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BioLPG

The Renewable Future

Innovation & Technology

Atlantic Consulting

The World LPG Association

The WLPGA was established in 1987 in Dublin, Ireland, under the initial name of The World LPG Forum.

It unites the broad interests of the vast worldwide LPG industry in one organisation. It was granted Category II Consultative

Status with the United Nations Economic and Social Council in 1989.

The WLPGA exists to provide representation of LPG use through leadership of the industry worldwide.

Acknowledgements

This report has been developed by Atlantic Consulting, jointly with the World LPG Association, WLPGA, Innovation &

Technology Network and the European LPG Association, Liquid Gas Europe – AEGPL, Policy Coordination Group.

Nikos Xydas (WLPGA) and Jaume Loffredo (Liquid Gas Europe - AEGPL) coordinated this project.

Disclaimer This report has been authored by Atlantic Consulting in collaboration with WLPGA and Liquid Gas Europe - AEGPL. Ownership of the contents, data and conclusions in this report remains jointly with the author and the LPG associations. The content has been compiled and/or derived from public sources believed to be reliable. Nevertheless, this report is provided ‘as is’ without any representations or warranty. It is within the responsibility of the user of this report to verify and to assess the validity and integrity of the content. The user uses this report and its content at his/her own risk. The author disclaims any and all representations and warranties, expressed or implied, such as, but without limitation, merchantability, fitness for any particular purpose, accuracy, completeness, correctness, infringement of third party intellectual property rights. To the extent permitted by applicable law, the author disclaims any and all liability for direct damages and/or indirect damages (e.g. consequential damages, loss of income, business or profit, reputation) occurring from the use of this report. Citation Atlantic Consulting (2018), BioLPG: The Renewable Future: A survey of markets, feedstocks, process technologies, projects and environmental impacts. Commissioned by Liquid Gas Europe – AEGPL/WLPGA., Gattikon (Zürich), Switzerland

Atlantic Consulting

Atlantic Consulting provides independent research and analysis about energy and chemicals to companies, governments and other interested organisations. Its work is focused on assessment of environmental impacts, markets and economics. The company was founded in 1994 in London, and since 2000 has been based in Gattikon, just outside of Zürich, Switzerland.

Bio LPG

The Renewable Future

A survey of markets, feedstocks, process

technologies, projects and

environmental impact

BioLPG: The Renewable Future

Contents Page

CHAPTER ONE

Introduction 6

CHAPTER TWO

Executive summary 7

CHAPTER THREE

What are LPG and BioLPG? 9

CHAPTER FOUR

BioLPG production and consumption, to 2022 10

4.1 Production in 2018 10

4.2 Consumption in 2018 11

4.3 How will this change by 2022? 11

CHAPTER FIVE

Potential BioLPG production and consumption, 2030-2050 13

5.1 Global potential 13

5.2 European potential 14

5.3 Method of estimation 14 5.3.1 Feedstock availability 14 5.3.2 Technology selection and conversion efficiency 15 5.3.3 Demand for liquid fuels and biofuels 15 5.3.4 Will potential become reality, and how will this split geographically? 15

BioLPG: The Renewable Future Page 4

CHAPTER SIX

Possible feedstocks for BioLPG 16

6.1 Close feedstocks 17

6.2 Distant feedstocks 17

CHAPTER SEVEN

Process technologies and projects for BioLPG 18

7.1 Structure of this chapter 19

7.2 Conventional chemical processes and projects 20 7.2.1 Hydrotreatment 20

7.2.1.1 Process description 20 7.2.1.2 Technical readiness 21 7.2.1.3 Process developers/licensors 21 7.2.1.4 Projects and production 21

7.2.1.4.1 Bio-oils 22 7.2.1.4.2 Two feedstock approaches: exclusive bio and co-process 22 7.2.1.4.3 Fatty acids (do not make biopropane) 23 7.2.1.4.4 Propylene and butylene 24 7.2.1.4.5 DME (dimethyl ether) 24

7.2.1.5 Hydrotreatment projects for BioLPG 25 7.2.2 Dehydration 30

7.2.2.1 Process description 30 7.2.2.2 Technical readiness 30 7.2.2.3 Other, possible dehydration feedstocks 31

7.3 Biological processes and projects 32 7.3.1 Fermentation 33 7.3.2 Hydrolysis and fermentation of cellulose 34 7.3.3 Digestion of organic wastes 35

7.3.3.1 Biomethane to propane, Alkcon 35 7.3.3.2 Bio-CO2 to propane and methane, ’FutureLPG’ 36

7.4 Advanced chemical processes and projects 36 7.4.1 Process descriptions 36

7.4.1.1 Gaseous conversion 36 7.4.1.1.1 Gasification 37 7.4.1.1.2 Pyrolysis 37

7.4.1.2 Liquid conversion 37 7.4.1.3 Synthesis 37

7.4.2 Technical readiness (with biomass/waste feedstock) 38 7.4.3 Process developers/licensors 38 7.4.4 Projects and production 39


7.4.4.1 Gaseous conversion and synthesis, cellulosics 40 7.4.4.1.1 Syngas synthesis 40 7.4.4.1.2 Pyrolysis and fast hydropyrolysis (IH2) 44

7.4.4.2 Gaseous conversion and synthesis projects (cellulosics) 44 7.4.4.3 Gaseous conversion and synthesis, mixed wastes (Advanced Conversion Technologies) 47 7.4.4.4 Liquid conversion and synthesis 48 7.4.4.5 Table of liquid conversion and synthesis 48

7.5 Other: Atmospheric carbon dioxide 49

CHAPTER EIGHT

BioLPG’s policy drivers 50

CHAPTER NINE

Marketing and distribution 51

CHAPTER TEN

Environmental impact 52

10.1 Carbon footprint of BioLPG 53 10.1.1 Carbon footprint of hydrotreated biopropane 53 10.1.2 Carbon footprint of biomass gasification & synthesis 54

10.2 The threat to palm oil and other vegetable oils 54

10.3 Carbon footprints/LCAs relevant to BioLPG 55

REFERENCES 58


Chapter One

Introduction

This report is aimed at the LPG industry, both its producers and distributors. It is also useful for readers who are interested or involved in energy policy. A modest amount of technical knowledge is assumed, but this is a survey, not an engineering study. The report surveys the markets, feedstocks, process technologies, projects and environmental impacts for BioLPG. It casts a broad net, i.e. it covers all the known, potentially feasible possibilities of production. It is based on public information, gathered over the course of years, and compiled in January-May 2018. To avoid any possible infraction of competition law, the report does not address economics and pricing. The report has been written on a ‘best efforts’ basis by Atlantic Consulting.


Chapter Two

Executive summary

BioLPG has made significant progress. In the past four years, production volumes have grown some 50% to around 200 thousand tonnes annually, and sales of branded BioLPG have begun in Europe and the USA. Although this is less than 1% of the market for fossil LPG, it is a robust start. And it is very much needed: now the LPG industry has a bio-alternative to match its competitors and to demonstrate its ‘bio credibility’ to both governments and customers. In the short term, the biggest potential for further expansion is co-processing, i.e. making BioLPG in conventional refineries using conventional hydrotreaters. This is attractive, because it uses existing processing units that already connect to the LPG distribution network. It could be considered a ‘drop in’ production method. Several refiners have entered co-processing already, and others are known to be exploring the possibility. At the same time, BioLPG faces two big challenges. The first is that government policy on biofuels, particularly European, has been inconsistent. Only a decade ago, some governments offered direct subsidies and rebates to biofuels. This proved too costly, so they moved to mandates, i.e. requiring a certain share of market to consist of biofuels. As many the industry’s numerous failed projects and bankruptcies suggest, economics and profits have been highly uncertain. The latest uncertainty is European governments’ policy on vegetable oils. Controversies of ‘food vs fuel’, indirect land-use change and destruction of natural habitat are driving possible restrictions or bans, particularly on palm but on other vegetable oils as well. Because these are major feedstocks of the today’s BioLPG industry, restricting them could maim or kill the industry just as it’s getting started. Longer term, there is a much bigger challenge: even if the maximum amount of BioLPG within bio-oil (available for biofuels) were produced, this would displace total LPG production by less than 2%. For individual LPG producers and distributors, this is an opportunity, but the industry as a whole would earn a black mark from many governments. The European Union, for example, is targeting an 80% reduction in carbon emissions by 2050: 2% BioLPG does not come close. The way to bridge this gap is called advanced chemical processing. Its main processes here are gasification, pyrolysis, Fischer-Tropsch and methanol-to-gasoline. Its highest-volume feedstock, by far, is cellulosics – residues from agriculture and forestry plus on-purpose energy crops. Another significant feedstock could be municipal waste. Its volumes are smaller and the technology more complex, but waste is readily available and comes with a ‘gate fee’ payment. If cellulosics and waste were to go seriously commercial, they could displace about one-third of LPG worldwide in 2030-2050. Will that happen? There are two main variables. First is government policy. Building and operating advanced chemical processes requires huge investments and huge changes in policy. Second is design choice. BioLPG output can vary, from one advanced chemical process to the next, from as low as zero to as much as 10% and maybe more. For policy makers and process developers to choose BioLPG, they need to:

know it exists have some incentive to choose it over other fuels they can make.

Making matters more complicated is BioLPG’s by-product status. Like fossil LPG, BioLPG is and will be usually produced as a minor output of a process aimed at making something else. This is a function of fuel chemistry and market demand, and so is not easy to change.


Recommendations LPG companies and industry associations can do several things to encourage BioLPG. Explore co-processing with refiners. Co-processing is the most-attractive short-term target. For it to

succeed, however, will require someone to…. Protect vegetable-oil use as biofuel feedstock. The arguments against vegetable oil are highly political –

and countless examples show that political opinion can change. The industry can join the debate, on behalf of existing and future producers.

Analyse and monitor governments’ plans to go bio. The ambition and enforcement of decarbonisation – the driving force behind biofuels – varies from place to place and, over time, within those places themselves. Ultimately, it is mainly governments that will drive production of biofuels in general and BioLPG in particular, or not.

Promote BioLPG-rich options. Governments serious about going bio, and some certainly are, should know how design choices can encourage or discourage BioLPG. Governments often do not know much about LPG, so must be taught. Biofuel-process-developers and -operators should be reminded, too. They know what LPG is, but they often lose sight of it. Even governments not serious about going bio probably should be told of BioLPG, just in case they someday decide to get serious.

Table 1: What the LPG industry can do to encourage BioLPG

Actors

Action LPG industry associations LPG producers/distributors

Explore co-processing Support Lead

Protect vegetable oil Lead Support

Analyse plans to go ‘bio’ Lead Support

Promote BioLPG-rich options Support Lead


Chapter Three

What is LPG and BioLPG?

Liquefied petroleum gas (LPG) describes hydrocarbon mixtures in which the main components are propane, butane, isobutane, propene, and butenes. Most commonly this term is applied to mixtures of propane and butane (Figure 1) (Thompson et al., 2011). Mixtures vary by market, and sometimes contain as much as 10% olefins. In the USA, LPG is 100% propane, while some markets (particularly in Asia) offer 100% propane and 100% butane. BioLPG is any of the above, except from not a ‘fossil’ source, but a ‘biological’ source. So BioLPG is any of the following, either by itself or mixed with each other:

BioPropane BioButane BioPropylene (biopropene) BioButylene/BioIsobutylene (biobutene/bioisobutene)

Figure 1: Structures of propane and butane, from bio or fossil sources

These bio products are, in commercial practice, identical to their fossil counterparts. That is, their chemical structure and physical properties are the same

1 – they just come from different sources.

With respect to fuels, the adjectives ‘fossil’ and ‘bio’ are well-established and generally understood. In theory, they could be confusing, because fossil fuels also stem from biological sources, i.e. ancient aggregations of plants and animals that over millions of years transformed into oil, gas and coal. In practice, however, most fossil- and bio-fuels are clearly delineated – certainly in the case of BioLPG they are. There are other names used for biofuels, not always entirely accurate: renewable fuels, natural fuels and more. Biofuels is probably most common, and most accurate, so it is used in this report.

1 Actually, their isotopic structures differ, and this difference is exploited to do radiocarbon dating of fossils. It is also used to identify and quantify ‘bio content’ of fuel samples. This isotopic structure is not known to affect their use as fuels, chemicals or propellants.


Chapter Four

BioLPG production and consumption, to 2022

Global production of BioLPG today is around 200 kilotonnes/year, just under 0.1% of all LPG production (Table 2, for more detail see Table 11). About half of BioLPG is branded as such for sale, the other half is consumed as fuel gas or as LPG. Nearly all the current output is biopropane, produced as a byproduct of hydrotreating bio-oils to make biodiesel.

4.1 Production in 2018

Production has increased by some 50% since the last public survey of the market (UK Dept of Energy & Climate Change et al., 2014). The biggest production trend is that of conventional refiners making BioLPG by co-processing bio-oils together with petroleum intermediates at a blend of around 30% bio and 70% fossil (see Section 7.2). Co-processing results in a mixed stream of diesel/biodiesel and another, smaller stream of mostly BioLPG. Co-processing can be done in existing hydrotreaters or hydrocrackers that undergo some modifications. At least one refiner is experimenting with co-processing bio-oil in a fluid catalytic cracker: again, BioLPG comes out as a by-product to biodiesel.

