Accepted Manuscript

Waste-to-Methanol: Process and Economics Assessment

Gaetano Iaquaniello, Gabriele Centi, Annarita Salladini, Emma Palo, Siglinda

Perathoner, Luca Spadaccini

PII: S0960-8524(17)31076-3
DOI: http://dx.doi.org/10.1016/j.biortech.2017.06.172
Reference: BITE 18409

To appear in: Bioresource Technology

Received Date: 24 April 2017

Revised Date: 28 June 2017
Accepted Date: 29 June 2017

Please cite this article as: Iaquaniello, G., Centi, G., Salladini, A., Palo, E., Perathoner, S., Spadaccini, L., Waste-
to-Methanol: Process and Economics Assessment, Bioresource Technology (2017), doi: http://dx.doi.org/10.1016/
j.biortech.2017.06.172

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Waste-to-Methanol: Process and Economics Assessment
Gaetano Iaquaniello,a, c Gabriele Centi,*,b Annarita Salladini,a Emma Palo,c Siglinda Perathoner,b and Luca

Spadaccinid

a Processi Innovativi, Via Guido Polidoro 1 - 67100 L'Aquila, Italy

b Univ. Messina and INSTM/CASPE, Dept. MIFT - Industrial Chemistry, V.le F. Stagno D’Alcontres 31 –

98166 Messina, Italy.

c KT – Kinetics Technology S.p.A., Viale Castello della Magliana 27, 00148 Rome, Italy

d OESA Srl, Via Pontina 545 - 00128 Roma, Italy.

CORRESPONDING AUTHOR

* Gabriele Centi, Univ. Messina and INSTM/CASPE, Dept. MIFT - Industrial Chemistry, V.le F. Stagno

D’Alcontres 31 – 98166 Messina, Italy. E-mail: centi@unime.it

KEYWORDS: methanol from waste, RdF, municipal solid waste, waste-to-methanol process.

1
ABSTRACT: The waste-to-methanol (WtM) process and related economics are assessed to evidence

that WtM is a valuable solution both from economic, strategic and environmental perspectives. Bio-

methanol from Refuse-derived-Fuels (RdF) has an estimated cost of production of about 110 €/t for a new

WtM 300 t/d plant. With respect to waste-to-energy (WtE) approach, this solution allows various

advantages. In considering the average market cost of methanol and the premium as biofuel, the WtM

approach results in a ROI (Return of Investment) of about 29%, e.g. a payback time of about 4 years. In a

hybrid scheme of integration with an existing methanol plant from natural gas, the cost of production

becomes a profit even without considering the cap for bio-methanol production. The WtM process allows to

produce methanol with about 40% and 30-35% reduction in greenhouse gas emissions with respect to

methanol production from fossil fuels and bio-resources, respectively.

2
1. Introduction

Municipal solid waste (MSW) are a main source of carbon that should be addressed between the various

usable C-based wastes for bioenergy and bioproducts production,1 but incineration/thermovalorization of

MSW is still the major solution adopted on a worldwide basis.2,3 Waste-to-fuels or -chemicals is an

attractive alternative option,1,4 but still largely underestimated as a viable solution. We showed earlier,5 that

urea (one of the major chemical products) can be produced from the RdF (Refuse Derived Fuel) fraction of

MSW in a sustainable and economic process. Enerkem, a Canadian Company specialized in the waste to

biofuel business, operates both a demonstration plant and a pilot facility in Quebec and is beginning

operations at Enerkem Alberta Biofuels, its first full-scale commercial facility for a RdF to methanol, ethanol

and green chemicals.6 However, scientific data on these industrial solutions, for example the details of the

process layout, unit operations and process economics, are not reported in literature.

Methanol is a valuable target for the waste-to-chemical process for various reasons. Methanol is a large

volume product, which find use as both chemical and fuel in several applications. The current world

demand is over 80 Mt (year 2016) and the outlooks is that its production will be about 100 Mt in 2020. The

currently main production route of methanol involves the synthesis of syngas from fossil sources (natural

gas - NG, especially) and its further catalytic conversion to methanol. About 80% of methanol production is

based on NG, while the remaining derives from coal (17%) and small amounts of oil. The process from NG

involves the generation of syngas by steam reforming of methane, the compression of the syngas, the

catalytic synthesis of methanol and finally the distillation of the crude methanol. Although the process is

well established, the energy and exergy efficiencies for the overall process are both close to 40%.7 The

impact of the synthesis of methanol in terms of GHG is thus relevant, and even higher considering the

impact related to production and distribution of NG on Life Cycle Analysis (LCA) bases. Producing

methanol from RdF will reduce this impact, reduce the consumption of fossil fuels and associated

emissions, and provide an alternative, more sustainable option to incineration/ thermovalorization of MSW.

