process for producing soil conditioning additives and nutrient release from effluent and / or liquid waste comprises the following steps:
a. Deixar o efluente e/ou o resíduo líquido em contato com a composição de material adsorvente definida acima, na proporção de 1 a 60% de adsorvente no efluente, por tempos de residência de 10 segundos a 12 horas; The. Leave the effluent and / or liquid residue in contact with the adsorbent material composition defined above, in the proportion of 1 to 60% of adsorbent in the effluent, for residence times of 10 seconds to 12 hours;
b. Recolher o material adsorvente; B. Collect adsorbent material;
c. Descontaminar o material adsorvente. ç. Decontaminate adsorbent material.
[028] Na etapa a^ o efluente pode ser selecionado do grupo compreendendo efluentes industriais e/ou efluentes domésticos livres de metais pesados ou moléculas orgânicas tóxicas e devem conter concentrações de fosfato superiores a 10 mg/L ou 0,03 ppm. In step a the effluent may be selected from the group comprising industrial effluent and / or domestic effluent free of heavy metals or toxic organic molecules and shall contain phosphate concentrations greater than 10 mg / l or 0.03 ppm.
[029] Na etapa a^ os resíduos líquidos são preferencialmente urina humana ou animal, livres de metais pesados ou moléculas orgânicas tóxicas, com concentrações de fosfato entre 100-1000 mg/L e de ureia na ordem de 1 -20 g/L, sendo que o material adsorvente pode estar contido em um invólucro, como sachês ou estojos. Na etapa c_, a descontaminação do material adsorvente pode ser realizada pela utilização de NaCIO, 03, H202, luz UV artificial (lâmpada de Hg) ou natural (sol), combinados ou não.
[030] A invenção também se refere a um dispositivo para adsorção de fósforo e/ou nitrogénio de efluentes ou resíduos líquidos e produção de aditivos para condicionamento de solo e liberação de nutrientes, compreendendo a composição para adsorção de fósforo e/ou nitrogénio definida na presente invenção contida em um invólucro, como sachês ou estojos, que permita a passagem dos efluentes ou resíduos líquidos e retenha a composição, para reutilização. Os invólucros devem possuir resistência mecânica e química suficientes para não se degradarem e/ou romperem quando em contato com o efluente/resíduo líquido. Desde que observadas as características de permeabilidade e resistência (tanto química quanto mecânica) a maleabilidade dos invólucros dependerá do seu uso. In step a1 the liquid residues are preferably human or animal urine, free of heavy metals or toxic organic molecules, with phosphate concentrations between 100-1000 mg / l and urea on the order of 1-20 g / l, wherein the adsorbent material may be contained in a wrapper, such as sachets or cases. In step c, the decontamination of the adsorbent material can be carried out by using NaCIO, 0 3 , H 2 0 2 , artificial (Hg lamp) or natural (sun) UV light, combined or not. The invention also relates to a device for phosphorus and / or nitrogen adsorption of effluents or liquid waste and production of soil conditioning and nutrient release additives, comprising the phosphorus and / or nitrogen adsorption composition defined in The present invention is contained in a casing, such as sachets or cases, which allows effluent or liquid waste to pass through and retains the composition for reuse. Shells shall have sufficient mechanical and chemical resistance not to degrade and / or rupture when in contact with effluent / liquid waste. Provided that the permeability and resistance characteristics (both chemical and mechanical) are observed, the malleability of the enclosures will depend on their use.
[031 ] Além disso, a presente tecnologia trata do aditivo para condicionamento de solo e liberação de nutrientes obtido pelo processo proposto. [031] In addition, the present technology addresses the additive for soil conditioning and nutrient release obtained by the proposed process.
[032] Uma propriedade importante desses aditivos para condicionamento de solo é que são capazes de adsorver nutrientes somente a partir de meios aquosos e em concentrações superiores a 10 mg/L ou 0,03 ppm. Quando alocados em solos, eles permitem a liberação controlada desses nutrientes. [032] An important property of these soil conditioning additives is that they are capable of adsorbing nutrients only from aqueous media and at concentrations above 10 mg / L or 0.03 ppm. When allocated in soils, they allow the controlled release of these nutrients.
[033] A composição proposta pode ser usada para adsorção de fósforo e/ou nitrogénio para tratamento de efluentes industriais e/ou domésticos ricos em fósforo e/ou nitrogénio; ou para a produção de aditivos para condicionamento de solo e liberação de nutrientes. [033] The proposed composition may be used for phosphorus and / or nitrogen adsorption for treatment of phosphorus and / or nitrogen rich industrial and / or domestic effluents; or for the production of additives for soil conditioning and nutrient release.
[034] O material pode ser utilizado também como base para leito de armazenagem de rejeitos de aves. Nesse processo, os dejetos aviários entram em contato com a composição da presente invenção e os nutrientes desses dejetos são adsorvidos/retidos no material, que pode
posteriormente ser utilizado como aditivo para condicionamento de solo e liberação de nutrientes. [034] The material may also be used as a bed for poultry tailings storage bed. In this process, poultry manure comes into contact with the composition of the present invention and the nutrients from such manure are adsorbed / retained on the material, which may later be used as an additive for soil conditioning and nutrient release.
[035] A presente invenção pode ser mais bem compreendida através dos exemplos que se seguem, não limitantes. The present invention may be better understood by the following non-limiting examples.
EXEMPLO 1 " Preparação da composição com diferentes materiais de suporte EXAMPLE 1 " Preparing the Composition with Different Support Materials
[036] A composição para adsorção de fósforo e/ou nitrogénio de efluentes e/ou resíduos líquidos compreende pelo menos um material de suporte selecionado do grupo serpentinito, vermiculita, carvões vegetais e lodo de estação de tratamento de efluentes ricos em fosfato; sendo os materiais de suporte impregnados com cálcio, zinco, cobre, manganês, molibdênio, boro, cobalto e/ou níquel; e calcinados. The phosphorus and / or nitrogen adsorption composition of effluent and / or liquid waste comprises at least one support material selected from the serpentinite, vermiculite, charcoal and phosphate-rich effluent treatment plant sludge group; the support materials being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined.
