Field of Invention

Agricultural is the deep and wide term for everything." That comes into growing crops and raising animals. It is one of the important sectors in India. India has a growing economy, but there are many problems in the management of agricultural crop residues. The farmers dispose of the residues by burning them, which results in air pollution and respiratory problems. Many crop residues are rich in cellulosic and other contents. These residues are used as alternative raw materials for pulp and paper industries. Use crop residues to produce numerous benefits by solving the crop residue management problem and providing a solution for alternative raw materials for wood. The wood is converted to pulp by pulping. It is the process of cooking the raw materials which is separate the fibers. The Significance of paper and paper products is that the per capita consumption of paper has always been considered as an index of civilization. Paper provides the means of recording, storage and dissemination of information. Virtually all writing and printing is done on paper. It is also the most widely used wrapping and packaging material. The uses and applications for paper and paper products are virtually limitless. New specialty products are continuously being developed. At the same time, the industry is aware of inroads and competitions from other sectors, notably plastics and electronic media for markets traditionally served by Paper. New technologies are being developed so that the industry can remain competitive in the existing markets and be prepared for new opportunities.
Background of Invention

Paper is made from wood fiber, flax, cotton linters, and bagasse are also used in some papers. Used paper is also recycled. The wood from trees takes a long time to grow (5 to 6 years). In our country, many agricultural products will be produced but the residuals are not used in a useful way, there is difficult in the management of agriculture residues because of high quantity of production of agriculture produce. So, the farmers bum the residues, which cause air pollution in the environment and respiratory problems in humans. How can the agricultural residuals be used? So, we choose three kinds of agricultural residuals [groundnut shell, corn cob, and Mesta], which have the same chemical and strength properties as wood. These types of agricultural residuals are used for fuel purposes and textiles. So, we find the alternative way in agricultural residuals is a paper-making process.
Object of Invention

o CORNCOB

Scientific Name: zea mays.L Common Name: Maize

o MESTA

Scientific Name: Hibiscus cannabinus Common Name: Roselle[Mesta]

o GROUNDNUT SHELL

Scientific name: Arachis hypogaea Common name: Peanut, Groundnut

o Cellulose

o Hemi cellulose

o Lignin

o Extractives also called commonly as resins and fatsSummary of Invention RAW MATERIALS

A generic term for a range of materials in the form of coherent sheet or web made by deposition of vegetable, mineral or synthetic fibers on their mixtures from a fluid suspension on to a suitable forming device with or without the addition of other substances. The most common and widely used fiber is Cellulose fiber. .

Probably half of the fiber used for paper today comes from wood that has been purposefully harvested; the remaining materials come from recycled newsprint, vegetable matter, and recycled cloth. Apart from this, agro-residues are preferred for the papermaking process because of their lignin and cellulosic fiber content. Due to the increasing demand for paper, non-wood materials are used.

CLASSIFICATION OF WOOD AND AGRICULTURAL RESIDUES

Botanically wood is classified into two major groups The Gymnosperms popularly called as softwoods or Conifers The Angiosperms or the hardwoods A tree can be considered to have three general parts The Crown comprising of leaves and branches The stem The root system

The plant develops due to the photosynthesis, which is the production of carbohydrates from Carbon di Oxide and Water in the presence of Chlorophyll and light.

SOFTWOODS

Also called conifers, are trees grown in cold and temperate climates. These trees have these needle-like leaves in water also. Softwoods are characterized by relatively simple wood anatomy consisting of 90-95% longitudinal fiber tracheid’s, 2.5 to 7 mm long and 25 to 60 pm wide; 5 to 10% ray cells and 0.5 to 1.0% resin cells.

HARDWOODS

Hardwood trees also called Angiosperms can be grown in warmer climates, and tropical climates. They are broad-leafed trees and deciduous. These trees lose their leaves in winter. The principal vertical structure of hardwoods is composed of both relatively long narrow cells, called libriform fibers, and much shorter and wider cells called vessels. Vessels in a typical hardwood sample are often large enough in diameter to be detected easily. Hardwoods
also have a vertical parenchyma system and a horizontal or ray parenchyma system. The cellular composition is 36-70% fiber cells, 20-55% vessel elements, 6-20% ray cells and about 2% parenchyma cells by volume. The fibers of hardwoods have the fiber length in the region of 0.9 to 1.5 mm and the fiber diameter in the region of 10-40 pm.