3
 The non-recyclable fraction of MSW is currently either disposed by landfill or used in combustion

processes to generate heat/electrical energy. However, the co-generated heat often cannot be exploited,

and thus the process energy efficiency is limited. In addition, the actual highly fluctuating demand for

electrical energy, due to the increasing role of renewable energy (RE) production, makes attractive the

possibility to produce products easy to store/distribute (like methanol) rather than electrical energy.

There are thus different strategic, economic and environmental motivations driving the need to develop a

waste to methanol (WtM) process. In addition, it must be considered the use of methanol deriving from non-

fossil fuel sources as alternative to biofuels. The Renewable Energy Directive in EU (2009/28/EC), for

example, considers methanol produced from MSW a biofuel that is counted double to reach the legislation

targets on the biofuel amount to be present in transport fuels.

In general, there are very few literature data on the aspects, which may be relevant to the development

of a WtM plant. In particular, the question of the optimal gasifier and process design for WtM process is still

open. This paper will thus discuss the process design and some aspects of the high temperature gasifier

(HT) together with an assessment of the process economics, because this is a key aspect, not earlier

reported in literature, for the evaluation of the suitability of the proposed approach for waste valorisation.

2. Materials and Methods

The value for RdF composition utilized in the estimations is shown in Table 1. These composition values

were provided by Colari srl (Italy), an Italian company specialized in the waste treatment and RdF plants.

The composition utilized agree with that reported in other studies.8

The results for HT gasifier derives from the thermogasification unit for RdF located in Malagrotta (Italy)

and designed to operate with 500 t/d RdF on three parallel lines, although only one line was put in

operation for about 3 years.

4
 The process was simulated by using process simulator PROII. Block diagram for the WtM process will be

discussed later. The core of the process is the high temperature converter where RdF is mixed with oxygen

to produce a syngas followed by the methanol synthesis reactor where the syngas after purification and

conditioning is converted into raw methanol. The overall material balance is based on a 300 t/d methanol

production, based on a 716 t/d RdF feed (Figure 1).

Economic parameters used to estimate the cost of production (COP) of methanol are summarized in

Table 2 for two cases investigated:

A. 300 t/d new methanol production

B. an hybridization scheme with an existing 900 t/d methanol unit.

The investment for the new plant has been determined using standard estimating tool and the

experience in building industrial plant. The overall capital expenditure (CAPEX) is calculated as a

percentage of the delivered equipment costs, a method commonly used for preliminary estimates.9

3. Results and Discussion

3.1 Process layout

The general process layout for a 300 t/d methanol production plant is reported in Figure 2. There are

three gasification lines at high temperature (HT gasifier) in order to guarantee maintenance, while

maintaining continuity of the production. In fact, due to high temperature of gasification (see later), it is

necessary to consider a periodic maintenance of the reactors. Three units of syngas purification are

associated to the three HT gasifiers, in order to guarantee the flexibility of operations. For smooth

operations, it is necessary to consider also an intermediate storage of the syngas to minimize gas

fluctuation. The syngas is then compressed and sent to the methanol synthesis unit. Part of the stream is

sent to a water gas shift unit followed by CO2 removal to reach the necessary CO/H2/CO2 composition

specifications for methanol synthesis.

5
 Being not discussed in literature the WtM process, we could compare here the scheme reported in

Figure 2 with only the very simplified scheme for the announced Enerkem process.6,10 This process

scheme reports a bubbling fluidized bed gasifier followed by a water scrubbing system before to go directly

to the catalytic reactor for syngas conversion. The water scrubbing system is not ideal to reach the

purification levels and CO2 concentrations needed to operate efficiently the methanol unit, and may be also

questioned whether bubbling fluidized bed gasifier allows to obtain the low-level tars and toxic chemicals

necessary for correct operations. Catalysts for methanol synthesis need to operate at high pressure and

temperatures about 220°C, and it is thus not possible to send directly the gas after water scrubbing. There

is an optimal amount of CO2, H2O and COx/H2 ratio in the feed to methanol synthesis unit, and these values

are typically not achieved in conventional gasification of MSW.11-13 The process scheme shown in Figure 2

reports the use of three HT gasifiers in parallel, in order to account the need for periodic maintenance,

without stopping the production. Moreover, the addition of a storage tank allows to properly manage syngas

flowrate fluctuation which are characteristic of this process thus assuring more stable operation for

downstream sections.

More details on the characteristics of the HT gasifier and purification unit and downstream section are

discussed in the following sections.

The syngas composition from the HT gasifier does not fit the requirements for the methanol synthesis,

expressed typically with the R ratio:

(1)

R for methanol synthesis should range from 2 to 2.1 and values are % in volumes. The syngas

composition from HT gasifier is indicated in Table 3, with also typical variation ranges. The composition

refers to the type of HT gasifier discussed below, operating under typical reaction conditions. There is a

rapid quenching after the HT gasifier to avoid the formation of toxic chemicals. The syngas leaves the HT

6
gasifier at a temperature of around 38°C (in the 30-50°C range) with a pressure of about 4 kPa (4-10 kPa

range). This is connected to a threshold fixed at 5 kPa as safety-element intervention value.