[037] Para preparar os materiais, são realizadas impregnações, combinadas ou não, de cálcio, zinco, cobre, manganês, molibdênio, boro cobalto e níquel. Posteriormente, alguns desses materiais são tratados termicamente em temperaturas variando entre 300° e 700 °C por três horas. [037] To prepare the materials, impregnations, whether or not combined, of calcium, zinc, copper, manganese, molybdenum, cobalt boron and nickel are performed. Subsequently, some of these materials are heat treated at temperatures ranging from 300 ° to 700 ° C for three hours.
[038] Para a obtenção dos materiais adsorventes à base de serpentinito, vermiculita ou lodo ETE, o material base foi submetido à calcinação, acompanhado da impregnação de cálcio na superfície, com CaO (cal) ou CaCI2, em meio aquoso, com aquecimento e agitação constante para evaporação da água e impregnação do cálcio na superfície do material, homogeneamente. As temperaturas de calcinação variam de 100 a 900QC com o aumento de 10QC por minuto com patamares de 180 minutos na temperatura final. [038] In order to obtain adsorbent materials based on serpentinite, vermiculite or ETE sludge, the base material was calcined, accompanied by surface calcium impregnation with CaO (lime) or CaCl 2 in aqueous medium with heating. and constant stirring for water evaporation and calcium impregnation on the material surface evenly. Calcination temperatures range from 100 to 900 Q C with an increase of 10 Q C per minute with 180-minute levels in the final temperature.
[039] O processo de calcinação, acompanhado da impregnação de cálcio na superfície dos materiais, torna-se capaz de capturar fosfato pela adsorção via ligações químicas com os grupos de fosfato presente em solução, conforme a seguinte equação:
Equação (1): 3Ca2+ (aq) + Ρ04 3" {3ς) ¾ Ca3(P04)2(s). [039] The calcination process, accompanied by calcium impregnation on the surface of the materials, becomes able to capture phosphate by adsorption via chemical bonds with the phosphate groups present in solution, according to the following equation: Equation (1): 3Ca 2+ (aq) + Ρ0 4 3 " {3ς) ¾ Ca 3 (P0 4 ) 2 (s) .
[040] Para preparação da composição utilizando vermiculita como material de suporte, utilizou-se vermiculita comercial, previamente expandida. A vermiculita utilizada apresentou partículas entre 0.3"0.6 cm e composição aproximada de (Al0.3o Ti0.04 Fe0.63 Mg2.00) (Si3.2i Al0.79) (O10 (OH)2 Mg0. i 3 Na0.02 o.10 (H20)n). Foram realizadas impregnações, combinadas ou não, em concentrações variando de 0,5 a 50% (m/m) de Ca, Zn, Cu, Mn, Mo, B, Co e Ni. Para a realização das impregnações, os sais/óxidos dos metais foram solubilizados em água. A vermiculita foi adicionada à suspensão e o sistema foi mantido sob aquecimento e agitação até total secura. Após essa etapa, o material foi levado ao forno para calcinação por 3 horas nas temperaturas 300°C, 500°C e 700°C. Outro procedimento utilizado foi a impregnação sem a posterior calcinação. [040] For preparation of the composition using vermiculite as a support material, previously expanded commercial vermiculite was used. The vermiculite used had particles between 0.3 " 0.6 cm and approximate composition of (Al 0. 3 o Ti 0. 0 4 Fe 0. 6 3 Mg 2. 00 ) (Si 3. 2 i Al 0. 79 ) (O 10 ( OH) 2 , Mg 0. at 0 i 3. O.10 2 0 (H 2 0) n). impregnations were carried out, whether or not combined, in concentrations ranging from 0.5 to 50% (w / w) Ca, Zn, Cu, Mn, Mo, B, Co and Ni For the impregnation, the salts / oxides of the metals were solubilized in water, the vermiculite was added to the suspension and the system was kept under heating and stirring to dryness. After this step, the material was bake for 3 hours at 300 ° C, 500 ° C and 700 ° C. Another procedure used was impregnation without further calcination.
[041 ] As amostras da rocha serpentinito de fórmula geral Mg3Si205(OH)4 foram extraídas em uma mina e apresentam teores de Mg e Fe de 12-17% m/m e 2-3% m/m, respectivamente. Utilizou-se o serpentinito na forma de pó e com granulometria variando entre 1 e 5 mm. As amostras de serpentinito foram pulverizadas e retidas em peneiras malha 200. A composição contendo o serpentinito como suporte foi preparada da mesma maneira que a com a vermiculita. Os íons metálicos foram dispersos em água, adicionou-se o serpentinito e o sistema foi deixado sob aquecimento e agitação até total secagem. Após a impregnação dos metais, em concentrações variando entre 0,5 - 50% (m/m), os materiais foram submetidos à calcinação por 3 horas nas temperaturas de 300°C, 500°C e 700°C. Esses materiais podem ser preparados sem a etapa de impregnação, sendo realizadas apenas calcinações por três horas a 500°C, 700°C e 900°C para o material na forma de pó e calcinação a 700°C por três horas para o material com granulometria variando entre 1 e 5 mm.
