• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Nitrate adsorption process by active modified silica from rice straw ash. The present invention relates to a process of adsorption of water nitrates by active modified silica from rice straw ash, comprising the following steps: a) add silica from rice straw ash to a mixture of alcohol and water to obtain a suspension, b) add the catalyst to the suspension of step a) and keep under stirring at room temperature, c) add an aminoalkoxysilane compound to the mixture of step b) and stir, at room temperature, obtaining modified silica, d) continuous recirculation treatment of the modified silica obtained in step c) with an acid obtaining active modified silica, e) contacting the active modified silica obtained in step d) with the water from which the nitrates are to be removed. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2727673A1
    申请号:ES201930133
    申请日:2019-02-18
    公开日:2019-10-17
    发明作者:Carmem Tatiane Primaz；Martinez Neus Jornet；Navarro Lorenzo Sanjuan；Estopinan Cristina Elia Moliner；Falco Pilar Campins；Legua Carmen Molins；Greus María Desamparados Ribes；Valiente José David Badia；Juanes Roberto Teruel；Castell Oscar Gil；Barbara Bosio；Elisabetta Arato
    申请人:Universidad Politecnica de Valencia；Universitat de Valencia；Universita degli Studi di Genova；
    IPC主号:
    专利说明:

    [0001]
    [0002] NITRATE ADSORTION PROCEDURE BY MODIFIED SILICA
    [0003]
    [0004] Field of the Invention
    [0005]
    [0006] The present invention relates to a process of adsorption of nitrates in water or aqueous solutions by active modified silica from rice straw ash.
    [0007]
    [0008] State of the art
    [0009]
    [0010] Currently, nitrate contamination is a growing problem that affects both the quality of surface water and groundwater. The use of chemical fertilizers has increased considerably in recent decades, causing harmful environmental processes, including pollution of water resources. This contamination of water can have effects on human health through its intake, either dissolved in water or in food. The consumption of water with high concentrations of nitrates poses a health risk, since nitrates can form nitrosamines and nitrosamides, potentially carcinogenic compounds.
    [0011]
    [0012] Silica particles are widely used in many fields as filler, catalyst carrier, biological and medicinal materials. To improve application performance, their surfaces generally need to be modified by functional chemical groups. The surface of the silica particles can be modified by different processes and one of the most attractive is organofunctionalization, where the modifying and coupling agent is an organic group. A possible coupling agent may be 3-aminopropyltriethoxysilane (APTES) since it allows a fixation of molecules through their terminal amines and also exhibits self assembly. For its part, the Stober method is a widely used method for the synthesis of nanoparticles such as silica, where tetraethyl orthosilicate (TEOS) and other silicates combine in a mixture of water, ethanol and ammonia and are stirred to form particles. whose size depends on the concentration of solvents and silicate additives.
    [0013] In WO2012025943A1 a method is described for the purification of water using as filters, rice straw ashes functionalized with an aqueous solution of 3-aminopropyltriethoxysilane (APTES) to obtain RHA (rice straw ashes), and subsequently heated to get pretreated RHA to which a disinfectant is added.
    [0014] The documents “Humic acids removal from water by aminopropyl functionalized ríce husk ash; Journal of Hazardous Materials; 2010; Volume 184, Issues 1-3, Pages 775-781 " and" Evaluation of a rice husk filter system for rainwater treatment "Andrés Suárez, Paola Mesa, Víctor Bravo and Andrés Prieto; MUTIS, Vol. 5 ( 1) pp.
    [0015] 21-27, January-June 2015; DOI: https://doi.org/10.21789/22561498.1015; They refer to rice husk. In the first one, it is pretreated with HCl and thermally at 700 ° C and chemically modified with APTES for use as a suitable adsorbent for humic acids in water. While, in the second, the use of rice husk to filter the water is described without carrying out any functionalization treatment of the rice husk.
    [0016]
    [0017] Patent application US2007267349A1 describes the use of silica filter media treated with silane, such as rice husk ashes. In one of the examples, it refers to rice straw ashes functionalized with, among others, 3-aminopropyltrimethoxysilane for use in filters that are used for protein filtration.
    [0018] In the present invention, the modification of rice silica is described. Silica particles can be optionally treated with TEOS, while then APTES is added which modifies the surface of the silica and activates it. The silica obtained allows adsorption of the nitrates present (Figure 1) between 30 and 98%.
