ASSIGNMENT 1 CB E 697 BIOREFINERIES DR NIK RAIKHAN NIK HIM FACULTY OF CHEMICAL ENGINEERING (EH220) PRODUCTION OF BIOETHANOL FROM WASTE PAPER NAME
ID
SEMESTER SEMESTER
MOHAMAD SALMI SAL MI BIN MOHD FUDZI
2015673968 2015673968
7
WAN MUHAMMAD HAFIZ BIN WAN MUSTAPHA
2015674024 2015674024
7
MOHAMAD FATHMI BIN MASOR @ MANSOR
2015673982 2015673982
7
PUTERA AMIRUL HAIKAL HAIK AL BIN ROSLI
2014452974 2014452974
5
ABSTRACT Based on current and past researches, the production of bioethanol can be done from the waste feed stock or also known as biomass feedstock. Currently, production of bioethanol still can be done by the use first generation such as sugar, starch and animal fats. However, in terms of environment and cost, first generation sources will not be relevant in future. Basically, this report study on overview production of bioethanol by th e second generation which is coming from solid waste such as wood and paper. It is believe that in future, chemical industry will be depend upon biomass as alternative sources. Bioethanol production by biomass, it needed for a pretreatment of biomass before it pass through main method which are cellulose hydrolysis and sugar fermentation. An overview for the past studies shown the different result of content of waste paper in terms of moisture, lignin and ash. Four types of different paper used which are newspaper, office paper, magazine and cardboard. Meanwhile, these four types of paper also been study in enzymatic hydrolysis and component in different type of waste paper such as glucose, xylose, cellobiose, galactose, mannose and arabinose are recorded. In nutshell, biological treatments is the best pretreatment for waste paper by using high-boiling solvents.
1.0 INTRODUCTION Current economic development in whole countries in the world have heig htened the necessity for changes such renewable sources because of some disaster of environmental affect based on fossil fuels usage. After two centuries of almost absolute belief in technical and economic advancement, human society is certainly in a period of reconsideration and expansion of new alternative for continuing new century to accomplish the demand of customers. The welldocumented drawbacks of fossil fuels are shows the several crisis such as their finite supply, greenhouse gaseous emission relating global warming affect, and the unexpected price of sources. All the crisis have forcing human society to catch another way that concern with new alternatives, renewable, sustainable, and economically viable fuel such as bioethanol. Bioethanol can be either mixed with gasoline or used as a sole fuel using dedicated engines, moreover, it has higher heat of vaporization and o ctane number compared to gasoline. The progress made by our civilization, with an explosive rise in world population has led to an enormous consumption increase of resources and to an equal th reat to the environment. Ethanol is combine with gasoline had been tested and supports by vehicle manufacturers have resulted in vehicles that can use up to an 85% ethanol-15%ethanol gasoline mixture (Mood et al., 2013). Thus, gasoline can use bioethanol as an oxygenated fuel to increase its oxygen content, causing better hydrocarbon oxidation and diminishing greenhouse gasses. In the future, our energy systems will need to be renewable and sustainable, more efficient and cost-effective, convenient and safe. In the second generation, lignicellulosic materials are cheaper than first generation, abundant and renewable, are chosen as feedstock in ethanol production. First generation bioethanol production, basically expensive starch and sugar derived from sugar cane and maize are employed as feedstock. Based on these materials, most of industries are tend to use lignicellulosic materials because of low price and easy to obtain raw materials. In addition, this cheap material does not negatively affect the human food supply chain by eliminating the food in favor of bioethanol production. . Lignocellulosic biomass in nature is by far the most abundant raw material from hardwood, softwood, grasses and agricultural residues. Ethanol produced from lignocellulosic materials has the potential to be a valuable substitute for, or complement to, gasoline. In the future, the chemical industry will depend o n biomass as an alternative source (Gupta et al., 2015). In worldwide, the bioethanol production has been used many agro- residues such as sugarcane bagasse, cotton stalk, and solid waste due to available feed stocks. Based on Gupta (2015), first generation such as sugar, starch, animal fats, and vegetable oils were being used in biofuel production like as bio-ethanol biodiesel and biogas while second generation is coming
from solid waste such as sugarcane bagasse, wheat straw, wood and paper. Production of ethanol based on cellulosic material has been studied for a long time ago and it is improving the process to produce more sustainable and renewable raw material in order to save the environment from bad affect. Lignocellulosic materials can be defined into four group based on type of resource which are waste paper, crop residues resources, municipal solid waste and forest residues. These things basically coming from second generation is the most promising feedstock due to great of availability and low cost, however, the problem might exist when implying into big commercial or large-scale production of fuel bioethanol (Balat, 2016). Major benefits of biofuels are shown in table below:
Figure 1.1: Benefits of biofuel
It denotes the significant, renewable liquid fuel used for motor vehicles. Chemical composition of lignocellulosic materials is a key factor disturbing efficiency of biofuel manufacture during conversion processes. The structural and chemical composition of lignocellulosic materials is highly inconstant because of genetic and environmental influences and their interactions. When using waste paper as a feedstock in ethanol manufacturing, it can reduce greenhouse gas emission and also reducing the waste resulting saving space for landfill. According to EPA, paper makes up about 28% of solid trash in landfills. Most of the newspaper readers, they will remove newspaper without any taking of benefits from this materials. In additional, using waste paper can helps environment and also economically responsible.
