ALL K.L &Co 1 1.

1 CHEMICAL REACTIONS IN KRAFT PULPING IN COOKING The main objective is to facilitate the disintegration of wood into fibrous product. This is achieved by breaking the bonds in the lignin macromolecule. The main chemical reactions in the cooking process can be described as !a"# $ !a%& $ 'ood !a(org. $ %(org. $ !a#% 'here the wood represents many different organic compounds such as Lignin) Cellulose) #emi(cellulose) and *esins. #emi(cellulose can be divided into three major organic group +lucomannan) ,ylan and other hydrocarbon groups. These are present in following proportions in wood./ Cellulose +lucomannan ,ylan "ther hydrocarbons Lignin *esins 01( 2& 3 &(&4 3 5(04 3 673 &4(04 3 &( 8 3

The chemical composition of the pulp final product is- ./ Cellulose +lucomannan ,ylan "ther hydrocarbons. Lignin *esins 5&(50 3 &(.4 3 .4(04 3 6. 3 &(7 3 6. 3

Cellulosa is basically a long molecule chains formed by the monomer of glycose. Any reaction with the cellulose molecule is not wanted in the pulp production - ./. 1.1.1 Consumption of Alk li The solution of %odium sulphite and %odium hydro9ide in water is generating a e:uilibrium as follows - 0/ %&( $ #&" 6;;< %#( $ "#( %#( $ #&" 6;;< %&# $ "#( Alkali in the cooking li:uor is basically consumed in three different reactions- 0/ .. 'ith lignin) &. !eutralisation of organic acids) 0. 'ith resins in the wood.

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ALL K.L &Co *?ACT@"!% '@T# L@+!@! As the carbon to carbon bond are stable in alkaline conditions) the cleavage of o9ygen ( carbon bonds are the most significant reaction in the cooking process. This reaction will take place and is producing phenolic hydro9yl groups from the cleavage of the aryl(alkyl(ether bounds. - .&. / "ne of the main products being the phenyl coumaran. The phenolic carbons are in the following reaction mainly converted to stilbene. %ee also the reaction description in appendi9 .. !?AT*AL@%AT@"! "B "*+A!@C AC@C% Dost of the alkaline is consumed in the cooking process by the saccharine acids formed in the degradation of hemicelluloses. #emicellulose is a polysacchrridic substance which includes galactoglucomannan) arabinoglucoron9ylan) arabinos) arabinogalactane) glucoron9ylan) glucomannan) and acids from glucorans and galactorons. The saccharinic acids formed by the degradation contains = isosaccharidic acids) milk acid) formic acid and acetic acid. *?ACT@"!% '@T# *?%@!% "B '""C @n the cooking reaction many of the resins forms sodium salts of fatty and harts resins this are occurring a soap. And are usually skimmed of from the black li:uor in the evaporation area. They are also processed to produce tall oil. %ee below. 1.1.! Sulp"i#it$ in K% ft pulpin& %ulphidity is defined as .44 E !a&%F> -E!a"#F$E!a&%F/ where the concentrations are e9pressed as e:uivalents of !a&" or !a"#) respectively. The function of sulphide in the kraft process is two(fold= it promotes and accelerates the cleavage of the ether links in phenolic units and is reduces the e9tent of undesirable condensation. CL?AGA+? "B ?T#?* L@!K% "nly the arylglycerol($(ethers are direct reactive of all the non(phenolic units in lignin. Ander influence of a high temperature they are converted to free glycerol side(chains and new phenolic groups. T#? A!C?%@*AHL? C"!C?!%AT@"!

& #"C#&(C8#2-"#/("C#0 $ & #&% ((< #0C"(-"#/C8#2(C#&(%(%(C#&(C8#2-"#/("C#0 $ & #&" The condensation of dissolved material is larger in the case of pine kraft pulp then in the case of Hirch Kraft pulp. This may be due to the different contents of hemicellulose ) as Hirch has mostly 9ylan hemicellulose while Iine contain both 9ylan and glucoman hemicellulose -2/.
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ALL K.L &Co *?ACT@"!% I*"CAC@!+ DAL"C"A*"A% +A%?% Anwanted reactions are the once producing org. $ %( C#0%# - g/ org. $ %( C#0%C#0 - g/ org. $ %( C#0%&C#0 -g/ These are all gases which is limited dissolved in the black li:uor e9iting the cooking process. HJ(I*"CACT% Also turpentine and methanol is a by(product of the cooking reaction ) this is usually about 4). ( 4)7 kg > ACt) 1.! IN 'LEACHING Hleaching of Kraft pulp is essentially degrading of the few per cent of aromatic products) originated from lignin) which could not be dissolved during cooking. This is called residual lignin and is of a phenolic type. Dany phenolic groups have a conjugated double bond on side chain forming stilbene) styrene and enol(gruops -7 /. The bleaching agents can be classified in three different groups +roup @ Chlorine - Cl&/ - C/ "Kone - "0/ -L/ *eacts with any phenolic group $ double bond +roup @@ Chlorine dio9ide - Cl"&/ - C/ "9ygen - "&/ -"/ *eacts with free phenolic groups -$ double bond/