    [0019]
    [0020] Description of the invention
    [0021]
    [0022] In this document, the acronym "TEOS" refers to tetraethyl orthosilicate.
    [0023]
    [0024] The acronym "APTES" refers to the compound 3-aminopropyltriethoxysilane.
    [0025]
    [0026] The acronym "APTMS" refers to the compound 3-aminopropyltrimethoxysilane.
    [0027]
    [0028] Here, the expression "rice silica" is used with a meaning equivalent to "rice straw silica" and "rice straw ash silica", and they are used interchangeably.
    [0029]
    [0030] "Rice straw ash" refers to the residue that results from burning rice straw.
    [0031]
    [0032] "Ammonia" as used in the present invention refers to ammonia as an aqueous solution, from a solution of the ammonium chloride salt in water.
    [0033] "Ambient temperature" refers in this invention to a temperature between 5 and 35 ° C, more preferably between 15 ° C and 30 ° C.
    [0034]
    [0035] "Medium speed" here refers to a speed between 400 and 600 rpm, and preferably between 450 and 550 rpm, more preferably 500 rpm.
    [0036]
    [0037] In this document the expression "water nitrates" has a general meaning, which encompasses aqueous solutions, and therefore is used in an equivalent manner to the expression "water nitrates or aqueous solutions". Both expressions are also equivalent to "nitrates in water" or "nitrates in water or in aqueous solutions".
    [0038]
    [0039] In this document the term "room temperature" refers to a temperature between 10 and 35 ° C, preferably between 15 and 30 ° C.
    [0040]
    [0041] The present invention relates to a process of adsorption of nitrates in waters by active modified silica from rice straw ash.
    [0042]
    [0043] A first aspect of the invention relates to a process of adsorption of water nitrates or aqueous solutions by active modified silica from rice straw ash, which comprises the following steps:
    [0044] a) add silica from rice straw ash to a mixture of alcohol and water to obtain a suspension,
    [0045] b) add a catalyst to the suspension of step a) and keep under stirring at room temperature,
    [0046] c) add an aminoalkoxysilane compound to the mixture of step b) and stir, at room temperature, obtaining modified silica,
    [0047] d) treat by continuous recirculation the modified silica obtained in step c) with an acid obtaining the active modified silica,
    [0048] e) contacting the active modified silica obtained in step d) with the water or aqueous solution from which the nitrates are to be removed.
    [0049]
    [0050] It is important to note that the synthetic stages take place at room temperature (considered as a wide range between 10 ° C and 35 ° C, preferably 15 ° C to 30 ° C) since there is no need for extra energy consumption or instrumentation etc. to heat or cool the solutions.
    [0051] In step a) the rice straw silica is added to a mixture of alcohol and water under continuous stirring.
    [0052]
    [0053] In step a) the silica ratio of rice straw ash to alcohol and water mixture is between 100 and 200 mL of liquid per gram of silica, more preferably 120 mL of liquid per gram of silica (120/1).
    [0054]
    [0055] In a particular embodiment, the alcohol / water volume ratio in step a) is comprised between 3/1 to 6/1, more preferably 5/1.
    [0056]
    [0057] The alcohol of step a) can be selected from ethanol and methanol. In a preferred embodiment, the alcohol is ethanol.
    [0058]
    [0059] In step b) the catalyst is preferably added at room temperature as defined above, and preferably between 15 and 30 ° C, both temperatures included.
    [0060]
    [0061] The catalyst added in step b) is selected from ammonia, ammonium acetate, ammonium carbonate, magnesium oxide, calcium hydroxide, triethanolamine and dicyclohexylamine. More preferably, this compound is ammonia.
    [0062]
    [0063] In step b) the proportion of catalyst compound may be comprised between 0.05-1.5% (v / v) [ercentage of compound volume with respect to total volume], preferably 0.1-0.8% ( v / v) and more preferably 0.15-0.25% (v / v).
    [0064]
    [0065] Optionally, an alkoxysilane compound can be added in step b), which may be tetraethyl orthosilicate, trimethoxysilane or methyltriethoxysilane. Preferably, the alkoxysilane compound is tetraethyl orthosilicate. The alkoxysilane compound may be present in a proportion between 0.0-6.0%, preferably 0.0-4.5% and more preferably between 0-3% (v / v), [volume percentage of the compound with respect to volume total].