Table 3 shows that the R ratio from HT gasifier is around 0.5. To increase this value to a 2.0-2.1 range,

two strategies could be implemented: (1) add hydrogen or (2) remove the excess of carbon. The first

approach requires producing either hydrogen separately or integrating the RdF conversion unit into a

process, where an excess of hydrogen exists. In the first case, H2 should derive from renewable sources

such as by electrolysis using renewable electrical energy (RE). This could be a strategy to use low-cost

excess RE, when available (for example excess production by wind or solar energy), as outlined in Figure

2. Electrolysis requires 4-4.1 kWh per Nm3 of hydrogen and thus to produce H2 at a cost of 1-2 €/ton, RE

should have a cost less than 2-3 ¢/KW, which is possible only in very specific situations.14 Apply

electrolysis for H2 production is thus possible only when energy cost is quite low, for example when an

excess of power exists in the grid, for instance during the night. By using excess RE, the electrolysis step

will also act as stabilizer of the power grid.15 In a longer-term perspective, direct H2 production by

photocatalytic methods (water splitting) may become commercially feasible. In both cases (electrolysis

using RE or direct photocatalytic water splitting), O2 will be produced as byproduct. As outlined in Figure 2,

oxygen produced in this way may lower the amount of oxygen produced in a separate oxygen unit and

used as feed for the RdF HT gasifier unit. H2 may be produced from also other sources not based on fossil

fuels, such as photoreforming or catalytic aqueous phase reforming of waste aqueous biomass streams.

Also in these cases, costs are still high, but may be lowered in the future. We thus consider here, for

economic estimation, only case 2 of removal excess carbon. However, a second scenario (use of excess

H2 in other processes) will be also considered later in terms of economics.

Actually, thus the second strategy of CO2 removal to obtain the proper R ratio is the most feasible, even

though the C-based efficiency of the process is lower. CO should be reacted with water (water gas shift -

WGS) with formation of CO2 and H2, with carbon dioxide being removed in a following step. The CO2

7
removal unit could be a conventional amine sorption technology (based on monoethanolamine - MEA as

solvent) or preferably the KM-CDR (Kansai Mitsubishi Carbon Dioxide Recovery) process® based on the

use of the sterically-hindered amine (KS-1®) developed by Mitsubishi,16 which allows a reduction of process

costs. A cryogenic step is an alternative, while membrane separation technology or the adsorption based

on solid adsorbents are still under development.17

The block diagram for R ratio adjustment is schematically included in Figure 2, where only a fraction of

syngas is treated for such a purpose. In such a scheme, purge gas from the synthesis loop, after H2

recovering with a PSA (pressure swing adsorption) is used as supporting fuel in the RdF conversion step.

In such a way, the only carbon form leaving the system is the CO2 stream.

3.2 The HT Gasifier and Purification Unit

The core of the process is the HT converter (modified gasifier) schematically presented in Figure 3a, where

RdF from battery limits is mixed with oxygen to produce a syngas with a composition reported in Table 3.

The outlet syngas stream contains also some impurities as described in Table 4. All these components

need to be removed before any further catalytic treatment.

The high temperature and the appropriate temperature profile are the key parameters to achieve the

proper performance of the reactor.18 In particular, hydrogen content increases and tar content remarkable

decreases at temperatures higher than 1000°C, methane and other hydrocarbons tend to decompose at

temperatures above 600°C, a small amount of char is present even at temperature as high as 1600°C, and

is discharged into the slag. Moreover, the absence of an oxidizing atmosphere in all sections of the gasifier

eliminates one of the steps of the dioxins synthesis mechanisms19 and strongly reduces their formation to a

not detectable level. Each HT gasifier unit produces about 13,500 kg/h (15,510 Nm3/h) of syngas stream

with the composition reported in Table 3. The yield in syngas is about 1,500 Nm3/kgRdF, which corresponds

to a yield in methanol of 0.40-0.42 kgMeOH/kgRdF. The design characteristics for each HT gasifier unit are the

8
following: amount RdF treated, 10t/h; RdF (LHV), 15,000 kJ/kg; Natural Gas, 287 kg/h; Oxygen, 6,464 kg/h;

HCl, 183 kg/h; NaOH, 183 kg/h; Water, 1,422 kg/h.

The high selectivity to H2 and CO is related to the elevated temperature maintained inside reactor and to

the reducing environment. These conditions avoid CH4 formation, thus favouring selectivity to CO and H2.

The characteristics of the feedstock have been reported in Figure 1. Composition of the RdF feedstock is

about the following: (1) Moisture = 10-25%w; (2) Ash = 10-25%w and (3) CHO = 50-80%w.

