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Rice Husk Derived Nano Zeolite (A.M.2) as Fertilizer, Hydrophilic and Novel Organophillic Material

Hassan AZA, Abdel Wahab M Mahmoud, G. Turky*

Department of Microwave Physics & Dielectrics, National Research Centre (NRC), 33 El Bohouthst.(former ElTarirst.), Dokki, Giza, P.O.12622, Egypt

Abstract: The investigation aimed to convert mixture rice husk with aluminum foils (as houses and restaurants wastes) into Nano Zeolite (NZ) enrich by elements, safety, and eco-friendly fertilizer using calcinations and zeolitization processes. The end product has undergone various techniques: Crystallization, phases, physic-chemical characteristics and surface morphology were studied. Transmission electronic microscope (TEM) appeared the crystals of NZ in nano size (uncontrolled growth particles), using scanning electron microscope (SEM) coupled with energy dispersive spectroscope (EDS) showed that NZ gave different shapes and size during calcinations process, Stereo microscope illustrated that, the crystals growth of NZ were in three dimensions and take different shapes after calcinations and zeolitization processes. X-ray diffraction (XRD) recorded that the dominant mineral was zeolite with accessories minerals. X-ray fluorescence (XRF) was used to verify the type of NZ and whether if it is hydrophilic or hydrophobic. Furthermore, the XRF revealed a high composition of silica and alumina in Nano material with high Si/Al ratio, potassium and calcium were the major single extra-framework cations in NZ. Surface area values, pore sizes distribution, pore volume, pore width, two and three dimension images and roughness particles were estimated using atomic force microscope (AFM). The highest CEC value of NZ was recorded. Light microscope showed that, nitrogen fixing and phosphorus solubilizing bacterial cells were existing on NZ particles as novel carrier material (consider as organophillic). In addition to previous analyses, dielectric and electrical properties measurements were examined for NZ particles using broadband dielectric spectroscope (BDS). NZ particles have been proved to be hydro-cracking, has characteristics of Faujasite family and could enrich soil fertility and improve plant growth particularly in arid and semi arid zones.

Keywords: aluminum foils, calcinations, hydrophilic, hydrophobic, nano zeolite, rice husk, zeolitization

Citation: Hassan AZA, Abdel Wahab M Mahmoud, G. Turky, Rice Husk Derived Nano Zeolite (A.M.2) as Fertilizer, Hydrophilic and Novel Organophillic Material. American Journal of Nanomaterials, 5 (1). 11-23. January 2017. doi:10.12691/ajn-5-1-3

1. Introduction

The total amounts of rice annual world production about 80 million tons [1,2,3]. It is depicted that nearly 0.23 tons of husk was formed for every ton of rice product hence, open burning for agricultural land clearing was mainly practiced in many countries, Rice straw after harvesting vulnerable to intensive open burning during the dry season, which led to the ambient air pollution. Example case study like most Asian countries, where rice is the major agricultural product, the area of annual harvested rice paddies, including both the major crop (growth season: May-October) and minor crop (November-April), is about millions hectares [4]. The rice paddies during the high harvesting season (November- December) about 90% of them were burned. A large amount of pollutants were emitted due to open burning of rice straw (RHA) in the field is incomplete combustion in nature including toxic gases such as (carbon monoxide (CO), carcinogenic polycyclic aromatic hydrocarbons) fine/inhalable particles and volatile organic compound (VOC), [5,6,7]. Smoke which resulting from rice husk burning (RHA) has been potentially toxic [8,9]. Smoke release into the atmosphere, those pollutants migrate to the surrounding areas, and then undergraduate physical and chemical conversion eventuality harmful effects on human health, an outstanding example to increased asthma attacks in children in a prefecture in Japan [10]. Agricultural wastes in many countries after intensive burning contribute to the appearance of the atmospheric brown cloud that affects the quality of local air, earth climate and atmospheric visibility [11,12]. Evaluation of the effect of the open burning for rice straw on the air quality is challenging as those fires occur during short periods, in small rice paddy areas which distributes over a vast area.

