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Energy Fuels 2010, 24, 2791–2794   : DOI:10.1021/ef1001106
Published on Web 04/13/2010


                              Biodiesel Production from Municipal Sewage Sludges
                                                                     David M. Kargbo*
                     U.S. EPA Region III, Office of Innovation, Environmental Assessment & Innovation Division,

                                                  Philadelphia, Pennsylvania 19103


                                 Received January 29, 2010. Revised Manuscript Received March 30, 2010




             Biodiesel is a fuel comprised of monoalkyl esters traditionally derived from vegetable oils or animal fats.
             There is currently an unprecedented increase in interest and demand for biodiesel and other fuels derived
             from renewable biomass. However, pure vegetable or seed oils are expensive and constitute between 70%
             and 85% of the overall biodiesel production cost. Municipal sewage sludge is gaining traction in the U.S.
             and around the world as a lipid feedstock for biodiesel production. It is plentiful and consists of significant
             concentrations of lipids that can make production of biodiesel from sludge profitable. However, there are
             challenges to be faced by biodiesel production from waste sludge. Determining how best to collect the
             different fractions and treat them for maximum lipids extraction is a major challenge. To accelerate
             biodiesel production, cosolvents and high shear mixing have been proposed. Nevertheless, there is very
             little information on the cost-effective means of increasing lipid solubility. Alkali-catalyzed transesterifi­
             cation is much faster than acid-catalyzed transesterification and is most often used commercially. How­
             ever, for lipid feedstocks with greater than 1% free fatty acids (FFAs) such as in sludge, acid catalysis
             followed by base catalysis is recommended because of soap formation with alkali-catalyzed transester­
             ification and high FFA. To boost biodiesel production, it is suggested that wastewater operators utilize
             microorganisms that are selected for their oil-producing capabilities. This could increase biodiesel
             production to the 10 billion gallon mark, which is more than three times the nation’s current biodiesel
             production capacity. The presence of pharmaceutical chemicals in sludge poses a great challenge. This
             requires a careful selection of treatment technologies and microbes that are selective for these pharma­
             ceutical chemicals. Finally, biodiesel production from sludge could be very profitable in the long run.
             Currently, the estimated cost of production is $3.11 per gallon of biodiesel. To be competitive, this cost
             should be reduced to levels that are at or below the current petro diesel costs of $3.00 per gallon.


                              Introduction                                                   Municipal sewage sludge is gaining traction in the US and
                                                                                          around the world as a lipid feedstock for biodiesel production.
   Biodiesel holds significant promise as a potential displace­
                                                                                          First, municipal sewage sludge contains significant concentra­
ment fuel for petroleum-based diesel fuel. The United States
                                                                                          tions of lipids derived from the direct adsorption of lipids onto
(US) and the world are witnessing an unprecedented increase
                                                                                          the sludge. These energy-containing lipids include triglycerides,
in interest and demand for biodiesel and other fuels derived
                                                                                          diglycerides, monoglycerides, phospholipids, and free fatty acids
from renewable biomass. For example, the production of
                                                                                          contained in the oils and fats. In addition, microorganisms used
biodiesel in the US has increased from 75 million gallons in
                                                                                          in the wastewater treatment process utilize organic and inorganic
2005 to 250 million gallons in 2006 and 450 million gallons in
                                                                                          compounds in the wastewater as a source of energy, carbon, and
2007,1 with an expected total capacity of well over 1 billion
                                                                                          nutrients. The cell membrane of these microorganisms is a major
gallons in the next few years. Nevertheless, this is still a very
                                                                                          component of sewage sludge and is composed primarily of
infant industry compared to petroleum-based diesel. For
                                                                                          phospholipids.3 It is estimated at 24% to 25% of dry mass of
example, in 2007, the US burned over 60 billion gallons
                                                                                          the cell4,5 and yields about 7% oil from the dried secondary
of petroleum-based diesel compared to 450 million gallons
                                                                                          sludge. Other studies6 have demonstrated that up to 36.8 wt %
of biodiesel. The increasing demand for biodiesel has led
                                                                                          of the dry sludge is comprised of fatty acids and steroids. With
to an increasing need for lipid feedstocks such as soybean,
                                                                                          the fatty acids from sludge predominantly in the range of C10 to
canola, rapeseed, sunflower, palm, and coconut oils. Cur­
                                                                                          C18, these are excellent for the production of biodiesel.
rently, pure vegetable or seed oils are expensive and constitute
                                                                                             Second, sludge is plentiful. In the US alone, approximately
between 70% and 85% of the overall biodiesel production
                                                                                          6.2 million dry metric tons of sludge is produced annually by
cost.2 As a result, the use of alternative nonedible feedstocks
                                                                                          wastewater treatment facilities7 and is expected to increase in
such as Jatropha, animal fats, and waste cooking oil is on
                                                                                          the future due to increasing urbanization and industrialization.
the rise.
