Field of the invention:
[0001] The present disclosure generally relates to the use of rice stubble and othernon-wood alternative natural fibresalong with waste from paper industry, a polymer (starch-based raw materials), a plasticizer (glycerin), a solvent (water) and anacid (acetic acid) to develop a 100% biodegradable composite material. The compaction resistance and resiliency of rice stubble makes the new material a very good candidate for packing industry. The developed composition provides sufficient mechanical strength to replace the conventional hardwood fiber in multiple applications such astableware, paper, card board boxes, packaging material, high density and moderate density boards for doors and furniture etc.
Background of the invention:
[0002] Burning of rice crop residue in the states of Punjab, Haryana and (Jttar Pradesh hasbeen identified as a major health hazard. In addition to causing exposure to extremely high levels of Particulate Matter concentration to people in the immediate vicinity, it is also a major regional source of pollution, contributing between 12 and 60 per cent of PM concentrations.
[0003] The main cause of the problem is two-fold. Firstly, paddy is a water intensive crop and due to scarcity of ground water, government has restricted sowing of paddy till mid-June in some areas, which is when monsoons typically arrive in India. This delays the harvesting time which in turn leaves the farmers with very little time to sow wheat. Secondly, the harvesters leave about 40-50 cm of crop residue in the field which takes about 45 days to decompose. Also, tilling the straw left on the ground into the soil may be expensive. Therefore, for farmers, the burning of stubble seems theeasiest and fastest way to get rid of straw. Additionally, farmers findstubble burning an economic way of managing the agro-waste as there is no assured returns associated with the waste. Although burning of rice stubble seems to be the rapid, andinexpensive method* the pollution generated by rice straw burning poses a major threat to the environment.
[0004] A study estimated that crop residue burning released 149.24 million tonnes of carbon dioxide (CO2), over 9 million tonnes of carbon monoxide (CO), 0.25 million tonnes of oxides of sulphur (SOX), 1.28 million tonnes of particulate matter and 0.07 million tonnes of black carbon, These directly contribute to environmental pollution and are also responsible for the haze in Delhi and melting of Himalayan glaciers.
[0005] The heat from burning paddy straw penetrates I centimetre into the soil, elevating the temperature to 33.8 to 42,2 degree Celsius, This kills the bacterial and fungal populations critical for a fertile soil
[0006] According to another report, one tonne stubble burning leads to a loss of 5.5-kilogram nitrogen, 2.3 kg phosphorus, 25 kg potassium and more than 1 kg of sulphur - all soil nutrients, besides organic carbon.A study conducted in 2016, revealed that 84.5 per cent people were suffering from health problem due to increased incidence of smog. It found that 76.8 per cent

people reported irritation in eyes, 44.8 per cent reported irritation in nose, and 45.5 per cent reported irritation in throat.
[0007] Therefore, there exists a need for providing analternative to the rice stubble burning issue. Additionally, the solution for rice stubble management must meet both agriculture production and environmental stewardship objectives. Farmers will stop burning rice stubble only if they can see lucrative incentive associated with the agro-waste.Although some previous efforts have attempted to use rice stubble to use as combustion material, for power generation poultry litter, etc., but there is a lack of sustainable attempts to produce an economic and eco-friendLy solution. As a result, the present disclosure fills such gaps by providing solution to the management of residuals from agricultural as well as paper industry which can help to reduce environmental impact as well as carborifootprint (measured in eCOz units)
Objectives of the invention:
[0008] The primary objective of the invention is to provide analternativeto the rice stubble burning issue by utilising the rice stubble and other non-wood alternative natural fibers along with waste from paper industry, a polymer (starch-based raw materials), a plasticizer (glycerin), a solvent (water) and an acid (vinegar) to develop a 100% biodegradable bioplastic composite material.
[0009] Another objective of the invention is to convert the agriculture and paper industry residual as a profitable raw material for application in various industries.
[0010]Yet another objective of the invention is to produce the bags, packaging material using the new eco-friendly material to resolve environmental problems that occur with the disposal of conventional plastics.
[0011] Further objective of the invention is to provide a cost-effective process of making the bioplastic composite from stubbie.
Brief Summary of the Invention:
[0012] The present invention comprises of the methods of making a 100% biodegradable bioplastic composite material by utilising the rice stubble and other non-wood alternative natural fibres along with waste from paper industry, a polymer (starch-based raw materials), a plasticizer (glycerin), a solvent (water) and an acid (vinegar). The biodegradable composite from rice stubble may not only mitigate the problems associated with the burying or burning of rice straw, but may also provide an environmentally friendly alternative to the environmental hazard/havoc created by non degradabiity of plastic and benefit the farmers economically. Rice stubble comprises of approximately 35% cellulose, 30% hemicellulose, 15% ligmn and about 20% ash. The cellulose fibres in rice stubble are interconnected to each other to form large bundles and are further connected to each other by films. Thus, these fibres are too short (0.4

