Resources, Conservation and Recycling 53 (2009) 513–528

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Resources, Conservation and Recycling
journal homepage: www.elsevier.com/locate/resconrec

Basic petrochemicals from natural gas, coal and biomass: Energy use and CO2 emissions
Tao Ren ∗ , Martin K. Patel
Department of Chemistry, Copernicus Institute for Sustainable Development and Innovation, Utrecht University, Heidelberglaan 2, 3584 CS Utrecht, The Netherlands

a r t i c l e

i n f o

a b s t r a c t
While high-value basic petrochemicals (HVCs) are mostly produced through conventional naphtha and ethane-based process routes, it is also possible to produce them through coal and biomass-based routes. In this paper, we compared these routes in terms of energy use and CO2 emissions per ton of HVCs. (The term ton and abbreviation t should be read in this paper as a metric ton or 1000 kg.) Within the cradle-to-grave system boundary, we found the following:

Article history: Received 22 October 2008 Received in revised form 22 March 2009 Accepted 1 April 2009 Available online 9 May 2009 Keywords: Coal Biomass Basic petrochemicals Energy use and CO2 emissions

• The total energy use of the conventional routes is the lowest (about 60 GJ/t HVCs, of which 50 GJ is the
calorific value of HVCs) whereas that of the methane-based routes is 30% higher, and that of the coal and biomass-based routes is about 60–150% higher. • The total CO2 emissions of conventional and methane-based routes are about 4–5 tons CO2 /t HVCs whereas those from the biomass-based routes range from 2 tons CO2 /t HVCs (a maize-based ethanol related route) to 4 tons CO2 avoided per ton HVCs (a lignocellulosic biomass-based Fischer–Tropsch route). Avoided CO2 emissions are due to electricity co-generation. The total CO2 emissions of coalbased routes are by far the highest (8–11 tons CO2 /t HVCs). An exception is a coal-based route with CO2 capture and sequestration features, for which CO2 emissions are similar to those of the conventional routes. It is technically possible to add CO2 capture and sequestration features to any of the routes mentioned above. Given the large differences shown above, more research into energy efficiency improvement of coal and biomass-based routes is recommended. However, the total energy use of biomass and coal-based routes is unlikely to match that of the conventional state-of-the-art routes any time soon. © 2009 Elsevier B.V. All rights reserved.

1. Introduction Basic petrochemicals such as ethylene, propylene and aromatics are the building blocks of the chemistry industry. Currently, most of them are produced via conventional process routes utilizing naphtha (derived from crude oil) and ethane (derived from natural gas). In 2004, the production of basic petrochemicals accounted for about 3 EJ of primary energy use (due to the combustion of fossil fuels; the calorific value of basic petrochemicals excluded) and about 200 million tons1 of CO2 emissions2 (due to the combustion of fossil

∗ Corresponding author. Tel.: +31 30 253 7600; fax: +31 30 253 7601. E-mail address: taoinholland@gmail.com (T. Ren). 1 The term ton and abbreviation t should be read in this paper as a metric ton or 1000 kg. 2 3 EJ is about 20% of the total final energy use (combusted fuels; calorific value of chemicals excluded) in the global chemical industry while the 200 million ton of CO2 is about 18% of the total CO2 emissions from the global chemical industry (IEA, 2007). Also, 3 EJ is less than 1% of the global primary energy use while 200 million is 0921-3449/$ – see front matter © 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.resconrec.2009.04.005

fuels) (IEA, 2007; Neelis et al., 2006). Recently, alternative process routes utilizing methane, coal and biomass to produce basic petrochemicals have attracted a great deal of attention. Studies into the energy use and CO2 emissions of these routes may be of interest. With respect to biomass-based alternative routes that produce petrochemicals via ethanol and syngas (Fischer–Tropsch synthesis), a number of recent studies indicate that the CO2 emissions of these routes can be quite low (Gielen and Yagita, 2002; Joosten, 2001; Patel et al., 2005). With respect to making feedstocks suitable for petrochemicals production, one study argued that not only biomass-based technologies but also coal-based technologies with CO2 capture and sequestration features can potentially achieve very low CO2 emissions (Williams, 2005). We compared methane-based routes with state-of-the-art conventional routes utilizing naphtha

less than 1% of CO2 emissions related to global energy use (IEA, 2007). Data on CO2 emission factors for the production of one ton of basic petrochemicals can be found in Neelis et al. (2005).

