III. PRIMEROS LEGADOS TRAS LA CONVERSIÓN DEL REINO DE TOLEDO
3. La evolución del pallium y su relación con los vicariatos apostólicos
Mikko Hupa
Åbo Akademi/Process Chemistry Centre Biskosgatan 8, FI-20500 Åbo
Tel. +358 2 21531 Email: [email protected]
Markku Auer
ÅA/VTT/Process Chemistry Centre Porthansgatan 3, FI-20500 Åbo Tel. +358 5025 947
Email: [email protected]
Abstract
The biorefinery concept may be compared to an oil refinery and petrochemical plant, where fuels and numerous intermediates are produced for further processing into high-value and speciality materials. In biorefineries, the raw material instead of mineral oil is bio-based materials. Biorefinery development at the US and European level mostly covers the use of annual crops and other bio-based materials. However, in this project focus is on non-food materials primarily in industrial pulp and paper processes and this project is limited to forest-based biorefineries. The aim of the project is also to preserve the molecular structures created by the nature as much as possible, to explore new separation and purification methods and look at new applications in the areas such as: functional food, nutritional additives, functional additives in paper making, antioxidants, new biobased materials and biobased energy. As the area, in spite of efforts to limit it, is very large, we have selected to focus on a limited number of concretized projects, which to our knowledge are complementary with other efforts for promoting biorefinery concepts.
Furthermore, this project has focus on chemistry. The aim being that the created fundamental knowledge can later or parallel be used for product development and development of new process technologies.
Keywords: biorefinery, forest, pulping, side streams, pyrolysis, synthesis gas, functional additives, bark, black liquor, lignin, resveratrol, lignans, flavonoids, arabinogalactans, bioenergy
1 Project background and goals
“Replacing petroleum-based synthetic materials and energy with wood-derived materials”
Åbo Akademi Process Chemistry Centre has solid background in research of chemistry in the products and processes of forest industry. Here the basic idea is to find information on the molecular level about material streams in the forest industry. The aim is to use renewable materials and develop processes in more intelligent ways than before, utilising in-depth knowledge in chemistry.
Research work is on three areas: specialty chemicals and materials, metals in trees and fibres, and
The emphasis of the project is in the areas that still are mostly unexplored or where the options for renewing of process chemistry or products are greatest.
2 Project work programme
Work packages are (R – research, I – information): WP 1 Bio-based materials – R&I
x Biomass fractionation chemistry and technology x Derivatives of hemicelluloses
x Cellulose derivatives as replacement for petroleum-based plastics WP 2 Bioactive compounds from tree biomass – R&I
x Hemicelluloses as bioactive compounds x Polyphenols as protective chemicals x Specialty sugars
WP 3 Metals in trees, fibres and fuels – R
x Metal ions and functional groups in trees and pulp x Removal of metal ions from process liquors x Presence of trace elements in biofuels
x Analysis of ash from combustion of biomass based fuels x On-line methods to monitor the papermaking process WP 4 Bio-based chemicals and fuels – R&I
x Influence of the impurities on the catalyst behaviour
x Options for catalysts for catalytic production of bio based liquid fuels WP 5 Energy production options in the biorefinery – I (Information WP)
x Gasification based concepts to bark and forest residues and black liquor
x Advanced combustion and gasification characterization of various biomass fractions in a forest biorefinery
As highlights about promising areas are derivatisations of both hemicelluloses as well as cellulosic materials. The goals here are twofold; we are looking for the additional functionalities from polyphenols and hemicelluloses and on the other hand search for new applications. Hemicelluloses in many applications would benefit from the modification of the structure, especially to improve compatibility and solubility challenges in some applications.
We will increase our effort to improve our technologies for biomass fractionation. The idea being that the structure–preserving isolation would be beneficial for applications such as food products, functional chemicals in paper and as source for specialty sugars.
The project focus is around the processes of existing chemical and mechanical pulping, as illustrated in Figure 1 for Kraft pulping.
Figure 1. Project work packages around Kraft pulping process. round wood stemwood knots chips black liquor paper com- bustion pyrolysis gasifica- tion ash emissions residues heat power synthesis gas P biofuels (l) harvesting recycling debarking chipping extraction pulping synthesis pulp extraction & bark separation P P P pulping chemicals extraction P P pulping chemicals pyrolysis products WP3 WP 2 WP2 WP2 WP4 WP5 WP5 WP1 WP1 WP5
Table 1. Basic information of the project.
