WO2019092671A1 - Procédé d'ajustement des caractéristiques ioniques du sol et composition adaptée à cet effet - Google Patents

Procédé d'ajustement des caractéristiques ioniques du sol et composition adaptée à cet effet Download PDF

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Publication number
WO2019092671A1
WO2019092671A1 PCT/IB2018/058889 IB2018058889W WO2019092671A1 WO 2019092671 A1 WO2019092671 A1 WO 2019092671A1 IB 2018058889 W IB2018058889 W IB 2018058889W WO 2019092671 A1 WO2019092671 A1 WO 2019092671A1
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Prior art keywords
soil
sulphur
suspension
hydrophilic
aqueous suspension
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Ceased
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PCT/IB2018/058889
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English (en)
Inventor
Alberto Renato DE ANGELIS
Paolo Pollesel
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Eni SpA
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Eni SpA
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Priority to GB2007420.9A priority Critical patent/GB2582086B/en
Publication of WO2019092671A1 publication Critical patent/WO2019092671A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics

Definitions

  • This invention refers to a method for regulating the acidity and salinity of a soil.
  • this invention refers to a method for modifying and optimising the level of acidity and the mineral composition of a soil that has experienced soil salinization or changes in the optimal level of acidity as a result of natural phenomena or anthropic activities.
  • Soil salinization means the phenomenon of the accumulation of salts having a greater solubility product than that of gypsum. Most of the times, the salts are sodium-based (Na + ), and therefore salinization is recognised as one of the most dangerous soil threats, such as to produce serious consequences on the natural biological, biochemical, hydrological cycles and on erosive processes.
  • the direct impact on the soil loss of multifunctionality translates into a reduction and alteration of the balance of ecological processes and an accentuated limitation of agricultural production, causing a substantial reduction of arable land.
  • the increase in salinized surfaces is viewed as a socio-cultural problem, as the emergence of soils which are no longer cultivable due to soil salinity is one of the causes of the increase of migrants from the most disadvantaged areas.
  • Each soil has a natural content of salts, essential for plant growth, which can become excessive due to various natural and anthropic processes.
  • primary salinization is the case of soils derived from evaporitic rocks (consisting of soluble salts) such as those found in the inland areas of Arabicy and Sicily.
  • Another case of primary salinization is that of soils originating from the physicochemical alteration of rocks rich in carbonate minerals and feldspars. In wet areas, the salts released due to alterations are collected and removed by leaching soil profiles with meteoric water.
  • Soil salinity can also be caused by events such as the submersion of a pre-existing soil by marine waters (especially in low-lying areas facing the seas and oceans), or may occur due to the action of marine aerosol deposition along coastal areas. Soil salinization nowadays is mainly due to human activity (“secondary salinization”), and this is the main cause of desertification along the coasts of the Mediterranean and in large areas of the Near and Middle East.
  • Soil salinity is due to the presence of salts that are more soluble than gypsum, consisting mainly of inorganic solutes (mainly sodium, calcium and magnesium chlorides and sulphates).
  • salts that are more soluble than gypsum, consisting mainly of inorganic solutes (mainly sodium, calcium and magnesium chlorides and sulphates).
  • inorganic solutes mainly sodium, calcium and magnesium chlorides and sulphates.
  • the pH in saturated paste of saline soils does not exceed 8.2 and the high content of neutral soluble salts maintains flocculated the clay fraction, which is why the soils have a well defined structure.
  • the high osmotic pressure in the soil solution leads to a reduced water absorption by the roots of plants, with consequent radical stress and limitations in growth.
  • Salinization does not only have environmental and ecological repercussions but, by influencing production, generates negative effects also at an economic level. In particular, it represents one of the most important threats to sustainable agriculture, especially in arid and semi-arid regions.
  • gypsum is certainly the most frequent due to its accessibility and application at low cost compared to others.
  • the positive effects of gypsum are difficult to predict as they depend both on its solubility and on the movement of water along the soil profile
  • numerous experiments attest a noticeable improvement in the quality of saline and alkaline- saline soils with the use of sulphur (Hilal and Abd-Elfattah, see above) which, besides favouring an increase in crop production and quality, are able to improve soil features with positive effects on plant growth as described, for example in Zhang et al., "Study on the effect of S fertilizer application on crops and the balance of S in soil”; Journal of Agricultural Science, 1999, vol.
  • Elemental sulphur is considered an economic and successful soil improver for saline-sodium soils, in accordance with Kubenkulov et al. (in the publication "Reclamation efficiency of elemental sulfur on the soda saline soil", in World Applied Science Journal, vol. 23(9) (2013), pp. 1245-1252) they used elemental sulphur from the refinery as a soil saline-sodium soil improver and obtained interesting results.
  • literature describes the benefits of sulphur for various crops on saline-sodium soils such as corn, sunflower, rapeseed and wheat.
