Chapter 22 - Integrated Biorefinery for Bioenergy and

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C H A P T E R

22

c0022

Integrated Biorefinery for Bioenergy and Platform Chemicals B. Bharathiraja1, M. Chakravarthy1, R. Ranjith Kumar1, J. Jayamuthunagai2, R. Praveen Kumar3 1Vel

Tech High Tech Dr. Rangarajan Dr. Sakunthala Engineering College, Chennai, Tamil Nadu, India; 2Anna University, Chennai, Tamil Nadu, India; 3Arunai Engineering College, Chennai, Tamil Nadu, India

O U T L I N E

22.1 Integrated Biorefinery of Biodiesel and Platform Chemicals2 22.1.1 Biodiesel 2 22.1.2 Oil Source and Characteristics 3 22.1.3 Biorefining and Bioconversion 3 22.1.4 Platform Chemicals 3 22.2 Integrated Biorefinery of Bioethanol and Platform Chemicals 22.2.1 Sources 22.2.2 Pretreatment 22.2.3 Conversion

22.4 Agroindustrial Wastes as Feedstock for Bioenergy and Platform Chemicals13 22.4.1 Cellulose and Hemicellulose 14 22.4.2 Lignin 15 22.4.3 Energy and Platform Chemicals15 22.4.4 Future Outlook of Agrowaste Conversion17

5 5 6 6

22.3 Integrated Biorefinery of Platform Chemicals and Biogas Production10

Platform Chemical Biorefinery http://dx.doi.org/10.1016/B978-0-12-802980-0.00022-5

22.3.1 Production Through Anaerobic Digestion10 22.3.2 Biomass Resources 10 22.3.3 Pretreatment of Biomass 12

References17

1

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22. INTEGRATED BIOREFINERY FOR BIOENERGY AND PLATFORM CHEMICALS

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The population-driven demand for energy and materials is increasing at an exponential rate. Petroleum-based refineries suffer from serious drawbacks such as environmental pollution, depleting fossil resources, and the global energy demand. Among all available sources, biomass stands out as a promising feedstock for energy and chemical production because of its cheap and easy availability all over the world. Biomass constitutes about 10% of the global energy demand and is mainly used in power generation, heating, transportation biofuel production, and chemical synthesis. About 90% of the fossil is used only for fuel generation, and less than 10% is used to derive platform chemicals. This strategy is not likely to be followed with biomass-based biorefineries. Diverse integration technologies can be adopted to convert a variety of molecules available in the biomass to products that can be used in the production of polymers, cattle feed, fertilizers, organic acids, alcohols, food, pharmaceuticals, paper, etc. The operation of any biorefinery is analogous to the petrochemical refinery that produces fuel as a main product and various platform chemicals as value-added products. Biomass ingredients are comprised of cellulose, hemicellulose, oil, and lignin. These sources can be harvested in bulk amounts directly from farms or recovered from waste streams such as agroindustrial waste, furniture waste, and construction waste. The price of biomass is cheaper than fossil resources, and for this reason, this chapter will focus on the possibility of producing platform chemicals from biomass that has a large market volume and great economic importance.

