Using NIR technology to reduce the number of hazardous samples in resin production

Abstract. The goal of this master’s thesis was to clarify the potential of the NIR technology to reduce the number of the hazardous samples and survey useful of the NIR technology in the resin production. The phenolic resin samples are toxic for the health and the NIR technology is the newest technology, whose potential was reviewed during the master’s thesis. The purpose of the experimental section was to be created the NIR calibration models for each resin material and study how reliably the NIR technology can analyze the property 1, the property 2 for the resins, the properties 3 and 4 in the resin production. During the experimental section was collected the data from final samples of the various resin materials using with the NIR probe in the manufacturing laboratory to be created the NIR spectra set. The resins were produced in the batch reactors in the resin plant and the data was arranged in the cooperation of the manufacturing operators. The reference analyzes were performed within the data collection in cooperation of the manufacturing operators and the reference results were created to be compared to the NIR results. There was found the exact the wavenumbers of the near-infrared spectroscopy to be predicted the properties 1 and 2, but not was found the exact wavenumbers to be predicted the properties 3 and 4. NIR technology can be used to be predicted the property 1 using with the wavenumber of 6102–5446 cm-1 and the property 2 using with the wavenumber of 6846–6900 cm-1. The wavenumber region of 4000–12000 cm-1 to be predicted the properties 3 and 4. According to the results the NIR technology requiring the exact calibration models for each analyzable property of the resin and there is needed approximately 40–50 samples to be created models, which are enough precise to be predicted the results of the reference analyzes in the resin production. NIR is able to predict the results of the reference analyzes with the little sample set, but then the models are not the statistically significant. The linear model was noted to be the best model to predict the results of the reference analyzes, but the precise models were not achieved during the master’s thesis process. The results can be utilized for the resin production and the hazardous samples can be reduced using with the NIR technology, if the models are the statistically precise and the creation of the calibration models need the patience.Tiivistelmä. Diplomityön tavoitteena oli selvittää NIR teknologian potentiaalisuutta vähentää haitallisten näytteiden määrää sekä kartoittaa NIR teknologian käyttöä hartsituotannossa. Fenoliset hartsinäytteet ovat terveydelle haitallisia ja NIR on uusinta teknologiaa, jonka potentiaalisuutta tarkasteltiin diplomityössä. Työn kokeellisen osion tarkoituksena oli luoda NIR kalibraatiomallit erilaisille hartsimateriaaleille ja tutkia, kuinka luotettavasti NIR teknologialla voidaan analysoida ominaisuutta 1, hartsien ominaisuutta 2, ominaisuuksia 3 ja 4 hartsituotannossa. Työn kokeellisessa osiossa kerättiin dataa hartsien loppunäytteistä tuotannon laboratoriossa käyttäen NIR anturia NIR spektrien luomiseen. Hartsit valmistettiin liimatehtaan panosreaktoreissa normaalin tuotannon yhteydessä ja datan keruu toteutettiin yhteistyössä tuotannon operaattoreiden kanssa. Referenssianalyysit suoritettiin datan keruun yhteydessä tuotannon operaattoreiden toimesta ja samalla luotiin referenssitulokset NIR:n antamille tuloksille. Ominaisuuksien 1 ja 2 ennustamiseen löydettiin tarkat lähi-infrapunaspektroskopian aaltolukualueet, mutta ominaisuuksien 3 ja 4 ennustamiseen ei löydetty tarkkoja aaltolukualueita. NIR teknologia käyttää ominaisuuden 1 ennustamiseen aaltolukualuetta 6102–5446 cm-1 ja ominaisuuden 2 ennustamiseen aaltolukualuetta 6846–6900 cm-1. Ominaisuuksien 3 ja 4 ennustamiseen käytettiin aaltolukualuetta 4000–12000 cm-1, joka kattaa lähes koko lähi-infrapunaspektroskopian aaltolukualueen. Tulosten perusteella NIR teknologia vaatii tarkat kalibraatiomallit hartsin jokaiselle analysoitavalle ominaisuudelle ja mallien luomista varten tulee kerätä arviolta 40–50 näytettä, jotta malleista saadaan riittävän tarkkoja ennustamaan referenssianalyysien tuloksia hartsituotannossa. NIR pystyy ennustamaan vähäiselläkin näytemäärällä referenssianalyysien tuloksia, mutta mallit eivät ole tilastollisesti merkittäviä normaalijakauman mukaisesti. Lineaarinen malli todettiin olevan paras malli ennustamaan referenssianalyysien tuloksia, mutta riittävän tarkkoja malleja ei saatu aikaiseksi diplomityön aikana. Tuloksia voidaan hyödyntää hartsituotannossa, sillä tuloksien mukaan haitallisten näytteiden määrää voidaan vähentää NIR teknologialla, jos malleista saadaan tilastollisesti riittävän tarkkoja ja kalibraatiomallien luominen opetusdatalla vaatii pitkäjänteisyytt