    [0066]
    [0067] In a particular embodiment, in step b) the mixture is kept under stirring for a time between 2 and 5 hours, preferably 2 to 4 hours and more preferably 3 hours.
    [0068] In a further particular embodiment, the stirring of step b) is carried out magnetically at a speed of 500 rpm for a time between 2 and 5 hours, preferably 2 to 4 hours and more preferably 3 hours.
    [0069] In another particular embodiment, the aminoalkoxysilane of step c) is selected from 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
    [0070]
    [0071] The proportion of aminoalkoxysilane compound may be 2 mL per gram of silica (2/1) and more preferably 1 mL per gram of silica (1/1).
    [0072]
    [0073] In stage c) the mixture of stage b) can be kept under stirring at an average speed of 400-600 rpm preferably at 500 rpm.
    [0074] The stirring time in this stage is between 2 and 12 hours, preferably between 3 and 9 hours, and more preferably between 5 and 7 hours.
    [0075] In a particular embodiment, the stirring of step c) is carried out magnetically at a speed of 500 rpm for a time between 2 and 12 hours, preferably between 3 and 9 hours, and more preferably between 5 and 7 hours.
    [0076]
    [0077] In another particular embodiment, the process further comprises a stage of decanting and air drying between steps c) and d) of the modified silica obtained.
    [0078]
    [0079] The volume of acid treatment in step d) may be between 6-20 times the mass of modified silica used, more preferably between 10-15 times the mass of modified silica used.
    [0080] In a particular embodiment, the acid from step d) is selected from hydrochloric acid and acetic acid. Preferably, the acid is hydrochloric acid. The hydrochloric acid may be in a concentration between 0.05-2M, preferably 0.05-0.6M, and more preferably between 0.08 and 0.2M, in a proportion 6-20 times the mass of silica, preferably 8 -15 times and more preferably 10 mL of acid per gram of modified silica.
    [0081]
    [0082] In the continuous treatment carried out in step d), the material obtained is treated for a time of 1 to 5 hours, preferably 2 to 3 hours, without heating.
    [0083] In a particular embodiment, in step e), the water or aqueous solution from which the nitrates are to be removed is passed through a column containing the silica. modified active obtained in step d), such that the flow of water or the aqueous solution passing through the solid is from 2 to 40 mL / min, more preferably 5 to 15 mL / min. Aliquots of 1 mL can be collected every 30 seconds and measured by visible ultraviolet spectrophotometry at 220 nm.
    [0084]
    [0085] According to particular embodiments, the process comprises:
    [0086] a) add rice straw ash silica to a mixture of alcohol and water in a proportion between 100 and 200 mL of liquid per gram of silica, more preferably 120 mL of liquid per gram of silica (120/1), obtaining a suspension,
    [0087] b) add catalyst to the suspension of step a) in proportion between 0.05-1.5% (v / v) [ercentage of compound volume with respect to total volume], preferably 0.1 0.8% (v / v) and more preferably 0.15-0.25% (v / v) and an alkoxysilane compound in proportion between 0.0-6.0%, preferably 0.0-4.5% and more preferably between 0- 3% (v / v) to the suspension of step a) and keep under stirring for a time between 2 and 5 hours, preferably 2 to 4 hours and more preferably 3 hours at 500 rpm speed and room temperature,
    [0088] c) add an aminoalkoxysilane compound in proportion 2 mL per gram of silica (2/1) and more preferably 1 mL per gram of silica (1/1) to the mixture of step b) and keep stirring for a period between 2 and 12 hours, preferably between 3 and 9 hours, and more preferably between 5 and 7 hours, at a speed of 500 rpm and room temperature, subsequently a decantation of the modified silica and air drying is performed,
    [0089] d) continuous recirculation treatment (Figure 11) of the modified silica obtained in step c) with hydrochloric acid between 0.05-2M, preferably 0.05-0.6M, and more preferably between 0.08 and 0, 2 M, in proportion 6-20 times the mass of silica, preferably 8-15 times and more preferably 10 mL of acid per gram of silica c), obtaining the active modified silica,
    [0090] e) the water or aqueous solution from which nitrates are to be removed is passed through a column containing the active modified silica obtained in step d), such that the water flow or the aqueous solution passing through of the solid is 5 to 40 mL / min, more preferably 10 to 20 mL / min. Aliquots of 1 mL can be collected every 30 seconds and measured by visible ultraviolet spectrophotometry at 220 nm.