  • a first aim of this invention is therefore a method for modifying the chemical composition of the soil, of soil, comprising the treatment of said soil with a suitable amount of an aqueous suspension of hydrophilic sulphur with a concentration in S comprised between 0.5 and 300 g/L, preferably between 5 and 200 g/L, more preferably between 15 and 150g/L, pH comprised between 0 and 4, preferably between 0.5 and 2, said sulphur having an average granulometry of between 2 and 100 ⁇ (micron), measured with the "light scattering" method.
  • a second aim of this invention is also an aqueous suspension of hydrophilic sulphur suitable as soil improver, having the following features: concentration in S comprised between 15 and 300 g/L, preferably between 15 and 150 g/L, pH between 0 and 4, preferably between 0.5 and 2, PZC comprised between 1 and 3, said sulphur having an average particle size of between 2 and 100 ⁇ (micron), measured by the "light scattering" method.
  • oil refers to a polymorphic granular solid composite material of natural or artificial origin, suitable, or potentially suitable for the growth of plant organisms endowed with roots.
  • aqueous suspension means a suspension of a solid particulate in a liquid consisting of more than 80%, preferably over 90%, of water, which may possibly comprise other components, such as for example, suspending agents, emulsifiers, organic solvents such as alcohols, fertilisers, plant protection products and other products useful for agriculture, traces of salts such as salts contained in mineral water and groundwater.
  • Figure 1 represents a typical laboratory apparatus for the treatment of soil based on the method of this invention and the collection of the percolate to be analysed.
  • the aqueous suspension of hydrophilic sulphur suitable for the process according to this invention can be generally obtained by making sulphur dioxide and hydrogen sulphide react in an aqueous liquid medium, preferably water, to reach the desired sulphur concentrations.
  • a preferred method for preparing oligomeric hydrophilic sulphur suspensions suitable for the method of this invention is the process described in the aforementioned international patent application WO2005/095271 (in the Applicant's name), the contents of which have been included in this application by reference.
  • a gaseous stream of H 2 S preferably diluted with an inert gas with concentration between 5 and 35% in terms of volume of H 2 S
  • S0 2 which is absorbed in water
  • the solution thus obtained is made to react with H 2 S, preferably in gaseous form, by simple contact, preferably by bubbling or another suitable method of gas distribution in the liquid, at a temperature equal to or lower than 100°C, preferably between 5°C and 40°C, more preferably at room temperature.
  • reaction (I) of elemental sulphur formation is obtained:
  • suspensions obtained with the previous process are characterised by properties particularly suitable for use according to the method of this invention, as they contain sulphur in a very pure and finely dispersed form in water, which is therefore already prepared for distribution in the soil. Moreover, the process described to obtain them is easy to apply even on a small scale.
  • the hydrophilic sulphur suspension does not include suspension agents or emulsifiers and is more preferably essentially constituted by S (also in the form of polythionic acids) and water.
  • suspension agents known to be suitable for the purpose can be added, such as, for example, 0.1% by weight of Agar-agar.
  • the hydrophilic S aqueous suspension in accordance with this invention preferably has a stability of at least 10 days, preferably at least 30 days, more preferably at least 60 days, where by stability what is meant is the number of days after which the suspension produces a sediment greater than 0.5 % in volume in an Imhoff Cone, applying the method and the equipment as reported in the literature, for example in the publication by APHA, AWWA, WEF (1998): “Standard Methods for the Examination of Water and Wastewater", XX Ed. (Washington, APHA), pages 2-54/2-59.
  • the Applicant however, has verified that any sediments produced, even after months of racking, can be removed in a stable manner (within the meaning of what has been mentioned above) purely by mechanical stirring.
  • the stable aqueous suspension of hydrophilic sulphur which can be used in accordance with this invention comprises, in mixture, both neutral molecular sulphur, having the known orthorhombic crystalline structure formed by cyclic molecules predominantly of the S 8 formula, and sulphur with a linear structure, essentially constituted by polythionic acids having chains from 2 to 80, preferably from 3 to 60, S atoms and their ends are bonded to -SO3H groups (in the protonated form), or -S03 ⁇ (in the dissociated form), which, besides favouring the stabilisation of the suspension, confer high acidity to the latter, usually having pH values (measured directly on the suspension at room temperature) ranging from 0 to 4, preferably from 0.2 to 2.0, more preferably lower than 2.0, even more preferably from 0.5 to 1.95.
  • said hydrophilic S suspensions comprise from 0.05 to 10.0 %, preferably from 0.1 to 5 %, by weight of polythionic acids, with respect to the total weight of the suspension.
  • the hydrophilic sulphur in the stable aqueous suspension of this invention is in the form of suspended particulate matter having a medium particle size, in terms of average particle diameter, ranging from 1 to 100 ⁇ (microns), preferably between 2 and 30 ⁇ , measured with the light scattering method using a laser diffraction granulometer.
  • the stable hydrophilic sulphur suspension shows a PZC (point of zero charge) comprised between 1 and 3, measured by potentiometric titrations with various ionic strengths, at increasing concentration of transport electrolytes, as described in Int. J. Electrochem. Sci., 7 (2012) 6142 - 6153.