Gasification Kinetics in Continuous Supercritical Water Reactors

Supercritical water gasification (SCWG) is an emerging technology with synergistic applications in renewable energy and waste processing. Supercritical water (SCW) functions as a green reaction medium during the gasification process, serving to dissolve and decompose complex organic molecules via ionic, radical, hydrolysis, and pyrolysis reaction mechanisms. Researchers investigate the decomposition of model compounds in order to predict product yields and conversion efficiencies during the gasification of heterogeneous biomass waste, food waste, sewage sludge, and other available feedstocks. Continuous, laboratory-scale reactors are often employed to study reaction kinetics, pathways, and mechanisms. This chapter synthesizes previous work investigating model compound gasification in continuous supercritical water reactors (SCWRs). A summary of continuous reactor design strategies is presented for practical benefit, followed by a discussion on reaction chemistry in the supercritical water environment. Reaction pathways and mechanisms have been investigated for several model compounds, lending insight toward the conditions needed for the complete conversion of real-world feedstocks. Several studies assume first-order reaction kinetics and propose Arrhenius parameters for the decomposition reaction. The first-order rate assumption must be carefully evaluated, and the applicable temperature range must be specified. Opportunities for further research are discussed

Supercritical Water Gasification: Practical Design Strategies and Operational Challenges for Lab-Scale, Continuous Flow Reactors

Optimizing an industrial-scale supercritical water gasification process requires detailed knowledge of chemical reaction pathways, rates, and product yields. Laboratory-scale reactors are employed to develop this knowledge base. The rationale behind designs and component selection of continuous flow, laboratory-scale supercritical water gasification reactors is analyzed. Some design challenges have standard solutions, such as pressurization and preheating, but issues with solid precipitation and feedstock pretreatment still present open questions. Strategies for reactant mixing must be evaluated on a system-by-system basis, depending on feedstock and experimental goals, as mixing can affect product yields, char formation, and reaction pathways. In-situ Raman spectroscopic monitoring of reaction chemistry promises to further fundamental knowledge of gasification and decrease experimentation time. High-temperature, high-pressure spectroscopy in supercritical water conditions is performed, however, long-term operation flow cell operation is challenging. Comparison of Raman spectra for decomposition of formic acid in the supercritical region and cold section of the reactor demonstrates the difficulty in performing quantitative spectroscopy in the hot zone. Future designs and optimization of SCWG reactors should consider well-established solutions for pressurization, heating, and process monitoring, and effective strategies for mixing and solids handling for long-term reactor operation and data collection

Biological Fixed-Film Systems

The Microbiological Degradation of Wastewater and its Application using a Fixed-Film Reactor is Reviewed. the Technical and Technological Characteristics, as Well as the Efficiency of Nitrification and Denitrification Processes Were Taken into Consideration. the Review Elucidated the Experimental Measurements of Effective Diffusive Permeabilities and Effective Diffusion Coefficients of Biofilms

Application of advanced oxidation processes for treatment of air from livestock and industrial facilities

