Study and Characterization of Polyphenolic Compounds From Black Liquor of Kraft Pulping

Study and Characterization of Polyphenolic compounds from Black Liquor of Kraft Pulping
1. INTRODUCTION:
The focus of this project is to study the lignin yield after precipitation of lignin in the wood and bagasse Kraft spent black liquor (chemical pulp mill 1 &2 liquor) by acidification. The pulp mill of today produce an energy surplus occurring from the combustion of wood residuals in the recovery boiler. At the sometime, the recovery boiler is the battle neck of the process at many mills. One way to utilize the energy surplus at the same time as a production increase is obtained is to extract lignin from Kraft spent black liquor before the combustion in the recovery boiler to produce a biofuel. Extraction of lignin can be done by fractionation of Kraft spent black liquor in a lignin rich and a lignin-depleted stream by ultrafiltration, another way is to precipitate the lignin in the spent black liquor by acidification. The precipitate is separated by filtration followed by a washing step. Both methods involve problems. The fuel produced by ultra-filtration contains too high an ash content. The ash contains high amounts of spent cooking chemicals, i.e. sulphur and sodium, which would cause problems during combustion of the fuel. By precipitation, the ash content is lower but problems during combustion of the fuel. By precipitation, the ash content is lower but problems are induced at the mills occurring from the need of aftertreatment of the filtrate and the wash liquid.
Fundamental research aimed at improving pulping and bleaching processes almost invariably requires an understanding of the structural details of residual Kraft lignin. For such endeavors it is essential that the lignin remaining on the fiber be isolated from the black liquor in high yield and purity, unaltered and in the absence of contaminants. Isolation of lignin can be done many methods in that of acid hydrolysis using hydrochloric acid, sulphuric acid and hydrofluoric acid. Currently, a sulphuric acid
Department of Chemistry, Govt.SC, Bommankatte
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method is use for the isolation of residual lignin from black liquor. Despite extensive research efforts, aimed at obtaining residual lignin that it would completely comply with the above criteria both of these methods have limitations that need to be addressed. The acid hydrolysis technique, while it offers a residual lignin preparation of high purity, is plagued with relatively low yields and the possibility of structural alterations induced during the acidic treatment.
The Kraft process was developed by Carl.F.Dahl in 1879,with the name of the process coming from the German word Kraft, meaning strength/power. The Kraft process describes a technology for conversion of wood into wood pulp consisting of almost pure cellulose fibres.The first Kraft mill in the United States was not built until 1911 and was located in Pensacola, Florida. Today, the process is used in approximately 80% of paper production. Those companies using the Kraft process are easy to recognize by their strong, offensive smell. This is because one of the byproducts of the process is hydrogen sulfide gas and other sulfur gas compounds. The Kraft pulping process involves the digesting of wood chips at elevated temperature and pressure in white liquor, which is a water solution of sodium sulfide and sodium hydroxide. The white liquor chemically dissolves the lignin that binds the cellulose fibers together.
The invention of the recovery boiler by G.H.Tomlinson in the early 1930s was a milestone in the advancement of the Kraft process. Most Kraft pulp mills adopted this technology to recover and burn much of the black liquor, generating steam and recovering the cooking chemicals (sodium hydroxide and sodium sulfide used to separate lignin from cellulose fibers needed for papermaking).In fact this enhancement not only managed to deal with pollution load reduction and chemical recovery increase but also made Department of Chemistry, Govt.SC, Bommankatte Page 2
it possible for Kraft pulp mills to become self-sufficient energetically. In efficient recovery boiler mills the amount of energy is more than necessary to run the process and the surplus can be sold. Approximately 7 tonnes of black liquor (15%solids by weights of which 10% is inorganic).
Lignin is a complex chemical compound most commonly derived, from wood, and an integral part of the secondary cell walls of plants and some algae. The term was introduced in 1819 by De-Candolle and is derived from the Latin word lignum, meaning wood. Lignin polymers are mostly made of phenylpropanoid units linked to each other through different kinds of bonds. As a biopolymer, lignin is unusual because of its heterogeneity and lack of a dened primary structure. Its most commonly noted function is the support through strengthening of wood (xylem cells) in trees and improves water transport.
Resin is a natural or synthetic compound which begins in a highly viscous state and hardens with treatment. Typically, resin is soluble in alcohol, but not in water. There are a number of different classes of resin, depending on exact chemical composition and potential.
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WOOD CHEMISTRY:
1.1 TYPES OF WOOD:
Wood is the hard, fibrous substance found beneath bark in the stems and branches of trees and shrubs. Practically all commercial wood, however, comes from trees. It is plentiful and replaceable. Since a new tree can be grown where one has been cut, wood has been called the world's only renewable natural resource.
Two most important properties of any papermaking cellulosic raw material are, how much cellulose fiber it has and how long the fibers are. The amount of cellulose fiber in wood determines the pulp yield, ease of pulping and cost of pulp produced. The importance of fiber length is explained in pulp properties. The maximum average fiber length pulp will have is that of wood because whatever pulping method, full chemical to full mechanical, fiber is going to damage. In mechanical pulping the damage is physical (cutting, bruising etc.) and in chemical pulping it is chemical degradation (lower degree of polymerization).It has been estimated that based on a mixture of softwoods and hardwoods 12 meters (40 ft) tall and 15-20 centimeters (68 in) in diameter, it would take an average of 24 trees to produce 0.9 tonne (1 ton) of printing and writing paper, using the Kraft process (chemical pulping).
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CHEMICAL COMPOSITION OF WOOD:

Average chemical contents of wood: Elements Carbon Hydrogen Oxygen Nitrogen Sulphur Share, % of dry matter weight 45-50% 6.0-6.5% 38-42% 0.1-0.5% max 0.05
Wood is mainly composed of cellulose, Hemicellulose, lignin and extractives. The following table provides main chemical components of some wood species.
Constituents Cellulose (%) Hemicellulose (%) Lignin (%) Total Extractive (%)
Scot Pine 40.0 28.5 27.7 3.5
Spruce 39.5 30.6 27.5 2.1
Eucalyptus 45.0 19.2 31.3 2.8
Silver Burch 41.0 32.4 22.0 3.0
Wood Components Cellulose Hemicellulose Lignin Pectin Starch
Hardwood (%) 40 - 50 25 - 35 20 - 25 1-2 Trace
Softwood (%) 40 - 50 25 - 30 25 - 35 1-2 Trace
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PHYSICAL PROPERTIES OF WOOD: ASH CONTENT:

Ash is a solid particulate, inorganic combustion residue left after the wood is burnt. Ash content varies with different components of trees. Stem wood: 0.4-0.6% Stem bark: 2.0-5.0% & 1.0-2.0% As a mean value wood can be expected 1-2% ash content.
MOISTURE CONTENT: Wood may contain 50% moisture. Wood moisture provides lubrication to ground stone & keep the temperature low in grinding zone. Wood moisture help better chemical penetration during cooking due to diffusion.
1.2 PULPING:
Pulp is a dry fibrous material prepared by chemically or mechanically separating fibers from wood or fiber from wood or fiber crops. Pulp can be either fully or formed into thick sheets. The latter form is used if the pulp must be transported from the pulp mill to a paper mill. Pulp which is shipped and sold as pulp is referred to as market pulp. When suspended in water the fibers disperse and become more pliable. This pulp suspension can be laid down on a screen to form a sheet of paper, and this is the primary use for wood pulp. Wood pulp is the most common material used to make paper. The timber resources used to make wood pulp are referred to as pulpwood. Wood pulp comes from softwood trees such as spruce, pine, fir, larch, and hemlock and hardwoods such as eucalyptus,aspen,and birch.
1.3 BLACK LIQUOR

Department of Chemistry, Govt.SC, Bommankatte Page 6
Black liquor is a byproduct of the Kraft process, during the production of paper pulp. Wood is decomposed into cellulose fibers, hemicelluloses and lignin fragments. Black liquor is an aqueous solution of lignin residues, hemicellulose, and the inorganic chemicals used in the process. The black liquor contains more than the half of the energy content of the wood fed into the digester. Early Kraft pulp mills discharged black liquor to watercourses. Black liquor is quite toxic to aquatic life, and causes a very dark CocaCola color in the water. In chemical pulping a large part of the wood is dissolved during digestion. The dry matter content of the generated black liquor is typically 12 to 18 wt. %.In the case of Kraft liquors four main groups of organic constituents are present,30-45wt% ligneous material,2535wt% saccharinic acids, about 10wt% formic acid and acetic acid, and 35wt% extractives. It also contains about 1wt% methanol and many inorganic elements, mainly sodium(17-20wt %) and sulphur (3-5wt%).The exact composition of the black liquor varies considerably between different mills depending on the cooking conditions and feedstock. The vast majority of lignin in the spent liquors of pulp mills is used as in house fuel for the recovery of chemicals.
2. VISION:
Million tonnes of black liquor generation in a small scale will be money saving, time and energy.
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3. MPM AT A GLANCE:
Mysore paper mill was established in the year 1936. It is one of largest mill in India. MPM is located on the banks of Bhadra River. This mill used bamboo, euca, acacia, pine and bagasse as raw material for paper making.
This mill has three pulping plant, out of 3, two are chemical pulp mills that is CPM2 for hard wood and other one is for bagasse pulp plant called CSRMP ( cold soda refiner mechanical pulp plant ) this pulp is used to news print like papers.
Raw materials are used in MPM required mainly two sources 1. Captive sources 2. Privative sources
Captive plantation sources are requires mainly in 4 areas like 1. Tirathahalli 2. Sagara 3. Hosanagar 4. Bhadravathi
Hear all the activities are controlled by forest officer weighed woods are stored in the different stocks based on their quality, size & durability. it is very essential homogenize the different type of RM in the form 5-7 feet logs & diameter in 5-6 inch & those logs are made free roots, barks, knots & other undesirable impurities, which are not useful for paper making. According to the need of for chipper house. The stored RM is issued.
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Chipper house means the RM that is logs are cut in to small pieces (chips) with the help of chipper, & the pieces are stored in a tank called SILO. The materials rich in cellulosic fiber are used as RM. chipper are classified Into 2 types MPM based on the wood. Each chipper contains two types of blades for chipping. One is dead knife & other one is fly knife. Fly knife rotates with the help of motors. Chipping converts heterogeneous type of chipper into homogeneous & uniform type of chips.
1. Gsualiar chipper: - 5 chipper is working. 2. Pallmann chipper: - 2 chipper is working.
Gsualiar Chipper: - It is also called disk chippers. It is used to cut the hard wood like euca and acacia. In this chipper fly knife are added to big disc which is rotating with the help of motors.
Pallmann Chipper: - It is also called drum chipper. It is used to chip the soft wood like bamboo. Here the fly knife is adjusted to drum which is rotating with the help of motor. In pallmann chipper Feed roller are used to crust the RM.
The chips will conveyed to chip screener for separating the dust & oversized chips from accepted chips. The accepted chips are stored in SILO. The dust is sent to boiler as a source of energy. The oversized chips will go re chipper for making small chips. Chipper size: - Very important to maintain the size of chips. Because in CPM the liquor should penetrate easily. Length ----------13 to 25 mm Breadth ------------ 10 to 12 mm Width --------------- 06 to 05 mm Department of Chemistry, Govt.SC, Bommankatte Page 9
SILO: - SILO is a big tank for storing the chips. This comes from the chipper house. It has the capacity to store 700 tones of chips. It is classified into 3 different chambers. 1. Bamboo storage. 2. Euca storage. 3. Acacia & bamboo mix storage.
PULPING TECHNOLOGIES AT MPM: In MPM 3 varieties of pulp is producing. They are.
1. CSRMP: - (cold soda refiner mechanical pulping) for euca & Acacia. 2. CPM 1: - Chemical pulp mill for bagasse 3. CPM 2: - Chemical pulp mill for bamboo & wood.
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4. HISTORY OF LIGNIN:
For many years wood was considered to be uniform chemical compound. In 1811, Gay Lussac and Thenard carried the elementary analysis of wood and found its components consists entirely of carbon, hydrogen and oxygen and that no other elements, and that no other elements, such as sulfur and nitrogen, or only traces of the latter, are present. At about the same time, Prout reported same analysis of wood bers which he called fibres ligneux. These chemists believed that wood is a chemical entity.
With the development of the organic chemical experimental technique over a hundred years ago, however, chemists succeeded in separating wood into individual components. About 1815, Raspail expressed the opinion that wood may consists of several components and he suggested that the cell wall is buildup of gum and lime. That wood is not a uniform chemical compound was shown in 1819 by Braconnot and three years later by Authenrieth and Bayer hammer, when they found that wood gives glucose in boiling with dilute sulfuric acid. None of them, however, mentioned any other reaction products.
In 1834, Runge discovered that wood gives a green color reaction with phenol and hydrochloric acid, and a yellow color with aniline hydrochloride, but he did not realize the signicance of these reactions. The rst serious attempt to study the chemical composition of the cell wall of lignied plants was made in 1838 by Anselme Payen by the intelligent applications of different reagents; he succeeded in isolating a uniform compound which he called Cellules. He treated wood alternatively with nitric acid and caustic soda and in this way obtained cellulose bres
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which are considered as the basic substance of cell membrane. From the elementary analysis of wood and their celluloses, from the lignin it uses to be 55.6% carbon, 5.8% hydrogen and 38.6% oxygen.
From this he arrived at a formula, C19H24O10, for lignin. The carbon content he calculated ifs considerably lower than that he found for lignins isolated by newer methods. This is not surprising because the lignin content found by Schulze is much too high and includes a considerable portion of carbohydrates which lowers the carbon content. All attempts by Schulze to isolate lignin as such for a direct analysis failed. An attempt to isolate it by alkali fusion and acidication of alkaline solution resulted in very small amount of precipitate which had been altered chemically.
That interest in chemistry of lignin has continued to increase is shown by the fact during that decade since 1948, when the manuscript for The Chemistry of Lignin was completed, the amount of research carried out and the numbers of reviews written on the subject have exceeded those of any previous decade.
The brief history revives shows that the problem of lignin is an old one. Although a tremendous work had been carried out, particularly during the last quarter century, we are still remote from the nal solution of its constitution.
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4.1 HISTORY OF RESIN:

Plant resins have a very long history that was documented in ancient Greece by Theophrastus, in ancient Rome by Pliny the Elder, and especially in the resins known as frankincense and myrrh, prized in ancient Egypt.[1] These were highly prized substances, and required as incense in some religious rites. Amber is a hard fossilized resin from ancient trees. The English word originates from the late 14th century Old French resine, from L. resina "resin," from Greek rhetine "resin of the pine," of unknown earlier origin.
The first commercial attempts to prepare resins from epichlorohydrin were made in 1927 in the United States. Credit for the first synthesis of bisphenol-A-based epoxy resins is shared by Dr. Pierre Castan of Switzerland and Dr. S.O. Greenlee of the United States in 1936. Dr. Castan's work was licensed by Ciba, Ltd. of Switzerland, which went on to become one of the three major epoxy resin producers worldwide. Ciba's epoxy business was spun off and later sold in the late 1990s and is now the advance materials business unit of Huntsman Corporation of the United States. Dr. Greenlee's work was for the firm of Devoe-Reynolds of the United States. Devoe-Reynolds, which was active in the early days of the epoxy resin industry, was sold to Shell Chemical (now Momentive Specialty Chemicals, formerly Hexion, Resolution Polymers and others).
Early varnishes were developed by mixing resin, like pine sap, with a solvent and applying them with a brush to get the golden and hardened effect one sees in today's varnishes.[1] The ancient Egyptians were well acquainted with the art of varnishing, but its origin appears to be far east of there in India, China and Japan, where the practice of lacquer work, a species of
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varnish application, was known at a very early date. It has been claimed that Japan was acquainted with the art of lacquering by 500 or 600 B.C., but the majority of authorities place its first usage there to the 3rd century AD, as an art acquired from their neighbors, the Koreans. The Chinese and Indian peoples probably knew the art much earlier than the Japanese. Varnish and lacquer work are, however, generally treated in the arts as separate and distinct.
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Pulp is a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibres from wood, fibre crops or waste paper. Wood pulp is the most common raw material in papermaking. Pulp can be manufactured using mechanical, semi-chemical or fully chemical methods (Kraft and sulfite processes). The finished product may be either bleached or non-bleached, depending on the customer requirements. The aim of pulping is to break down the bulk structure of the fibre source, be it chips, stems or other plant parts, into the constituent fibers.
Chemical pulping achieves this by degrading the lignin and hemicellulose into small, water-soluble molecules which can be washed away from the cellulose fibers without depolymerizing the cellulose fibres.
Pulp category Chemical -Kraft -Sulfite -Semi chemical Mechanical
Production [M ton] 131.2 117.0 7.0 7.2 37.8
4.1.1 TYPES OF PULPING There are a number of different processes which can be used to separate the wood fibres.
Thermo mechanical pulp Thermo mechanical pulp is pulp produced by processing wood chips using heat (thus thermo) and a mechanical refining movement (thus mechanical). It is a two stage process where the logs are first stripped of Department of Chemistry, Govt.SC, Bommankatte Page 15
their bark and converted into small chips. These chips have a moisture content of around 25-30% and a mechanical force is applied to the wood chips in a crushing or grinding action which generates heat and water vapor and softens the lignin thus separating the individual fibers. The pulp is then screened and cleaned, any clumps of fiber are reprocessed. This process gives a high yield of fibre from the timber (around 95%) and as the lignin has not been removed, the fibres are hard and rigid.
Chemithermo Mechanical Pulp Wood chips can be pretreated with sodium carbonate, sodium hydroxide, sodium sulfite and other chemicals prior to refining with equipment similar to a mechanical mill. The conditions of the chemical treatment are much less vigorous (lower temperature, shorter time, less extreme pH) than in a chemical pulping process since the goal is to make the fibres easier to refine, not to remove lignin as in a fully chemical process. Pulps made using these hybrid processes are known as chemithermo mechanical pulps (CTMP).
Chemical pulp Chemical pulp is produced by combining wood chips and chemicals in large vessels known as digesters where heat and the chemicals break down the lignin, which binds the cellulose fibres together, without seriously degrading the cellulose fibres. Chemical pulp is used for materials that need to be stronger or combined with mechanical pulps to give product different characteristics. The Kraft process is the dominant chemical pulping method, with process being second. Historically soda pulping was the first successful chemical pulping method.
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Bleaching The pulp produced up to this point in the process can be bleached to produce a white paper product. The chemicals used to bleach pulp have been a source of environmental concern, and recently the pulp industry has been using alternatives to chlorine, such as chlorine dioxide, oxygen, ozone and hydrogen peroxide.
4.2 KRAFT PULPING:

The kraft process (also known as kraft pulping or sulfate process) describes a technology for conversion of wood into wood pulp consisting of almost pure cellulose fibers. The process entails treatment of wood chips with a mixture of sodium hydroxide and sodium sulfide, known as white liquor, that break the bonds that link lignin to the cellulose.
The kraft pulping process involves the digesting of wood chips at elevated temperature and pressure in "white liquor", which is a water solution of sodium sulfide and sodium hydroxide. The white liquor chemically dissolves the lignin that binds the cellulose fibers together.
There are 2 types of digester systems, batch and continuous. Most Kraft pulping is done in batch digesters, although the more recent installations are of continuous digesters. In a batch digester, when cooking is complete, the contents of the digester are transferred to an atmospheric tank usually referred to as a blow tank. The entire contents of the blow tank are sent to pulp washers, where the spent cooking liquor is separated from the pulp. The pulp then proceeds through various stages of washing, and possibly bleaching, after which it is pressed and dried into the finished product.
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Fig: Kraft pulping process
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4.3 AIM AND OBJECTIVES

