Description:TITLE OF THE INVENTION: DEVELOPMENT OF ZROX/SIO2 CALALYST FOR HIGHER YIELD OF BIO-OIL FROM BIOMASS BY USING GREEN SYNTHESIZED ZROX NPS AND SILICA DERIVED FROM RICE HUSK
FIELD OF THE INVENTION
The invention leads to development of ZrOx/SiO2 calalyst for higher yield of bio-oil from biomass by using green synthesized ZrOx NPs and silica derived from Rice husk.
BACKGROUND OF THE INVENTION
References which are cited in the present disclosure are not necessarily prior art and therefore their citation does not constitute an admission that such references are prior art in any jurisdiction. All publications, patents and patent applications herein are incorporated by reference to the same extent as if each individual or patent application was specifically and individually indicated to be incorporated by reference.
Several patents have been issued for catalyst but none of these are related to the present invention. For example, CN103314078B relates to the fuel area of biomass source. It relates in addition carrys out thermochemistry production liquid (bio oil) by biomass. Particularly, the present invention relates to the method for improving quality of bio oil. More specifically, it relates to a kind of method for improving quality of bio oil, it comprises hydrocarbon liquid, the dispersed mixture of the bio oil of bio oil and part upgrading is enough to the certain hour of the oxygen level reducing this bio oil with the catalyzer containing transition metal and hydrogen at the temperature of about 330 ° of C and the contacted under pressure of about 1700psi (11.7MPa), become containing aqueous phase and organic phase to make it by refrigerated separation, optionally this organic phase is carried out hydro treatment further, hydrocracking or catalytic cracking, to produce boiling point at gasoline, hydrocarbon mixture in diesel oil and jet fuel range.
Another patent, US20160168283A1 provides a molecular precursor chromium compounds and chromium on silica catalyst precursors suitable for sure in producing chromium on silica catalysts are disclosed. The molecular precursor compounds can be chromium(II) and/or chromium(III) and/or chromium (IV) compounds wherein all ligands are easily removable, in particular ligands selected from the group consisting of anionic ligands of the type —O—CR3R4—CH—R1—R2 or —O—Si—(O—CR3R4—CH—R1R2)3 wherein R1, R2, R3 and R4 may be the same or different and may be any group that does not affect decomposition of the ligand via elimination of beta-hydrogen from —CR3R4—CH—R1R2, amide anionic ligands of the type —N—Si—R5R6R7 and/or —N—C—R5R6R7, wherein R5, R6 and R7 can be the same or different and are preferably selected from hydrogen, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, tert-butyl groups or aromatic groups; as well as coordinating solvents. These molecular precursors can be grafted to silica and—if need be—either before or after heat treatment during which the ligands are removed, oxidized to Cr(III). The chromium on silica catalyst is characterized by the absence of any organic ligands.
Another patent, US8741258B2 provides a a method of generating hydrogen from a bio-oil, comprising hydrogenating a water-soluble fraction of the bio-oil with hydrogen in the presence of a hydrogenation catalyst, and reforming the water-soluble fraction by aqueous-phase reforming in the presence of a reforming catalyst, wherein hydrogen is generated by the reforming, and the amount of hydrogen generated is greater than that consumed by the hydrogenating. The method can further comprise hydrocracking or hydrotreating a lignin fraction of the bio-oil with hydrogen in the presence of a hydrocracking catalyst wherein the lignin fraction of bio-oil is obtained as a water-insoluble fraction from aqueous extraction of bio-oil. The hydrogen used in the hydrogenating and in the hydrocracking or hydrotreating can be generated by reforming the water-soluble fraction of bio-oil.
Another patent, CN108456121A provides a kind of nucleocapsid slow-release or control-release fertilizer and preparation method thereof is provided, sustained-controll-release fertiliser production field is related to.A kind of nucleocapsid slow-release or control-release fertilizer comprising fertiliser granulates core and the uramit coating layer for being coated on fertiliser granulates core surfaces, urea and formaldehyde mole ratio are 1 2.5 in the raw material of uramit:1, uramit includes at least the uramit that carbon atom quantity is 25.Uramit molecular size range can be changed by adjusting reaction condition to form the membrane structure of different carbon chain lengths, the nucleocapsid slow-release or control-release fertilizer not only controls the sustained release of nitrogen, phosphorus, potassium macronutrient, sustained release micro- in calcium, magnesium, iron, zinc etc. can also be controlled, demand of the Different Crop to nutrient is adapted to.