The gas leaves the converter at around 1100°C and is quenched with water to reach near ambient

temperature to enter into a first absorption tower which contains water and then into a second tower

containing an alkaline solution to remove particulate, salts and HCl (Figure 3b). A wet electrostatic

precipitator (WESP) will act as a final cleaning unit. The raw syngas coming from the different lines is sent

then to an atmospheric tank (Figure 2).

3. 3 Downstream section

The syngas need a further purification to meet specifications of methanol synthesis, in addition to adjust

the R ratio. From the storage unit, the gas is compressed and COS (carbonyl sulfide) is hydrolyzed to H2S,

which in turn is removed by a redox sulphur removal unit, followed by an H2S deep polishing unit. In fact,

sulphur is a particularly severe poison for the WGS and the methanol synthesis reactors, and is not

efficiently removed by the scrubber systems shown in Figure 3b. A proper desulphurization system is

required in order to reduce sulphur compounds to less than 0,1ppm or even lower. The limit for chloride

contamination is below 5ppb. Chloride content is detrimental for catalysts adopted for syngas conditioning

and methanol synthesis.

Sulphur is present in syngas deriving from RdF mainly as hydrogen sulfide (H2S) and carbonyl sulfide

(COS), although minor amounts of carbon disulphide and other sulphur compounds are also present. Ratio

H2S/COS is typically around 10 to 1. The catalytic conversion by hydrotreatment is not very efficient in

removing COS in presence of CO and H2, considering also the side reaction of methanation. In addition,

9
the presence of relevant amounts of H2S does not allow the use of zinc oxide absorbents, due to high

costs. The scheme for removing sulphur components is based on the following steps: COS hydrolysis, H2S

removal throughout a redox system as the LO-CAT® Merichem Company20 followed by guard-bed to

remove traces level of all sulphur contaminants.17

After sulphur removal, the process gas is split into two streams, one going directly to the methanol

synthesis and the other sent to the WGS reactor in order to convert CO into CO2, which is then removed

throughout a cryogenic unit. A rather pure CO2 is produced. After adjusting the R ratio to a value of about

2.1, the syngas is sent to the methanol synthesis reactor (Figure 2). After recovering the methanol, which is

sent to an eventual methanol purification stage (depending on quality requirements), the gas stream is sent

to a pressure swing adsorption (PSA) unit to recover H2, while the purge gas is recycled to the HT reactor

to support the RdF conversion (Figure 2). In this way, all the carbon present in RdF is incorporated in the

methanol, except for the part rejected as CO2.

The overall material balance for a 300 t/d methanol plant is shown in Figure 1, where around 716 t/d of

RdF are used as feedstock.

3.4 Process economics

The economic parameters used to estimate the cost-of-production (COP) of methanol are summarized

in Table 2 for two cases analysed: (A) 300 t/d green field methanol production (e.g. a new plant of

methanol synthesis from RdF) and (B) a hybrid scheme with an existing 900 t/d methanol plant. The latter

is the integration with an existing methanol production plant using NG as feedstock, where excess of H 2

present in the syngas is used to feed an RdF-based methanol plant to boost overall methanol productivity.

The investment for the new plant has been using standard estimating tools and the experience in

building industrial plants. The estimated cost of equipment (delivered) for the different process sections of

the plant are the following: HT converter reactors (3 lines), 28 M€; syngas shift & CO 2 removal units, 8 M€;

methanol synthesis unit, 12 M€; air separator and compressor units, 10 M€. Table 5 provides the overall

10
CAPEX (capital expenditure), calculated as a percentage of the delivered equipment costs. The overall cost

estimated of the plant for a production of 300 t/d of methanol is 189 M€. For the hybrid scheme the CAPEX,

which is relevant only to the RdF conversion and purification (on two single lines), is reduced to 80 M€.

Figure 4 reports the costs and incomes breakdown in a single unit, for a production of 105,000 t/y based

on the operating and economic parameters indicated in Figure 1 and Table 2. COP is calculated by

deducing the income from the annual operating costs. The COP per to methanol results about 111 €/t for

an Italian site. About half of the operation cost is related to the depreciation and 20% to the power

consumption (ASU - air separation unit, syngas compression etc.). As far as the income is concerned,

about 80% are coming from RdF and 20% from the avoided cost of emitting CO2.

