IN DEGREE PROJECT MATERIALS SCIENCE AND ENGINEERING,SECOND CYCLE, 30 CREDITS

, STOCKHOLM SWEDEN 2017

Catalytic fast pyrolysis of softwood under N2 and H2 atmosphere

SHULE WANG

KTH ROYAL INSTITUTE OF TECHNOLOGYSCHOOL OF INDUSTRIAL ENGINEERING AND MANAGEMENT

ABSTRACT Bio-oil generated from biomass is becoming one of the most promising

alternatives as potential energy sources to replace fossil fuels in the transportation

sector. Fast pyrolysis of biomass is one of the most economically feasible ways to

produce bio-oil according to recent research on thermochemical conversion of

biomass. Upgrading of oils derived from to hydrocarbon fuels requires oxygen

removal and molecular weight reduction. Catalytic cracking and hydrotreating

are two efficient processes to upgrade bio-oil. Hydrotreating requires that

hydrogen is added in the process to increase the H/C ratio of the product.

Normally, catalytic fast pyrolysis and hydrotreating are two separated processes.

In order to increase the energy efficiency of the process, exploring the fast

pyrolysis of biomass with in-situ catalyst under the hydrogen atmosphere, i.e.

catalytic hydropyrolysis shall be very interesting, and this is the objective of this

work.

In this work, biomass pyrolysis experiments using softwood have been performed

in hydrogen and nitrogen atmospheres with/without catalyst. It was found that in

the case of the H2 atmosphere, a higher yield on oil phase and a reduced water

production is found. More oxygen was removed as CO and CO2. The catalytic fast

pyrolysis (CFP) under H2 atmosphere also produce relatively more PAH (polymer

aromatic hydrocarbon) and less MAH (monomer aromatic hydrocarbon) than

under N2 atmosphere.

Contents 1. Introduction ............................................................................................................................. 1

1.2. Objectives ......................................................................................................................... 2

2. Technology background ..................................................................................................... 2

2.1. Biomass and Pyrolysis ................................................................................................... 2

2.2. Biomass fast pyrolysis and catalytic reaction ......................................................... 5

3. Methodologies ..................................................................................................................... 11

3.1. Experimental facilities and procedures .................................................................. 11

3.1.1. Pyrolysis reactor and procedures .................................................................... 11

3.1.2. Experimental parameters set up ...................................................................... 12

3.2. Raw material .................................................................................................................. 13

3.3. Catalyst preparation .................................................................................................... 14

3,4. Products analysis and characterization ................................................................. 15

3.4.1. Gas analysis ............................................................................................................. 15

3.4.2. Liquid analysis ........................................................................................................ 15

3.4.3. Catalyst characterization ..................................................................................... 15

3.5. Experimental plan ......................................................................................................... 16

4. Results and Discussion ....................................................................................................... 16

4.1. Liquid analysis ........................................................................................................... 16

4.2. Gas analysis ................................................................................................................ 20

4.3. Coke characterization ............................................................................................. 22

4.4. Mass balance and product distribution ............................................................. 23

4.5. Comparison with ideal yield of liquid hydrocarbon fuel .............................. 24

4.6. Discussion on environmental feasibility ............................................................ 25

5. Conclusions ........................................................................................................................... 26

6. Further work on H2 effect on CFP process ................................................................... 26

7. Acknowledgement .............................................................................................................. 27

8. References .............................................................................................................................. 28

Appendix. Basic result from four cases tests ................................................................... 31

1

1. Introduction In the transportation sector, increasing energy demand, shortage of fossil fuel and

the soaring CO2 emission require the research and development on renewable

energy. One of the most important requirements for liquid fuel is that the new

energy technology should be able to produce energy with high energy density.

Furthermore, this technology should be compatible with the existing infrastructure

[1]. Liquid hydrocarbon fuel is the most preferable energy source in the

transportation sector because of its superior performance on stability and heat

value. Also, the infrastructure for hydrocarbon refining and upgrading is well-

developed [2].

Lignocellulosic biomass, the most promising renewable energy source is

becoming more popular in recent years because of it is a kind of sustainable

resource which exists as wood, grass and agricultural waste. It has been identified

that there are three different ways to produce liquid fuel from lignocellulosic

biomass. They are pyrolysis, gasification and biochemical. An analysis showed that

the pyrolysis process could produces liquid fuel from lignocellulosic biomass with

the lowest cost around $2.00-5.50 per gallon [3]. Nevertheless, the bio-oil

produced through pyrolysis is generally considered as a kind of liquid which has

low heating value, high acidity, high viscosity and poor stability. These could be

explained by the high oxygen content in the bio-oil, which together with the high

water content are the main difference between bio-oil and hydrocarbon fuels. On

the other hand, the relatively low pH (2-3) of bio-oil makes it quite unstable and

may cause corrosion in for example storage containers [4]. To get a better

utilization of bio-oil in transportation field, improvement of its overall quality is

necessary. The main pathway is removing the oxygen from bio-oil to gain the

hydrocarbon fuel. The catalytic fast pyrolysis (CFP) of biomass into bio-oil is

known as one of the best way to produce fuel and chemicals from biomass. By

using the certain catalyst, the oxygen could be removed from the bio-oil [5] [6]. -

5 is a kind of microporous catalyst. It has been proved that ZSM-5, as one of the

most promising catalyst using for biomass pyrolysis, has strong shape selectivity

of aromatic hydrocarbons, especially the protonated HZSM-5 which can convert

the big oxygenate molecules into aromatic hydrocarbons to remove oxygen from

bio-oil [7].