[042] Os carvões vegetais, ativados ou não, são submetidos ou não a processos oxidativos para inserção de grupos ácidos em sua superfície através da reação com HN03 concentrado a quente (80 a 100 °C) por 5 a 30 minutos. Posteriormente, realiza-se a etapa de impregnação dos metais, Ca2+, Zn2+, Cu2+, Mnx+, Mo6+, B+, Co2+ e ΝΓ, em concentrações entre 0,5 " 50% (m/m). O carvão ativado utilizado nesse exemplo foi produzido a partir de casca de coco e ativado utilizando vapor de água a 800°C, apresentando área superficial entre 600-800 m2/g e teor de cinzas da ordem de 5%. Serpentinite rock samples of the general formula Mg 3 Si 2 0 5 (OH) 4 were extracted in a mine and had Mg and Fe contents of 12-17% m / m and 2-3% m / m, respectively. . Serpentinite powder was used, with particle size ranging from 1 to 5 mm. Serpentinite samples were sprayed and retained on 200 mesh sieves. The composition containing the serpentinite as support was prepared in the same manner as with vermiculite. The metal ions were dispersed in water, the serpentinite was added and the system was left under heating and stirring until complete drying. After metal impregnation at concentrations ranging from 0.5 - 50% (w / w), the materials were calcined for 3 hours at temperatures of 300 ° C, 500 ° C and 700 ° C. These materials can be prepared without the impregnation step, with only calcination for three hours at 500 ° C, 700 ° C and 900 ° C for powdered material and calcination at 700 ° C for three hours for material with particle size ranging from 1 to 5 mm. [042] Activated or not activated charcoals are subjected or not to oxidative processes for insertion of acidic groups on their surface by reaction with hot concentrated HN0 3 (80 to 100 ° C) for 5 to 30 minutes. Subsequently, the metal impregnation step, Ca 2+ , Zn 2+ , Cu 2+ , Mn x + , Mo 6+ , B + , Co 2+ and ΝΓ, are carried out at concentrations between 0.5 " 50% ( The activated carbon used in this example was produced from coconut shell and activated using water vapor at 800 ° C, with a surface area between 600-800 m 2 / g and ash content of the order of 5%.
[043] Para a composição utilizando lodo de estação de tratamento de efluente (ETE) da indústria automobilística, o material base foi submetido à calcinação, acompanhado da impregnação de cálcio na superfície, com CaO (cal) ou CaCI2, em meio aquoso, com aquecimento e agitação constante para evaporação da água e impregnação do cálcio na superfície do material. [043] For the composition using automobile effluent treatment plant (ETE) sludge, the base material was calcined, accompanied by surface calcium impregnation with CaO (lime) or CaCl 2 in aqueous medium. with constant heating and stirring for water evaporation and calcium impregnation on the material surface.
[044] A caracterização das amostras de borra de fosfato e do lodo gerado na estação de tratamento da empresa automobilística analisada, por fluorescência de Raios-X, evidencia alta concentração de fósforo. As análises indicam a ausência de arsénio, cádmio, chumbo e mercúrio, metais potencialmente tóxicos na agricultura. O cromo, único metal tóxico presente nas amostras, encontra-se abaixo dos limites estabelecidos pela Instrução Normativa 27 de 5 de junho de 2006 do Ministério da Agricultura e Pecuária (MAPA IN 27/2006), o que evidencia o potencial dos mesmos na agricultura. A tabela 1 apresenta os resultados obtidos por fluorescência de Raios-X. [044] The characterization of phosphate sludge samples and the sludge generated at the car company treatment station analyzed by X-ray fluorescence shows a high concentration of phosphorus. Analyzes indicate the absence of arsenic, cadmium, lead and mercury, potentially toxic metals in agriculture. Chromium, the only toxic metal present in the samples, is below the limits established by Normative Instruction 27 of June 5, 2006 of the Ministry of Agriculture and Livestock (MAP IN 27/2006), which shows their potential in agriculture. . Table 1 presents the results obtained by X-ray fluorescence.
Tabela 1 " Caracterização da Amostra por Fluorescência de Raios-X ELEMENTOS DOSADOS (%) BORRA DE FOSFATO LODO DA ETE Table 1 " Sample Characterization by X-Ray Fluorescence DOSED ELEMENTS (%) Phosphate Sludge WWTP
41 ,83 38,10
Fe203 30,80 1 1 ,33 ZnO 18,66 6,47 41, 83 38.10 Fe 2 0 3 30.80 1 1, 33 ZnO 18.66 6.47
Si02 2,90 3,06 CaO 0,80 31 ,77 Si0 2 2.90 3.06 CaO 0.80 31, 77
NiO 0,83 1 ,99 NiO 0.83 1.99
MnO 1 ,70 1 ,81 MnO 1, 70 1.81
K20 2,16 0,65 SrO <0,01 0,086 K 2 0 2.16 0.65 SrO <0.01 0.086
Al203 <0,10 2,66 Ti02 <0,01 1 ,19 S03 <0,01 0,54 Cr203 0,09 0,08Al 2 0 3 <0.10 2.66 Ti0 2 <0.01 1, 19 S0 3 <0.01 0.54 Cr 2 0 3 0.09 0.08
ND = Não detectado ND = Not Detected
EXEMPLO 2 " Testes de eficiência de adsorção de fósforo e/ou nitrogénio EXAMPLE 2 " Phosphorus and / or nitrogen adsorption efficiency tests
[045] Para se averiguar a eficiência dos materiais preparados conforme exemplo 1 , foram realizados testes com soluções padrão de fosfato e ureia nas concentrações encontradas na urina humana, 300 mg/L e 7, 1 g/L. Nesses testes, os padrões foram deixados em contato com os materiais sob leve agitação por períodos entre 3 e 12 horas. Após esse tempo, os materiais foram recolhidos e as soluções filtradas e analisadas. To ascertain the efficiency of the materials prepared according to example 1, tests were performed with standard phosphate and urea solutions at concentrations found in human urine, 300 mg / L and 7.1 g / L. In these tests, the standards were left in contact with the materials under slight agitation for periods of between 3 and 12 hours. After this time, the materials were collected and the solutions filtered and analyzed.