Odours emitted from livestock and industrial facilities are unpleasant, and they can cause tension between producers and nearby residents and negatively affect their quality of life. It is necessary to develop proper air cleaning technologies for odour abatement. However, current technologies are limited by the removal efficiency and by the selectivity towards certain odorants. In particular, removal of reduced sulphur compounds is a challenge. Advanced oxidation processes (AOPs), as a set of chemical reactions to generate OH· radicals, are considered as an alternative technology to overcome the limitations, because the OH· radical is a relatively non-selective reactant and can react with a wide range of compounds with high reaction rate. The key hypothesis of the current PhD-project is that the odorous compounds emitted from livestock and industrial facilities, especially reduced sulphur compounds, can be effectively removed by the AOP-based reactors. The objectives were: 1) to develop AOP-based reactors for odour abatement, 2) to assess the removal efficiency of odorous compounds by using AOPs, 3) to characterize the AOP processes in detail, including assessment of the role of hydroxyl radicals, 4) to investigate relevant by-products after the AOPs from the reactors, and 5) to identify possibilities for optimization of the AOP processes.Two types of AOP-based reactors were designed and assessed: 1) photocatalytic monolith reactors (UV/TiO2) and 2) wet scrubbers run with the peroxone process (O3 + H2O2). The processing conditions were attempted to be close to realistic conditions, such as high air flow rates and low residence time, low initial concentration (ppbv level), room temperature and ambient pressure. Proton-transfer-reaction mass spectrometry (PTR-MS) was used to monitor the concentrations of the odorous compounds before and after the reactor, as well as to investigate the Langmuir-Hinshelwood kinetic data for photocatalytic oxidation of reduced organic sulphur compounds with low adsorption. By-products from the two reactors were detected by PTR-MS, gas chromatography with mass spectrometry and gas chromatography with sulphur chemiluminescence detection.Two photocatalytic monolith reactors were assessed. A bench-scale reactor, with one TiO2 filter installed, was used for evaluating potential influencing factors (initial concentration, air flow rates and UV intensity), establishing Langmuir-Hinshelwood model for kinetic studies of reduced sulphur compounds (methanethiol (MT), dimethyl sulphide (DMS), and dimethyl disulphide (DMDS)) and for investigating their by-product. More than 80% of the concentrations of reduced sulphur compounds can typically be removed at a residence time greater than 0.12 s and at the initial concentration lower than 150 ppbv. Data from PTR-MS were fitted very well by the Langmuir-Hinshelwood kinetic model (generally R2 > 0.99) with uncertainties of < 20% on Langmuir adsorption constants (K) and reaction rate constants (k). It is the first time to present the uncertainty of the kinetic model for highly volatile compounds. According to the investigation of the by-products, odour was significantly removed by photocatalytic oxidation of MT and DMDS. However, around 2% of DMS was oxidised to MT, which has a low odour threshold value (0.07 ppbv), to the extent that degradation of DMS is predicted (based on odour threshold values) to increase odour. Furthermore, all reduced organic sulphur compounds produced formaldehyde, which is a carcinogen. In order to reduce the production of by-products, it is suggested to connect an additional TiO2 filter in series to remove MT and formaldehyde. In a pilot-scale reactor with three TiO2 filters installed, removal of eight odorous compounds (reduced sulfur compounds, carboxylic acids and 1-butanol) was tested and more than 80% of them could be removed at a residence time greater than 0.1 s. However, H2S could not be effectively removed from the current photocatalytic reactors, and it is suggested that the application of the investigated technology is best suited for the abatement of odours that do not contain H2S.Two types of wet scrubbers run with the peroxone process (O3 + H2O2) were also investigated. More than 90% of DMS could be removed in a bubble reactor with the peroxone process. Therefore, a packed-bed wet scrubber with direct air injection of O3 was assessed. Both H2S and DMS could be removed at with efficiency above 90%. However, the removal of MT was not as high as H2S and DMS (23.5%). It is suggested that O3 is the main reactant in the packed-bed scrubber, and that OH· radicals play a minor role under the conditions applied. Therefore, it is necessary to improve the wet scrubber. In addition, there was an excess O3 emission, and further optimization is needed to optimise the O3 uptake and to reduce the outlet concentration of O3.In this PhD-project a thorough examination of the potential of using AOP for air cleaning with focus on odour reduction and removal of volatile sulfur compounds. Two AOP-based reactors were assessed at processing conditions close to realistic operating conditions. The photocatalytic monolith reactor could effectively remove most of the odorous compounds, except H2S, and the packed bed wet scrubber was effective on removal of H2S and DMS, but not on MT. Therefore, appropriate techniques have to be carefully selected to maximise the odour removal. Further research is necessary to optimise the reactor setup and apply the reactor on site