Table 2: Production of BioLPG, 20182

Owner/Operator Country Is biopropane

extracted? Biopropane, kt/y

3

Americas

Petrobras BR No NA

AltAir Fuels USA No 7

Renewable Energy Group USA Probably 1.3

Valero: Diamond Green Diesel USA Small quantities? 10

Europe

Global Bioenergies D Biobutylene, yes Biobutylene, 0.1

CEPSA ES Maybe NA

Repsol ES Probably starting in 2018 NA

Total F Starting in 2018 30

Eni I Yes 20

Irving Oil IE No 3

Neste Oil NL, SF Yes 90

GALP P Maybe NA

PREEM4 SE Yes 15

2 All information taken from public sources.

3 Production of biopropane has been estimated as a fraction of the reported production of HVO biodiesel.

Biobutylene production has been reported in the trade media. 4 The main feedstock for this is tall oil, which yields biodiesel but not biopropane. PREEM also processes other types of bio-oils that do yield biopropane.


Asia

Hitachi Zosen JP No 0.0

Neste Oil Singapore Yes Included in the

Neste total above

SUM Estimated 200

4.2 Consumption in 2018

Consumption of branded BioLPG – i.e. product explicitly labelled as such – is estimated at about 100 kilotonnes/year in 2018 (Table 3). The other production does not disappear; it just is not sold as BioLPG. Branded BioLPG has entered the market only in the past two years or so. At the time of the last public survey of the market (UK Dept of Energy & Climate Change et al., 2014), branded BioLPG sales were negligible.

Table 3: Consumption of branded BioLPG, 20185

Marketer

Producer Product

name Country Quantity,

kt/yr6

AGA PREEM? Ecoblend N, S NA

Butagaz Global Bioenergies Isobutylene D, F 0.1

NA Diamond Green Diesel Renewable naphtha

7 USA 3

ENI ENI Green LPG I 20

Kosangas PREEM Biomix DK, N NA

Not yet disclosed8 NA Biopropane USA NA

NA Renewable Energy Group Biopropane USA NA

SHV Energy Neste BioLPG D, DK, F, IR, UK 45

NA Total NA F 25

SUM Estimated 100

4.3 How will this change by 2022?

Two additional co-processing plants are planned: one at ENI’s refinery in Gela, Sicily, and another at PREEM’s refinery in Gothenburg, Sweden. Given that some 50 kilotonnes of co-processing capacity has been added in the last few years, we expect that other refiners are likely to add capacity as well. Global Bioenergies is reportedly planning a commercial-plant to make bio-isobutylene. Brazilian production continues to be a mystery: Petrobras built substantial hydrotreatment capacity, but never operated it to make biodiesel /biopropane, and then reportedly sold it BSBios earlier in 2018. Perhaps BSBios will operate some of it. Our rough estimate is that production will increase by 100 kt to 300 kt in 2022. Most or all of this production increase will come to market as branded BioLPG, we estimate. So consumption of branded BioLPG in 2022

5 All information taken from public sources.

6 Quantities have been estimated, based on public information about production and marketing.

7 Biopropane is blended with higher bio-hydrocarbons and sold as a naphtha blend.

8 A US marketer has made public, through government filings, that it will start marketing BioLPG. However, the

marketer asked the study author that its name not yet be published.


would rise to around 200 kt. The main threat to this scenario is a possible ban or restriction on the use of bio-oils as feedstock (see Section 10.2). If that happens, all bets are off. What about other sources of BioLPG? There are no others – yet. Longer term, the biggest potential comes from cellulosics and organic wastes being converted to liquid fuels by advanced chemical processes. The outlook for this is presented in the next chapter.


Chapter Five

Potential BioLPG production and consumption, 2030-2050

How much BioLPG could be produced in the long term? The production potential or technical limit for BioLPG is presented in this chapter: first, the global potential, then the European potential, and finally, the method used to estimate these potentials. This is not a forecast: it is an estimate of what could be. If this potential is to become reality, it will require enormous effort: from governments, from the energy industry in general and the LPG industry in specific. Converting wastes and cellulosics into liquid fuels – rather than producing those fuels in conventional petroleum refineries – is a massive undertaking, not just technologically but financially, legally and economically. Surely this is not something the LPG industry can bring about by itself, but it can be part of the part of the trend by partnering with governments, technology developers (see Chapter 0) and other energy producers/distributors. For LPG companies, this will likely be a balancing act. On one hand they cannot afford to invest heavily in every new technology that comes along: there will be false starts and dead ends, as there always are in business. On the other hand, they cannot afford to ignore the ‘bio’ imperative. In some markets, not going bio – at least to some extent – raises a serious threat of being restricted, taxed out of existence or even banned.

5.1 Global potential

Today’s BioLPG production is negligible in percentage terms, but if advanced chemical processes are commercialised to process cellulosics and mixed waste feedstocks, and if bio-oil hydrotreating is maximised, enough BioLPG could be produced in 2030-2050 to cover up to one third of global LPG production.

Table 4: Potential global BioLPG production in the long term (million tonnes/year)

Feedstock 2018 2030 2040 2050 Process path

Cellulosics 0 94

101 108 Advanced chemical processes

Mixed waste 0 15


Bio-oils 0.2 3.3 4.2 5.2 Hydrotreating

Sugar < 0.1 0.15 0.15 0.15 Fermentation

Product

BioLPG 0.2 112 120 128

% LPG demand 0.07% 33% 33% 33%

Cellulosics – agricultural and forest residues plus energy crops such as switchgrass and poplar – are the key. These are by far the largest supply of biological hydrocarbons. Mixed waste (mainly municipal waste) is significant as well, but still nearly an order-of-magnitude less available than cellulosics (International Renewable Energy Agency, 2016). Bio-oils, if exploited to the maximum, could also deliver significant output. As noted above, producing fuels from wastes and cellulosics would require enormous effort. If this does not happen, a ‘business-as-usual’ potential for BioLPG would not include cellulosics and mixed waste. Potential would be limited to production from bio-oils and sugar (Table 4).


5.2 European potential

Today’s BioLPG production is negligible in percentage terms, but if advanced chemical processes are commercialised to process cellulosics and mixed waste feedstocks, and if bio-oil hydrotreating is maximised, BioLPG could be produced in 2030-2050 in quantities of some 20-25 million tonnes per year (Table 5).

Table 5: Potential European BioLPG production in the long term (million tonnes/year)

Feedstock 2018 2030 2040 2050 Process path

Cellulosics 0 15


Mixed waste 0 1

1.5 2 Advanced chemical processes

Bio-oils 0.15 2 2.5 3 Hydrotreating

Sugar < 0.1 0.15 0.15 0.15 Fermentation

Product

BioLPG 0.15 18 21 24

In 2030 and 2040, potential European BioLPG production amounts to 82% and 97%, respectively, of European LPG demand as estimated by (IHS Markit, 2016). As noted above, producing fuels from wastes and cellulosics would require enormous effort. If this does not happen, a ‘business-as-usual’ potential for BioLPG would not include cellulosics and mixed waste. Potential would be limited to production from bio-oils and sugar (Table 5).

5.3 Method of estimation

Potential production is a function of: feedstock availability; technology selection and the efficiency of those technologies; and demand for liquid fuels and biofuels. These are discussed in the first three subsections. A final subsection discusses how potential might convert into reality, and how this might split geographically.

5.3.1 Feedstock availability

To estimate future feedstock availability, three sources were used: for cellulosics and mixed wastes, a report from (International Renewable Energy Agency, 2016, Annex C); for vegetable oils, a report from an industry association (UFOP, 2017); and for inedible tallow and grease, industry publications

9.

For cellulosics and mixed wastes, availability estimates were taken straight from Annex C of (International Renewable Energy Agency, 2016) (Table 6).

Table 6: Cellulosic and mixed-waste feedstock availability, 2030-2050 (exajoules10

/year)

Cellulosics

Mixed waste Ag residues Forest residues Energy crops Total

Availability 2030 13 25 18 40 96

Availability 2050 13 41 20 96 170

9 http://pubs.rendermagazine.com/2016-04/pubData/source/Render_Apr16.pdf and

http://www.crbtrader.com/fund/articles/tallow.asp 10

An exajoule is 1018

joules.

http://pubs.rendermagazine.com/2016-04/pubData/source/Render_Apr16.pdf

http://www.crbtrader.com/fund/articles/tallow.asp


For inedible tallow and grease availability, current production of 7 million tonnes per year was projected forward at the current growth rate of 0.5%. Vegetable oils availability was based on current production and growth rates projected forward, plus a factor of how much of this production will be made available as biofuel feedstock (see Section 10.2). This factor is projected to stay constant, at today’s level, of 5%. The triglyceride content of these availabilities is assumed to be converted into biopropane (Table 7).

Table 7: Bio-oil feedstock availability, 2030-2050 (million tonnes/year)

1962 2002 2012 2018 Annual

growth rate 2030 2050

Inedible tallow & grease

7 0.50% 7 8

Vegetable oils 16 93 162 195 3.14% 283 524

Vegetable oil % for biofuels

5.04%

14 26

Total triglycerides to biofuel 22 35

Triglyceride mol wt, typical 292 292

Propane mol wt

44 44

Biopropane, Mtonne

3.3 5.2

5.3.2 Technology selection and conversion efficiency

For bio-oils, the technology is assumed to be hydrotreatment (see Section 7.2.1) and efficiency (of converting triglycerides to biopropane) is assumed at 100%. For cellulosics and mixed wastes, we have assumed that 70% (estimate of this report’s author) of these would be processed by gasification and synthesis (see Section 7.4) at a process efficiency of 61% (International Renewable Energy Agency, 2016, p 111), giving a BioLPG of 7.5% (see Section 7.4).

5.3.3 Demand for liquid fuels and biofuels

Future, global demand for liquid fuels and biofuels was taken from (International Renewable Energy Agency, 2016, p 17), and from this was imputed the future, global demand for LPG.

5.3.4 Will potential become reality, and how will this split geographically?

This is a potential, a technical limit, which raises the question of how will this translate to reality? This will depend on three main variables, in descending order of importance:

Government policy to promote advanced chemical processes for production of biofuels. These processes are outlined in the next chapter.

Design choices that maximise (or not) output of BioLPG. Advanced chemical processes can be designed to generate no BioLPG or up to 10% by weight of total output.

Government support for use of bio-oils in making biofuels. Economics of course play a role as well. But probably the biggest factor in energy economics – at least

in the time-frame considered – is how governments define the economic playing field. This can be done with a variety of policy instruments: mandates, tax breaks, subsidies, white/green certificates as well as restrictions or bans.

As for the geographic split, the potential for Europe (Table 5) was derived from the global potential (Table 4). It is assumed that cellulosics and mixed wastes will be processed in the region they are produced, because collection costs are a key economic barrier, and that favourable government policies and public demand will encourage a disproportionate amount of bio-oil processing. This final point is of course debatable (see Section 10.2).


Chapter Six

Possible feedstocks for BioLPG

Feedstocks and processes for making BioLPG have a chicken-and-egg relation: close, and difficult to say which one comes first. In this chapter we’ll start with feedstocks. In theory, any biological sources of carbon and hydrogen can be synthesised to BioLPG. In practice, the most attractive feedstocks will be those already close in structure to the targets: propyl or butyl hydrocarbons. Those ‘close’ feedstocks are:

Bio-oils (triglycerides) Bio C3/C4 compounds Sugars (C5/C6 compounds)

‘Distant’ feedstocks are of three types:

Cellulosics Organic wastes (not of the ‘close’ type) Atmospheric carbon dioxide

These close and distant feedstocks can be fit into a matrix against the processes that can convert them into BioLPG ( Figure 2). Processes are grouped into three types:

Conventional chemical Biological Advanced chemical

This matrix defines the structure of this feedstock-process analysis presented in this report. This chapter focuses on feedstocks, the next chapter on the processes.

Figure 2: The feedstock-process matrix for BioLPG

Feedstock Type

CLOSE Bio-oils, bio C3/C4 compounds and

sugars

DISTANT Cellulosics, organic wastes and

atmospheric CO2

Pro

cess

Typ

es Conventional

chemical Hydrotreatment

Dehydrogenation

Biological Fermentation Hydrolysis and fermentation

Digestion

Advanced chemical

Gaseous conversion and synthesis Liquid conversion and synthesis

The other key classification for biofuel feedstocks is: product, residue or waste. This classification can have a major impact on a biofuel’s carbon footprint, but it does not fit neatly into the feedstock-process matrix, because it is not defined consistently. At present, a feedstock’s status as product/revenue/waste can be determined only on a case-by-case basis. This is reviewed in Chapter 0. There are other ways to classify biofuels. Perhaps the most-common way is by ‘generations’: 1

st-generation

biofuels, 2nd

-generation biofuels and so on. Unfortunately, except to insiders, ‘generation’ says little about what it members are. And even insiders are inconsistent. For instance, (United Nations Conference on Trade and Development (UNCTAD), 2015, p 10) defines first generation biofuels as ‘from seeds, grains or sugars’ and


second generation as ‘from lignocellulosic biomass, such as crop residues, woody crops or energy grasses’. But (Stephen and Periyasamy, 2018, p 624) says that first generation is from ‘food products’, second generation includes waste oils such as used cooking oil, third generation is from algae, and fourth generation starts with carbon-dioxide from carbon capture and storage. A review of similar literature reveals similar disagreement and variation.

6.1 Close feedstocks

There are a limited number of bio feedstocks are that are relatively close to C3 or C4 hydrocarbons (Table 8).

Table 8: Close feedstocks for BioLPG

Feedstock Structure Sources

Bio-oils Triglyceride – the propyl backbone can be converted to propane

Algae Animal fats/tallow Plant oils: Jatropha, Palm, Peanut, Rapeseed (Canola), Soybean, Sunflower.

Bio C3 or C4 Propyl and butyl Bio-propylene (3) Glycerine (3) Bio-butylene (4) Butyric acid (4)

Bio C5 or C6 Penta and Hexa Sugars and starches

6.2 Distant feedstocks

There are a limited number of bio feedstocks are that are relatively close to C3 or C4 hydrocarbons (Table 9).