In Egypt the amount of rice straw discarded annually is around three million tons, then it was burnt to release nutrients for the next growing season at harvesting time, and to get rid of the huge quantity of it. So the process accumulation of residue rice straw was considered disadvantage, but rice husk derived silica nano particles were used for catalysis, in many fields such as ceramics and chromatography [13,14]. the disposal of bulky RHA could be a problem caused by its black or gray color and has a light weight, but adsorbent metal ions such as Cd2+, Zn2+, and Ni2+, and heavy metal such as lead , mercury and make purification for aqueous solution [15]. When Rice husk burning it gives 14–20% ash, which contains 80–95% silica in the crystalline form and few amounts of metallic elements. Amorphous silica of ultra fine size and reactivity can be produced via time and temperature control of burning process. Silica with high purity was produced by Pretreatment of the husk with mineral acids followed by controlled ash produced, and it is consider as a source for preparing advanced materials (e.g. Sic, Si₃N₄, elemental Si and Mg₂Si). [16]

Recent researches reported that, rice husk ash (RHA) was used as a silica source for zeolite Beta synthesis because it is an agriculture waste containing crystalline tridymite and α-cristobalite [17]. Moreover, to produce high purity amorphous SiO₂ for use in the synthesis of ZSM-5 zeolite and silicate, the hydrothermal processes were done [18]. Also (RHA) was used from combustion boiler for energy for synthesis of sodium silicate. The silicate was obtained by means of ash fusion with sodium hydroxide at a temperature of 1200°C for 2 hours. For the synthesis of 4A-zeolite was performed hydrothermal reaction of sodium silicate [19].

In Egypt after rice harvesting the farmers used to burn the rice husk to avoid the high costs of accumulation and transportation processes out fields which consider disadvantage way out. In present research we spare no efforts to convert rice husk mixed aluminium foil (as a houses and restaurants wastes)into nano zeolitic materials (NZ)enrich by potassium as novel safety fertilizer, hydrophilic, organophillic material (fitting for living beneficial microorganisms represent in two strains of bacteria, Azotobacter chroococeom for nitrogen fixation to compensate the deficiency of nitrogen inside zeolite and Bacillus megaterium for phosphorus solubilizing)and environmental friendly product to pass up atmospheric black cloud and its harmful effects.

2. Materials and Methods

2.1. Chemical analysis of Rice Husk

This research was conducted in November 2014. Rice husk was obtained from a rice mill located in Sharkyia province of Egypt, then divided into two equal weight, the first amount was crushed into small parts and used as control which mixed with aluminium foil 100:1 w/w, and then spread on plastic trays and other extraneous materials like broken rice grains were removed. Rice husk were digested then, chemically analyzed according to [20] Table 1.

Table 1. Chemical analysis of rice husk

Same previous steps were followed with the second amount of rice husk then added 10 ml from TEOS (chemical reagent for bonding destruction and catalysis of chemical reactions) as a precursor and source of silica then the mixture dropped by NaOH (50 ml) as a caustic media. The mixture was left over night, then was transformed into autoclave under 1.5 (P.S.I.), for three days. Then mixture was transformed into oven at different calcinations temperature starting as follow: (200, 300, 400, 500, 600, 700, 800, 900 and 1000°C) for 5 days. After completion of crystallization some vis. Instruments were done to identify the NZ particles as follow:

EDX, scanning electron microscope (SEM) model JSM.6390LA (JEOL) analytical scanning electron microscope was done at Holding Company for Drinking Water and Waste Water, Greater Cairo Company for Drinking Water, Central Laboratory.

TEM transmission electronic microscope Model JEOL (JEM-1400 TEM) was used as a technique capable to magnification image of a thin samples with about 1 million times. It is consider accurate tools for visualization at the nano scale at TEM lab (FA-CURP) Faculty of Agriculture Cairo University Research Park.