                                                                                             (3) Rittmann, B.; McCarty, P. Environmental Biotechnology: Princi­
    *To whom correspondence should be addressed. E-mail: kargbo.david@                    ples and Applications; McGraw-Hill: New York, 2006.
epa.gov.                                                                                     (4) Nelson, D.; Cox, M. Principles of Biochemistry; W.H. Freeman and
   (1) National Biodiesel Board. Biodiesel, 800-841-5849. 2007. Available                 Company: New York, 2005.
at www.biodiesel.org/pdf_files/fuelfactsheets/backgrounder.pdf (accessed Apr                 (5) Dufreche, S.; Hernandez, R.; French, T.; Sparks, D.; Zappi, M.;
2010).                                                                                    Alley, E. J. Am. Oil Chem. Soc. 2007, 84, 181–187.
   (2) Haas, M. J.; Foglia, T. A. Alternate feedstocks and technologies                      (6) Jard6, E.; Mansuy, L.; Faure, P. Water Res. 2005, 39, 1215–1232.
                                                                                                     e
for biodiesel production. In Biodiesel Handbook 2005; Knothe, G., Krahl,                     (7) Activated sludge MOP OM-9, 2nd ed.; Water Environment Federa­
J., Gerpen, J. V., Eds.; AOCS Press: Urbana, IL, 2005; pp 42-61.                          tion: Alexandria, Virginia, 2002.

                                                r 2010 American Chemical Society   2791     pubs.acs.org/EF
Energy Fuels 2010, 24, 2791–2794   : DOI:10.1021/ef1001106
   Third, sludge management poses formidable environmen­                   extraction. For example, the yield of FAMEs from primary
tal challenges. Land application for agricultural purposes has             sludge (maximum yield of 14.5 wt %) is significantly affected
attracted opposition due to odor and the presence of heavy                 by the interactive effects of temperature, acid catalyst con­
metals and recently, the potential exposure to emerging                    centration, and the methanol-to-sludge mass ratio, while the
pharmaceutical chemicals. Similarly, sludge incineration has               yield of FAMEs from secondary sludge (maximum yield of
resulted in emissions that contain dioxins and heavy metals.               2.5 wt %) is significantly affected by the independent effects
Consequently, biodiesel production from sludge as a viable                 of the above three factors. Control over these factors can
alternative to land disposal will help to solve both energy and            significantly influence the cost of production.
environmental problems.                                                       Production Challenges. The optimum production of bio­
   Finally, studies5 show that integrating lipid extraction pro­           diesel is faced with huge challenges. First, the lipids contain­
cesses in 50% of all existing municipal wastewater treatment               ing fatty acids are usually extracted and then transesterified.
plants in the US and transesterification of the extracted lipids           Recently, an in situ transesterification procedure where the
could produce approximately 1.8 billion gallons of biodiesel,              fatty acid containing lipids are simultaneously extracted and
which is roughly 0.5% of the yearly national petroleum diesel              transesterified has been being practiced. This reduces the
demand.                                                                    reaction time and the amount of solvent and samples requi­
   Biodiesel is comprised of fatty acid alkyl esters (FAAEs)               red compared to separate lipid extraction and transesterifi­
produced via base- and/or acid-catalyzed transesterification               cation processes. This is an ongoing area of intense research.
of lipids using alcohol. Fatty acid methyl ester (FAME) is the             Transesterification reaction times can be shortened by increa­
term for biodiesel made when methanol is the alcohol used in               sing the temperature and the addition of enzymes. For
the transesterification process. Equation 1 is an example of               example, the addition of 9-17% lipase enzymes significantly
biodiesel production through transesterification of fat or oil in          decreased the transesterification reaction of tung oil and
the presence of an acid catalyst producing a mixture of                    hence increased the ester conversion of tung oil.8
FAMEs and glycerol.                                                           The optimal conditions were reported to be a 2.2:1 molar
                                                                           ratio of methanol to oil, a reaction time of 18 h, a reaction
                                                                           temperature of 43 oC, and a lipase amount of 14%. Second,
                                                                           reaction completeness (>98% complete) and fuel deteriora­
                                                                           tion (acid value) continue to be challenging aspects of bio­
                                                                           diesel production from traditional feedstocks and should be
                                                                           no different with sludge feedstock. Using higher tempera­
                                                                           tures to accelerate the reaction requires pressure vessels
                                                                           because the alcohol (methanol) boils at 148 oF (65 oC). The
                                                                           addition of cosolvents and high shear mixing have also been
                                                                           proposed as ways to accelerate the reaction. Third, the
  In the above transesterification process, R1, R2, and R3 are             careful selection of catalysts is a key component of successful
long fatty acid chains with only five of these chains common in            biodiesel production from lipid feedstocks such as sludge.
most vegetable oils and animal fats. The physical properties of            The catalyst acts to deprotonate the alcohol to make it a
the resulting biodiesel (e.g., octane number, cold flow, and               stronger nucleophile for reaction with the lipids. Current
oxidative stability) are usually determined by the relative                catalysts are slower, require higher temperature and pres­
amounts of the fatty esters. In the above transesterification,             sure, require longer reaction times, and require high volumes
approximately one volume of oil or fat yields about one volume             of alcohol. Considerable catalyst research is also being
of biodiesel.                                                              carried out. However, the research is restricted to solid phase,
                                                                           fixed bed catalysts. The correct choice of a catalyst may
                                                                           reduce glycerin cleanup costs. Finally, to minimize produc­
                             Challenges
                                                                           tion costs, there is a need to minimize excess alcohol require­
   Biodiesel production from sewage sludge poses huge chal­                ments. In addition to incorporating a faster reaction with less
lenges to overcome if commercial opportunities are to be rea­              energy input, a current industry trend is to use reactors that
lized. Some of these challenges are not unique to biodiesel                incorporate separations and internally recycle alcohol. This
production from waste sludge but to the biodiesel industry as              should be useful also when sludge is the feedstock.