[046] Para a análise de fósforo nas amostras foi utilizado um método colorimétrico a base de molibdato em meio ácido. Esse ânion, na presença de ácido ascórbico, reage com o fósforo presente na amostra formando o
azul de molibdênio, permitindo, assim a análise por espectrofotometria na região do UV-Vis (leitura realizada em 840 nm), conforme as equações abaixo: For the phosphorus analysis in the samples a molybdate based colorimetric method in acid medium was used. This anion, in the presence of ascorbic acid, reacts with the phosphorus present in the sample forming the molybdenum blue, thus allowing analysis by spectrophotometry in the UV-Vis region (reading performed at 840 nm), according to the equations below:
Equação (2): P04 3" +12Mo04 2" +27H+" H3P04(Mo03) i 2+12H20 Equation (2): P0 4 3 " + 12Mo0 4 2" + 27H + "H 3 P0 4 (Mo0 3 ) i 2 + 12H 2 0
Equação (3): H3P04(Mo03)12 + C6H806" azul de molibdênio Equation (3): H 3 P0 4 (Mo0 3) + C 12 H 8 0 6 6 "molybdenum blue
[047] Para se quantificar a ureia presente nas amostras após os experimentos de adsorção, foram realizadas leituras no COT (Carbono Orgânico Total) e o método do indofenol antes e após cada experimento. [047] In order to quantify the urea present in the samples after the adsorption experiments, total organic carbon (TOC) readings and the indophenol method were taken before and after each experiment.
[048] Para a utilização da composição, foram desenvolvidos, nesse exemplo, dispositivos na forma de sachês para a utilização em banheiros químicos e na forma de estojos para mictórios. O sachê e o estojo devem permitir a passagem do resíduo líquido e impedir a entrada de materiais sólidos. Além disso, devem reter a composição e permitir a sua recuperação, para preparar aditivos para condicionamento de solo e liberação de nutrientes. [048] For the use of the composition, in this example, devices have been developed in the form of sachets for use in chemical toilets and in the form of urinal cases. The sachet and case should allow liquid waste to pass through and prevent solid material from entering. In addition, they must retain the composition and allow its recovery to prepare additives for soil conditioning and nutrient release.
EXEMPLO 2.1 " Testes de eficiência de remoção de fosfato com materiais à base de serpentinito EXAMPLE 2.1 " Phosphate Removal Efficiency Tests with Coil-Based Materials
[049] Os ensaios de captura foram realizados utilizando uma massa padrão de 80 mg do material sintetizado em 40 mL da solução padrão de fosfato, em que o material permanece em contato com a solução durante cerca de 8 horas, com agitação constante de 100 a 180 rpm. Todas as soluções padrão iniciais tinham concentração inicial de 300 mg/L, com as remoções em porcentagem calculadas a partir desta concentração. Capture assays were performed using a standard mass of 80 mg of the material synthesized in 40 mL of the standard phosphate solution, where the material remains in contact with the solution for about 8 hours, with constant stirring at 100 to 180 rpm. All initial standard solutions had an initial concentration of 300 mg / L, with percentage removals calculated from this concentration.
Tabela 2 - Remoções de fosfato com serpentinito não impregnados Table 2 - Unpregnated serpentinite phosphate removals
Temperatura de Cone. Final Remoção Cone Temperature. Final Removal
Amostra Sample
calcinação (°C) (ppm) (%) calcination (° C) (ppm) (%)
Serpentinito Serpentinite
500 279 7 moído 500 279 7 ground
Serpentinito 700 266 1 1
moído Serpentinite 700 266 1 1 ground
Serpentinito Serpentinite
900 291 3 moído 900 291 3 ground
Serpentinito 0 297 1 Serpentinite 0 297 1
Serpentinito 700 280 7 Serpentinite 700 280 7
[050] No segundo teste observa-se que o serpentinito granular calcinado a 700QC é capaz de remover mais fosfato que o serpentinito sem o tratamento térmico. Isso se deve à exposição e consequentemente à disposição do magnésio para se ligar ao fosfato. No serpentinito moído nota-se um pequeno aumento de remoção devido à maior área específica quando comparado ao serpentinito granular. [050] In the second test, it is observed that the 700 Q C calcined granular serpentinite is capable of removing more phosphate than serpentinite without heat treatment. This is due to exposure and consequently the disposition of magnesium to bind to phosphate. In ground serpentinite there is a small increase in removal due to the larger specific area when compared to granular serpentinite.
Tabela 3 - Remoções de fosfato com serpentinito impregnado com 2% de CaCI2. Table 3 - Removals of 2% CaCl 2 impregnated serpentinite phosphate.
Temperatura de calcinação Cone. Final Remoção Cone calcination temperature. Final Removal
Amostra Sample
(°C) (ppm) (%) (° C) (ppm) (%)
Serpentinito Serpentinite
700 204 32 1 700 204 32 1
Serpentinito Serpentinite
700 191 36 2 700 191 36 2
Serpentinito Serpentinite
700 196 34 3 700 196 34 3
[051 ] Nos materiais à base de serpentinito impregnados com CaO, percebeu-se a formação de um precipitado branco durante a realização do teste de remoção. Acredita-se então que parte do fosfato de cálcio precipitado seja lixiviado do material para a solução. Portanto partiu-se para a estratégia de impregnar o serpentinito com cloreto de cálcio, pois como
este é muito solúvel em água, acredita-se que durante o processo de impregnação, a dispersão no serpentinito seja maior. In CaO-impregnated serpentinite-based materials, a white precipitate was noted during the removal test. Part of the precipitated calcium phosphate is then believed to be leached from the material to the solution. Therefore, we started with the strategy of impregnating serpentinite with calcium chloride, because as a This is very soluble in water, it is believed that during the impregnation process, the dispersion in the serpentinite is greater.
[052] Durante o teste de remoção, nos materiais impregnados com cloreto de cálcio as remoções de fosfato foram em média 34%. [052] During the removal test, on calcium chloride impregnated materials, phosphate removals averaged 34%.