    [0091] Prior to the process of the invention, the burning of rice straw is carried out by a known process. The burning process is produced by raising the temperature to 500 ° C. Burning time can last up to 8 hours.
    [0092] In order to carry out the process of the invention, the burned rice straw is previously obtained under conditions that may be, for example: burning the straw by means of a temperature ramp that reaches up to approximately 500 ° C in a time of 5 hours and with a Total heat treatment up to 8 hours. A concrete example with the rise in temperature and times is shown in Figure 3: The temperature is raised at a speed of 5 ° C / minute, maintaining a temperature of 180 ° C for one hour, again it rises to 310 ° C at a speed of 5 ° C / minute and one hour is maintained at 310 ° C, and it continues to rise at 5 ° C / minute to 450 ° C keeping 4 hours at this temperature, to then descend to 5 ° C / minute of descent speed
    [0093]
    [0094] Description of the figures
    [0095]
    [0096] In order to help a better understanding of the characteristics of the invention, a set of drawings is attached as an integral part of said description, where, as an illustration, the following has been represented:
    [0097]
    [0098] Figure 1: Shows a scheme of the stages of silica modification, according to a particular embodiment.
    [0099]
    [0100] Figure 2: Shows a graph of the thermal decomposition profile of rice straw with the thermogravimetry (TGA) technique.
    [0101]
    [0102] Figure 3: Shows a graph of temperature and burn times of rice straw.
    [0103]
    [0104] Figure 4: Shows some images of the study by SEM (180x, 500x, 500x) for ashes of rice straw.
    [0105]
    [0106] Figure 5: Shows a graph of the elementary mapping of the ash surface of rice straw.
    [0107]
    [0108] Figure 6: Sample modified active silica from rice straw
    [0109]
    [0110] Figure 7: Shows the infrared spectrum of rice straw ash, commercial silica and silica extracted from the rice straw ashes.
    [0111]
    [0112] Figure 8: Shows the infrared spectrum for silica and modified silica.
    [0113]
    [0114] Figure 9: Shows the results from the continuous adsorption test using a well water sample with a nitrate concentration of 45.67 ppm.
    [0115] Figure 10: Shows the results from the continuous adsorption test using a sample of waste water with a nitrate concentration of 172.24 ppm.
    [0116]
    [0117] Figure 11: Assembly of continuous recirculation of the analysis system.
    [0118]
    [0119] Examples
    [0120]
    [0121] Next, the invention will be illustrated by tests that demonstrate the effectiveness of the product of the invention.
    [0122]
    [0123] Example 1. Procedure for obtaining ashes from rice straw residues
    [0124]
    [0125] The recovery of rice straw residues is carried out according to a temperature controlled system according to the following characteristics:
    [0126]
    [0127] - Obtaining thermal decomposition profile of rice straw with the TGA technique (Thermogravimetry). Decomposition rate of 5 ° C / min in oxidizing atmosphere (Figure 2)
    [0128] - Definition of temperature ranges and burn times to ensure obtaining high quality ashes (figure 3).
    [0129]
    [0130] In this way, the first stage of decomposition ensures the complete elimination of moisture (up to T1), the second stage ensures the elimination of volatiles (up to T2) and the third oxidation of fixed carbon (above T3). Thus T3 can be defined as the minimum temperature that implies a complete combustion of rice straw and therefore a maximized amount of ash in amorphous state.
    [0131]
    [0132] Example 2. Procedure for obtaining ashes from rice residues
    [0133]
    [0134] 2.0 g of rice silica, from rice straw ash, was added to a mixture of 200 ml of ethanol and 40 ml of distilled water, under continuous stirring. Then a solution of 5.0 ml ammonia (30% by volume) and between 0 and 6.0 ml of TEOS (tetraethyl orthosilicate) were added to the suspension. The reaction was allowed to continue for 3 hours under stirring. Then 2.0 ml of APTES (3-aminopropyltriethoxysilane) was added and the mixture was stirred for 6 hours at room temperature, until the solution remained white and the sol-gel formed. After the reaction was completed, the products were collected by decantation and air dried, then the material was acidified by continuous recirculation, to protonate the amino groups with positive charges responsible for adsorption of anions. Recirculation was performed taking into account the following proportion: 1 g of the material obtained in 10 ml of 0.1 M HCl for 2-3 hours without heating. Silica residues containing nitrates will be delivered to a ceramic company for later inclusion in manufacturing processes.
