Conversion of Solid Waste to Diesel via Catalytic Pressureless

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Conversion of Solid Waste to Diesel via Catalytic Pressure-less Depolymerization: Pilot Scale Production and Detailed Compositional Characterization Arturo Gonzalez Quiroga, Marko R Djokic, Kevin Marcel Van Geem, and Guy B Marin Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b01639 • Publication Date (Web): 31 Aug 2016 Downloaded from http://pubs.acs.org on September 1, 2016

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Energy & Fuels

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Conversion of Solid Waste to Diesel via Catalytic

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Pressure-less Depolymerization: Pilot Scale

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Production and Detailed Compositional

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Characterization

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AUTHORS’ NAMES: Arturo Gonzalez-Quiroga, Marko R. Djokic, Kevin M. Van Geem, Guy B.

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Marin

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AUTHORS’ ADDRESS: Laboratory for Chemical Technology, Ghent University,

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Technologiepark-Zwijnaarde 914 - 9052 Ghent, Belgium.

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Journal: Energy & Fuels (IF=2.835; Q1 Chemical Engineering - miscellaneous; Publisher:

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ACS)

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KEYWORDS: Solid recovered fuel, Refuse derived fuel, Municipal solid waste, Deoxy-

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liquefaction, Energy conversion, Synthetic diesel, GC × GC-FID/TOF-MS.

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ABSTRACT

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Solid waste is considered as one of key feedstocks for the chemical industry to stimulate the

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World’s transition towards a circular economy. Therefore a novel production process, the

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Catalytic Pressure-less Depolymerization (CPD), for conversion of waste to high energy density

ACS Paragon Plus Environment

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liquid fuel has been studied. More specifically, the organic fractions recovered from demolition

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waste and municipal solid waste were liquefied and deoxygenated in a CPD pilot plant with 150

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L h-1 (4.2 × 10-5 m3 s-1) liquid fuel capacity. The produced fuels were characterized by elemental

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analysis, Comprehensive Two-Dimensional Gas Chromatography (GC × GC) and the ISO tests

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for automotive diesel established by the EN 590:2009 Standard. The studied fuels showed very

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low oxygen contents (< 0.4 wt. %) and a high share of paraffins (> 40 wt. %). The carbon range

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of the fuel obtained from demolition wood was wider than that of the fuel obtained from

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municipal solid waste (C5-C29 vs. C6-C22). The flash points (54, 46 °C), the sulfur contents (40,

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80 ppmw) and the cetane numbers (43, 33) did not comply with the respective requirements for

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automotive diesel (i.e., ≥ 55 °C, < 10 ppmw and ≥ 51). Nevertheless, both fuels showed salient

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cold filter plugging points (-14, -15 °C) and cloud points (-15, -44 °C), which are indicative of

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good fuel performance at extreme winter conditions. The wide carbon number distribution,

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especially toward the lower range (i.e., carbon number < C12), suggests that the studied fuels can

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be split into a kerosene-like and a diesel-like cut. Overall, the fuels from the CPD process exhibit

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great potential as alternative transportation fuel, however selecting the starting material is crucial

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for minimizing costly hydrotreating.

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INTRODUCTION

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New processes for the production of transportation fuels starting from lignocellulosic biomass

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and organic wastes are a major area of research because of their potential as alternative energy

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resources and to increase sustainability.1, 2 Although thermochemical processes such as

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pyrolysis3-5 and gasification6, 7 have great potential, their outlet streams require expensive and

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energy-intensive post-processing. For example, pyrolysis oils produced from biomass are


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deoxygenated by adding extra hydrogen in a high-pressure (∼ 10 MPa) catalytic reactor operated

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at temperatures of ≈ 350-400 °C.8-10 A different approach is the Integrated Hydropyrolysis-

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Hydroconversion process (IH2) in which the feedstock undergoes hydropyrolysis and

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hydroconversion in separate low-pressure (~ 1 MPa) catalytic reactors operated at temperatures

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of ≈ 350-430 °C.11-14 In this work the focus is on an alternative catalytic process in which

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lignocellulosic biomass, organic wastes and mixtures thereof can be potentially liquefied and

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deoxygenated in a single step at reduced pressure and temperature. The process, known as

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Catalytic Pressure-less Depolymerization (CPD), produces a mixture of hydrocarbons and minor

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amounts of oxygenates which can be upgraded to transportation fuels by distillation and an

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optional hydrotreating step. Two different feedstocks for the process are studied: post-processed

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demolition waste and post-processed Municipal Solid Waste (MSW). These feedstocks were

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selected because they represent a broad spectrum of non-hazardous wastes which are

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commercially available, are enriched in plastics and cannot be recycled.15 Elemental analysis,

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ISO tests for automotive diesel and for the first time a detailed compositional analysis of the

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liquid fuel from the CPD process were determined.

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The CPD process (also called the KDV process from the German abbreviation

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KATALYTISCHE DRUCKLOSE VERÖLUNG) transforms lignocellulosic biomass and

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organic wastes into a liquid fuel (hereinafter referred to as CPD fuel) with an elemental

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composition comparable to that of petroleum diesel.16 In the CPD process the feedstock is mixed

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with an alkali-doped alumino-silicate catalyst in an oily suspension and subjected to viscous

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heating in a high shear in-line mixer until ≈ 270-320 °C at an absolute pressure of ≈ 90 kPa.16-18

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CPD fuel, non-condensable gases, asphalt-like residue and inorganics are the main product

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streams that are obtained. Two distinguishing features of the CPD process are the heat transfer


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mechanism and the range of temperatures in the catalytic reactor. Conventional heating through

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the wall, which rely on temperature differences, is replaced by viscous heating in the high shear

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in-line mixer. Besides, the temperature in the catalytic reactor ranges from 270 to 320 °C which

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is substantially lower than the typical ranges for other processes like hydro-deoxygenation,

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pyrolysis and gasification. As a consequence, non-uniformities in temperature and heat flux

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distribution are virtually eliminated. Coking is thus not expected to be a major issue for the CPD

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process.