to 1.0 mm in length) arid/or too weak to be used for various applications. However, the new developed material has following advantages: raw materials and auxiliary materials are natural substances, free of soil harmful substances; low cost, ease of production; in the production process does not produce any pollution, and utilization of agricultural waste, It cati be used for various everyday applications such as disposable tableware, carry bags, as packaging material, etc, and helps in reducing CChemission and plastic wastes.
Detailed invention disclosure:
f0013]The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. As used herein, the singular forms "a,** "an," and "the** are intended to include the plural forms as well as the singular forms, unless the context clearly indicates otherwise. It will be further understood the terms "comprises" and/or "comprising" when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof.
|0014] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one having ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
[0015]In describing the invention, it will be understood that a number of techniques and steps are disclosed. Each of these has individual benefit and each can also be used in conjunction with one or more, or in some cases ail, of the other disclosed techniques. Accordingly, for the sake of clarity, this description will refrain from repeating every possible combination of the individual steps in an unnecessary fashion.
[0016] New 100% biodegradable composite material, and process for preparing the same are discussed herein. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be evident, however, to one skilled in the art that the present invention may be practiced without these specific details.

[0017] The present disclosure is to be considered as an exemplification of the invention and is not intended to limit the invention to the specific embodiments illustrated by the figures or
description below;
[00l8]For instance, a method of making a novel 100% biodegradable composite from agricultural waste products including rice straw has been disclosed. In this method, rice stubble may be chopped into lengths of about 40 to 80 cm in length and supplied to a pulping chamber containing about 50-100 times water. In the pulping chamber 200 - 400 gm of paper industry waste per kg of stubble may be added. The grinding and mixing of stubble and paper industry waste may be carried out for approximately 5 to 20 minutes to yield a smooth pulp. The pH of the solution is preferred to be in the range of 9-12 pH for this treatment. The dilute pulp is then concentrated to 1/10 volume by passing through a sieve and fed into a second chamber. The concentrated pulp may contain 5-10 times water and is fed to a slurry tank containing agitator and a heater. In slurry tank, Glycerine may be added approximately 50 - 300 mL in 200- 500 gm stubble with 1000 -3000 ml water. In the same slurry tank; 50 - 500 gm starch may be added and 50-300 mL acetic acid may also be added to make the material more flexible and strong. Water plays an important role in the production of the material. First, it acts as a solvent to dissolve the starch. Secondly; it helps the starch molecules to stay disrupted after heating. Acetic acid liberates acetate ions and hydrogen ions in solution. This is important, because ions react with the starch polymers and make them be disordered more easily in the solution. This disorder, resulting from the disruption by the water and the ionization by the acetic acid, makes the resulting cast film more homogenous. We may heat the slurry in the tank containing pulp, starch, glycerine and acetic acid to boiling approximately 90-200°C The modified hot slurry may start forming a bioplastic composite in 10-40 minutes at 90-180°C. The bioplastic composite is then passed through a rotary drum with vacuum at one end and other end exposed to atmospheric pressure. The biopiastic composite starts spreading like a sheet On the belt wound around rotary drum. To ensure smooth sheet formation temperature of bioplastic should not go below 75-1.00°C before uniform sheet is formed. Otherwise, non-uniform spreading arid hence non-uniform sheet would be formed. To maintain the temperature above the belt steam shower at approximately 100-180 °C may be given. After bioplastic is formed the belt moves to a region where no steam shower is present and quickly cools down and forms a sheet that is rolled onto another drum. The final bioplastic composite material may be of 15-250 microns.
10019] Non-woodfibre sources such as rice straw kenaf flax, bamboo, cotton, jute, hemp, sisal,bagasse, com. waste, wheat straw, marine or freshwater algae/ seaweeds, or aquatic plants such as water hyacinth, account for only about 5-10% of global pulp production for a variety off reasons including seasonal availability, silica content, etc. Use of alternative non-wood natural, fibres such asusing field crop fibres and agricultural residues instead of wood fibres enhance environmental sustainability. Advantages of using these sources are I) a much shorter harvest cycle thantraditional wood-based pulp sources, 2) low cost due to itsresidual nature, 3} no need of fibre bleaching, requiring lessenergy consumption, and 4) pulling carbon dioxide out of theair to reduce global greenhouse gas effect (i.e., reduced overall "carbon footprint' or eC02 values).

