The purpose of the study was to investigate how different types of filtrates (oxidized and unoxidized) would effect on oxygen delignification for softwood pulp, as well as study its impact on yield final-pH, viscosity and kappa number.

A series of laboratory oxygen delignification were performed in this study at constant oxygen pressure and consistency to study the response of the pulp to the different process parameters, i.e. reaction temperature, reaction time, soda addition, and mechanical pretreatment, to the zero span tensile strength loss. The basic chemistry of the oxygen delignified pulps was under study including fiber charge, celluloses/hemicelluloses, and hexenuronic acid. The fiber structure such as curl, kink, fines, and fiber length were also discussed. NaOH charge can be reduced as much as 50 % by applying mechanical pretreatment to obtain the same level of selectivity at the oxygen delignification conditions described in this study.Mechanical pretreatment prior to oxygen delignification promoted a better selectivity for both Acacia mangium and MHW pulps. MHW kraft pulp did not show a significant extractive removal in all pretreatment methods during oxygen delignification. The ultrasonic pretreatment followed by filtering induced the best extractive removal among the other three methods.

Energy utilization is a determining factor for the standards of living around the world, and the current primary source of energy is fossil fuels. A potential source of liquid fuels that could ease the strain caused by diminishing petroleum resources is bioethanol. Effective exploitation of biomass materials requires a pretreatment to disrupt the lignin and cellulose matrix. The pretreatment utilized for this research was oxygen delignification, which is a standard process stage in the production of bleached chemical pulp. The model substrate utilized as a feedstock for bioethanol was recovered fibre. An analysis of the substrates digestibility resulted in a hexose yield of approximately 23%, which justified the need for an effective pretreatment. An experimental design was performed to optimize the delignification conditions by performing experiments over a range of temperature, caustic loadings, and reaction times. Equations were developed that outline the dependence of various response parameters on the experimental variables. An empirical model that can predict sugar concentrations from enzymatic hydrolysis based on the Kappa number, enzyme loading, and initial fibre concentration was also developed. A study of hydrolysis feeding regimes for untreated recovered fibre (87 Kappa), pretreated recovered fibre (17 Kappa), and bleached pulp (6 Kappa) showed that the batch feeding regime offers reduced complexity and high sugar yields for lower Kappa substrates. In order to evaluate the possibility of lignin recovery, the pH of delignification liquor was reduced by the addition of CO₂ and H₂SO₄, resulting in up to 25% lignin yield. An experiment that looked at effect of post-delignification fibre washing on downstream hydrolysis found that a washing efficiency of approximately 90% is required in order to achieve a hexose sugar yield of 85%.

Energy utilization is a determining factor for the standards of living around the world, and the current primary source of energy is fossil fuels. A potential source of liquid fuels that could ease the strain caused by diminishing petroleum resources is bioethanol. Effective exploitation of biomass materials requires a pretreatment to disrupt the lignin and cellulose matrix. The pretreatment utilized for this research was oxygen delignification, which is a standard process stage in the production of bleached chemical pulp. The model substrate utilized as a feedstock for bioethanol was recovered fibre. An analysis of the substrates digestibility resulted in a hexose yield of approximately 23%, which justified the need for an effective pretreatment. An experimental design was performed to optimize the delignification conditions by performing experiments over a range of temperature, caustic loadings, and reaction times. Equations were developed that outline the dependence of various response parameters on the experimental variables. An empirical model that can predict sugar concentrations from enzymatic hydrolysis based on the Kappa number, enzyme loading, and initial fibre concentration was also developed. A study of hydrolysis feeding regimes for untreated recovered fibre (87 Kappa), pretreated recovered fibre (17 Kappa), and bleached pulp (6 Kappa) showed that the batch feeding regime offers reduced complexity and high sugar yields for lower Kappa substrates. In order to evaluate the possibility of lignin recovery, the pH of delignification liquor was reduced by the addition of CO₂ and H₂SO₄, resulting in up to 25% lignin yield. An experiment that looked at effect of post-delignification fibre washing on downstream hydrolysis found that a washing efficiency of approximately 90% is required in order to achieve a hexose sugar yield of 85%.