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Technical information on the CPD process can only be found in patents.19, 20 The CPD process

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seems strongly related to the (co-)deoxy-liquefaction process, which has been applied and

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demonstrated at laboratory scale to produce a so-called “bio-petroleum” starting from crop

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residues21, 22, oil crops23, 24, woody biomass25, 26, aquatic plants27, 28, weeds29, 30, macroalgae31, 32

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as well as mixtures of different biomasses and vegetable oils33-36. Both, CPD and (co-)deoxy-

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liquefaction, are single-step processes, their operation temperature is lower than that of pyrolysis

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(i.e., ≈ 270-320 °C for CPD and ≈ 350-450 °C for deoxy-liquefaction vs. ≈ 450-550 °C for

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pyrolysis), and their liquid products contain less than 6 wt. % oxygen and exhibit excellent High

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Heating Value (HHV) (i.e., 38-45 MJ kg-1). In addition, the composition and energy content of

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biopetroleum obtained from different biomasses, with and without catalyst, are comparable.31, 37

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This suggests that minerals in the feedstock act as catalyst in the deoxy-liquefaction process,

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similar to the formation of crude oil from organic matter in geological systems.38 However, there

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are some important differences as well. First of all, scale-up has not evolved at an equal pace.

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The CPD process is already carried out at pilot scale while the (co-)deoxy-liquefaction process

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has only been reported at laboratory scale. Second, the CPD process uses a high shear in-line

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mixer to boost the contact between the feedstock and the catalyst in an oily slurry while the (co-


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)deoxy-liquefaction process is commonly carried out in a sealed chamber in the presence of

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either 10-20 wt. % water or 20-90 wt. % vegetable oil as a medium. Third, and the main

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difference, in the CPD process energy is transferred to the reaction medium by viscous heating in

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the high shear in-line mixer while in the deoxy-liquefaction process thermal energy is transferred

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through the walls at heating rates from 0.1 to 1.3 °C s-1.21-36

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A potential feedstock for the CPD process is the Solid Recovered Fuel (SRF, also known as

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Refused Derived Fuel or RDF) from the Mechanical-Biological Treatment (MBT) of household,

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industrial and commercial wastes.15, 39 MBT plants employ size reduction, air classification and

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bioconversion (e.g., composting) which result in a solid product of lowered moisture content that

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is enriched in plastics.15 The European Committee for Standardization (CEN) has established

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five classes for SRF based on the heating value, chlorine and mercury content.40 Standardization

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is a potential key advantage for SRF over alternative feedstocks due to the impact of feedstock

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quality on process safety and performance, and product quality.

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To the best of the authors’ knowledge there are no published studies about the CPD process at

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laboratory scale. In the few studies on the quality of the CPD fuel it has been demonstrated that

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the density and viscosity comply with the requirements for transportation diesel established by

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the European Standard EN 590:200941.16, 18, 42 These same studies show that the sulfur content

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exceeds the EN 590:2009 limit of 10 ppmw. These global properties indicate that CPD fuel can

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be an interesting candidate to assist in the transition towards a more sustainable energy policy.43,

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44

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polyolefins45 and it has also been suggested for biomass-based biorefineries17.

The CPD is the process with the highest potential for the production of liquid fuel from waste


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However, the lack of knowledge about the detailed chemical composition of the CPD fuel

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hinders its further development. This work closes that gap and also compares the chemical

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composition of CPD fuel obtained from two different SRFs to that of petroleum diesel.

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Elemental analysis, Comprehensive Two-Dimensional Gas Chromatography (GC × GC) and ISO

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tests for automotive diesel are used for that purpose. Next to a description of the pilot plant with

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the detailed characterization of the SRFs and their corresponding CPD fuels, guidelines are

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provided to improve the CPD process.

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EXPERIMENTAL SECTION

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Pilot plant. A schematic of the CPD pilot plant is shown in Figure 1 and it can be divided into

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three main sections. The first section consist of a pretreatment step which takes place in the

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mixing tank connected to the rectifier column I. The second section is the catalytic reaction zone.

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This is carried out in the adiabatic reactor, which is connected in a loop with the high shear in-

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line mixer, the hydro-cyclone and the rectifier column II. In the third section the raw CPD fuel is

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purified and upgraded by distillation.

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Pilot plant experimental procedure. Before feeding starts, a suspension of carrier oil, lime and

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catalyst at ≈ 180 °C was prepared in the mixing tank. The mixing tank was heated electrically

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through the walls. A fraction of the suspension was sent to the reactor and circulated through the

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high shear in-line mixer. The dosage of feedstock, lime and catalyst depends on the feedstock

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and needs to be optimized. New additional catalyst (as the inherent minerals in the feedstock are

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catalyst for the CPD process) is continuously added and spent catalyst is continuously separated

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at the bottom of the reactor at a rate of ≈ 0.2 g/s compared to a feed rate of 8 g/s in this set of

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experiments. Based on experience, lime is added to hold the pH above 8.5 for the proper


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functioning of the catalyst although pH or acidity measurements (e.g., Total Acid Number, TAN)

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were not carried out in this work. Solid waste, lime and catalyst were fed by means of a

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volumetric screw feeder while the mixing tank is continuously agitated. The added catalyst and

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lime corresponded to ≈ 5 wt. % of the mass of feedstock. The concentration of solid waste in the

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carrier oil corresponded to ≈ 15 wt. %. Catalyst and lime were added in equal amounts and

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together corresponded to ≈ 5% of the mass flow of solid waste. In the mixing tank the moisture

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in the feedstock is evaporated, volatile organic compounds are released and most of the plastics

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in the feedstock are melted. The resultant slurry was fed into the catalytic converter.

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Figure 1. Process Flow Diagram of the Catalytic Pressure-less Depolymerization pilot plant.

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The slurry was recirculated inside the high shear in-line mixer in which additional energy was

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added by viscous heating. The high speed rotation of the rotor (> 150 revolutions per second)


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exerts suction which results in transporting the slurry from the reactor. The temperature in the

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catalytic conversion stage varied within the range 270-320 °C. The atmosphere of the reactor is

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mainly composed of water vapor, non-condensable gases (mostly CO2) and the generated

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organic vapors. The lightest products were continuously separated as vapors in the hydrocyclone

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and sent to the rectifier column II. Slurry from the reactor was sent back to the pretreatment tank

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to keep a minimum liquid level which was continuously mixed with fresh feed. A solid by-

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product which consisted of spent catalyst, alkaline salts and ashes settled at the bottom of the

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reaction tank. Non-condensable gases, water and raw CPD fuel were separated at the top of the

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rectifier column II. The raw CPD fuel was further upgraded in the distillation column. The top

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product corresponded to the CPD fuel, while the bottom product was a heavy residue that

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strongly resembled asphalt.