2.0 SENTIVITY ANALYSIS ON PROCESS ANALYSIS
The way to analyse the parameter is to investigate the influence on the process as it being economical. Below are some parameters that need to be reconsidered in the process: 1. Solid loading in saccharification, fermentation efficiency, anaerobic digestion efficiency. 2. Xylan conversion efficiency in DA pre-treatment in the state-of-the-art process for paper to bioethanol The process parameter and their range are listed in Table 1. 15% (w/w) of solid loading saccharification was used in the base line scenarios. A higher loading at 20% (w/w) was set in the sensitive analysis. The pulp time for this loading in for this loading is reported as 30 min and energy consumption is 15kE/dry tonne [22]. Sugar yield in saccharification archived at these various solid loading was assumed anchanged. For fermentation, xylose conversion efficiency is reported in varying from 76% to 80% while those mannose and galactose vary from 0% to 40% [25]. The data used in the basedline scenarios are the higher of the experimental data.
Table 1: Process parameter and their range
For anaerobic digestion, efficient data are summarised in Table 2. The average value of these range for the COD removal efficiency and the biogas productionrate are used in the baseline scenarios. For the office paper with DA pre-treatment the set of data xylan conversion efficiency was reported from 2011 update NERL report [25].
Table 2: Anaerobic digestion
3.0 METHODOLOGY
3.1 PRETREATMENT
3.1.1 PHYSICAL PRETREATMENT This pretreatment such as milling, grinding, freezing, radiation is to increase the surface area and reduce the size of lignocellulosic [29]. This process will lead to decrease in degree of polymerization and decrystallization of the feedstock.
3.1.1.1 MILLING Usually milling will be reconsidered as the first step of pretreatment there are many type of milling and grind are use in production of bioethanol. At the end of the particle size will reduce to 10-30 mm and 0.2-2 mm, respectively [30]. The most important drawback of milling is that it consume high energy consumption.
3.1.2 CHEMICAL PRETREATMENT
3.1.2.1 ACID PRETREATMENT Sulphuric acid are usually used by the industries as a chemical pretreatment for lignocellulosic biomass where polysaccharide are hydrolysed to monosaccharide which may leads to higher accessibility of cellulose. This pretreatment are more economical as it performed at the uses of high concentration and low temperature, but there are few reconsideration that need to take note as the toxicity, corrosiveness of equipment, acid recovery[30], degradation of glucose and the formation of fermentation inhibitor. At this condition this process might leads to produce unwanted product e.g. formic and levulinic acid [46]. At this condition, industries are now reconsider the uses of diluted acid which generate less amount of fermentation inhibitor. For instance, rice straw was pretreated with 1%(w/w) sulphuric acid with 1-5 min retention time at 160 ℃ follow by enzymatic hydrolysis, which result in the maximal sugar yield at 83% [47].