.Stereo microscope LEICA M216 was used to show the growth of crystals of NZ in three dimensions at Cairo univ. Faculty of Agric. Microbiology Research Lab.

XRD Analysis of NZ particles was determined using X-ray diffraction of powder samples. For sample EMPYREAN diffract meter, with Anode material Cu, generator setting at 45 kV, 30 m A was used. A step size of 0.0260° 2θ and a counting time of 4 second per step were applied over a 2θ range of 5.01313° to 79.9711°, at National Research Centre, Giza. Egypt.

X-ray fluorescence analysis (XRF) of NZ particles was determined by using Axioms, sequential, Wdxrf Spectrometer analytical 2005, at National Research Centre, Giza. Egypt.

Atomic force microscope (AFM) at Cairo University, Faculty of Science, Micro Analytical Center, Atomic Force Lab.

2.2. Dielectric and Electrical Measurements

Broadband dielectric spectroscopy (BDS) was employed to study the dielectric and electrical properties of the prepared NZ. In the frequency range 0.1 - 10 MHz The measurements were carried out isothermally every 5 C from 20 to 60 C. The temperature of the sample is controlled by a Quattro Novo control cryo system with temperature stability better than 0.1 C. The dielectric function ε* (= ε'- iε") was measured in parallel plate geometry. Details about the used technique can be found in many recent publications [21].

2.3. Ion Exchange Capacity Analysis

The pH titration method was used to determine the cation and anion exchange capacity of formed NZ [22].

2.3. Preparation of Azotobacter chroococeom and Bacillus megaterium Strains for Loading on Nano Zeolite (NZ)

Both strains of bacteria were provided by Microbiology department, soil, water and environment Research Institute, Agric. Res. Center (ARC), Giza, Egypt. Azotobacter chroococeomt was grown on modified Ashy, s medium [23]. Liquid cultures of A. chroococcum (10⁸ CFU/ml.) in 250ml conical flasks were grown on modified Ashby, s medium for five days at 28-30°C. Whereas Bacillus megaterium active strain was cultivated in 250 ml. conical flasks containing 100 ml. Pikovskaya medium [24] for three days at 30°C, then strain enriched an nutrient broth medium [25] for 48 hr. at 28°C to reach (1*10 ⁸ cell/ml.).

After preparation of two strains we mixed nano zeolite NZ with determine amount of both strains solution of and observed the growth of colonies for three days. Light microscopy was used to observe the growth of two strains imbedded in NZ (A.M.2) formed.

3. Results and Discussion

3.1. Stereo Microscope Study

Figure 1 involved images (a, b, c and d) showed that water molecules attached to synthesized rice husk derived nano zeolite particles and surround by water film (a, c) meanwhile, in (b, d) images show that the particles of nano zeolite grown in three dimension and has hydrocracking with different shapes.

Figure 1. Images (a,b,c, and d) Rice husk with aluminum foil derived NZ particles using calcinations and zeolitization processes

From Figure 2, images (a, b, c, and d) after calcinations and zeolitization processes NZ (A.M.2) particles enhanced that the completion of crystallization gave conglomerates (aggregates) with cloud shapes. These nano particles take three dimensions in their growth (uncontrolled growth particles) [26].

Figure 2. images (a, b, c, and d) NZ (A.M.2) particles after calcinations and zeolitization processes

3.2. SEM –EDX Study

Figure 3, images (a, b, c and d) of NZ (A.M.2) particles after calcinations and zeolitization processes showed conglomerates (aggregates) of compact crystals, with thin fibers. Some particles of NZ (A.M.2) had monoclinic symmetrical blades with a coffin-like shape, where as the sight particles composed mainly of flaky material with little crystals.

Figure 3. images (a, b, c and d)NZ (A.M.2) particles after calcinations and zeolitization processes

Concerning Figure 4, images (a, b, c, and d) it was observed that, thin fibers were also presented, the particles showed cluster crystals, these crystals assemblage occurred as plates cluster closely together, while the flaky materials were associated with the crystals minerals such as halite, siderite, quartz, aluminum silicate, hematite, and dolomite, which is consistent with the later XRD results. Generally Clinoptilolite has coffin-shaped crystals and occurs in monoclinic symmetries.