a whole. They include challenges from (i) collecting the sludge,              Maintaining Product Quality. Modern diesel engines are
(ii) optimum production of biodiesel, (iii) maintaining pro­               very sensitive to fuel quality. Consequently, maintaining
duct quality, (vi) soap formation and product separation,                  biodiesel product quality is essential for the growth of the
(v) bioreactor design, (vi) pharmaceutical chemicals in sludge;            biodiesel industry. To be classified as diesel, the product
,(vii) regulatory concerns, and (viii) economics of biodiesel              must meet ASTM D 6751 specifications for the flash point,
production.                                                                closed cup, water and sediment, viscosity, sulfated ash, total
   Collecting Sludge. Primary sludge is a combination of floa­             sulfur, copper strip corrosion, cetane number, cloud point,
ting grease and solids collected at the bottom of the primary              carbon residue, acid number, free and total glycerin, phos­
clarifier of a wastewater treatment plant after screening and              phorus, and vacuum distillation end point. Primary sludge
grit removal. Secondary or activated sludge is composed                    from wastewater treatment facilities is a source of low-quality
mainly of microbial cells and suspended solids produced                    fats and grease. Given that the yield of primary (low-quality)
during the aerobic biological treatment of wastewater and                  sludge is higher than that of secondary (higher-quality) sludge,
collected in the secondary clarifier. Biodiesel production from            there is a need to improve lipid solubility in the reaction
both primary and secondary sludges is currently undergoing
intense research. Challenges do exist in determining how best                (8) Xu, G.; Zhang, B.; Liu, S.; Yue, J. Ag. Sci. China 2006, 5 (11), 859–
to collect these fractions and treat them for maximum lipids               864.
                                                                    2792
Energy Fuels 2010, 24, 2791–2794   : DOI:10.1021/ef1001106
mixture during transesterification. This is usually solved by                   oil, borage oil, coffee oil, safflower oil, etc.) and fish oil
the addition of hexane, which significantly increases the                       and bird oil have been employed as excipients in cosmetic
biodiesel production cost. A challenge is to find a more cost-                  formulations.
effective means of increasing lipid solubility.                                    Fatty acids used as lipid regulators are also occurring in
   Soap Formation and Product Separation. Base-catalyzed                        wastewaters as emerging contaminants that could end up in
transesterification is much faster than acid-catalyzed trans­                   sludges.11 The pharmaceutical industry is concerned about
esterification and is most often used commercially.9 How­                       traces of its organic chemicals (that may not be adequately
ever, a high concentration of free fatty acids (FFA) in the                     treated) adsorbing on sludge surfaces. There is therefore a
sewage sludge can result in problems such as soap formation                     need to evaluate the effectiveness of the transesterification
and difficulty in product separation (eq 2).                                    process to treat these chemicals and convert them to biodie­
                                                                                sel. This may require a careful selection of treatment tech­
                                                                                nologies and microbes that are selective for these chemicals.
                                                                                Conversion of these emerging contaminants to biodiesel will
                                                                                not only help solve an energy problem but will also remove
                                                                                from the environment one of the fastest growing and chal­
                                                                                lenging groups of chemicals.
                                                                                   Regulatory Concerns. Sludge is classified as either Class A
                                                                                or Class B, depending on the type of treatment it has
                                                                                received. Class A sludge has benefited from both pretreat­
                                                                                ment and treatment at the wastewater facility. While most
                                                                                sludge used for biodiesel production may fall under Class A,
   The soaps formed can gel at ambient temperature, causing                     its use offsite for biodiesel production may come under
the entire product mixture to form a semisolid mass instead                     scrutiny by regulators and the public. With the added cost
of biodiesel. Soaps can also cause problems with glycerol                       of transportation, biodiesel producers may want to establish
separation and washing. Consequently, biodiesel formation                       their operations next to the sludge production facility. Stan­
is not suitable for high FFA feeds such as trap grease. For the                 dards for Class B sludge are less stringent, and their use is
lipid feedstocks in sewage sludges containing >1% FFA,                          therefore more regulated. Biodiesel producers may not re­
acid catalysis followed by base catalysis is recommended.                       move the Class B sludge from its production site.
Here, FFAs are first converted to methyl esters until FFA <                        Economics of Biodiesel Production. Although biodiesel is
0.5%, when additional methanol is added followed by the                         one of the premier forms of alternative energy, its cost of
addition of a base catalyst to transesterify the triglycerides to               production has hindered its growth and has made it uncom­
biodiesel. The efficient separation of glycerol is important                    petitive compared to petro diesel. Analysis by researchers12
given that the separated glycerol can be used by industry for                   indicates that in biodiesel economics, the feedstock (oil) is
manufacturing cosmetics and pharmaceutical formulations.                        about 80% of the production cost.
   Water can also be a problem as it hydrolyzes fats to form                       This makes the availability of cheap and reliable biodiesel
free fatty acids, which then form soap (eq 3).                                  feedstock a very important issue in biodiesel production.