  • the aqueous hydrophilic sulphur suspension is distributed on the soil to be treated by means of suitable techniques and equipment suitable for the purpose, normally used by sector operators for similar distribution operations of suspensions or aqueous suspensions such as spreaders, sprayers, etc.
  • suitable techniques and equipment suitable for the purpose normally used by sector operators for similar distribution operations of suspensions or aqueous suspensions such as spreaders, sprayers, etc.
  • the choice of hydrophilic sulphur suspension quantities to be distributed on the soil and of the most suitable application method is within the reach of the technician with normal technical knowledge, without the need for further original solutions. In particular, it is possible to choose a wide range of values, depending on the soil's saline features and acidity, concentration of the suspension, compatibility with organisms already present in the soil, desired recovery times.
  • the amount of said aqueous suspension is preferably selected so that the average amount of S distributed in the soil is between 10 and 500 g/m 2 of soil, preferably between 50 and 300, g/m 2 of soil, more preferably comprised between 100 and 300, g/m 2 of soil.
  • Suitable soils for the method of this invention may be all soils characterised by a saline or acidity imbalance with respect to values deemed as normally suitable or tolerable for the desired cultivation, as reported in scientific and technical-applicative publications of the agricultural sector.
  • Particularly suitable soils are those having a pH (measured as hereinafter specified) greater than or equal to 6.5, preferably greater than or equal to 7.0, and / or a saline concentration such as to result in an electrical conductivity of the medium greater than 1.0 dS m "1 , preferably greater than 2.0 dS m "1 .
  • Soil electric conductivity is measured by a conductivity meter on an aqueous extract of the soil obtained by treating lOg of soil with 250 mL of distilled water.
  • the method of this invention can, however, be applied also to soils having acceptable values of pH and electrical conductivity, but that are unbalanced with respect to the concentration of one or more specific salts.
  • the salt content of treated soils in particular the Na, Ca, Mg, Al content
  • the soil treatment method entails a more rapid and effective fertilisation, understood as an improvement in the growth and rooting of cropland with respect to the treatment with the same quantities of commercial granular sulphur.
  • a solution of sulphur dioxide and a gaseous stream containing hydrogen sulphide is made to react during an aqueous phase.
  • the reaction product consists of highly hydrophilic sulphur, able to give stable suspensions in water for a long period.
  • the reaction is carried out in a bench-top system, maintained at 25°C by means of a thermostatic bath, comprising a 5 L glass reactor equipped with mechanical stirring, and lines for feeding the gaseous H 2 S.
  • a portion of 50 g of the suspension thus prepared was dried under high vacuum (lOPa), obtaining a sulphur residue weighing 4.15 g. Assuming the residue consists only of sulphur and polythionic acids, a sulphur concentration in the suspension is calculated equal to 8.02% by weight with respect to the total weight of the suspension.
  • the suspension of S thus obtained remained stable for at least 30 days, during which the soil treatment tests were prepared.
  • the experimental system was set up as shown in Figure 1, by means of glass columns with an internal diameter of 8 cm and a height of 1 cm, equipped with a PTFE tap, supported by sample-holding columns.
  • a percolated filtration system has been placed, composed of an absorbent paper disc with a porosity of about 20 ⁇ with 2-3 g of glass wool on top.
  • the pH of the hydrophilic S suspension and eluate samples is determined by direct immersion into the liquid of an electronic pH meter probe.
  • the pH is the measure of the soil's reaction.
  • a 10 g of sample for each type of soil was placed in a plastic container and deionized water was added to the soil: water ratio of 1 :2.5. The mixture was placed in a mechanical stirrer for 2 hours and allowed to stand for 30 hours to allow the deposit of the particles.
  • electrodes in this case semi-micro electrodes
  • a reference electrode Al
  • a thin glass bulb to separate the solution to be measured from an acid with a known, saturated AgCl concentration.
  • the two electrodes are connected by a salt bridge consisting of a 4M KC1 solution, saturated by AgCl; on the glass bulb an electric voltage is created which is proportional to the concentration of H + of the suspension of the soil to be measured.
  • the instrument is calibrated with reference solutions of known concentrations (pH 4, 7 and 10). Once the calibration is complete, the electrode is washed with distilled water, dried and immersed in the sample.
  • ICP-OES Inductively Coupled Plasma
  • the experimentation was conducted on five different soils: one volcanic, two alkaline and two alkaline-saline.
  • the soils chosen for the experiment have been selected on the basis of specific geological and pedological features.
  • a sulphur quantity equal to 2 grams is then introduced from the top of the column, except for the control examples.
  • the commercial sulphur powder of the comparative examples is introduced as such, without preliminary suspension in water.
  • the hydrophilic sulphur suspension according to the invention is introduced in a quantity equal to 24 mL.
  • the column is eluted for each soil sample with distilled water, adding a portion of 50mL in about 18-30 hours and collecting the eluate until the supernatant liquid layer disappears. The same operation is repeated every 5 days for a duration of the experiment of 90 days in total, bringing together the eluates for each soil.
  • the elements of interest were quantitatively determined on the overall collection.
  • the soil's pH and electrical conductivity were also measured at the end of the treatment. The results are shown in the following table 2.