3.1.3 BIOLOGICAL PRETREATMENT Unlike chemical or physicochemical pretreatment method, this biological are more environmental friendly pretreatment of converting lignocellulosic biomass by using microorganisms especially fungi into more accessible compound for hydrolysis and subsequent bioethanol production this is because we don’t have issue with chemicals [104]. in contrast most of the pretreatment require high operation and capital cost, at this stage the only advantages method is white-,brown-,softrot fungi to enhance the hydrolysis of lignocellulosic biomass [105]. To promote highest efficiency among the biological pretreatment can be archive by lignin degradation only attack cellulose. In biological pretreatment, particle size, moisture content time operation, pH and temperature will effect lignin degradation and enzymatic hydrolysis yield. A researcher has discover up to 31% lignin degradation while maintaining 94% of cellulose during an 18-d pretreatment. Plus the highest glucose yield of 66.61%, was archive at 28 ℃ with moist content 75% and particle size at 5mm. In the end, since it use low energy consumption, eco-friendly and no chemical requirement, it has drawback in practice for commercial. This include long process time, large space requirement and continuous monitoring.
3.1.4 COMBINATION OF PRETREATMENT Previously various pretreatment have some drawback and limit their applicant. As combination method introduce to overcome this problem which increase efficiency of sugar production, decrease the formation inhibitor, shorter time and
4
3.1.4.1 COMBINATION OF BIOLOGICAL AND DILUTE ACID PRETREATMENT (bio-DA) The using dilute acid is suitable method to dissolve hemicellulose, meanwhile biological pretreatment by using fungas will distrupt the lignin shealth thus low energy require and mild enviroment. Eventhough both have some limitation but Fuying et al. [115] prove that combination of biological and diluted acid pretreatment (bio-DA) in order to enhance enzymatic hydrolysis of water. The combination of Echinodotinuim taxodii and H2SO4 successfully led to enhancement of enzymatic hydrolysis, elevated of reducing sugars and also ethanol yield.
3.2 HYDROLYSIS OF PRETREATED SUBSTRATE At this stage the maximum cellulose which are released during the pretreatment stage was hydrolysed by the isolated cellulose degrade by the bacteria. This pretreated substrate was washed with distilled water for a several times to neutralise the acid. Then, the substrate was heated with oven till dried at constant weight an pH was adjuste to a rchive 7. According to National Collection of Industries (NCIM), pure culture of Cytophagahutchisonni was introduce (NCIM2338) (CH) and isolated organism is taken from Department of Biotechnology, BEC Bagalkot. Comparison study between isolated cellulose degrading bacteria and the pure culture of CH was performed. As a result, after 24hr grown in innocolumn of isolated cellulose degrading bacteria and pure culture was added to substrate and then preheated. Reducing sugar release during substrate hydrolysis were analysed by Dinitrosalicylic Acid (DNS) method every 24hr, for both (zahid anwar et al., 2011). Then maximum sugars was releasedduring this period are taking to the fermentation to generate bioethanol.
3.3 FERMENTATION OF HYDROLYSED BROTH In this stage ferentation was carried out by using yeast since it commerciallly available. The pH was adjusted to archive pH4.6 and an innocolumn of active yeast (in lag phase) was added into the hydrolysed broth.this process will operate at 36 oc until maximum sugar are converted into bioethanol. The reducing sugar utilization during fermentation was analyze by DNS method which prposed by (Zahid Anwar et al., 2011), and the bioethanol production was analyze bu using specific gravity, (Sahail J et al., 2011). The calculation as showend below:
1 − 2 3 − 1
=
Where, W1= empty weight of specific gravity bottle W2=weight of sample+ specific gravity of bottle W3=weight of distilled water + specific gravity of bottle
Bioethanol production in pulp and paper industry is presented below. The steps of the process are schematically in Figure 1.2
Figure 1.2: Bioethanol production in pulp and paper industry