The commercial market value of methanol depends on many parameters. After reaching a peak up to

500-600 €/t around year 2014, the current average value (beginning year 2017) is around 250-300 €/t,

although clearly depends on regions, delivery, contracts etc. However, bio-methanol produced by wastes is

qualified by the EU’s Renewable Energy Directive (RED) for double recognition. In other words, a supplier

needs only half of the quantity of such bio-fuel in place of 1st generation ethanol to meet their obligations for

gasoline. Current gasoline biofuels, particularly those of second generation, have a cost in the 600-800 €/t

range. Therefore, considering a market value of 300-400 €/t for biomethanol (to be competitive over bio-

ethanol), it may be estimated a product value in the 150÷250€/t range. It may be also recalled that other

bio-methanol productions, for example from wood, agricultural residues or byproducts such as glycerine, or

from CO2 (if not extremely cheap renewable energy sources are available) are all estimated significantly

higher (2-3 times higher)21 than this estimated COP for biomethanol from RdF.

3.5 Sensitivity analysis

Considering that 2.4 t of RdF are consumed for each t of methanol produced (Figure 1) in the WtM plant

discussed above, an urban area producing around of 700,000 t/y of MSW (assuming that 35% of them will

be converted into RdF), is required for a 300 t/d bio-methanol plant. This corresponds in terms of

11
population to about 1.0-1.5 Million of inhabitants' equivalent, by considering that RdF should be transported

to less than 100-150 km to reduce costs and environmental impact, and the average MSW production per

habitant. In Europe, this corresponds to a population density of about 35 person/km 2, while in a large part

of Europe the population density is above 50 person/km2. It is thus a feasible situation for many urban

areas.

The incomes generated by RdF disposal are the main driver to reduce the COP. Such a value may vary

from country to country and it is related to the distance from the installed incinerator capacity as well as

their efficiency. The proposed new architecture (WtM) will have enhanced advantages, where RdF is

landfilled and limited incineration capacity is available, or when in the latter case, the co-generation of heat

is not exploited (in many south Europe areas, for example). The sensitivity analysis of the impact of RdF

price on the methanol COP evidences that the latter linearly decreases from about 160 €/t for RdF price of

50 €/t to about 85 €/t for RdF price of 80 €/t, with a parallel linear increase of the industrial margin from

about 240 €/t to about 315 €/t.

3.6 Return on investment (ROI)

For shareholder, the return on shareholders’ equity, e.g. the payback time of the investment, is a simple,

but critical element to evaluate quickly the process economics. In order to provide a simplified ROI, the

following data were considered: (1) a net sales of 42.0 M€, based on a methanol price of 400 €/t (250 €/t

COP + 150 € as price cap); (2) other incomes for 21.5 M€; (3) less costs for 16.7 M€; (4) less loan

repayment (loan is 2/3 of CAPEX, equity 1/3 of CAPEX; repayment calculated on 20 years with 6% interest

rate) of 11.0 M€. These data allow obtaining a pretax profit of 35.7 M€, which applying a 50% tax, indicates

a ROI of 28.7 %. The payback time of the investment results thus is about 4 years, a quite interesting value

for investments in the area of biofuels. For a smaller bio-methanol plant having a capacity of 50,000 t/y,

ROI results around 18%, with thus slightly higher payback times, but lower risks of investment, being

CAPEX reduced.

12
 The possible alternative for bio-methanol are the following:

i. the production of biogas by anaerobic fermentation, separation of biomethane from CO 2, and then

conventional methanol catalytic synthesis via syngas,

ii. the gasification of byproducts in biofuels production (specifically, glycerine from biodiesel), waste

biomass (forest residue) or of other biomass waste (like black liquor gas) and then, after purification

of syngas, conventional methanol catalytic synthesis.

No economics are available in literature on these alternatives, but a rough estimation is of payback times

over 6 years, thus about 50% higher.

3.7 Methanol production in a hybrid NG + RdF process

The proposed hybrid process is shown in Figure 5a. The concept is to install only a section of the plant,

which provides HT conversion and cleaning of RdF, producing a syngas with high CO/CO2 content to

balance the excess of hydrogen produced in a conventional methanol plant where NG is the feedstock. As

reference, a methanol plant having a capacity of 900 t/d has been considered. A commercial copper-based

catalyst has been considered for conversion of syngas to methanol. To balance such a plant two lines of

RdF conversion have been envisaged to treat about 375 t/d of RdF (Figure 5b).

The CAPEX for this hybrid approach is estimated in 80 M€. Reduction of NG with overall material

balance is indicated in Figure 5b. Figure 6 provides the breakdown of the COP, where depreciation has

been considered only for the new HT conversion section. In such favourable condition, the COP becomes a

profit even without considering the CAP for bio-methanol production. Although the proposed hybridization

looks very attracting from the economical point of view, it is important to stress that availability of RdF

nearby a methanol plant may be often limited and the number of plants, where this could be implemented in

such a way, is then low. Nevertheless, a number of alternative schemes may be imaged, for example a

hybrid approach, where the methane is also deriving from biosources (biogas). This could be in principle a

13
solution to retrofit some small methanol plants. A hybrid bioNG + RdF plant will have a COP in between the

examined cases, depending on availability of digestors and biomethane separation units.