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The stability of the carrier oil still needs further assessment and it is reasonable to assume that a

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carrier oil make-up will be required for long-time operation. Recent experimental work on the

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continuous liquefaction of biomass in Light Cycle Oil (LCO) at 320 °C and solids loading of

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around 20 wt. % (operation conditions comparable to those of our work) showed that a steady-

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state production of bio-oil over eight recycles of LCO can be reached.46 That study supports the

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view that the carrier oil could be mainly needed for starting the process, although the required

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make-up flow is still to be determined.

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The pilot plant runs continuously for approximately 8.5 h. During the first 2-2.5 h the mixing

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tank is heated up and the carrier oil is recirculated through the high shear in-line mixer until

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reaching 270 °C. At this time, the feeding of the feedstock starts. After around 0.5 h the flow of

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CPD fuel stabilized and the samples for analysis were taken. It is expected that during start-up

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fluctuations of the composition of the CPD fuel are unavoidable before reaching a steady state.


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The continuous addition of fresh catalyst and removing spent catalyst has as objective to produce

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a CPD fuel with a stable composition. Further studies are needed to confirm this.

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Feedstocks. The feedstocks consisted of SRF from demolition waste (SRF-DW) and SRF from

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municipal solid waste (SRF-MW). SRF-DW and SRF-MW with a maximum particle dimension

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of ≈ 2 cm was processed in the 150 L h-1 (4.2 × 10-5 m3 s-1) CPD pilot plant of Alphakat GmbH

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located in Hamburg-Eppendorf (Germany).

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Chemicals for analysis. Analytical gases (He, N2, H2, CO2 and Air) with a purity of 99.99%

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were used. 3-Chlorothiophene with a purity of 98% was chosen as the internal standard for GC ×

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GC-FID analysis.

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Elemental and ash analyses. The elemental composition of the SRFs and their corresponding

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CPD fuels was determined with a Flash EA2000 (Interscience, Belgium) equipped with a

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Thermal Conductivity Detector (TCD). The ash content of the SRFs was determined with a

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muffle furnace (Nabertherm LT 15/13) set to 575 °C. The elemental composition and the ash

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content of the SRFs are reported relative to the 105 °C oven dry weight of the sample. The sulfur

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content of the CPD fuels was determined with a Flash EA2000 (Interscience, Belgium) equipped

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with a Flame Photometric Detector (FPD).

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Sample preparation for GC × GC analysis. The concentration of internal standard (i.e., 3-

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chlorothiophene) was optimized to give peak height comparable to those of the quantified

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components. This resulted in 3.43 wt. % 3-chlorothiophene for the CPD fuel obtained from SRF-

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DW and 2.87 wt. % 3-chlorothiophene for the CPD fuel obtained from SRF-MW.


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GC × GC analysis. GC × GC has proven to be a powerful chromatographic technique for the

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compositional analysis of kerosene47, diesel48, gas oil49, shale oil50 and different types of

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pyrolysis oil51-53, yielding accurate results with enhanced resolution. The GC × GC analysis of

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the CPD fuels was carried with two Thermo Scientific TRACE GC × GC’s (Interscience,

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Belgium). Both devices were equipped with a dual stage cryogenic CO2 modulator. Two

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different detectors, i.e. a FID and a Time-Of-Flight Mass Spectrometer (TOF-MS), mounted on

7

different GC × GC’s were used. A Programmed Temperature Vaporization (PTV) injector was

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used for the FID analysis and a Split/Splitless (SSL) injector was used for the TOF-MS analysis.

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For the FID analysis the volumetric flows of H2, N2 (make-up gas) and air were set at 35, 350

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and 35 mL min-1, respectively. The FID temperature was set at 300 °C and its data acquisition

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rate was 100 Hz. For the TOF-MS the data acquisition rate was 30 Hz with a scanning range of

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25-500 amu. The oven temperature program for the CPD fuel originating from SRF-DW started

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at 40 °C and went up to 300 °C at a heating rate of 3 °C min-1. For the CPD fuel obtained from

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SRF-MW, the oven temperature program started at 40 °C and went up to 280 °C at a heating rate

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of 2 °C min-1.

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The columns set consisted of a non-polar first dimension column (Rxt-1 PONA, 50 m Long ×

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0.25 mm I.D. × 0.5 µm df) and a mid-polar second dimension column (BPX-50, 2 m Long × 0.15

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mm I.D. × 0.15 µm df) positioned in the same oven. The modulation time was optimized to give

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a compromise between resolution in the first dimension and minimization of wrap-around in the

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second dimension. This resulted in a modulation time of 7 s for the CPD fuel obtained from

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SRF-DW and a modulation time of 5 s for the CPD fuel originating from SRF-MW.

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Data acquisition and quantification. Data acquisition and processing were performed using

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Thermo Scientific’s Chrom-Card system for the FID and Thermo Scientific’s Xcalibur software


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for the TOF-MS. The raw GC × GC data files were processed with GCImage software (Zoex

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Corporation, USA). Contour plotting, retention time measurement, peak fitting and blob

3

integration were carried out with GCImage software. Each blob was tentatively identified based

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on its chemical group and its number of carbon atoms. The identification of the blobs was based

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on the Kovats retention indices54 and the mass spectra. The procedure for the quantification of

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the mass fractions of the detected compounds can be consulted in the Supporting information.

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RESULTS AND DISCUSSION

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Elemental composition and ash content of the Feedstocks. The elemental composition of the

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feedstocks together with their ash content and heating value are shown in Table 1. A visual

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inspection of the SRFs allowed the identification of plastic, paper, wood, cardboard, insulation

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material and textile. Both SRFs have higher carbon and ash content, higher molar H/C ratio, and

12

lower oxygen content when compared to woody and agricultural biomass.55, 56 SRF-DW has

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more than two times higher sulfur content than SRF-MW. The studied SRFs show comparable

14

nitrogen contents. An important question is where the nitrogen and the sulfur in the SRFs will

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end up due to the stringent regulations and requirements for those elements in transportation

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fuels. SRF-MW shows a higher energy content, which is consistent with its lower oxygen

17

content.