4.0 PROCESS DESCRIPTION At the begining of the stage the feed is cooled in heat exchanger and resulting a steam, S3, and directly to the fermentor , R1, the reaction described in the previous part occur in the reactor. The resulting stream S4 is splitted. S5 containing CO2 is realesed to the atmosphere while the liquid stream S6, is pumpto anather heat exchanger E-3, in order to modified the temperature and pressure of the input stream (S9) to the first distilation column C-1. Ethanol is concentrated up to 50% in this column. Then the ethanol solution contain approximately 50%of water and 50% of ethanol. In order to make the ethanol more concentrated thus a secondary distillation C2 is nessasary. The stream from the first column S15, is send to the second distillation column C2, the second column S21 is splited again to obtain pure ethanol in S23. The quantity of ethanol obtained for the production 11596.5 lbs/hr. The bottom stream of both column (S16 and S22) are mixed in M-1 and used to heat S8. Stream S10 contains the steam requested to heat the reboiler of both distillation column. The outlet stream of reboiler as well as th e stream of the condense are mixed in M-2, respectively m-3, and are used in other process. Figure 1.3 shown the ethanol production
Figure 1.2: Process flow diagram for ethanol production
5.0 COMPARISON Nowadays, second generation ethanol production from lignocellulosic materials are extensively studied around the world as it is renewable and sustainable fuels form. Lignocellulosic biofuels proved it is relatively fewer environmental impacts and low gre enhouse gases emissions compare to other alternative biofuels such traditional biofuels industry from oil-rich crops and sugars (Albarelli, Ensinas, & Silva, 2014) . Moreover, Ethanol produced from lignocellulosic materials has the potential to be a valuable substitute for, or complement to, gasoline. Along with this acceptance has come increased interest in commercializing technology for production of e thanol from potentially inexpensive cellulosic feedstocks (“Bioethanol Production in Pulp and Paper Industry,” 2007). In this study we are focused on used of waste paper as second generation ethanol production. To produce a bioethanol from a waste paper there are several process such analyze the content of raw materials, pr etreatment, enzymatic hydrolysis and fermentation.
5.0 COMPARISON Nowadays, second generation ethanol production from lignocellulosic materials are extensively studied around the world as it is renewable and sustainable fuels form. Lignocellulosic biofuels proved it is relatively fewer environmental impacts and low gre enhouse gases emissions compare to other alternative biofuels such traditional biofuels industry from oil-rich crops and sugars (Albarelli, Ensinas, & Silva, 2014) . Moreover, Ethanol produced from lignocellulosic materials has the potential to be a valuable substitute for, or complement to, gasoline. Along with this acceptance has come increased interest in commercializing technology for production of e thanol from potentially inexpensive cellulosic feedstocks (“Bioethanol Production in Pulp and Paper Industry,” 2007). In this study we are focused on used of waste paper as second generation ethanol production. To produce a bioethanol from a waste paper there are several process such analyze the content of raw materials, pr etreatment, enzymatic hydrolysis and fermentation.
5.1 ANALYZE CONTENT OF WASTE PAPER Before waste water to be analyze it need to be cut into small pieces. There are various methods in order to determine the content such Anthrone method and conventional methods of chemical analysis (Byadgi & Kalburgi, 2016). Normally, anthrone method use to estimate their cellulose content and total carbohydrates in substrate. For conventional methods of chemical analysis are to estimate the ash content and moisture content (Ioelovich, 2014). Below are the composition of waste papers that get by Saccharification process.
Table 1: Composition of waste papers Types waste
News paper
Offic e Paper
Magazine
Cardb oard
paper Moisture
7.25
4.90
4.40
5.90
Lignin
16.82
5.78
14.19
14.86
Ash
9.49
7.57
28.83
9.32
5.2 PRE - TREATMENT In this steps are very important as need huge of investment cause it affects the cost of others steps such size reduction and enzymatic hydrolysis. Normally, in this steps there are using organic solvent, acid, alkali, or steam (Lee, Cho, Kim, & Kim, 2010). For example of acid use are sulphuric acid by using different concentration depending on the temperature and heating period time (Byadgi & Kalburgi, 2016). The acid used is because to adjust the pH of the raw materials
due to its alkalinity (Wang, Sharifzadeh, Templer, & Murphy, 2013). Besides, the example for organic solvent in pretreatment are use either high or low boiling solvent. The example of organic solvent using low boiling solvent is ethanol. But as it is highly flammable and volatile it will negligible. Whereas for alternative pulping method which use high boiling solvents such as ethanolamine, phenol, glycerol and ethylene g lycerol (EG) can be consider as it suitable in liquefy the lignocellulosic biomass. The example pretreatment of using alkali is by oxidative lime (OL). Normally the OL are used for waste paper type such newspapers. In this steps normally need a machine such mixer or blender in order to mix the waste papers with fluid. From the variety type of study on pretreatment to waste paper (Wang et al., 2013).
