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A review report on

CO-PYROLYSIS OF SPENT ENGINE OIL & JUTE WITH LIFE CYCLE ANALYSIS & PARAMETRIC SENSITIVITY ANALYSIS

NAMRATA T BISWAS

ROLL NO: 19

M.E 1ST YEAR

DEPARTMENT OF CHEMICAL ENGINEERING

JADAVPUR UNIVERSITY

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C O N T E N T S

Topic Pg No.

1. Introduction 3

2. Literature 4

3. Conclusion 18

4. References 18

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1.0 INTRODUCTION

Pyrolysis is a thermo chemical decomposition of organic material at elevated temperatures in the absence of oxygen. It involves the simultaneous change of chemical composition and physical phase, and is irreversible.Pyrolysis is a type of thermolysis, and is most commonly observed in organic materials exposed to high temperatures. It is one of the processes involved in charring wood, starting at 200–300 °C (390–570 °F). It also occurs in fires where solid fuels are burning or when vegetation comes into contact with lava in volcanic eruptions. In general, pyrolysis of organic substances produces gas and liquid products and leaves a solid residue richer in carbon content, char. Extreme pyrolysis, which leaves mostly carbon as the residue, is called carbonization.The process is used heavily in the chemical industry, for example, to produce charcoal, activated carbon, methanol, and other chemicals from wood, to convert ethylene dichloride into vinyl chloride to make PVC, to produce coke from coal, to convert biomass into syngas and biochar, to turn waste into safely disposable substances, and for transforming medium-weight hydrocarbons from oil into lighter ones like gasoline. These specialized uses of pyrolysis may be called various names, such as dry distillation, destructive distillation, or cracking. Pyrolysis is also used in the creation of nanoparticles,zirconia and oxides utilizing an ultrasonic nozzle in a process called ultrasonic spray pyrolysis (USP).

Pyrolysis also plays an important role in several cooking procedures, such as baking, frying, grilling, and caramelizing. In addition, it is a tool of chemical analysis, for example, in mass spectrometry and in carbon-14 dating. Pyrolysis has been assumed to take place during catagenesis, the conversion of buried organic matter to fossil fuels. Pyrolysis differs from other high-temperature processes like combustion and hydrolysis in that it usually does not involve reactions with oxygen, water, or any other reagents. In practice, it is not possible to achieve a completely oxygen-free atmosphere. Because some oxygen is present in any pyrolysis system, a small amount of oxidation occurs.

What is LCA?

Compilation and evaluation of the inputs, outputs and the potential environmental impacts of a product system throughout its life cycle”

This establishes an environmental profile of the system!

• Life-cycle analysis (LCA) is a method in which the energy and raw material consumption, different types of emissions and other important factors related to a specific product are being measured, analyzed and summoned over the products entire life cycle from an environmental point of view.

– Life-Cycle Analysis attempts to measure the “cradle to grave” impact on the ecosystem.

• LCAs started in the early 1970s, initially to investigate the energy requirements for different processes.

– Emissions and raw materials were added later.

LCAs are considered to be the most comprehensive approach to assessing environmental impact.

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Life cycle assessment (LCA) is the standard procedure to evaluate the environmental performance of a process (Cano-Ruiz & McRae, 1998; Hugo et al., 2004). LCA is an objective process for evaluating the environmental burdens associated with a product, process or activity (IRAM-ISO-14040, 2006). The first step in the application of LCA is setting the boundaries for the LCA analysis, defining the objective of the analysis, the functional unit, and the environmental metrics followed by identification and quantification of the energy and material used in a process. The next step is estimation of waste released to the environment associated with the energy use and material processing. This information is further converted into a set of environmental impacts that can be aggregated into different groups.

2.0 LITERATURE REVIEW

The existing literature has been discussed into three categories.

2.1 Literature on co-pyrolysis

CO-PYROLYSIS OF LOW RANK COALS AND BIOMASS: PRODUCT DISTRIBUTIONS

Ryan M. Soncini, Nicholas C. Means, Nathan T. Weiland.

Pyrolysis and gasification of combined low rank coal and biomass feeds are the subject of much study inan effort to mitigate the production of green house gases from integrated gasification combined cycle(IGCC) systems. While co-feeding has the potential to reduce the net carbon footprint of commercial gasification operations, success of this strategy requires investigation of the effects of coal/biomass co-feeding on reaction kinetics and product distributions. Southern yellow pine was pyrolyzed in a semi-batchtype drop tube reactor with either Powder River Basin sub-bituminous coal or Mississippi lignite at several temperatures and feed ratios. Product gas composition of expected primary constituents (CO, CO2,CH4, H2, H2O, and C2H4) was determined by in situ mass spectrometry while minor gaseous constituents were determined. Product distributions are fit to linear functions of temperature, and quadratic functions of biomass fraction, for use in computational co-pyrolysis simulations. The co-pyrolysis product distributions evolve more tar, and less char, CH4, and C4H2, than an additive pyrolysis process would suggest. For lignite co-pyrolysis, CO and H2 production are also reduced. The data suggests that rapid pyrolysis of biomass produces hydrogen that stabilizes large radical structures generated during the early stages of coal pyrolysis. Stabilization causes these structures to be released as tar, rather than cross linking with one another to produce secondary char and light gases.