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne un procédé de changement et d'optimisation du niveau d'acidité et de la composition minérale d'un sol qui a subi une salinisation ou des changements du niveau optimal d'acidité en conséquence de phénomènes naturels ou d'activités anthropiques, ledit procédé comprenant le traitement du sol avec une suspension aqueuse de soufre hydrophile ayant des caractéristiques particulières d'acidité et de granulométrie de la phase en suspension. Le traitement ci-dessus permet simultanément une fertilisation rapide du sol et est une manière plus rapide et plus efficace d'éliminer l'excès de soufre résultant des processus de purification de combustibles fossiles.
PCT/IB2018/058889 2017-11-13 2018-11-13 Procédé d'ajustement des caractéristiques ioniques du sol et composition adaptée à cet effet Ceased WO2019092671A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB2007420.9A GB2582086B (en) 2017-11-13 2018-11-13 Method for adjusting the ionic features of a soil and composition suitable for the purpose

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102017000128986 2017-11-13
IT201700128986 2017-11-13

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WO2019092671A1 true WO2019092671A1 (fr) 2019-05-16

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB202613A (en) * 1922-08-16 1923-12-27 Heinrich Vogel Process for the manufacture of colloidal sulphur
US3186826A (en) * 1963-10-09 1965-06-01 Rendon Margarita Del Muro De Soil improver and process for preparing same
GB2228490A (en) * 1989-02-23 1990-08-29 Sandoz Ltd Oxidised sulfur dye dispersions purified by membrane separation
EP0949221A1 (fr) * 1998-04-06 1999-10-13 Holland Chemical International N.V. Composition utilisable comme engrais contenant du soufre sous forme d'un acide polythionique ou d' un de ses sels
WO2000078893A1 (fr) * 1999-06-18 2000-12-28 Ultimate Products (Aust) Pty Ltd Amendement synthetique liquide
WO2005095271A2 (fr) * 2004-03-31 2005-10-13 Eni S.P.A. Procede de production de soufre a partir du sulfure d'hydrogene contenu dans le gaz naturel ou dans le gaz associe et elimination eventuelle du soufre ainsi obtenu
EP2629606A2 (fr) * 2010-10-18 2013-08-28 Ceradis B.V. Nouvelles préparations à base de bio-soufre
WO2016097378A1 (fr) * 2014-12-19 2016-06-23 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un agent d'amélioration de sol contenant du soufre

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB202613A (en) * 1922-08-16 1923-12-27 Heinrich Vogel Process for the manufacture of colloidal sulphur
US3186826A (en) * 1963-10-09 1965-06-01 Rendon Margarita Del Muro De Soil improver and process for preparing same
GB2228490A (en) * 1989-02-23 1990-08-29 Sandoz Ltd Oxidised sulfur dye dispersions purified by membrane separation
EP0949221A1 (fr) * 1998-04-06 1999-10-13 Holland Chemical International N.V. Composition utilisable comme engrais contenant du soufre sous forme d'un acide polythionique ou d' un de ses sels
WO2000078893A1 (fr) * 1999-06-18 2000-12-28 Ultimate Products (Aust) Pty Ltd Amendement synthetique liquide
WO2005095271A2 (fr) * 2004-03-31 2005-10-13 Eni S.P.A. Procede de production de soufre a partir du sulfure d'hydrogene contenu dans le gaz naturel ou dans le gaz associe et elimination eventuelle du soufre ainsi obtenu
EP2629606A2 (fr) * 2010-10-18 2013-08-28 Ceradis B.V. Nouvelles préparations à base de bio-soufre
WO2016097378A1 (fr) * 2014-12-19 2016-06-23 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un agent d'amélioration de sol contenant du soufre

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GB2582086A (en) 2020-09-09
GB2582086B (en) 2022-04-13

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