Tabela 4 - Remoções fosfato serpentinito 5% CaCI2 Amostra Temperatura de calcinação (°C) Cone. Final (ppm) Remoção (%) Serpentinito 7ÕÕ 179,90 40 Table 4 - Serpentinite phosphate removals 5% CaCl 2 Sample Calcination temperature (° C) Cone. Final (ppm) Removal (%) Serpentinite 7ÕÕ 179,90 40
[053] No serpentinito impregnado com 5% de cloreto de cálcio observou-se um aumento na remoção quando comparado ao serpentinito impregnado com 2% de CaCI2. [053] In the 5% calcium chloride impregnated serpentinite, there was an increase in removal when compared to the 2% CaCl 2 impregnated serpentinite.
Tabela 5 - Efeito da agitação sobre as remoções de fosfato com Table 5 - Effect of agitation on phosphate removals with
serpentinito impregnado com 2% e 5% de CaCI2 serpentinite impregnated with 2% and 5% CaCl 2
Teor de Temperatura de Cone. Final Remoçã Cone Temperature Content. Final Removal
Amostra Sample
CaCI2 calcinação (°C) (ppm) o (%) CaCl 2 calcination (° C) (ppm) o (%)
Serpentinito em Serpentinite in
2% 700 241 19 2% 700 241 19
repouso rest
Serpentinito sob Serpentinite under
5% 700 231 23 5% 700 231 23
agitação frenzy
Serpentinito em Serpentinite in
2% 700 139 54 2% 700 139 54
repouso rest
Serpentinito sob Serpentinite under
5% 700 256 15 5% 700 256 15
agitação frenzy
Tabela 6 - Remoções fosfato serpentinito 7% CaCI2 Table 6 - Serpentinite phosphate 7% CaCl2 removals
Temperatura de Cone. Final I Remoção Cone Temperature. Final I Removal
Amostra Sample
calcinação (°C) (ppm) (%) calcination (° C) (ppm) (%)
Serpentinito em Serpentinite in
700 221 26 700 221 26
repouso
Serpentinito sob rest Serpentinite under
700 700
agitação frenzy
[054] Os materiais impregnados com cloreto de cálcio foram estudados sob o parâmetro da agitação durante o teste. Para isso os materiais impregnados com 2; 5; e 7% de CaCI2 foram testados sob agitação, e em repouso. Observa-se que na maioria dos casos a agitação favorece a remoção de fosfato. [054] Calcium chloride impregnated materials were studied under the stirring parameter during the test. For this the materials impregnated with 2; 5; and 7% CaCl 2 were tested under stirring and at rest. It is observed that in most cases agitation favors phosphate removal.
EXEMPLO 2.2 " Testes de eficiência de remoção de fosfato com materiais à base de vermiculita EXAMPLE 2.2 " Phosphate Removal Efficiency Tests with Vermiculite Based Materials
[055] Testes similares aos feitos com serpentinito foram feitos com as amostras de vermiculita, sob as mesmas condições de impregnação e remoção de fosfato. Similar tests to those made with serpentinite were made with vermiculite samples under the same conditions of phosphate impregnation and removal.
[056] Um teste com vermiculita calcinada e impregnada com 10% de cal e calcinada a 500, 700 e 900 QC foi realizado em batelada com agitação de 180 rpm. Os resultados se encontram na tabela abaixo: [056] A test with 10% lime impregnated and calcined vermiculite at 500, 700 and 900 Q C was carried out in a 180 rpm agitation batch. The results are in the table below:
Tabela 7 - Remoção de fosfato com composição à base de vermiculita impregnada com cal 10% Table 7 - Phosphate removal with 10% lime impregnated vermiculite composition
Temperatura de Cone. Final Remoção Cone Temperature. Final Removal
Amostra Sample
calcinação (T) (ppm) (%) calcination (T) (ppm) (%)
Vermiculita 500 156,40 48 Vermiculite 500 156.40 48
Vermiculita 700 162,85 46Vermiculite 700 162.85 46
Vermiculita 900 147,10 51 Vermiculite 900 147.10 51
[057] Percebe-se que a variação da temperatura de calcinação da vermiculita impregnada com cal altera pouco a remoção de fósforo em solução. Realizou-se também um teste com impregnação de cálcio na vermiculita utilizando cloreto de cálcio, todos tratado termicamente à 900QC,
com diferentes concentrações de CaCI2. Os dados se encontram na tabela 8. [057] It is noted that the variation in calcination temperature of lime impregnated vermiculite slightly alters the removal of phosphorus in solution. Also a test was carried out with calcium uptake in vermiculite employing calcium chloride, all heat treated at 900 Q C with different CaCl 2 concentrations. The data are in table 8.
Tabela 8 - Remoção de fosfato com diferentes teores de CaCI2 Table 8 - Phosphate removal with different CaCl 2 contents
Amostra Teor de CaCI2 Cone. Final (ppm) Remoção (%) Sample CaCl 2 Cone content. Final (ppm) Removal (%)
Vermiculita 2% 265 12 Vermiculite 2% 265 12
Vermiculita 5% 249 17 Vermiculite 5% 249 17
Vermiculita 7% 198 34 Vermiculite 7% 198 34
Vermiculita 10% 203 33 Vermiculite 10% 203 33
Vermiculita 20% 1 100 Vermiculite 20% 1 100
[058] O aumento da utilização de CaCI2 também aumentou a captura de fósforo da solução. Porém, com o teor em 20%, apesar da máxima remoção, percebeu-se na solução elevada turbidez, indicando a precipitação de fosfato de cálcio fora do material. Portanto, os efeitos desejados de adsorção na superfície do material são melhores obtidos nos teores de 5 e 7% de CaCI2. [058] Increasing CaCl 2 utilization also increased phosphorus uptake of the solution. However, with the content at 20%, despite the maximum removal, it was noticed in the solution high turbidity, indicating the precipitation of calcium phosphate outside the material. Therefore, the desired surface adsorption effects are best obtained at 5 and 7% CaCl 2 .