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Table 1. Elemental composition on a dry basis, ash content and heating value of the Solid

19

Recovered Fuels. Analysis/parameter

Solid Recovered Fuels SRF-DW

C [wt. %]

41.5a ± 1.9b

SRF-MW 50.7 ± 2.0


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H [wt. %]

5.55 ± 0.5

7.50 ± 0.9

O [wt. %]

34.5 ± 1.9

28.1 ± 2.9

N [wt. %]

0.87 ± 0.3

1.17 ± 0.2

S [wt. %]

0.84 ± 0.2

0.36 ± 0.1

Ash [wt. %]

16.8 ± 0.9

12.1 ± 0.9

Molar H/C ratio

1.6

1.8

Molar O/C ratio

0.6

0.4

HHV [MJ kg-1]57

17.2

23.4

1

a

Average of six measurements, bStandard deviation.

2

Together with the elemental composition of the feedstock, deoxygenation reactions determine

3

the CPD fuel yield. Decarboxylation, i.e., release of oxygen as CO2, is the most effective

4

mechanism to guarantee a molar H/C ratio comparable to that of petroleum diesel (i.e., > 1.8)

5

because the hydrogen in the feedstock is preserved. Experimental results for (co-)deoxy-

6

liquefaction have consistently shown non-condensable gases with molar CO/CO2 ratios of ≈ 0.1.

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Those results show that the (co-)deoxy-liquefaction process favors decarboxylation over

8

decarbonilation.28, 36, 37 Low oxygen content along with high molar H/C ratio are feedstock

9

characteristics that provide a good indication of a high yield of CPD fuel. A mass balance

10

analysis based on the elemental composition of the feedstocks and the CPD fuels reveals that, on

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a dry feedstock basis, the yield of CPD fuel from SRF-DW is approximately 1.5 times higher

12

than that of the CPD fuel from SRF-MW. For the CPD fuel from SRF-MW a maximum yield of

13

35 wt. % is calculated, while for SRF-DW the maximum calculated yield is 24 wt. %. The mass

14

balance analysis is described in the Supporting information.

15

Table 1 shows that SRF-MW is superior over SRF-DW in terms of the expected yield of CPD

16

fuel. An important characteristic of the studied SRFs is their high ash content, as minerals in the

17

ash have been reported to act as catalysts in the CPD process. This means that the consumption


12

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of extra catalyst for the processing of this type of feedstocks should be low. Although elemental

2

analysis of the feedstocks gives a first indication of the expected yields of CPD fuel, elemental

3

and compositional analyses of the fuel are essential for assessing its quality.

4

Elemental composition of the CPD fuels. Table 2 shows that carbon and hydrogen represent ≈

5

99% of the mass of the CPD fuels. These carbon and hydrogen contents are comparable to those

6

typical for petroleum diesel.16 The molar H/C ratio of the studied CPD fuels is comparable to

7

those of petroleum diesel and biopetroleum. Additionally, their oxygen content is much lower

8

than those reported for petroleum diesel16 and biopetroleum25, 27. The reductive atmosphere of

9

the reactor (consisting primarily of CO, CO2, H2 and light hydrocarbons) could enhance the

10

deoxygenation affect as has been demonstrated for the fast pyrolysis of biomass.58

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Table 2. Elemental composition of the CPD fuels compared to biopetroleum from co-deoxy-

12

liquefaction and petroleum diesel. Analysis/parame ter

Origin of the CPD fuel

24

SRF-DW

13

Biopetroleum

Petroleum diesel16

SRF-MW

Raw fuel

Distilled fuel

Distilled fuel

C [wt. %]

85.9a ± 0.2b

86.1 ± 0.1

85.1 ± 0.2

82.9

86.4

H [wt. %]

13.1 ± 0.2

13.2 ± 0.1

13.7 ± 0.1

13.6

13.0

O [wt. %]

0.50 ± 0.01

0.37 ± 0.01

0.16 ± 0.01

1.4

0.55

Molar H/C ratio 1.8

1.8

1.9

1.9

1.8

Molar O/C ratio 4.0 × 10-3

3.0 × 10-3

1.0 × 10-3

1.2 × 10-2

5.0 × 10-3

a

Average of three measurements, bStandard deviation.


13

Energy & Fuels

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Page 14 of 36

1

Raw CPD fuel, i.e., liquid fuel withdrawn at the top of the rectifier column II, originating from

2

SRF-DW shows carbon and hydrogen contents similar to those of the final CPD fuel, although

3

its oxygen content is 35% higher. The final distillation does not significantly change the carbon

4

and hydrogen contents of this raw CPD fuel. On the other hand, the molar H/C ratio of the CPD

5

fuel originating from SRF-DW is slightly lower than that of the CPD fuel obtained from SRF-

6

MW (i.e., 1.8 vs 1.9) which is consistent with the lower molar H/C ratio of the corresponding

7

feedstock. In addition, the CPD fuel obtained from SRF-DW has more than two times higher

8

oxygen content than the CPD fuel obtained from SRF-MW which is also consistent with the

9

higher oxygen content of the corresponding feedstock. These results also indicate that the CPD

10

fuel obtained from SRF-MW has a higher energy content than the CPD fuel obtained from SRF-

11

DW. To further improve understanding of the CPD process a more detailed compositional

12

analysis of the fuels is needed.

13

Chemical composition of the CPD fuels. The GC × GC-FID chromatograms of the CPD fuels

14

are shown in Figure 2. Different group types of hydrocarbons (i.e., n-paraffins, isoparaffins,

15

naphthenes, aromatics, napthenoaromatics, diaromatics, napthenodiaromatics and triaromatics)

16

and oxygenates are identified and quantified. As can be seen from Figure 2 the fuel obtained

17

from SRF-DW is more complex than the fuel obtained from SRF-MW. The internal standard

18

(i.e., 3-chlorothiophene) is adequately separated from the other compounds. The quality of the

19

separation between peaks is assessed by the two-dimensional resolution which was always

20

greater than 1.6.59 Two-dimensional resolutions greater than one are considered as acceptable.


14

Page 15 of 36

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Energy & Fuels

1

2 3

Figure 2. GC × GC-FID chromatograms of the CPD fuels with different hydrocarbon group

4

types. a) CPD fuel obtained from SRF-DW and b) CPD fuel obtained from SRF-MW.