Table 9: Distant feedstocks for BioLPG

Feedstock Structure Sources

Cellulosics Polymeric hydrocarbons with about 25% oxygen content by weight

Agricultural residues Corn (maize) stover (stalks and leaves) Food processing waste Rice husks Sugarcane bagasse Wood Woody biomass

Forest residues Small round wood Arboricultural arisings Sawmill co products Short rotation forestry

Wheat straw, other straw

Mixed waste Hydrocarbons and cellulosics. About 20-30% of the total hydrocarbons in municipal waste are fossil-based.

Municipal waste Sewage sludge

Atmospheric carbon

dioxide11

Air and water

11 Strictly speaking, this yields renewable LPG, but not BioLPG. Water is not bio, it is considered an inorganic, non-biological resource. Of atmospheric carbon dioxide, only about one-quarter is biological, the rest is inorganic. So these fuels would be renewable, but not biological.


Chapter Seven

Process technologies and projects for BioLPG

The process types presented in the preceding chapter can be detailed as process classes and summarised with feedstocks, product/by-product status and technical readiness (Table 10). The two in green are most promising:

Hydrotreating of bio-oils is already producing 200 kilotonnes of biopropane, with additions to come (see Chapter 0).

Gaseous conversion & synthesis of cellulosics and organic waste does not yet generate any BioLPG, but BioLPG production this way is technically feasible, is under exploration and potential feedstock availability is huge.

Dehydrogenation offers some potential, mainly in the use of fluid catalytic crackers to process bio-oils and make some by-product biopropane. Glycerine also can be dehydrogenated, and this is being explored. Fermentation already is producing small amounts of biobutylene, and planning in underway for commercial production. Fermentation to biopropane has been proven at laboratory scale, but does not seem to be progressing further. The two other biological process classes, hydrolysis & fermentation and digestion, do not offer serious promise of generating BioLPG. Neither does liquid conversion & synthesis, which technically is not all that different than gaseous conversion and synthesis, but attracts significantly less attention from developers.

Table 10: Feedstock-process summary for BioLPG

Feedstock Process class Product/

Byproduct

Technical Readiness

Bio-oil Hydrotreating By Commercial

Bio-oil

Glycerine Dehydrogenation

By

Pro

Demonstration

Pilot

Sugars Fermentation Pro Demonstration

Cellulosics Hydrolysis & fermentation -- Concept

Wet wastes Digestion -- Concept

Cellulosics

Organic waste

Gaseous conversion & synthesis

By Demonstration

Concept

Cellulosics

Organic waste Liquid conversion & synthesis By Concept

In most cases, BioLPG is produced as a by-product, or perhaps it could be called a ‘minor’ output of a multi-product process. Moreover, BioLPG’s proportion of output can vary according to detailed process design: for example, the advanced chemical processes can produce BioLPG at anywhere from 0-10% of output.


7.1 Structure of this chapter

As noted in the preceding chapter, there are three process types that lead to BioLPG: conventional chemical, biological and advanced chemical. These have been used to organise process classes and individual processes that are presented in this chapter. Each of these is covered in a section of this chapter, subsections are devoted to the individual processes and the projects pursuing those. Each process type is described, and then the individual processes and projects are described by feedstock type. All known BioLPG processes are covered. Project is defined broadly. To them we have applied the following classifications of ‘technology readiness’ that are widely used in the process industries:

Concept Laboratory Pilot Demonstration First commercial Commercial For license (this applies to processes developed explicitly for licensing to 3

rd-party owner/operators)

Projects can be associated with owner/operators, with process licensors or with both. The way this report approaches BioLPG is similar to how biofuels are approached in general (Figure 3). The three process types correspond fairly closely to the ‘conversion steps’.

Figure 3: Bio-feedstock conversion to biofuels

Source: (Dovetail Partners et al., 2017)


7.2 Conventional chemical processes and projects

These are synthetic processes that are well-known and commercially well-established: hydrotreatment and dehydration. Hydrotreatment is, to date, the only significant source of BioLPG. Dehydration produces negligible BioLPG so far, but could be expanded. The biggest market trend is that of conventional refiners making BioLPG by co-processing bio-oils together with petroleum intermediates at a blend of around 30% bio and 70% fossil. This results in a mixed stream of diesel/biodiesel and another, smaller stream of mostly BioLPG. Co-processing can be done in existing hydrotreaters or hydrocrackers that undergo some modifications. At least one refiner is experimenting with co-processing bio-oil in a fluid catalytic cracker: again, BioLPG comes out as a by-product to biodiesel.

7.2.1 Hydrotreatment

Hydrotreatment, or hydrogenation, is the only significant source today of BioLPG production, an estimated 200 kilotonnes per year (Table 11 for detail, for a summary see Table 2). About 100 kilotonnes of the biopropane produced is extracted for sale as BioLPG, the rest is used as a process fuel. None of the production is ‘on-purpose’, i.e. the biopropane is an unavoidable byproduct. The ‘on-purpose’ product is HVO biodiesel, often called renewable diesel. By weight the ratio of biodiesel:biopropane output is about 9-10:1. Neste is the largest producer of BioLPG (biopropane), making about 90 kilotonnes/year at three locations. ENI is second-largest, making a 20 kilotonnes/year and planning another 20-kt project. Projects of all types number to about 40, about 25 of those are commercial or first-commercial operations, and about 10 of those are believed to be in operation. All of them convert bio-oils to biodiesel and produce biopropane as a byproduct. Neste and ENI, plus two US producers operate ‘exclusive’ biodiesel/biopropane plants, i.e. they run exclusively on bio feedstocks. Another six producers are conventional oil refiners that are co-processing bio-oils together with petroleum streams at approximately a 30/70 ratio by weight. This produces a mixed stream of diesel/biodiesel and propane/biopropane. Other refiners are known to be investigating this opportunity. Most if not all of the biopropane producers hydrotreat some bio fatty acids along with bio-oils. The fatty acids convert to biodiesel, but they do not yield any biopropane. The hydrotreatment process is well understood and is available from several vendors for license. Other feedstocks than bio-oils could be hydrotreated to synthesise biopropane or biobutane. None of these are close to commercialisation.

7.2.1.1 Process description

Hydrotreatment is a reaction of a hydrocarbon stream with hydrogen, usually in the presence of a catalyst, at moderate temperature and pressure. It is applied mainly in two ways: to hydrogenate unsaturated bonds, to remove oxygen or to reduce inorganic components such as nitrogen or sulphur. Depending on conditions, the process can cause a variety of reactions can occur (Figure 4). In the context of BioLPG, the most important of these are decarboxylation, hydrodeoxygenation and hydrogenation (Soucek et al., 2016) (ecoresources and Natural Resources Canada, 2012). With regard to BioLPG, hydrotreatment goes by a variety of names. The process for converting triglyceride bio-oils to biodiesel and biopropane is often called ‘HVO’, which comes from ‘Hydrotreated Vegetable Oil’ or ‘Hydrogenated Vegetable Oil’. Other names for it include: ‘HDRD’ for ‘Hydrogenation Derived Renewable Diesel’, ‘Non Ester Renewable Diesel’, ‘Renewable Hydrocarbon Diesel’, ‘HBD’ for ‘Hydro-generated Biodiesel’ (Engman et al., 2016) and ‘HEFA’ for ‘hydroprocessed esters and fatty acids’. Another generic name would be


‘hydrogenation’, however, this is usually linked to the manufacturing of margarine12

, so hydrotreatment seems to be the best generic choice.

Figure 4: The reactions of hydrotreating

7.2.1.2 Technical readiness

Hydrotreating in general is mature, commercial process. It is widely used in petroleum refineries, particularly to remove sulphur from refined products. Refiners also practise a more severe form of hydrogenation, at higher temperatures and pressures, called hydrocracking (Figure 4). This cracks or splits longer hydrocarbons into shorter ones. Hydrotreating is also applied to make margarine. Liquid vegetable oils are saturated by hydrotreating, to create a solid: hydrogenated vegetable oil. Hydrotreating to create biodiesel and biopropane is less mature, maybe 20 years old, but still well established. Nearly 30 commercial or first-commercial projects exist worldwide (Table 11), and several vendors offer a version of the biodiesel/biopropane process for license.

7.2.1.3 Process developers/licensors

Six companies offer a biodiesel hydrotreatment process for license (Table 11). This report reckons UOP and ENI as one company, in this respect, because they jointly offer a process. Petrobras is not on the list. Although the Brazilian oil company has developed its own process, H-BIO, it is not clear whether this is available for license to third parties.

7.2.1.4 Projects and production Several feedstocks can be hydrotreated to create BioLPG: bio-oils, propylene, butylenes and dimethyl ether (DME). The only commercially significant one is bio-oil. In turn, it is the only significant source of BioLPG.

12

Another instance of hydrotreatment.


7.2.1.4.1 Bio-oils

This is the only significant source today of BioLPG production, an estimated 200 kilotonnes per year (Table 11 for detail, for a summary see Table 2). About 100 kilotonnes of the biopropane produced is extracted for sale as BioLPG, the rest is used as a process fuel. None of the production is ‘on-purpose’, i.e. the biopropane is an unavoidable byproduct. The ‘on-purpose’ product is HVO biodiesel, often called renewable diesel. By weight the ratio of biodiesel:biopropane output is about 9-10:1. Biopropane is a byproduct, because bio-oils (natural oils from animals and plants) all come in the form of a triglyceride. These (Figure 5) are long-chain hydrocarbons (in yellow) connected by an ester linkage (where yellow and brown meet) to a three-carbon (in brown) backbone.

Figure 5: A typical triglyceride (natural oil or fat)

Hydrogen is reacted with the triglycerides at temperature and pressure in the presence of catalysts to hydrogenate the double bonds in the fatty acid chains in the triglyceride. Next, the glycerol backbone is broken and the oxygen removed, leaving paraffinic n-alkanes – the biodiesel – and the hydrogenated three-carbon backbone, biopropane (ecoresources and Natural Resources Canada, 2012) (Figure 6).

Figure 6: A schematic view of the process, bio-oil to biodiesel and biopropane

7.2.1.4.2 Two feedstock approaches: exclusive bio and co-process

For hydrotreating bio-oils, there are two approaches to feedstocks. One is to process only bio feedstocks. Neste and ENI, plus two US producers Renewable Energy Group and Valero do this. They operate ‘exclusive’ biodiesel/biopropane plants that run exclusively on bio feedstocks. Another is to co-process bio and fossil feedstocks. Five producers – CEPSA, Galp, Irving Oil, PREEM and Repsol – are conventional oil refiners that are co-processing petroleum streams together with bio-oils at approximately a 70/30 ratio by weight. This produces a mixed stream of diesel/biodiesel and


propane/biopropane. Other refiners are known to be investigating this opportunity: Naftna Industrija Srbije at Novi Sad, Serbia (Soucek et al., 2016), ÖMV and PKN Orlen. They are using existing refinery hydrotreaters that have been modified to handle bio-oils. Modifications are required, because bio-oils are oxygenates (the ester linkage), so they react differently to their petroleum counterparts (Haldor Topsoe et al., 2010) (De Paz Carmona et al., 2018). PREEM is known to have applied Haldor Topsoe’s Hydroflex process for its modifications. Total is believed to have used the VEGAN process from Axens/IFP.

7.2.1.4.3 Fatty acids (do not make biopropane)

Fatty acids are also suitable feedstocks to make HVO biodiesel, but not for BioLPG. If fatty acids were to displace bio-oils in hydrogenation processes, biopropane production would disappear. Most of the commercial projects making HVO biodiesel (Table 11) use bio-oils as feedstocks. Because these are triglycerides, they also automatically produce biopropane. However, some of the projects also take fatty acids as feedstock. The fatty acids usually are mixed into the bio-oil, but in some cases the feedstock is all fatty acid:

PFAD, or palm fatty acid distillate – crude palm oil has a fraction of fatty acids that usually is removed by distillation and sold separately.

Tall oil – this comes from wood, and is produced as a byproduct of pulping (to make paper). It is not an oil, but a collection of fatty acids.

Fatty acids are similar to triglycerides in that they have a long chain hydrocarbon connected to a carboxyl group (Figure 7), but the carboxyl stops there – it is the acid. It does not connect to a three-carbon backbone that could be converted to biopropane.

Figure 7: Structure of a typical fatty acid

Just one HVO biodiesel producer (Table 11) is known to use only fatty acid feedstock: UPM in Lappeenranta, Finland. The plant takes tall oil from a nearby pulping operation. The HVO production of PREEM in Gothenburg, Sweden, reportedly ran only on tall oil when it began operations, but has since moved to triglycerides (to what fraction is unclear). Other HVO producers take some fraction of fatty acids along with bio-oils, often as acid-oil mixtures. These mixtures tend to be cheaper, are inedible to humans, and sometimes classified as wastes (which leads to a lower carbon footprint, as discussed in Chapter 10.1).


7.2.1.4.4 Propylene and butylene

Biopropylene could be hydrotreated to biopropane, and biobutylene could be hydrotreated to biobutane. While these are chemically feasible options, they are unlikely to attract much commercial interest, because either biopropylene or biobutylene could be sold on their own, without further processing. Bio-olefins (ethylene, propylene, butylene) are not plentiful. Some bio-ethylene is produced in Brazil (from sugarcane), and this is sold to make bio-polyethylene. Braskem, the Brazilian chemical company, has investigated making bio-propylene, but has mothballed the idea as uneconomic. Bio-butylene is being produced in small quantities (see Section 7.3.1.), but this is sold as such and not committed further to hydrotreating.