AIM: Identification and Utilization of value added polyphenolic compounds from pulp mill waste. (Extraction of lignin from CPM-1 and CPM-2, wood and bagasse Kraft spent black liquor which is a byproduct of pulp mills, Kraft process and yield obtained and IR characterization of the lignin.)
Objective: Small scale Pulp mills generate a million tons of black which is sewered. Where as large scale industries are installing chemical recovery units to recover the chemicals. Due to environmental facts utilization of value added products like polyphenols from black liquor in bagasse Kraft pulping method could saves environment, energy and money.
Is to extract the lignin present in the bagasse Kraft spent liquor which is a bit expensive process but it is worth putting money for all the advantages we are going to get from it. By doing so instead of only burning it in boiler which is the bottle neck process for pulp industries for only power purpose it can also be employed in many use full ways. Where pulp industries are producing much more power than they are required to sustain, which can be sold out, but along with that it is necessary to use part of it to extract lignin which can be used in many ways. Lignin can be used to synthesize many alternatives like, an alternative to plastic, vanillin, agricultural chemicals and many more and also raw materials for several chemicals and high quality bleached paper. Create new projects using lignin as raw material and in the eld of lignin characterization.
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5. CHARACTERIZATION OF BLACK LIQUOR:

The Kraft black liquor used in this study was supplied by Mysore Paper Mills, Bhadravathi, and Shimoga Dist. The Monsteras paper mill is situated on the edge of the Bhadra River in the east of the Bhadravathi town. The Monsteras pulp mill uses a continuous digester. The cooking temperature is about 165-170C and delignication is done to a kappa number of 29-3 . The liquor was withdrawn between digester and preimpregnation as softwood pulp was being processed.
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5.1 METHODOLOGY:
Production of Black liquor: The Kraft pulping process involves the digesting of wood chips at elevated temperature and pressure in white liquor which is a water solution of sodium sulfide and sodium hydroxide. The white liquor chemically dissolves the lignin that binds the cellulose fibers together.
There are 2 types of digester systems, batch and continous.Most Kraft pulping is done in batch digesters, although the more recent installations are of continuous digester. In MPM (Mysore Paper Mills) the batch digester process is done, in a batch digester, when cooking is complete, the contents of the digester are transferred to an atmospheric tank usually referred to as a blow tank. The entire contents of the blow tank are sent to pulp washers, where the spent cooking liquor is separated from the pulp. The pulp then proceeds through various stages of washing, and possibly bleaching, after which it is pressed and dried into the finished product. The blow of the digester does not apply to continuous digester systems. The balance of the Kraft process is designed to recover the cooking chemicals and heat. Spent cooking liquor and the pulp wash water are combined to form weak black liquor which is concentrated in a multipleeffect evaporator system to about 55% solids. The black liquor is then further concentrated to 65% solids in a direct-contact evaporator, by bringing the liquor into contact with the flue gases from the recovery furnace, or in an indirect-contact concentration. The strong black liquor is then fired in a recovery furnace. Combustion of the organics dissolved in the black liquor provides heat for generating process steam and for converting sodium sulfate to sodiumsulfite.Inorganic chemicals present in the black liquor collect as a molten smelt at the bottom of the furnace. Department of Chemistry, Govt.SC, Bommankatte Page 21
The smelt is dissolved in water to form green liquor, which is transferred to a caustic zing tank where quicklime (calcium oxide) is added to convert the solution back to white liquor for return to the digester system. A lime mud precipitates from the caustic zing tank, after which it is calcined in a lime kiln to regenerate quick lime.
The characteristic odor of the Kraft mill is caused by the emission of reduced sulfur compounds, the most common of which are hydrogen sulfide, methyl mercaptan,dimethyl sulfide, and dimethyl disulfide, all with extremely low odor thresholds. The major source of hydrogen sulfide is the direct contact evaporator, in which the sodium sulfide in the black liquor reacts with the carbon dioxide in the furnace exhaust. Indirect contact evaporators can significantly reduce the emission of hydrogen sulfide. The lime kiln can also be a potential source of odor, as a similar reaction occurs with residual sodium sulfide in the lime mud. Lesser amounts of hydrogen sulfide are emitted with the non-condensable of off gases from the digesters and multiple-effect evaporators.
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5.2 LIGNIN ISOLATION FROM BLACK LIQUOR:

Several different enzymatic, chemical and mechanical methods have been developed for the isolation of lignin from black liquor.however,due to the heterogeneity that exists between individual fibres,no method is currently available for the quantitative isolation of native or residual lignin without the risk of structural changes during the isolation. Even if the perfect isolation technique could be found, the product would at best represent the average structure of native or residual lignin components. However, the information gained about the chemical reactivity and structure of isolated lignin is valuable. Thus, the three most commonly employed methods for isolating residual lignin are described below.
Lignin can be isolated currently, by two methods they are isolation of residual lignin from Kraft pulp that of enzymatic hydrolysis using cellulolytic enzymes, and that of acid hydrolysis of black liquor using a solution of hydrogen chloride and sulfuric acid in dioxane/water.
5.4 EXPERIMENTAL PROCEDURE:

Bagasse Kraft Spent Liquor obtained after production of paper, which is highly dilute in nature is passed and stored in the CPM-2 processor plant to evaporate to some extent. And then it is passed to CPM-1 plant to evaporate it to much more extent than in the CPM-2 evaporator plant and then it is passed to evaporator where it is evaporated to larger extent to get a highly concentrated black liquor which is passed to boiler for combustion to produce steam which in turn to produce power. The black liquor taken for our project to isolate lignin is from the CPM-2 is highly dilute in nature and its solid content is about 14-18%.Out of the three types of black liquor CPM-
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2 is the better one to isolate lignin in good yield. Other than that CPM-1 and evaporator black liquor are having concentration and solid content.
Precipitation: About 1litre of Dilute Bagasse Kraft Black Liquor (CPM-2liquor) is taken in a beaker and it is treated with 70% sulfuric acid which is added slowly, the whole set up is kept in ice water bath, constant stirring is done to prevent spilling. Constant pH is maintained in between 2-3 with the help of the pH-meter. A gelatinous solution of dark blackish brown in color is obtained. It allowed for 24hours settling down.
And then it is filtered using vacuum pump the filtrate is washed with dilute sulfuric acid of 3% and washed with hot distilled water until the sulfuric acid content is removed completely and also the sulphates and chlorides. The sulfuric acid lignin often contains 2-5% sulfur which is Department of Chemistry, Govt.SC, Bommankatte Page 24
mostly removed by heating with 1litre 0.5%hydrochloric acid for about 8-10 hours. The cake is reddish brown in color, waxy in nature, dried in open hot air drier at 60C a luster yellowish brown of lignin separates. A technical sulfuric acid lignin is known as Scholler Lignin.
5.5 METHODS OF PREPARATION OF LIGNIN:

In order to isolate lignin from lignied substance, a carefully selected starting material must be used like when woods are utilized knots, bark, and resin are used, but when coming to industrial products or by products pulp, bagasse, and Kraft spent liquor may be used. In our project We are using Wood & Bagasse Kraft Spent Liquor as the starting material for the isolation of lignin. Lignin can be isolated from black liquor by many methods they are as follows,
Sulfuric Acid Lignin or Klason Lignin:

The isolation of lignin by means of sulfuric acid is based on a discovery of Braconnot in 1819. In spite of earlier reports, Klason in198O was the rst to propose the use of 64 72% sulfuric acid for the hydrolysis of the carbohydrates in the isolation of lignin. This method is therefore generally associated with his name in the literature and the product obtained is referred to as Klason Lignin or Sulfuric Acid Lignin. The conditions he recommended for quantitative lignin determination can also be applied to the preparation of lignin on a large scale.
5.6 GENERAL PROPERTIES OF LIGNIN:

It is a resinous material. Soluble in Water, coagulates, colloidal solution.
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Melting Point is 18000. Lignin is co-precipitated with natural GRS and Nitrile Elastomers. It provides sufcient formaldehyde reactants. It follows condensation reaction due to polyhydroxy groups. Inhibiting properties of lignin: Inhibitory efcacy has been determined by the method of the weight losses of steel in acid with native lignin, hydrolysis lignin, ammoniated native lignin, chlorinated hydrolysis lignin, and ammoniated hydrolysis lignin, and Without these additives. It has been established that the efcacy of lignin and its modications as inhibitors of acid corrosion increases with a rise in the number of carboxyl groups in the macromolecule, and therefore the ammoniated hydrolysis lignin is the most effective. It is capable of forming water proof bonds and wood derivatives/substrates after hydroxyl methylation.
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5.7 GENERAL PROCEDURE:
5.8 CALCULATIONS:
Black liquor initial PH: CPM 1 =13.27 CPM 2 =13.06
Black liquor +sulphuric acid: CPM 1 =4 CPM 2 =4
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CPM 1: Weight of empty sintered glass crucible( W1) =50.170g Weight of sintered crucible + precipitate (W2) =50.198g CPM 1 (W) =W2-W1 =50.198 -50.170 =0.028g CPM 1 =2.8g/liter
CPM 2: Weight of empty filter paper (W1) =1.543g Weight of filter paper + precipitate (W2) =1.721g CPM 2 (W)= W2-W1 =1.721-1.543 =0.17g CPM 2=1.78g/lite
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6. GENERAL PROPERTIES OF RESIN:

High tensile strength, Heat distortion temperature, Low water absorption, Mould shrinkage, High surface hardness, Volume resistance Excellent mechanical properties over temperatures from below -40C (40F) to above 148C (300F) Self-extinguishing, non-dripping characteristics Excellent dimensional stability and low water absorption Resistance to aqueous chemical environments
Excellent impact strength
The practical melting point varies with different specimens, some being semi-fluid at the temperature of boiling water, others melting at 100C to 120C. It is very flammable, burning with a smoky flame, so care should be taken when melting it. It is soluble in alcohol, ether, benzene and chloroform.
STRUCTURE OF RESIN:
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6.1 PREPARATION OF RESIN: ALCOHOL BENZENE SOLUBILITY METHOD:

Reagent: Alcohol benzene Mixture: Mix one volume of
approximately 95 % Ethanol and two volumes of Benzene.
Sulphuric acid 72 % carefully pour 665 ml of concentrated sulphuric acid into about 300 ml of water and after cooling, dilute to one liter. Standardize against standard NaOH solution using methyl orange as indicator.
Adjust the acid to strength of 72 +/- 0.1 % by addition of water or concentrated sulphuric acid as may be found necessary.
6.2 METHODOLOGY:
Weigh the oven dried test specimen of approximately 10-g to the nearest 0.01 g in tarred extraction thimbles.
Clean, and then dry the sox let- extraction flask. Place the extraction flask with 150 cm of the required solvents. Connect the flask to the extraction apparatus and start water flow to the condenser section. Adjust the extraction apparatus and start water flow to the condenser section. Adjust the heaters to provide a boiling rate, which will cycle the specimens for not less than 24 extractions over a 4-5 hour period. Remove the flask from the apparatus and partially evaporate the solvent in the extraction flask to a volume 20-25 cm.
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Transfer the extract to the tarred weighing dish by washing with small amounts of fresh solvent. Handle the weighing dish with forceps or tongs. If using benzene, evaporate the solvent to near dryness, while in the chemical fume hood. Dry the dish and contents in an oven for 1 hr at 105degree c cool in a desiccators, and weigh to the nearest 0.1- milligram. Run a blank determination with the solvent used in the test. Evaporate 150 cm of the solvent to dryness, and weigh the residue to the nearest 0.1 milligram. Correct the weigh the residue to the nearest 0.1 milligram. Correct the weight of the dried extract by the weight of residue found.
6.3 CALCULATION:
Weight of thimbles+ concentrated sample=15.788g Weight of concentrated moisture less thimbles=14.498g Difference in Weight of concentrated sample=1.29g
Weight of thimbles + firing sample=15.880g Weight of firing moisture less thimbles =14.748g Difference in Weight of firing sample=1.132g AFTER THE PITCH PROCESS:
FOR CONCENTRATED BLACK LIQUOR:
Weight of round bottom flask( W1)=179.776g Weight of round bottom flask + Resin (W2)=180.901g W=W2-W1 = 180.901-179.776 =1.125g Percentage for concentrated liquor:17.33%
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FOR FIRING BLACK LIQUOR: Weight of round bottom flask(W1)=115.253g Weight of round flask + Resin(W2)=116.338 W=W2-W1 = 116.338-115.253 =1.085g Percentage of firing liquor =17.78%
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7. CHARACTERIZATION
At Infrared -spectroscopy:
Infrared (IR) radiation is electromagnetic radiation whose wavelength is longer than that of visible light (400-700 mn), but shorter than that of terahertz radiation (100 um - l mm) and microwaves (~30,000 um). Infrared radiation spans roughly three orders of magnitude (750nm and 100 pm).
Common Applications:
Identication of compounds by matching spectrum of unknown compound with reference spectrum (ngerprinting). Identication of functional groups in unknown subtend the light our eyes see is but a small part of a broad spectrum of electromagnetic radiation. On the immediate high energy side of the visible spectrum lies the ultraviolet, and on the low energy side is the infrared. The portion of the infrared region most useful for analysis of organic compounds is not immediately adjacent to the visible spectrum, but is that having a wavelength range from 2,500 to 16,000 nm with a corresponding frequency range from 1.9*103 to 1.2*10 Hz.
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Simplified optical layout of typical FTIR spectrometer.
A Fourier transform is a mathematical operation used to translate a complex curve into its component curves. In a Simplied optical layout of typical FTIR spectrometer.(Reprinted by Fourier transform infrared instrument, the complex curve is an interferogram, or the sum of the constructive and destructive interferences generated by overlapping light waves, and the component curves are the infrared spectrum. The standard infrared spectrum is calculated from the Fourier-transformed interferogram, giving a spectrum in percent transmittance (%T) vs. light frequency (cm-1). IR spectroscopy regions have been classied in to three regions, Near IR (12,500 - 4000m") Mid IR (4000 0- 4400m") Far IR (400 - 10cm") The mid region IR is fundamental IR region which is more useful region for organic compounds and inorganic compounds. IR spectra of the
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compounds were recorded by KBr pellet technique in the range of 4000 550 cm-1.
Structure of lignin:
A. Ketonic Structure of Lignin. Lignin is a cross-linked racemic macromolecule with molecular masses in excess of 10,000 amu. It is relatively hydrophobic and aromatic in nature. The degree of polymerization in nature is difcult to measure, since it is fragmented during extraction and the molecule consists of various types of substructures which appear to repeat in a haphazard manner. Different types of lignin have been described depending on the means of isolation. There are three monolignol monomers, methoxylated to various degrees: p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. These lignols are incorporated into lignin in the form of the phenylpropanoids phydroxyphenyl (H), guaiacyl (G), and syringal (S) respectively. Molecular fonnula of Protolignin is C92H108O38.
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B is the structure of on-Lignin and C is the B-Lignin.
7.1 CONSTITUENTS GROUPS OF LIGNIN:

Lignin structure consists of following constituents like methoxyl group, hydroxyl group, carbonyl group, carboxylic group, double bonds. Which are conformed as follows bellow,
i. Methoxyl Groups; A qualitative test for alkoxide groups in lignin was developed by Kratzl and Osterberger. In this method the alkoxide iodide as obtained in the Zeisel determination is allowed to react with thiourea, and the alkyl thiourea is isolated as its picrate. Kratzl and Gruber separated and determined quantitatively the methoxyl and ethoxyl groups in lignin preparation by means of gas-liquid chromatography [3].Lignin mainly contains methoxyl OCH3; which show a very little afnity towards water molecule. It cannot participate in the hydrogen with the available electronegative atoms or groups either in the water or cellulosic bers.
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ii. Hydroxyl Groups; The hydroxyl groups, there differentiation and quantitative
determination have played an important role in recent lignin chemistry. There is no doubt that lignin contains phenolic and aliphatic hydroxyl groups and, since some them may be etheried and form either alkyl ether or heterocyclic (furan or pyran) rings, their quantitative determination may contribute to the elucidation of structure of lignin molecule.
iii. Carboxyl Groups; The presence of carboxyl groups in lignin and lignosulphonic acids has been the subject of controversy for many years. While it is generally believed that protolignin does not contain any carboxyl group, Regestad and Samuelson and Freudenberg and co Workers reported that they had found such groups in lignosulphonic acid; Kullgren also reported their presence in the lignosulphonic acid in unbleached sulte pulp.
iv. Double Bonds; The presence of aliphatic double bonds in lignin is still doubt. According to Aulin Erdtman, ultraviolet absorption analysis show that spruce protolignin contains less than 0.03 to 0.04, double bond, conjugated with a phenolic ring, per methoxyl groups. Alder and Ellmer believed they have denitely proven the presence of coniferyl aldehyde groups in lignin by the phloroglucinol-hydrochloric acid color reaction given by lignosulphonic acid after treatment with sodium hydroxide. This treatment splits off not only the sulfurous acid which is loosely combined to the aldehyde group but also the sulfonic acid which is attached to the oi carbon atom of the coniferyl aldehyde side chain in lignosulphonic acid and thus regenerates the double bond in this side chain. Department of Chemistry, Govt.SC, Bommankatte Page 37
Weather this double bond is present in protolignin is still debatable, since a hydroxyldihydriconiferyl structure with a hydroxyl group at or position may occur in protolignin and this hydroxyl would be replaced by a sulfonic acid group in the lignosulfonic acid. In protolignin and soluble native lignin, the hydroxyl group may be split off as water by the action of the mineral acid in the Wiesner reagent.
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8. APPLICATIONS OF LIGNIN:
1. Lignin in Wood Adhesives:
Lignin-based wood adhesives are obtained that satisfy the requirements of relevant international standards for the manufacture of exterior-grade wood particleboard, They are prepared and tested for application to wood panels such a particleboard. The adhesives yield good internal bond strength results for the panels which are good enough to comfortably pass relevant international standard specifications for exteriorgrade panels. The adhesives also show sufficient reactivity to yield panels in press times comparable to that of formaldehyde-based commercial adhesives.
In the manufacture of certain types of water soluble glues and adhesive lignosulfonates is due partly to their sugar content. Adhesive of superior performed and with a wide range of applications are made from lignosulfonates in solution of high viscosity. Typical examples are glues from mixture of lignosulphonates with polyvinyl alcohols and
polyacrylamide.
2. Agriculture: Lignosulfonate from suspension or dispersion in variety of stable insecticide, fungicide, or herbicide. They are compactable with other anionic tension active and are frequently used in conjunction with wetting agents, improving the action of lost.
By precipitating their black liquor with acid or acids evolved gases like CO2 are sustentions used in conjunction with wetting agents Agricultural pesticides. Generally, agricultural pesticides are manufactured in the form of Department of Chemistry, Govt.SC, Bommankatte Page 39
dilute suspension or dispersions for doing so, it is necessary to incorporate a high active dispersant lignosulfonates act as grinding acids, as well as dispersants.
The suspension should not only from spontaneously but should also be maintained during the period of application, zinc, copper, iron, magnesium etc. complexes of lignosulphonates be incorporated in the composition of fertilizers t supplement micro nutrients to the plants.
3. Lignin in biodegradable composites: Composites from alkali lignin and wheat gluten, modified with different percentages of sodium silicate, were prepared and characterized. Moreoreover, the addition of silica to the aforementioned composites was studied with the aim of improving the thermal and mechanical properties. The effect of wheat gluten percent and the extent of its modification on the blends properties were investigated via diametric tensile strength, thermo mechanical analysis (tma), scanning electron microscope (SEM), thickness swelling and thermo gravimetric analysis (tga). The results showed significant improvement in the diametric tensile strength, thickness swelling, uniformity in the fracture surface, and the shift of glass transition temperature (tg) toward higher values with increasing wheat gluten percent and its modification extent.
4. Engineering plastics from lignin:

Hydroxypropylation of lignin in a batch reactor under alkaline conditions at 180C was studied using propylene oxide (PO) by itself and PO in combination with several lignins like model compounds and with Kraft lignin.
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5. Lignin based paint:

A method is provided for producing a painted article comprising: (a) preparing a lignin solution comprising lignin and a dye or pigment; (b) mixing the lignin solution with a phenol oxidizing enzyme; (c) incubating the mixture from said step (b) under conditions and for a time sufficient to form a solution of a desired viscosity; (d) contacting or spreading the mixture from the step (c) on an article to be painted; and
6. Fire Extinguishers:
Lignosulfonates have as applications as foam stabilizers for the extinguishing foams (such as in airports, oil refiners etc) lignosulfonate stabilized foams are prepared from hydrolyzed protein extracts.
7. The Biological application of Lignin-Contained Compounds:

The investigation of biological properties of lignin-contained compounds (LCC) as multitonnage wastes of woodworking industry is very actual from the viewpoint of estimation of their treatment on ecosystems. The purpose of this work was to study the relationship between macromolecular, mutagenic and growth-regulating properties of LCC. LCC in water medium and in swelling state (at moisture 3 60%) behave as polyanions and/or neutral molecules according to value of pH, whose action on biological objects is connected with competition mechanisms. They disturb the structural-functional systems of cells: genetical, membraneous, ferment-protein.
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8.1 APPLICATION OF RESIN: 1. Wood Protection:

Hydrocarbon resins are widely used in wood protection coatings because of their water-repellant and fixing properties, i.e. fixing fungicides, insecticides and helping to prevent "blooming" of wood preservatives.
2. Agriculture: Most recent studies point out that resin is a good inducer for defense mechanisms in plants. It has also been assessed as a fertilizer that can improve overall crop yields. The EPA regulates chitin for agricultural use within the USA. Chitosan is prepared from chitin by deacetylation.
3. Industrial: It used in industry in many processes. It is used as an additive to thicken and stabilize foods and pharmaceuticals. It also acts as a binder in dyes, fabrics, and adhesives. Industrial separation membranes and ionexchange resins can be made from chitin. Processes to size and strengthen paper employ chitin.
Also, there is potential for applications in solar cells and cell phone screens; when chitin is treated in hydrochloric acid, sodium hydroxide and ethanol to strip the material of minerals, proteins, lipids, fats and pigments, and supplemented with acrylic resin monomer, a clear product results. Crushed and spread into a nanocomposite film it forms a useful component for solar cell and cell phone screens.
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4. Paints and Varnishes: Many traditional solvent based coatings contained a so-called hard resin. These resins are used to improve hardness, gloss, dry time and improve water repellency and resistance to saponification. Hydrocarbon resins with softening points of 100 -120 C are often used in the formulation of aluminum and bronze paints, aerosol paint, primers and alkyd paint modifiers.
5. Temporary Rust Protection Coatings: In steel construction as well as other applications, temporary rust prevention is very important. Hydrocarbon resins are commonly used along with waxes, anticorrosion agents and a low KB solvent such as mineral spirits.
6. Floor Tiles: Hydrocarbon resins are commonly used in the manufacture of floor tile based on PVC or SBR rubber. They are mainly used as processing aids. A wide range of resins may be used with choice depending mainly on price and end use requirements.
7. Medicine: Resins are flexible and strong material make it favorable as surgical thread. Its biodegradability means it wears away with time as the wound heals. Moreover, it has some unusual properties that accelerate healing of wounds in humans.
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9. RESULTS:
Characterization of the lignin is an extremely difficult task because of their diversity in respect with both sources and extraction methods. The heterogeneity of lignin is due to the changes in polymer composition, size of morphological units, crosslinking, nature of the functional groups, linkage types between various moieties such as phenylpropanoic.p-hydroxylphenyl, guaicyl, siryngyl,etc. Lignins from Black liquor with different chemical composition and properties can be obtained by use of several extraction methods. Commercial chemical pulping processes produce lignosulfonates and Kraft lignins as residues. Recently commercialized alkaline pulpingprecipitation process supply sulfur-free, free-flowing lignin.
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Figure 1: FT-IR Spectrum EBL-M
Page 45
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10. DISCUSSION:
The result given by the IR spectra shows and confirms the lignin present in the bagasse Kraft spent liquor. With this result we can say that using black liquor only for power purpose is not the only use it can be used to isolate lignin for commercial purpose which can be used in alternative for many products, in the alternative form of lignin. In this method of isolation of lignin is easy and there is not much complicated or risk it can be adapted in pulp mills as an additional plant which helps in converting the spent liquor not only to produce power but also to isolate lignin. From that lignin many derivatives can be synthesized which can be used in many fields, like Agriculture, paint industries, adhesives, and many more.
Lignin can undergo many reactions which give derivatives of lignin in which one of the important derivative is the sulfonated lignin and vanillin. Some of the reactions which lignin undergo are as follows, Sulfonation of lignin. Nitration of lignin Alkylation of lignin Amination Methylation Compost formation.
Synthetic Vanillin is one of the most important derivative which is synthesized from the lignin which is a flavoring agent used in the alternative for the natural lignin.
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Lower molecular weight compounds and polymer products are synthesized from the lignin.
Low molecular compounds are, Vanillin Phenolic compounds
The Polymer products are, Lignin Sulfonates Cement and Concrete. Binders and Adhesives Rubber Additives Emulsifier and Stabilizers
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11. CONCLUSION:
In small scale ,Its better usage of lignin from black liquor Small scale Pulp mills generate a million tons of black liquor, which is sewered. Where as large scale industries are installing chemical recovery units to recover the chemicals. Due to environmental facts utilization of value added products like polyphenols from black liquor in bagasse Kraft pulping method could saves environment, energy and money. Using better quality raw material to achieve desired brightness, Manipulation of raw material quality enables use of lesser quantity of bleaching chemicals, hence requires less water quantity of bleaching and washing. Black Liquor spills can be collected in tank and recycled back to the system. This reduces fresh water consumption required for floor washing. All native lignins are heterogeneous biopolymers linked to polysaccharides Alkaline or acidic processes result in both lignin degradation and repolymerisation The up-grading of technical lignins require purification steps Several options exist for an increased lignin use Increased pulp production in small scale. Reduced thermal load in the recovery boiler. Reduced oil consumption Go Green Excess energy can be avoided. IR data showed that lignin particles are present in the black liquor in their altered form.
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Lignin was precipitated successfully from black liquor at different pH values, precipitates of good quality
It is very difficult to elucidate the structure of lignin because of different structure of lignin is present in different wood. Instead of using lignin for only combustion to produce power but it can be used to isolate lignin which is commercially demanded. Not all the lignin produced from black liquor is used for power production, some of it is treated and let to water recourses. Lignin can be used to synthesis many alternatives like, an alternative to plastic, vanillin, agricultural chemicals and many more and also raw materials for several chemicals and high quality bleached paper. From which we can conserve our natural resources from getting vanished from the face of the earth and preventing pollution of our environment.
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PHOTOS:
Fig: Semisolid Black Liquor.
Fig: Wood Barks
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Fig: Wood chips
Fig: black liquor
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REFERENCES:
Advances in biochemical engineering /biotechnology by H.jhanshekar & A.Fietcher. Purification of lignin fuel from Kraft pulping of black liquor by diafiltration Cecilia Johansson., Lund university. The chemistry of lignin by, Friedrich Emil Braun. The institute of paper chemistry, Appleton, Wisconsin. Wood and Cellulosic chemistry by, David N.S.Hon.Nobuo shiraishiMarcel Dekker 2001. Wood and Cellulosic Chemistry (second edition) books.
www.cplbookshop.com/contents/C157.htm Ingentaconnect Wood and Cellulosic Chemistry - dn-S. Hon and N ... Wood and Cellulosic Chemistry - dn-S. Hon and N. Shiraishi, editors, 2nd ed., revised and expanded. Marcel Dekker, Inc. New York, Basel. ISBN 0-8247-0024-4. ... www.ingentaconnect.com/content/els/01413910/2001/00000073/0000 0003/art00147;jsessionid=5bip0o6qtg93l.alice?format=print Journal of Photochemistry and Photobiology B: Biology :
Yellowing ...In: dn-S. Hon and N. Shiraishi, Editors, Wood and Cellulosic Chemistry (2nd Edition ed.),, Marcel Dekker, New York (2000), pp. 512546. ... linkinghub.elsevier.com/retrieve/pii/S1011134402004128 BEST AVAILABLE TECHNIQUES FOR THE PULP AND PAPER INDUSTRY,CEMBUREAU 2000 http://www.cembureau.be/Documents/Publications/CEMBUREAU_B AT_Reference_Document_2000-03.pdf
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Energy and Cost Reduction in the Pulp and Paper industry A Benchmarking Perspective, Canada 2002 http://oee.nrcan.gc.ca/publications/infosource/pub/cipec/pulp-paperindustry/pdf/pulppaper-industry.pdf http://inventors.about.com/library/inventors/blpapermaking.htm#general http://www.hurterconsult.com/nonwood_uses.htm (non-wood pulping)
Kraft Pulping Peder Kleppe inTappi Journal 53(1):35 (1970) Chemical and Physical Performance of Kraft Cooking: The Impact of Process Alternatives.Panu Tikka, Martin MacLeod, & Kari Kovasin Tappi Journal 70(11):47 (1991)
S. Quideau, D. Deffieux, C. Douat-Casassus, & L. Pouysgu, 2011. Plant polyphenols: chemical properties, biological activities, and synthesis. Angew Chem Int Ed Engl. 2011, 50(3):586 621; doi:10.1002/anie.201000044
Plant polyphenols (vegetable tannins): gallic acid metabolism. Haslam E. and Cai Y., Nat Prod Rep, 1994, 11, pp. 41 66, doi:10.1039/NP9941100041
J.W. Drynan, M.N. Clifford, J. Obuchowicz & N. Kuhnert, The chemistry of low molecular weight black tea polyphenols, Nat. Prod. Rep., 2010, 27, 417-462
www.naturalproductsinsider.com/articles/2008/08/polyphenols-andflavonoids-in-product-formulation.aspx Grant, Roger and Grant, Claire; Grant and Hockh's Chemical Dictionary (5th ed.); McGraw-Hill Book Company; 1987
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Study and Characterization of Polyphenolic Compounds From Black Liquor of Kraft Pulping