5

Figure 3 shows the detailed compositional analysis by group type and carbon number of the CPD

6

fuel obtained from SRF-DW. The normalized composition by group type and carbon number,


15

Energy & Fuels

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Page 16 of 36

1

including oxygenates, is shown in Table S2 of the Supporting information. Paraffins, which have

2

a high cetane number, account for 42 wt.% of the CPD fuel originating from SRF-DW. Other

3

major groups in this CPD fuel are monoaromatics (21 wt. %) and mononaphthenes (16 wt. %).

4

The carbon number of the CPD fuel originating from SRF-DW ranges from C6 to C29 with a

5

maximum at C12. Approximately half of the mass of this CPD fuel consists of compounds with

6

carbon numbers ≤ C12.

7 8

Figure 3. Detailed chemical composition by group type and carbon number of the CPD fuel

9

obtained from SRF-DW. Results correspond to the average of three repeated injections and error

10

bars represent twice the standard deviation.

11

The detailed compositional analysis by group type and carbon number of the CPD fuel

12

originating from SRF-MW is shown in Figure 4. The normalized composition by group type and


16

Page 17 of 36

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Energy & Fuels

1

carbon number, including oxygenates, is shown in Table S3 of the Supporting information.

2

Approximately 70 wt. % of this CPD fuel consists of paraffins, i.e., a content of paraffins 1.7

3

times higher than that of the CPD fuel originating from SRF-DW. Monoaromatics (16 wt. %)

4

and mononaphthenes (8.2 wt. %) are the other major groups in this CPD fuel. The respective

5

contents of monoaromatics and mononaphthenes of this CPD fuel are 75% and 50% of those in

6

the CPD fuel originating from SRF-DW.

7 8

Figure 4. Detailed chemical composition by group type and carbon number of the CPD fuel

9

obtained from SRF-MW. Results correspond to the average of three repeated injections and error

10

bars represent twice the standard deviation.

11

The CPD is a catalytic process which involves a large variety of individual reactions (e.g.,

12

cracking, alkylation, hydrogenation, dehydrogenation, hydration, etc.). Giannakopoulou et al.


17

Energy & Fuels

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Page 18 of 36

1

proposed a reaction network for the co-deoxy-liquefaction of biomass and vegetable oil which

2

hypothesizes how a spectrum of products, including those quantified in our work, can be

3

formed.34 For example, from the reactions scheme proposed by Giannakopoulou et al.34 a

4

possible path for the formation of triaromatics is the reaction between aromatic radicals and

5

aromatic molecules, accompanied by hydrogen abstraction and cyclization. Reactions in the CPD

6

process are significantly affected by the chemical composition, acidity and pore size of the

7

catalyst and further studies are required to elucidate the fundamental mechanism.

8

The most pronounced differences between the studied CPD fuels stem from their contents of

9

isoparaffins and their carbon number ranges. The CPD fuel obtained from SRF-MW contains

10

over twice as much isoparaffins as the CPD fuel obtained from SRF-DW. The carbon number of

11

the hydrocarbons in the CPD fuel originating from SRF-DW ranges from C6 to C29 while the

12

respective carbon number in the CPD fuel from SRF-MW ranges from C5 to C22. This difference

13

in carbon number distribution is reflected in a 63 °C difference in their ASTM D-2887 T90

14

values (temperature at which 90 wt. % of the sample evaporates) as can be seen from the

15

simulated distillation curves in Figure 5.

16

Among the different hydrocarbon group types n-paraffins have the highest cetane numbers, the

17

longer the backbone carbon chain the higher the cetane number. Isoparaffins have a lower cetane

18

number compared to those of n-paraffins. Aromatics and naphthenes typically have lower cetane

19

numbers than isoparaffins unless they have a long n-paraffin side chain.60 Although both CPD

20

fuels show comparable contents of n-paraffins (17 and 19 wt. %), the CPD fuel obtained from

21

SRF-DW contains over twice as much n-paraffins with carbon number ≥ C15 as the CPD fuel

22

obtained from SRF-MW. A higher cetane number is thus expected for the CPD fuel originating

23

from SRF-DW.


18

Page 19 of 36

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Energy & Fuels

1 2

Figure 5. Simulated distillation curves of the CPD fuels. The curves were obtained from the GC

3

× GC-FID results according to ASTM D-2887.

4

Comparison between CPD fuel and petroleum diesel. The composition of the CPD fuels is

5

further compared to that of a series of petroleum diesels reported by Gieleciak and Fairbridge.48

6

These petroleum diesels were arranged around three fuel properties, i.e., cetane number,

7

aromatics content and T90 as given in Table 3, and then analyzed by GC × GC-FID. Those

8

properties are good indications of ignition quality, volatility and chemical composition. The

9

comparison with the CPD fuels shown in Figure 6 reveals that the major hydrocarbon group

10

types in petroleum diesel are also present in the studied CPD fuels. The CPD fuel obtained from

11

SRF-DW resembles petroleum diesels PD9 and PD3. The corresponding properties in Table 3

12

indicate that these diesels (i.e., PD9 and PD3) were characterized by low-to-medium cetane

13

numbers, medium-to-high aromatics contents and low-to-medium T90s. The CPD fuel

14

originating from SRF-MW shows the best correspondence with diesels PD1 and PD2. These

15

petroleum diesels (i.e., PD1 and PD2) were characterized by low cetane numbers, low aromatics


19

Energy & Fuels

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Page 20 of 36

1

contents and opposing trends for the T90s temperatures. Although these findings should be

2

interpreted with caution because the effect of the carbon range is not explicitly included, they

3

already give a first indication of the quality of the CPD fuel.

4

Table 3. Petroleum diesels with different fuel properties analyzed by GC × GC-FID.48 Petroleum Diesel (PD) sample

Fuel property Cetane number

Aromatics [wt. %]

T90 [°C]

PD1

Low

Low

Low

PD2

Low

Low

High

PD3

Low

High

Low

PD4

Low

High

High

PD5

High

Low

Low

PD6

High

Low

High

PD7

High

High

Low

PD8

High

High

High

PD9

Medium

Medium

Medium

5


20

Page 21 of 36

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Energy & Fuels

1 2

Figure 6. Comparison between CPD fuel and different petroleum diesels in terms of their major

3

hydrocarbon groups.