Another patent, US10118159B2 provides a catalyst composition for conversion of biomass to crude bio oil. The composition comprises at least one metal compound, at least one support and at least one stabilizing/solubilizing agent. Also disclosed are processes for the preparation of catalyst composition, and hydrothermal conversion of biomass to crude bio oil.
Another patent WO2008151269A2 provides palladium-catalyzed hydro of bio-oils and certain organic compounds. Experimental results have shown good results for palladium-catalyzed hydro of organic compounds typically found in bio-oils.
Fuels created from biological sources, biomass or plants is -called "biofuels" which is now being sought for and developed to either mix with conventional fuel or even replace conventional fuels that are sourced from diminishing resources of petroleum. The production of liquid transportation fuels from biomass can be accomplished using the hydrothermal or thermochemical processing. In this study Silica was derived from Rice husk which is agricultural waste, Husk contains about 20-25 % silica which is derived by simply pyrolysis in muffle furnace above 450°C and Zirconium oxide nanoparticles were synthesized by using green method from Leaf extract of Sambuca Canadensis. Leaves were collected, crushed and dipped in water and then extract was heated and treated with zirconium nitrate or zirconium chloride or zirconium sulphate solution till color of salt solution is changed, change is color shows reaction of salt into zirconium oxide nano particles. So obtained Silica and zirconium oxide nano particles are mixed in different ratio. Zirconium oxide is taken about 20 to 50% of the Silica and then mixed in a closed vessel or crucible and then heated for 1-3 hrs, at 600°C or above to get finely divided nano particles of composite in the range of 10-15 nm. Such prepares composite is used for conversion of biomass into bio -oil then it is observed that conversion efficiency of biomass into bio-oil is increased by 20 -35% as compared to with and without catalyst. And varying the concentration and size of catalyst used.
The work in the present invention relates to catalysts that may be used in catalytic processes or more specifically, it relates to catalysts that can be used in a catalytic process for conversion of solid biomass material into biofuels with higher efficiency and higher yield.
Biomass is obtained from waste of biological materials. Biological materials may be deal plant parts or dead animal or any algae etc. Agricultural waste, specially rice husk or waste left after removing rice from its plant contains higher percentage of silica due to which cattles do not like to eat it. Silica may vary from 15 to 30% in various agri residues. Such biomass is dried and crushed and then silica can be extracted from it. This silica when converted into nano particles along with zirconium then it can give useful composite which has good adsorption capacity and catalytic activity to convert bio mass into bio-oil. The optimization of the liquid products as an oil known as bio-crude or bio-oil is accomplished with the application of flash pyrolysis. The fast pyrolysis of biomass is made possible by high heating rates and short residence durations. This helps to reduce the amount of vapor cracking that occurs, which in turn maximizes the yields of liquid products and achieves efficiencies of up to roughly 70 percent on a weight basis. Using an acid as a catalyst, cracking processes in bio-oils are able to take place even at atmospheric pressure. Silica or hyrdosilicate with Zirconium may play good role of catalyst for same purpose. Zirconium is obtained as oxide nanoparticles by green synthesis of leaf extract of plants like Leaf extract of Sambuca Canadensis.
Catalytic upgrading of bio-oil derived from the non-catalytic pyrolysis of biomass can also yield biofuels and fuel additives. This upgrading can be performed by low temperature esterification with alcohols (followed by water separation) or by high temperature gasification, cracking or hydro treating processes.
The primary object of the invention is to develop ZrOx/SiO2 catalyst for higher yield of bio-oil from biomass by using green synthesized ZrOx NPs and Silica derived from Rice husk.
The another object of the invention is using green synthesized ZrOx NPs and Silica derived from Rice husk.
The another object of the invention is to develop ZrOx/SiO2 catalyst for higher yield of bio-oil from biomass.
These and other objects and advantages of the present invention will become readily apparent from the following detailed description.
SUMMARY OF INVENTION
This summary is not a comprehensive overview of the disclosure and does not reflect the main/essential features of the establishment or specify the scope of the establishment. Its sole purpose is to present some of the concepts presented here in a simpler way as a precursor to more detailed explanations presented later.
The primary object of the invention is to develop ZrOx/SiO2 catalyst for higher yield of bio-oil from biomass by using green synthesized ZrOx NPs and Silica derived from Rice husk.
In some embodiments of the present invention, soxhlet extraction was employed to prepare the leaf extract. The thimble was filled with the leaf material. The soxhlet's primary chamber received this thimble. On a heating mantle, water was poured into a flask with a round bottom.
In some embodiments of the present invention, following the attachment of the condenser, the soxhlet extractor was fixed to the RB. Water was boiled for two hours after the device was set up in order to obtain the leaf extract. Whatmann filter paper was used to filter the resultant extract, which was then placed in a beaker for later use.