Primary energy sources. 2006). (2008).e. the term primary energy sources refers to crude oil. The main research method used in this paper is the analysis of energy and CO2 emissions. Given this knowledge gap. This raises the question which of the numerous options of biomass use is most attractive from an environmental point of view.. Full range naphtha is the most often used naphtha for petrochemicals production. state-of-the-art technologies are assumed. natural gas. several conclusions and recommendations are given in Section 6. A sensitivity analysis was conducted to analyze the effect of different HVC definitions on the results of the energy and CO2 emissions analysis (Ren et al. meaning that light olefins are given 100% weighting per unit mass. wherever applicable. This type of process is now being used in hundreds of refinery sites worldwide. 2008). 2008). we first describe the process routes. the refinery processes produce two types of naphtha: light naphtha. is assumed to have been produced by the fractional distillation of air in a process that uses electricity.. total energy use and total CO2 emissions are used as the main indicators. The state-of-the-art conventional steam-cracking routes utilizing naphtha derived from crude oil and ethane derived from natural gas are being used as the benchmark for comparison (Ren et al. expressed as lower heating values (LHVs). No significant differences were found. In the past. The analysis in this paper is based on scientific and technical journals.g. which has been described in (Blok. 6 In case of an endothermic reaction. whereby electricity is assumed to come from a standalone natural gas-fired power plant at an energy efficiency of 55% (Ren et al. 5 HVCs can also be defined on a mass basis. fuels) and the calorific values of the reactants (e.. twenty-four routes based on crude oil. In order to comprehensively answer this question. coal refers to black coal (i. bituminous. . Ren. Ren et al. which have not yet been used in the current production of basic petrochemicals on the commercial scale and are therefore alternatives to conventional primary energy sources. Energy use and CO2 emissions The term cumulative process energy use refers to the sum of energy use in the two steps of a whole route. Electricity Excess electricity is treated with the credit approach. However. Then. the alternative routes are compared against the conventional routes in terms of their energy use and CO2 emissions. See further explanations on endothermicity in Ren et al. However. Conservation and Recycling 53 (2009) 513–528 and ethane (Ren et al. 2006. M. 4 In general.. sub-bituminous and anthracite). biomass).5 2.2. For comparison purposes. 2008). then characterize them in terms of energy use and CO2 emissions. The content of this paper is as follows. In Section 4. books. we do not include the theoretical energy requirement (i. The calorific value of HVCs is assumed to be lost here as we 3 There are many purposes for biomass use.514 T. Depending on whether electricity is imported or cogenerated. 2. the amount of primary energy use needed to produce co-generated electricity is also deducted. crude oil) that are currently dominant in the production of basic petrochemicals. biomass). Patel / Resources. The energy use and related CO2 emissions of this process are much lower than those of steam cracking (at around 800–1000 ◦ C). it is nevertheless of interest to study their energy use and CO2 emissions based on the current knowledge. Finally. First.g. The alternative routes refer to those routes that utilize alternative primary energy sources (i. conferences proceedings and technical papers. 2008). definitions and methodologies used in this paper are explained in Section 2. For some biomassbased routes. biomass3 and plastic waste. heat of reaction) in the energy use (following the definition of “energy use” in this paper). and finally discuss uncertainties. methane. methanol and ethanol. Each route consists of feedstock production and petrochemicals production.1. which is the sum of the process energy (e. We expect the alternative routes mentioned in this paper possibly to be applied in the long-term future (or 2030–2050). we chose technologies that have recently been researched and that are relatively well understood (meaning that sufficient data for analysis exist). Definitions 2. Patel. Since there is an increasing demand for biomass for these applications. which utilize the conventional primary energy sources (e.. HVCs are defined on the basis of their economic values. heavy naphtha and full range naphtha. This finding is also valid for all of the 24 routes discussed in this paper. (2006). 2008). which focuses on basic petrochemicals. Oxygen. Sensitivity tests regarding other energy efficiencies will be discussed in Section 5. Steam cracking (heat of reaction at about 4–5 GJ/t HVCs) and the conversion of ethanol to ethylene (heat of reaction at about 1. In recent years.6 The term cumulative process CO2 emission refers to the sum of CO2 emissions from the same two steps. When mentioned in this paper.g. Their calorific values on a dry basis are shown in Table 1. Energy use is calculated by subtracting the calorific values of all products from the total energy input. the research question is: how do alternative routes score in comparison with conventional routes in terms of energy use and CO2 emissions? The conventional routes here refer to the most commonly used routes. plastic waste. Feedstocks refer to intermediate products such as naphtha. all options would need to be assessed simultaneously. whereas non-olefins are given 50% weighting per unit mass (Ren et al. energy use for electricity production is either added to or subtracted from the actual input of fossil energy. While it is impossible to predict exactly when these routes will be used. it is becoming increasingly common to convert light naphtha into high-octane gasoline through isomerization. 2. the input of fossil energy is less than the fossil energy use avoided (fossil energy use is avoided because biomass energy is used to produce electricity that would otherwise have to be produced using fossil fuels) and the total fossil energy use is therefore negative (these cases are shown in Table 4). coal and biomass as primary energy sources are briefly described in Section 3. These terms have been used in Ren et al. biomass is becoming an increasingly scarce resource. In this paper. we did not find any studies that have compared all the routes mentioned above in terms of energy use and CO2 emissions. The main indicators are the total energy use and the total CO2 emissions per ton of high-value basic petrochemicals. if used. coal. As far as the alternative routes are concerned. This is far beyond the scope of this paper. scattered information is available which makes it possible to provide a first reply to the question: Patel (2008) argued that biomassbased ethanol (even when the current technologies are used) can reduce more fossil energy use (GJ saved per ton of ethanol) when used to substitute for petrochemical ethanol in comparison to its use as a transportation fuel (i. It should be noted that the black coal found at different locations can have different calorific values (see Table 1) and chemical compositions (see Table 3). uncertainties are discussed.e. it was often said that heavy naphtha was suitable for producing gasoline through catalytic reforming while light naphtha was suitable for making petrochemicals through steam cracking.K. this paper is a prospective study. This indicates that biomass use for the production of basic petrochemicals is an attractive option even under the condition that biomass is a scarce resource.e. For conventional routes. feedstocks and petrochemicals In this paper. such as biomass-derived transportation fuels.. coal. When applying this method.6 GJ/t ethylene) discussed in this paper are endothermic reactions. The reasoning behind this approach is that the energy invested in an endothermic reaction is embedded in the end products and is therefore not lost (from an energy balance perspective) during the process. electricity and wood and bio-based chemicals apart from olefins. In Section 5. The economics of these routes have been discussed in Ren (2009) and will therefore not be included in this paper.3.4 ethane.e. as a replacement for gasoline. or HVCs. natural gas. The term total energy use is the sum of cumulative process energy use and the calorific value of HVCs. 2008).

Williams et al. Conservation and Recycling 53 (2009) 513–528 20 (Gray.092 t CO2 /GJ) (Larson and Ren. ETE I.1 to get GJ/t for each type of coal) 1 GJ/t sugar cane. used in Waste Naphtha SC (Spath and Dayton. 5% of natural gas on the energy basis) Coal (CO2 emission factor 0. GJ/t) 43 (typical) (IEA. III. which consists of methane. 2003) 26 (Larson and Ren. Oil Byproduct CC Crude oil (not used for combustion) Ethane SC FT Naphtha SC Methane MTO. maize 16 and sugar cane 18 (Hamelinck. IPCC.Table 1 Overview of primary energy sources. 2003) Naphtha 45 GJ/t naphtha Natural gas (CO2 emission factor of methane 0. Williams et al..056 t CO2 /GJ (IPCC. M. assumed to be refinery gas (i. 2006) (Coal FT Naphtha II SC: sulfur 9 GJ/t) Ligno FT Naphtha SC I and II Ligno MTO. Patel et al.1 tons CO2 per ton propylene and 3. 2003) Coal (CO2 emission factor 0. 2004a) Carbon content of HVCs (IPCC. maize starch ETE and sugar cane ETE Primary energy sources and their calorific values (LHV. assumed to be methane (i. 2005) Lignocellulosic biomass 20. 120 GJ/t H2 .) (compare 50 GJ/t for pure methane) (IPCC. assumed to be diesel (CO2 emission factor 0.e. Smeets. 2003. 2003. 2006) 2 GJ/t natural gas. etc.118 t CO2 /GJ) (Gray. 2004a. 2006). 2004a) LHVs (GJ/t HVCs) (IEA. Ren.. energy use for making H2 is 62 GJ/t H2 . 2005.1 tons CO2 per ton ethylene and 3. II. 2006 0.092 t CO2 /GJ) (Bechtel. 50% of whose weight are counted as HVCs) CO2 emissions due to combustion of basic petrochemicals: 3.K. propylene and other basic petrochemicals..4 GJ/t crude oil. feedstocks and high-value chemicals (HVCs) on a dry basis.087 t CO2 /GJ) (Williams and Larson. 2003) Coal (CO2 emission factor 0. II and CCS Coal Direct Naphtha SC Coal FT Naphtha SC I Coal FT Naphtha II SC and Coal-ligno FT Naphtha SC Coal (CO2 emission factor 0. natural gas liquids. water. Waste Naphtha SC. MTP Methane OCM I and II Coal MTO I.e.1 GJ coal to produce 1 GJ coal (Ogden et al. 2 GJ/t lignocelluloses and 3 GJ/t maize (Hamelinck. 2004. ethane not used for combustion) 44 (typical for natural gas. 2004) 0.5 tons per ton HVCs on average 515 . ethane.074 t/GJ) Methanol 20 GJ/t methanol Ethanol 26 GJ/t ethanol 47 GJ/t ethylene Ethane 47 GJ/t ethane Methane 45 GJ/t naphtha Methanol Methane Methanol Naphtha 20 GJ/t 50 GJ/t 20 GJ/t 45 GJ/t naphtha methanol methane methanol 47 GJ/t for ethylene. Routes Oil Naphtha SC. 2005) Biomass (no CO2 emission assumed) T. Patel / Resources. on average 50 GJ/t for HVCs produced by naphtha and methanol-related routes (only negligible differences) (these routes also produce aromatics and other non-olefins. 2006) 29 (Bechtel. 2004) (multiply the calorific values of different types of coal by 0. 2008). 2006) Energy use for producing primary energy source Feedstock LHVs (GJ/t feedstock) (IEA. 1% of crude oil on the energy basis). 2003) 32 (Williams and Larson..