AGRO RESIDUES

After wood, non-wood raw materials are the second major source of raw materials for the manufacture of pulp, cellulose, and other fibrous products. The annual plants used in the pulp and paper industry can be grouped into four main classes. Plants specially grown for

cellulosic fibers.
Detailed Description of Invention

EVALUATION OF COOKING PARAMETER

> Dry matter content of the sample

> Active alkali charge

> Volume of white liquor (WL) required

> Bath ratio

> Volume of weak black liquor (WBL) required

> H- factor

ANALYSIS OF DRY MATTER CONTENT OF SAMPLE

The dry matter content of the sample has to be known in the cooking calculations.

The dry matter content is expressed as percentage of the undried weight. The determination of Moisture by weighing a sample (about 100 g) before and after drying. Two determinations are made from each sample. The sample are dried in an oven at 105 0 C for 16-24 h. After drying in the oven, the samples must be cooled down in a desiccator for 45 minutes, and weighed after that.

Calculations:

Air dry chips: Empty tray weight Wig

With Sample Weight W2 g

Oven-dried chips weight W3 g

The Moisture content of the chips: (W2-W3 /W2-W1) x 100 % = X %

The dry matter content of the chips: 100-X= Y

Weight of OD chips: 100/Y * OD = Chips (g) (1)

WHITE LIQUOR ANALYSIS Purpose

To analyze white liquor, and weak white liquor.

Total Titratable Alkali (TTA)

Pipetted out 5ml of the liquor sample into a 250ml conical flask, added 50ml of water and titrated against HCI using methyl orange as indicator. Pink color is obtained. (M)

TTA as Na20 gpi ~ = T. Vx 6.2 ~
Total active alkali (TAA)

Pipetted out 250ml of the liquor sample into a 250 ml standard flask, added 70ml of 20% BaCl2 and made up to the mark with water. Shaken well and kept it for setting. Pipetted out 50ml of the made up solution into a conical flask, added phenolphthalein indicator and titrated against 1 N HCI. Noted the point of disappearance of pink color ‘(p)’ and added 2 drops of methyl orange indicator. The titration is continued. Appearance of pale yellow color is the end point, (m)

NaOH as Na20 gpl = (2p - m) x 6.2 Na2S as Na20 gpl = (m-p) x 2 x 12.4 TAA as Na20 gpl = NaOH + Na2S

Sulphidity % = x 100

TAA

ACTIVE ALKALI ANALYSIS

Determination of active alkali charge For these Pulping Process

Total Amount of active alkali required for Pulping Process

Total AA% Required = 20/100*300= 60 %-— (A)

VOLUME OF WHITE LIQUOR

Volume of white liquors that contains required amount of active alkali for each process is calculated using the formula

1000

Volume of WL = * weight of OD chips taken = ml— (2)

To be charged amount of TAA in

WL(gpl)

Where A is the amount of AA required BATH RATIO

The parameter also had been fixed through previous trials. Bath ratio maintained during cooking is L4 that is for one part of oven dry chips, three part of cooking liquor (WL

+ WBL/Water) is taken.
300 : 1200 = 1500-— (3)

Solid: liquid = Total

BLACK LIQUOR ANALYSIS

VOLUME OF WEAK BLACK LIQUOR/WATER

The purpose of weak black liquor or Water is to maintain the bath ratio of cooking

process.

For an effective cook, an optimum volume of WBL or Water is added. This volume is calculated as follows. Let,

Volume of WL charged = (2) ml

Weight of Air-dry chips charged = (1) g

Then volume of WBL or Water required = (3) - (1+2)

H Factor

The temperature and relative rate of heating were determined with the help of H-factor. The overall rate of bulk delignification follows pseudo first order kinetics, then dL

= K(L-Ld)

dt

L is the lignin remaining undissolved at time’s’

Ld -> is the difficult to remove lignin

K -> rate constant

The laboratory beating treatment was used to develop the ultimate strength of a pulp using PF1 mill (Pulp Freeness Index) disintegrated for 25 minutes by using disintegrator. Removal of lignin during Kraft process.

Alter 25 minutes disintegration in pulp disintegrator the 24gms of pulp was diluted to 10 liter, which ensured a low pulp concentration to permit an accelerate measurement of long fibred stock for the individual sheets. For preparing model sheets after stirring 400 ml volume of pulp slurry was taken in a cylinder and hand sheets were made using sheet former. They were on a-couple of blotters moist sheet were.separated.and dried by-placing in it an oven at110°C for 10 minutes. Then the dried sheet was weighed. From the weight of the sheet and volume taken, the volume needed for the standard sheet was calculated and then standard sheet was made.