Co-pyrolysis of southern yellow pine with a sub-bituminous powder River Basin coal and Mississippi lignite at several temperatures and feed ratios have been shown in this study to yield significant nonlinearities, particularly at higher temperatures and for decreasing coal rank. The data from this study suggests that rapid pyrolysis of biomass produces hydrogen that stabilizes large radical structures generated during the early stages of coal pyrolysis. Stabilization causes these structures to be released as tar, rather than cross linking with one another to produce secondary char and light gases. For this to occur, coal and biomass particles have to undergo rapid heating during co-pyrolysis, and the particles should be in close proximity to one another so that the fresh biomass volatiles can interact with the pyrolyzing coal particles. This study shows the evolution of atomic hydrogen from biomass can take either the form of H2, CH4, or other hydrocarbons. which may be used to stabilize the aromatic coal pyrolysis radicals. In addition, the rapid evolution and quenching inherent in

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these experiments shows that tar is the primary synergistic product of co-pyrolysis. This was verified in coal pyrolysis experiments in a hydrogen environment, which produced more tar and less char than those in an inert environment, with gas production being largely unaffected. Finally, it is shown that, for the two coal types tested, co-pyrolysis synergies are more significant as coal rank decreases, likely because the initial coal structures contain increasingly larger pores and smaller clusters of aromatic structures, which are more readily retained as tar in rapid co-pyrolysis. This study provides the information that hydrogen donation from biomass promotes non-additive tar production on rapid co-pyrolysis with low rank coals, additional studies could provide further proof of this mechanism. In particular, analysis of heavier tar compounds from co pyrolysis would shed some light on whether the synergistic portion of the tar production does in fact originate with the coal feedstock. Likewise, a detailed analysis of the resulting char structures may indicate whether secondary char formation is reduced in co pyrolysis,as suggested by this study’s data. Finally, increasing pyrolysis pressures, increasing particle sizes, or decreasing sweep gas flow rates may give a sense for the effect of tar cracking on the overall co-pyrolysis product distributions, and suggest kinetic rates for these reactions.

CO-PYROLYSIS OF PALM SHELL AND POLYSTYRENE WASTE MIXTURES TO SYNTHESIS LIQUID FUEL Faisal Abnisa, W.M.A. Wan Daud, Sujahta Ramalingam, Muhamad Naqiuddin Bin M. Azemi, J.N. Sahu The mixtures of palm shell and polystyrene waste were pyrolyzed to obtain a high-grade of pyrolyticliquid that potentially could be used as a fuel. Three effective parameters were chosen: temperature, feed ratio, and reaction time. The first phase of the study was a screening test to select the range point of each parameter that resulted in high production of liquid. The selected points were then used as reference data for an optimization study using response surface methodology. The maximum liquid yield of approximately 68.3% was obtained under optimum conditions, which were shown to be a temperature of 600 C , a palm shell/polystyrene ratio of 40:60, and a reaction time of 45 min. The characterization results showed that the high heating value of the liquid obtained was 40.34 MJ/kg with a water content of 1.9 wt% and an oxygen content 4.24 wt%. The liquid mainly consisted of aliphatic and aromatic hydrocarbons.

Process flow diagram:

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The study was divided into several parts. The first part was to study the influence of reaction time on co-pyrolysis yields by applying the fixed parameters of feed ratio (50:50) and temperature (400 C). The reaction times were varied from 15 to 75 min.The second stage was to obtain the temperature effect. With the feed ratio fixed at 50:50 and reaction time constant at 30 min, the temperatures were varied in 100 C increments from 300 to 700 C.

Characterization of pyrolytic liquid: The liquid products were produced with the optimum parameters conditions were characterized for viscosity, density, pH, water content, elemental analysis, and FTIR. Viscosity data are essential for various heat transfer considerations, calculating pressure drop, distillation calculations and mixing system considerations. Viscosity was determined using a rotational viscometer equipped with an SC4-18 spindle. Density describes the quantity of mass material divided by its volume. In this study, a 25 ml pycnometer was used to determine the density of the pyrolytic liquid.

The maximum oil yield of 61.6 wt% was obtained at a reaction time of 45 min. The oil yield shows a significant increase after the pyrolysis temperature reached 400

C and beyond. This may be explained through thermal decomposition of the polystyrene

The polynomial model obtained fits well to predict the response with a high determination coefficient of R2 (0.972) and Q2 (0.610).

The characteristic results showed that the HHV and the composition of the pyrolytic liquid were very close to those of conventional fuel.

CHARACTERISTICS OF THE UPPER PHASE OF BIO-OIL OBTAINED FROM CO-PYROLYSIS OF SEWAGE SLUDGE WITH WOOD, RAPESEED AND STRAW Janat Samanya*, Andreas Hornung, Andreas Apfelbacher, Peter Vale The bio-oil obtained from the pyrolysis process has shown to have lower sulphur and nitrogenoxide emissions. Bio-oil obtained from the pyrolysis process is rather different to other oils. There has beenan increase of sewage sludge due to environmental limitations of its disposal . Sewage sludge has shown great potential of being utilised as a fuel due to its availability, low cost and high energy content obtained from the bio-oil. There is a need to utilise this waste to obtain quality products. Sewage sludge was pyrolysed with 40% mixed wood, 40% rapeseed and 40% straw. The reason for the mixture of different biomass is to investigate the impact of co-pyrolysis on the upper phase of bio-oil in terms of changes to composition, elemental analysis, viscosity, water content, pH, higher heating value and acid number that could impact on their applications.

The biomass was pyrolysed in a laboratory at 450 ◦C and bio-oil was collected from two cooling traps. The bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw was analysed for composition using the gas chromatography mass spectrometry. The upper phase from the co-pyrolysis process was also characterised for ultimate analysis, higher heating values, water content, viscosity, pH and acid number.

Pyrolysis yield: The co-pyrolysis of sewage sludge with other biomass produced a variation in product yield. The amount of gases produced was determined by difference from the mass balance. The co-pyrolysis with rapeseed produced the highest char yield of 53.3% while sewage sludge and wood fraction has the lowest char yield. The rapeseed and sewage sludge fraction have the highest bio-oil content of 33.2% with equal amount of the upper and bottom phase .The increase in the percentage of the upper phase originates from the pyrolysis of

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rapeseed. This is because the pyrolysis of sewage sludge only yields 10% of the upper phase compared to 30% of the bottom phase. On the other hand, straw and sewage sludge produced the least amount of bio-oil. The upper phase obtained from the co-pyrolysis of sewage sludge with mixed wood, straw and rapeseed have varying characteristics. The upper phase from sewage sludge with rapeseed has the highest heating value compared to other fractions. It also decreases the viscosity of sewage sludge upper phase. The 40% rapeseed increases the bio-oil yield compared to the pyrolysis of sewage sludge on its own. It also increases the hydrogen content and lowers the sulphur content found in the upper phase of sewage sludge bio-oil. The co-pyrolysis of mixed wood and sewage sludge improved some of the properties found in the upper phase of wood bio-oil. The co-pyrolysis with 40% mixed wood, increased the higher heating value from an average of 17 to 31.3 MJ/kg. The carbon content was significantly improved. It was also found to reduce the acidity of bio-oil found in wood alone. However the viscosity was found to be the highest amongst the upper phase fractions. The wood mixture also benefits the sewage sludge upper phase of bio-oil by reducing the nitrogen content. The changes in bio-oil characteristics found with the co pyrolysis of 40% straw were not very significant.