3.8 WtM versus WtE for RdF disposal

In the proposed scheme for WtM (Figure 2, case 2), the energy efficiency (determined from the energy

balance) is calculated to be about 56-57% in terms of feed + fuel LHV. To analyse the impact on GHG

emissions, it is necessary to calculate the CO2 emissions from WtM plants. This value could be determined

by making a carbon and energy balance on the process indicated in Figure 2 (case 2 of removal excess

carbon) and is found to be 1.2 kg CO2 per kg of methanol (MeOH). Typical CO2 emissions from MeOH

production range between 0.5 tCO2eq/tMeOH for steam reforming with primary reform and 1.4 tCO2eq/tMeOH for

partial oxidation of residual oil.22 In the case of European plants, due to the use of both technologies, the

average CO2 emissions (direct and indirect) are assumed to be 0.76 tCO2eq/tMeOH.22 However, for a proper

comparison of the GHG impact of producing methanol from RdF, it should be considered that RdF should

be disposed, for example in the WtE process to produce electrical energy. On the average, current WtE

processes produce about 1 kWh/kgRdF. Therefore, the comparison of production of MeOH from RdF or from

fossil fuels should consider that there is an additional CO2 emission associated to RdF combustion to

produce electrical energy, but that this electrical energy should be alternatively produced from fossil fuels.

Currently, gas turbines using natural gas has an average emission of 0.4 tCO2/MWh. The comparison of the

GHG impact of the WtM versus WtE should consider for the latter the sum of 1.2 tCO2/tMeOH and of about 1.0

tCO2/tMeOH emitted to produce the electrical energy equivalent to that which can be produced by

thermovalorization of an equivalent amount of RdF (WtE process). This value (2.2 tCO2) should be

compared with the average of 0.76 kg CO2 per kg of MeOH from fossil fuels plus the CO2 emissions

associated to RdF combustion. In current RdF incinerators, the average emissions are 1.23 t CO2/tRdF, which

translate to 2.9 tCO2/tMeOH by considering the yields of production of methanol from RdF. Therefore, the 2.2

tCO2 for WtM process should be compared with 0.76+2.9 = 3,66 tCO2 for methanol production from fossil

14
fuels, at an equivalent use of RdF and production of electrical energy. There is thus a reduction of about

40% in terms of impact on GHG emissions.

Furthermore, the WtM approach with respect to WtE solution for RdF disposal shows the strategic

advantage related to produce a liquid fuel rather than electrical energy. This allows the easy storage of the

fuel and distribution even on a long distance, while electrical energy strongly depends on the capacity of

the grid to accept the introduction of the electrical energy, which in turn depends on the highly fluctuating

demand, being electrical energy storage still not effective on large scale. Therefore, WtM approach

depends less on market demand fluctuations, which are an increasing issue. In other words, may operate

under pseudo-constant capacity, differently from WtE plants, thus with a benefit in terms of amortization

and economics. Methanol, in addition, has the double market as fuel (or raw material to produce fuel

components, for example MTBE - methyl terbuthyl ether) and chemical. For the latter, incentives equivalent

to those for biofuel do not exist currently, but may be perhaps introduced in the future. Nevertheless, the

possibility of double market allows having a greater flexibility and thus reducing the investment risks.

In considering the average methanol market cost and the premium as biofuel, this result in a ROI of

about 29%, e.g. a payback time of about 4 years. These values reduce slightly for a smaller size plant.

Instead, they can be significantly increased for a hybrid scheme of integration with an existing methanol

plant from NG. In this case, the COP becomes a profit even without considering the CAP for bio-methanol

production. Alternative schemes, for example by integrating methanol production from biomethane (biogas)

and RdF could be considered.

3.9 WtM versus alternative bio-methanol routes

Bio-methanol is an attractive alternative biofuel for direct blending or as feedstock for producing other

biofuels, besides as a valuable raw material for chemicals. While methanol is currently made in large scale

essentially from fossil fuels, production of methanol from other carbon-containing feedstock (including

biogas, biomass, waste streams and CO2) is attractive for the decrease of GHG emissions and the

15
possibility of counting twice to meet biofuel targets. However, current approaches indicate a COP of bio-

methanol between 1.5-4.0 times higher than the cost of NG-based methanol.21 We have shown here that

producing bio-methanol from RdF may result in a competitive COP, estimated of about 110 €/t for a new

WtM 300 t/d plant.