each route will be described in two steps: the first step is feedstock production and the second step is petrochemicals production. etc.9 3. especially of CO2 and N2 O. When products derived from HVCs eventually become waste and if they are incinerated. methanol or ethanol is produced. which is a conventional primary energy source used for petrochemicals production. less than 0. for the purpose of cross comparison. Ethane SC is steam cracking of ethane derived from natural gas and catalytic cracking is termed Oil Byproduct CC. Ren. The combustion of final products made from biomass-based HVCs does not add CO2 to the atmosphere.516 T. so they are only briefly described here. Also. 7 There are many methods for waste management.2. dashed lines refer to technologies that are not yet commercialized). Alternative routes In contrast to conventional routes. ethanol dehydration or a methanol-to-olefins process is used to produce petrochemicals. The carbon content of HVCs originates from CO2 existing in the atmosphere and was captured by biomass during plant growth. 1.2. a small amount of methane (a greenhouse gas or GHG) is leaked or flared due to a variety of factors (Delucchi. For biomass-based routes. 3. 3. 8 These GHG emissions given in Delucchi (2003) are less than 2% of the total CO2 emissions (in terms of t/t HVCs) of crude oil.2. Route description Conventional routes and several methane-based routes have already been discussed before (Ren et al. 2 (mostly related to methanol or ethanol). The main focus here is on alternative routes that utilize coal and biomass. it is sufficient here to assume a single waste management method.K. the CO2 emitted will cancel out the CO2 captured by biomass earlier. 1 (mostly naphtha-related) and Fig. These indirect GHG emissions are also not significant and they have a minor effect on the results of the CO2 emissions analysis. the design of Oil Byproduct CC is based on the fluidized catalytic cracking process (FCC). Conservation and Recycling 53 (2009) 513–528 Fig. In the first step (feedstock production). M. The schemes of all routes are shown in Fig. In the following sections. the total CO2 emissions are the sum of cumulative process CO2 emissions and from the combustion of end products derived from HVCs (i. Conventional routes The conventional routes are the basis for comparison with all other routes. 2006. Patel / Resources. This is currently only applied at a few locations in the world. (2006). naphtha.1. 9 Based on Smeets (2008) and Hamelinck (2004). Oil Byproduct CC is considered a conventional route in this paper because its feedstocks (heavy oils. assume waste incineration of products derived from HVCs without energy recovery. we found that these indirect emissions are not significant (i. the waste incineration of biomass-derived products does not lead to net CO2 emissions—unlike the waste incineration of products derived from fossil energy.) are byproducts derived from crude oil.7 For fossil energy-based routes. Therefore. the total CO2 emissions are the emissions from fossil energy use only. . which is a conventional technology used to produce gasoline and propylene. natural gas and coal-based routes discussed in this paper. naphtha steam cracking. assuming that the carbon content of the HVCs is released into the atmosphere). Data for the first steps are shown in Tables 2–4 while data for the second step are shown in Tables 5–7.1 ton CO2 equivalent per ton HVCs) and they do not affect the results of the CO2 emissions analysis (no percentage is given here because some routes have negative emissions). Steam cracking of naphtha derived from crude oil as a feedstock is referred to as Oil Naphtha SC..e. 2003). In the second step (petrochemicals production). but each method would have nearly the same effect on all of the routes. Similarly. Naphtha-related conventional and alternative routes to basic petrochemicals (solid lines refer to technologies that are already commercialized. See our results on CO2 emissions in Section 4. See the results in Section 4. 2008). Therefore.e. In the petrochemicals production step of Oil Byproduct CC. The indirect GHG emissions given in Delucchi (2003) are in CO2 equivalents not significant if compared to our results on CO2 emissions. During the production processes of crude oil. natural gas and coal. the feedstocks used in alternative routes are derived from alternative primary energy sources. the catalytic pyrolysis process (CPP) is used.8 The production and use of fertilizers required for biomass cultivation leads to the release of GHG emissions. Details of these routes are given in Ren et al.

2002..K. 2002.) Fossil energy use (GJ/t feedstock). 2000) Separation of C2 H6 from others 1–15% (depending on the chemical composition of the natural gas) 2 (Hydrocarbon Processing... 2006) Routes Feedstock Feedstock production Crude oil distillation Oil Naphtha SC Waste Naphtha SC Naphtha Hydrogen pyrolysis Oil Byproduct CC Byproducts Separation from refinery/petrochemical products Separation of C4 –C9 or heavier than C10 Up to 70% (depending on the chemical composition of the byproducts) 3 (Xie and Wang.T. 2008) FT Naphtha SC Naphtha Syngas production and Fischer–Tropsch process CH4 + O2 → CO + 2H2 O. 2002) Ethane SC Ethane Separation from natural gas Natural Gas details can be found in (Ren et al. no electricity co-generation 3 (Hydrocarbon Processing. Patel / Resources. 2003) 517 . 1992) Reaction Separation of paraffinic rich C5 -C11 10% of refinery products Breaking up of polymers (C2 H4 )n or (C3 H6 )n 45% (35% aromatics and conversion gases. 2006) 17 (energy use of current technologies is 10–20% higher than 17 (Navqvi. Ren. Neelis et al. 1998). 80% naphtha-value equivalent) 8 (ECN. calorific value of feedstock excluded. CH4 + H2 O → CO + 3H2 nCO + 2nH2 → Cn H2n + nH2 O 15–30% (81% naphtha-value equivalent) Methane MTO and Methane MTP Methanol Methanol synthesis Methane OCM I and Methane OCM II Methane Natural gas process (separation and purification of methane) Separation and purification of CH4 from natural gas Methane 80–95% (depending on the chemical composition of the natural gas) 2 GJ/t methane (Swanenberg. Primary energy source Crude Oil details can be found in (Ren et al. 3 GJ/t oxygen (van Ree. Conservation and Recycling 53 (2009) 513–528 Table 2 Feedstock production in crude oil and natural gas-based routes (the 1st step of a route). M.. Neelis et al. 2000) 10 (Lurgi. 2006) CO + 2H2 → CH3 OH Methanol 145% of natural gas Yield of feedstock (wt.