The bio-oil obtained from the co-pyrolysis process was analysed for composition using the gas chromatograph mass spectrometry. The main compounds detected are from 40% rapeseed with fewer phenol compounds. The compounds from sewage sludge bio-oil as shown in Table 5 are aromatic hydrocarbon , silicon compound, phenols and indole .The compounds from rapeseed bio-oil are aromatic hydrocarbon , phenol , alkane hydrocarbon , long chain alkenes.

There was an increase in the amount of upper phase produced with co-pyrolysis of 40% rapeseed. It was also found that the upper phase from sewage sludge with mixed wood has the highest viscosity, acid number and lowest pH. The bio-oil containing 40% straw was found to have a pH of 6.5 with a very low acid number while the 40% rapeseed was found to have no acid number. Sewage sludge with 40% rapeseed was found to have the highest energy content of 34.8 MJ/kg, 40% straw has 32.5 MJ/kg while the 40% mixed wood pyrolysis oil has the lowest energy content of 31.3 MJ/kg. The 40% rapeseed fraction was found to have the highest water content of 8.2% compared to other fractions.

THERMAL AND KINETIC BEHAVIORS OF BIOMASS AND PLASTIC WASTESIN CO-PYROLYSIS Ozge Cepeliog˘ullar, Ays_e E. Putun Unreasonable consumption of the natural resources resulted in an ecological and economical imbalance besides an increase in consumption habits demanding on the enhancement in population. This depletion brings several problems such as treatment of wastes which needs to be solved urgently. the consumption of plastic materials due to their practical usage, low-cost and high-resistance has increased drastically . When it comes to creating clean energy, biomass still protect sits place and importance in the past decade regarding the industrial development of thermo chemical conversion plants. In general, biomass is (i) clean, (ii) low-cost, (agricultural wastes, forest residues, food industry wastes, and daily garbage of houses), (iii) abundant, (iv) easy to grow and (v) renewable

In this study, in order to compare the thermal and kinetic behaviours of individual raw materials with the mixtures, biomass- plastic materials were blended in definite ratio (1:1, w/w) and pyrolyzed with a heating rate of 10oC min -1 from room temperature to 800oC in the

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presence of N2 atmosphere with a flow rate of 100 cm3 min_1 in thermo gravimetric analyzer. Cotton stalk, hazelnut shell and sunflower residue which are the most important agricultural wastes from different parts of Turkey and arid land plant Euphorbia rigida were chosen as biomass materials. Additionally, polyvinyl chloride (PVC) and polyethylene terephthalate (PET) as the most encountered plastic materials used in both daily life and industry were used as plastic waste materials. With the obtained TG data, kinetic equations among pyrolysis process were derived and decomposition temperatures and thermal behaviours of mixtures were determined.Kinetic parameters such as activation energy and pre-exponential factor of the pyrolysis mechanism were derived with the obtained TGA data. According to the weight loss–temperature curves, small amount of weight loses occurred until 150 _C which were the indicative of inherent water being released within the biomass samples. It is observed that biomass–PVC mixtures when compared with the thermal degradation of individual raw materials that the rate of decomposition was slow at the beginning, however with the increasing temperatures weight losses started to increase at the medium temperature regions. And, the thermal degradation was completed earlier, nearly at 500–600 _C. This means that biomass– PVC mixtures showed similarity with the thermal behaviours of PVC which decomposes mostly as gaseous products. On the other hand, for biomass–PET mixtures the opposite case occurred. Since, PET is a complex polymer which decomposes at two stages; the temperatures for the thermal decomposition of biomass–PET mixtures were higher than the individual materials.

In order to determine the parameters of the pyrolysis (pre exponential factor and activation energy), was used. When it comes to comparing the calculated kinetic parameters of the mixtures, it is cleared that clearly the temperature and energy need is higher for the decomposition of biomass–PET mixtures than the biomass–PVC mixtures. Since PET is a complex compound with an aromatic ring in the structure, energy barrier needed to be brought through requires more energy. Varying activation energies shows that biomass–plastic mixtures have different pyrolysis reactivates at different temperatures ranges. Also, the good correlation coefficient indicates that the corresponding independent first-order reaction model fits the experimental data very well.Thermal degradation of biomass materials took longer than the plastic materials and higher temperatures were needed in order to provide structural breakdown. In addition, biomass decompositions were divided into three main stages. These are; moisture drying, main devolatilisation and light devolatilisation. On the other hand, plastic decomposition followed different paths. Plastics lost nearly 8085% of their initial weight within the temperature range of 250–600 _C unlike biomass materials. In parallel with these experimental results, mixtures had the characteristics of both biomass and plastic materials during thermal decomposition. According to calculated activation energies, it was determine that the energy barrier of plastic materials in order to start the pyrolysis reactions were higher. The experimental results obtained from TG have an important role in the determination of the pyrolysis mechanism and process conditions while designing/implementing a thermo chemical conversion method where biomass–plastic materials were preferred as raw materials.