                                                                                Currently, the estimated cost of production of biodiesel from
                                                                                dry sludge is $3.11 per gallon of biodiesel13,14 compared to
                                                                                $3.00 per gallon for petro diesel (as of January 2010). The
                                                                                biodiesel price is broken down to $2.06/gal for centrifuge,
                                                                                drying, and extraction processes and $1.05/gal for other
                                                                                expenses. To be competitive, this cost may need to be reduced
                                                                                to levels that are at or below petroleum diesel costs. One
                                                                                possible solution is for the US Congress to enact a modified
                                                                                biodiesel tax incentive. The 2005 biodiesel tax incentive by
                                                                                Congress sparked a dramatic growth in the biodiesel industry.
                                                                                The credit amounted to $1.00 per gallon blended if the
  Bioreactor Design. The bioreactor for wastewater treat­                       lipid is derived from most major oilseeds grown within the
ment contains microorganisms that use pollutants as the                         US or animal-based lipids. All other lipid feedstocks receive
food source to maintain the metabolism of the microorga­                        $0.50 per gallon when blended. This tax incentive should
nisms and to generate new microorganisms. A challenge in                        be modified to give equal credit to sludge as biodiesel feed­
boosting biodiesel production from sewage sludge is for waste­                  stock. Also, the use of high-frequency ultrasound to signifi­
water operators to utilize microorganisms that are selected                     cantly reduce production costs of biodiesel has recently been
for their oil-producing capabilities. This could increase                       reported.15
biodiesel production from sewage sludge to the 10 billion
gallon mark, which is more than three times the nation’s
                                                                                   (11) Razavi, B.; Song, W.; Cooper, W. J.; Greaves, J.; Jeong, J.
current biodiesel production capacity.                                          J. Phys. Chem. A 2009, 113, 1287.
  Pharmaceutical Chemicals in Sludge. A review of the                              (12) Van Gerpen, J. Business management for biodiesel producers;
applications of lipids in the pharmaceutical field10 shows                      National Renewable Energy Lab: Golden, CO, 2004.
                                                                                   (13) Susanne, R. S. Making the best of wastewater. Available at http://
that several vegetable oils (almond oil, apricot oil, avocado                   www.biodieselmagazine.com/article-print.jsp?article_id=2776 (accessed Apr
                                                                                2010).
  (9) You, Y.; Shie, J.; Chang, C.; Huang, S.; Pai, C.; Yu, Y.; Chang,             (14) Mondala, A.; Liang, K.; Toghiani, H.; Hernandez, R.; French, T.
C. H. Energy Fuels 2008, 22, 182–189.                                           Bioresour. Technol. 2009, 100, 1203–1210.
  (10) Alvarez, A. M. R.; Rodriguez, M. L. G. Grassas Y Aceites 2000,              (15) Mahamuni, N. N.; Adewuyi, Y. G. Energy Fuels 2009, 23 (5),
51, 74–79.                                                                      2757–2766.
                                                                         2793
Energy Fuels 2010, 24, 2791–2794   : DOI:10.1021/ef1001106
                             Summary                                        because of soap formation with alkali-catalyzed transesterifi­
                                                                            cation and high FFA. Few have attempted to address this
   Biodiesel is a fuel comprised of monoalkyl esters of long-
                                                                            challenge by using supercritical methanol, high shear mixing,
chain fatty acids traditionally derived from vegetable oils or
                                                                            and the use of cosolvents. A fifth challenge to boost biodiesel
animal fats. The US and the world is witnessing an unprece­
                                                                            production is to utilize microorganisms that are selected for
dented increase in interest and demand for biodiesel and other
                                                                            their oil-producing capabilities. This could increase biodiesel
fuels derived from renewable biomass due to rising petroleum
                                                                            production to the 10 billion gallon mark, which is more than
fuel costs, increasing concern for the environmental impact of
                                                                            three times the nation’s current biodiesel production capa­
emissions from the combustion of conventional fossil fuels,
                                                                            city. Developing an easier glycerol cleanup is also a difficult
increasing reliance on foreign oil sources, and decline in domes­
                                                                            challenge. Finally, the presence of pharmaceutical chemicals
tic oil production. However, pure vegetable or seed oils are
                                                                            in sludge poses a great challenge. This requires a careful
expensive and constitute between 70% and 85% of the overall
                                                                            selection of treatment technologies and microbes that are
biodiesel production cost. As a result, the use of alternative
                                                                            selective for these chemicals but can also produce FFAs in
nonedible crops such as Jatropha, animal fats, and waste
                                                                            the process.
cooking oil is on the rise.
                                                                               From a regulatory viewpoint, most sludge that will be used
   Municipal sewage sludge is also gaining traction in the US
                                                                            for biodiesel production may fall under Class A. Nevertheless,
and around the world as a lipid feedstock for biodiesel
                                                                            its use offsite for biodiesel production may come under
production. First, MSS consists of significant concentrations
                                                                            scrutiny by regulators and the public. Biodiesel producers
of lipids. Second, it is plentiful. Third, sludge management
                                                                            may not remove the Class B sludge from its production site.
poses formidable environmental challenges.