ANALYSIS OF BLACK LIQUOR YIELD

Yield is a measure of amount of pulp obtained from a specific amount of wood (Raw material) used for cooking process. Yield determines the input of raw material gives how much of pulp (output). In order to maintain higher productivity target that is input to output ratio we select optimum activity alkali range. Yield is calculated using the equation

Output

Yield = *100

Input

Where, Output- weight of oven dry pulp Input - weight of oven dry wood

WEAK BLACK LIQUOR ANALYSIS PROCEDURE

1. pH

Check the pH using a pH meter.

2. Total Solids

Weigh a clean and dry petri dish with neutral sand.to the nearest 0.01 g, (A).

Pipette out 10 ml of the WBL and weigh it quickly, (B).

Dry 105 + 2°C in an oven.

Cool and weigh, (C).

C - A

Total Solids, % = -—-xl00

B-A

Total Solids, g/1 = C-A/10*100

Total Titratable Alkali (TTA)

1. Pipette out 25 ml of the WBL in a beaker.

2. Add around 50ml of DM Water.

3. Titrate against 1 N HC1 up to 4.3 pH, using pH meter.

4. Note the titre value TV.

7Vx31

TTA, g/1 as Na20 = = TV x 1.24

Residual Active Alkali (RAA)
]. Pipette out 25 ml of WBL into a 250 ml standard flask.

2. Add 100 ml of 20 % BaC12 and then make up to the mark using DM water.

3. Mix well and allow to settle.

4. Pipette out 25 ml of the supernatant solution into a 250 ml beaker.

5. Add 2 to 3 ml of neutral formaldehyde.

6. Titrate it against N/l 0 HC1 up to 7.0 pH using pH meter.

7. Note the titre value TV.

RAA g/1 as Na20 = 250 x TV x 1 x 31 x 1000 _ ^ ^ ^

25x25x10x1000

KAPPA NUMBER Definition

The kappa number in the number of ml of 0.1N KMn04 consumed by one gm of pulp under specified condition and corrected to 50% consumption of permanganate. Procedure

Washed the pulp over ASTM 352 mesh and make into a slurry. Determine the slurry filtering 100ml of the slurry thro’ previously dried and weighted filter paper, drying and weighing the pad. Measure pulp slurry equivalent to 2.5g pulp of H.W & 5.0 O.D for CB pulp and make up to 700ml in a measuring cylinder and taken in a 2 liter beaker. The slurry at

constant speed.

Pipetted out 100ml of 0.1N KMn04 into a 250ml beaker and measured 100ml of 4N H2S04 and poured into it. Added the H2S04, KMn04 mixture rapidly to the pulp noting the time. Added the rinsing of 250ml beaker with 100ml of water to the pulp to make the total volume 1000ml. exactly at the end of 10th minutes added about 20nl of 10%. KI to the pulp suspension and titrated the liberated Iodine against N / 5 this using starch indictor. Nearing end of the titration. Note the titrate value as TV carry out a blank as mentioned above but without pulp. Note the titre reading as “Blank* calculate the kappa number by using the formula.

(Blank)-(T.V)x2xC.F

Kappa Number = -

OD Taken Wt (g)

Blank = ml of thio used in the blank T V = ml of thio used in test

f = correction factor to 50% KMn04 consumption
w- O.D wt.of pulp
Detailed Description of Drawings

(]) Figure (i) shows the Block Diagram

(2) Figure (ii) shows the Cellulose

For the fibers to be useful in papermaking, they must be capable of being matted and pressed imo uniform sheet. The degree of fiber conformability is characterized and measured on sheet f ormation while the degree of bonding reflects the tensile and bursting strength of the sheets. In plant fibers, it is the chemical compound Cellulose that determines the characteristics of the fiber, and permits its use in papermaking. Cellulose is a Carbohydrate compound of Carbon, hydrogen and Oxygen having a general formula (CH2O) n to be more precise, (CgHioOs) n on a molecular level. Cellulose is a linear polymer of anhydro-D-Glucose of conformation with 1-4 linkages between adjacent glucose units as given in Figure.