[0020] The biocomposite of the present disclosure can include various amounts of non-wood alternativenatural pulp fibres. The composition can have a combinationof elements where there is at least one non-wood alternative-natural pulp fibreand waste from paper industry. For example, the amount of non-wood alternativenatural pulp fibres of the present disclosure can be present inan amount of from about 5%, from about 10%, from about 20%, from about 25%, from about 30% to about 40%, toabout 50%, to about 60%, to about 75%, by weight of the composition. The compositions ofthe present disclosure can also include the paper industry waste in an amount of from about 5%, from about 10%t fromabout 20%, or from about 30%, to about 40%, to about 50%,to about 60% or to about 70%, by weight of the composition.
[0021 ] Generally, the oligosaccharide in the biocomposite can be any suitable oligosaccharide, or its ester or ether derivative that can be obtained by the hydrolysis of a polysaccharide from a natural source. The oligosaccharide can be used directly in the preparation or it can be generated during the process of preparation of the biocomposite. Examples of polysaccharides include starch, cellulose, agar, and their mixtures. Starch is a biodegradable polysaccharide biopolymer composed of D-glucose units (C6H10O5)n. it consists of the polymers amylase and amylopectin.
[0022]The cleavage of a( 1 —>4) in straight chains or the cleavage of a(l —>4) glycosidic linkages such as at the branching points creates a homogenous mass of long, straight polymers or oligomers, which can be achieved by using acid for hydrolysis process or by elevated temperatures.
[0023] Acids that can be used in assisting the hydrolysis in present invention include cafboxylic acids, organophosphoric acids, organosulfonic acids, and organoboric acids. Examples of carboxylie acids include formic acid, acetic acid, propionic acid, oxalic acid, malonic acid* succinic acid, glutaric acid, adipic acid, maieic acid, malic acid, oleic acid, salicylic acid, gallic acid, citric acid, lactic acid, tartaric acid, glycolic acid, trifluoroacetic acid, benzoic acid, 4-hydroxybenzoic acid, aminobenzoic acid, and p-toluenesulfonic acid. Also, phenols, such as pyrogallol (benzene-1,2,3-triol) and catechol (benzenediol) can also be used as acids. Anhydrides (e.g., acetic anhydride, succinic anhydride, trifluoroacetic anhydride) may also be employed.
[0024] Plasticizers are materials which helps a polymer structure to become soft and loose by reducing the intermolecular forces and increasing the intermolecular mobility of the polymer. As used herein, "plasticizef * refers to materials* including compounds, capable of plasticizing or softening a biopolymer. Examples of plasticizers include low molecular weight polymers, oligomers, copolymers, small organic molecules, low molecular weight polyols, glycol ethers, poly(propyiene glycol), low molecular weight polyethylene glycol), citrate ester-type plasticizers, triacetin, propylene glycol, sugar alcohols, glycerin, urea, urea derivatives and mixtures thereof.
[0025] A L00% biodegradable composition can be prepared by combining predetermined amounts of rice stubble, paper industry waste, polysaccharide obtained from a renewable source, such as a starch, a plasticizer, and an acid in a solvent such as water. The combined

components can be heated with stirring to make a homogeneous melt. Alternately ^ the above components can be premixed without the addition of water and stored such that the mixture can be heated together with water to thrill a melt just before processing the biocomposite. Any type of melt blending device can be used with a mechanical stirrer. Depending on the desired shape and application of the biocomposite, the melt can be processed. Examples of processing include moulding, blowing, flat die extruding, and casting. The sample can be dried under ambient condition.
[0026] While preferred raw material for new biocomposite has been described, the 100% biodegradable biocomposite is not limited by these materials. Rice stubble and other non-wood alternative natural fibers along with waste from paper industry, a polymer (starch-based raw materials), a plasttcizer (glycerin), a solvent (water) and an acid (acetic acid) may comprise some or all of the elements of the new biocomposite.
[0027] It will readily be apparent that numerous modifications and alterations can be made to the processes described in the foregoing examples without departing from the principles underlying the invention* and all such modifications and alterations are intended to be embraced by this application.
Brief description of figure
Figure 1 shows a schematic representation of Industrial process and plant design to make biodegradable bioplastic composite from, agricultural waste wherein
EQU 101: Mixing and Pulping Unit
EQU 102: Storage and transfer tank with cup & cone system
EQU 103: Temperature controlled mixing tank
EQU 104: Rotary Drum to collect bioplastic
EQU 105: Rotating belt with delay timer
EQU 106: Levelled gauge glass for controlled addition of reagents
EQU 107: Excess/waste water collection tank

