TCF-valkaisimon laatuvaihtelun pienentäminen

Tämän diplomityön tavoitteena oli pienentää TCF-valkaisimon laatuvaihtelua ja vähentää kemikaaleista aiheutuvia kustannuksia. Työn kirjallisuusosassa tarkasteltiin valkaisuun vaikuttavia tekijöitä. Valkaisukemikaaleista olivat mukana TCF-valkaisussa käytettävät otsoni ja vetyperoksidi. Lisäksi selvitettiin metallien poistoa massasta sekä vesikierron sulkemisesta aiheutuvia ongelmia. Kokeellisessa osassa etsittiin Oy Metsä-Botnia Ab Rauman tehtaan valkaisuprosessin suurimmat laatuominaisuuksien vaihteluun vaikuttavat tekijät. Tavoitteena oli pienentää vaihtelua valmiin massan laatuominaisuuksissa sekä vähentää raaka-aineista ja kemikaaleista aiheutuvia kustannuksia laatuominaisuuksien tasoa laskematta. Tutkimuksessa käytettiin hyväksi Taguchi-menetelmää sekä monimuuttuja-analyysiä. Tutkimuksessa tehtiin kaksi Taguchi-koetta, joissa tutkittiin valkaisimon ensimmäistä otsonivaihetta sekä koko valkaisimoa. Otsonivaiheen merkittävimmiksi tekijöiksi osoittautuivat otsoniannos, otsonin väkevyys sekä pH. Kaikkia valkaisimon vaiheita tutkittaessa löydettiin merkittävimmiksi tekijöiksi ensimmäisen peroksidivaiheen lämpötila, vetyperoksidin jakaminen peroksidivaiheisiin, kelatointi sekä otsonivaiheen otsoniannos ja pH. Optimiajomallin avulla saatiin valkaisimon laatuvaihtelua pienennettyä. Kemikaalikustannuksiin vaikuttavista tekijöistä merkittävimmiksi osoittautuivat kelatoinnin vaikutus, vetyperoksidin annosteleminen molempiin vaiheisiin sekä ensimmäisen peroksidivaiheen lämpötila. Optimiajomallien avulla vetyperoksidikulutusta saatiin pienennettyä noin 24 %.

Water circulations for effective bleaching of high-brightness mechanical pulps

The amount of water available is usually restricted, which leads to a situation where a complete understanding of the process, including water circulations and the influence of water components, is essential. The main aim of this thesis was to clarify the possibilities for the efficient use of residual peroxide by means of water circulation rearrangements. Rearranging water circulations and the reduction of water usage may cause new problems, such as metal induced peroxide decomposition that needs to be addressed. This thesis introduces theoretical methods of water circulations to combine two variables; effective utilization of residual peroxide and avoiding manganese in the alkaline peroxide bleaching stage. Results are mainly based on laboratory and mill site experiments concerning the utilization of residual peroxide. A simulation model (BALAS) was used to evaluate the manganese contents and residual peroxide doses. It was shown that with optimum recirculation of residual peroxide the brightness can be improved or chemical costs can be decreased. From the scientific perspective, it was also very important to discover that recycled peroxide was more effective pre-bleaching agent compared to fresh peroxide. This can be due to the organic acids i.e. per acetic acid in wash press filtrate that have been formed in alkaline bleaching stage. Even short retention time was adequate and the activation of residual peroxide using sodium hydroxide was not necessary. There are several possibilities for using residual peroxide in practice regarding bleaching. A typical modern mechanical pulping process line consist of defibering, screening, a disc filter, a bleach press, high consistency (HC) peroxide bleaching and a wash press. Furthermore there usually is not a particular medium consistency (MC) pre-bleaching stage that includes additional thickening equipment. The most advisable way to utilize residual peroxide in this kind of process is to recycle the wash press filtrate to the dilution of disc filter pulp (low MC pre-bleaching stage). An arrangement such as this would be beneficial in terms of the reduced convection of manganese to the alkaline bleaching stage. Manganese originates from wood material and will be removed to the water phase already in the early stages of the process. Recycling residual peroxide prior to the disc filter is not recommended because of low consistencies. Regarding water circulations, the novel point of view is that, it would be beneficial to divide water circulations into two sections and the critical location for the division is the disc filter. Both of these two sections have their own priority. Section one before the disc filter: manganese removal. Section two after the disc filter: brightening of pulp. This division can be carried out if the disc filter pulp is diluted only by wash press filtrate before the MC storage tower. The situation is even better if there is an additional press after the disc filter, which will improve the consistency of the pulp. This has a significant effect on the peroxide concentration in the MC pre-bleaching stage. In terms of manganese content, it is essential to avoid the use of disc filter filtrate in the bleach press and wash press showers. An additional cut-off press would also be beneficial for manganese removal. As a combination of higher initial brightness and lower manganese content, the typical brightness increase varies between approximately 0.5 and 1% ISO units after the alkaline peroxide bleaching stage. This improvement does not seem to be remarkable, but as it is generally known, the final brightness unit is the most expensive and difficult to achieve. The estimation of cost savings is not unambiguous. For example in GW/TMP mill case 0.6% ISO units higher final brightness gave 10% savings in the costs of bleaching chemicals. With an hypothetical 200 000 ton annual production, this means that the mill could save in the costs of bleaching chemicals more than 400 000 euros per year. In general, it can be said that there were no differences between the behavior of different types of processes (GW, PGW, TMP and BCTMP). The enhancement of recycling gave a similar response in all cases. However, we have to remember that the utilization of residual peroxide in older mills depends a great deal on the process equipment, the amount of water available and existing pipeline connections. In summary, it can be said that processes are individual and the same solutions cannot be applied to all cases.