5.3 ENZYMATIC HYDROLYSIS In this step there are huge various enzyme use such isolated cellulose degrading bacteria will hydrolysed the cellulose released during pretreatment by added 24hr grown inoculum of isolated cellulose degrading bacteria and pure culture, Cytophagahutchisonni (CH) (Byadgi & Kalburgi, 2016). Other than that are hydrolyzed waste water with a mixture of commercial cellulolytic enzyme – cellulase, Accelerase-1500 and β–glucosidase Novozyme-188. The concentration of the glucose in the hydrolyzate was tested by the HPLC method. In addition the results for table below is obtained experimentally by enzymatic hydrolyses at 160 mg Cellic Ctec 1 liquid product as supplied/g glucan (equivalent to 16.8 FPU/g glucan) after 72 h (Ioelovich, 2014). Below are the percentage of component present in waste paper based on different types.
Table 2: Component in different type of waste paper Types of
Glucose
Xylose
Cellobiose
Galactose
Mannose
Arabi nose
waste
(%)
(%)
(%)
(%)
(%)
(%)
paper Newspaper
55.5
57.7
3.3
57.0
56.2
28.3
Office Paper
76.1
62.8
5.4
-
-
-
Cardboard
62.2
61.8
2.2
62.4
60.1
31.7
Magazine
49.8
41.8
2.1
44.8
46.7
19.6
From the results the highest glucose and xylose yields which are important part in producing bioethanol are come from office paper. It is probably due to low lignin content in office paper which is 5.78% and shorter fibres compare to other types of paper. Same as cardboard who had second highest glucose yields which contain low lignin compare with newspaper and magazine therefore
a higher potential for enzyme accessibility. The less yields of glucose for magazine and newspapers probably due to its relatively high impurities content such coatings and paper fillers (Wang et al., 2013).
5.4 FERMENTATION This steps is last step before bioethanol will be produce from the waste papers. In this steps also have varieties of methods. For the first method was carried out using commercially available yeast, Saccharomyces cerevisiae. The pH of hydrolysed broth was adjusted to 4.6 and an inoculum of active yeast (in log phase) was added to the hydrolysed broth. T he fermentation was carried out at 360 oC until maximum sugars are converted into bioethanol (Byadgi & Kalburgi, 2016). Another method are using of the sugar-containing hydrolyzate to produce bioethanol was carried out in a laboratory fermentor “Biostat A Plus” (Sartorius AG) using the yeast of Saccharomyces cerevisiae at 35°C for 3 days (Ioelovich, 2014).
6.0 CONCLUSIONS In conclusions, biological treatments is the best pretreatment for waste paper by u sing high-boiling solvents. Among the high-boiling point solvent EG was consider in this process as it have much lower viscosity than other solvent. In addition, for this process do not need high pressure equipment and have ability to enhance enzymatic digestibility which can easier removal of additives in waste paper such inks and fillers (Lee, Cho, Kim, & Kim, 2010).
7.0 FUTURE PERSPECTIVE Renewable chemistry research has conventionally focused on finding another possibility to changes petro-chemical based fuels. The population in our planet always grows causing demands for energy and more chemical is increasing by time. This demand could be get-together with environmentally friendly, without leaving economics sense. Even though there is public support for sustainable products and manufacturing, among the consumers, they are not yet willing to fee premium. Then, the alternatives one should standing on good product, including best quality which low effect on environmental issue and the price not higher too far between petrochemical. In global scope, industry of pulp and paper manufacturing produces about 300-350 million tons of various types of board and paper (Loelovich, 2014). Unfortunately, there is smaller part of waste paper materials is recycled, while most of the used materials (waste paper) are thrown out and burned. By using this material as feedstock, the percentage of recycling used paper will increase also resulting lower of environmental affect.
The international market in bioethanol product is in its early stage and it’s still in development process that requires the diversification of manufacturing, in both type of feedstock and number of manufacturing countries (Calle et al. 2006). Sustainable creation should become a necessity for which authorization looks to be requirement, but should be well- defined to ensure sustainability in a far-reaching sense so that it does not impose additional barriers to trade. The strategies should be defined to bring market more effectiveness and sustainable development. According
to
Talebnia
(2015),
both
biological
and
thermochemical
pathways
(technologies) required significant or high capital investment and it is involving several sophisticated processing steps with higher cost of operating compared with the first generation ethanol. Currently, both pathways almost similar with respect to environmental merit and energy efficiency (Foust et al. 2009: Tablenia 2015). Last few decades, both technologies are still under continual development and always in evaluation process. It is h aving several technical issues and environmental blocks yet to be solving. Based on this study, the characteristics of feedstock, efficiency of pretreatment methods, hydrolytic enzymes, and overall process integration are play important role that might be challenges to select the best one that required further improvement on the next study.
