ASSIGNMENT 1 CBE 697

BIOREFINERIES
DR NIK RAIKHAN NIK HIM
FACULTY OF CHEMICAL ENGINEERING (EH220)
PRODUCTION OF BIOETHANOL FROM WASTE PAPER

NAME ID SEMESTER

MOHAMAD SALMI BIN MOHD FUDZI 2015673968 7

WAN MUHAMMAD HAFIZ BIN WAN MUSTAPHA 2015674024 7

MOHAMAD FATHMI BIN MASOR @ MANSOR 2015673982 7

PUTERA AMIRUL HAIKAL BIN ROSLI 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 the 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 heightened 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 well-
documented 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 octane 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 threat 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 on 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-,soft-
rot 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 archive 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:

𝑊1 − 𝑊2
= 𝑆𝑃𝐸𝐶𝐼𝐹𝐼𝐶 𝐺𝑅𝐴𝑉𝐼𝑇𝑌
𝑊3 − 𝑊1

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 the 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 greenhouse 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 ethanol
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, pretreatment, 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 Newspaper Office Paper Magazine Cardboard
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 glycerol (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 Arabinose
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. The 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 using 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 having 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 newspaper 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 production 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 on 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 process, 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.