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2.multinutrient Phosphate-Based Fertilizers From Seawater Bitterns PDF
2.multinutrient Phosphate-Based Fertilizers From Seawater Bitterns PDF
2.multinutrient Phosphate-Based Fertilizers From Seawater Bitterns PDF
ISSN: 0378-1844
interciencia@ivic.ve
Asociación Interciencia
Venezuela
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MULTINUTRIENT PHOSPHATE-BASED FERTILIZERS
FROM SEAWATER BITTERNS
SUMMARY
Seawater bittern, a by-product from seawater solar halite which is separated from the mother liquor by filtration, washed and
plants is rich, among other chemical elements in Mg, K and B. The dried. Under appropriate reaction conditions of pH 10 and 15ºC,
potential advantages of low solubility Mg-K-PO4 fertilizers for use for 60min, bittern density of 1.250g/ml, bittern dilution with water
in acidic tropical soils has been recognized. The salt can supply of 100% and stirring speed of 350rpm, it is possible to produce a
Mg, K and P over long periods of time since it has a low solubility, salt with 54% PO4, 18% Mg, 5% K and 0.05% B. The recovery
about 0.02g per 100g of water. A novel method is presented for the efficiencies were about 100% for PO4, Mg and K, and 90% for B.
recovery of the these elements from seawater bittern as a Mg-K- X-ray powder diffraction analysis showed the product to be mainly
PO4 salt also containing some B. The method consists, essentially, MgKPO4·3H2O and Mg3(PO4)2·4H2O. Some MgNaPO4·3H2O was
in mixing the NaH2PO4 with seawater bittern, followed by neutral- also present. SEM photographs of the crystalline product showed a
ization with NaOH solution to precipitate the multinutrient salt uniform crystal grain of orthorhombic shape and size of 20-75µm.
Introduction interesting separation methods the solid products obtained into the reactor. A Beckman
for the recovery of several and iii) to establish the size pH meter, with slurry type
Studies aimed to develop chemicals from seawater bittern and morphology of the crys- electrodes installed into the re-
and modernize agriculture in are predominantly conventional talline products. The main actor is used to follow the pH
tropical and subtropical regions processes of evaporation-crys- variables of the process inves- changes in the suspension. The
have revealed large differences tallization, cooling-crystalliza- tigated were: reaction tem- temperature in both units is
in soil types, generally of tion, solvent extraction, ion ex- perature and pH, and neutral- kept constant by cooling water
acidic nature, and nutrient con- change and salting out, and izing and digestion times. The circulated through the jackets
tents, as well as in crop types have been widely reviewed in basic chemical reaction de- of a constant temperature circu-
and nutrient requirements. The the literature (Kakihama et al., scribing the process is lating system.
need exists to know what 1993; Fernández-Lozano,
should be the correct level of 2001).
4MgCl2+KCl+3NaH2PO4+6NaOH→MgKPO4↓+Mg3(PO4)2↓+9NaCl+6H2O
water solubility for phosphatic New methods for the recov- (1)
base fertilizers and what ele- ery of Mg, K and B from sea-
ments a multinutrient fertilizer water bittern as PO4 complex
should contain (Quin, 1985; salts have recently been re- Methods Materials
Wilson, 1988; Sinden, 1990; ported (Fernández-Lozano and
Robesova et al., 2000). Colmenares, 1994; Rosas, Apparatus The reactants used in this
The fertilizer industry has 1995; Fernández-Lozano, 1996; work were residual bittern
recognized the potential advan- Fernández-Lozano et al., 1999; The experimental set-up is from a local seawater solar
tages of long term controlled Fernández-Lozano and Manili, presented in Figure 1, the main salt plant (density and compo-
release of Mg-K-PO4 salts. The 2000). The main differences item being the stirred batch re- sition in Table I), commercial
efficiency of these fertilizers for among these methods rest on actor. This is a cylindrical QVF grade monohydrated NaH2PO4
plant growth has been demon- the PO4 carrier and neutralizing glass vessel, 100mm internal and NaOH.