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Study and Characterization of Polyphenolic Compounds From Black Liquor of Kraft Pulping

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Study and Characterization of Polyphenolic compounds from Black Liquor of Kraft Pulping

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

CHEMICAL COMPOSITION OF WOOD:

Scot Pine 40.0 28.5 27.7 3.5

Spruce 39.5 30.6 27.5 2.1

Eucalyptus 45.0 19.2 31.3 2.8

Silver Burch 41.0 32.4 22.0 3.0

Wood Components Cellulose Hemicellulose Lignin Pectin Starch

Hardwood (%) 40 - 50 25 - 35 20 - 25 1-2 Trace

Softwood (%) 40 - 50 25 - 30 25 - 35 1-2 Trace

Department of Chemistry, Govt.SC, Bommankatte

PHYSICAL PROPERTIES OF WOOD: ASH CONTENT:

1.3 BLACK LIQUOR

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

1. Gsualiar chipper: - 5 chipper is working. 2. Pallmann chipper: - 2 chipper is working.

PULPING TECHNOLOGIES AT MPM: In MPM 3 varieties of pulp is producing. They are.

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

4.1 HISTORY OF RESIN:

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

Pulp category Chemical -Kraft -Sulfite -Semi chemical Mechanical

Production [M ton] 131.2 117.0 7.0 7.2 37.8

Department of Chemistry, Govt.SC, Bommankatte

4.2 KRAFT PULPING:

Department of Chemistry, Govt.SC, Bommankatte

Fig: Kraft pulping process

Department of Chemistry, Govt.SC, Bommankatte

4.3 AIM AND OBJECTIVES

Department of Chemistry, Govt.SC, Bommankatte

5. CHARACTERIZATION OF BLACK LIQUOR:

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

5.2 LIGNIN ISOLATION FROM BLACK LIQUOR:

5.4 EXPERIMENTAL PROCEDURE:

Department of Chemistry, Govt.SC, Bommankatte

5.5 METHODS OF PREPARATION OF LIGNIN:

Sulfuric Acid Lignin or Klason Lignin:

5.6 GENERAL PROPERTIES OF LIGNIN:

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

5.7 GENERAL PROCEDURE:

Black liquor +sulphuric acid: CPM 1 =4 CPM 2 =4

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

6. GENERAL PROPERTIES OF RESIN:

Excellent impact strength

Department of Chemistry, Govt.SC, Bommankatte

6.1 PREPARATION OF RESIN: ALCOHOL BENZENE SOLUBILITY METHOD:

approximately 95 % Ethanol and two volumes of Benzene.

Department of Chemistry, Govt.SC, Bommankatte

FOR CONCENTRATED BLACK LIQUOR:

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

Simplified optical layout of typical FTIR spectrometer.

Department of Chemistry, Govt.SC, Bommankatte

Department of Chemistry, Govt.SC, Bommankatte

B is the structure of on-Lignin and C is the B-Lignin.