Figure 4. images (a, b, c and d) NZ (A.M.2) particles after calcinations and zeolitization processes

Figure 5 images (a, b) clarify that, NZ (A.M.2) particles were formed conglomerates including pores different in their diameters with range from 1.40 to 9.40 µm. Moreover images(c, d) showed that the circumferences of conglomerate particles were ranged between 412.51 µm- 1.04 mm. In addition, images (e, f) showed that the coarse grained crystals of NZ (A.M.2) have three axis dimensions (X, Y, and D µm.) more than Nano dimension (nm).

Figure 5. images(a, b, c, d, e and f) NZ (A.M.2) particles after calcinations and zeolitization

3.3. Specimen Atoms Mapping of Pure Elements of Conversion Rice Husk with Aluminium Foil into NZ (A.M.2) Particles

The EDX method able to identify the nature of the atoms present in the sample at a depth of 100-1000 nm from the surface reveals the distribution of the O, Al, Si, Na, K. It can be observed the spreading of particles in irregular shapes. Figure 6 including images of atoms distribution and Table 2 illustrated that the images of specimen atoms mapping of NZ after calcinations and zeolitization processes the alumina was the majority component of NZ while silica took second place. the elements and atom ratios between Si/Al were (0.22 and 0.21) these ratios indicated that, rice husk with aluminium foil converted into Nano zeolite became hydrophilic and organophillic material .The most abundant single extra-framework cations in nano zeolite sample was found to be sodium(Na) and potassium (K), making nano zeolite enrich by potassium .Nano zeolite of low Si/Al ratio for both elements and atoms less than 4, meaning with high content of aluminium elements and atoms, tend to be hydrophilic and organophillic. These results are convenient with the International Mineralogical Association, Commission on New Minerals and Mineral Names’s (IMACONMMN) third rule, only heulandite and clinoptilolitezeolites can exclusively be discriminated on the sources of the silica and aluminium skeleton. Heulandite has a Si/Al ratio of less than 4, whilst clinoptilolite has a Si/Al of equal or more than 4. Zeolites of low Si/Al ratio (less than 4), denotation with high aluminium atoms content, lean to be hydrophilic and organophillic, whilst a high silica zeolite will tend to be hydrophobic. [29]

Figure 6. (image 1 and Table 2) of specimen atoms mapping of pure elements of NZ (A.M.2) particles after calcinations and zeolitization processes

Table 2. Specimen atoms of pure elements of NZ (A.M.2) particles after calcinations and zeolitization processes

3.4. Specimen Atoms Mapping of Elements Oxides of Conversion Rice Husk with Aluminium Foil into NZ (A.M.2) Particles

Figure 7 (image 2 and Table 3)enhanced the images of specimen atoms mapping of NZ (A.M.2) particles from rice husk and aluminium foil after calcinations and zeolitization processes, the alumina oxide was the majority component of NZ (A.M.2) followed by silica oxide as the second component .The elements oxides and atom ratios between Si/Al were (0.18 and 0.17) these ratios indicated NZ (A.M.2) particles became hydrophilic and organophillic material as mentioned previously above. [29].

Figure 7. (image 2 and Table 3) Specimen atoms mapping of elements oxides of NZ (A.M.2) particles by using calcinations and zeolitization processes

Table 3. Specimen atoms of elements oxides of NZ (A.M.2) particles by using calcinations and zeolitization processes

3.5. Specimen Atoms Mapping of Conversion Rice Husk with Aluminium foil into Nano Zeolite

Figure 8 (image 3 and Table 4) augmented the images of specimen atoms mapping ofNZ (A.M.2) after calcinations and zeolitization processes that the alumina compound was the mainstream component of NZ (A.M.2) particles followed by silica compound as the second component, then the last compounds were occupied this categories Na, K, Mg, Fe, S, Ca, P .the compounds ratio between Si/Al were (0.26) these ratio indicated that NZ (A.M.2) became hydrophilic and organophillic material.