Detailed Description of Figure:
[0028] FIGURE 1 is a side cross-sectional view of the preferred process. The entire process
comprises of seven major components labelled as EQU -101-107. The process begins at EQU
101 which is the mixing and pulping unit, wherein stubble (parali) is added along with water
from EQU 107(waste water collection tank) and waste material from paper making industry in
specified ratios and ground using a high speed motor of 50-1.00 HP and is collected in the next
chamber EQU 102, where there is a cup and cone system to continuously transfer the pulp into
the next chamber. Next is the temperature controlled mixing tank EQU 103, that is the main
reaction chamber. Here pulp enters from EQU 102; and the polysaccharide, acid & plasticizer
enter from EQU 106 that comprises of levelled gauze made up of glass containing the three
aforementioned components. There is also a heater & temperature controller and an agitator
within EQU 103, which regulate the heating process and maintain homogeneity respectively.
As seen in the figure, EQU 104 is the rotary drum with which when switched on, coats the
bioplastic and transfers it to the rotating belt with delay timer EQU 105 which has a hot steam
shower above it to ensure uniform spreading and at the farther end has another drum where
cooled bioplastic composite is obtained.

CLAIMS
Claim I. 100% biodegradable biopiastie composite material acquired from compounding a mixture comprising
Agricultural-waste (rice stubble and other non-wood alternative natural fibers) along with waste from paper industry, at least one polymer (starch-based raw materials), at least one plasticizer, at least one solvent and at least one acid, wherein the agricultural waste is in 15-75% by weight of total composition; the paper industry waste is in 20-40% by weight of total composition; at least one starch is between 5% and 50%, the at least one plasticizer is between 5% and 40%, and the at least one acid is between 5% to 40 %.
Claim 2. The bioplastic composition of Claim 1, wherein the agricultural waste is selected from the group consisting of rice stubble and other nori-wood alternative natural fibers, and combinations thereof.
Claim 3. The bioplastic composition of Claim 1, wherein the agricultural waste is mixed and ground with paper industry waste for 5 to 20 minutes to yield a smooth pulp.
Claim 4. The bioplastic composition of Claim 3, wherein the pH of the solution is preferred to be in the range of 9-12.
Claim 5. The bioplastic composition of Claim 1, wherein the agricultural waste is in between 15-75% of total but preferably between 20-40% of the total composition.
Claim. 6. The bioplastic of Claim 1, wherein the oligosaccharide is obtained by hydrolysis of starch, cellulose, agar, or a combination thereof.
Claim 7. The bioplastic of claim 1, wherein the at least one plasticizer is selected from the group consisting of polyethers, polyols;ureas, polyethylene glycols, glycerol, and sorbitol.
Claim 8. The bioplastic composition of Claim 1* wherein the at least one acid is selected from the group consisting of carboxylic acids* organophosphoric acids, organosulfonic acids* and organoboric acids. Also* phenols* such as pyrogallol (benzene- l*2*3-triol) and catechol (benzenediol) can also be used as acids. Anhydrides (e.g.* acetic anhydride, succinic anhydride* and trifluoroacetic anhydride).
Claim 9. A process for making a 100% biodegradable composition, the method comprising:
combining predetermined amounts of rice stubbie* paper industry waste* polysaccharide obtained from a renewable source, such as a starch, a plasticizer* and an acid in a solvent such as water.; the combined components can be heated to a temperature between 90-200 degrees ceisius with stirring to make a homogeneous melt; alternately, the above components can be premixed without the addition of water and stored such that the mixture can be heated together with water to obtain a melt just before processing the biocomposite; any type of melt blending device can be used with a mechanical stirrer* Depending on the desired shape and application of the biocomposite* the melt can be processed; the sample can be dried under ambient condition.
Claim 10. A bioplastic obtained by the process of claim 9.