In general, estimates of CO2 emissions from bio-methanol production (on LCA bases) may range from

0.56 tCO2eq/tMeOH from forest residues to 0.64 tCO2eq/tMeOH methanol for short rotation coppice21,23,24 with

respect to methanol from fossil fuels (average of 0.76 tCO2eq/tMeOH). The emission reduction is thus around

16-26%, slightly lower than that estimated for wood-based bio-methanol production (24-40%).25 For a new

WtM plant, the CO2 equivalent emissions are higher than in all these cases (1.2 tCO2eq/tMeOH), but it has to

be accounted that RdF are alternatively converted, as discussed in the previous section. The RdF

incineration generates electricity substituting the equivalent amount by public power generation (European

electricity mix) with a net CO2 eq. emission of about 330 kg/tRdF.26 By considering this aspect, the WtM

process allows to produce methanol with about 40% and 30-35% reduction in GHG emissions with respect

to methanol production from fossil fuels and bio-resources, respectively.

Between the additional advantages of producing a liquid fuel rather than electrical energy is the

possibility of easy storage of the fuel, while electrical energy strongly depends on the capacity of the grid to

accept the introduction of the electrical energy. Methanol produced is a biofuel, and count twice to meet

biofuel targets. GHG emissions are lower than those associated to incineration of MSW. Finally, there is an

easier integration with RE sources. In fact, if excess of RE is available at low cost (for example, by wind

during night), it may be used to produce H2, which allows to be co-fed together with CO2 to the methanol

reactor to enhance the productivity.

The energy efficiency, estimated considering the LHV of the product (methanol) with respect to the LHV

of inlet RdF, is 68,8% which slightly reduces considering the energy input necessary for producing the O2

required for HT converter. The energy efficiency remains higher, however, than for WtE plants without heat

16
co-generation. These indications pointed out that WtM is a valuable solution both from economic, strategic

and environmental perspectives.

4. Conclusions

Bio-methanol can be produced from RdF at an estimated cost of 110 €/t for a new WtM 300 t/d plant

(ROI about 29%), making it competitive as a biofuel blend. With respect to the WtE approach for RdF

disposal, this solution shows various advantages. In a hybrid scheme of integration with an existing

methanol plant from NG, the cost of production becomes a profit even without considering the cap for bio-

methanol production. The WtM process allows to produce methanol with about 40% and 30-35% reduction

in GHG emissions with respect to methanol production from fossil fuels and bio-resources, respectively.

Acknowledgment

This work was supported by Kinetics Technology s.p.a. and the Maire Tecnimont Group, which are

gratefully thank for their financial support to this activity. The authors like to thank the Colari srl group for

providing data about the composition values of RdF and the RdF thermogasification plant located in

Malagrotta (Italy).

Appendix A. Supplementary data

Supplementary data associated with this article can be found in Appendix A, which contains also the list of

abbreviations utilized.

17
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20
 TABLES

Table 1. Chemical composition of RdF and variation range. LHV waste: 14,0 MJ/Kg (varies in the 12-16
MJ/Kg range)

Organic
Composition, Wood Paper Plastic Textile Inert fraction
Fraction
% wt.
3 29 31 7 12 18
Range
1-4 10-34 26-36 7-8 10-14 10-27
variability, % wt.
Composition, C H O H2O Ashes
% wt. 33,5 4,5 16,5 20,25 25,25
Range
29-38 4-5 14-18 19-22 17-30
variability, % wt

21
 Table 2. Key economic assumptions and parameter.

RdF price (flock type), €/t (Italian basis) 70

Electricity price, €/MWh 50
Natural gas, €/kg (considering 11500 kcal/kg) 0.15
Slag disposal costs, €/t 20
300 t/d new bio - Hybridization with a NG
Case
methanol plant based 900 t/d methanol unit
CAPEX, M€ 189 80
Labor, M€/y 3 1
Methanol capacity, t/y 105,000 55,000
Maintenance cost, M€ (1) 4.0 2.4
Plant factor, h 8400
Depreciation factor (2) 0.0875
Other costs, M€ 2.0 0.6
Calculated cost of excess CO2 capture, €/t 15
(1) based on 1% of CAPEX for syngas-methanol section and 3% of the CAPEX for the conversion/purification section.
(2) based on 20-year life and 6% interest rate

22
Table 3. Chemical composition of syngas produced from HT gasifier unit (before purification step): typical
value (considered in estimation) and variation range (min-max values). Values are percentage in volume.
Syngas is in saturation condition.

Parameter
Typical Min Max
and Unit

H2, vol % 40,0 36 40

CO, vol % 41,0 37 43
CO2, vol % 13,0 8 16
H2O, vol % 5,0 6 8
N2, vol % < 4,0 1 5
O2, vol % < 1,0 - <2
CH4, vol % < 3,0 - <5
Argon, vol % < 1,0 - <2

23
Table 4. Impurities present in the syngas produced from HT gasifier unit (before purification step): typical
value (considered in estimation) and variation range (min-max values). Values are in mg/Nm3.