                                                                               Finally, biodiesel production from sludge could be very
   There are numerous challenges faced by biodiesel produc­
                                                                            profitable in the long run. Currently, the estimated cost of
tion from waste sludge. First, challenges exists in determining
                                                                            production is $3.11 per gallon of biodiesel. To be competitive,
how best to collect the different fractions (primary and/or
                                                                            this cost may need to be reduced to levels that are at or below
secondary sludges) and treat them for maximum lipids extrac­
                                                                            petroleum diesel costs.
tion. Second, in the transesterification process, the critical
reaction properties are total glycerol, acid value, and reaction
completeness. To accelerate the reaction, cosolvents and high                  Acknowledgment. The author thanks the U.S. EPA for pro­
                                                                            viding the opportunity to develop this article. However, informa­
shear mixing have been proposed. There is however very little
                                                                            tion contained in this article represents the opinion of the author.
information on cost-effective means of increasing lipid solu­               It does not reflect the views and policies of the agency, nor does it
bility. Third, alkali-catalyzed transesterification is much faster          represent the opinion of the management of the regional or
than acid-catalyzed transesterification and is most often                   national offices of the U.S. EPA. The accuracy of the information
used commercially. However for lipid feedstocks with >1%                    contained herein is not guaranteed and the mention of trade
FFA, acid catalysis followed by base catalysis is recommended               names is not an endorsement by the authors or the USEPA.




                                                                     2794

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Biodiesel From Sewage Sludges

  • 1. Energy Fuels 2010, 24, 2791–2794 : DOI:10.1021/ef1001106 Published on Web 04/13/2010 Biodiesel Production from Municipal Sewage Sludges David M. Kargbo* U.S. EPA Region III, Office of Innovation, Environmental Assessment & Innovation Division, Philadelphia, Pennsylvania 19103 Received January 29, 2010. Revised Manuscript Received March 30, 2010 Biodiesel is a fuel comprised of monoalkyl esters traditionally derived from vegetable oils or animal fats. There is currently an unprecedented increase in interest and demand for biodiesel and other fuels derived from renewable biomass. However, pure vegetable or seed oils are expensive and constitute between 70% and 85% of the overall biodiesel production cost. Municipal sewage sludge is gaining traction in the U.S. and around the world as a lipid feedstock for biodiesel production. It is plentiful and consists of significant concentrations of lipids that can make production of biodiesel from sludge profitable. However, there are challenges to be faced by biodiesel production from waste sludge. Determining how best to collect the different fractions and treat them for maximum lipids extraction is a major challenge. To accelerate biodiesel production, cosolvents and high shear mixing have been proposed. Nevertheless, there is very little information on the cost-effective means of increasing lipid solubility. Alkali-catalyzed transesterifi­ cation is much faster than acid-catalyzed transesterification and is most often used commercially. How­ ever, for lipid feedstocks with greater than 1% free fatty acids (FFAs) such as in sludge, acid catalysis followed by base catalysis is recommended because of soap formation with alkali-catalyzed transester­ ification and high FFA. To boost biodiesel production, it is suggested that wastewater operators utilize microorganisms that are selected for their oil-producing capabilities. This could increase biodiesel production to the 10 billion gallon mark, which is more than three times the nation’s current biodiesel production capacity. The presence of pharmaceutical chemicals in sludge poses a great challenge. This requires a careful selection of treatment technologies and microbes that are selective for these pharma­ ceutical chemicals. Finally, biodiesel production from sludge could be very profitable in the long run. Currently, the estimated cost of production is $3.11 per gallon of biodiesel. To be competitive, this cost should be reduced to levels that are at or below the current petro diesel costs of $3.00 per gallon. Introduction Municipal sewage sludge is gaining traction in the US and around the world as a lipid feedstock for biodiesel production. Biodiesel holds significant promise as a potential displace­ First, municipal sewage sludge contains significant concentra­ ment fuel for petroleum-based diesel fuel. The United States tions of lipids derived from the direct adsorption of lipids onto (US) and the world are witnessing an unprecedented increase the sludge. These energy-containing lipids include triglycerides, in interest and demand for biodiesel and other fuels derived diglycerides, monoglycerides, phospholipids, and free fatty acids from renewable biomass. For example, the production of contained in the oils and fats. In addition, microorganisms used biodiesel in the US has increased from 75 million gallons in in the wastewater treatment process utilize organic and inorganic 2005 to 250 million gallons in 2006 and 450 million gallons in compounds in the wastewater as a source of energy, carbon, and 2007,1 with an expected total capacity of well over 1 billion nutrients. The cell membrane of these microorganisms is a major gallons in the next few years. Nevertheless, this is still a very component of sewage sludge and is composed primarily of infant industry compared to petroleum-based diesel. For