7.2.1.4.5 DME (dimethyl ether)

Japan’s University of Kitakyushu has developed a laboratory-scale process for the conversion of DME to LPG by hydrogenation (NREL - National Renewable Energy Laboratory, 2018, p 30).

This could be done using bio-DME, to yield BioLPG. Bio-DME can be produced by catalytic dehydration of bio-methanol. Bio-DME can also be made from bio-syngas, i.e. gasified cellulosics or organic wastes (see

Section 7.4.4.1.1.).


7.2.1.5 Hydrotreatment projects for BioLPG

Table 11: Hydrotreatment projects for BioLPG, by technological readiness13

Owner/ Operator

Country Location Feedstock(s) Process Process licensor

Prime Product

Prime Product capacity

kt/y

Is biopropane extracted?

Bioprop capacity

kt/y14

Status 2018

COMMERCIAL

AltAir Fuels

USA Paramount, CA

Tallow Hydrocracker UOP

Biodiesel 130

No 7 Operating

BP AUS Bulwer Island Bio oil HVO

Biodiesel

No 3 Shut down

CEPSA ES Tenerife UCO

Hydrotreater? Co-process

Biodiesel

NA

Operating

CEPSA ES Huelva & Algeciras-San Roque

Bio oil Hydrotreater? Co-process

Biodiesel 180 NA

Operating

Eni I Porto Marghera

Bio oil HVO UOP/ENI

Biodiesel 580 Yes 20 Operating

Eni I Gela, Sicily Bio oil HVO UOP/ENI

Biodiesel 500

Startup later in year?

Galp P Sines Bio oil Hydrotreater Co-process

Biodiesel 250

Irving Oil (former ConocoPhillips)

IE Whitegate Soybean oil Hydrogenation, co-processing

ConocoPhillips

Biodiesel 46

Possible, but company says is 'technically difficult'

3.22 Operating

13

All information taken from public sources. 14

These have been estimated from biodiesel capacities.


Owner/ Operator


Prime Product


kt/y


Bioprop capacity

kt/y14

Status 2018

Neste Oil NL Rotterdam Bio oil HVO Neste-Jacobs

Biodiesel 1,000 yes 40 Operating

Neste Oil SF Porvoo Bio oil HVO Neste-Jacobs

Biodiesel 380 Yes? 10 Operating

Neste Oil Singapore

Singapore Bio oil HVO Neste-Jacobs

Biodiesel 1,000 No 40 Operating

Petrobras P

Bio oil

Biodiesel

NA

PREEM SE Gothenburg Tall oil, now also triglycerides

Hydrogenation, co-processing

Haldor-Topsoe

Biodiesel 300 Yes, sold to Kosan Gas No, tall

oil?

Operating Capacity addition planned

Renewable Energy Group (former Dynamic Fuels)

USA Geismar, LA

High and low FFA feedstocks, heavy on tallow

HVO Syntroleum Biodiesel 270

1.3

Repsol ES

La Coruña, Tarragona, Bilbao and Cartagena Palm oil

Hydrogenation, co-processing

Biodiesel 60 starting 2018

Valero: Diamond Green Diesel

USA Norco, LA Tallow HVO

UOP/ENI

Biodiesel 500 Small quantities?

10

FIRST COMMERCIAL

BSBios

BR

Passo Fundo, Marialva

Bio oil HVO & FAME Petrobras Biodiesel 2 x 230

Owner/ Operator


Prime Product


kt/y


Bioprop capacity

kt/y14

Status 2018

Emerald Biofuels

USA Jennings, Louisiana

Non-edible oils/fats

HVO

UOP/ENI

Biodiesel 280

Construction?

Endicott Biofuels

USA Port Arthur, TX

Bio oil

Biodiesel 90

Concept only?

Hitachi Zosen

J Kyoto Bio oil HVO Nippon Oil or Hitachi Zosen

Biodiesel 1 No 0.0 Operating

Pertamina Indonesia

Palm oil? HVO?

Biodiesel 500

Petrixo UAE Fujairah Bio oil HVO

UOP/ENI Biodiesel 400

Probably cancelled

Petrobras BR Passo Fundo, Marialva

Bio oil HVO & FAME

Biodiesel 2 x 230 No NA Shut down 2016-17

Sinopec PRC Shanghai? Bio oil HVO

Biodiesel 20

Planned?

Total FR La Mède Bio oil HVO

Axens/IFP Biodiesel 650 Planned 30 Construction

UPM SF Lappeenranta Tall oil HVO UPM Biodiesel 100 No No, tall

oil? Operating


Owner/ Operator


Prime Product


kt/y


Bioprop capacity

kt/y14

Status 2018

DEMONSTRATION

Gas Technology Institute

India Bangalore

Residues, wood, stover, bagasse, algae

Hydrogenation, fluid bed

Gas Technology Institute

Gasoline, jet, diesel

Commissioning

LABORATORY

La Laguna Univ ES

UCO and atmospheric gasoil

Hydrogenation, co-processing with Atm gasoil

Biodiesel

Mississippi, University of USA

Oils, fats

Mississippi, University of

Biopropane

NIS Serbia Novi Sad Bio oil HVO

Biodiesel

Study

ÖMV A

Bio oil Hydrogenation, co-processing Biodiesel

PKN Orlen PL

Bio oil Hydrogenation, co-processing

Biodiesel

Sun Carbon

SE Tygelsjö Lignin, from pulp mills

Lignin-to-biodiesel

SunCarbon Biodiesel

Small amounts would be produced

Design

Unipetrol CZ

UCO and atmospheric gasoil

Hydrogenation, co-processing with Atm gasoil

Biodiesel

FOR LICENSE

Axens/IFP FR

HVO Axens/IFP Biodiesel

Owner/ Operator


Prime Product


kt/y


Bioprop capacity

kt/y14

Status 2018

Chevron USA

HVO Chevron Biodiesel

Haldor-Topsoe DK

Bio oil HVO

Haldor-Topsoe

Biodiesel

Hulteberg C&Engineering SE

Bio oil Hydrogenation, co-processing

Biodiesel

Design

Syntroleum USA

Bio oil HVO

Syntroleum Biodiesel

UOP/ENI USA/I

Bio oil HVO UOP/ENI Biodiesel

Sources : The information presented above has been compiled from public sources, including periodicals, reports, company websites and communications with the industry, plus estimates based on all of those.


7.2.2 Dehydration

Dehydration is a possible route to BioLPG. Minor quantities of BioLPG are being produced by 2-3 operators. Another operator is considering commercial-scale production. Two feedstocks come into primary consideration: bio-oil and glycerine. Dehydration is also used to create longer-chain hydrocarbons from alcohols. So far, nobody appears to be working with propanol or butanol, but both are technically possible.

7.2.2.1 Process description

Dehydration is the removal of water (H2O) from a larger molecule. The most common application is the conversion of alcohols to alkanes or alkenes. For instance, there is some commercial production of ethylene from ethanol, and styrene from benzyl alcohol.

7.2.2.2 Technical readiness

As a chemical process in general, dehydration is a mature, commercial one. Most of the knowledge is not focused on the production of BioLPG. Nonetheless, three processes are at a pilot-demonstration level for producing biopropane (Table 12).

Table 12: Dehydration projects that might produce BioLPG

Owner/Operator Country Location Feedstock(s) Process Prime

Product Tech

Readiness

BioFuel Solution SE Limhamn Glycerol

Dehydrogenation

Biopropane Laboratory

Enysn USA

Bio-oil?

Fluid catalytic cracking

Biodiesel Unknown

Petrobras BR Sao Mateus do Sul

Petroleum gasoil 80-90% + bio-oil 10-20%

Fluid catalytic cracking

Biodiesel Demonstration

Renewable Energy Group

USA Geismar, LA Glycerin Dehydrogenation

Biopropane Concept

Tesoro USA Martinez, CA Bio-oil Fluid catalytic cracking

Biodiesel Demonstration

Petrobras and Tesoro are reportedly feeding bio-oils to fluid catalytic crackers (FCCs) at conventional petroleum refineries, respectively in Brazil and the USA. (Ensyn, a US-based company, is also reportedly testing cat-cracking of bio-oils, and is also reportedly working with Tesoro in California.) FCCs are a significant source of C3s and C4s in refineries, but these are mostly olefinic, i.e. propylene and butylenes. Some propane and butane are usually co-produced. The outputs of these particular FCCs is not clear. The third process to go beyond a concept is dehydration of glycerol to biopropane. Glycerol is a logical feedstock candidate for propane, because of their similar structures (Figure 8). BioFuel Solution has published a detailed paper on its process (Brandin et al., 2008) and in 2015 secured a European Patent EP 2 358 653 B1

15

for it. The process involves a number of intermediate reactions between glycerol and propane.

15

https://patents.google.com/patent/EP2358653B1/en


At least one producer is considering converting glycerine to biopropane. Renewable Energy Group is investigating the production of some 65 kilotonnes/year of biopropane from about twice as much glycerine feedstock (Renewable Energy Group, 2017). Renewable Energy appears to be considering a direct conversion of glycerine to propane (Figure 8).

Figure 8: Renewable Energy Group’s glycerine-to-biopropane process

7.2.2.3 Other, possible dehydration feedstocks

There are other possibilities for dehydration to BioLPG – all of them fairly remote from commercialisation. (Bio) propanol and butanol are could be dehydrated into propane and butane. As (E4tech, 2017) reports, short chain alcohols (such as ethanol, methanol, n-butanol and isobutanol) can be catalytically converted to hydrocarbon fuels, but most of the work in this area is aimed at gasoline, diesel and jet fuel. The conversion of ethanol or butanol molecules typically involves a combination of dehydration (to ethene or butene), then oligomerisation reactions (combining molecules into longer-chains), followed by hydrogenation (adding hydrogen), isomerisation (branching to meet fuel specifications) and finally distillation into the required product streams. There is no known production of biopropanol, but a BP/DuPont joint-venture called Butamax has pursued development of biobutanol. The work has gone on for at least a decade, with plants announced but then not built. Its current commercial status is unclear. In any case, the target market for that biobutanol (should it ever be produced) is as a high-octane additive to gasoline. Bio-methanol can be converted to propylene via the Lurgi process, and then further dehydrogenated to propane (NREL - National Renewable Energy Laboratory, 2018, p 26). Bio-methanol can also be converted to gasoline, which generates BioLPG as a byproduct (E4tech, 2017) (see Section 7.4.4.1.1.2). Bio-ethanol is the starting point of a Braskem process that can produce biopropane (Figure 9) (NREL - National Renewable Energy Laboratory, 2018, p 29). Braskem is known to operate the dehydration to ethylene, which is sold to make polyethylene. That bio-polyethylene is sold mainly for packaging of bio-cosmetics and so fetches a premium price. Although the conversion to propylene/propane is technically possible, Braskem says it is not pursuing other uses of the ethylene.


Figure 9: Braskem process for ethanol to propane

Several bioalcohol-to-hydrocarbon projects have been identified during this project (Table 13). This list is not exhaustive, and because none of them are believed to make BioLPG, it is not meant to be exhaustive. Nonetheless, it is one more possible route to BioLPG.

Table 13: A selection of alcohol-to-hydrocarbon projects

Owner/Operator Country Feedstock(s) Prime

Product Tech Readiness

Swedish Biofuels / KTH S Ethanol, butanol Jet fuel Laboratory

Swedish Biofuels S Wood, wastes Jet fuel First commercial

Byogy / Texas A&M University

USA Ethanol Diesel Unknown

Energy Biosciences Institute/BP

USA Corn (Maize) Diesel Unknown

Gevo USA Corn (Maize) Jet fuel First commercial

Gevo USA Corn (Maize) Jet fuel Demonstration

PNNL / Imperium / Lanzatech

USA Wood syngas Jet fuel Demonstration

Sundrop Fuels / ExxonMobil

USA Wood syngas + nat gas H2 Gasoline First commercial

Swedish Biofuels / Lanzatech

USA Syngas, steel mill Jet fuel Demonstration

7.3 Biological processes and projects

These three biological processes that can lead to BioLPG are fermentation, hydrolysis & fermentation, and digestion. All are well-known, and both fermentation and digestion are commercially well-established, albeit not for BioLPG. Hydrolysis & fermentation is in initial stages of commercialisation, also not for BioLPG. Fermentation generates a small amount of BioLPG (biobutylene), and commercial-scale production is planned. Fermentation of biopropane has been proven at laboratory scale. Hydrolysis & fermentation has produced BioLPG at a laboratory scale. Digestion is being tried by one demonstration project.

Propane

+H2

Catalytic

Hydrog.


7.3.1 Fermentation

Fermentation is the conversion of sugars by bacteria, yeasts or other microorganisms, in the presence of air (aerobic), into other products. The best-known example is the fermentation of alcoholic beverages: yeast convert sugars into ethanol. Alcohol is fermentation’s best-known product, but fermentation can generate other products, including BioLPG (Table 12). Biobutylene is only BioLPG produced by fermentation: this has so far been done only at a demonstration scale. Global Bioenergies converts sucrose (sugar) from sugar beets and sugarcane to isobutylene at a demonstration plant in Leuna, Germany. Capacity is reported at around 150 tonnes/year. Plans are underway to build a commercial-scale plant somewhere in France, reportedly of 50-kilotonne/year size. Global Bioenergies has its own process, IBN-One process, that uses genetically engineered microorganisms to convert sugar to propylene, butylenes, propanols and butanols. By tweaking the process, it can be directed to one or more of those possible products. Most fermentation processes require significant amounts of energy to separate the product from the fermentation broth (e.g. distillation of the alcohol from the mash). However, with IBN-One propylene and butylenes are emitted as gases, which avoids the need for distillation (Global Bioenergies and Anissimova, 2015).