Energy utilization is a determining factor for the standards of living around the world, and the current primary source of energy is fossil fuels. A potential source of liquid fuels that could ease the strain caused by diminishing petroleum resources is bioethanol. Effective exploitation of biomass materials requires a pretreatment to disrupt the lignin and cellulose matrix. The pretreatment utilized for this research was oxygen delignification, which is a standard process stage in the production of bleached chemical pulp. The model substrate utilized as a feedstock for bioethanol was recovered fibre. An analysis of the substrates digestibility resulted in a hexose yield of approximately 23%, which justified the need for an effective pretreatment. An experimental design was performed to optimize the delignification conditions by performing experiments over a range of temperature, caustic loadings, and reaction times. Equations were developed that outline the dependence of various response parameters on the experimental variables. An empirical model that can predict sugar concentrations from enzymatic hydrolysis based on the Kappa number, enzyme loading, and initial fibre concentration was also developed. A study of hydrolysis feeding regimes for untreated recovered fibre (87 Kappa), pretreated recovered fibre (17 Kappa), and bleached pulp (6 Kappa) showed that the batch feeding regime offers reduced complexity and high sugar yields for lower Kappa substrates. In order to evaluate the possibility of lignin recovery, the pH of delignification liquor was reduced by the addition of CO₂ and H₂SO₄, resulting in up to 25% lignin yield. An experiment that looked at effect of post-delignification fibre washing on downstream hydrolysis found that a washing efficiency of approximately 90% is required in order to achieve a hexose sugar yield of 85%. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