strated (Worthom, 1991; Will- agent used. In the present work diameter by 130mm height,
iam, 1995; Robesova et al., NaH2PO4 was used as PO4 car- equipped with a four-blade pro- Procedure
2000). rier and the neutralization was peller stirrer and two vertical,
Residual bittern produced as conducted with NaOH. evenly spaced, baffles. The in- The constant temperature cir-
a by-product from seawater so- The main objectives were: jector consists of two concen- culating bath was set to the de-
lar halite plants is rich, among i) to determine the effective- tric 80mm and 120mm internal sired temperature, with circula-
other chemical elements, in ness of NaH2PO 4 for the re- diameter glass tubes 150mm tion through both reactor and
Mg, P and B. However, with covery of Mg, K and B from long and a rotameter. This unit injector vessel jackets. Seawater
few exceptions these are residual seawater bittern, ii) to is used to feed the NaOH solu- bittern was charged into the re-
wasted back to the sea. Some determine the components of tion through a graduated device actor and sufficient amount of
José A. Fernández Lozano. Che- partment of Chemical Engi- Chemical and Petrochemical Cruz, Anzoátegui, Venezuela.
mical Engineer. Ms., Univer- neering, University of Oriente Processes, Núcleo of Anzoá- e-mail: braisf@hotmail.com
sity of Tulsa. Ph.D., Notting- (UDO), Venezuela. Coordina- tegui, UDO. Address: Apartado Lerida Sanvicente. Student of
ham University. Professor, De- tor, Center for Research in de Correos N° 4526, Puerto la Chemical Engineering, UDO.
Las salmueras marinas amargas son un producto secundario precipitar la sal multinutriente, que es separada del licor madre por
de las plantas solares de producción de NaCl (halita) del agua de filtración, lavada y secada. Bajo condiciones apropiadas de pH 10
mar, ricas en Mg, K y B. Las ventajas potenciales de los y 15ºC, durante 60min, densidad de salmuera 1,250g/ml, dilución al
fertilizantes de Mg, K y PO4 de baja solubilidad para uso en suelos 100% con agua y velocidad de agitación 350rpm, es posible
tropicales ácidos han sido reconocidas. Estas sales pueden suplir producir una sal con 54% PO4, 18% Mg, 5% K y 0,05% B. La
Mg, K y PO 4 por largos períodos de tiempo dada su baja eficiencia de recuperación fue de aproximadamente 100% para
solubilidad, aproximadamente 0,02g por 100g de agua. Se presenta PO4, Mg y K, y 90% para B. Análisis por difracción de rayos X
un método novedoso para la recuperación de estos elementos de revelan que el producto es principalmente MgKPO 4·3H 2O y
salmueras amargas como sales de Mg, K y PO4, conteniendo algo Mg3(PO4)2·4H2O. Algo de MgNaPO4·3H2O también está presente.
de B. El método consiste, esencialmente, en mezclar NaH2PO4 con Fotografías SEM del producto cristalino muestran cristales de grano
salmuera y seguidamente neutralizar con solución de NaOH para uniforme y forma rómbica y tamaño de 20-75µm.
RESUMO
As salmouras marinhas amargas são um produto secundário sal multinutriente, que é separado do licor matriz por filtração,
das plantas solares de produção de NaCl (halito) da água do mar, lavada e secada. Sob condições apropriadas de pH 10 e 15ºC,
ricas em Mg, K e B. As vantagens potenciais dos fertilizantes de durante 60 min, densidade de salmoura 1,250g/ml, diluição a
Mg, K e PO4 de baixa solubilidade para uso em solos tropicais 100% com água e velocidade de agitação 350 rpm, é possível
ácidos tem sido reconhecidas. Estes sais podem suprir Mg, K e produzir um sal com 54% PO4, 18% Mg, 5% K e 0,05% B. A efi-
PO4 por longos períodos de tempo, devido sua baixa solubilidade, ciência de recuperação foi de aproximadamente 100% para PO4,
aproximadamente 0,02g por 100g de água. Apresenta-se um méto- Mg e K, y 90% para B. Análises por difração de raios X revelam
do inovador para a recuperação destes elementos de salmouras que o produto é principalmente MgKPO4·3H2O e Mg3(PO4)2·4H2O.
amargas como sais de Mg, K e PO4, contendo algo de B. O mé- Algo de MgNaPO4·3H2O também esta presente. Fotografias SEM
todo consiste essencialmente, em misturar NaH2PO4 com salmoura do produto cristalino mostram cristais de grão uniforme e forma
e em seguida neutralizar com solução de NaOH para precipitar o rômbica e tamanho de 20-75µm.
TABLE III
EFFECTS OF pH ON COMPOSITION OF PRODUCTS AND RECOVERY OF REACTANTS
TABLE IV
EFFECTS OF DIGESTION TIME ON COMPOSITION OF PRODUCTS AND RECOVERY OF REACTANTS