Parameter Typical Min Max

H2S, mg/Nm3 < 500 100 1500
COS, mg/Nm3 < 50,0 10 150
Other sulphur compounds (CS2, etc.) < 10,0 - < 10
HCl, mg/Nm3 < 1,0 - <5
HF, mg/Nm3 < 1,0 - <1
HCN, mg/Nm3 < 5,0 - <10
Hg, mg/Nm3 < 0,2 - < 0,2
Ti plus Cd, mg/Nm3 < 0,2 - < 0,2
Heavy metals (Sb, As, Pb, Cr, Co, Mn, Ni, V,
< 1,0 - <1
Sn. Ca, Ta), mg/Nm3 (total)
particulate matter, mg/Nm3 < 1,0 - <3

24
Table 5. Estimated investment costs

% of delivered
M€
equipment cost
Equipment costs (delivered) 58 100
Bulk materials (piping, instrumentation,
40 70
electrical)
Building & civil works 12 20
TOTAL DIRECT COSTS 110 190
Engineering & site supervision 13 22
Construction 41 71
TOTAL DIRECT + INDIRECT COSTS (TOT) 164 283
Contractor profit 5% 8 14
Contingency 10% 17 28
Fixed capital investment (CAPEX) 189 328

25
 FIGURES

RdF (716 t/d)

COFEED BYPRODUCTS
CO2 (367 t/d)
Power (16 MWh)
Waste to Methanol Inert material (143 t/d)
Process Sulfur (1,7 t/d)
Demiwater (107 t/d)
Salts (3 t/d)

CH3OH (300 t/d)

Figure 1. Overall material balance for a 300 t/d WtM plant.

26
 RdF
O2

Air Separation
Unit 1 Unit 2 Unit 3
Unit
HT Gasifier
N2
Utilities Power

Purge gas recycled

O2 renewable Unit 1 Unit 2 Unit 3
H2O energy Syngas Purification

Electrolysis
Storage

H2 Steam Compression
Sulphur removal

Shift & CO2 H2

CO2 PSA
removal
CH3OH
synthesis

CH3OH
Methanol
purification

Figure 2. Block diagram for a 300 t/d WtM plant.

27
 RdF Feed System
a) HT Gasifier b)

Stabilizing Area
 1150-1100°C
Quench

Temperature Profile
HT Gasifier

Re-heating Area
 800-1150°C Syngas
Oxygen
WESP
Fixed-bed
RdF
Level

Gasification Area
 1600-800°C Molten Slag
Oxygen (granulated)
Melting Area Sedimentation
Molten slag
 1600°C tank Acid
scrubber
Alkaline
scrubber

Figure 3. (a) HT converter for WtM plant with indications of different reaction zones and of the temperature

profile. (b) Unit of HT gasification and related purification section.

28
 CO2 use

CO2 avoided

Rdf disposal 111 €/tCH3OH

TOTAL INCOMES

TOTAL COSTS

Labor

Other costs

Depreciation

Maintenance

Slag disposal COSTS

INCOMES
Power

0 5 10 15 20 25 30 35

COP , M€/y

Figure 4. Breakdown of the estimated costs of production (COP) of methanol for a single unit (105,000 t/y)

in a 300 t/d new WtM plant.

29
 a) b)
RdF RdF CO2 Methanol
495 t/d 900 t/d
power
O2 NG
HT HT Primary Primary Reformer
500 t/d
Air Separation Converter Converter Reforming & Conversion to
Unit Demi water
620 t/d Methanol
Syngas Syngas
Cleaning Cleaning Methanol
RdF
Synthesis
375 t/d RdF Conversion
Storage / Power to Syngas
Compression Methanol 3,7 MW/h
Purification
Inert material Sulfur Salts
74 t/d 1 t/d 1,5 t/d
Methanol

Figure 5. (a) Block Diagram for the hybrid RdF/natural gas to methanol. (b) Overall material balance.

30
 Reduction NG cost

CO2 avoided

Rdf disposal

TOTAL INCOMES

TOTAL COSTS

Labor
-65 €/tCH3OH
Other costs

Depreciation

Maintenance

Slag disposal COSTS

INCOMES
Power

0 5 10 15 20 25

COP , M€/y

Figure 6. Breakdown of the estimated costs of production (COP) of methanol for a hybrid NG + RdF

methanol plant.

31
TOC/Abstract Graphic

716 t/d CH3OH (300 t/d)

Waste to
RdF Methanol Process

CO2 (367 t/d) + inert materials

The waste-to-methanol (WtM) process and related economics are assessed to evidence that WtM is a

valuable solution both from economic, strategic, and environmental perspectives.

32
HIGHLIGHTS
 Bio-methanol production via high temperature conversion of Refuse-derived-fuel (RdF)
 Waste-to-methanol (WtM) process and related economics were assessed
 Estimated cost of production of bio-methanol is 110 €/t for a new WtM 300 t/d plant.
 ROI (Return of Investment) of about 29%, e.g. a payback time of about 4 years.
 WtM process halves GHG emissions with respect to methanol production from natural gas

33