    [0135]
    [0136] The study and characterization of the surface morphology of the ashes was carried out by scanning electron microscopy (SEM) and through X-ray energy dispersion spectrometry (EDS) analysis, it was possible to elementary mapping the surface of the materials and also a qualitative and quantitative reading of the chemical elements. For the analyzes a SEM-EDS device (SEM HITACHI S4800) was used. The samples were mounted on metal supports that were subsequently coated with a layer of platinum and gold for 2 minutes. The analyzes were carried out at room temperature with a voltage of 20 kV.
    [0137]
    [0138] The study by (SEM) and (EDS) for rice straw ashes is presented in sequence in Figures 4 and 5 and Table 1.
    [0139]
    [0140] Table 1 : Quantification of the main elements of the ash surface of rice straw.
    [0141]
    [0142] Spectrum 1
    [0143] Unn. C Norm. C Atom. C
    [0144] Element Series Error [wt.%]
    [0145] [wt.%] [wt. %] [at. %]
    [0146] Oxygen K-series 20.28 56.42 70.96 3.0 Magnesium K-series 1.32 3.67 3.04 0.1 Silicon K-series 9.71 27.01 19.36 0.4 Potassium K -series 4.63 12.90 6.64 0.2
    [0147] Total 35.94 100.00 100.00
    [0148]
    [0149] The ashes of the rice straw have an irregular and lamellar surface morphology, where the fibrous structure of the straw can also be observed, which remained even after burning. It is not possible to visualize pores on the surface of the material. The EDS result for this sample presented Si, O, K and Mg as the main components, with silicon and oxygen being the major components.
    [0150] Example 3. Characterization of the material obtained
    [0151]
    [0152] To evaluate the functional groups present in the samples of ash, rice silica and commercial silica, the Fourier Transformed Infrared Spectroscopy (FT-IR) analysis was performed. A Carry 630 FT-IR (Agilent) device was used. The spectrum was obtained with a resolution of 4 cm-1 in the range 4000-600 cm-1.
    [0153]
    [0154] Figure 7 presents the results of the FT-IR infrared analyzes for the purpose of comparing the spectra of commercial silica, rice silica and rice ashes.
    [0155] The three samples have very similar profiles, with the main adsorption bands at 1066 cm-1 and 809 cm-1, these bands represent vibrations for the Si-OH and Si-O-Si groups respectively indicating the main functional groups present on the surface and composition of the material.
    [0156]
    [0157] The results of the infrared analysis for the modified and unmodified rice silica are presented in Figure 8, and the characteristic bands 1525 cm-1 and 1637cm -1 corresponding to the NH bond vibrations of the amino groups can be observed of the modified silica.
    [0158]
    [0159] Example 4. Nitrate Adsorption
    [0160]
    [0161] Contact tests of the material with nitrate concentrations were performed, and a second test with distilled water (considered as white). Real water samples have also been processed.
    [0162]
    [0163] 5 ml vials with approximately 100 mg of the adsorbent material (active modified silica), 2 ml of distilled water for white and 2 ml of the nitrate-containing solution were used. A stir bar was introduced into all vials, and they were left on the magnetic stirrer, under constant stirring for 1 hour.
    [0164]
    [0165] After 40 minutes of contact the solution is transferred from the vial to test tubes, centrifuged for 30 minutes at a rotation of 6000 rpm (to avoid particles suspended in the solution) and then absorbance measurements are made in Carry spectrophotometer equipment 60 UV-Vis ( Agilent technologies). For all tests it It initially performs a measurement of distilled water for the baseline and the 25 mg / L nitrate solution is also measured for use as a standard.
    [0166]
    [0167] To calculate the adsorption percentage, the absorbance values of the pollutant must be selected, which for nitrates is 220 nm and a higher absorbance value, for example, 700 nm, for the correction of the baseline and was taken into account. It counts the contribution of the values of the targets made with distilled water, which are discounted from the absorbance values.