The long-term trend regarding wood is an increase in price. Because wood contributes to a large part of production costs, the efficient utilisation of wood is greatly desired to reduce production costs for kraft pulp producers. During the 1990s, the development of improved modified kraft cooking began, which led to higher yields. There was also a trend of terminating kraft cooking at a higher kappa number to maximise the overall yield. For hardwood, the defibration point became a critical setback in allowing this termination at a high kappa number. This thesis discusses how this issue has been tackled in the laboratory by using improved modified kraft cooking combined with extended impregnation to enable a decrease in reject content and shift the defibration point towards a higher kappa number for hardwood. This lab concept is referred to as extended impregnation kraft cooking (EIC), and this thesis reveals that EIC cooking efficiently reduces the reject content for both birch and eucalypt. By using EIC cooking, the defibration point was shifted to a kappa number of ca. 30 from ca. 20 using conventional kraft cooking. This study demonstrates the great potential for achieving a higher overall yield for eucalypt by terminating the EIC cooking at a high kappa number, but with the conditions used in this thesis, no improvement in yield was observed for birch.   An important issue is that the termination of kraft cooking at high kappa number increases the demand for extended oxygen delignification to reach a similar kappa number into bleaching, i.e., due to cost and environmental reasons. Extended oxygen delignification was shown to be possible for both birch and eucalypt EIC pulps (i.e., from kappa number 27 to 10) with an acceptable pulp viscosity number.   The other part of this thesis addresses aspects regarding the limitations in oxygen delignification. It has previously been shown in the literature that a high xylan yield of kraft cooking could negatively affect the efficiency of subsequent oxygen delignification. In this work, the increased xylan content in eucalypt kraft pulp within the range of 8–18% had only a marginally negative impact on the oxygen delignification efficiency after correcting for the HexA contribution to the kappa number. It is also desired to extend the oxygen delignification towards lower kappa number, i.e., below kappa number 10 to decrease the bleaching chemical requirement. In this study, the hypothesis that the reduced efficiency of oxygen delignification at low kappa numbers could partly be due to the formation of oxidisable carbohydrate-related structures (i.e., HexA and/or other non-lignin structures) was also tested. No formation was established. On the other hand, a final oxygen delignification stage in the bleaching could be an attractive alternative for reducing yellowing and enhancing brightness; in fact, this has led to the development of a patent (SE 528066). / Ved står för en stor del av produktionskostnaderna vid framställning av sulfatmassa. Då vedpriserna har ökat genom åren är ett effektivt utnyttjande av veden önskvärt för att kunna sänka produktionskostnaderna. Under 1990-talet förbättrades den modifierade sulfatkokningen vilket innebar möjlighet till högre massautbyte. För att maximera massautbytet styrdes kokningsprocessen mot ett högre kappatal. Detta har visat sig vara svårare för lövved än för barrved, eftersom defibrerbarhetspunkten utgör ett kritiskt hinder. I denna avhandling har laborationsstudier utförts där förbättrad modifierad sulfatkokning kombinerats med förlängd impregnering för att kunna sänka spethalten och därmed förskjuta defibrerbarhetspunkten mot ett högre kappatal. Detta koncept kallas för extended impregnation kraft cooking (EIC). EIC-kokning visade sig vara en effektiv metod för att minska spethalten hos björk och eukalyptus. Med EIC-kokning kunde defibrerbarhetspunkten höjas från cirka 20 till cirka 30. I denna avhandling klarläggs att det finns stora möjligheter att öka massautbytet för eukalyptus genom att avsluta sulfatkoket vid ett högre kappatal. För björk kunde ingen ökning av massutbytet uppnås genom ovanstående metod.   Vid ett högre kappatal efter sulfatkoket ställs även krav på förlängd syrgasdelignifiering, för att kunna behålla samma kappatal in till blekeriet. Det visade sig vara fullt möjligt att förlänga syrgasdelignifieringen för de EIC-kokade björk- och eukalyptusmassorna (d.v.s. från kappatal 27 till 10) med accepterad massaviskositet.   Den andra delen av avhandlingen tar upp aspekter på syrgasdelignifieringens begränsningar. Tidigare studier har visat att ett högre utbyte av xylan vid sulfatkokning kan vara negativt för syrgasdelignifieringens effektivitet.  I denna studie har det påvisats att en ökad xylanhalt i intervallet 8–18 procent i eukalyptusmassa endast har en marginell negativ inverkan på syrgasdelignifieringens effektivitet efter att kappatalet korrigerats för HexA. Det är önskvärt att förlänga syrgasdelignifieringen till ett lägre kappatal än 10 för att minska förbrukningen av blekkemikalier. I den här studien prövades hypotesen att syrgasdelignifieringens begränsningar vid låga kappatal, under 10, delvis skulle kunna bero på bildning av oxiderbara kolhydratrelaterade strukturer (d.v.s. HexA och/eller andra okända ”non-lignin”-strukturer). Ingen bildning kunde dock observeras. Däremot indikerades att ett syrgassteg i slutet av bleksekvensen skulle kunna vara ett eftersträvansvärt alternativ för minskad eftergulning och ökad ljushet, vilket ledde till ett patent (SE 528066). / QC 20120507

This study first examined the kinetic changes of fiber carboxyl group content in bulk fiber, polysaccharide, and residual lignin of oxygen delignified pulps during one-stage oxygen delignification of a low kappa (32.5) kraft pulp. The carboxyl group contents determined in different chemical components of oxygen delignified pulps was used to establish the distribution of carboxyl groups in lignin and pulp polysaccharide and decouple the responses from residual lignin and polysaccharide. Following this study, two high kappa (~ 49.0) SW kraft pulps prepared were delignified through two-stage oxygen delignification. Fiber carboxyl group profiles of these pulps were elucidated to investigate the effect of lignin content of incoming unbleached kraft pulps on fiber carboxyl group formation. Due to a limitation to enhance fiber carboxyl groups only by parameter optimization during one- and two- stage oxygen delignification, a catalytic oxidation program was developed to enhance fiber carboxyl groups by 52.2 116.0 % employing 0.10 - 0.18% of a bismuth ruthenium pyrochlore oxide catalyst during oxygen delignification. The mechanism of fiber carboxyl group formation through the catalytic oxidation was proposed. The main factor on carboxyl group formation in pulp carbohydrate was identified to follow the order: NaOH > oxygen pressure> reaction temperature through a 3-factor at 3-level (L933) orthogonal experimental design and the optimal conditions were found at 2.5% NaOH, 85-100 oC, and 800-960 kPa O2 during the catalytic oxidation. ECF bleaching study was also conducted on these pulps with higher amount of fiber carboxyl group enhanced at early pulping and oxygen delignification processes. The bleaching results demonstrated that the early-stage enhanced fiber carboxyl groups were partially retained through ECF bleaching. Additionally, fiber carboxyl groups of fully bleached kraft pulps were ~ 20% different from typical bleaching protocols, depending on bleaching chemicals used and the bleaching sequences such as DEDED, (D+C)EDED, ODEDD, and OQPZP. This study finally demonstrated that an increase of fiber carboxyl groups by 17.4-62.1% through chemical oxidation resulted in reduced fiber curl, increased fiber WRVs, 4.3-25.5 % increase in paper tensile index at comparable pulp viscosity; and 4.4 -30.1% increase in paper dry tensile stiffness.

