Management of hydrogen sulphide generation at a Kraft paper mill

A local integrated pulp and paper Kraft mill had come under pressure from the local communities and mill personnel to reduce the odours that were perceived to be generated at the Farm Dams and irrigation farm situated adjacent to the mill. The typical odours associated with Kraft mills are due to the generation of four reduced sulphur compounds such as hydrogen sulphide (H2S), methyl-mercaptan (CH3SH), dimethyl-sulphide (CH3)2S and dimethyl-disulphide (CH3)2S2. These compounds are collectively referred to as Total Reduced Sulphur (TRS) components which are generated as a direct result of the Kraft pulping and chemical recovery process. These components can either be in the gaseous or aqueous phase depending on the characteristics of the effluent. Gaseous and aqueous TRS profiling of the mill indicated that hydrogen sulphide (H2S) was the main odour component generated and emitted from the Clarifiers and the Treated Effluent Transfer Sump (TETS) at the effluent treatment plant. The hydrogen sulphide (H2S) emission levels were affected by process upsets, sludge removal frequencies, chemical composition of the effluent, Sulphate Reducing Bacteria (SRB) activity, pH and temperature fluctuations. Treatment options such as pH control using slaked lime, dosing of biocides, addition of biomodifiers and/or a sulphate reduction inhibitor were investigated. The use of slaked lime, Ca(OH) 2, for pH control was not practical due to continuous pH fluctuations, increasing the pH would increase the scaling tendencies of the effluent and would also affect the soil cation-anion exchange properties of the irrigated farm land. The use of non-oxidising biocides was effective in reducing SRB activity between 99.2% and 99.8% at dosages between 4 mg/l and 25 mg/l. However, the use of biocides was not considered as a long term treatment option due to the various disadvantages such as the stability of the biocides at fluctuating pH and temperatures, half-life, environmental accumulation, toxicity and costs. The aqueous H2S level was reduced by 79% using different combinations of biomodifiers (nitrates, nitrites, molybdenum). Increasing the dosages of the biomodifiers (> 500mg/l) would be required to increase the reduction of H2S levels by more than 79%. The increased dosages would significantly increase the cost of the treatment programme. The accumulation of nitrates, nitrites and molybdenum could affect the soil texture, cation-anion exchange capacity, permeability, Sodium Absorption Ratio (SAR) and nutrient availability. A more environmentally friendly and cost effective treatment was found using sodium nitrate (biomodifier) together with AQ (sulphate reduction inhibitor). The continuous dosing of 50 mg/l sodium nitrate together with 4 mg/l AQ would be effective in reducing the average aqueous H2S levels (40 mg/l) by at least 92%. This treatment would also be compatible with aeration or oxidation procedures to further increase the removal of H2S to achieve an aqueous H2S level of <1 mg/l. Aeration or oxidation would also increase the dissolved oxygen and COD levels, increase the inhibition of SRB activity and oxidise any reduced sulphur. The dosing of sodium nitrate and AQ to control the generation of H2S is not patented in South Africa. It can, therefore, be used to treat the Kraft mill effluent without violating any intellectual property rights in South Africa.Dissertation (MSc(Applied Science))--University of Pretoria, 2008.Chemical Engineeringunrestricte

Removal of hard COD, nitrogenous compounds and phenols from a high-strength coal gasification wastewater stream

The objective of this study was to identify the factors affecting the suspended and fixed biomass in the removal of hard COD, nitrogenous compounds and phenols from a coal gasification wastewater (CGWW) stream using a hybrid fixed-film bioreactor (H-FFBR) process under real-time plant operational conditions and actual wastewater composition. The composition of the influent and effluent was studied to determine which compounds were not removed by hydrolysis (bacterial activity) and how this correlated to the suspended and fixed biomass activity, COD and phenol removal. A H-FFBR with 12 g∙m−3 attached biomass and 440 mg∙ℓ−1 suspended biomass achieved 78% phenol removal and 49% COD removal but insignificant removal of nitrogenous compounds. During the operation period, fixed biomass concentration was higher than the suspended biomass. Parameters such as pH, phenols, alkalinity, metal ions, conductivity, total dissolved solids and aeration rate affected the fixed biofilm properties such as adhesion, thickness and structure. It can be concluded that the composition of the effluent had a direct effect on the fixed biomass properties and thus a direct effect on the removal of phenols, COD and nitrogenous compounds in the wastewater.The authors would like to thank Buckman Africa for funding the chemical, EDX, GC-MS and SEM analyses and Sasol Technology (Pty) Ltd for the use and operation of the pilot plant.http://www.wrc.org.zaam201