    [0168]
    [0169] The amount of nitrates adsorbed was calculated according to the value obtained for the nitrate standard and the value obtained for the solution that remained 40 minutes in contact with the adsorbent.
    [0170]
    [0171] On the other hand, a continuous test was also performed using the assembly of Figure 11 without recirculating the sample. In this case, about 150 mL of sample was passed through the active modified silica, which was retained in a column as specified below. Progressively, sample aliquots were collected every 30 seconds and analyzed by visible ultraviolet spectroscopy, observing that there was greater adsorption for the first aliquots, which was decreasing as the silica became saturated. These data can be seen in Figures 9 and 10, in which two types of samples with different nitrate concentrations are used.
    [0172]
    [0173] Adsorption values are reproducible and the functionalization process is efficient for application of rice silica as a nitrate adsorbent.
    权利要求:
    Claims (13)
    [1]
    1. Process of adsorption of water nitrates by active modified silica from rice straw ash, comprising the following steps:
    a) add silica from rice straw ash to a mixture of alcohol and water to obtain a suspension,
    b) add the catalyst to the suspension of step a) and keep under stirring at room temperature,
    c) add an aminoalkoxysilane compound to the mixture of step b) and stir, at room temperature, obtaining modified silica,
    d) continuous recirculation treatment of the modified silica obtained in step c) with an acid obtaining active modified silica,
    e) contacting the active modified silica obtained in step d) with the water from which the nitrates are to be removed.
    [2]
    2. The method according to claim 1, wherein the alcohol / water volume ratio in step a) is. 3/1 to 6/1.
    [3]
    3. The method according to claim 1, wherein the alcohol of step a) is selected from ethanol and methanol.
    [4]
    4. Method according to the preceding claim, wherein the alcohol is ethanol.
    [5]
    5. The process according to claim 1, wherein the catalyst added in step b) is selected from ammonia, ammonium acetate, ammonium carbonate, magnesium oxide, calcium hydroxide, triethanolamine and dicyclohexylamine.
    [6]
    6. Method according to the preceding claim, wherein the catalyst is ammonia.
    [7]
    7. The method according to claim 1, wherein in step b) an alkoxysilane compound is selected which is selected from tetraethyl orthosilicate, trimethoxysilane and methyltriethoxysilane.
    [8]
    8. The process according to the preceding claim, wherein the alkoxysilane compound is tetraethyl orthosilicate.
    [9]
    9. The method of claim 1, wherein the aminoalkoxysilane of step c) is selected from 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
    [10]
    Method according to claim 1, further comprising a stage of decanting and air drying between step c) and d) of the modified silica obtained.
    [11]
    11. The method according to claim 1, wherein the volume of acid treatment in step d) is between 10-15 times the modified silica mass used.
    [12]
    12. The method of claim 1, wherein the acid from step d) is selected from hydrochloric acid and acetic acid.
    [13]
    13. The method according to the preceding claim, wherein the acid is hydrochloric acid.
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    同族专利:
    公开号 | 公开日
    EP3929161A1|2021-12-29|
    ES2727673A8|2019-10-24|
    ES2727673B2|2021-03-03|
    WO2020169862A1|2020-08-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2012025943A1|2010-08-27|2012-03-01|Tata Consultancy Services Limited|Method for purifying water by contacting water with a porous rice husk ash and clay mixture and apparatus therefor|
    US7264728B2|2002-10-01|2007-09-04|Dow Corning Corporation|Method of separating components in a sample using silane-treated silica filter media|
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201930133A|ES2727673B2|2019-02-18|2019-02-18|NITRATE ADSORPTION PROCEDURE BY ACTIVE MODIFIED SILICE FROM RICE STRAW ASH|ES201930133A| ES2727673B2|2019-02-18|2019-02-18|NITRATE ADSORPTION PROCEDURE BY ACTIVE MODIFIED SILICE FROM RICE STRAW ASH|
    EP20759616.4A| EP3929161A1|2019-02-18|2020-02-14|Method for adsorbing nitrates by means of active modified silica from rice straw ash|
    PCT/ES2020/070099| WO2020169862A1|2019-02-18|2020-02-14|Method for adsorbing nitrates by means of active modified silica from rice straw ash|
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