Table 14: Fermentation projects relevant to BioLPG

Owner/Operator Country Location(s) Feedstock(s) Prime

Product Tech Readiness

C3 BioTechnologies GB Manchester Glucose Unknown Unknown

Global Bioenergies D Leuna Sugarcane, sugar beet, (LC sugars)

Isobutene (gas)

Demonstration

Global Bioenergies & Cristal Union: IBN-One

F In planning

Sugar beet co-products

Isobutene Commercial

University of Turku, Imperial College London

SF, GB Turku, London

Glucose, butyraldehyde

Biopropane Laboratory

Fermentation of biopropane has been proven at laboratory scale. A team from Finland’s University of Turku and England’s Imperial College London have published two papers detailing the experiments (Kallio et al., 2014) (Menon et al., 2015) that involve the microorganisms cyanobacteria and e. coli. It is not known that there are any plans to scale up beyond the laboratory. Converting sugars to chemicals is an active area of development by ‘bioproduct’ companies, including venerable names like DSM, DuPont and Total as well as newcomers such as Amyris, Myriant, GEVO and of course Global Bioenergies. Except for Global Bioenergies’s isobutylene, none of the target products are fuels, they are chemical intermediates such as acrylic acid, adipic acid, farnesene, polylactic acid and succinic acid. Sugars can of course be fermented to alcohols that in turn can be converted to BioLPG. (NREL - National Renewable Energy Laboratory, 2018, p 28) reports a possible route from sugars to propanol or propionic acid as intermediates, with subsequent catalytic dehydration to propylene followed by catalytic hydrogenation of propylene to propane (Figure 10).


Figure 10: A possible fermentation pathway from sugar to biopropane

A final pathway similar to fermentation is the conversion of butyric acid to biopropane. As (NREL - National Renewable Energy Laboratory, 2018, p 28) reports, genetically engineered microbes can do the reaction of (butyric acid) C4H7COOH → C3H8 + CO2. Most butyric acid today is produced synthetically from fossil feedstocks, but it can be made from bio feedstocks as well.

7.3.2 Hydrolysis and fermentation of cellulose

Cellulose is generally believed to be the most abundant bio-material on earth. It is the structural material of most plants. Its chemical structure is a polysaccharide, i.e. a polymer of sugar molecules. Cellulose is made only of glucose (C6), while the less-abundant hemi-cellulose is polymerised from a variety of sugars. The sugar in cellulose cannot be fermented conventionally, because microorganisms are not capable of breaking down the polymer into its constituent sugars. (Starch is also a polysaccharide, but its polymer can be broken down into sugars relatively easily.) Hydrolysis is a process to break down cellulose (or hemi-cellulose) into its sugars. These then can be fermented into other products, as reviewed above. There are two general approaches to hydrolysis: treating the cellulose with steam and acid to break it down, or treating the cellulose with special enzymes that also can break it down. Much research and development has gone into this over the past 40 years, precisely because cellulose is so abundant and could supply large proportions of fuels and chemicals. Even so, the process has only reached the technological readiness of ‘first commercial’, and even that is tenuous. Most of the development has been driven by the aim to make cellulosic ethanol, by hydrolysis to sugar and then fermentation. Common feedstocks for this are straw and stover (the stalk and leaves of a corn/maize plant). Wood is also possible, but less suitable, because it requires more up-front processing to chop it up. The first commercial scale plants to do this, one owned by Abengoa and the other a joint venture of DSM and POET, opened in the USA in 2014. Abengoa subsequently went bankrupt – which is symptomatic of the industry: the economics are not self-sustaining, subsidies are required. Sugars produced from hydrolysis can in principle be fermented similarly to ‘natural’ sugars. Indeed, Global Bioenergies reports that its IBN-One process to convert sugar to BioLPG has been successfully tested on cellulosic-derived sugar at a laboratory scale (Global Bioenergies and Anissimova, 2015)


7.3.3 Digestion of organic wastes

Organic wastes with high water content – such as manure, sewage sludge or food remnants – sometimes are treated by digestion, i.e. anaerobic fermentation. The output is biogas, typically around 50% methane, most of the rest carbon dioxide with small amounts of organic acids, nitrogenous and sometimes sulphurous compounds as well. Biogas is also produced ‘naturally’ at waste landfills, from the digestion of waste organics that can be either bio or fossil in origin. Biogas is used as energy in two main ways. One is to combust it onsite in an internal-combustion engine that runs an electric generator. This has been done with landfill-biogas for decades now. The other is to clean and upgrade it to biomethane (90% purity), and inject that into the natural gas grid. This has become a significant industry in the past 10-15 years. A third way is also possible: the digestion-gas could be synthesised into higher hydrocarbons. Two companies have worked on this process, both at laboratory scale.

7.3.3.1 Biomethane to propane, Alkcon IN 2016 A US-based company, Alkcon Corporation, announced a process for converting methane, purified from digested biogas, to propane (Figure 11). No details are available. According to (NREL - National Renewable Energy Laboratory, 2018, p 30), presumably this is a thermochemical route which involves conversion of methane to ethane (first reactor) with subsequent conversion of ethane plus methane to propane (second reactor). Hydrogen is produced as a by-product

Figure 11: Alkcon’s process for methane to propane


7.3.3.2 Bio-CO2 to propane and methane, ’FutureLPG’ A German consortium led by the Technical University of Clausthal plans to test a digestion-based process at laboratory scale for 30 months, starting in 2019. Unlike the Alkcon process that uses methane from biogas as feedstock, FutureLPG uses the carbon dioxide produced in digestion. This will be reacted with hydrogen (produced by electrolysis of water, using low-carbon power) in a Fischer-Tropsch synthesis to produce biomethane and BioLPG (the mix of propane/butane is not clear). This approach shares some aspects in common with those using atmospheric carbon dioxide as feedstock (see Section 7.5).

7.4 Advanced chemical processes and projects

These are two advanced chemical process types that can lead to BioLPG: gaseous conversion and synthesis, and liquid conversion and synthesis. They are advanced, because they are technically challenging and not well-established commercially. The feedstocks for these are cellulosics and waste (see Section 6.2). Neither of these process types currently deliver commercial quantities of BioLPG. Still they are interesting, because they offer the possibility of using cellulosic- and waste-feedstocks at a large scale, and so potentially could produce significant volumes of BioLPG.

7.4.1 Process descriptions

All these processes break down the large, complex molecules of biomass into smaller, simpler ones. These smaller, simpler molecules are then synthesised/refined into fuels. There are two main steps: gaseous or liquid conversion, followed by synthesis. The most promising route to BioLPG is gasification and synthesis, because the other routes usually are directed at longer-chain or more-complex hydrocarbons (Figure 12).

Figure 12: Advanced chemical paths to BioLPG16

7.4.1.1 Gaseous conversion

Gaseous conversion (of biomass) can be done in two main ways: gasification and pyrolysis. Gasification is done at severe temperatures and pressures, in the presence of air and/or steam, while pyrolysis is more moderate and without air or steam. Gasification blasts the feedstocks into syngas, a gaseous mixture of small molecules, mostly carbon monoxide and hydrogen. Pyrolysis ‘cooks’ the feedstock into an oil.

16 An important exception to pyrolysis is the fast hydropyrolysis process branded as IH2 (see Section 7.4.4.1.2).


7.4.1.1.1 Gasification

A gasifier hits its hydrocarbon feedstock with high temperatures (700+ C) and pressures (5-10 bar) plus air or oxygen and often steam as well. The harsh conditions blast apart long molecules into a mix of short ones, called syngas, composed mainly of carbon monoxide and hydrogen, but there usually is also some carbon dioxide, some methane and small amounts of other compounds. The precise mix of these depends on the gasification conditions and on the composition of the feedstock. Natural gas

17 (CH4) delivers a hydrogen-rich

syngas, whereas coal (say, C240H90O4NS for anthracite) delivers a more carbon-rich syngas. Biomass (mostly cellulose, C6H10O5) delivers a more oxygen-rich syngas.

7.4.1.1.2 Pyrolysis

A pyrolyser hits its hydrocarbon feedstock with moderate temperatures (300-600 C) and limited oxygen or air, usually at ambient pressure. The hydrocarbons react with each other, forming a combination of oils, gases and solids (char). The precise mix of these depends on the pyrolysis conditions

and on the composition of the feedstock. Unlike gasification, pyrolysis mostly generates mid-sized molecules, say C5 to C20, and these are mostly still hydrocarbons. When biomass is pyrolyzed, because it contains

significant oxygen, oxygenates are produced such as carboxylic acids, phenols, sugars and water. A well-known application of pyrolysis is the conversion of wood to charcoal. The product here is the char, while the gases and oils are vented. Of more interest in this study is pyrolysis that leads mainly to pyrolysis oil, sometimes called bio-oil – which is broadly similar in composition to vacuum gasoil.

7.4.1.2 Liquid conversion

A liquefaction process hits a wet hydrocarbon feedstock with moderate temperatures (up to 400 C) and high pressures. Sometimes the conditions are enough to make the water go supercritical. As in pyrolysis, the hydrocarbons react with each other, and with the water, but the product is mainly an oil, also sometimes called bio-oil – which is broadly similar to petroleum (Kumar et al., 2018).

7.4.1.3 Synthesis

Synthesis takes the smaller, simpler molecules created by gaseous or liquid conversion, and converts them into fuels. Syngas from gasification is mainly carbon monoxide and hydrogen. It must be cleaned of tars and other contaminants, and carbon dioxide is also removed. The CO and hydrogen are then catalytically reacted to make longer-chain hydrocarbons

18. The precise mix depends on conditions and on the syngas composition, but

typically it covers about the same range as that of a petroleum refinery. Of course this is by design. In fact, the target range can be adjusted towards a majority of longer-chain or shorter-chain hydrocarbons, including those for BioLPG. Pyrolysis oil is similar to vacuum gasoil (VGO), a common refinery intermediate, except that when made from biomass, it has more oxygen. The py-oil can be processed (synthesised) similarly to VGO in a conventional refinery, even directly blended with fossil VGO at 10-20%. It can be cat cracked, or hydro-deoxygenated and then hydrocracked.

17 Yes, natural gas can be gasified (admittedly, the terms are confusing). Indeed, steam reforming of natural gas – a specific type of gasification – is the main industrial source of hydrogen. 18 Syngas can be used other ways, most notably to produce hydrogen for industrial use. But this report is about BioLPG and fuels.


Bio-oil from liquefaction is similar to petroleum, except that when from biomass, it has more oxygen. Accordingly, it can be refined similarly into fuels, with adjustments made for the oxygen.

7.4.2 Technical readiness (with biomass/waste feedstock)

For biomass or organic wastes, none of the advanced chemical processes have gone commercial (Table 15). This is mainly due to their economic unattractiveness, but technical challenges can also be considerable. For the first two, however, there is considerable know-how that has been built up in their application to fossil hydrocarbons, especially for gasification and synthesis.

Table 15: Technical readiness of advanced chemical processes

Process type Fossil feedstocks Biomass feedstocks

Gasification and synthesis Commercial Demonstration

Pyrolysis and synthesis Demonstration Demonstration

Liquefaction and synthesis Not known Demonstration

Gasification and synthesis is used commercially for fossil feedstocks. Probably the best-known examples are the coal-to-liquids (fuel) plants operated by Sasol in South Africa. Another well-known example is the Great Plains Synfuels Plant in American North Dakota, opened in 1986, that converts coal to fuel gas. These processes have never caught on widely, because the economics are unattractive. South Africa, and in earlier times Germany, turned to coal-to-liquids for political reasons, i.e. they had limited access to crude oil. Other prominent examples of gasification and synthesis are natural gas-to-liquids plants in Malaysia and Qatar, and methanol-to-gasoline in China and New Zealand. Pyrolysis and synthesis has for years been proposed for the treatment of disused tyres, which can be a disposal problem and a fire hazard. The barrier to their commercialisation has been more economic than technical.

7.4.3 Process developers/licensors

For gaseous conversion and synthesis from biomass or waste that could potentially lead to BioLPG, several developers and licensors are active (Table 16). Same is the case for liquid conversion and synthesis (Table 17).

Table 16: Developers/licensors of relevant gaseous conversion and synthesis processes

Process Process name Developer/licensor

Gasification + Fischer-Tropsch Biomass to liquids Choren

Gasification + Fischer-Tropsch Biomass to LPG Japan Gas Synthesis

Gasification + Fischer-Tropsch

Maverick Synfuels


Shell


Velocys

Gasification & pyrolysis MILENA ECN and Royal Dahlman

Gasification-to-power

Energos


Outotec


Syngas Products

Methanol-to-gasoline/LPG TIGAS Haldor-Topsoe

Methanol-to-propylene

Lurgi

Pyrolysis RTP Enysn

Pyrolysis (hydropyrolysis) IH2 Gas Technology Institute

Pyrolysis Biomass catalytic cracking KiOR

Synthetic natural gas

ECN


Process Process name Developer/licensor


Göbigas

Table 17: Developers/licensors of relevant liquid conversion and synthesis processes

Developer/licensor Process name

Biochemtex /ETH/KLM /RECORD

Chalmers University

Licella Cat-HTR

Muradel

Next Fuels

Shell HTU

Southern Oil Refining

Steeper Energy/Aalborg University Hydrofaction

Altaca/SCF Technologies

Chemtex

Genifuel/PNNL

Research Triangle Institute

Virent Bioforming

7.4.4 Projects and production

These are divided into three groups. For gaseous conversion and synthesis of cellulosics, about 50 projects have been identified (Table 19), divided into five classes. These are discussed in the first subsection. For gaseous conversion and synthesis of mixed waste, a list has not been compiled, because this is not yet a clear route to BioLPG. Nonetheless, the concept is presented in the second subsection. Cellulosics and mixed waste are separated, because process developers tend to view them separately. There are two main reasons for this:

Cellulosics – say, wood chips or straw or forest residues – can be relatively homogeneous, regardless of whether they are products or wastes. A process can be adjusted carefully to specific feedstocks. Mixed wastes, on the other hand, by definition are of varying composition. Trying to convert them into intermediates that can be further converted into products is technically challenging. Several plants have been built but later shut down because of fouling in their processes (see Section 7.4.4.3).