Supercritical Water Gasification of Biomass & Biomass Model Compounds

Supercritical water gasification (SCWG) is an innovative, modern, and effective destruction process for the treatment of organic compounds. Hydrogen production using SCWG of biomass or waste feedstocks is a promising approach towards cleaner fuel production while simultaneously providing novel solution for hard-to-treat organic wastes. The main premise of this work was to experimentally examine real waste biomass sources i.e. hog manure and waste biomass model compounds using SCW gasification while examining various commercial catalysts. The improvement of the SCWG process requires an understanding of the waste/biomass reaction chemistry, and thus the knowledge of the reaction mechanisms is critically important for proper catalyst selection and design. The main possible reactions that occurred through the formation and disappearance of intermediate compounds as well as the final gaseous and liquid final products are reported. In this work, gasification and partial oxidation of glucose 0.25 Molarity (M) was conducted using different metallic Ni loadings (7.5, 11, and 18 wt %) on different catalyst supports (θ-Al2O3 and γ-Al2O3) in supercritical water at 400-500°C, and compared with a commercial catalyst (65 wt % Ni on Silica-Alumina). Results showed that the presence of metallic Nickel increases the yield of gases and the total gas yield increased with increasing nickel in the 7.5-18 wt % Ni/Al2O3 catalyst. This study showed that the same hydrogen yield can be obtained from the synthesized low nickel alumina loading (18 wt %) catalyst as the high (65 wt %) nickel on silica-alumina commercial catalyst. In this work, oleic acid was examined as a model compound for lipids. Results showed that an increase of temperature coupled with the use of catalyst enhanced the gas yield dramatically. The H2 yield was 15 mol/ mol oleic acid converted using both the pelletilized Ru/Al2O3 and powder Ni/Silica-alumina catalysts which yielded 4 times higher than the calculated equilibrium yield of 3.5 mol/mol oleic acid fed. The composition of residual liquid products was studied and a generalized reaction pathway of oleic acid decomposition in SCW reported. The catalytic co-gasification of starch and catechol as models of carbohydrates and phenol compounds was investigated. Employing TiO2 as a catalyst alone had no significant effect on the H2 yield but when combined with CaO increased the hydrogen yield by 35%, while promoting higher total carbon (TOC) reduction efficiencies. The process liquid effluent characterization showed that the major non-polar components were phenol, substituted phenols, and cresols. An overall reaction scheme was provided. Cysteine gasification in supercritical water in the presence of Ru/Al2O3, Ru/AC and activated carbon (AC) catalysts was also investigated. The main sulfur-containing compound in the gaseous effluents in all experiments was H2S. It was found that the formation of H2S was neither dependent on temperature nor on the catalyst. The composition of residual liquid products revealed the presence of residual organic sulfur components that include diethyl sulfide, diethyl tri sulfide, and ethanone. A generalized reaction pathway for organo-sulfur compounds was reported. Catalytic hydrogen production with various catalysts from hog manure using supercritical water partial oxidation was investigated. The order of H2 production was the following: Pd/AC \u3e Ru/Al2O3 \u3e Ru/AC \u3e AC \u3e NaOH. A 35% reduction in the H2 and CH4 yields was observed in the sequential gasification partial oxidation (oxidant at an 80% of theoretical requirement) experiments compared to the gasification experiments (catalyst only). Moreover, this reduction in gas yields coincided with a 45% reduction in the liquid effluent chemical oxygen demand (COD), 60% reduction of the ammonia concentration in the liquid effluent, and 20% reduction in the H2S concentration in the effluent gas. The scientific contribution of this study culminated in the development of a qualitative mechanistic understanding of the reaction chemistry of organic matters presented in waste streams such as waste biomass, sewage sludge, and hog manure. This understanding of the SCW reaction chemistry is required for the potential applications of SCW for energy recovery from waste streams through hydrogen production

Laccase-catalyzed removal of various aromatic compounds from synthetic and refinery wasterwater

Laccase SP 504 from Trametes villosa, a fungal laccase, was investigated for its capacity to catalyze the oxidative polymerization of hazardous aromatic pollutants (phenol, o-, m-, p-cresol, aniline, o-, m-, p-toluidine) in the presence of O2. Experiments were conducted to determine the optimum pH, minimum enzyme concentration for ≥ 95% conversion of substrate, minimum PEG concentration for optimum effect (if applicable), and the effect of PEG molecular weight on removal efficiencies. Other factors investigated were: the fate of PEG in the reactor, removal over a 3 h reaction period, activity over 3 h reaction period, and the effect of reducing anions and halides in p-cresol conversion. For the three cresol isomers a preliminary kinetic study was done with and without PEG. Lastly the effectiveness of laccase in the removal of phenol in 5 refinery samples was compared to the removal of phenol in synthetic wastewater

Inherent Environmental Protection Analysis For Process Plant

This paper presents an approach considering environmental factor in earlier stage of designing a plant design. The objective of this research is to develop a framework using inherent concept to take consideration the environment factor in earlier design stage. This approach is developed to improve the available methods in minimizing the waste, effluent and pollution that been discharge to the environment. This approach will be applied in flow sheeting stage. The framework applies the inherent concept and takes into account the environmental factor such as waste, effluent and pollution issues to be assess as the pollutants. The result for each pollutant will be benchmarked to the environment indices that are following the environmental law. This research has developed a demonstrative tool by using HYSYS simulation and Microsoft Excel as the platform. This project will be test on a refinery plant model to approve that the framework can be realized. The tool was developed to minimize the waste, effluent and pollution in a propose process by using inherent environmental protection methods. It is expected that by using this developed inherent waste minimization and environment will reduce the amount of waste, effluent and pollution that are released to the environment