CO-PYROLYSIS OF RESIDUAL OIL AND POLYETHYLENE IN SUB- AND SUPERCRITICAL WATER

Fan Bai, Chun-Chun Zhu, Yin Liu, Pei-Qing Yuan*, Zhen-Min Cheng, Wei-Kang Yuan

In this paper, experimental investigation of co-pyrolysis of residual oil and LDPE in sub- and supercritical water (sub-CW and SCW) was done and compared with existing pyrolysis

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results. The experiment was carried out in an autoclave of capacity 0.1 litre equipped with flat paddles whose stirring rate was kept at 1000 rpm during reaction. After the reaction product separation was done following the Industrial Standard of Chinese Petrochemical NB/SH/T 0509-2010. The phase structure of residual oil in the presence of sub-CW and SCW was calculated using Aspen Engineering Suite 2006. The Soave–Redlich–Kwong (SRK) cubic equation of state was implemented, and this method used Kabadi–Danner mixing rule to deal with the water–hydrocarbon system. It was fond that, in sub-CW or SCW, the pyrolysis of residual oil is characterized by the dealkylation of aromatic radicals at the early reaction stage and by the condensation at the middle and later reaction stages, while pyrolysis of LDPE mainly follows FSS mechanism.

LDPE used in this work has the density of 0.92 g/cm3 and a melting point between 378 and 388 K. The weight mean molecular weight of LDPE is 1.25×105. In a typical run for co-pyrolysis, 0.5 g of LDPE and 10 g of water were loaded into the autoclave first. After purging with high purity N2, the reactor was sealed and pre-heated to 633 K. Then, 20 g of residual oil and a certain amount of water were charged into the reactor with two metering pumps in 5 min, by which the water density in the reactor was adjusted between 0.10 and 0.30 g/cm3. Subsequently, at a slope of 15 K/min the reactor was heated to 693 K. After 20 to 60 min's reaction, the reactor was subjected to forced air cooling to rapidly terminate the reaction. In general, the process for pyrolysis was similar to that of co-pyrolysis except that no LDPE was loaded into the autoclave.

Co-pyrolysis of residual oil and LDPE with the mass ratio of 40:1 was surveyed at 693 K and water densities ranging from 0.10 to 0.30 g/cm3, with the results at the reaction time of 1 h. H-rich paraffins, the main pyrolysis product of polyethylene, are released continuously into the reaction system. With the increase of water density, it was found that the yield of saturates increases from 21.0 to 32.9 wt.% and that of aromatics increases slightly from 18.4 to 19.4 wt.%. But, the yield of asphaltenes presents a decreasing tendency but that of resins increases from 10.8 to 13.9 wt.%. The yield of coke decreases drastically from 36.0 to 25.8 wt.%, whereas the hydrogen balance increases from 84% to 96%. However, the H/C ratio of the liquid co-pyrolysis products varies merely between 1.25 and 1.30. It was found that the yields of aromatics, resins, and asphaltenes in co-pyrolysis are higher than those in pyrolysis. Coupling between the pyrolysis networks of residual oil and LDPE was experimentally confirmed, together with the significant change in the product distribution. It was also found that the phase structure of the co-pyrolysis system may evolve from a liquid/liquid/ solid three-phase structure to a liquid/solid two-phase one. The dealkylation of aromatic radicals can follow the favourable mechanism by which the production of coke-inducing components is effectively depressed.

PREPARATION AND CHARACTERIZATION OF HIGH SURFACE AREA ACTIVATED CARBONS FROM CO-PYROLYSIS PRODUCT OF COAL-TAR PITCH AND ROSIN

Cheng Zenga, Qilang Lina,∗, Changqing Fangb,∗, Dongwei Xua, Zhichao Maaa

In this paper, the preparation of ACs from the co-pyrolysis product by KOH activation, and then structures and electrochemical performance of the ACs were studied. Co-pyrolysis product of coal-tar pitch and rosin was used as a precursor to prepare high surface area activated carbons (ACs) by KOH activation. The influences of AC precursor origin, KOH/AC

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precursor weight ratio and activation time on the pore characteristics of the ACs were investigated, and mean while their electrochemical performance was studied.

Lower C/H ratio and higher cycloparaffin content, which could reduce the polymerization velocity for hydrogenation of coal-tar pitch upon pyrolysis. The most KOH have been depleted when the activation time is 1.5 h.

This study has demonstrated that the co-pyrolysis product of coal-tar pitch and rosin was a suitable precursor for the low-cost production of high surface area activated carbons (ACs) by KOH activation. The adding rosin results in a decrease in the C/H atomic ratio of the AC precursor as well as a significant increase in its mesophase content. The effect of AC precursor origin on the porosity characteristics of the ACs can be illustrated by increases in the BET surface area from 1846 to 2847 m2/g, the total pore volume from 1.09 to 1.57 cm3/g and the average pore diameter from1.81 to 2.39 nm. In addition, the main factor affecting the porosity characteristics of the ACs is the KOH/AC precursor weight ratio. It is recommended that a KOH/AC precursor weight ratio of 7:1,an activation temperature of 850◦C and a residence time of 1.5 hare the optimum parameter values for producing high surface area ACs with good electrochemical performance. The resulting AC has the maximum specific capacitance of 203 F/g and exhibit good rectangular-shaped I–V curves in cyclic voltammetry.

CO-PYROLYSIS OF HEAVY OIL AND LOWDENSITY POLYETHYLENE IN THE PRESENCE OF SUPERCRITICAL WATER: THE SUPPRESSION OF COKE FORMATION Xue-Cai Tan, Chun-Chun Zhu, Qing-Kun Liu, Tian-Yi Ma, Pei-Qing Yuan*, Zhen-Min Cheng, Wei-Kang Yuan

The co-pyrolysis of heavy oil and LDPE as well as the pyrolysis of heavy oil alone in the presence of SCW was investigated with the focus on the coking mechanism involved. On the basis of experimental results, the possible pathway of the H-donation responsible for the suppression of coke formation in co-pyrolysis was proposed. Then, the influence of SCW on the H-donation was further discussed. In what follows, “copyrolysis” means in particular the thermal cracking of heavy oil accompanied by LDPE, while “pyrolysis” is the thermal cracking alone of heavy oil or LDPE.