4

Oxygenates in the CPD fuel. Oxygenates in the CPD fuel, in particularly low-molecular weight

5

carbonyl compounds, could increase acidity and intensify corrosion. The concentrations of

6

oxygenates in the studied CPD fuels are shown in Figure 7. The oxygenates identified and

7

quantified by GC × GC-FID/TOF-MS account for 2.5 wt. % of the CPD fuel originating from

8

SRF-DW and 0.85 wt. % of the CPD fuel obtained from SRF-MW. Non-aromatic ketones have

9

the highest weight fraction accounting for approximately 50% of the oxygenates in both CPD

10

fuels. In the CPD fuel from SRF-DW, non-aromatic ketones are followed in abundancy by

11

phenols, alcoxybenzenes and aldehydes (17%, 12% and 9% of the quantified oxygenates,

12

respectively). Besides, furans and carboxylic acids are also present in this CPD fuel, although in


21

Energy & Fuels

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Page 22 of 36

1

minor concentrations (< 5% of the quantified oxygenates). A difference in the abundancy pattern

2

is observed in the CPD fuel obtained from SRF-MW. In this case non-aromatic ketones are

3

followed by phenols, aldehydes (25% and 6% of the quantified oxygenates, respectively), and

4

minor amounts of furans and carboxylic acids (< 3% of the oxygenates). The concentrations and

5

functionalities of oxygenates in the studied CPD fuels do not raise special concern with respect

6

to corrosion beyond of that expected for petroleum diesel. For comparison purposes, the pH of

7

fast pyrolysis bio-oils is approximately 2-3 and bio-oils typically contain 3-6 wt. % of volatile

8

carboxylic acids.61 After volatile carboxylic acids, the most acidic compound groups found in

9

CPD fuel (pKa 3-5) are phenols and alcoxybenzenes (pKa ~ 10)61 however the former group

10

accounts for less than 0.1 wt. % and the latter groups combined account for less than 0.8 wt. %

11

of the CPD fuel. These results indicate that bio-oils are ≈ 30-60 times more acidic than CPD fuel.

12

The concentrations and functionalities of the oxygenates in the studied CPD fuels can also be

13

related to the feedstocks. The higher oxygen content of the CPD fuel originating from SRF-DW

14

is consistent with the higher oxygen content of the starting material. Non-aromatic oxygenates

15

typically originate from the depolymerization of cellulose and hemicellulose which are the two

16

more abundant constituents of woody biomass. Most of the aromatic oxygenates (e.g., phenols

17

and alcoxybenzenes) originate from the fractionation of lignin, the third most abundant

18

constituent of woody biomass. The presence of aromatic and non-aromatic oxygenates in both

19

CPD fuels are indicative of the presence of lignocellulosic biomass. That fraction is substantially

20

lower in SRF-MW. Paper and cardboard, which are mainly composed of cellulose, are expected

21

to contribute primarily to the oxygenates in SRF-MW. The different woody biomass content of

22

the starting materials thus explains why aromatic oxygenates in the CPD fuel from SRF-MW are


22

Page 23 of 36

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Energy & Fuels

1

only one-third of those in the CPD fuel from SRF-DW. This information provides guidelines for

2

selecting the feedstock for the CPD process.

3 4

Figure 7. Concentrations of oxygenates in the CPD fuels according to their functionality. Results

5

correspond to the average of three repeated injections and error bars represent twice the standard

6

deviation.

7

In a previous study, comparative spectral analysis based on Fourier Transform Infrared

8

Spectroscopy (FTIR) suggested the presence of aldehydes, ketones and carboxylic acids in CPD

9

fuel obtained from miscanthus.42 In addition to these oxygenates, furans, phenols and

10

alcoxybenzenes are also identified and quantified in the CPD fuels studied in this work.

11

Noticeable, the oxygenates in the CPD fuels identified and quantified in the present study were

12

also identified in bio-petroleum from the deoxy-liquefaction process.30, 31 Special emphasis has

13

been given to the production of valuable phenolic derivatives from biomass by deoxy-

14

liquefaction62, but also by pyrolytic processes63. The co-production of valuable phenolic


23

Energy & Fuels

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Page 24 of 36

1

derivatives by the CPD process is particularly suited for feedstocks with high oxygen contents

2

like lignocellulosic biomass. The economic feasibility of any biomass-, or waste-to-liquid

3

process strongly depends on the co-production of valuable chemicals to cover a part of the

4

production costs. The co-production of valuable phenolic compounds seems attractive to be

5

explored by changing the feedstock, the catalyst and the operation conditions of the CPD

6

process.

7

Standardized properties of the CPD fuels. The characterization of the CPD fuels is further

8

extended by measuring ISO fuel properties applicable to petroleum diesel as specified by the EN

9

590:2009 Standard. Table 4 shows that the density at 15 °C and the kinematic viscosity at 40 °C

10

of the CPD fuel obtained from SRF-DW comply with the requirements of the EN 590:2009

11

Standard. On the contrary, the density and the kinematic viscosity of the CPD fuel originating

12

from SRF-MW are both lower than the minima established by these norms and resemble more

13

the typical values for kerosene.64 Flash Points measurements indicate that both CPD fuels are

14

more flammable than petroleum diesel and do not comply with the specified norm. The Flash

15

Point of the CPD fuel obtained from SRF-DW is 7.5 °C higher than that of the CPD fuel

16

obtained from SRF-MW, which confirms the higher volatility of the latter in line with the results

17

from the compositional characterization. The Cold Filter Plugging Point (CFPP), which is the

18

lowest temperature at which a given volume of diesel fuel still passes through a standardized

19

filtration device, can have a maximum value of -44 °C for arctic class 4 petroleum diesel.41 The

20

CFPPs of the studied CPD fuels, together with their Cloud Points, are indicative of good

21

performance at extreme winter conditions, which has also been pointed out by other

22

researchers.16, 42


24

Page 25 of 36

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Energy & Fuels

1

Table 4. Standardized fuel properties of the CPD fuels compared to those of petroleum diesel

2

and the requirements for diesel established by the EN 590:2009 Standard. Property (Standard)

CPD fuel from SRFDW

CPD fuel from SRFMW

Petroleum diesel16

EN 590:2009 requiremen t

Density at 15 °C (ISO 12185), kg m-3

840

807

842

820-845

Kinematic viscosity at 40 °C 2.52 (ISO 3104) mm2 s-1

1.49

2.94

2.0-4.5

Flash Point (ISO 2719), °C

53.5

46.0

68

≥ 55

Cold Filter Plugging Point (EN 116), °C

-14

-47

-5

n.s.a

Cloud Point (EN 23015), °C

-15

-44

6

n.s.