EXEMPLO 2.3 " Testes de eficiência de remoção de fosfato com materiais à base de lodo ETE EXAMPLE 2.3 " Phosphate Removal Efficiency Tests with ETE Sludge Based Materials
[059] O lodo de ETE de processos de tratamento de superfícies metálicas pode possuir um alto teor de fósforo quanto de seus materiais capturadores devido ao processo de superfícies metálicas usados na indústria metalúrgica, chamado fosfatização por imersão. Este consiste em criar na superfície metálica, após a remoção de impurezas, cristais de fosfato do metal, convertendo-a de metálica a não metálica. Por consequência, a fosfatização melhora a aderência das tintas e torna a superfície metálica até 700 vezes mais resistente. [059] WWTP sludge from metal surface treatment processes may have a high phosphorus content as well as its capture materials due to the metal surface process used in the metallurgical industry, called diphosphating. This consists in creating on the metallic surface, after the removal of impurities, phosphate crystals of the metal, converting it from metallic to non-metallic. As a result, phosphating improves paint adhesion and makes the metal surface up to 700 times stronger.
[060] Através de uma caracterização por fluorescência de raio-x, foi possível determinar o teor de elementos presentes no lodo de ETE das plantas de fosfatização de uma empresa do ramo automobilístico (Tabela 9)
Tabela 9: Teor de elementos presentes no lodo de ETE [060] Through x-ray fluorescence characterization, it was possible to determine the content of elements present in the ETE sludge of phosphating plants of an automobile company (Table 9). Table 9: Content of elements present in WWTP sludge
Elementos dosados Lodo da ETE Dosed elements WWTP sludge
P205 5,00P 2 0 5 5.00
Fe203 41 ,00Fe 2 0 3 41.00
ZnO 1 ,52ZnO 1, 52
Si02 9,30Si0 2 9.30
CaO 41 ,00CaO 41.00
NiO <0,10NiO <0.10
MnO 0,35MnO 0.35
K20 0,23K 2 0 0.23
SrO 0,13 SrO 0.13
[061 ] Percebe-se através da caracterização o alto teor de ferro e cálcio no lodo de ETE, possibilitando as mesmas propriedades dos materiais já testados. [061] It is noticed through the characterization the high iron and calcium content in the WWTP sludge, enabling the same properties of the materials already tested.
[062] Testes simples de remoção e captura de fósforo foram conduzidos também com o lodo ETE e os resultados obtidos estão descritos na tabela 10. [062] Simple phosphorus removal and capture tests were also conducted with the ETE sludge and the results obtained are described in table 10.
Tabela 10: Remoção de fósforo de efluente sintético utilizando Table 10: Phosphorus removal from synthetic effluent using
adsorventes à base de lodo de ETE ETE sludge-based adsorbents
Temperatura de Cone. Final RemoçãoCone Temperature. Final Removal
Amostra Sample
calcinação (°C) (ppm) (%) calcination (° C) (ppm) (%)
Lodo de ETE 0 16 44WWTP sludge 0 16 44
Lodo de ETE 900 48 83 ETE sludge 900 48 83
[063] Percebe-se que a calcinação foi imprescindível para a melhora de desempenho do material. [063] It is noted that calcination was essential for improving material performance.
[064] Estudos cinéticos e isotermas de adsorção foram feitos para melhor entendimento das capacidades do material. Foi conduzido um teste cinético simples para entender o comportamento do material calcinado e seus
tempos mínimos de atuação. Com o lodo em contato com a solução padrão de fosfato, alíquotas da solução foram analisadas nos tempos indicados na tabela abaixo: [064] Kinetic studies and adsorption isotherms were made to better understand the capabilities of the material. A simple kinetic test was conducted to understand the behavior of the calcined material and its minimum operating times. With sludge in contact with the standard phosphate solution, aliquots of the solution were analyzed at the times indicated in the table below:
Tabela 11 : Teste cinético de adsorção utilizando adsorventes à base de lodo de ETE Table 11: Kinetic Adsorption Test Using WWTP Sludge-Based Adsorbents
Amostra Tempo (s) Cone. Final (ppm) Remoção (%) Sample Time (s) Cone. Final (ppm) Removal (%)
cin1 30 165 45 cin1 30 165 45
cin2 60 198 34 cin2 60 198 34
cin3 180 1 14 62 cin3 180 1 14 62
cin4 300 1 12 63 cin4 300 1 12 63
cinõ 600 123 59 600 600 123 59
cin6 1800 7 98 cin6 1800 7 98
[065] Percebe-se uma diminuição já esperada no aumento das remoções de fósforo do meio com o passar do tempo. Em cerca de 30 segundos de contato com o material, 45% do fósforo em solução foi capturado, comprovando o desempenho rápido do lodo calcinado a 900°C. [065] An expected decrease in the increase in phosphorus removals from the medium over time is noted. In about 30 seconds of contact with the material, 45% of the phosphorus in solution was captured, proving the fast performance of calcined sludge at 900 ° C.
[066] A isoterma de adsorção foi feita repetindo a massa do material e o volume, 200 mg e 20 mL, respectivamente, com o aumento gradual da concentração de fósforo no meio. O material ficou em contato com a solução cerca de 8 horas, para garantir o equilíbrio de adsorção e dessorção de fósforo em sua superfície. The adsorption isotherm was made by repeating the material mass and volume, 200 mg and 20 mL, respectively, with the gradual increase of phosphorus concentration in the medium. The material was in contact with the solution for about 8 hours to ensure phosphorus adsorption and desorption equilibrium on its surface.