s0010

22.1 INTEGRATED BIOREFINERY OF BIODIESEL AND PLATFORM CHEMICALS

s0015

22.1.1 Biodiesel

Biodiesel fuel is attracting increasing attention worldwide as a blending component or replacing component of petro fuels in vehicular engines (Demirbas, 2009). The production and product refining from oil sources are recent, and this is the most researched area for the cause of neutralizing the increasing demand for petroleum products and environmental issues (Marchetti et al., 2005). The production process of biodiesel includes various techniques, among which the notable ones are pyrolysis and transesterification. Pyrolysis suffers from energy intensiveness and the production of undesired products from the whole biomass. The transesterification process involves the use of extracted oil to react with a suitable acyl acceptor for the production of fatty acid alkyl esters (FAAEs) and by-products, depending on the process conditions and the catalyst employed (Bharathiraja et al., 2014). Extracted oil has triacylglycerols (TAGs) and free fatty acids (FFAs). TAGs on reaction with alcohols give long chain esters of corresponding fatty acid side chains (FAAE) and glycerol. FFAs on esterification give FAAE and water as the by-products. The effect of both homogeneous and heterogeneous acid/base catalysts has been exclusively reviewed (Borugadda and Goud, 2012). Homoge- [AU1] neous (H2SO4, trifluoro acetic acid, HCl, etc.) and heterogeneous (SO4/SnO2, ZrO2/SO42−, S-ZrO2, Al2O3/ZrO2/WO3, etc.) acid catalysts are used for the conversion of oil with high [AU2] FFA content (Yin et al., 2008). Alkali catalysts (NaOH, KOH, KF/Al2O3, CaO/Al2O3, lithium- doped ZnO, Ca(OCH2CH3)2, etc.) are conventionally used for biodiesel production from lowFFA oil. Enzymes are good possible biological catalysts to produce biodiesel. Enzymes can easily treat fatty acid as well as triglycerides to produce biodiesel from nonedible or waste oil, [AU3] reaching a high conversion (Bajaj et al., 2010). The use of an immobilized enzyme and a whole cell catalyst gives a clear glycerol and biodiesel product (Bharathiraja et al., 2014). p0015

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3

22.1.2 Oil Source and Characteristics

Oil is used as fuel because of the following main characteristics: (1) liquid nature, (2) higher hydrogen and carbon content, (3) high heat content, (4) low sulfur content, (5) biodegradability, and (6) lower aromatic content. The quality of oil feedstock is considered by evaluating [AU5] the FFA and water content (Marchetti, 2009). A problem of the biodiesel biorefinery is the unsustainability of the oil supply for continuous fuel production. Various oil feedstocks have been researched and established, as presented in Table 22.1. The research focuses on microand macroalgae cultivation as feedstock for biorefineries, and advancements include the integration of farms with power plants, wastewater treatment plants, and sugar refineries. The quality of the biodiesel product is greatly affected by the oil composition of the feedstock and the process of conversion. p0020

s0025

22.1.3 Biorefining and Bioconversion

p0025 Stirred-tank reactors and packed-bed reactors are used for biodiesel production (Fijerbaek [AU6] et al., 2009). Since chemical catalyst (usually NaOH, KOH, and sodium methoxide) mediated processes are instant, continuous flow reactors and stirred-tank reactors are opted. This process has been favored by industries since the conversion is high and instant. However, notable drawbacks include the difficulty in glycerol recovery and the biofuel purification process. Oil used in the process should be pure, and the process consumes a high alcohol quantity to reach the maximum conversion. The recovery of homogeneous catalysts is difficult; the glycerol obtained is contaminated with salts, and thus the commercial value of the process decreases. Noncatalytic supercritical processes involve a high energy consumption together with the risk of high temperature and pressure conditions that are the main inhibitory factors despite satisfactory conversion results. For this reason alternate methods of biodiesel catalysis are being researched. Enzymatic catalysis has grabbed much attention by biorefineries since it seems to be a solution to almost all of the problems confronted by chemical catalysts. Lipases are versatile, and commercially used enzymes are glycerol ester hydrolases, which catalyze the cleavage of ester bonds in TAGs, releasing FFA and glycerol to favor transesterification and esterification reactions in water-controlled systems. The oil used in biocatalysis can even be of a low quality since lipases also convert FFA, but the presence of water may have negative effects with some kinds of lipases. The energy consumption is too low and a significant yield (>95%) is obtained at room temperature (30–40°C). High-quality glycerol obtained by a simple separation process and a recovery of immobilized enzymes for reuse will be valueadded strategies. Though the biocatalysis concept is advantageous, it is not yet an industrial reality, owing to enzyme cost. Other inhibitory factors such as yield, catalyst inactivation, and inhibition also need to be researched (Table 22.2). [AU7] s0030

22.1.4 Platform Chemicals

p0030

Short chain primary alcohols such as methanol, ethanol, and butanol are widely employed in FAAE production. Secondary alcohols include isopropanol and 2-butanol for industrial production. Methanol and ethanol are used because of their availability and low cost. Ethanol is less toxic but yields a lower conversion efficiency than methanol. Alcohol requirements are based on the type of lipase or chemical catalyst and reactor used for the process. Glycerol

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[AU4]

Oil Composition

Scientific Name

Common Name

Oil (%)

Use

Cyanobacteria

Microlgae

20–60

Ricinus communis

Castor

Gossypium hirsutum

C14:0

C16:0

C18:0

C18:1

C18:2

C18:3

C20:0

C20:1 C22:0 C24:0

Animal feed, nutrition, – biofertilizer, PFAs, rProteins

12–1

1–2

58–68

4–20

14–30

–

–

–

–

46–55

Adhesives, coatings, soaps, lubricants, paints, dyes

0

1.1

3.1

4.9

1.3

0

0

0.3

–

–

Cotton

18–25

Dairy, cattle feed, furniture, etc.