(3) Figure (iii) shows the Hemicellulose

The non-cellulosic carbohydrates are classified as Hemicelluloses. By contrast to cellulose, which is a polymer of only glucose, hemicelluloses are polymers of other monosaccharides. Hexoses - Glucose, Mannose, Galactose Pentoses - Xylose and Arabinose The plural form should be used to describe them genetically. Physically hemicelluloses are white solid materials that are rarely crystalline or fibrous in nature. They form some of the “flesh” that helps to fill out the fiber. Hemicellulose increases the strength of paper especially tensile and bursting strength, and the pulp yield. However, when dissolving grade pulp, more commonly known as Rayon grade pulp is produced, they are not desired and are removed in the process of separation of cellulose from the raw material (Dissolving pulps are used as raw material in the manufacture of synthetic fibers such as Rayon, viscose staple fiber) Hemicelluloses are much more soluble and susceptible to chemical degradation than is Cellulose. Hemicelluloses are essentially linear polymers except for single sugar side chains and acetyl substituents. These low molecular weight hemicelluloses become soluble in dilute alkali at elevated temperature.

(4) Figure (iv) shows the Lignin Structure

Lignin is a complex polymer consisting of phenyl propane units and has an amorphous three-dimensional structure (A). Its principal role is to form the middle lamella, the intercellular material which cements the fiber together. There are three basic lignin monomers that have been found. They are,
> Coniferyl alcohol (B) lignin, is also known as Vanillin base

> Sinapyl alcohol (C) the lignin is also known as Syringaldehyde base

> p-Coumaryl alcohol (D)

Non woody plants like Straw, grasses, Bagasse contain all the three basic lignin monomers. Hardwoods contain both coniferyl alcohol (50-75%) and Sinapyl alcohol (25-50%) while softwoods contain only coniferyl alcohol. Extensive studies conducted on lignin isolated from Bagasse as well as wheat straw have shown that these non-wood lignins contain, in addition to guaicy) propane i.e. coniferyl alcohol based monomer (G) and Syringyl propane units i.e. Sinapyl alcohol (S) based monomer significant amount of p-Coumaric acid /alcohol (PA) moiety.

(5) Figure (v) shows CCL Digester

Lab Pulping Unit - Oil Bath, is a compact unit and specially designed for “Laboratory Production of Chemical Pulp” by cooking agricultural residues in “Six Individual Acid Proof Stainless Steel Autoclaves”, each of capacity 2.0 liter suitable for 300 gm. bone dry agricultural residues. These autoclaves are rotating in the “Hot Glycol Bath” and supported on a geared motor driven rotating shaft. The Lab Pulping Unit is used for cooking of raw materials, such as crop residues and various fibrous materials under specified & controlled conditions of Pressure, Temperature & Time, prior to "Producing the Pulp". It consists of Water Circulation System for Cooling the Glycol, Oil Drain Valve, Fumes Hood, Temperature Sensor & Pressure Gauge, completes with the Operational Control Panel provided with “Programmable Digital Temperature Indicator-Cum-Controller”.

(6) Figure (vi) shows Cooking vessel

Time required to rise temperature, insight the bath of ethylene glycol which is electrically heated at regular intervals of 10 min time to rise 100C. The temperature is reached to 1600 C within two hours, which is called steaming reaction time. Auto heating coil maintain the 1600 C for another 1 and half hours, with the help of digital temperature indicator. The half an hour period of chips at 1600 C is called cooking reaction time. Then bomb is removed from CCL digester and cooled in a water bath for half an hour the cooked raw materials is poured over tree line cloth where BL squeezed of manually and separately collected in a beaker and used for BL analysis. The pulp is disintegrated and then washed with water to remove all cookingchemicals manually which turn will be tested for kappa number pulp yield, reject percentages, brightness and freeness of pulp.

(7) Figure (vii) shows Separation of black liquor

After 3 hours of cooking, the cooking vessel kept in the bath tub for decreasing the temperature is unlocked, the screws are removed, and the cooked pulp is transferred to the cotton cloth for filtering the black liquor into the beaker to determine the total solids in the

black liquor.

(8) Figure (viii) shows Washing process

Following the separation of the black liquor from the pulp, further mixing of the pulp with water for 20 minutes will break down the fiber bond. After the pulp can be washed in pure water to remove the remaining black liquor filters from the pulp, the water is removed from the pulp.

(9) Figure (ix) shows Sample preparation

The pulp consists of large particles. So, the pulp is even and small in size. To breakdown the panicle size, there will be a size reduction of pulp. The pulp will be stored.

(10) Figure (x) shows DO Process

In this stage, H2SO4 and CLO2 are used. It is also known as the chlorine dioxide stage in bleaching or the DO stage because CLO2 is mixed with pulp. H2SO4 is added to the mixed pulp, which results in lowering the pH (2.2). This helps in the removal of lignin and dust particles present in pulp. This process takes place at 65 °C for 3 hours. It results in 10-20% delignification.