Project partners Steering group: Danisco Sweeteners Oy, Fortum Oyj, Neste Oil Oyj, Oy Metsä-Botnia Ab, Pöyry Forest Industry Consulting Oy, Stora Enso Oyj, UPM-Kymmene Oyj, KCL, Top Analytica Oy, Forestcluster Ltd. & PCC Management
Research Partners: KCL, Forestcluster Ltd, Top Analytica Oy Duration of the project 1.1. 2009–31.12.2011
Funding of the project Tekes, Industry, Åbo Akademi
Total funding 834 143 €, Tekes share 500 000 €
3 Project results
The project started from the beginning of year 2009 and the work is in progress. In the WP for biobased material it was noted that GGM can be extracted from spruce in high yields and deacetylation snd hydrolytic cleavage can be avoided. Here control of pH plays important role. In modification of GGM the physicochemical properties of GGM were studied with the aim of utilizing them as hydrocolloids in various applications and products. Chemical and enzymatic modification (e.g. cationisation) was done to obtain novel functionalities and properties that could be used also in specialty paper grades.
In the studies with bark it was found that there are more hemicelluloses in inner bark than in outer bark. The composition of hemicelluloses is different than those in wood.
In Metals in trees, fibres and fuels it was Metal ions are essential in the growing process of trees and are taken up through the roots from the soil and therefore metals will inevitably be carried to the pulping process. Inorganic compounds are minor constituents, less than 1%, of the wood material but are still of importance for the entire paper making process. Metals come in the process also with make up water, with added chemicals and through corrosion of the process machinery. In the studies of metals in wood the research in all together 17 natively occurring metals in wood. Differences in morphological parts of spruce were found to contain 2–3 times more Mn compared to same parts in aspen. In spruce early wood from both sapwood and heartwood as well as juvenile wood contains the highest concentrations of Mn. Spruce also contains more Ca than aspen, especially the early wood in the heartwood and juvenile wood. Also a method for labeling of anionic groups in wood has also been developed.
In the study of pyrolysis different zeolite catalysts were studied to produce bio-oils. It was found that it is possible to produce bio-oils from different raw materials. Important parameters were the structure of catalyst, temperature and the type of raw material.
The work in BIORAFF in fuels area is to follow up the different gasification concepts under development and to test and develop laboratory methods for the characterization of the various biomass feedstocks with respect to their potential and behavior in the different processes. This follow-up is partially based on the results of a parallel project in the Process Chemistry Centre, “ChemCom”, which focuses on chemical details of the thermal conversion of biomass based feedstocks.
Gasification processes are of major interest for the forest based biorefinery concepts. The final products from these processes under development are the Fischer-Tropsch hydrocarbon “waxes” which can further be refined to liquid fuels for cars. The solid biomasses of the greatest interst are bark and forest residues. The gasifier, especially in gas phase, is sensitive to a number of fuel characteristics such as ash forming matter, volatile matter, and the char oxidation reactivity. In connection with the BIORAFF project effective laboratory techniques is under development to evaluate these characteristics. Forest residues with high share of green parts of the wood appear challenging in their gasification behavior due to their high content of some elements – for example potassium, phosphorus and chlorine - which may be harmfuil to the gasifier operation.
4 Impact of the results
The project serves the aims of the Biorefine programme in developing innovative technologies in relation to biorefineries and in processing of woody biomass. It also is a valuable additional resource for increasing knowledge in chemistry in biorefinery processes, products and applications for chemicals, materials, and fuels. Ultimate goal is to replace petroleum-based synthetic materials
and energy with wood-derived materials. 5 International cooperation
The project has international collaboration with around twenty research groups in Europe, USA, Canada and China. In addition close collaboration with partners in the European Polysaccharide Network of Excellence (EPNoE), all working with the same topic, biorefinery.
6 Future plans
The project follows the roughly the frame of the approved research plan. During the project a close contact with collaborating industry takes place in the form of follow-up meetings and seminars. Thus the collaborating industry has the possibility to use the cumulated knowledge in their own development of processes and products.
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