The use of exogenous microbial species to enhance the performance of a hybrid fixed-film bioreactor treating coal gasification wastewater to meet discharge requirements

The objective of this study was to determine whether inoculating a hybrid fixed-film bioreactor with exogenous bacterial and diatoma species would increase the removal of chemical oxygen demand, nitrogenous compounds and suspended solids from a real-time coal gasification wastewater to meet environmental discharge requirements specified for petrochemical refineries. The COD removal increased by 25% (45% to 70%) at a relatively high inoculum dosage (370 g∙m−3) and unit treatment cost (12.21 €∙m−3). The molar ratio of monovalent cations to divalent cations (M/D >2) affected nitrification, settling of solids and dewatering of the sludge. The use of a low-charge cationic flocculant decreased the suspended solids in the effluent by 70% (180 mg∙L−1 to 54 mg∙L−1) and increased the sludge dewatering rate by 88% (61 s∙L∙g−1 to 154 s∙L∙g−1) at a unit treatment cost of 2.5 €∙t−1 dry solids. Organic compounds not removed by the indigenous and exogenous microbial species included benzoic acids (aromatic carboxylic acids), 2-butenoic acid (short-chain unsaturated carboxylic acid), I(2H)-isoquinolinone (heterocyclic amine), hydantoins (highly polar heterocyclic compounds), long-chain hydrocarbon length (carbon length > C15) and squalene. These organic compounds can thus be classified as poorly degradable or nonbiodegradable which contributed to the 30% COD not removed by the H-FFBR. The use of exogenous microbial species improved the quality of CGWW; however, not sufficiently to meet discharge requirements. The cost of such treatment to meet discharge requirements would be unsustainable. Alternative technologies need to be investigated for reusing or recycling the CGWW rather than discharging.The authors would like to thank Buckman Africa for financing the chemical and microbiological analyses and Sasol Group Technology (Pty) Ltd for the use and operation of the pilot plant.http://www.wrc.org.zaam2016Chemical Engineerin

Bioaugmentation of coal gasification stripped gas liquor wastewater in a hybrid fixed-film bioreactor

Coal gasification stripped gas liquor (CGSGL) wastewater contains large quantities of complex organic and inorganic pollutants which include phenols, ammonia, hydantoins, furans, indoles, pyridines, phthalates and other monocyclic and polycyclic nitrogen-containing aromatics, as well as oxygen- and sulphur-containing heterocyclic compounds. The performance of most conventional aerobic systems for CGSGL wastewater is inadequate in reducing pollutants contributing to chemical oxygen demand (COD), phenols and ammonia due to the presence of toxic and inhibitory organic compounds. There is an ever-increasing scarcity of freshwater in South Africa, thus reclamation of wastewater for recycling is growing rapidly and the demand for higher effluent quality before being discharged or reused is also increasing. The selection of hybrid fixed-film bioreactor (HFFBR) systems in the detoxification of a complex mixture of compounds such as those found in CGSGL has not been investigated. Thus, the objective of this study was to investigate the detoxification of the CGSGL in a H-FFBR bioaugmented with a mixed-culture inoculum containing Pseudomonas putida, Pseudomonas plecoglossicida, Rhodococcus erythropolis, Rhodococcus qingshengii, Enterobacter cloacae, Enterobacter asburiae strains of bacteria, as well as the seaweed (Silvetia siliquosa) and diatoms. The results indicated a 45% and 79% reduction in COD and phenols, respectively, without bioaugmentation. The reduction in COD increased by 8% with inoculum PA1, 13% with inoculum PA2 and 7% with inoculum PA3. Inoculum PA1 was a blend of Pseudomonas, Enterobacter and Rhodococcus strains, inoculum PA2 was a blend of Pseudomonas putida iistrains and inoculum PA3 was a blend of Pseudomonas putida and Pseudomonas plecoglossicida strains. The results also indicated that a 70% carrier fill formed a dense biofilm, a 50% carrier fill formed a rippling biofilm and a 30% carrier fill formed a porous biofilm. The autotrophic nitrifying bacteria were out-competed by the heterotrophic bacteria of the genera Thauera, Pseudaminobacter, Pseudomonas and Diaphorobacter. Metagenomic sequencing data also indicated significant dissimilarities between the biofilm, suspended biomass, effluent and feed microbial populations. A large population (20% to 30%) of unclassified bacteria were also present, indicating the presence of novel bacteria that may play an important role in the treatment of the CGSGL wastewater. The artificial neural network (ANN) model developed in this study is a novel virtual tool for the prediction of COD and phenol removal from CGSGL wastewater treated in a bioaugmented H-FFBR. Knowledge extraction from the trained ANN model showed that significant nonlinearities exist between the H-FFBR operational parameters and the removal of COD and phenol. The predictive model thus increases knowledge of the process inputs and outputs and thus facilitates process control and optimisation to meet more stringent effluent discharge requirements.Thesis (PhD)--University of Pretoria, 2017.Chemical EngineeringPhDUnrestricte