At 693 K and water density of 0.30 g/cm3, the co-pyrolysis of heavy oil and low density polyethylene (LDPE) in the presence of supercritical water (SCW) was investigated with the emphasis on the coking mechanism involved. The co-pyrolysis in SCW was found to have the significant advantages of the decreasing yield of coke and the increasing yield of aromatics over the pyrolysis of heavy oil alone in SCW. With the increase in the loading of LDPE, the suppression of condensation in co-pyrolysis is gradually intensified, suggesting the essential role of LDPE as an external H-source in co-pyrolysis. Only in the continuous SCW phase can the H-donation between the pyrolysis networks of heavy oil and LDPE be effectively accomplished, by which the condensation of light oil fractions to heavy oil fractions and the deep condensation of asphaltenes to coke are partly suppressed.

Essentially, the pyrolysis of heavy oil is an H-deficient process. Once it was believed that H atoms could be transferred from SCW or superheated steam into the pyrolysis product of heavy oil. In a typical run for co-pyrolysis, 20 g of heavy oil, 30 g ofwater and a certain

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amount of LDPEwere loaded into the autoclave first. After being purged with N2 of high purity, the reactor was sealed. sealed. Then, the reactor heated to 693 K at a slope of 10 K/min. The reaction lasting 30 to 60 min finally was terminated by subjecting the reactor into forced air cooling. Basically, the procedure of pyrolysis was similar to that of co-pyrolysis expect that no LDPE was loaded into the autoclave.

SYNERGISTIC EFFECTS ON CO-PYROLYSIS OF LIGNITE AND HIGH-SULFUR SWELLING COAL Jinxia Fei, Jie Zhang, Fuchen Wang, Jie Wang*

They presented a review of new studies on pyrolysis of biomass to produce fuels and chemical feedstock. A number of biomass species, varying from woody and herbaceous biomass to municipal solid waste, food processing residues and industrial wastes, were subjected to different pyrolysis conditions to obtain liquid, gas and solid products.

Co-pyrolysis of a lignite coal and a bituminous coal was carried out on a fixed-bed reactor. The lignite was enriched with calcium, and the bituminous coal featured in high sulphur and strong swelling. Experiments were also conducted for the blends using the acid-washed lignite and/or the acid washed bituminous coal to address the influences of calcium in the lignite on the synergistic behaviours. Calcium in the lignite exhibited some aspects of synergy including the catalytic cracking reactions of tar, the retention of sulphur in the char, and the catalyzed poly aromatization and gasification of char. These synergies impacted the differences in the product distribution and gas composition between the co-pyrolytic results and the additive ones. Moreover, there appeared to be a synergistic effect on the cross-linking reaction of volatile matter, resulting in an increase in the char yield irrespective of coal demineralization. The co-pyrolysis also observed to destroy the swelling of coal. This synergistically increased the tar yield due to less resistant escaping of tar from the intra-particles of coal.

The results of various biomass pyrolysis investigations connected with the chemical composition and some properties of the pyrolysis products as a result of the applied pyrolysis conditions were combined. The characteristics of the liquid products from pyrolysis were examined, and some methods, such as catalytic upgrading or steam reforming, were considered to improve the physical and chemical properties of the liquids to convert them to economic and environmentally acceptable liquid fuels or chemical feedstocks. Outcomes from the kinetic studies performed by applying thermo-gravimetric analysis were also presented.

BIOFUELS PRODUCTION THROUGH BIOMASS PYROLYSIS — A TECHNOLOGICAL REVIEW Mohammad. Jahirul , mohammad g. Rasul *, ashfaque ahmed chowdhury and Nanjappa ashwath There has been an enormous amount of research in recent years in the area of thermo-chemical conversion of biomass into bio-fuels (bio-oil, bio-char and bio-gas) through pyrolysis technology due to its several socio-economic advantages as well as the fact it is an efficient conversion method compared to other thermo-chemical conversion technologies.

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However, this technology is not yet fully developed with respect to its commercial applications.

In this study, more than two hundred publications were reviewed, discussed and summarized, with the emphasis being placed on the current status of pyrolysis technology and its potential for commercial applications for bio-fuel production. Aspects of pyrolysis technology such as pyrolysis principles, biomass sources and characteristics, types of pyrolysis, pyrolysis reactor design, pyrolysis products and their characteristics and economics of bio-fuel production are presented. It was found from this study that conversion of biomass to bio-fuel has to overcome challenges such as understanding the trade-off between the size of the pyrolysis plant and feedstock, improvement of the reliability of pyrolysis reactors and processes to become viable for commercial applications. Further study is required to achieve a better understanding of the economics of biomass pyrolysis for bio-fuel production, as well as resolving issues related to the capabilities of this technology in practical application.

EFFECT DURING CO-PYROLYSIS/GASIFICATION OF BIOMASS AND SUB-BITUMINOUS COAL Supachita Krerkkaiwan, Chihiro Fushimi, Atsushi Tsutsumi, Prapan Kuchonthara*

In this work, the co-pyrolysis of Indonesian coal (sub-bituminous) and two types of biomass, rice straw andLeucaena leucocepha wood, was studied using a drop tube fixed-bed reactor. The gasification reactivity of the obtained co-pyrolyzed char with steam was examined using a rapid heating thermobalance reactor.