Figure 8. (image 3 and Table 4) Specimen atoms mapping of compounds of nano zeolite after conversion rice husk and aluminum foil by using calcinations and zeolitization processes.

Table 4. Specimen atoms of compounds of NZ (A.M.2) particles by using calcinations and zeolitization processes

3.6. Dielectric and Electrical Investigations

BDS is employed to measure the permittivity, ε' and dielectric loss, ε'', of the produced NZ as well as the real conductivity, σ', and the dissipation factor tan (δ) on a wide frequency band ranging from 0.1 Hz up to 1 MHz and at temperatures from 20 to 60°C. These dielectric parameters are equivalent and related to each other as expressed by the following equations:

[picture] | (1)

[picture] | (2)

[picture] | (3)

In which εo, the vacuum permittivity and ω is the radial frequency.

Typical dielectric and electrical parameters are illustrated graphically in figure (Ga1) against frequency and at temperatures as indicated. Similar behavior is shown for both real and imaginary parts of the complex dielectric function, implying that they are not independent. Both parameters increase gradually with decreasing frequency. Remarkable effect of temperature could be noticed at lower frequencies that all the considered parameters increases by increasing temperatures. This is due to the expected thermal dynamics of the molecules and the groups on the surface of NZ. The effect of the change of temperature decreases gradually with increasing frequency this indicated that the frequency plays the main role on the dielectric properties rather than the temperature. The dissipation factor, tan (δ) shows, on the other hand, a two dynamic relaxation peaks. [27] The high frequency one is sharper and shifted to higher frequencies (becomes more faster) with increasing temperature. The origin of this dynamic is the polar groups on the surface, which has much more degree of freedom. It is reasonable, as many dynamics, that being faster with heating.

Figure 9. Permittivity, Dielectric loss, conductivity and dissipation factor as a function of frequency at 3 different temperatures as indicated

The lower frequency relaxation peak seems to be due to the clusters, agglomerates, or aggregates shown in the SEM images (Figure 3 & Figure 4). This reflects the long time (low frequency) of its dynamic due to the bigger size of the moving moiety [14]. It is very broad explaining its feature as super- position of more than one relaxation peak due to the different species or moieties of clusters.

Figure 10 shows the effect of temperatures on some selected dielectric parameters, namely, permittivity ε', real part of the complex conductivity σ' and dissipation factor tanδ.

Figure 10. ε', σ' andtan δ against temperatures at the indicated frequency spot points

It is very interested to notice that the trends are mostly linear increasing. At lower frequency (100 Hz) the rate of change of the three parameters under investigations is high and attenuated gradually with increasing frequency. The figure also shows that the lower the frequency, the higher is the permittivity and dissipation factor but the lower is the conductivity.

The conductivity at some selected frequency points is determined at temperatures 20 and 60°C as illustrated graphically in Figure 11. The figure shows, once again, the linear increase of conductivity with frequency due to the increase of the mobility and density of the free charge carries. It is well known that the conductivity is a multiplication of.

Figure 11. The conductivity σ against frequency at temperatures 20 and 60°C

Both parameters and of the charge constant σ = qnμ. One can concluded that both frequency and temperature plays a dominant role in increasing the mobility and density of charges due to the fact both are directly related to energy that that converted to kinetic energy reflected in increase of the charge transportation. [28].

3.7. Transmission Electron Microscope (TEM) Study

Figure 12 images (a, b, c and d) demonstrated that, NZ (A.M.2) particles after calcinations and zeolitization processes agglomerates with diameter 0.191 micron including cages with dimensions 0.557 micron in width, and 2.62 micron in length between agglomerates as shown in (a) image, Meanwhile (b) image explained NZ particles were ranging between 0.0735 to 0.0783 microns (73.5-78.3 nm),with diameter cage 1.16 microns.