In some embodiments of the present invention, to 10 ml of leaf extract, we added 30 ml of 0.01M solution of zirconium oxychloride, then it was stirred for 10 hr until the color change was observed. Color change confirms the formation of nanoparticle. The remaining liquid was dried after which it was calcinated in muffle furnace at 300 c for about 30 minutes. As a result, the brown colored nanoparticles were obtained.
These and other aspects of the embodiments herein will be better appreciated and understood when considered in concurrence with the following explanation and the accompanying drawings. It should be understood, however, that the following descriptions, while indicating preferred embodiments and numerous specific details thereof, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the embodiments herein without departing from the spirit thereof, and the embodiments herein include all such modifications.
Brief summary of the figures
Figure 1. XRD Analysis
Figure 2. FTIR Spectroscopy Analysis
Figure 3. SEM analysis
DETAILED DESCRIPTION
These embodiments are described in sufficient detail to enable those skilled in the art to practice the embodiments and all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In some embodiments of the present invention, soxhlet extraction was employed to prepare the leaf extract. The thimble was filled with the leaf material. The soxhlet's primary chamber received this thimble. On a heating mantle, water was poured into a flask with a round bottom.
In some embodiments of the present invention, following the attachment of the condenser, the soxhlet extractor was fixed to the RB. Water was boiled for two hours after the device was set up in order to obtain the leaf extract. Whatmann filter paper was used to filter the resultant extract, which was then placed in a beaker for later use.
In some embodiments of the present invention, to 10 ml of leaf extract, we added 30 ml of 0.01M solution of zirconium oxychloride, then it was stirred for 10 hr until the color change was observed. Color change confirms the formation of nanoparticle. The remaining liquid was dried after which it was calcinated in muffle furnace at 300 c for about 30 minutes. As a result, the brown colored nanoparticles were obtained.
In some embodiments of the present invention, several analytical methods were used to characterize the Green Synthesized zirconium oxide Nanoparticles. UV-Vis spectroscopy was utilized to identify ZrO nanoparticles based on their optical characteristics. Powdered XRD investigations were utilized to determine the crystal system and crystalline size of the nanoparticles.
In some embodiments of the present invention, the fabrication of nanoparticles' shape and particle size were examined using a scanning electron microscope (Zeiss-evo 18). FTIR was used to examine the surface of ZrO/Sio2 nanoparticles for the presence of various functional groups (Thermo Scientific).
In some embodiments of the present invention, agri waste i.e. Rice husk which is waste left after removing rice from its plant contains higher percentage of silica due to which cattles do not like to eat it. Silica may vary from 15 to 30% in various agri residues. Such biomass is dried and crushed and then silica can be extracted from it. This silica when converted into nano particles along with zirconium then we get useful composite which has good adsorption capacity and catalytic activity to convert bio mass into bio-oil. It has shown 25 to 35% higher yield.
A development of ZrOx/SiO2 calalyst for higher yield of bio-oil consists of:
Sambucus canadensis leaves, zirconium nitrate or zirconium chloride or zirconium and silica, zirconium oxide nanoparticles.
A method of development of ZrOx/SiO2 calalyst as claimed in claim 1, wherein the development of ZrOx/SiO2 calalyst for higher yield of bio-oil from biomass by using green synthesized ZrOx NPs and silica derived from Rice husk comprising the steps of:
collecting the leaves, crushed and dipped in water;
heating the extract and treated with zirconium nitrate or zirconium chloride or zirconium sulphate solution till color of salt solution is changed;
showing change in color that reaction of salt into zirconium oxide nano particles;
mixing the obtained Silica and zirconium oxide nano particles in different ratio in a closed vessel or crucible; and
heating for 1-3 hrs at 600°C or above to get finely divided nano particles of composite in the range of 10-15 nm.
The method as claimed in claim 2, wherein 10 ml of leaf extract was added to 30 ml of 0.01M solution of zirconium oxychloride.
The method as claimed in claim 2, wherein zirconium oxide is taken 20 to 50% of the Silica and then mixed in a closed vessel or crucible.
EXAMPLE 1
EXPERIMENTAL SECTION
Preparation of Leaf extract:
Soxhlet extraction was employed to prepare the leaf extract. The thimble was filled with the leaf material. The soxhlet's primary chamber received this thimble. On a heating mantle, water was poured into a flask with a round bottom. Following the attachment of the condenser, the soxhlet extractor was fixed to the RB. Water was boiled for two hours after the device was set up in order to obtain the leaf extract. Whatmann filter paper was used to filter the resultant extract, which was then placed in a beaker for later use.