0.7

28.7

0.9

13

57.4

0

0

0

0

0

Jatropha curcas

Jatropha

40–60

Candles, soap, cosmetics

1.4

15.6

9.7

40.8

32.1

0.2

0.4

–

0–0.2

14

Pongamia pinnata

Karanja

30–40

Tanning leather, soap, illuminating oil, lubricant, water-paint binder, pesticides

0

14.1

10.9

56

15

3.6

2.1

2.4

1.9

2.4

Moringa oleifera

Moringa

33–41

Medicinal ingredients, skin diseases

–

7

4

78

1

1

4

–

4

–

Erytheasal vadorensis

Palm

20–21

Cosmetics, soap, lubricants, etc.

1

42.6

4.4

40.5

10.1

0.2

0

0.1

0

0

Oryza sativa

Rice bran

16–32

Nonedible vegetable oil for lubrication

0.4–0.6 11.7–16.5 1.7–2.5

39.2–43.7 26.4–35.1 0.6

0.4–0.6 –

–

0.4–0.9

Enteromorpha compressa

Macroalgae 10–15

–

2.16

2.38

–

–

–

70.26

2.95

18.54

–

–


t0010 TABLE 22.1 Feedstock Oil Composition and Uses (Borugadda and Goud, 2012)


22.2 INTEGRATED BIOREFINERY OF BIOETHANOL AND PLATFORM CHEMICALS

t0015

[AU8]

5

TABLE 22.2 Comparison of Biodiesel Properties (Bharathiraja et al., 2014) Properties Acid value (mg KOH/g) Cold filter plugging point

(oC)

Density (kg/L) Flash point

(oC)

H/C ratio Heating value (MJ/kg) Solidifying point Viscosity

(oC)

(mm2/s,

cSt at 40°C)

Algal Biodiesel

Petro Diesel

ASTM Biodiesel Standard

0.374

Max 0.5

Winter max HAS > AB

Ash yield

AB > CB > HAS > HAB > HAR > HAG > WWB

Volatile matter

HAG > WWB > HAB > HAS > HAR > CB > AB

Fixed carbon

HAR > HAB > WWB > HAS > HAG > AB > CB

ULTIMATE COMPOSITION Carbon

AB > CB > WWB > HAR > HAB > HAS > HAG

Oxygen

HAG > HAS > HAB > HAR > WWB > CB > AB

Hydrogen

AB > CB > HAR > (WWB, HAB) > (HAG, HAS)

Nitrogen

AB > CB > HAR > (HAB, HAS) > HAG > WWB

Sulfur

AB > CB > HAR > (HAB, HAS) > HAG > WWB

Chlorine

AB > HAS > CB > HAG > HAB > HAR > WWB

HIGH-TEMPERATURE ASH COMPOSITION SiO2

HAG > HAS > CB > HAB > HAR > WWB > AB

CaO

AB > WWB > CB > HAR > HAB > HAS > HAG

K2O

HAR > HAB > HAG > HAS > WWB > AB > CB

P2O5

AB > HAR > HAG > HAB > HAS > CB > WWB

Al2O3

CB > WWB > HAR > HAB > HAS > AB > HAG

MgO

HAR > WWB > HAB > HAS > HAG > CB > AB

Fe2O3

CB > HAR > WWB > HAB > HAS > HAG > AB

SO3

AB > HAR > HAG > HAB > CB > HAS > WWB

Na2O

AB > HAR > WWB > HAB > CB > HAS > HAG

TiO2

CB > WWB > HAR > HAB > HAS > HAG > AB

Mn

WWB > HAG > HAR > CB > HAB > HAS > AB

WWB, wood and woody biomass; HAB, herbaceous and agricultural biomass; HAG, herbaceous and agricultural grass; HAS, herbaceous and agricultural straw; HAR, herbaceous and agricultural residue; AB, animal biomass; MB, mixture of biomass; CB, contaminated biomass; AVB, all varieties of biomass.