The other big differences between cellulosics and mixed waste are availability and economics (revenues).

Availability: mixed waste is available. Logistics already exist, it is collected, it must go somewhere. By contrast, logistics and collection of cellulosics are thin on the ground. Most cellulosics are not collected centrally, and initiating collection would incur investment and operating costs.

Economics: because mixed waste usually comes with a ‘gate fee’, i.e. a payment to dispose of it, there is a ready revenue stream to help finance (say, a gaseous conversion and synthesis plant to do that). Cellulosics generally do not have an attendant ‘gate fee’. This could be created, just as they have been for some recyclables and wastes (used cooking oil, for example), but again, it would incur investment and changes in operating practice.

For liquid conversion and synthesis of biomass, about 14 projects have been identified (Table 20). These are discussed in the third subsection.


7.4.4.1 Gaseous conversion and synthesis, cellulosics

Five processes are of interest. The first four are gasification and synthesis: gasification and Fischer-Tropsch; gasification-to-methanol; methanol-to-gasoline/LPG; and synthetic natural gas. The final one is pyrolysis and synthesis.

Table 18: Potential (maximum) yield of BioLPG as a fraction of total output by weight

Process general description Potential BioLPG yield

Specific process Detail

Fischer-Tropsch 7.5% Larson theoretical design Section 7.4.4.1.1.1.

Fischer-Tropsch 50% Japan Gas Synthesis Section 7.4.4.1.1.1.1.

Methanol-to-gasoline/LPG 8.4% ‘Green Gasoline’ Section 7.4.4.1.1.2

Fast hydropyrolysis 10% IH2 process Section 7.4.4.1.2

7.4.4.1.1 Syngas synthesis

Syngas from a gasifier can be further processed in a lot of directions (Figure 13). This report aims to cover only those relevant to BioLPG: Fischer-Tropsch, syngas-to-methanol-to-gasoline(and LPG); repurposed methanol; and synthetic natural gas.

Figure 13: Processing options for syngas Source : (NREL - National Renewable Energy Laboratory et al., 2003, p 20)

7.4.4.1.1.1 Fischer-Tropsch One option for syngas is to synthesise it into liquid fuels with the Fischer-Tropsch (FT) process. About 25 projects have been identified (Table 19) that use FT process to do this, starting from cellulosic feedstocks. None of those actually operating are believed to be commercial, although some commercial projects reportedly are in the works.


Do they or will they produce BioLPG? Probably very little, if at all (with one exception, see Section 7.4.4.1.1.1.1). These projects are targeted at mainstream refined products: gasoline, diesel and jet fuel. This report estimates the BioLPG output at 2-3% by weight. Or it could be less: FT processes are often designed to use most or all their LPG output as process fuel. Could they produce BioLPG? Yes. A published model of a biomass FT plant (Larson and Jin, 1999) yields about 7.5% by energy content of LPG. About 5% is butane, 2.5% propane. In the same design, much of the butane is cannibalised in the process, but one of the authors, Larson, has said that this butane could be replaced by other process fuels. Moreover, FT plants are capable of producing LPG when they run on fossil feedstocks. At Sasol’s coal-to-liquids plant in South Africa, total LPG yield is around 5% (some is cannibalised, actual LPG production is lower). In a design study for the US Department of Energy, (Bechtel, 1998) engineered 9 different configurations of FT with coal as feedstock. Propane/butane yields ranged from 3.5-6.5% by weight of all outputs. About 2/3

rds of that

output was butane, 1/3rd

propane. Lab-scale research19

at Canada’s University of Saskatchewan has used fossil syngas feedstocks to achieve C3/C4 yields of nearly one-third of the output. While FT will always produce hydrocarbons in a range of lengths, the focus can be moved from long to short or vice versa, depending on feedstocks and process conditions (Figure 14).

Figure 14: Products distributions for different coal-to-liquid FT processes, catalysts and reactors

Source: Atlantic Consulting FT synthesis is of syngas reacted over metallic catalysts to produce a mixture of longer-chain hydrocarbons. These can be upgraded via standard refinery processes (such as hydrocracking and distillation). FT plants can also generate excess electricity for sale to the grid. Overall yield, however, is very low. The Sasol coal-to-liquids plant’s products are only 18% by weight on the incoming coal feedstock. For a biomass FT plant, the energy efficiency is only about 50% (Larson and Jin, 1999)

7.4.4.1.1.1.1 A specific Fischer-Tropsch process for biomass to LPG: Japan Gas

Japan Gas Synthesis Co. Ltd. and the University of Kitakyushu have developed a biomass gasification and FT process that maximises output of LPG. The work was part of a larger effort to synthesise DME, iso-paraffins, methanol and LPG using FT (Fujimoto, 2004). An overview of the LPG pathway was presented to an IEA Bioenergy conference in Vienna in 2012 (Ogi et al., 2012).

19

https://doi.org/10.1002/cjce.5450810208

https://doi.org/10.1002/cjce.5450810208


The LPG concept was proven at laboratory scale. Japanese cedar wood was gasified to syngas: 49% carbon, 45% oxygen and the rest hydrogen. The syngas was reacted in one pass at 260 C and 20 bar over a combination of catalysts: zeolites and commercial catalysts used for methanol synthesis. For 100 t of wood input, the yield was 12.3 t LPG plus around 12 t of other off-gases (presumably other hydrocarbons). In 2012, Japan Gas proposed to build a 100-200 t/day (36-72 kilotonne/year) commercial plant, based on this design. The proposal is not known to have been realised.

7.4.4.1.1.2 Syngas-to-methanol (-to-gasoline and LPG) Another option for syngas is to convert it to methanol. This is less complex and costly than Fischer-Tropsch, and methanol is a fungible product that can be sold globally. Or, methanol can be converted to gasoline – which happens to produce LPG as a significant by-product (Figure 15). This has been done with biomass at a demonstration scale, and with fossil feedstocks at a commercial scale.

Figure 15: Schematic of the gas/coal/biomass-to-methanol-to-gasoline/LPG process

Source: ExxonMobil Most of the world’s methanol is produced this way, but not from biomass, rather from ‘stranded’ natural gas (or sometimes coal), gas or coal that are too remote to be used locally or to be transported somewhere else. In most cases, the methanol is sold onward as methanol, but there are cases where it is converted on to gasoline and LPG:

New Zealand: in 1985, the New Zealand government opened a commercial-scale natural-gas-to-syngas-to-methanol-to-gasoline plant, at Montuni, to exploit a natural gas field offshore. The process technology was supplied by Mobil, now ExxonMobil. Technically, the plant operated as planned, but the economics were unattractive, so as of 1997 it stopped making gasoline but continued making methanol – which it still does today

20.

China: in 2009, the Jincheng Anthracite Mining Group started up a commercial plant in Shanxi that follows the same process as in New Zealand, except starting with coal. A second, much-larger plant came onstream in 2017. Process technology was supplied by ExxonMobil.

United States: G2X Energy is planning a world-scale methanol plant at Lake Charles, Louisiana, that it calls the Big Lake Fuels project. As of early 2018, the plant has been permitted, but not built. G2X has licensed ExxonMobil’s methanol-to-gasoline process, but it is unclear: if the project will be built, and if built, if it will include gasoline or just stop at methanol. ExxonMobil has also licensed its process to DKRW Advanced Fuels, which planned to build a coal-to-methanol-to-gasoline plant near to a coal mine at Medicine Bow, Wyoming. The plant, announced in 2009, was to have started operation in 2014, but construction never started, due to lack of funding and permitting problems.

20

http://www.techhistory.co.nz/ThinkBig/Petrochemical%20Decisions.htm

http://www.techhistory.co.nz/ThinkBig/Petrochemical%20Decisions.htm


All of these run on syngas from fossil fuels: what about biomass to biogasoline and BioLPG? This has been proven at a demonstration scale. A ‘Green Gasoline from Wood’ project, funded mainly by the US Department of Energy and led by the Gas Technology Institute, ran from 2010-2014 at a plant in Des Plaines, Illinois. The methanol-to-gasoline section was supplied by Haldor Topsoe, with its TIGAS process. In the plant, wood chips are gasified to syngas, synthesised to methanol/DME and further reacted to naphtha (gasoline) and LPG (Figure 16). The LPG is about two-thirds butane, one-third propane. The demonstration plant was fed about 19 tonnes/day of wood chips and produced 23 barrels/day of gasoline plus 3 barrels/day of LPG. Based on the demo plant results, the project delivered a conceptual design of a commercial-scale plant that would intake 2,088 kilotonnes/year of wood at 50% moisture

21 to produce 175 kt

of biogasoline and 16 kt of BioLPG (US Dept of Energy, 2015, p 13-10). LPG yield is 8.4% by weight of the output.

Figure 16: Schematic flow-sheet of the wood-to-gasoline/LPG demo plant ‘Green Gasoline from Wood’

Will wood-to-biogasoline/BioLPG go commercial? Haldor Topsoe would surely license TIGAS to an interested operator, and so would ExxonMobil, which says its MTG process could be adapted to biomass feedstock (Hindman, 2017). These are the only known licensors of the process. Which leaves the question of BioLPG yields. For coal feedstock, Exxon has reported yields of 10% butane, 5% propane plus another 1% butylenes, i.e. 16% LPG of the total output by weight. Haldor Topsoe has reported that its TIGAS process could be optimised to make 20-25% LPG, but this seems to be for fossil feedstocks (Gas Technology Institute, 2010, pp A-1 and A-2). As a working figure, we estimate that the 8.4% proven at ‘Green Gasoline’ could be improved to 10%.

7.4.4.1.1.3 Repurposed methanol: glycerine to BioLPG?

There is speculation that conventional methanol plants (which gasify natural gas to syngas and then react that syngas to methanol) could be repurposed to convert bioglycerine - which is massively available at low prices – to BioLPG. The example is Bio-MCN, which operates a plant in The Netherlands (Table 19) that gasifies glycerine and converts the syngas to methanol. It is a special case: an existing natural-gas-to-methanol plant on the site was

21

Freshly harvested wood is usually around 50% moisture. Air-dried wood is about 20% moisture. Oven-dried wood is around 10% moisture.


shut down, for economic reasons, and with heavy subsidy by the Dutch Government it was modified to run not on gas but on bioglycerin. Discussions with experts suggest that this plant could be further modified, with relative ease, to produce BioLPG instead of biomethanol. If this is indeed feasible, it is a larger opportunity than just this plant. Methanol is a very cyclical business, and plants are regularly mothballed or shut for economic reasons. Moreover, methanol plants are sometimes moved from one location to another where the economics (i.e. natural gas prices) are more attractive. Converting them to BioLPG could be another option.

7.4.4.1.1.4 Synthetic natural gas The third relevant option for syngas-to-BioLPG is a variant of the process known as synthetic natural gas. It could be modified to produce BioLPG. The name is confusing (is it synthetic or natural?), but what it means is bio-syngas converted to methane, which then is used in the same way as natural gas. Three projects have been identified (Table 19) based on cellulosic feedstocks, and another one is in development using mixed waste (see Section 7.4.4.3). SNG has been researched since at least the 1990s, but it has never reached commercialisation, because its economics have never been attractive enough. However, as some governments force bio or renewable content into their gas grids, its economics might turn attractive. As the name suggests, SNG is aimed at methane. Nonetheless, discussions with developers suggest that the process could be modified to produce a combination of SNG and BioLPG. At present, no such research or development is known to be underway in this area.

7.4.4.1.2 Pyrolysis and fast hydropyrolysis (IH2)

A final gaseous conversion and synthesis option for BioLPG is a process that pyrolyzes cellulosic biomass and then synthesises those pyoils into liquid fuels. About 20 projects that pyrolyse and synthesise fuels from cellulosics have been identified (Table 19). None of those actually operating are believed to be of commercial-scale, although the Envergent project in Canada would be, if it is ever built. Do they or will they produce BioLPG? Probably very little, if at all, with one exception: the IH2 process, developed by the Gas Technology Institute (GTI) and available for license through a Shell subsidiary, CRI/Criterion, can produce biopropane at about 10% volume of the total output, presumably this is about 6% of the output by weight

22 (Gas Technology Institute, 2010) (Gas Technology Institute, 2014). IH2 has been

piloted a 50-kg/day plant operated by GTI and at a 5-tonne/day plant operated by Zeton Inc in Ontario, Canada. A demonstration-sized unit has reportedly been built in Bangalore, India. This process is two-staged: first a medium pressure, catalytic ‘fast’ hydropyrolysis in a fluid bed under moderate hydrogen pressure. The hydrogen comes from the back end of the process: low-value C1 and C2 hydrocarbons are steam-reformed to make the hydrogen. Intermediates from the first stage enter a hydroconversion step, where a hydrodeoxygenation catalyst removes remaining oxygen and produces gasoline, diesel, jet and LPG. Because it is pyrolysis, there is some solid (char) produced as well.

7.4.4.2 Gaseous conversion and synthesis projects (cellulosics)

Table 19: Gaseous conversion and synthesis projects for BioLPG, by process

22

Assuming approximate density of 0.5 kg/litre for LPG and 0.8 for diesel, gasoline and jet fuel.