Esteves et.al. 2020 visade att syrgasdelignifiering ökar den totala fiberladdningen men leder inte alltid till ökad pappersstyrka. Denna studie syftar till att undersöka hur fiberladdning påverkar massans egenskaper.  För att testa hypotesen att ökningen av dragstyrkan beror på den större mängd sekundärt finmaterial som orsakas av malningen, testades vissa egenskaper hos massan, såsom vattenabsorption, med och utan malning avmassan. Två kraftmassor med olika initialt kappatal, 91 respektive 52, syrgasdelignifierades med olika alkalilsats under varierad tid. De massor som hade den lägsta och högsta mängden totala fiberladdningar maldes med PFI-kvarn. Water Retention Value (WRV), Schopper-Riegler (SR), Fiber Saturation Point (FSP) och finmaterial analyserades. WRV testades också efter att finmaterialet avlägsnats från massan.  Resultaten tyder på att massan med en större ökning av den totala fiberladdningen jämfört med den kraftkokta massan vid ett givet kappantal kan resultera i en högre ökning av FSP och WRV. Massor med större ökning av den totala fiberladdningen bildade mer finmaterial vid malning, vilket resulterar i en högre ökning av SR. / According to a previous study from Esteves et. al. 2020, it was found that oxygen delignification can increase the total fiber charge but does not always increase the paper strength. This study aims to investigate how fiber charge has an impact on pulp properties.  To test the hypothesis that the increase in mechanical strength for the fiber is due to the bigger increase of secondary fines caused by the refining process, some properties of the pulp such as water holding capacity were tested with different treatments: refining and no refining. Two kraft cooked pulp with different initial kappa numbers of 91 and 52 were subjected to oxygen delignification with different alkali charges and reaction times. When the characterization tests such as, kappa number and total fiber charge measurement have been determined, the samples which had the lowest and the highest total fiber charge were PFI refined and other analysis such as, water retention value (WRV), Schopper-Riegler degree (SR), fiber saturation point (FSP), and fine content, were done. WRV was also tested without fines.  The results suggest that the pulp with a higher increase in total fiber charge when compared to the kraft cooked pulp at a given kappa number can result in a higher increase in FSP and WRV. A higher increase in total fiber charge can also have a high tendency to create fines, due to the higher swelling ability, resulting in a higher increase in SR.