petro industry that scores 107 million tons/year of production. Propene (50 million tons/year production) can be synthesized from acetone (3 million tons/year production), which in turn is obtained by acetone–butanol–ethanol fermentation of sugars. Succinic acid can be produced from butane or butadiene, which has a production capacity of a few kilo tons/year due to its limited market demand (Bos et al., 2010). However, there are many possible derivatives that can value succinic acid production in the existing market (Sauer et al., 2008). The modification of succinic acid to produce pyrrolidinones, butane diol, and tetrahydrofuran addresses

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References

t0045 TABLE 22.8 Agrowaste as Biobriquettes (Veeresh and Narayana, 2012)

Materials

Moisture Content (%)

Bulk Density (kg/m3)

Particle Density (kg/m3)

Fixed Carbon (%)

Calorific Value (MJ/kg)

Sawmill dust

1.84

14.74

98.22

78.86

1.75

18.59

17.55

Ground nutshell

1.67

12.60

104.81

79.50

1.67

18.35

19.07

Press dug

2.75

31.43

98.26

68.58

12.28

19.50

15.06

Tamarind shell

2.96

33.37

115.24

76.12

3.27

20.53

15.10

Castor seed cake

2.22

63.19

305.30

90.21

0.84

8.99

20.09

Jatropha seed cake

1.99

42.32

216.33

88.91

0.95

10.53

18.87

Volatile Matter (%)

Ash Content (%)

the large succinic acid market in the near future. The lactic acid fermentation of the sugar fraction is well established with a global production of 0.25 million tons/year, which is steadily increasing by 10% (Jem et al., 2010). Lactic acid upon dehydration and reduction can give acrylic acid and 1,2-propane diol, respectively. These chemicals have a global market of 2 and 1.5 million tons/year, respectively. The catalytic oxidation of glucose produces glucaric acid that can be used in nylon production. The catalytic hydrogenation of glucose can produce sorbitol for the production of isosorbide, a monomer that helps in enhancing the transition point of polymers. Sorbitol has a market potential of 1.5 million tons/year and finds potential applications in surfactant and polymer production. Xylitol, itaconic acid, and furfurals can be obtained by a prior modification of 5-carbon sugars using appropriate catalytic techniques (Kamm et al., 2006; Patel, 2006; Bos et al., 2010). s0095

22.4.4 Future Outlook of Agrowaste Conversion

p0150

The success of chemical production from biomass-based biorefineries is greatly promoted by novel conversion techniques. A focus toward catalytic conversion techniques and advancements in downstream procedures can aid in uplifting the process economy to a greater extent. Implementing an enzyme and whole cell catalyst will ensure a greater product quality. Hybrid reactors (chemostats with enzyme catalysis), nanocatalyst-aided reactors for conversion, are the widely debated platforms in this arena. Technological advancements with added benefits such as low energy consumption, high yield of desired product, low by-product yield, low process cost, simple downstream procedures, moderate product cost, and enhanced environmental benefits providing large opportunities are highly desired and need to be researched and explored further.

s0105

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10022-KAUR BRAR-9780128029800

KAUR BRAR: 22 Non-Print Items Abstract Population driven demand for energy and materials are the increasing at an exponential rate. Petro refineries are found with intensifying drawbacks such as environmental pollution, depleting fossil resource and global energy demand. Among all other sources, biomass resource stands as promising feedstocks for energy and chemical production because of its cheap availability all over the world. Biomass constitutes about 10% of the global energy demand and is mainly used in power generation, heating, transportation biofuel production and chemical synthesis. In today’s scenario about 90% of the fossil is used only for fuel generation and less than 10% is used to derive platform chemicals. Diverse integration technologies adopted to convert variety of molecules available in the biomass to products that can be used in production of polymers, cattle feed, fertilizers, organic acids, alcohols, food, pharmaceuticals, paper etc. Keywords: Agro industrial waste; Biobutanol; Biodiesel; Bioethanol; Biogas; Biomass.