phospholipids.3 It is estimated at 24% to 25% of dry mass of example, in 2007, the US burned over 60 billion gallons the cell4,5 and yields about 7% oil from the dried secondary of petroleum-based diesel compared to 450 million gallons sludge. Other studies6 have demonstrated that up to 36.8 wt % of biodiesel. The increasing demand for biodiesel has led of the dry sludge is comprised of fatty acids and steroids. With to an increasing need for lipid feedstocks such as soybean, the fatty acids from sludge predominantly in the range of C10 to canola, rapeseed, sunflower, palm, and coconut oils. Cur­ C18, these are excellent for the production of biodiesel. rently, pure vegetable or seed oils are expensive and constitute Second, sludge is plentiful. In the US alone, approximately between 70% and 85% of the overall biodiesel production 6.2 million dry metric tons of sludge is produced annually by cost.2 As a result, the use of alternative nonedible feedstocks wastewater treatment facilities7 and is expected to increase in such as Jatropha, animal fats, and waste cooking oil is on the future due to increasing urbanization and industrialization. the rise. (3) Rittmann, B.; McCarty, P. Environmental Biotechnology: Princi­ *To whom correspondence should be addressed. E-mail: kargbo.david@ ples and Applications; McGraw-Hill: New York, 2006. epa.gov. (4) Nelson, D.; Cox, M. Principles of Biochemistry; W.H. Freeman and (1) National Biodiesel Board. Biodiesel, 800-841-5849. 2007. Available Company: New York, 2005. at www.biodiesel.org/pdf_files/fuelfactsheets/backgrounder.pdf (accessed Apr (5) Dufreche, S.; Hernandez, R.; French, T.; Sparks, D.; Zappi, M.; 2010). Alley, E. J. Am. Oil Chem. Soc. 2007, 84, 181–187. (2) Haas, M. J.; Foglia, T. A. Alternate feedstocks and technologies (6) Jard6, E.; Mansuy, L.; Faure, P. Water Res. 2005, 39, 1215–1232. e for biodiesel production. In Biodiesel Handbook 2005; Knothe, G., Krahl, (7) Activated sludge MOP OM-9, 2nd ed.; Water Environment Federa­ J., Gerpen, J. V., Eds.; AOCS Press: Urbana, IL, 2005; pp 42-61. tion: Alexandria, Virginia, 2002. r 2010 American Chemical Society 2791 pubs.acs.org/EF
  • 2. Energy Fuels 2010, 24, 2791–2794 : DOI:10.1021/ef1001106 Third, sludge management poses formidable environmen­ extraction. For example, the yield of FAMEs from primary tal challenges. Land application for agricultural purposes has sludge (maximum yield of 14.5 wt %) is significantly affected attracted opposition due to odor and the presence of heavy by the interactive effects of temperature, acid catalyst con­ metals and recently, the potential exposure to emerging centration, and the methanol-to-sludge mass ratio, while the pharmaceutical chemicals. Similarly, sludge incineration has yield of FAMEs from secondary sludge (maximum yield of resulted in emissions that contain dioxins and heavy metals. 2.5 wt %) is significantly affected by the independent effects Consequently, biodiesel production from sludge as a viable of the above three factors. Control over these factors can alternative to land disposal will help to solve both energy and significantly influence the cost of production. environmental problems. Production Challenges. The optimum production of bio­ Finally, studies5 show that integrating lipid extraction pro­ diesel is faced with huge challenges. First, the lipids contain­ cesses in 50% of all existing municipal wastewater treatment ing fatty acids are usually extracted and then transesterified. plants in the US and transesterification of the extracted lipids Recently, an in situ transesterification procedure where the could produce approximately 1.8 billion gallons of biodiesel, fatty acid containing lipids are simultaneously extracted and which is roughly 0.5% of the yearly national petroleum diesel transesterified has been being practiced. This reduces the demand. reaction time and the amount of solvent and samples requi­ Biodiesel is comprised of fatty acid alkyl esters (FAAEs) red compared to separate lipid extraction and transesterifi­ produced via base- and/or acid-catalyzed transesterification cation processes. This is an ongoing area of intense research. of lipids using alcohol. Fatty acid methyl ester (FAME) is the Transesterification reaction times can be shortened by increa­ term for biodiesel made when methanol is the alcohol used in sing the temperature and the addition of enzymes. For the transesterification process. Equation 1 is an example of example, the addition of 9-17% lipase enzymes significantly biodiesel production through transesterification of fat or oil in decreased the transesterification reaction of tung oil and the presence of an acid catalyst producing a mixture of hence increased the ester conversion of tung oil.8 FAMEs and glycerol. The optimal conditions were reported to be a 2.2:1 molar ratio of methanol to oil, a reaction time of 18 h, a reaction temperature of 43 oC, and a lipase amount of 14%. Second, reaction completeness (>98% complete) and fuel deteriora­ tion (acid value) continue to be challenging aspects of bio­ diesel production from traditional feedstocks and should be no different with sludge feedstock. Using higher tempera­ tures to accelerate the reaction requires pressure vessels because the alcohol (methanol) boils at 148 oF (65 oC). The addition of cosolvents and high shear mixing have also been proposed as ways to accelerate the reaction. Third, the In the above transesterification process, R1, R2, and R3 are careful selection of catalysts is a key component of successful long fatty acid chains with only five of these chains common in biodiesel production from lipid feedstocks such as sludge. most vegetable oils and animal fats. The physical properties of The catalyst acts to deprotonate the alcohol to make it a the resulting biodiesel (e.g., octane number, cold flow, and stronger nucleophile for reaction with the lipids. Current oxidative stability) are usually determined by the relative catalysts are slower, require higher temperature and pres­ amounts of the fatty esters. In the above transesterification, sure, require longer reaction times, and require high volumes approximately one volume of oil or fat yields about