Figure 12. Images (a, b, c and d) NZ (A.M.2) particles after calcinations and zeolitization processes

From image (c and d) it was remarkable that the NZ particles were ranged between 10 to 14and 9 to 27 nm respectively with homogenous size surrounded by water molecules as in image (c).

3.8. XRD Analysis

From Figure 13 the first four peaks was indicated that, the present of zeolite mineral followed by two peaks represented by gypsum mineral ,these peaks are represent the majority minerals of NZ (A.M.2) accompany with impurities minerals as halite, sederite, quartz, aluminum silicate, hematite, and dolomite.

Figure 13. XRD of NZ (A.M.2) particles after calcinations and zeolitization processes

3.9. XRF Study of the NZ (A.M.2) Particles

The data of XRF analysis presented in Table 5 used to distinguish the rice husk with aluminium foil derived nano zeolite NZ (A.M.2) particles and determined its properties either hydrophilic or hydrophobic. Regarding to the International Mineralogical Association, Commission on New Minerals and Mineral Names' (IMACONMMN) third rule [29] illustrated that, only heulandite and clinoptilolite zeolites can solely be distinguished on the basis of the silica and aluminium framework, heulandite has a Si/Al ratio of less than 4, whilst clinoptilolite has a Si/Al of equal or more than 4. On the basis of our results a high composition of aluminium against silicon with Si/Al ratio equal 0.39 less than 4, therefore tend NZ (A.M.2) particles to be hydrophilic. Calcium (Ca) and Potassium (K) were the major single extra-framework cations, create NZ (A.M.2) Heulandite type, while sodium, iron and titanium were recorded low content elements.

Table 5. XRF analysis of the Nano zeolite derived rice husk with aluminium foil after zeolitization and calcinations process at 1000 °C

3.10. Atomic Force Microscope

Since using atomic force microscope has become major technique for high quality characterization of nanoscale materials we can illustrate our data as follow:

3.10.1. 3D Image

To examine the nano zeolite surface and to measure its surface topology Atomic force microscopy was used. Figure 14, images (a, b) show the bi- and three-dimensional structures of NZ (A.M.2) particles. Where, the surface of rice husk derived nano zeolite exposed a high root-mean-square roughness value of 80.84 nm, over an area of 5×5um. In a 2D image bright domains refer to the inorganic particles. To investigate more accurately surface, the 2D image Figure 14 was reconstructed as a 3D image, which shows that inorganic particles seem to be embedded in the surface NZ (A.M.2) particles, (image a). Also 3D image of atomic force microscopy illustrated that after calcinations and zeolitization processes the crystals of were grown in three dimensions, this indicated that the completion of NZ (A.M.2) crystals.

Figure 14. images(a, b) of atomic force microscope of NZ (A.M.2) aftercalcinations and zeolitization

From Table 6 and Figure 15, it can be concluded that, the average value for mean radius of NZ (A.M.2) particles was (0.032 nm) after calcinations and zeolitization processes.

Table 6. Statistics values analysis of NZ (A.M.2) particles by atomic force microscope

Figure 15. Mean radius (u m) of synthesized nano zeolite particles from rice husk

3.10.2. Surface Area of synthesize Nano zeolite from Rice Husk

Data from atomic force microscopy depicted that NZ (A.M.2) particles have low surface area by average value (7nm). The low surface area of product was thought to be underestimates of actual and accurate surface area measurements. This can be attributed to pore constrictions smaller than 0.5 nm which hinder N2 gas adsorption and lead to miscalculate for surface area of NZ (A.M.2) particles [30,31].

3.10.3. Particle Analysis Image

From Table 6 and Figure 16 it was clear that, the volume of NZ (A.M.2) particles has average value (281074 nm³), while the roughness particles recorded an average (0.973 um).In addition, Particles analysis image showed that the NZ (A.M.2) particles with high thickness value (80.84 nm).