M. CO + 2H2 → CH3 OH (CH0. H: 4–5% in bituminous. SOx . all fossil energy Electricity co-generated (GJe /t feedstock) Energy use (GJ/t feedstock) after deducting fossil energy use for electricity production (calorific value of feedstock excluded).8 )Ox Sy Nz is gasified and cleaned. 70–80% in sub-bituminous and 65–70% in lignite (lignite used for Coal Direct Naphtha SC only). 12C6 H5 + 36O2 → 72CO + 30H2 . but suitable for others) Coal FT Coal MTO I Coal MTO II Coal MTO CCS Coal Direct Naphtha SC Naphtha SC I Methanol Methanol production (via syngas) Naphtha Direct liquefaction (no syngas involved) Cm Hn Oo Sp Nq is converted into Cn H2n and other C4 –C22 liquids (also CO2 . and other less valuable byproducts) Naphtha 10% (the total yield of naphtha-value equivalent products is 42%) 38 Fischer–Tropsch (via syngas) Coal and biomass Routes Feedstock Feedstock production Coal FT Naphtha SC II FT Naphtha Coal-ligno FT Naphtha SC T.) 74% 30% 74% Energy use (GJ/t feedstock) before deducting fossil energy use for electricity production (calorific value of feedstock excluded). sub-bituminous and lignite (C: 80–90% H: 3–4% and O: 2–5% in anthracite. and other less valuable byproducts. SOx . all fossil energy References 17 70 18 Naphtha 9% (the total yield of naphtha-value equivalent products is 31%) 30 Naphtha 5% (the total yield of naphtha-value equivalent products is 18%) 124 88 0 17 20 34 0 18 0 38 0 30 36 59 19 53 (32 from coal and 21 from biomass) Williams (2005) and Williams et al. N: 1–2% in bituminous.8 )Ox Sy Nz is gasified and cleaned. there are also CO2 . Patel / Resources.518 Table 3 Feedstock production in coal-based routes (the 1st step of a route).K. 10–20% in sub-bituminous and 20% in lignite. not suitable for Coal Direct Naphtha SC. (2006) Larson and Ren (2003) Williams and Larson (2003) Bechtel (2003) and Gray (2005) . O: 5–10% in bituminous. SOx . excluding minerals/metals) Coal C: 75–85% in bituminous. 12C6 H5 + 36O2 → 72CO + 30H2 . Primary energy source Content (wt. Conservation and Recycling 53 (2009) 513–528 Main reactions (CH0. there are also CO2 . Ren. NOx . sub-bituminous and lignite. sub-bituminous and lignite. and other less valuable byproducts. S: 1–10% in bituminous. NOx . NOx . CO + 2H2 → CH3 OH Yield of feedstock (wt.

K. 2005. the products are syngas (a mixture of CO and H2 ) and a small amount of CO2 . 2004. Spath and Dayton. CH4 .. Patel / Resources. Conservation and Recycling 53 (2009) 513–528 Biomass Routes Feedstocks Ligno FT Ligno FT Naphtha SC I Naphtha SC II FT naphtha (Hamelinck. Patel et al. Ren. 2004) Fischer–Tropsch (via syngas) Ligno MTO Methanol (Hamelinck. 2004) Methanol production (via syngas) Ligno ETE I Ligno ETE II Ligno ETE III Maize Starch ETE Sugar Cane ETE Feedstock production Main reactions Lignocelluloses C6 H10 O5 are gasified. sugar/starch 3C5 H10 O5 → 5C2 H5 OH + 5CO2 31% 25% 27% 46% 19% Yield of feedstock (wt.) Energy use GJ/t feedstock before deducting energy use for electricity production (calorific value of feedstock excluded) Electricity co-generated (GJe /t feedstock) Energy use GJ/t feedstock after deducting energy use for electricity production (calorific value of feedstock excluded) Naphtha 3% (the total yield of naphtha-value equivalent products is 12–14%) 17 (fossil) 13 (fossil) 124 (biomass100 (biomassderived) derived) 12 −5 (fossil) 100 (biomassderived) 38 −56 (fossil) 124 (biomassderived) 49% 6 (fossil) 21 (biomassderived) 0 6 (fossil) 21 (biomassderived) 9 (fossil) 32 (biomassderived) 3 4 (fossil) 32 (biomassderived) 8 (fossil) 47 (biomassderived) 14 −18 (fossil) 47 (biomassderived) 8 (fossil) 33 (biomassderived) 3 2 (fossil) 33 (biomassderived) 20 (fossil) 9 (biomassderived) 0 20 (fossil) 9 (biomassderived) 7 (fossil) 61 (biomassderived) 10 −11 (fossil) 61 (biomassderived) 519 . and H2 O.Table 4 Feedstock production in biomass-based routes (the 1st step of a route). 2003) Ethanol (C5 H10 O5 ) production through hydrolysis and fermentation (no syngas involved) Lignocelluloses (C6 H10 O5 )n + nH2 O → n(C6 H12 O6 ). T. M. glucose/sugar C6 H12 O6 → 2C2 H5 OH + 2CO2 . nCO + 2nH2 → Cn H2 CO n2H H2 O n ++ 2 → CH3 OH Ethanol (Hamelinck.

Ethane SC Steam cracking C2 H6 cracked into C2 H4 C5 -C11 cracked into C2 H4 . C2 H6 + (1/2)O2 → C2 H4 + H2 O 50% (19 GJe /t HVCs cogenerated) 17 (energy use for electricity production 35 excluded) 15% (148 GJe /t HVCs co-generated) 14 (energy use for electricity production 269 excluded) 6 5 9 6 5 9 . Patel / Resources. Conservation and Recycling 53 (2009) 513–528 Yield (wt. M. (2006) Routes Petrochemical production Reactions Oil Naphtha SC Steam cracking C5 –C11 cracked into C2 H4 . etc. C3 H6 . C3 H6 . (2008) FT Naphtha SC Methane MTO Methane MTP Methane OCM I Methane OCM II T. etc.K. H3 COCH3 is dehydrated and the main products are C2 H4 and C3 H6 (no C2 H4 is produced in the case of MTP) 43% 40% Oxidative coupling 2CH4 + (1/2)O2 → C2 H6 + H2 O. see details in Ren et al.520 Table 5 Petrochemicals production in crude oil and natural gas-based routes (the 2nd step of a route). etc.) of HVCs as % of feedstocks Energy use (GJ/t HVCs). Ren. no electricity co-generation except for Methane OCM I and II. Waste Naphtha SC Oil Byproduct CC Catalytic cracking C4 –C9 catalytically cracked into C3 H6 . Primary energy sources Crude oil. calorific value of HVCs excluded 70% 50% 84% 75% Methanol dehydration 2CH3 OH → H3 COCH3 + H2 O. Natural gas see details in Ren et al.