Tabela 12: Teste cinético de adsorção utilizando adsorventes à base de lodo de ETE Table 12: Kinetic Adsorption Test Using WWTP Sludge-Based Adsorbents
Cone. inicial Cone. final m adsorvato/m adsorventeCone. initial cone. final m adsorbent / m adsorbent
Amostra Sample
(ppm) (ppm) (mg/g) (ppm) (ppm) (mg / g)
isol 25 2,50 2,25 isol 25 2.50 2.25
iso2 50 0,00 5,00
iso3 100 0,00 10,00 iso4 150 0,50 14,95 iso5 300 48,40 25,15 iso6 500 40,10 45,99 iso7 800 390,85 40,92 iso8 1000 268,60 73,14 iso2 50 0.00 5.00 iso3 100 0.00 10.00 iso4 150 0.50 14.95 iso5 300 48.40 25.15 iso6 500 40.10 45.99 iso7 800 390.85 40.92 iso8 1000 268.60 73.14
EXEMPLO 3 " Ensaios de fertilização de solo EXAMPLE 3 " Soil Fertilization Tests
[067] Os ensaios realizados com o lodo de estações de tratamento de unidades de fosfatização demonstraram ausência de metais potencialmente tóxicos e alta concentração de fósforo determinados por análise de fluorescência. Os ensaios de solubilidade realizados têm por finalidade determinar a disponibilidade do fósforo no solo em caso de aplicação dos materiais na agricultura. Para isso, são realizados ensaios de solubilização em água e em solução de ácido cítrico 2%. A tabela 13 apresenta estes resultados obtidos conforme metodologia proposta no Manual de Métodos Analíticos Oficiais para Fertilizantes e Corretivos (MAPA, 2014). [067] Tests carried out with phosphate treatment plant sludge have shown the absence of potentially toxic metals and the high concentration of phosphorus determined by fluorescence analysis. The solubility tests carried out aim to determine the availability of phosphorus in the soil in case of application of the materials in agriculture. For this, solubilization assays are performed in water and 2% citric acid solution. Table 13 presents these results obtained according to the methodology proposed in the Manual of Official Analytical Methods for Fertilizers and Correctives (MAPA, 2014).
Tabela 13 - Ensaio de Solubilização em água e ácido cítrico 2% Table 13 - Water Solubilization Assay with 2% Citric Acid
LODO DA MUD
ANÁLISE BORRA DE FOSFATO ETE ETE PHOSPHATE BLANK ANALYSIS
P205 Total (%) 33,10 22,75P 2 0 5 Total (%) 33.10 22.75
P205 (%) em água 0,80 0,04 P 2 0 5 (%) in water 0.80 0.04
P205 (%) em Acido Cítrico 2% 12,99 17,79 P 2 0 5 (%) in 2% Citric Acid 12.99 17.79
PH 5,0 6,0 PH 5.0 6.0
Um idade (%) 52,36 66,82
Geração Média (T/mês) 6,0 60,0 One age (%) 52.36 66.82 Average Generation (T / month) 6.0 60.0
[068] A análise dos dados indica a baixa solubilidade do fósforo total em água. Tal característica pode ser favorável para aplicação na agricultura porque reduz a disponibilidade imediata do nutriente e por consequência minimiza a perda por lixiviação. [068] Data analysis indicates the low solubility of total phosphorus in water. Such a feature may be favorable for agricultural application because it reduces immediate nutrient availability and therefore minimizes leaching loss.
[069] A solubilidade em ácido cítrico simula a disponibilidade do nutriente quando associado a raízes com micorrizas, ou seja, nesta condição o fósforo disponibilizado é absorvido pela planta, obtendo maior aproveitamento do mesmo, logo, esta característica é extremamente favorável para produção fertilizante.
[069] Solubility in citric acid simulates nutrient availability when associated with roots with mycorrhizae, ie, in this condition the available phosphorus is absorbed by the plant, obtaining greater use of it, so this feature is extremely favorable for fertilizer production.
Claims
1 . COMPOSIÇÃO para adsorção de fósforo e/ou nitrogénio de efluentes ou resíduos líquidos, caracterizada por compreender pelo menos um material de suporte selecionado do grupo compreendendo serpentinito, vermiculita, carvões vegetais (modificados por tratamentos oxidativos ou não) e/ou lodo de estação de tratamento de efluentes ricos em fosfato; sendo tal material de suporte impregnado com cálcio, zinco, cobre, manganês, molibdênio, boro, cobalto e/ou níquel; e calcinado. 1 . Composition for phosphorus and / or nitrogen adsorption of effluent or liquid waste, characterized in that it comprises at least one support material selected from the group comprising serpentinite, vermiculite, charcoals (modified by oxidative or non-oxidative treatments) and / or treatment plant sludge. phosphate-rich effluents; such support material being impregnated with calcium, zinc, copper, manganese, molybdenum, boron, cobalt and / or nickel; and calcined.
2. PROCESSO para preparação da composição definida na reivindicação 1 , caracterizado por compreender as seguintes etapas: a) Adicionar o material suporte a uma solução aquosa 0,5 a 50% (m/m) de sais/óxidos de Ca, Zn, Cu, Mn, Mo, B, Co e/ou Ni; b) Manter o sistema sob aquecimento entre 90 e 1 10°C e agitação até secagem total; Process for preparing the composition as defined in claim 1, characterized in that it comprises the following steps: a) Adding the support material to an aqueous solution 0.5 to 50% (w / w) Ca, Zn, Cu salts / oxides Mn, Mo, B, Co and / or Ni; (b) keep the system under warming at 90 to 110 ° C and stirring until completely dry;
c) Calcinar o material impregnado obtido em (b) a temperaturas entre 100 e 900°C, por 2 a 5 horas. c) Calcining the impregnated material obtained in (b) at temperatures between 100 and 900 ° C for 2 to 5 hours.
3. PROCESSO, de acordo com a reivindicação 2, etapa a_, caracterizado pelo material de suporte ser selecionado do grupo compreendendo serpentinito, vermiculita, carvões vegetais (ativados ou não) e/ou lodo de estação de tratamento de efluentes ricos em fosfato. Process according to claim 2, step a, characterized in that the support material is selected from the group comprising serpentinite, vermiculite, charcoal (activated or not) and / or phosphate-rich effluent treatment plant sludge.