Figure 16. NZ (A.M.2) particlesanalysis after calcinations and zeolitization processes

3.10.4. Study on the Ion Exchange Capacity

The results of the determined total cation and anion exchange capacities of NZ (A.M.2) particles were summarized in Table 7.

Table 7. Ion exchange capacity analysis

According to natural zeolites analyses which has a low but acceptable cation exchange capacity compared to the theoretical capacity of clinoptilolite (CEC is (2.16 meq/g). our synthetic NZ (A.M.) [30] had the lowest cation exchange capacity of 0.45 meq. /g., whilst the anion exchange capacity of NZ (A.M.2) proved to be extremely low, (0.01meq. /g.) confirming that, it was not supreme for anion exchanging, unless pre-treated or modified.

Regarding zeolites minerals, that consider as porous crystalline aluminosilicates exhibiting an identical pore structure and having ion-exchange behavior. So that "ion sieving" becomes feasible. In accordance with previous results the natural zeolites could potentially be used as cation exchangers, but not anion exchangers. [30] Stated that synthesized NZ (A.M.) has cation exchange capacity value (0.32 meq./g.) in the company of low anion exchange capacity.

3.10.5. Particles of NZ (A.M.2) Asnovel Carrier Material for Microorganism Cells

Figure 17 (a, b, c, d and e) Images represented TEM and SEMare evidence for that Azotobacter choorococcum and Bacillus mgiterium cells grown on NZ (A.M.2) particles. Images (a, b and e) showed a mixture of two strains of mentioned bacteria exist on NZ (A.M.2) particles. While (c & d) images focuses on individual cells of Bacillus mgiterium and Azotobacter choorococcum using 63,000X and 210000X magnification.

Figure 17. (a, b, c, d and e) NZ (A.M.2) particles and microorganisms by transmission electronic microscope and scan electron microscope

Figure 18 Showed, the presence of Azotobacter choorococcum and bacillus megeterium mixture cells on NZ particles converted from rice husk by light microscope. As mentioned above the rice husk with aluminum foil derived NZ particles was hydrophilic in nature, non toxic, exchanger cations and low anions capacities also surfactant NZ (A.M.2) create single layer on its surfaces, hence success to posses exchangeable anions (negative charges).This results are agreement with [32] who reported that surfactant modified zeolite has been exposed to be an effectual and economical sorbent for non-polar organics, inorganic anions, and inorganic cations suspended in water.

Figure 18. images (a, b) Azotobacter choorococcum and bacillus mgiterium cells exist on NZ (A.M.2) particles using light microscope

From above results we can expire that nitrogen fixing bacterial and phosphorus solubilizing bacterial cells were adsorbed on NZ (A.M.2) particles which get grasp of enrich soil fertility and advanced plant growth via hold up nitrogen and phosphorus availability. So, NZ A.M.2) particles can be natural safety material used as adsorbed and a novel carrier material for the two given microorganisms.

4. Conclusion

The conversion rice husk with aluminium foil (as houses and restaurants wastes) into NZ particles by using calcinations and zeolitization processes in order to create fertilizer enriched by elements, safety and eco-friendly was effectively done. Crystallization, phases, Physic-chemical characteristics and surface morphology were studied by visual techniques represented in, transmission electron TEM, scanning electron microscope (SEM), coupled with energy dispersive spectroscopy (EDS), Stereo and lightmicroscope, XRD, XRF, atomic force microscope (AFM) and broadband dielectric spectroscopy (BDS) for dielectric and electrical properties as well. Regarding chemical measurements, the highest CEC value indicated that NZ has cation exchange, but low anion exchange property. An after effect result that, synthesized NZ particles have been proved to be cracking and hydro cracking catalysts belong to Faujasite family and could enrich soil fertility and improve plant growth via support nitrogen fixation and phosphorus solubilizing bacterial, a novel organophillic microorganisms carrier and hydrophilic material which can used as safety fertilizer and eco-friendly for both soils and plants particularly in arid and semi arid zones.

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