2. naphtha production. Ethane. methanol and ethanol-related routes and methane processing by oxidative coupling routes. 2003. 3. Currently. Patel / Resources. no electricity co-generation. Coal can be converted into naphtha via either direct or indirect liquefaction (Bechtel. However. This route has been applied by Shell in Malaysia and by Mossgas in South Africa.g. calorific value of HVCs excluded 75% (Ren et al. Ren.. 2002). Shell. Plastic waste. It is not yet being used on the commercial scale. Heyde and Kremer. the dominant methods for the disposal of plastic waste are landfills. Table 6 Petrochemicals production in coal-based routes (the 2nd step of a route). Coal MTO II and Coal MTO CCS Methanol Methanol dehydration 2CH3 OH → H3 COCH3 + H2 O. M. 1999). The route is hereafter referred to as Waste Naphtha SC. dashed lines refer to technologies that are not yet commercialized). 80–100% of natural gas found worldwide) can be converted into so-called Fischer–Tropsch (FT) naphtha through natural gas-to-liquids (GTL) processes. can be converted into naphtha through a series of liquefaction.. 2008) 5 (Ren et al. namely methane. Alternative routes can be categorized into naphtha. due to the lack of aromatics. 2003. Coal FT Naphtha SC II and Coal-ligno FT Naphtha SC FT naphtha Feedstock Petrochemical production Reactions Naphtha Steam cracking Fischer–Tropsch liquids (C5 –C11 ) are cracked into C2 H4 .. 2003.T.) of HVCs as % of feedstock Energy use (GJ/t HVCs). plastic waste. coal and biomass. 2006) 6 (Ren et al. plastic waste. methanol.2. Naphtha routes: from methane. 1).4 comes from biomass) . coal and biomass All the naphtha-related alternative routes are based on the same feedstock (naphtha) and the same petrochemicals production process (naphtha steam cracking) as the second step (see Fig.e. The ethylene yield from steam cracking of FT naphtha is about 40%. Zhang. incineration or making secondary plastics. but was later abandoned (ECN.6 comes from coal and 2. pyrolysis and separation processes. etc. 55% 8 (higher than the 6 in the column on the right because heavy naphtha is used) Yield (wt. The most recent overviews are presented in Navqvi (2000) and Smith (2004).K. 3. 2006) (in the case of Coal-ligno FT Naphtha SC. 2008) Coal Direct Naphtha SC Coal FT Naphtha SC I. However. C3 H6 . The route is referred to hereinafter as Methane FT Naphtha SC. the polypropylene used in plastic bags). 2000. Primary energy sources: Coal Routes Coal MTO I. nearly 10% higher than that of oil-derived naphtha (Dancuar et al. especially polyolefins (e. is based on different primary energy sources. We chose a natural gas-to-liquids (GTL) process with maximum naphtha yield and high-energy efficiency as the design of the first process step in the route. H3 COCH3 is dehydrated and the main products are C2 H4 and C3 H6 43% (Ren et al. The technology was developed by BASF to comply with regulations in Germany. the first step in these routes. Williams and Larson.. Conservation and Recycling 53 (2009) 513–528 521 Fig. and ethanol-related routes to basic petrochemicals (solid lines refer to technologies that are already commercialized.1.. the total yield of HVCs is only 5% higher than that of Oil Naphtha SC. Methane (i. The utilization of plastic waste for the production of naphtha and petrochemicals is a potential method for plastic waste disposal.

. C3 H6 . Ligno FT Naphtha SC II Ligno MTO Methanol Methanol dehydration 2CH3 OH → H3 COCH3 + H2 O.522 T. 2005) −72 14 8 −27 4 37 −17 137 170 53 51 76 54 12 100 . calorific value of HVCs excluded 75% (Ren et al.. 2006) 6 (biomassderived energy) (Ren et al. Conservation and Recycling 53 (2009) 513–528 Table 7 Petrochemicals production in biomass-based routes (the 2nd step of a route and a summary of both steps). Primary energy source: Biomass Routes Feedstock Petrochemical production Reactions Ligno FT Naphtha SC I FT naphtha Steam cracking C5 –C11 is cracked into C2 H4 . electricity use negligible.. 2006) −6 61% (Patel et al.. calorific value of HVCs excluded Total biomass-derived energy use in the 1st and 2nd steps (GJ/t HVCs).) Energy use in the 2nd step (GJ/t HVCs).. M. 2005) 2 (fossil energy) (Patel et al.K. H3 COCH3 is dehydrated and the main products are C2 H4 and C3 H6 43% (Ren et al. calorific value of HVCs excluded Total fossil energy use in the 1st and 2nd steps (GJ/t HVCs). etc. Ren. Patel / Resources.. 2008) C2 H5 OH → C2 H4 + H2 O Ligno ETE I Ligno ETE II Ligno ETE III Ethanol Ethanol dehydration Maize Starch ETE Sugar Cane ETE Yield of HVCs as % of feedstock (wt. 2008) 5 (fossil energy) (Ren et al.