In this study, the kinetic analysis of oxygen delignification of Turkish southern hardwood Kraft pulp was carried out. Kraft pulp was obtained from Mopak Dalaman pulp and paper mill. The kinetic rate data were collected in a 1 L high pressure batch reactor. The delignification experiments were carried out under a wide range of industrially significant conditions of temperature (90, 100 and 110 oC), alkali charge (1, 3, 5% on oven dry pulp), and oxygen partial pressure (0.5, 3.5, 6.5 bar). In order to achieve this objective, the study is separated into different stages. In the first stage of the work, the mass transfer effects were examined for different pulp consistencies. It was seen that the inter-fiber mass transfer resistances become negligible at the consistencies below 1%. Therefore, the experiments were performed at 0.5% consistency. In the following stage, the kinetics of oxygen delignification was studied and the governing rate equations were derived. Then, the kinetics of the carbohydrate degradation was analyzed in order to determine the extent of delignification without the reduction in the pulp strength. The delignification and the carbohydrate degredation rate during oxygen delignification increase with increasing in alkali concentration, oxygen partial pressure and temperature. However, the most effective parameters are the alkali concentration and temperature. The dimensionless terms for Kappa number, intrinsic viscosity and reaction time were used in order to generalize the results and to make them independent of the initial Kappa number, the intrinsic viscosity, experimental conditions and pulping conditions prior to oxygen delignification. These dimensionless parameters were fitted to nonlinear equations from which the control of the oxygen delignification towers can be done with a simple equation. The same approach was also used for the reported studies in the literature which allowed the comparison with the results of this study. In the final stage of the study, the simulation of the oxygen delignification unit preceding the CEHDED bleach plant is performed, in order to see the effect of oxygen delignification on the amount of total wastes coming out from the bleach plant. When an oxygen delignification unit is added to the existing CEHDED bleach plant, the amount of pollutants are decreased by 17.96% with output brightness of 92.95. When the overall process parameter optimization of the CEHDED bleach plant is done with oxygen delignification unit, the total amount of dissolved solids coming out from the six washers are decreased by 25.97% with output brightness of 89.5. In order to reduce the pollution load and chemical consumption in Mopak Dalaman pulp and paper mill, management has decided to install an oxygen delignification unit to the plant. Therefore, the rate equations obtained from this study can form a basis for the design and optimization of oxygen reactor in the mill.

Modern chemical technology is an efficient tool for solving problems, particularly within the complex environment of the pulp and paper industry, and the combination of experimental studies, mill data and mass balance calculations are of fundamental importance to the development of the industry. In this study various examples are presented, whereby chemical technology is of fundamental importance. It is well documented that under normal conditions the molten salt mixture from the kraft recovery boiler flows down into the dissolving tank without problems. However, in the case of  alternatives to the kraft recovery boiler, knowledge of more precise data of the molten salts is required for the design calculations. In this study the viscosity for the case of sodium carbonate and 30 mole% sulphide has been measured and is of the magnitude 2 – 3 cP at temperatures relevant for a recovery boiler, i.e. similar to water at room temperature. The presence of non-process elements (NPE) in a typical pulp mill has been investigated. The main input is with regards to the wood, and anticipated problems include; deposits in evaporators, high dead-load in liquor streams, plugging of the upper part of the recovery boiler and decreasing efficiency in the causticization department. Efficient green liquor clarification is of the greatest importance as an efficient kidney for many NPE. Mill data and calculations show that the magnesium added in the oxygen delignification does not form a closed loop. Integration of a prehydrolysis kraft pulp mill producing dissolving pulp with a plant producing viscose textile fiber could be highly beneficial. The prehydrolysis liquor will contain both sugars and acetic acid. It is however not possible to fully replace the sulphuric acid of the viscose spinning bath with acetic acid of own production. The sulphuric chemicals from the viscose plant can be partly taken care of in the kraft recovery area as well as the viscose plant which can be supplied with alkali and sulphuric acid. Zinc-containing effluents from the viscose plant can be treated with green liquor to precipitate zinc sulphide. / Modern chemical technology is an extremely efficient tool for solving problems particularly in a complicated environment such as the pulp and paper industry. Here, examples are studied during which chemical technology is of fundamental importance. At normal conditions the molten salt mixture from the kraft recovery boiler flows down into the dissolving tank without hindrance. However, for certain kraft recovery boiler alternatives, knowledge of more precise data of the molten salts is required. The viscosity for the case of sodium carbonate and 30 mole% sulphide has been measured and is of the magnitude 2 – 3 cP at relevant temperatures. The main input of non-process elements (NPE) is down to the wood, and known problems include deposits in evaporators and decreasing efficiency in the causticization department. Green liquor clarification is an efficient kidney for many NPE. Magnesium added in the oxygen delignification does not form a closed loop. Integration of a prehydrolysis kraft pulp mill producing dissolving pulp with a plant producing viscose textile fiber could be of significant interest, as the handling of both alkali and sulphuric compounds can be integrated. Problems will however arise as the capacity of the pulping line and the chemical recovery has to be adjusted.