+roup @@@ %odium hypochlorite - !a"Cl/ - #/ #ydrogen pero9ide - #&"&/ - I/ G%oup on( %( )tions n# %( )tion p%o#u)ts* The main reaction by chlorine and oKone is a electrophilic substitution on
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ALL K.L &Co aromatic rings) other reactions are cleavage of aryl(ether linkage i.e. demetho9ylation and depolymeriKation - 8/ . These reactions take place on any phenolic group -7/. The reaction products are mainly polychlorinated aromatic rings- with chlorine/ or carbo9ylates - with oKone /. Also formation of Duconic acid derivatives has been proposed in reactions between oKone and phenolic groups. G%oup t+o %( )tions n# %( )tion p%o#u)ts* These two agents have in common the fact that they are radicals. This again indicates that they primarily react with phenolic rings with free "# groups - of all residual lignin this is about 04 3 / - 5)1/. The reaction products in this case is carbo9ylic and carbo9ylate groups . These are soluble in alkaline medium. G%oup t"%(( %( )tions n# %( )tion p%o#u)ts The active species are here anions (""# and Cl"( . These anions reacts almost only with carbonyl groups - M).4/

1.,

IN CHEMICAL RECO-ER. @! HLACK L@NA"* HA*!@!+ The main reactions are - .(0 predominantly / !a&"$ C"& !a&C"0 !a $ $ #$ $ %&( !a#% !a$ "# ( !a"# !a&"$ %"& $ O "& !a&%"2 !a&% $ &"& !a&%"2 !a&%"2 $ !a&% $ "& & !a&%&"0 and other reactions !a&%"2 $ & C !a&% $ C"& !a&%"2 $ 2C" !a&% $ 2 C"& - 5/ -1/ - ./ - &/ -0/ -2/ - 7/ - 8/

Bly ash Fl$ s" is mainly consisting of !a&" $ %"0 !a&%"2

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ALL K.L &Co and !a&" $ C"& !a&C"0 @n the smelt there is e:uilibrium reactions !a&%-l/ $ & #&" #&% -g/ $ &!a"# and !a&%-l/$#&"$C"& #&%-g/ $ !a&C"0 These reactions are not + nt(#. Cooking li:uor production The green li:uor produced in the recovery boiler smelter is then further reduced by the caustiKising reaction !a&C"0 $ Ca-"#/& & !a"# $ CaC"0 After separation of the solid CaC"0- lime mud/) from the white li:uor containing !a"#) the solid is burnt in a lime kiln. CaC"0 Ca" $ C"& There is usually also some sodium present in the lime mud) which reacts with any sulphur introduced in the lime kiln &!a $ % $ &"& !a&%"2 And the burnt lime is then reacted with water to produce Ca" $ #&" Ca- "#/&

Literature .. Iuukemia) 'aldemar Pensen) .M55) %uomen paperi(insinQQrien Jhdistys *y. &. Chemie und Technologie der Lellstoff #erstellung) I. Lengyel & %. Dorvay) .M50) +untter(%tiab Gerlag) Hiberach>*iss. 0. Lignins ) occurrence) formation) structure and reactions) K.G. %arkanen & C.#. Ludwig) .M5.) Pohn 'iley & %ons) @nc. 2. The significance of glucomannan for the condensation of cellulose and lignin under kraft pulping conditions. " Karlsson) A 'estermark) !I&I *esearch P. !o. 0) vol. .&).MM5 7. Cegradation of *esidual Lignin in Kraft Iulp with "Kone application to Hleaching. C. Lachenal) D. Dauguet. 8 th @%'IC) .MM.. 8. A new mechanism for pulp delignification during Chlorination !@.J. =
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ALL K.L &Co +.P. Kubes and A.*.I. Gan #einingen) Pournal of Iulp and Iaper %ceince) .8- ./ P.0(P.M - .MM4/ 5. %tructural changes in lignin during o9ygen bleaching) +. +ellerstedt) K. +ustafsson and ?.L. Lindfors) !ordic Iulp and Iaper Pournal - 0/ .2( .5 - .M18/ 1. Chlorine dio9ide o9idation of lignin model phenols) +.H. %trumla and '.#. *appson) Iulp and Iaper Canada) 51 - .&/ ) T* ..M(.&8 - .M55/ M. Celignification mechanism using o9ygen and hydrgen pero9ide) A %ingh) Iroc. Tappi o9ygen Celignification %ymposium 70(7M - .MM4/ .4.Chemistry of delignification . A general concept. Iart @@) P. +ierer) #olKforschung 08 - ./ 77(82 - .M1&/ ...%GI(#I CL"& Irocess ) ?ka Chemicals) *ev. .&) - .MM5/ .&.Iuumassan valmistus @@) Iart &) !(? Girkola) %uomen paperi(insinQQrien Jhdistys *y) Turku) .M10.

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