Since methanol production and methanol to HVCs were described in details in Ren et al. Three designs. recycling and CO2 capture. this process will not be discussed further in this paper. The ethanol production technologies based on lignocellulosic biomass are still undergoing development and these 10 There are two other major direct liquefaction processes. 2004. In this paper. The Hague) through personal communication in 2006. The most recent and the most comprehensive study found so far is Larson and Ren (2003). (2008). one design has maximum output of FT liquids and minimum electricity co-generation and the other has maximum electricity co-generation and minimum output of FT liquids. Due to lack of data. It has been chosen because of its high-energy efficiency and high light-olefin yield. respectively. 2006). Coal FT Naphtha SC I. The yield of this process is similar to the two methods mentioned above.11 This route is hereafter referred to as Coal Direct Naphtha SC and has not yet been applied on the commercial scale. the route is referred to as Ligno MTO and it has not yet been used on the commercial scale. but there are plans to use them on the commercial scale in China (Zhang..e. respectively. i. One is the SRC (Solvent Refined Coal) process. Sunopta. we will focus on the first step of coal and biomass-based methanol routes only. followed by either microbial conversion (fermentation) (BRI. See reaction formulas in Table 4.e. 2005). Several designs for direct coal liquefaction10 have been studied in recent decades. but were shut down in the early 1990s when the oil prices fell. which was developed in the 1920s. 12 They were chosen for illustration purposes. comprehensive study found so far is Hamelinck (2004). 2008). followed by fermentation to ethanol. M. coal and lignocellulosic biomass (e.. 2005). the naphtha produced by this route is rich in aromatics and therefore leads to lower HVCs yields than oil-derived naphtha (estimated to be 15% lower than that of Oil Naphtha SC). a relatively small output of FT liquids is produced and a large amount of electricity is co-generated (Bechtel. Today. Ethanol routes: from biomass All ethanol related routes use the same petrochemicals production process as the second step. None of the three coal-based routes (Coal FT Naphtha SC I.g. . wheat and wood). Patel et al. 2005).g. Patel / Resources. H. 2008. there is no known ethylene production from biomass-derived ethanol in commercialscale operation. Ligno ETE II (with the most electricity co-generation) and Ligno ETE III (with moderate electricity co-generation).3. Williams et al.2. Coal MTO II (without recycling. Coal FT Naphtha SC II and Coal-ligno FT Naphtha SC. 3. feedstock production or ethanol production in this case. the “Methanol-To-Olefins” (MTO) technology developed by UOP PLC (Ren et al.000 ton of ethylene) were announced (Schut. methanol production from methane plus MTO) is referred to hereinafter as Methane MTO. Biomass of all kinds can be converted into methanol via processes that are similar to coal-based methanol production. The three routes are referred to hereinafter as Ligno ETE I (with the least electricity co-generation). wood and switchgrass) are used to produce FT liquids and a moderate amount of electricity is co-generated while nearly all the CO2 is captured and used for the purpose of enhanced oil recovery (EOR) (Williams. See reaction formulas in Table 4. 2005).. • Hydrolysis of lignocellulosic biomass (e..12 These three routes are referred to hereinafter as Coal MTO I (with recycling. Two improved ethanol process designs were chosen for the first method mentioned above (their energy requirements are 5–6 GJ/t ethanol lower than the current technologies) (Patel et al. Another route. such as electricity co-generation. Among the six designs described in Larson and Ren (2003). These two routes have not yet been used on the commercial scale. Their differences lie in the first step. 2005). The ethanol production technologies applied in these two routes are currently used in many locations throughout the world. Conservation and Recycling 53 (2009) 513–528 523 2005). Maize Starch ETE does not have electricity co-generation.. In this paper. (2005). the two routes with these two designs are referred to as Ligno FT Naphtha SC I and II. or so-called indirect liquefaction. Among many designs covered in Hamelinck (2004). where ethanol is converted into ethylene through a rather well-known dehydration process (ethanol to ethylene or ETE) (Patel et al. 11 This information was given by Mr. methanol production from coal and biomass. 2005). but Sugar Cane ETE does. without CO2 capture and with the smallest net electricity net co-generation). They were chosen because they include the full range of technical options regarding electricity co-generation.T. In the case of Coal FT Naphtha SC II. Methanol routes: from methane. which was developed by Gulf Oil and implemented in pilot plants in the US in the 1960s and 1970s. Coal-ligno FT Naphtha SC is chosen because it has the flexibility to use both coal and biomass. • Gasification of lignocellulosic biomass. plans for the construction of three such plants in Brazil (to be in operation in 2009–2011 with a total capacity of 600. 2005. another one has the most electricity co-generation and the last one has the moderate electricity co-generation (Hamelinck. with CO2 capture and with the greatest net electricity import).2. The most recent. 2007). without CO2 capture and with the most electricity co-generation) and Coal MTO CCS (with recycling. TSS. Biomass-based methanol production has been described in detail in Hamelinck (2004) and Patel et al. One utilizes maize starch while another utilizes sugar cane. coal and biomass Five of the six methanol-related routes discussed in this paper are based on the same petrochemicals production process. No recent data on these processes were found. has been chosen for its high propylene yield. Coal can also be converted into FT naphtha via FT processes. In 2007. This is referred to hereinafter as Methane MTP. 2005). they are referred to hereinafter as Maize Starch ETE and Sugar Cane ETE. van Steen (ABB Lummus. Methanol can be produced from coal via syngas. 2003).13 Three designs were chosen for the second method mentioned above: one design has the least electricity co-generation. 13 Sugar cane-based ethanol-to-ethylene plants in Brazil were in operation during the 1980s. 2005. biomass can also be converted into FT naphtha through FT processes. These routes are new. The other is the low temperature carbonization (LTC) or Karrick process. There are three well-known methods to convert biomass into ethanol: • Direct fermentation of sugar/starch rich biomass (sugar cane. agricultural waste. Ren.K. In contrast to FT naphtha (with no aromatics). The natural gas-based methanol route (i. Similar to methane and coal. Coskata. 2008) or chemical conversion (with a proprietary catalyst) (Rangefuels. but this route is currently experiencing a comeback. only FT liquids are produced and very little electricity is co-generated (Gray.2. we chose a design with the highest energy efficiency for this analysis. Among the designs described in Hamelinck (2004). II and Coal-ligno FT Naphtha SC) has been used on the commercial scale so far. sugar beet or maize starch) to ethanol (Patel et al. 3. In the case of Coalligno FT Naphtha SC.. have been selected for the following reasons: in the case of Coal FT Naphtha SC I. 2008. It is technically possible to add CO2 capture features to any of the routes mentioned. In this paper. based on Lurgi’s methanol-to-propylene (MTP). we chose three designs for methanol production since they cover a wide range of technical specifications.