Preparation of Nanoparticles:
To 10 ml of leaf extract, we added 30 ml of 0.01M solution of zirconium oxychloride, then it was stirred for 10 hr until the colour change was observed. Colour change confirms the formation of nanoparticle. The remaining liquid was dried after which it was calcinated in muffle furnace at 300 c for about 30 minutes. As a result , the brown coloured nanoparticles were obtained.

Characterisation of synthesised nanoparticles:
Several analytical methods were used to characterise the Green Synthesized zirconium oxide Nanoparticles. UV-Vis spectroscopy was utilised to identify ZrO nanoparticles based on their optical characteristics. Powdered XRD investigations were utilised to determine the crystal system and crystalline size of the nanoparticles. The fabrication of nanoparticles' shape and particle size were examined using a scanning electron microscope (Zeiss-evo 18). FTIR was used to examine the surface of ZrO/Sio2 nanoparticles for the presence of various functional groups (Thermo Scientific).
Agri waste i.e. Rice husk which is waste left after removing rice from its plant contains higher percentage of silica due to which cattles do not like to eat it. Silica may vary from 15 to 30% in various agri residues. Such biomass is dried and crushed and then silica can be extracted from it. This silica when converted into nano particles along with zirconium then we get useful composite which has good adsorption capacity and catalytic activity to convert bio mass into bio-oil. It has shown 25 to 35% higher yield.
Development of composite to work as catalyst-
Leaves were collected, crushed and dipped in water and then extract was heated and treated with zirconium nitrate or zirconium chloride or zirconium sulphate solution till color of salt solution is changed, change is colour shows reaction of salt into zirconium oxide nano particles. So obtained Silica and zirconium oxide nano particles are mixed in different ratio. Zirconium oxide is taken about 20 to 50% of the Silica and then mixed in a closed vessel or crucible and then heated for 1-3 hrs at 600°C or above to get finely divided nano particles of composite in the range of 10-15 nm. Such prepares composite is used for conversion of biomass into bio-oil then it is observed that conversion efficiency of biomass into bio-oil is increased by 20 -35% as compared to with and without catalyst. And varying the concentration and size of catalyst used.
EXAMPLE 2
Result and discussion:
Characterisation of synthesised nanoparticles:
UV-Visible spectroscopy:
The graph below depicts the UV-visible spectrum for zirconium oxide nanoparticles, synthesised from the Sambucus canadensis leaves, where absorption maxima is observed at 370nm, therefore confirming the presence of zirconium oxide nanoparticles.
Crystallographic Analysis:
To study crystalline structure of zirconium oxide/Sio2 nanoparticles, XRD was used. The various Bragg peaks were seen at: 28.38°, 40.55°, 50.51° and 66.37°, which confirm the formation of crsytalline nanoparticles.
SEM analysis:
As can be seen in the image below, SEM was employed to examine the surface morphology, crystallinity, shape, and size of synthesised zirconium oxide nanoparticles. The image makes it evident that nanoparticles are heavily aggregated and nearly irregular in shape.
ADVANTAGES OF THE INVENTION:
By this invention, and by using these prepared catalysts the efficiency of biomass to get converted into bio oil can be increased to a greater extent by 20 to 35% or more. Cost of process becomes lower. Efficiency increases. This will not only bring the cost but will also give a better yield.

, Claims:We claim:
1. A development of ZrOx/SiO2 calalyst for higher yield of bio-oil consists of:
Sambucus canadensis leaves, zirconium nitrate or zirconium chloride or zirconium and silica, zirconium oxide nanoparticles.
2. A method of development of ZrOx/SiO2 calalyst as claimed in claim 1, wherein the development of ZrOx/SiO2 calalyst for higher yield of bio-oil from biomass by using green synthesized ZrOx NPs and silica derived from Rice husk comprising the steps of:
a. collecting the leaves, crushed and dipped in water;
b. heating the extract and treated with zirconium nitrate or zirconium chloride or zirconium sulphate solution till color of salt solution is changed;
c. showing change in color that reaction of salt into zirconium oxide nano particles;
d. mixing the obtained Silica and zirconium oxide nano particles in different ratio in a closed vessel or crucible; and
e. heating for 1-3 hrs at 600°C or above to get finely divided nano particles of composite in the range of 10-15 nm.
3. The method as claimed in claim 2, wherein 10 ml of leaf extract was added to 30 ml of 0.01M solution of zirconium oxychloride.
4. The method as claimed in claim 2, wherein zirconium oxide is taken 20 to 50% of the Silica and then mixed in a closed vessel or crucible.