Content of ashes (ISO 6245), ppmw

350

< 10

n.r.b

≤ 100

Sulfur content, ppmw

40

80

9.0

< 10

Nitrogen content, ppmw

< 100

150

n.r.

n.s.

High Heating Value (ISO 8217), MJ kg-1

42.9

43.2

43.0

n.s.

Iodine number (EN 14111), g I2 (100g)-1

8.8

12.2

12

n.s.

Water content (ISO 12937), ppmw

118

96

21

≤ 200

Cetane number (ISO 5165)

43.0

33.1

51.6

≥ 51

3

a

b

4

On the other hand, the ash content of the CPD fuel originating from SRF-MW and the sulfur

5

content of both CPD fuels exceed the respective limits of 100 and 10 ppmw. Previous studies

6

have also reported sulfur contents of CPD fuel higher than 10 ppmw.16, 42 An upper limit for

7

nitrogen content is not specified by the EN 590:2009 Standard. The typical nitrogen content of

8

petroleum diesel is ≈ 30 ppmw. Diesel engines are the dominant source of Nitrogen Oxides

n.s. non-specified. n.r. non-reported.


25

Energy & Fuels

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Page 26 of 36

1

(NOx) emissions and excessive nitrogen contents compromise the durability of the catalytic

2

converters used to reduce NOx.65 The nitrogen content of the CPD fuel obtained from SRF-MW

3

is considerably higher than that of the fuel originating from SRF-DW (150 vs. < 100 ppmw)

4

which is consistent with the nitrogen content of the feedstocks.

5

The heat of combustion of the studied CPD fuels indicates a very high energy content, similar to

6

that of a typical petroleum diesel. The iodine number, which is used to assess the average degree

7

of unsaturation in biodiesel, provides an indication of the tendency of the fuel to oxidize when

8

exposed to air. The iodine number of petroleum diesel is significantly lower than that of

9

biodiesel. Table 4 shows that the studied CPD fuels are not susceptible to oxidize when exposed

10

to air as indicated by their iodine numbers comparable to that of petroleum diesel. The water

11

content of the studied CPD fuels is within the limits specified by the EN 590:2009 Standard.

12

A concern is that the studied CPD fuels show cetane numbers significantly lower than the

13

minimum specified for transportation diesel. The cetane number of the CPD fuel obtained from

14

SRF-DW is 30% higher than that of the CPD fuel originating from SRF-MW. This result

15

confirms the findings on the quality of the CPD fuel from the compositional analysis and from

16

the comparison with the petroleum diesels in Figure 6. The lower cetane number of the CPD fuel

17

from SRF-MW is mainly a consequence of its relatively high content of low carbon number

18

hydrocarbons (carbon number < C15).

19

Guidelines for improving the CPD process. A gross margin analysis of the CPD process

20

showed a strong sensitivity towards feedstock price, feedstock polyolefins content, process

21

energy efficiency and CPD fuel selling price.66 Transportation cost can easily exceed the cost of

22

the SRF itself, therefore locating the CPD plant as close as possible to a MBT plant is essential.


26

Page 27 of 36

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Energy & Fuels

1

SRFs with high polyolefins content enhance the yield of CPD fuel. Taken the HHV as an

2

indication of the polyolefins content, SRFs class 1 and class 2 exhibit the highest potential for

3

the CPD process.40 Elemental characterization, particularly to quantify nitrogen and sulfur, and

4

ash analysis to adjust the amount and type of catalyst, are key.

5

The energy efficiency of the CPD process, especially at increased plant capacities, can be greatly

6

improved by energy integration. Central to the energy integration of the CPD process is the

7

electric generator coupled to the high shear in-line mixer. Depending on fuel price and fuel

8

availability, the electric generator can be run either on natural gas from the network or on CPD

9

fuel. The exhaust gases from the electric generator can be thermally integrated to the reboiler of

10

the distillation column and to the mixing tank by a thermal oil loop. Depending on the

11

temperature of the exhaust gases after the heat recovery, they could also provide thermal energy

12

for feedstock drying. As an example, energy integration calculations on a CPD plant of over six-

13

fold the capacity of the current pilot plant, i.e., 1000 L h-1 (2.8 × 10-4 m3 s-1) liquid fuel, fed with

14

SRF-DW at a rate of 0.76 kg s-1 shows electric and thermal power demands of 520 and 640 kW,

15

respectively. The case study includes two distillation columns in series operating under vacuum

16

to split the CPD fuel into a kerosene-like cut and a diesel like-cut. These electric and thermal

17

power demands can be covered by a commercial 750 kW gas generator integrated with a Waste

18

Heat Recovery (WHR) heat exchanger and a thermal oil loop. However, the electric generator

19

and the WHR heat exchanger account for ≈ 40% of the installed cost of the plant and the Return

20

On Investment (ROI) could not be attractive for this plant capacity.

21

Splitting the CPD fuel into a kerosene-like cut with its carbon range distributed around C12 and a

22

diesel-like cut with its carbon range distributed around C16 is also suggested. Density, viscosity

23

and flash point are fuel properties that can be steered to comply with current Standards for


27

Energy & Fuels

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Page 28 of 36

1

petroleum-derived diesel and kerosene. This separation can be implemented by adding a second

2

distillation column. Vacuum operation is essential to decrease the temperature in the reboilers

3

allowing for an efficient thermal integration with the exhaust gases from the electric generator.