4. Energy use. are shown in Table 2 (oil and natural gas). 3. Total energy use in various routes to high-value chemicals (HVCs) (both fossil and biomass-derived energy included. These routes have not yet been used on the commercial scale. Ligno FT Naphtha SC I and II) is 9–13 times as much as that of conventional routes. Two oxidative coupling routes. Fig. 3 shows that the CO2 separation unit of Coal MTO CCS does not lead to substantially higher energy use than other two coalbased methanol routes. the carbon content of the HVCs . respectively). Coal FT Naphtha SC II. Coal MTO II. respectively. Electricity use for drying and compressing CO2 is about 0.14 3. The total energy use (consisting of fossil and biomass-based energy) of most of coal and biomass-based routes is in the range of 90–130 GJ/t HVCs. Table 6 (coal) and Table 7 (biomass). Fig. error bars representing the result of using an economic value-based allocation approach to allocate the total energy use to both electricity and HVCs). This is primarily due to the low yields of FT naphtha production in these two routes (12 and 14%. For biomass-based routes. This is in contrast to the case of the current electricity production based on various primary energy sources where power plants fired by natural gas (mostly methane) are the most energy efficient. methane can also be converted to ethylene through the oxidative coupling chemistry described in Swanenberg (1998).e. In particular. DSM OCM I and II. Patel / Resources. (2008) and they will be compared with other routes in this paper. The cumulative process energy use of most coal and biomassbased routes can even be 4–8 times as much as that of conventional routes. or the second step of each route. The energy impact of CO2 separation is limited because the concentration and pressure of CO2 are high after gasification. About 6% of the total coal input in primary energy terms is used in recycling and CO2 capture (in the case of Coal MTO CCS) (Larson and Ren. Results of CO2 emissions analysis There are currently several pilot plants in operation and a number of plans for the construction of commercial-scale lignocellulosic ethanol plants (above 10 million gallons ethanol per year) have been announced (Sunopta. are shown in Table 5 (oil and natural gas). 4 shows the total CO2 emissions (cradle-to-grave) of all routes. Conservation and Recycling 53 (2009) 513–528 Fig. 4.4.4 GJe /t CO2 .1. 4.2. This is about 30% more than those of conventional routes. or the first step of each route. Data on petrochemicals production.2. 2007).7 GJe is co-generated and 0. the conventional routes (based on crude oil and ethane) are the most energy efficient. When the total energy use (consisting of fossil and biomass-based energy) is compared. which are much less than the yields of feedstock production in other routes.5 GJe is imported). Their total energy uses are high: about 180 and 150 GJ/t HVCs. 14 Fig. 3.K. Data on feedstock production. M. 2003). Oxidative coupling routes: from methane Rather than being converted into HVCs via naphtha or methanol. The total energy use of the conventional routes is about 60 GJ/t HVCs (the cumulative process energy use of 10 GJ/t HVCs plus the calorific value of HVCs about 50 GJ/t HVCs). the cumulative process energy use of those routes with large amount of electricity co-generation (i.524 T. They are referred to hereinafter as Methane OCM I and II. Lower heating values (LHVs) and emission factors are shown in Table 1. 3 shows that the total energy use of coal and biomassbased routes is roughly 60–150% higher than that of conventional routes. The total energy use for Waste Naphtha SC is relatively high due to the use of hydrogen. technologies have not yet been used on the commercial scale to produce ethylene. The total energy use of methane-based routes is about 80 GJ/t HVCs.2 GJe /t methanol (2. Ren. were analyzed in detail in Ren et al. Table 3 (coal) and Table 4 (biomass). The total electricity consumption in Coal MTO CCS is 3. The yields of feedstock production in those routes are shown in Tables 4 and 7. Results of energy analysis The overall results of energy analysis for the routes discussed in this paper are shown in Fig. The routes with the highest total and cumulative process energy use are Ligno FT Naphtha SC I and II. CO2 emission analysis and land use Data used in the analysis of energy use and CO2 emissions for various routes are shown in Tables 2–7.

Land use for growing various type of biomass for biomass-based routes to high-value chemicals (HVCs) (the default is large round dots. the distance between the ends of the error bars represents a possible range of land use if an economic value-based allocation approach is used to allocate the total energy use to both electricity and HVCs). The total CO2 emissions of methane-based routes are about 10% more than those of conventional routes (Ren et al. Fig. . Patel / Resources. 4 shows that CO2 emissions from feedstock production due to the combustion of fossil fuels in several biomass-based routes are negative. CO2 emissions of the coal-based routes are the highest (8–11 tons CO2 /t HVCs) with an exception of Coal MTO CCS (with CO2 capture and sequestration features). electricity is always assumed to have been produced by a natural gas-fired power plant and electricity co-generation leads to CO2 emissions being avoided. dotted bars represent the fossil carbon physically embodied in HVCs. 5. This is because the CO2 emissions avoided by electricity co-generation are larger than the CO2 emissions due to the use of fossil energy. As Fig. If the products derived from HVCs (e.K. Ligno FT Naphtha SC II. the more avoidance of CO2 emissions it leads to. Total CO2 emissions (cradle-to-grave) in various routes for production of high-value chemicals (HVCs) (including the CO2 emissions from feedstock production and petrochemicals production as well as the carbon content of HVCs. It is technically possible to equip any route mentioned in this paper with CO2 capture/sequestration features to achieve very low CO2 emissions. Conservation and Recycling 53 (2009) 513–528 525 Fig. Table 2 and Fig. 3 show that the energy use in feedstock (naphtha) production of Methane FT Naphtha SC is 17 GJ/t naphtha.g.T. As stated earlier. Ren. the distance between two large round dots for each route represents a possible range of land use if the total energy use is allocated to HVCs only.. The total CO2 emissions of conventional routes are slightly more than 4 tons CO2 /t HVCs. M. The more electricity a biomass-based route co-generates. for which total CO2 emission is nearly the same as that of the conventional routes. avoids the most CO2 emissions. 4 indicates. 4. 2008). the biomass-based route with the most electricity co-generation. originates from the atmosphere (carbon captured by biomass from the air during plant growth) and is then sequestered in HVCs. polyethylene plastic bags) are incinerated in the context of post-consumer waste management. Not all biomass-based routes have electricity co-generation. the carbon content of HVCs produced through biomass-based routes is zero since it originates from the atmosphere). the carbon content of the HVCs is released to the atmosphere and finally cancels out the carbon that was originally captured by biomass. which Fig.