Owner/Operator Country Location Feedstock Prime

Product

Prime product capacity kt/y

Note


BIOENERGY 2020+ A

Wood FT liquids 0.04

BioTfuel - Uhde F

Torrefied wood

FT diesel, jet

0.064

Choren Industries D Freiberg (Sachsen)

Wood

13 Closed

Cutec D

Straw, wood, dried silage, organic residues

FT liquids 0

ENVIA Energy USA Natchez, Miss

Woody biomass

Diesel, naphtha, wax

61 Planned

ENVIA Energy USA Oklahoma City, OK

Landfill gas and natural gas

Diesel, naphtha, wax

0

Flambeau River BioFuels

USA Wisconsin Rapids, WI

Black/brown liquor

Frontline Bioenergy USA

Wood, sorted municipal waste

FT jet 0.04

Fulcrum Biofuels USA

Municipal waste, prepared

FT diesel, jet

30

Gridley Biofuels Project / Red Lion / Greyrock

USA

Agricultural residues

FT diesel 0.368

Haldor Topsoe & Gas Technology Institute

USA

Wood pellets FT gasoline 1.04

Japan Synthesis Gas, Kutakyushu University J

Wood

Joule Unlimited/Red Rock Biofuels

USA

Wood wastes & residues

FT diesel, jet

44 Planned

Kaidi PRC

Biogenic waste FT diesel 0.416

Kaidi SF

Forest residues FT diesel, jet

200 Planned

Maverick Synfuels USA Chapel Hill, NC Biomass

NewPage Corporation USA

NREL USA

Lignocellulosics FT liquids 0.048

Saskatchewan Univ CAN

Syngas C2-C4 olefins

Shell USA Houston Hydrocarbons

Southern Research Institute / TRI

USA

Wood waste & forest residues

FT liquids, mixed alcohols, industrial sugars

0

TRI USA

Wood waste & forest residues

FT liquids 0.016



Product


Note

TÜBİTAK MRC - ENERGY INSTITUTE

T

Hazelnut shell, olive cake, wood chip & lignite

FT liquids 0.256

Velocys A

Wood FT diesel 0.024

Gasification-to-methanol

Bio-MCN NL Groningen Glycerol Methanol

Operating

Methanol-to-gasoline/LPG

ExxonMobil USA Could run on biomass

Methanol and LPG

Has operated on coal and gas, but not bio feedstocks

Haldor-Topsoe DK

Wood Methanol and LPG

Demonstration in USA Green Gasoline


ECN NL

Biomass Synthetic natural gas

Demonstration

Engie F

Wood, straw


Demonstration?

Göbigas S Gothenburg Wood residues


Demo plant, now closed.

Pyrolysis

Bioliq / Karlsruhe Institute of Technology

D

Wood, waste wood, straws, hay

Pyrolysis oil, DME, gasoline

1.44

BTG NL Hengelo Wood biomass and/or residues

Pyrolysis oil

12 Subsidised by EU Research funding

Cool Planet USA

Wood residues & thinnings

Pyrolysis oil, Gasoline?

30 Said to be under construction

CRI (subsidiary of Shell)

USA

Straw, wood residues, wastes


1.68

Ensyn BR

Biomass and/or waste

Ensyn CAN Renfrew, ON

Lignocellulosics Pyrolysis oil

9

Ensyn Malaysia

Lignocellulosics

Envergent/Ensyn/UOP CAN

Forest residues & straw

Pyrolysis oil

320 Under construction?

Enysn CAN

Biomass and/or waste

Fortum, Valmet and PREEM

SF Joensuu Woodchips and thinnings

Pyrolysis oil

Commercial scale

Planned for 2020

Iowa / NREL / ConocoPhilips

USA

Biomass Gasoline, diesel, jet

3.2



Product


Note

KiOR USA

Biomass

LignoCat / VTT Fortum / UPM / Valmet

SF

Biomass Upgraded pyrolysis oil

Not yet public

Next BTL / Future Blends

GB

Lignocellulosics Pyrolysis oil

0.024

Petrobras / BTG BR


1.36

Petrobras / Ensyn / NREL

BR


1.76


USA

Lignocellulosics Bio-crude 0.024

SynSel / CRI N Grenland Forest residues Gasoline jet, diesel ,

1.68

UOP USA Oahu, Hawaii


0.16

Gas Technology Institute/Shell

USA Chicago, Ill Residues, wood, stover, bagasse, algae


0.008 Piloted in Chicago and Ontario

Gas Technology Institute/Shell

USA Bangalore Residues, wood, stover, bagasse, algae


Demonstration plant

Sources: The information presented above has been compiled from public sources, including periodicals, reports, company websites and communications with the industry, plus estimates based on all of those.

7.4.4.3 Gaseous conversion and synthesis, mixed wastes (Advanced Conversion Technologies)

Gaseous conversion and synthesis can also be applied to mixed wastes, most notably municipal waste. In this application, such processes are known as Advanced Conversion Technologies. ACTs can be appealing to waste-disposal authorities, who are keen to find alternatives to landfill (increasingly forbidden or restricted) and incineration (often opposed by local communities). ACTs are believed to emit fewer particulates and dioxins than ACTs, because they run at higher temperatures, and they can be built in smaller, less-obtrusive sizes (eunomia, 2016). ACTs are similar to their cousins that process cellulosics (see above). They gasify or pyrolyze the (waste) feedstock into syngas or pyoil. However, with a few exceptions, they do not turn that gaseous intermediate into a liquid product – typically they burn it in a gas engine or a gas turbine to generate electricity. Because it is classified as renewable power

23, government credits/funds for green electricity usually can be obtained.

Ironically, ACTs are less energy-efficient at than conventional incinerators, which run at 18-32% efficiencies (International Solid Waste Association, 2013, p 9) To date, ACTs have shown mixed results. Reportedly they work successfully in Japan, but in Europe, there have been a number of failures. Probably the best-known was an ACT planned for Teesside in the UK by Air Products that would have generated 100 MWatts of electricity. It was cancelled in 2016 while still under construction

24.

Reportedly its problem and the problem of ACTs in general is their tendency to create tars in gasification/pyrolysis that go on to foul the back end of the process.

23

In fact, about 20-40% of the hydrocarbons in municipal wastes are fossil based, mainly from plastics. Nonetheless, the renewable classification is usually applied. 24

https://www.ft.com/content/226c0e34-fb47-11e5-8f41-df5bda8beb40


Nonetheless, municipal waste is not about to go away, so interest will probably persist. Numerous developers are pointing to plasma gasification as the possible solution to the tar problem (Farzad et al., 2016) (eunomia, 2016): this has yet to be proven. Moreover, interest will persist in turning the syngas/pyoil into fuels or chemicals. No ACT projects are known to be targeting LPG, but three projects are aimed at not-distant chemicals:

Enerkem, Alberta, Canada, waste-to-methanol: since 2014, this plant makes 30 kilotonnes/year of methanol from municipal waste in Edmonton. It is believed to be the first successful waste-to-chemical plant.

Enerkem and partners, Rotterdam, The Netherlands, waste-to-methanol: this is tentatively planned for around 2020. It would convert 360 kt/year of waste to 220 kt of methanol. Partners include Air Liquide, Akzo Nobel and the Port of Rotterdam.

GoGreenGas, UK, waste-to-synthetic-natural-gas: the company owned mainly by Cadent, the UK’s gas grid operator, has pilot tested a process and is now planning to go to commercial scale. The SNG would be input to the gas grid.

How does this relate to BioLPG? Although no work is known to be going on in this direction, the above processes probably could be modified to produce LPG (see Sections 7.4.4.1.1.3 and 7.4.4.1.1.4), waste volumes are of course huge, and waste as a feedstock has an inherent economic-incentive of a gate fee.

7.4.4.4 Liquid conversion and synthesis

A final option for BioLPG is liquid conversion and synthesis: about 15 projects that apply this process type to cellulosics have been identified (Table 20). None of those are of significant scale or commercial significance to BioLPG. If bio-pyrolysis oil were to be produced in significant quantities, refining it presumably could produce similar proportions of BioLPG as conventional refineries make of LPG, around 5% by weight. Earlier this decade, there was an effort in the direction of BioLPG. Researchers at the Massachusetts Institute of Technology in the USA reportedly developed a process for converting starch/sugar from corn or sugarcane to propane. A company, C3 BioEnergy, was formed to commercialise the technology (UK Dept of Energy & Climate Change et al., 2014), but the company apparently was not able to pursue this and no longer exists.

7.4.4.5 Table of liquid conversion and synthesis

Table 20: Liquid conversion and synthesis projects for BioLPG, by owner/operator

Owner/Operator Country Feedstock(s) Prime Product Prime product capacity kt/y

Altaca / SCF Technologies

T Sewage sludge, food waste

Bio-crude 7.098

Biochemtex / ETH / KLM / RECORD

I Lignin Jet 1.95

Chalmers University S Lignin Bio-crude 0

Chemtex USA Lignin Bio-crude 0

Genifuel / PNNL USA Wastes, algae, wood, straws

Bio-crude 0.2496

Licella AUS Wood, energy crops, algae

Bio-crude 15.522

Muradel AUS Micro-algae Bio-crude 0.0156

Next Fuels NL Palm waste Bio-crude 0.3276


Owner/Operator Country Feedstock(s) Prime Product Prime product capacity kt/y

PNNL USA Lignocellulosics, algae

Bio-crude 0


USA Lignocellulosics Bio-crude 0.0234

Shell HTU NL Wastes, wood, residues

Bio-crude 0.039

Southern Oil Refining AUS Bio-crude Diesel, jet 0.2574

Steeper Energy /Aalborg Uni

DK DDGS, peat, wood, tall oil

Bio-crude 0.0156

Virent USA

Glycerol?, sugars, starches

Bio-crude

Sources: The information presented above has been compiled from public sources, including periodicals, reports, company websites and communications with the industry, plus estimates based on all of those.

7.5 Other: Atmospheric carbon dioxide

A final, distant route to consider is that of combining carbon from the atmosphere (in the starting form of carbon dioxide) with ‘renewable’ hydrogen to create LPG. Ambient carbon dioxide can be absorbed directly from the air, or from combustion exhausts (say, at a power plant). Renewable hydrogen can be hydrolysis from water using green electricity such as hydro, solar or wind. This is a real possibility: 7 companies are known to be pursuing it, albeit they are targeting higher-hydrocarbon fuels (Table 21). In principle, they could also pursue LPG. Not much detail is public about their processes, but presumably they are creating a syngas and then from that synthesizing fuels. Production so far is no more than laboratory scale, yet Carbon Engineering and Nordic Blue Crude claim to be pursuing commercial-scale plants.

Table 21: Companies pursuing atmospheric-carbon-to-fuels

Owner/Operator Location(s) Country

Audi Laufenberg CH

Carbon Engineering British Col. CAN

Climeworks Zürich CH

New CO2 Fuels Rehovot ISR

Nordic Blue Crude Herøya N

SOLETAIR Lappeenranta SF

Sunfire Dresden D

Would these generate biofuels? Not as such. Water is not bio, it is considered an inorganic, non-biological resource. Of atmospheric carbon dioxide, only about one-quarter is biological, the rest is inorganic. So these fuels would be renewable, but not biological. Therefore this process is classed for now as ‘other’.


Chapter Eight

BioLPG’s Policy drivers

Biofuels are generally more expensive to produce than fossil fuels, so for them to have more than a niche market presence requires the intervention of governments. Governments support biofuels mainly to reduce carbon emissions, but sometimes also to improve security of fuel supply. To encourage biofuels, governments usually employ one or more of the following policy tools:

Caps or restrictions on fossil fuels or on carbon emissions Carbon taxes (on fossil fuels) ‘Mandates’, i.e. mandatory market shares for biofuels/renewables Subsidies for biofuels/renewables Tax waivers on biofuels/renewables

To date, none of these are specifically directed at fossil LPG or BioLPG, except for carbon taxes, which do hit fossil LPG. BioLPG has so far been excluded from mandates, which have only been in transport, where its market shares are relatively small. BioLPG production is, nonetheless, driven by policy in two ways:

Mandates for biodiesel indirectly encourage the production of BioLPG (because the by-product of renewable diesel is biopropane – see Section 7.2.1).

BioLPG use in transport is credited as a contribution to mandates for liquid biofuels in European Union member states, for instance in the UK

25.

In Europe, legislation to promote biofuels began around 2006 in some EU member states and culminated in the passage of the Renewable Energy Directive in 2009. Initially there was widespread use of subsidies and tax waivers. However, governments soon realised that these were fiscally unsustainable, so they switched their emphases primarily to mandates. Carbon taxes have been introduced, although not as widely, and these do not necessarily promote biofuels (they can promote non-bio-renewables, or they can just suppress consumption). Caps and restrictions are starting to surface: for instance, several countries are seriously considering bans or restrictions on heating oil and even other fossil fuels. In the USA, the main driver for biofuels is the Renewable Fuels Standard, which applies mandates for transport fuels. BioLPG has not yet been included as such, because its volumes are relatively small. Other countries that have introduced biofuel mandates include: Angola, Australia, Argentina, Brazil, Canada, Colombia, Chile, China, Costa Rica, Ecuador, Ethiopia, Fiji, India, Indonesia, Malaysia, Jamaica, Kenya, Malawi, Mauritius, Mexico, Mozambique, New Zealand, Nigeria, Norway, Panama, Paraguay, Peru, The Philippines, South Africa, South Korea, Sudan, Taiwan, Thailand, Ukraine, Uruguay, Vietnam, Zambia and Zimbabwe. Almost all of these are simple mandates that require the blending of bioethanol into gasoline. Some of them also mandate a market share for biodiesel. None are known to be targeted specifically at BioLPG.