It was studied the co-pyrolysis of Indonesian sub-bituminous coal and two types of biomass, rice straw (RS) and Leucaena leucocepha wood (LN) was carried out in a drop tube fixed-bed reactor and investigated the effects of the biomass and coal blending ratio and biomass type on the product distribution, gas composition and product characteristics. The samples (coal, biomass and coal/biomass blends) were instantly dropped so that the heating rate of the particles was higher than other, typical fixed-bed reactors. The contact time of the pyrolytic products was also presumably longer than that in fluidized-bed reactors, owing to the fixed-bed section. A synergetic effect between coal and the biomass was observed in terms of higher gas and lower tar and char yields, with a special biomass to coal blending ratio of 1:1 (w/w). They explained the synergetic effect as the transfer of active OH and H radicals from the biomass to the coal as well as the catalytic role of potassium (K) from the biomass. The residual char after pyrolysis was characterized by SEM and BET analysis. In the SEM images the coal char appeared to have a smooth surface of dense hydrocarbon molecules with small pores, while thebiomass char had a more porous structure with larger pores This was attributed to the higher volatile matter content in the biomass. the synergetic effect in terms of the char gasification rate.

The pyrolytic tar and char were characterized with Brunauer–Emmitt–Teller (BET), scanning electron microcopy (SEM) and gas chromatography–mass spectrometry (GC–MS) techniques. They investigated the synergetic effect on the in situ char steam gasification rate was using a rapid heating thermobalance reactor.

Synergetic effect is in terms of the weight decrease of the char and the overall rate constant (k) was found from the coal/biomass blend. It was also found that the biomass type, RS or LN, influenced the magnitude of the synergetic effect during co-pyrolysis. Oxygenated tar released from RS potentially induced volatile-K to form phenolate groups on the char

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enhancing the char reactivity in steam gasification. On the other hand, aromatic or heavy tar produced from the pyrolysis of LN was likely to promote the deposition of K on the char which then played a catalytic role in the decomposition of the heavy tar itself.

Flash co-pyrolysis of biomass with polylactic acid. Part 1. Influence on bio-oil yield and heating value.

T. Cornelissen, J. Yperman,*, G. Reggers, S. Schreurs and R. Carleer

[A Report from Belgium]

In the present research paper, the objective of the authors is to reduce the amount of pyrolytic water by flash co pyrolysis of biomass/willow and PLA. The co-pyrolytic behaviour of the willow/PLA blends was investigated with a semi-continuous home-built pyrolysis reactor. With the aid of TG, TG/MS and TG/FTIR, the decomposition of the input materials over a broad temperature range was visualised. It was found that the flash co-pyrolysis of willow/PLA blends (10:1, 3:1, 1:1 and 1:2) exhibits synergetic interaction. The triple stage decomposition of willow is observed in all blends, however, in reduced form directly correlated with the addition of PLA. Most of the decomposition reactions were finalised at a temperature of about 673 K, justifying a maximum flash pyrolysis temperature of 723 K during the semi-continuous pyrolysis experiments. A higher bio-oil yield and lower water content as a function of the willow/PLA ratios has been obtained. The 1:2 willow/PLA blends showed the most pronounced synergy – an increase of 28 % in bio-oil yield, a decrease of 37% in water content, and an increase of 27 % in energy recuperation. Hence, the co-pyrolysis of willow and PLA is an energetically and economically attractive route to be pursued.

RAPID CO-PYROLYSIS OF RICE STRAW AND A BITUMINOUS COAL IN A HIGH-FREQUENCY FURNACE AND GASIFICATION OF THE RESIDUAL CHAR Shuai Yuan, Zheng-hua Dai, Zhi-jie Zhou, Xue-li Chen ⇑, Guang-suo Yu, Fu-chen Wang

In this paper, the authors have presented a comparative study on, rapid pyrolysis of rice straw (RS) and Shenfu bituminous coal (SB) separately as well as blend of the same in mass ratio of 1:4, 1:1, and 4:1. The experiment was carried out were carried out in a high-frequency furnace which can ensure both high heating rate and satisfying contact of fuel particles. Yields of char, gas, and the others (dry basis) under rapid pyrolysis of RS and SB at different temperatures were measured. It was found Char yields of RS and SB decreased, but gas yields increased with the increasing pyrolysis temperatures. Investigation of synergies between RS and SB during rapid co-pyrolysis was done. Intrinsic and morphological structures of residual char from copyrolysis, and their effects on gasification characteristics were also studied. During rapid co-pyrolysis of RS and SB (RS/SB = 1:4), synergies occurred and decrease in char yields and increase in volatile yields were noted. Char of the RS, SB, and the co-pyrolyzed char derived at 1200oC were chosen to be gasified at 1000oC. Gasification rates of RS char and SB char presented similar trends with respect to conversion of the char, which increased sharply to peak values in the low conversion ranges, and decreased sharply in the medium–high conversion ranges. Gasification rates of RS char were higher than gasification rates of SB. Synergies also happened during gasification of the char derived from co-pyrolysis of RS and SB with mass ratio of 1:4. As a comparison, char derived from co-pyrolysis of RS

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and SB with mass ratios of 1:1 and 4:1 were also investigated. The increase in the uniformity of the co-pyrolysis char was noticed. As a result, low biomass/coal mass ratio not only results in significant synergies during rapid co-pyrolysis and leads to an increase in volatiles, it also increases the gasification reactivity of the residual char whereas increased mass ratio of RS to SB not only weakens synergies during copyrolysis, but significantly reduced the gasification rates of the co-pyrolysis char compared to the calculated values.

2.2 Literature on Life Cycle Analysis

LIFE CYCLE ANALYSIS OF FUEL PRODUCTION FROM FAST PYROLYSIS OF BIOMASS Jeongwoo Han *, Amgad Elgowainy 1, Jennifer B. Dunn 2, Michael Q. Wang3 A well-to-wheels (WTW) analysis of pyrolysis-based gasoline was conducted and a comparison with petroleum gasoline is presented in this paper. This study develops and investigates three pathways: (1) a pathway with fuel gas/NG reforming for H2 (denoted as FN), (2) a pathway with pyrolysis oil reforming for H2 and biochar combustion for electricity generation (denoted as PO-Elec), and (3) a pathway with pyrolysis oil reforming for H2 and biochar application to soil (denoted as PO-Soil). The variation and uncertainty in the pyrolysis pathways was addressed by developing probability distributions for key parameters with data from literature. The impacts of two different hydrogen sources for pyrolysis oil upgrading and of two bio-char co-product applications were investigated. It was found, reforming fuel gas/natural gas for H2 reduces WTW GHG emissions by 60% (range of 55–64%) compared to the mean of petroleum fuels whereas reforming pyrolysis oil for H2 increases the WTW GHG emissions reduction up to 112% (range of 97–126%), but reduces petroleum savings per unit of biomass used due to the dramatic decline in the liquid fuel yield. Thus, a trade-off between fuel yields and GHG emissions reduction exists per unit fuel output and petroleum displacement per unit biomass used, stemming from the source of hydrogen. It was found biochar as a soil amendment has the potential to be used as a sequester of a large amount of carbon (36 gCO2e/ MJ gasoline) but its carbon content and carbon retention factor are highly uncertain.