e. 2006. In the case of naphtha production using Methane FT Naphtha SC. as indicated in the sources cited for this analysis. EIA. we also used the allocation approach. The range of land use has been narrowed to an extent that means almost all biomass-routes (except for Ligno FT Naphtha SC I) use a similar range of areas (less than one hectare) to produce one ton of HVCs. 3 GJ/t naphtha is supplied by the combustion of refinery gas. 5. Using these data. However. The economic value-based allocation approach mentioned above can also be used to correct the land use for those biomassbased routes that co-generate large amount of electricity (see Section 4. 5). 2004b. Smeets et al. The result of applying the economic value-based allocation approach is represented by the error bars in Fig. 2008. 2008. with Ligno FT Naphtha II requiring most biomass (e. The only significant uncertainty introduced by ourselves is the assumed energy efficiency in electricity co-generation. The unit cannot be $/ton (which would be meaningless for electricity).e. which is generally known to be lower than that of electricity production from natural gas. co-generated electricity is converted to tons of HVCs equivalent since their values in $/GJ are the same (as explained above). The values represented by large round dots in Fig. we have used a combined credit/allocation approach as the main approach in Sec- 15 The yield of lignocellulosic biomass has a wide range since it can be grown on poor land and can also come from agricultural wastes or forests (forest land is generally unfit for agricultural purposes). Conservation and Recycling 53 (2009) 513–528 is nearly 6 times that of Oil Naphtha SC (3 GJ/t naphtha). the yield of HVCs per ton of biomass can be calculated.3. we have assumed a default energy efficiency of 55% for the use of natural gas for electricity production. Smeets et al. the total energy use of methane-based routes is about 80 GJ/t HVCs and that of most biomass and coal-based routes is now in the range of 90–130 GJ/t HVCs (note: Ligno FT Naphth SC I is an exception). The biomass input differs substantially across the biomassbased routes studied. However. First. Tests using values of 40 and 60% against the default energy efficiency of 55% for those coal and biomass-based routes with electricity co-generation indicated that the total energy use in these routes is quite sensitive to the energy efficiency assumed for electricity co-generation. However. 5 represent the result of applying the economic value-based allocation approach. 2002). 55% is not valid as the energy efficiency for electricity production from coal or biomass. a figure can be calculated for the land use per ton of HVCs for each of the biomass-based routes (see large round dots in Fig. only the yield of HVCs per ton of biomass has been considered (i. Ren. 5 times more than Ligno MTO). Land use analysis Based on the yields of feedstock per ton of biomass (see Table 4) and the yields of HVCs per ton of feedstocks (see Table 7). A yield of 20 ton/ha/year is only possible under favorable conditions regarding fertilization effects. 3. 5). With the exception of Ligno FT Naphtha SC I/II and Ligno ETE II. The global market prices of HVCs in the past ten years were roughly in the range of $500/t to $800/t (largely following crude oil prices) (CMAI. 3 show. As the error bars in Fig. but not CO2 (see Table 2 for reaction equations). The results presented in Section 4 were calculated by applying a credit approach in those cases where electricity co-generation is involved. In the case of naphtha production by Oil Naphtha SC. 2004. Hoogwijk.3 and Fig. all other routes use less than one hectare to produce one ton of HVCs.03/kWh to $0. 4 shows that CO2 emissions for naphtha production from the former are only slightly higher than for the latter.e.e.e. HVCs and electricity can be considered to have the same economic value in terms of $/GJ. The error bars in Fig. which are $10/GJ to $16/GJ if expressed in terms of $ per GJ of calorific value. whether alone or combined. One way to tackle the two problems described above is to apply only the economic value-based allocation approach for all routes for allocating the total energy use to both the production of HVCs and electricity generation (therefore not using the credit approach at all). all biomass use is allocated to HVCs) while several routes (i. In Fig. Fig. The reasonable ranges of biomass yield in terms of tons/hectare/year in the medium term (now–2030) and the long term (2030–2050) are expected to be 6–20 (lignocellulosic). 5. 4. In the same period. we will discuss an alternative method for treating electricity in energy allocation. 2007). Pettman. The test results nevertheless do not change our earlier finding that coal and biomass-based routes use much more energy than the conventional routes. In fact. Discussion The data on individual routes can be affected by various uncertainties to a limited extent. 55%.05/kWh (largely determined by coal and gas prices) (EIA. as discussed in the last section.526 T. so $/GJ ($/GJe for electricity) is a more suitable common unit for expressing the values. Applying the economic value-based allocation approach leads to a clear convergence of energy use among these routes. Because the emission factor of methane is lower than that of refinery gas.. Ligno FT Naphtha SC I/II and Ligno ETE II) co-generate large amounts of electricity. The results will be discussed in Section 5. 2004. 3 and 4 show the significant differences between the feedstock production steps of conventional and alternative routes). we can simply treat electricity in the same way as HVCs. the difference between the biomass input of the route using the most biomass (i. which is based on economic values used for defining naphtha value-equivalent feedstocks and olefin value-equivalent HVCs. 2004. only 6 out of 17 GJ/t naphtha is supplied by the combustion of methane and the rest (11 GJ/t naphtha) is supplied by partial oxidation of methane. these uncertainties do not change the overall results in Section 4 (e.g. Ligno FT Naphtha II) and that of the route studied – can be assumed to be co-combusted in a coal co-fired power plant with an energy efficiency of 40%. climate and soil quality (Hoogwijk. This requires the values of HVCs and electricity to be expressed in common units. One can argue that a fair comparative analysis should assume identical biomass input across all biomass-based routes.. while using the credit approach. This poses two problems. This is the reason why the land use for Ligno FT Naphtha SC I/II and Ligno ETE II can be greater than one hectare per ton of HVCs. Secondly. As a thought experiment. in the cases where the credit approach based on a physical property (i. Excess biomass – i. the wholesale prices of electricity in major industrial countries were roughly in the range of $0.15 7–9 (maize) and 20–27 (sugar cane) (Hamelinck. It is possible to allocate biomass use to both HVCs and electricity through the use of an economic value-based approach. which are $8/GJe to $14/GJe if expressed in $/GJe . the CO2 emissions from the naphtha production step in these two routes are similar. tion 4. The combination of one physical property-based approach and another economic value-based approach could therefore raise questions about consistency and should be discussed further. M. The electricity generated in the co-fired power plant can be assumed to replace electricity that would otherwise . In this section. Patel / Resources. When the economic value-based allocation approach is used. We can therefore conduct an allocation approach based on the calorific content of HVCs and of the co-generated power. technological improvement. Figs. 5 are not fully comparable. 2005). Partial oxidation of methane leads to the formation of water and hydrocarbon liquids.g.K. 2007). Based on these historical data. the primary energy use in electricity production) is used. IEA.

Outlook for advanced biofuels.01. coal and biomass: energy use. Schut J. DC. better properties. 5 by fraunhofer institut für verfahrenstechnik und verpackung IVV). Energy Information Administration of the US Department of Energy. Illinois: Coskata Inc. Range Fuels. Introduction to energy analysis. Our first plant. Delucchi. Appendix E: methane emission from natural gas production. . Exceptions are Ligno FT Naphtha I (−1 tons CO2 per ton of HVCs).2. Navqvi S. Davis. Report No. M. Joosten. Switzerland: IPCC. The Netherlands: Utrecht University.nl/digiarchief/dip/diss/2004-0309-123617/full. IEA (International Energy Agency). doi:10. utilizing naphtha derived from crude oil and ethane derived from natural gas) and that of coal and biomass-based routes will be improved in the coming decades. IEA (International Energy Agency). Blok K. Amsterdam: Techne Press. Inc. Haije M.31(4):425–51. See also at: http://www. Petrochemicals from oil. Paris: IEA/OECD. Understanding bio-economics. 6. Sunopta. Smeets E. 2006. On the global and regional potential of renewable energy sources.doe.nl/dissertations/2005-0209-113022/. economics and innovation. Paris: IEA/OECD. the conventional routes were found to be far more energy-efficient than any of the alternative routes. Smith R. Refining processes 2002. Amsterdam: Shell Gas & Power. Bach P.nl/dissertations/1980386/UUindex. 2005 (see also: www.. Blok K.com/EthanolEnergyPositive. for the US National Energy Technology laboratory of US Department of Energy under the contract no. Ligno ETE II has more excess biomass and therefore offers more CO2 savings because of its high-energy efficiency (see Fig.08. EIA (Energy Information Administration). 2004b. Patel M.html.33(1):56–106. Medium and long-term opportunities and risks of the biotechnological production of bulk chemicals from renewable resources. Conservation and Recycling 53 (2009) 513–528 527 need to be produced in a natural gas-fired power plant. Patel M. Ren T.html. Kremer M. 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