one volume of alcohol. Considerable catalyst research is also being of biodiesel. carried out. However, the research is restricted to solid phase, fixed bed catalysts. The correct choice of a catalyst may reduce glycerin cleanup costs. Finally, to minimize produc­ Challenges tion costs, there is a need to minimize excess alcohol require­ Biodiesel production from sewage sludge poses huge chal­ ments. In addition to incorporating a faster reaction with less lenges to overcome if commercial opportunities are to be rea­ energy input, a current industry trend is to use reactors that lized. Some of these challenges are not unique to biodiesel incorporate separations and internally recycle alcohol. This production from waste sludge but to the biodiesel industry as should be useful also when sludge is the feedstock. a whole. They include challenges from (i) collecting the sludge, Maintaining Product Quality. Modern diesel engines are (ii) optimum production of biodiesel, (iii) maintaining pro­ very sensitive to fuel quality. Consequently, maintaining duct quality, (vi) soap formation and product separation, biodiesel product quality is essential for the growth of the (v) bioreactor design, (vi) pharmaceutical chemicals in sludge; biodiesel industry. To be classified as diesel, the product ,(vii) regulatory concerns, and (viii) economics of biodiesel must meet ASTM D 6751 specifications for the flash point, production. closed cup, water and sediment, viscosity, sulfated ash, total Collecting Sludge. Primary sludge is a combination of floa­ sulfur, copper strip corrosion, cetane number, cloud point, ting grease and solids collected at the bottom of the primary carbon residue, acid number, free and total glycerin, phos­ clarifier of a wastewater treatment plant after screening and phorus, and vacuum distillation end point. Primary sludge grit removal. Secondary or activated sludge is composed from wastewater treatment facilities is a source of low-quality mainly of microbial cells and suspended solids produced fats and grease. Given that the yield of primary (low-quality) during the aerobic biological treatment of wastewater and sludge is higher than that of secondary (higher-quality) sludge, collected in the secondary clarifier. Biodiesel production from there is a need to improve lipid solubility in the reaction both primary and secondary sludges is currently undergoing intense research. Challenges do exist in determining how best (8) Xu, G.; Zhang, B.; Liu, S.; Yue, J. Ag. Sci. China 2006, 5 (11), 859– to collect these fractions and treat them for maximum lipids 864. 2792
  • 3. Energy Fuels 2010, 24, 2791–2794 : DOI:10.1021/ef1001106 mixture during transesterification. This is usually solved by oil, borage oil, coffee oil, safflower oil, etc.) and fish oil the addition of hexane, which significantly increases the and bird oil have been employed as excipients in cosmetic biodiesel production cost. A challenge is to find a more cost- formulations. effective means of increasing lipid solubility. Fatty acids used as lipid regulators are also occurring in Soap Formation and Product Separation. Base-catalyzed wastewaters as emerging contaminants that could end up in transesterification is much faster than acid-catalyzed trans­ sludges.11 The pharmaceutical industry is concerned about esterification and is most often used commercially.9 How­ traces of its organic chemicals (that may not be adequately ever, a high concentration of free fatty acids (FFA) in the treated) adsorbing on sludge surfaces. There is therefore a sewage sludge can result in problems such as soap formation need to evaluate the effectiveness of the transesterification and difficulty in product separation (eq 2). process to treat these chemicals and convert them to biodie­ sel. This may require a careful selection of treatment tech­ nologies and microbes that are selective for these chemicals. Conversion of these emerging contaminants to biodiesel will not only help solve an energy problem but will also remove from the environment one of the fastest growing and chal­ lenging groups of chemicals. Regulatory Concerns. Sludge is classified as either Class A or Class B, depending on the type of treatment it has received. Class A sludge has benefited from both pretreat­ ment and treatment at the wastewater facility. While most sludge used for biodiesel production may fall under Class A, The soaps formed can gel at ambient temperature, causing its use offsite for biodiesel production may come under the entire product mixture to form a semisolid mass instead scrutiny by regulators and the public. With the added cost of biodiesel. Soaps can also cause problems with glycerol of transportation, biodiesel producers may want to establish separation and washing. Consequently, biodiesel formation their operations next to the sludge production facility. Stan­ is not suitable for high FFA feeds such as trap grease. For the dards for Class B sludge are less stringent, and their use is lipid feedstocks in sewage sludges containing >1% FFA, therefore more regulated. Biodiesel producers may not re­ acid catalysis followed by base catalysis is recommended. move the Class B sludge from its production site. Here, FFAs are first converted to methyl esters until FFA < Economics of Biodiesel Production. Although biodiesel is 0.5%, when additional methanol is added followed by the one of the premier forms of alternative energy, its cost of addition of a base catalyst to transesterify the triglycerides to production has hindered its growth and has made it uncom­ biodiesel. The efficient separation of glycerol is important petitive compared to petro diesel. Analysis by researchers12 given that the separated glycerol can be used by industry for indicates that in biodiesel economics, the feedstock (oil) is manufacturing cosmetics and pharmaceutical formulations. about 80% of the production cost. Water can also be a problem as it hydrolyzes fats to form This makes the availability of cheap and reliable biodiesel free fatty acids, which then form soap (eq 3). feedstock a very important issue in biodiesel production. Currently, the estimated cost of production of biodiesel from dry sludge is $3.11 per gallon of biodiesel13,14 compared to $3.00 per gallon for petro diesel (as of January 2010). The biodiesel price is broken down to $2.06/gal for centrifuge, drying, and extraction processes and $1.05/gal for other expenses. To be competitive, this cost may need to be reduced to levels that are at or below petroleum diesel costs. One possible solution is for the US Congress to enact a modified biodiesel tax incentive. The 2005 biodiesel tax incentive by Congress sparked a dramatic growth in the biodiesel industry. The credit amounted to $1.00 per gallon blended if the Bioreactor Design. The bioreactor for wastewater treat­ lipid is derived from most major oilseeds grown within the ment contains microorganisms that use pollutants as the US or animal-based lipids. All other lipid feedstocks receive food source to maintain the metabolism of the microorga­ $0.50 per gallon when blended. This tax incentive should nisms and to generate new microorganisms. A challenge in be modified to give equal credit to sludge as biodiesel feed­ boosting biodiesel production from sewage sludge is for waste­ stock. Also, the use of high-frequency ultrasound to signifi­ water operators to utilize microorganisms that are selected cantly reduce production costs of biodiesel has recently been for their oil-producing capabilities. This could increase reported.15 biodiesel production from sewage sludge to the 10 billion gallon mark, which is more than three times the nation’s (11) Razavi, B.; Song, W.; Cooper, W. J.; Greaves, J.; Jeong, J. current biodiesel production capacity. J. Phys. Chem. A 2009, 113, 1287. Pharmaceutical Chemicals in Sludge. A review of the (12) Van Gerpen, J. Business management for biodiesel producers; applications of lipids in the pharmaceutical field10 shows National Renewable Energy Lab: Golden, CO, 2004. (13) Susanne, R. S. Making the best of wastewater. Available at http:// that several vegetable oils (almond oil, apricot oil, avocado www.biodieselmagazine.com/article-print.jsp?article_id=2776 (accessed Apr 2010). (9) You, Y.; Shie, J.; Chang, C.; Huang, S.; Pai, C.; Yu, Y.; Chang, (14) Mondala, A.; Liang, K.; Toghiani, H.; Hernandez, R.; French, T. C. H. Energy Fuels 2008, 22, 182–189. Bioresour. Technol. 2009, 100, 1203–1210. (10) Alvarez, A. M. R.; Rodriguez, M. L. G. Grassas Y Aceites 2000, (15) Mahamuni, N. N.; Adewuyi, Y. G. Energy Fuels 2009, 23 (5), 51, 74–79. 2757–2766. 2793
  • 4. Energy Fuels 2010, 24, 2791–2794 : DOI:10.1021/ef1001106 Summary because of soap formation with alkali-catalyzed transesterifi­ cation and high FFA. Few have attempted to address this Biodiesel is a fuel comprised of monoalkyl esters of long- challenge by using supercritical methanol, high shear mixing, chain fatty acids traditionally derived from vegetable oils or and the use of cosolvents. A fifth challenge to boost biodiesel animal fats. The US and the world is witnessing an unprece­ production is to utilize microorganisms that are selected for dented increase in interest and demand for biodiesel and other their oil-producing capabilities. This could increase biodiesel fuels derived from renewable biomass due to rising petroleum production to the 10 billion gallon mark, which is more than fuel costs, increasing concern for the environmental impact of three times the nation’s current biodiesel production capa­ emissions from the combustion of conventional fossil fuels, city. Developing an easier glycerol cleanup is also a difficult increasing reliance on foreign oil sources, and decline in domes­ challenge. Finally, the presence of pharmaceutical chemicals tic oil production. However, pure vegetable or seed oils are in sludge poses a great challenge. This requires a careful expensive and constitute between 70% and 85% of the overall selection of treatment technologies and microbes that are biodiesel production cost. As a result, the use of alternative selective for these chemicals but can also produce FFAs in nonedible crops such as Jatropha, animal fats, and waste the process. cooking oil is on the rise. From a regulatory viewpoint, most sludge that will be used Municipal sewage sludge is also gaining traction in the US for biodiesel production may fall under Class A. Nevertheless, and around the world as a lipid feedstock for biodiesel its use offsite for biodiesel production may come under production. First, MSS consists of significant concentrations scrutiny by regulators and the public. Biodiesel producers of lipids. Second, it is plentiful. Third, sludge management may not remove the Class B sludge from its production site. poses formidable environmental challenges. Finally, biodiesel production from sludge could be very There are numerous challenges faced by biodiesel produc­ profitable in the long run. Currently, the estimated cost of tion from waste sludge. First, challenges exists in determining production is $3.11 per gallon of biodiesel. To be competitive, how best to collect the different fractions (primary and/or this cost may need to be reduced to levels that are at or below secondary sludges) and treat them for maximum lipids extrac­ petroleum diesel costs. tion. Second, in the transesterification process, the critical reaction properties are total glycerol, acid value, and reaction completeness. To accelerate the reaction, cosolvents and high Acknowledgment. The author thanks the U.S. EPA for pro­ viding the opportunity to develop this article. However, informa­ shear mixing have been proposed. There is however very little tion contained in this article represents the opinion of the author. information on cost-effective means of increasing lipid solu­ It does not reflect the views and policies of the agency, nor does it bility. Third, alkali-catalyzed transesterification is much faster represent the opinion of the management of the regional or than acid-catalyzed transesterification and is most often national offices of the U.S. EPA. The accuracy of the information used commercially. However for lipid feedstocks with >1% contained herein is not guaranteed and the mention of trade FFA, acid catalysis followed by base catalysis is recommended names is not an endorsement by the authors or the USEPA. 2794