LIFE CYCLE ANALYSIS OF GREENHOUSE GAS EMISSIONS FROM ORGANIC AND CONVENTIONAL FOOD PRODUCTION SYSTEMS, WITH AND WITHOUT BIO-ENERGY OPTIONS J.M. Cooper*, G. Butler, C. Leifert In this paper, a life cycle analysis of the greenhouse gas (GHG) emissions from organic and conventional production systems has been presented based on the crop production data for the first 4 years of the the Nafferton Factorial Systems Comparison experiments. In this analysis a full 8-year crop production cycle was studied. Actual yield and field activity data from two of the treatments in the experiments (a stocked organic system and a stockless conventional system) were used to determine the GHG emissions per hectare and per MJ of human food energy produced, using both the farm gate and wider society as system boundaries. Emissions from these two baseline scenarios were compared with six other modelled scenarios: conventional stocked system, a stockless system where all crop residues were incorporated

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into the soil, two stocked systems where manure was used for biogas production, and two stockless systems where all crop residues were removed from the field and used for bio-energy production. It is important to look at the full impact of GHG emissions beyond the farm gate, to effectively compare systems. The conventional systems in this study exported most of their emissions beyond the farm gate, resulting in externalized environmental costs that are not accounted for when the LCA stops at the farm gate. This was particularly evident when the emissions associated with pig were also included in the balance.

Considering the societal boundaries, which rely on more off-farm inputs, emissions were much greater per hectare. Food production being the primary goal the study also demonstrates the trade-offs that often exist between food production and environmental sustainability. The systems with the lowest emissions (O-SL and O-BC) also produced the lowest food energy per hectare; whereas highest emissions were associated with the most productive systems. But the fact remains that the highly productive, conventional systems in these scenarios were dependent on imported nutrients for their production. Incorporating on-farm bio-energy production into the system allowed GHG emissions to be offset by energy generation. In the case of the organic system that included pyrolysis of crop residues, net GHG emissions were negative, indicating that energy offsets and sequestration of C in biochar can completely offset emissions of GHG from food production. although it is a research field, improvements in nuse efficiency AT FARM LEVEL WILL FURTHER REDUCE emissions from food production systems, and at the same time minimize environmental damage.

LIFE CYCLE OPTIMIZATION FOR SUSTAINABLE DESIGN AND OPERATIONS OF HYDROCARBON BIOREFINERY VIA FAST PYROLYSIS, HYDROTREATING AND HYDROCRACKING Berhane h. Gebreslassie, maxim slivinsky, belinda wang, fengqi you∗

The main advantage of hydrocarbon biofuels is that they are more sustainable than their petroleum counterpart, because they produce less life cycle environmental impact and reduce the consumption of non renewable primary energy resources.

In this work, they have proposed a multiobjective nonlinear programming (NLP) model for the optimal design and operation of hydrocarbon biorefinery via fast pyrolysis, hydrotreating and hydrocracking of hybrid poplar feedstock. The hydrocarbon biorefinery includes several processing units such as a dryer, pyrolysis unit, cyclone, quench, demister, combustion unit, hydrotratear-1, hydrotreater- 2, high pressure flash, low pressure flash, de butanizer, naphtha splitter, distillation columns, knock out drum, hydrocracking unit, product splitter, steam reformer, high temperature shift, condenser and pressure swing adsorption (PSA). The multiobjective NLP model maximizes the NPV and minimizes the global warming potential (GWP) subject to design and operational constraints, which includes mass and energy balance constraints, and technoeconomic , life cycle environmental impact constraints. The model simultaneously determines the optimal decisions that include production capacity, size of each processing units, flow rates of species and streams at each stage of the process, hydrocarbon biofuels yield, consumption of feedstock, steam, electricity, and natural gas consumption, economic performance and environmental impacts. The economic objective function takes into account the processing limits, demand of products, costs of feedstocks, and selling price hydrocarbon biofuels.

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The hydrocarbon biorefinery involves the pyrolysis, hydrotreating, hydrocracking and separation and steam reforming processing sections. (a) The pyrolysis section includes dryer, pyrolyzer, cyclone, combustor, and quench. (b) Hydrotreating includes two consecutive hydrotreaters, low and high pressure flashes, PSA and de-butanizer. (c) Hydrocracking and separation includes naphtha splitter, diesel splitter, distillation columns, hydrocracker and product splitter. (d) Steam reforming includes steam reformer, high temperature shift, PSA, and cooler.

From the environmental impact perspective, the analysis shows that the environmental performance of the hydrocarbon biorefineries can be improved by compromising their economic performance. The main contribution to the GWP (83%) is the emissions from the operation of the biorefinery that includes emissions of the combustor exhaust, steam reformer exhaust and high pressure flash vent to air. Considering the CO2 uptake during the biomass growth, the 83% GWP contribution from the emissions will be offset and hence, the overall GWP reduces significantly. The unit production cost of the hydrocarbon biofuels range from $2.31/GGE in the maximum NPV design to $3.67/GGE in minimum GWP design. These results show that the hydrocarbon bio refineries via fast pyrolysis, hydrotreating, and hydrocracking are not only promising technologies in terms of greenhouse gas reduction but also they are economically viable.