(! 1) Figure (xi) shows EOP Process

After the completion of the first stage. The next stage is processing. The pulp obtained from the DO stage is referred to as the EOP stage. Sodium hydroxide (NaOH) is mixed with the pulp, allowing it to rest for a few seconds. Now oxygen (O2) is added to the pulp in alkaline extraction to increase the bleaching effect and decrease the volume of chemicals required in the bleaching process. It simulates the process at this stage effectively. The function was carried out at high pH, high temperature, and high pressure at 85°C. Oxygen works by improving the dissolution of lignin, and hydrogen peroxide is used with oxygen in the same settings. It helps in color removal. Redox-active metal ions catalyze the decomposition ofhydrogen peroxide (H2O2). It shows some improvement in the efficacy of bleaching in the

stage, up to 30-50%.

(12) Figure (xii) shows D1 Process

This stage, also referred to as the D1 stage, is done for the effect of bleaching on the fiber charge. CLO2 and H2SO4 are the chemicals used in the stage. The process takes place at 75°C. More than two buffering properties of the DO bleached sample became evident when H2SO4 was added to achieve a certain final pH in the D1 stage. In the previous stage, the unbleached pulp fibers had two types of acidic groups: ironic acids in xylan and carboxylic groups in residual lignin. Chlorine dioxide treatment results in better delignification and improves the brightness of pulp as much as 80-90%.

(13) Figure (xiii) shows Hand Sheet Formation

For the papermaking process, the consistency of the sample pulp is calculated. The hand sheet weight should be 2.4 g. The hand sheets are formed with the help of a cylinder, which consists of a hand wire plate surface. The cylinder is allowed to allow water to pass through the wire plate; next, add a sample pulp solution. After the water drained, the fibers remained uniformly on the surface. The couch roll is applied with no extra force five times with the disc.
Different Embodiment of Invention

i. It leads to the development of small-capacity, low-cost plants.

ii. It can reduce wood and cellulose fiber impurities in countries.

iii. It helps in the effective utilization of non woody materials.

iv. It consists of strength properties of paper such as Bursting, Tearing resistance tester, Tensile strength, Brightness, Bulk.

Bursting

The maximum pressure on the paper surface or paperboard in a perpendicular direction, required to rupture the paper Tearing resistance tester

The work required to tear a paper sample through a specified distance once the tear has been

started.

Tensile strength

I t is the elongation of the paper, which means, how much it can be stretched

Before it rips.

Brightness

Paper brightness is measured on a scale of 0 to 100. This scale determines How much light is reflected from the surface of a sheet of paper? The higher the Number, the brighter the paper.

Bulk

Ratio of the volume between the gram mage and the thickness of the paper, i. Which corresponds to the thickness in microns, divided by the gram mage.
Application of Invention

This study was conducted in order to find out the suitability of pulping characteristics and quality parameters of hand sheets produced from agriculture residues such as groundnut shell, corncob, and mesta stem. From these agro residues, pulping results indicate the yield, brightness level, and strength properties of pulp and paper. For comparison purposes, normal hard wood {casuarina) pulp was taken.

First of all, the total yield of pulp from normal hardwood (casuarina) is 48.4%. It has a kappa number of 20, and the brightness of the pulp is up to 86.5%. We found the same similarities in the above-mentioned agro residues.

Groundnut shell and corn cob have yields of 41% and 29.2%, respectively. For both agro residues, there is less fiber value when compared to normal hard wood pulp. Groundnut shell has less rejection due to the higher lignin (kappa number 12.5) content present in groundnut shell pulp. The level of brightness is low, at only 12.5%. So the groundnut shell pulp needs a high requirement of bleaching chemicals, whereas in com cob, the kappa number is only 13 due to the lower content of lignin. So naturally, the pulp obtained from com cobs has brightness up to 38%, but it has lesser strength properties when compared to normal hard wood. There is poor penetration of cooking liquor in com cobs. It leads to a high rejection of pulp, about 18.5%.

a. Apart from the pulp mentioned above, Mesta stem gives a better yield of 46.6%, and there is less rejection of pulp when screening. It has a Kappa number of 23.8%, which indicates the lignin content in the pulp. So it consumes more bleaching chemicals to reach the target brightness level of 86%. Mesta stem pulp has similar strength properties and a higher fiber value than normal hardwood pulp.