8.0 ACKNOWLEDGEMENT Gratefully acknowledge to University Technology Mara (UiTM) for let us conduct a research on this topic and given opportunity expose this course.
9.0 REFERENCES Adrian. (2008). Production of fuel ethanol from corn. Corn-based fuel ethanol project , 1-19. Balat, M. (2015). Bioethanol from Lignocellulosic Wastes: Current Status and Future Prospects. Springer Link, 175-206. Foust TD, A. A. (2009). An Economic and Environmental Comparison of a Biochemical and a Thermochemical lignocellulosic Ethanol Conversion Processes. Cellulose, 547-565. Loelovich, M. (2014). Waste Paper as Promising Feedstock for Production of Biofuel. Science Domain, 905-916. P. W. Bergeron, C. J. (1991). Waste paper as a feedstock for ethanol production . National Renewable Energy Laboratory, 1-19. Talebnia F, K. D. (2010). Production of Bioethanol from Wheat Straw: An Overview on Petreatment, Hydrolysis and Fermentation. Bioresour Technol, 4744-4753.
Albarelli, J. Q., Ensinas, A. V., & Silva, M. A. (2014). Product diversification to enhance economic viability of second generation ethanol production in Brazil: The case of the sugar and ethanol joint production. Chemical Engineering Research and Design , 92(8), 1470 – 1481. https://doi.org/10.1016/j.cherd.2013.11.016 Byadgi, S. A., & Kalburgi, P. B. (2016). Production of Bioethanol from Waste Newspaper. Procedia Environmental Sciences, 35, 555 –562. https://doi.org/10.1016/j.proenv.2016.07.040 Bioethanol Production in Pulp and Paper Industry. (2007). Ioelovich, M. (2014). Waste Paper as Promising Feedstock for Production of Biofuel. Journal of Scientific Research & Reports, 3(7), 905 –916. Lee, D. H., Cho, E. Y., Kim, C. J., & Kim, S. B. (2010). Pretreatment of waste n ewspaper using ethylene glycol for bioethanol production. Biotechnology and Bioprocess Engineering , 15(6), 1094 –1101. https://doi.org/10.1007/s12257-010-0158-0 Wang, L., Sharifzadeh, M., Templer, R., & Murphy, R. J. (2013). Bioethanol pro duction from various waste papers: Economic feasibility and sensitivity analysis. Applied Energy, 111, 1172 –1182. https://doi.org/10.1016/j.apenergy.2012.08.048 Zahid Anwar, Muhammad G, Javaid A, Ali S, 2011, Bioetahnol production from rice polish by optimization of dilute pretreatment and enzymatic hydrolysis, African Journal of Biotechnology, vol 11(4) pp.992-998 Sun Y, Cheng J, hydrolysis of lignocellulosic materials for ethanol production: review, bioresource technology, 2009 Larson S, Palmqvist E, Tengborg C, Stenberg K, the generation of of fermentation inhibitors during dilute acid hydrolysis of softwood. Enzyme Microbial Technology,1999 Shi J, Chinn M, Howell N,. Effect of Microbial pretreatment o n enzymatic hydrolysis and fermentation of cotton stalks for ethanol production. Bioresource technology 2010;96:1959 66 Fuying Ma Na, Yang Chunyan, Xu Hongbo, Yu Jianguo. Combination of Biological Pretreatment with mild acid pretreatment for enzymatic hydrolysis and ethanol production from water hyacinth, Bioresource Technology 2010;101:9600-4 Fabry B, Carre B. comparison between different type of pulper devote to deinking pro cess, in TAPPI fall conference & trade fair, San Diego, USA 2002 Humbird D, Aden A, biochemical production of ethanol from corn stover: 2008 state of technology model. National, renewable energy laboratory(NERL) ; 2009.