4

Sulfur content has become one of the most important properties for transportation fuels. The

5

sulfur content of the CPD fuel strongly depends on the quality of the feedstock. The presence of

6

materials of inherent high sulfur content like synthetic rubber, dyed textiles and leather should be

7

minimized. However, the production of ultra-low sulfur CPD fuel (≤ 10 ppmw) appears as

8

unfeasible without the addition of a hydrotreating stage. Although the hydrogen consumption

9

could be relatively low as compared to that for hydrodeoxygenation of bio-oils from

10

lignocellulosic biomass, blending of CPD fuel cuts and ultra-low sulfur petroleum fuels seems a

11

more practical alternative for commercialization. Blending with petroleum fuels has also been

12

suggested for enhancing the properties of the biopetroleum from the co-deoxy-liquefaction

13

process35 and the fuel from the IH2 process13.

14

Finally, the ash content of the CPD fuel obtained from SRF-DW is 3.5 times higher than the

15

upper limit of 100 ppmw established by the EN 590:2009 Standard. In contrast, the ash content

16

of the CPD fuel originating from SRF-MW shows a significantly lower value (≤ 10 ppmw).

17

Although the feedstock of the former CPD fuel has a higher ash content, that difference could

18

originate from the operation conditions in the hydrocyclone and the rectifier column II. A

19

combination of low liquid velocities and high vaporization rates can lead to excessive ash

20

entrainment.

21

The operation temperature of the catalytic conversion stage determines the extent of the (de-

22

)polymerization, deoxygenation and hydrogenation reactions. An in-depth technical evaluation


28

Page 29 of 36

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Energy & Fuels

1

of the CPD process requires the monitoring of the operation conditions and the characterization

2

of all input and output streams. The impact of initial carrier oil type and properties on the quality

3

of the product is yet to be established.

4

CONCLUSIONS

5

This work reports on the first detailed experimental data of the CPD process using solid waste as

6

feedstock, assessing the composition and properties of the produced fuel. SRFs from two

7

different sources, i.e., demolition waste and municipal waste, were converted in a CPD pilot

8

plant of 150 L h-1 (4.2 × 10-5 m3 s-1) liquid fuel capacity. The combination of elemental and

9

detailed compositional analyses, and ISO tests for automotive diesel established by the EN

10

590:2009 Standard, allowed for a thorough characterization of the obtained fuels. The fuels from

11

the CPD process proved to be comparable to petroleum diesel in terms of carbon and hydrogen

12

contents, as well as HHV. They also showed very low oxygen contents (≤ 0.4 wt. %), confirming

13

a deep deoxygenation during the conversion process. Compositional-wise, the studied fuels

14

resembled petroleum diesel of low-to-medium cetane number and medium aromatic content. The

15

detailed compositional analysis of oxygenates in the CPD fuel showed the presence of

16

nonaromatic and aromatic oxygenates. Nonaromatic ketones accounted for approximately 50%

17

by mass of oxygenates and carboxylic acids were detected at minor concentrations (< 100

18

ppmw). Significant compositional differences between the studied CPD fuels were found

19

depending on the starting material. In line with the compositional analysis, the flash points and

20

the cetane numbers showed much lower values than the minima specified by the EN 590:2009

21

Standard. The main reason was the high share of hydrocarbons with carbon number ≤ C12 (≈ 45

22

wt. %). The studied fuels consisted of a mixture of hydrocarbons susceptible to be separated in a

23

kerosene-like cut and a diesel-like cut. The ash and sulfur contents of the CPD fuels also


29

Energy & Fuels

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Page 30 of 36

1

exceeded the minima established for those properties. The former issue could be related to

2

operation conditions in the hydrocyclone, while the latter can be solved by hydrotreatment or by

3

blending CPD fuel and ultra-low sulfur fuel. Plant location, and polyolefins share and sulfur

4

content of the feedstock are critical factors for the techno-economic feasibility of the CPD

5

process. In addition, energy integration, and fuel purification and upgrading require substantial

6

process design considerations.

7

ASSOCIATED CONTENT

8

Procedure for the calculation of the mass fractions of the detected compounds by GC × GC-

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FID/TOF-MS. Mass balance analysis to calculate the yields of CPD fuel. Carbon, hydrogen and

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oxygen contents from elemental and compositional analyses are compared in Table S1.

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Normalized compositions, by group type and carbon number, of the CPD fuels are shown in

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Tables S2 and S3.

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AUTHOR INFORMATION

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Corresponding Author

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*Kevin M. van Geem

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Laboratory for Chemical Technology (LCT), Ghent University

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Technologiepark 918, B-9052, Ghent Belgium

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Tel.:+3292645677

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E-mail address: [email protected]

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Notes


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Energy & Fuels

1

The authors declare no competing financial interest.

2

Author Contributions

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The manuscript was written through contributions of all authors. All authors have given approval

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to the final version of the manuscript.

5

ACKNOWLEDGMENTS

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The research leading to these results has received funding from the European Research Council

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under the European Union’s Seventh Framework Programme FP7/2007-2013/ERC grant

8

agreement n° 290793 and the‘Long Term Structural Methusalem Funding by the Flemish

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Government’. This project has received funding from the European Union’s Horizon 2020

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research and innovation programme under grant agreement No 664876. The SBO proposal

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‘‘Bioleum” supported by the Institute for Promotion of Innovation through Science and

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Technology in Flanders (IWT) is acknowledged. This work was supported by ISTEMA N.V.

13 14

ABBREVIATIONS CEN

European Committee for Standardization

CFPP

Cold Filter Plugging Point

CPD

Catalytic Pressure-less Depolymerization

DW

Demolition Waste

FID

Flame Ionization Detector

GC × GC

Comprehensive Two-Dimensional Gas Chromatography

FPD

Flame Photometric Detector

FTIR

Fourier Transform Infrared Spectroscopy;

HHV

High Heating Value

IH2

Integrated Hydropyrolysis-Hydroconversion

ISO

International Organization for Standardization

KDV

Katalytische Drucklose Verölung (German)


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LCO

Light Cycle Oil

MBT

Mechanical-Biological Treatment

MSW

Municipal Solid Waste

MW

Municipal Waste

NOx

Nitrogen Oxides

PD

Petroleum Diesel

PTV

Programmed Temperature Vaporization;

RDF

Refuse Derived Fuel

ROI

Return On Investment

SRF

Solid Recovered Fuel

SSL

Split/Splitless

TAN

Total Acid Number

TCD

Thermal Conductivity Detector

TOF-MS

Time of Flight Mass Spectrometer

WHR

Waste Heat Recovery

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Conversion of Solid Waste to Diesel via Catalytic Pressureless

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