2.3 Literature on Sensitivity Analysis

SENSITIVITY ANALYSIS APPLIED TO INDEPENDENT PARALLEL REACTION MODEL FOR PYROLYSIS OF BAGASSE K.G. Santos, F.S. Lobato, T.S. Lira, V.V. Murata, Marcos A.S. Barrozo* Sugarcane bagasse is a lignocellulosic by-product of sugarcane processing to manufacture rawsugar and ethanol. Today, bagasse is often discarded or burned in power plants. Since raw bagasse produces low heat of combustion, its consumption as a primary fuel can be considered wasteful from the standpoint of energy. The transformation of bagasse into a secondary source of energy would significantly increase the total energy yield.Parametric sensitivity analysis has been used consistently in this literature to evaluate mathematical models, including the kinetics of various processes (Lira et al., 2009). Sensitivity equations can be solved analytically if the model equation has a known analytical solution.In this work, a model of three independent parallel reactions is used to estimate the kinetic parameters of sugarcane pyrolysis from thermo gravimetric experiments. The estimation is carried out by applying the Differential Evolution Algorithm. The activation energy, the pre-exponential factor of the Arrhenius equation and the mass fraction of each subcomponent of the biomass are calculated and compared with data reported in the literature. The DASPK 3.0 code is used in the sensitivity analysis of the IPR kinetic model.

The parameters related to hemicellulose and cellulose degradation are important in their respective ranges ofdecomposition, while the parameters related to lignin decomposition are extremely significant in the initial step of biomass degradation. This is because lignin has the largest range of decomposition temperatures and its contribution to the total biomass degradation is greater at the beginning, when hemicelluloses and cellulose have not yet started to decompose. This reinforces the importance of a kinetic model such as the

IPR model, which allows for the simultaneous degradation of subcomponents.

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SENSITIVITY ANALYSIS FOR PARAMETRIC GENERALIZED IMPLICIT QUASI-VARIATIONAL-LIKE INCLUSIONS INVOLVING P-Η-ACCRETIVE MAPPINGS. K.R. Kazmi*, F.A. Khan In this paper, the authors have considerd a parametric generalized implicit quasivariational- like inclusion problem involving P -η-accretive mapping (PGIQVLIP for short) in uniformly smooth Banach space. P -η-proximal mapping technique of P -η-accretive mapping and the property of the fixed point set of set-valued mapping have been used in this study. Using the previous techniques the behavior and sensitivity analysis of the solution set for PGIQVLIP was studied. Further, under suitable conditions, the Lipschitz continuity of the solution set with respect to the parameter has been proved. This work is an extension and compilation of several works published by different authors.

MICROWAVE-HEATED PYROLYSIS OF WASTE AUTOMOTIVE ENGINE OIL: INFLUENCE OF OPERATION PARAMETERS ON THE YIELD, COMPOSITION, AND FUEL PROPERTIES OF PYROLYSIS OIL Su Shiung Lam* , Alan D. Russell, Chern Leing Lee, Howard A. Chase

The production of waste automotive engine oil is estimated at 24 million tons each year throughout the world, posing a significant treatment and disposal problem for modern society. The waste oil, containing a mixture of aliphatic and aromatic hydrocarbons, also represents a potential source of high-value fuel andchemical feedstock.

Pyrolysis techniques have recently shown great promise as an economic and environmentally friendly disposal method for waste oil, the waste material is thermally cracked and decomposed in an inert atmosphere, with the resulting pyrolysis oils and gases able to be used as a fuel or chemical feedstock, and the char produced used as a substitute for activated carbon, though such practice is yet to become popular. The pyrolysis oil produced is of particular interest due to its easy storage and transportation as a liquid fuel or chemical feedstock. The oil can be catalytically upgraded to transport-grade fuels, or added to petroleum refinery feedstocks for further processing.

This study investigates the influence of process parameters (feed injection rate, purge gas flow, and heating source) on the yield and characteristics of the pyrolysis oils produced from microwave- heated pyrolysis of the waste oil, with a focus on their elemental and hydrocarbon composition, and potential fuel properties. These evaluations are important to assess the technical feasibility and applicability of the pyrolysis process as a route to energy recovery/feedstock recycling from waste oil.

N2 purge rate and waste oil feed rate, in addition to the use of a microwave heated bed of particulate carbon, were found to have effects on the fraction of original waste oil converted to pyrolysis gases, pyrolysis oils, and char residues. These process parameters also influenced the concentrations and molecular nature of the different hydrocarbons formed in the pyrolysis oils. These results, in combination with results from the work, demonstrate that microwave-heated pyrolysis generated an 88 wt.% yield of gasoline- like oil product that contains potentially valuable light aliphatic and aromatic hydrocarbons. The oil product is also relatively contaminant free with low levels of sulphur, oxygen, and toxic PAH compounds,

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and is almost entirely free of metals as reported in previous work, thereby reflecting its potential as a green energy source or chemical feedstock. The pyrolysis oil could potentially be treated and upgraded to transport grade fuels, or added to petroleum refinery as a chemical feedstock for further processing, although further studies are needed to confirm these possibilities. The microwave-heated pyrolysis can be performed in a continuous operation to treat high volumes of waste oil while showing both a positive energy ratio and a high net energy output. It is clear that microwave-heated pyrolysis offers an exciting green approach to the treatment and recycling of automotive lubricating oil. This unique combination of properties enables the potential generation of products with significant commercial value out of what would otherwise be a toxic and difficult to dispose of chemical liability.

3.0 CONCLUSION

3.0 REFERENCES

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15. Ozge Cepeliog˘ullar a, Ays_e E. Putun ; Thermal and kinetic behaviors of biomass and plastic wastes in co-pyrolysis; Energy Conversion and Management 75 (2013) 263–270

16. “Pyrolysis” Wikipedia 17. K.R. Kazmi*, F.A. Khan; Sensitivity analysis for parametric generalized implicit

quasi-variational-like inclusions involving P-η-accretive mappings;