Prediction of performance of the moving-bed biofilm pilot reactor using back-propagation artificial neural network (BP-ANN)

Coal gasification stripped gas liquor (CGSGL) wastewater contains large quantities of complex organic and inorganic pollutants which include phenols, ammonia, hydantoins, furans, indoles, pyridines, phthalates and other monocyclic and polycyclic nitrogen containing aromatics, oxygen- and sulphur containing heterocyclic compounds. Most conventional aerobic systems for coal gasification wastewater treatment are not sufficient in reducing pollutants such as chemical oxygen demand (COD), phenols and ammonia due to the presence of toxic and inhibitory organic compounds. The current paper reports on the degradation of aromatic compounds and the reduction of hard COD in CGSGL using a Moving-Bed Biofilm Reactor (MBBR) system. The inoculum contained a genetically enhanced mixed culture of Pseudomonas putida, Pseudomonas plecoglossicida, Rhodococcus erythropolis, Rhodococcus qingshengii, Enterobacter cloacae, Enterobacter asburiae strains of bacteria, seaweed and diatoma. Consistently high hard COD removal (>88 %) and degradation of targeted phenolic compounds (>93 %) was achieved in the reactor with no loss of biodiversity in the consortium culture. The performance of the reactor outside the observable range was projected using a Back-Propagation Artificial Neural Network (BP-ANN) developed in this study.The project was partially funded by National Research Foundation (NRF) through the Incentive Funding for Rated Researchers Grant No. IFR170214222643 awarded to Prof Evans M.N. Chirwa of the Department of Chemical Engineering, University of Pretoria. Buckman Africa provided funding for chemical and microbiological analyses.http://www.aidic.it/cetam2018Chemical Engineerin

Effect of carrier fill ratio on biofilm properties and performance of a hybrid fixed-film bioreactor treating coal gasification wastewater for the removal of COD, phenols and ammonia-nitrogen

The purpose of this study was to determine the effect different biofilm carrier filling ratios would have on biofilm morphology and activity and bacterial diversity in a hybrid fixed-film bioreactor treating high strength coal gasification wastewater (CGWW) for the removal of chemical oxygen demand (COD), phenols and ammonia-nitrogen. Results showed that a carrier fill of 70% formed a ‘compact’ biofilm, a 50% fill formed a ‘rippling’ biofilm and a 30% fill formed a ‘porous’ biofilm. The highest microbial activity was obtained with a 50% carrier fill supporting a relatively thin biofilm. The highest level of biofilm bound metals were aluminium, silicon, calcium and iron in the ‘compact’ biofilm; nitrogen, magnesium, chloride, sodium and potassium in the ‘rippling’ biofilm, and copper in the ‘porous’ biofilm. The bioreactor improved the quality of the CGWW by removing 49% and 78% of the COD and phenols, respectively. However, no significant amount of ammonia-nitrogen was removed since nitrification did not take place due to heterotrophic bacteria out-competing autotrophic nitrifying bacteria in the biofilm. The dominant heterotrophic genera identified for all three carrier filling ratios were Thauera, Pseudaminobacter, Pseudomonas and Diaphorobacter.Buckman Africa and the University of Pretoria.http://wst.iwaponline.com2016-11-30hb2016Chemical Engineerin

Management of hydrogen sulphide generation at a Kraft mill effluent plant

Communities surrounding an integrated Kraft mill noticed odours from the mill’s effluent treatment plant. A project was therefore commissioned by the mill to proactively manage the odours from both the pulp-processing operations and the effluent treatment plant. This project formed part of a co-ordinated study that was implemented by the mill to limit emissions of the total reduced sulphur (TRS) components from the pulp mill operations. It was found that sulphate-reducing bacteria(SRB) converted the sulphates present in the effluent to hydrogen sulphide (H2S) by dissimilatory respiration. The combined use of a nitrate-releasing biomodifier (Bulab® 9518) and an anthraquinone sulphate-reduction inhibitor (Busperse® 2432) was effective in reducing both SRB activity and H2S levels. The average aqueous H2S levels (40 mg/ℓ) were reduced to between 92% and 99%

Management of hydrogen sulphide generation at a Kraft mill effluent plant

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