The effect of pulp washing on bleaching efficiency

The main aim of this study was to inspect the influence of the ultrafiltration implementation on the washing and on bleaching efficiency. Four cases corresponding to four washing stages were observed: two with hardwood pulp and two with softwood pulp; each case had a reference and a trial experiment. The experiments with hardwood pulp were arranged in a manner to explore predominantly the possibility of bleaching performance improvement by applying for washing instead of untreated filtrate (reference case) the same treated one (trial case). Despite that the ultrafiltration reduced the COD of the wash filtrates allowing the decreasing of COD carry-over to the bleaching stage it didn’t affect the bleaching performance. Another set was used in the experiments with softwood pulp. It implied the ultrafiltration and recirculation of the filtrate to the same washing stage with the purpose to reduce the volumes and pollution of the bleaching effluents. In one case the negative result was obtained which was expressed by worse parameters of the pulp after bleaching. Another case showed the opportunity to replace hot water with the filtrate and reduce the fresh water consumption.

Ultrafiltration of pulp mill bleaching effluents

Main objective of this research was to find suitable polymeric ultrafiltration membranes with high retentions, good capacities and low fouling tendencies for the E2- and EP-effluent ultrafiltration. Purpose was to treat alkaline bleaching effluents with ultrafiltration in a way that permeates of the filtrations could be recycled back to process and the consumption of fresh water in the pulp mill could be reduced significantly. In the theoretical part of this work the challenges set by the pulp and paper indus-try processes for membranes were examined. An overview of the membrane tech-nology in the pulp industry was also provided. In addition process conditions in the chemical pulp bleaching and properties of bleaching effluents were discussed in literature study. In experimental part the E2- and EP-stage bleaching effluents from Stora Enso Imatra kraft pulp mill were ultrafiltered with CR250- and CR200-filters. Suitable membranes for ultrafiltration were chosen after screening experiments. Concentra-tion experiment was made for the E2-effluent in order to estimate water saving potential. The E2-effluent was finally ultrafiltered in the pulp mill in order to test the feasibility of ultrafiltration in a real industrial environment. Good membrane for the EP-effluent ultrafiltration based on the EP-screening ex-periments was polyethersulfone membrane UP020 with cut-off value of 20 000 Da. Polysulfone membrane UFX05 with cut-off value of 5 000 Da was promising membrane for the ultrafiltration of the E2-effluent. Based on the concentration filtration of the E2-effluent with UFX05 membrane the water saving potential could be 2.2 m3/Adt for the industrial scale ultrafiltration process. Retention re-sults, such as average COD retention of 60 %, from the trial filtration at the pulp mill with UFX05 membrane were modest compared to the screening experiments, where average COD retention was 75 %. Therefore tighter ultrafiltration mem-branes should be tested for the ultrafiltration of the E2-effluent. The UP020 mem-brane seemed to be suitable for the ultrafiltration of the EP-effluent however con-centration and pilot scale ultrafiltration experiments are needed to verify this.

Magnesium hydroxide-based peroxide bleaching of high-brightness mechanical pulps

A high final brightness is desired in most paper and board products. This requires bleaching processes that are able to produce high-brightness pulps. Mechanical pulps are widely bleached for high brightness using alkaline hydrogen peroxide with traditional sodium hydroxide and sodium silicate as additives. With high doses however, peroxide bleaching causes high organic loads in the mill effluent and anionic trash carry-over to papermaking. To alleviate the problems that arise from the use of sodium-based additives in peroxide bleaching, interest in the use of alternative magnesium-based chemicals has increased. In this study, a new, technical high-purity magnesium hydroxide-based bleaching additive was evaluated on laboratory-scale, pilot-scale and mill-scale experiments and trials for its ability to produce a high brightness in peroxide bleaching without the known problems of sodium-based chemicals. The key findings of this study include: a high brightening potential of peroxide bleaching using the Mg(OH)2-based additive, significant reductions (40-70%) in all categories of environmental load, and cationic demand lowered by 60-70% in bleached pulp with no loss in strength properties or in sheet bulk. When used in TMP refiner bleaching, the Mg(OH)2-based additive resulted in savings in specific energy consumption and provided a good bleaching response.