4. PROCESSO, de acordo com a reivindicação 3, caracterizado pelo serpentinito (Mg3SÍ205(OH)4) ser preferencialmente em pó, com granulometria entre 1 e 5 mm. Process according to Claim 3, characterized in that the serpentinite (Mg 3 Si 2 0 5 (OH) 4) is preferably powder, with a particle size between 1 and 5 mm.
5. PROCESSO, de acordo com a reivindicação 3, caracterizado pela vermiculita apresentar preferencialmente partículas entre 0.3"0.6 cm e composição aproximada de (Al0.30 Ti0.04 Fe0.63 Mg2.00) (Si3.2i Al0.79) (O10 (OH)2 Mgo.i3 Na0.o2 K0.i o (H20)n). 5. Process according to claim 3, characterized in that the vermiculite particles preferably have between about 0.3 "0.6 cm and approximate composition of (Al 0. 30 Ti 0. 4 0 Fe 0. 3 6 2 Mg. 00) (Si 3. i 2 Al 0. 79) (O 10 (OH) 2 In Mgo.i 3 0 0 .io .o2 K (H 2 0) n).
6. PROCESSO, de acordo com a reivindicação 3, caracterizado pelos carvões vegetais, ativados ou não, serem opcionalmente submetidos
a processos oxidativos para inserção de grupos ácidos em sua superfície, através da reação com HN03 concentrado a quente (80 a 100°C) por 5 a 30 minutos. Process according to Claim 3, characterized in that the activated charcoals, whether activated or not, are optionally subjected to oxidative processes for insertion of acidic groups on its surface by reaction with hot concentrated HN0 3 (80 to 100 ° C) for 5 to 30 minutes.
7. PROCESSO para produção de aditivos para condicionamento de solo e liberação de nutrientes a partir de efluentes e/ou resíduos líquidos, caracterizado por compreender as seguintes etapas: 7. PROCESS for the production of soil conditioning additives and nutrient release from effluents and / or liquid waste, characterized by the following steps:
a) Deixar o efluente e/ou o resíduo líquido em contato com a composição de material adsorvente definida pela reivindicação 1 , na proporção de 1 a 60% de adsorvente no efluente, por tempos de residência de 10 segundos a 12 horas; (a) leaving the effluent and / or liquid residue in contact with the adsorbent material composition defined in claim 1 in a proportion of 1 to 60% adsorbent in the effluent for residence times of 10 seconds to 12 hours;
b) Recolher o material adsorvente; (b) collect adsorbent material;
c) Descontaminar o material adsorvente. c) Decontaminate the adsorbent material.
8. PROCESSO, de acordo com a reivindicação 7, etapa a_, caracterizado pelo efluente ser selecionado do grupo compreendendo efluentes industriais e/ou efluentes domésticos, livres de metais pesados ou moléculas orgânicas tóxicas, contendo concentrações de fosfato superiores a 10 mg/L ou 0,03 ppm. Process according to claim 7, step a, characterized in that the effluent is selected from the group comprising industrial effluents and / or domestic effluents, free of heavy metals or toxic organic molecules, containing phosphate concentrations greater than 10 mg / l or 0.03 ppm.
9. PROCESSO, de acordo com a reivindicação 7, etapa a_, caracterizado pelos resíduos líquidos serem preferencialmente urina humana ou animal, livres de metais pesados ou moléculas orgânicas tóxicas, com concentrações de fosfato entre 100-1000 mg/L e de ureia na ordem de 1 -20 g/L. Process according to claim 7, step a, characterized in that the liquid waste is preferably human or animal urine, free of heavy metals or toxic organic molecules, with phosphate concentrations between 100-1000 mg / l and urea in the order 1-20 g / l.
10. PROCESSO, de acordo com a reivindicação 7, etapa a_, caracterizado pelo material adsorvente estar contido em um invólucro, como sachês ou estojos. A process according to claim 7, step a, characterized in that the adsorbent material is contained in a shell, such as sachets or cases.
1 1 . PROCESSO, de acordo com a reivindicação 7, etapa c_, caracterizado pela descontaminação do material adsorvente ser realizada pela utilização de NaCIO, 03, H202, luz UV artificial (lâmpada de Hg) ou natural (sol), combinados ou não.
1 1. A process according to claim 7, step c, characterized in that the decontamination of the adsorbent material is carried out by using NaCIO, 0 3 , H 2 0 2 , artificial (Hg lamp) or natural (sun) UV, combined or not. .
12. DISPOSITIVO para adsorção de fósforo e/ou nitrogénio de efluentes ou resíduos líquidos, caracterizado por compreender a composição definida pela reivindicação 1 , contida em um invólucro, como sachês ou estojos, que permita a passagem dos efluentes ou resíduos líquidos; retenha a composição, para reutilização; e apresente resistência química e mecânica. Apparatus for phosphorus and / or nitrogen adsorption of effluent or liquid waste, comprising the composition defined in claim 1, contained in a casing, such as sachets or cases, which allows the effluent or liquid waste to pass through; retain composition for reuse; and exhibits chemical and mechanical resistance.
13. ADITIVOS para condicionamento de solo e liberação de nutrientes, caracterizados por serem obtidos pelo processo definido pelas reivindicações 7 a 1 1 . Additives for soil conditioning and nutrient release, characterized in that they are obtained by the process defined by claims 7 to 11.
14. USO da composição definida na reivindicação 1 , caracterizado por ser na adsorção de fósforo e/ou nitrogénio para tratamento de efluentes industriais e/ou domésticos ricos em fósforo e/ou nitrogénio, ou como base para leito de armazenagem de rejeitos de aves. Use of the composition defined in claim 1, characterized in that it is in the adsorption of phosphorus and / or nitrogen for treatment of phosphorus and / or nitrogen rich industrial and / or domestic effluents, or as a basis for poultry tailings storage bed.
15. USO da composição definida na reivindicação 1 , caracterizado por ser na produção de aditivos para condicionamento de solo e liberação de nutrientes.
Use of the composition defined in claim 1, characterized in that it is in the production of additives for soil conditioning and nutrient release.
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