25https://assets.publishing.service.gov.uk/government/uploads/system/uploads/attachment_data/file/694300/rtfo-guidance-part-2-carbon-and-sustainability-year-11.pdf

https://assets.publishing.service.gov.uk/government/uploads/system/uploads/attachment_data/file/694300/rtfo-guidance-part-2-carbon-and-sustainability-year-11.pdf

https://assets.publishing.service.gov.uk/government/uploads/system/uploads/attachment_data/file/694300/rtfo-guidance-part-2-carbon-and-sustainability-year-11.pdf


Chapter Nine

Marketing and Distribution

In principle, BioLPG need not be separated from fossil LPG, because in performance they are identical. Marketers and distributors could treat BioLPG as just another supply, and blend it in the same as they do other supplies. Customers would not notice one way or another. However, in practice this is unlikely to happen, because:

Marketers/distributors and consumers will want evidence that they have supplied or consumed BioLPG rather than fossil LPG, and they will want a carbon footprint for the BioLPG supplied/consumed.

Governments will want verification of both and of the ‘sustainability’ of the BioLPG production.

This evidence/verification is referred to as the biofuels’ ‘chain of custody’ (CoC) and its sustainability certification. CoC is wanted by marketers/distributors and customers so they can take credit for biofuel supply and usage. It is wanted by governments to prevent double-counting, i.e. credit being taken more than once for a carbon reduction. CoC methods vary by stringency. They can require biofuels to be:

distributed completely separately to fossil fuels (physical segregation); mixed into the conventional (fossil) fuel supply network, but credited to specific customers, as is

commonly done already with biodiesel and bioethanol in transport fuels (mass balance); or decoupled of physical and ‘sustainability’ characteristics, i.e. the actual fuel is sold locally, but the

credits of its sustainability (say, carbon reduction credit) is sold elsewhere (book and claim). This method is applied to ‘green electricity’ and to biomethane injected to national grids in many countries.

Sustainability certification is meant to protect all parties from trading, using or crediting biofuels that somehow violate environmental or even social standards. For instance, biofuels produced on a protected natural area or with the use of illegal labour practices probably would not be certified. CoC evidence and sustainability certification are typically provided by one supplier. These often are ‘certification’ companies: well-known examples are Det Norske Veritas, TÜV and SGS, and there are many more lesser-known ones. Trading in BioLPG is still relatively new, so there are no statistics yet about CoC and sustainability certification. From anecdotal evidence, it is estimated that most if not all BioLPG sold today is certified for sustainability and its CoC is done according to the mass balance method.


Chapter Ten

Environmental impact

The mission behind development of BioLPG is to reduce the environmental impact of producing and consuming LPG. By most accounts, BioLPG fulfils that mission. In most cases its carbon footprint is lower than fossil LPG’s, and lower than that of conventional gasoline and diesel/heating oil, in some cases by a bit more than 90% (Figure 17, Figure 18). Non-carbon emissions are presumed to be identical to those of fossil LPG, because their chemical properties are identical.

Figure 17: Carbon footprints of BioLPG and competitors (base cases)

Figure 18: Carbon footprints reductions of BioLPG and fossil LPG to gasoline/diesel (base cases)

In one respect, however, BioLPG faces an ongoing controversy. The use of vegetable oils as biofuel feedstocks is condemned by some as environmentally damaging. This argument has gained traction with the European


Commission and the European Parliament. Both have entertained measures that aim to halt mostly or completely the production or consumption vegetable-oil-based biofuels – including BioLPG – in the European Union.

10.1 Carbon footprint of BioLPG

The main studies related to BioLPG’s carbon footprint are specifically about hydrotreated biopropane.

10.1.1 Carbon footprint of hydrotreated biopropane Hydrotreated of HVO biopropane’s carbon footprint is in most cases lower than fossil LPG’s. There is no single estimate of fossil LPG’s footprint, but the range is about 72-81 g CO2e/MJ at lower heating value (LHV). Those of fossil gasoline and diesel are in the range of 80-100 CO2e/MJ. According to the only peer-reviewed, comprehensive study of biopropane footprints (Johnson, 2017), they can be as low at 5 and as high as 47 g CO2e/MJ under most conditions (Table 22). Under one scenario, however, the biopropane footprints are actually higher. That is the one that includes iLUC, indirect land-use change

26 (see Section 10.2)

An extensive literature search has identified 27 reports that cover the carbon footprint of hydrotreating bio-oils to produce renewable diesel and biopropane (Table 23). Only three of these explicitly cover biopropane – the rest cover only the renewable diesel. Of the three, one covers only tallow feedstock (NREL - National Renewable Energy Laboratory, 2018), and another (Delage et al., 2017) is derived from the only comprehensive, peer-reviewed one (Johnson, 2017).

Table 22: Biopropane’s carbon footprint by feedstock, g CO2e/MJ

Source: (Johnson, 2017) Most of these reports are focused on renewable diesel – they report footprints for it ranging from 5 to 98 g CO2e/MJ. Generally speaking, this would be the same footprint as for its co-product biopropane, but most of the reports are not transparent enough for this to be said with absolute certainty.

26

All scenarios include direct land-use change.


Why the huge range? Part of it is the varying footprint of feedstocks: e.g. cultivating rapeseed is significantly more carbon intensive than cultivating palm oil. But the biggest variations come the scope and accounting rules of the carbon-footprint study. Is allocation done by energy content or economic value, is indirect land-use change included, what is considered a waste or a residue? (Table 22)

10.1.2 Carbon footprint of biomass gasification & synthesis

Three of the reports surveyed for this report (Table 23) publish footprints for liquid fuels produced by gasification and synthesis of cellulosics. The footprints range from 8 to 32 g CO2e/MJ. They are not explicitly for BioLPG – indeed it is not clear that they include BioLPG – but the figures still should be broadly indicative of what might be expected for BioLPG. A study by (Farzad et al., 2016) lists another 17 studies in this area, but none of them covers BioLPG.

10.2. The threat to palm oil and other vegetable oils

The use of vegetable oils as biofuel feedstocks is condemned by some, who argue that it:

inflates the cost/price of food, sometimes referred to as the ‘food or fuel’ dilemma, and causes direct and indirect land-use change, which

drive destruction of natural forests along with their fauna, particularly in Brazil, Indonesia and Malaysia, by converting them to soybean or palm oil plantations.

cause massive emissions of greenhouse gases through that same destruction, by releasing carbon sequestered in swamps and peaty soils.

So far there is no political consensus as to their truth. Nonetheless, driven by these concerns:

The European Commission has for several years considered amending the Renewable Energy Directive to include indirect land-use change (iLUC) factors in biofuel carbon footprints. For BioLPG, this corresponds to the iLUC line in Table 22, which are all clearly higher than fossil LPG footprints.

In January 2018, the European Parliament proposed to cap the production of biofuels from non-waste vegetable oils and to phase out the use of palm oil to make biofuels.

Both measures aim to halt mostly or completely the production or consumption of vegetable-oil-based biofuels in the European Union. BioLPG today is mostly vegetable oil based, and so would suffer accordingly.


10.3 Carbon footprints/LCAs relevant to BioLPG

Table 23: Carbon footprints/LCAs relevant to BioLPG (footprints in g CO2e/MJ)

Author/Sponsor Report BioLPG footprint Renewable diesel footprint Other

Argonne Labs Argonne Labs, 2008. Life-Cycle Assessment of Energy and Greenhouse Gas Effects of Soybean-Derived Biodiesel and Renewable Fuels. Argonne National Laboratory.

Not reported Only comparisons, not

absolute figures

Argonne Labs Han, J., Elgowainy, A., Wang, M., 2013. Development of Tallow-based Biodiesel Pathway in GREET, Not Mentioned.

Not reported Not explicitly reported

Atlantic Johnson, E., 2017. A carbon footprint of HVO biopropane. Biofuels Bioprod. Biorefining 1–10. doi:10.1002/bbb.1796

9 to 19 for variety of feedstocks with

economic allocation. 21 to 47 with energy

allocation

40, for palm oil base case

Atlantic SRI Consulting, 2007. Carbon footprints of biofuels & petrofuels, Greenhouse Gases.

Not reported 34

Biograce BioGrace, 2015. BioGrace: Harmonised Calculations of Greenhouse Gas Emissions in Europe, V 4d.

Not reported 47

CARB California Air Resources Board, 2009. Detailed California-Modified GREET Pathway for Biodiesel Produced in California from Used Cooking Oil.

Not reported 28.9

CARB California Air Resources Board, 2017. List of Certified LCFS pathways. March 20 2017

Not reported 32 average

Diamond Green Diesel

Diamond Green Diesel, 2013. HVO biodiesel carbon footprint.

Not reported

European Commission

Renewable Energy Directive Not reported 50

EVEA ETBE footprint, for Global Bioenergies Report unavailable

EVEA/Butagaz 2018 - Comparative LCA of butane and bioisobutene for bottle gas application (french and english report)

Bio-isobutylene footprint is 50% lower

than fossil butane’s

Full report to be released in mid-

2018

GTI

Maleche, E., Glaser, R., Marker, T., Shonnard, D., 2014. A Preliminary Life Cycle Assessment of Biofuels Produced by the IH2 Process. Environ. Prog. Sustain. Energy 33, 322–329. doi:doi:10.1002/ep.11773

Not reported 4 to 63.6, for gasoline and

diesel

Helsinki Univ of Technology

Nikander, S., 2008. Greenhouse gas and energy intensity of product chain: case transport biofuel. Master Sci. Eng.

Not reported 16 to 74

IFEU 2006 study for Neste, Renewable diesel LCA Report unavailable

Joint Research Commission, European Commission

Joint Research Centre of the EU Commission, EUCAR, CONCAWE, 2006. Well-to-Wheels analysis of future automotive fuels and powertrains in the European context.

41

Kyoto University

Yano, J., Aoki, T., Nakamura, K., Yamada, K., Sakai, S., 2015. Life cycle assessment of hydrogenated biodiesel production from waste cooking oil using the catalytic cracking and hydrogenation method. Waste Manag. 38, 409–423. doi:10.1016/j.wasman.2015.01.014

Not reported Not explicitly reported

Lappeenranta University of Technology

Uusitalo, V., Väisänen, S., Havukainen, J., Havukainen, M., Soukka, R., Luoranen, M., 2014. Carbon footprint of renewable diesel from palm oil, jatropha oil and rapeseed oil. Renew. Energy 69, 103–113. doi:10.1016/j.renene.2014.03.020

Not reported 21-23 for palm oil, ~35 for

jatropha, ~55 for rapeseed

Minnesota, Univ of and St Olaf College

Hill, J., Nelson, E., Tilman, D., Polasky, S., Tiffany, D., 2006. Environmental, economic, and energetic costs and benefits of biodiesel and ethanol biofuels. Proc. Natl. Acad. Sci. 103, 11206–11210. doi:10.1073/pnas.0604600103

Not reported

48.8

MIT MIT Lab. for Aviation and the Environment, 2010. Life Cycle Greenhouse Gas Emissions from Alternative Jet Fuels.

Not reported 39.4 jatropha, 39.8 palm,

97.9 rapeseed, 97.8 soybean oil

9 to 17.7 for jet fuel, produced

from cellulosics by gasification and Fischer-Tropsch

NREL NREL - National Renewable Energy Laboratory, 2018. Bio-propane: Production Pathways and Preliminary Economic Analysis.

29.4 for tallow, 22.6 if biomass-derived

hydrogen is used in hydrotreating

Primagaz

Delage, W., Benhamou, J., Khelil, T. Ben, Briendt, A. de, Johnson, E., 2017. Proposition de facteurs d’émissions de GES associés au biopropane issu d’huiles végétales hydro-traitées (HVO) à la Base Carbone® de l’ADEME.

16.8

UOP Kalnes, T.N., Marker, T., Shonnard, D.R., Koers, K.P., 2008. Green diesel production by hydrorefining renewable feedstocks. Biofuels Technol. 7–11.

Not reported ~5 for tallow, ~25 to 50 for

palm oil

UOP

Kalnes, T.N., Koers, K.P., Marker, T., Shonnard, D.R., 2009. A Technoeconomic and Environmental Life Cycle Comparison of Green Diesel to Biodiesel and Syndiesel. Environ. Prog. Sustain. Energy 28, 111–120. doi:doi.org/10.1002/ep.10319

Not reported

8 for diesel from wood by

gasification and Fischer-Tropsch

UOP

Shonnard, D.R., Williams, L., Kaines, T.N., 2010. Camelina‐derived jet fuel and diesel: Sustainable advanced biofuels. Environ. Prog. Sustain. Energy 29, 382–392. doi:doi:10.1002/ep.10461

Not reported ~18 to 25

US DoE

Life cycle inventory of biodiesel and petroleum diesel for use in an urban bus’’, National Renewable Energy Laboratory, US Department of Energy, 1998, NREL/SR-580-24089 UC Category 1503

Not reported 17.3

US DoE US Dept of Energy, 2015. Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes, DE-EE0002874. doi:10.2172/1173129

Not reported

24.0 to 31.6, for gasoline

US EPA

US EPA, Renewable Fuel Standard, Changes to RFS Program, 40 CFR Part 80. Federal Register, [EPA–HQ–OAR–2005–0161; FRL–9112–3] [EPA–HQ–OAR–2011–0542; FRL–9608–8]. US Environmental Protection Agency, WAshington DC, USA, pp. 14669–5320 (2010).

Not reported 39


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Copyright © 2018 World LPG Association. All rights reserved. Neither this publication nor any part of it may be reproduced, stored in any retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of the publishers. All information in this report is verified to the best of the authors’ and publisher’s ability. They do not guarantee the accuracy of the data contained in the report and accept no responsibility for any consequence of their use.

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