Most of the research on CFP process of biomass has been done is in inert

atmosphere (such as N2), but quite few studies focused on CFP process under

reactive atmosphere (such as H2). Suchithra et al. found the higher molecular

weight oxygenates in bio-oil was reduced in pyrolysis under H2 atmosphere as

compared to pyrolysis under inert gas [8]. But no information of product yields

2

from CFP process under H2 could be found.

1.2. Objectives The objectives of this work are to experimentally study the performance of the

catalytic hydropyrolysis of biomass under the atmospheric pressure.

More specific:

Experiments of biomass pyrolysis with/without catalyst under hydrogen /nitrogen

atmosphere have been performed. Mass balance of the pyrolysis has been

evaluated, pyrolysis gas, pyrolysis liquid to bio-oil have be collected and analyzed.

2. Technology background 2.1. Biomass and Pyrolysis Lignocellulosic biomass (also known as woody biomass) mainly consists of

cellulose, hemicellulose and lignin. The lignocellulosic biomass is synthesized

under the combination of plant, carbon dioxide, water and solar energy.

Hemicellulose and cellulose are polymers built up from sugar monomers, the

composition of lignin is usually plant specific. This complex polymer usually

consists of hydroxyl bonds and methoxy-substituted phenylpropane units on the

edges. Phenolics polymerized and cross lined to form lignin [9]. Figure 2.1(a)

shows the basic compound proportions of lignocellulose biomass. Figure 2.1(b)

shows the chemical structure of the three main compounds [10].

(a)

Cellulose, 50%

Hemicellulose,

33%

Lignin, 27%

Composition of lignocellulosic biomass

3

(b)

Figure 2.1 Composition of Lignocellulosic biomass

There are mainly three different methods to utilize energy from biomass,

combustion, gasification and pyrolysis. Combustion of biomass was developed

from the ancient period which is an oxidation reaction of biomass. However, the

main problem of this process is the low energy efficiency which is about 10%.

Gasification process provide the possibility to convert solid fuel into gaseous fuel

through a partially oxidizing reaction. Compared to these two processes, pyrolysis

provides liquid and gas fuel from the biomass through the thermal degradation

without the oxidizing agent [11].

Pyrolysis of biomass occurs in the temperature range of 350—550℃. The long

polymeric chains of organic compounds in biomass is thermally fragmentized into

smaller molecules, which generates three types of products: bio-oil, bio-char and

gas. The proportion of the different products depends on several factors. Scott et al. investigated the proportion of products by varying on the pyrolysis

temperature, shown in the Figure 2.2.

4

Figure 2.2. Relative proportions of end products in pyrolysis of biomass [12]

Three types of pyrolysis could be classified based on different process conditions:

a) Slow pyrolysis

b) Fast pyrolysis

c) Flash pyrolysis

Process temperature, heating rate and solid residence time, are key factors of

definition on type of pyrolysis.

Slow pyrolysis is characterized by high vapor residence time which could reach

5min to 30min. The long residence time means the reactive vapor has enough

time to react with each other to form char and liquid products. However, the

primary pyrolysis products could crack during the long residence time which affect

the bio-oil yield and quality adversely [11].

Fast pyrolysis has a shorter residence time than slow pyrolysis. It produces 60-75%

bio-oil, 15-25% char and 10-20% gas. The liquid product usually prefers to form

in low temperature and high heat transfer rate environment. [11] This process, fast

pyrolysis has been proved as the best way to convert the biomass into liquid fuels

by taking economically feasibility into consideration. [3]

Flash pyrolysis could be seemed as a quick devolatilization process in an inert

atmosphere. The reaction happens in temperature between 450℃ to 1000℃ with

high heat transfer rate and short gas residence time. [11]

5

Table 2.1. Typical operating parameters and products for pyrolysis process [11]

2.2. Biomass fast pyrolysis and catalytic reaction Cellulose, hemicellulose and lignin have different thermal stability and their

degradation procedures are different from each other during pyrolysis. As shown

in Figure 2.3, Yang et al. investigated the thermal decomposition behavior of these

three components’. The hemicellulose has the lowest thermal stability and can be

decomposed completely below 400℃, followed by cellulose and lignin shows a

high stability during the pyrolysis process, observed by its low weight loss.

Figure 2.3. Decomposition rate of individual biomass components with pyrolysis

Temperature [13]

Fast pyrolysis of cellulose Cellulose is a kind of polysaccharide with a linear chain of hundreds of β(1→4)

linked D-glucose units [14]. Since it is the most abundant component in

lignocellulose, the cellulose pyrolysis progress has been studied widely.

The thermal decomposition of cellulose under inert atmosphere could happen in

two pathways (a and b) after it transforms to liquid state at the beginning of the

reaction.

a) Cellulose break down into smaller molecules directly. For example, furan,

levoglucosan, glycolaldehyde, and hydroxyl acetone.

b) Cellulose break down into lower oligomers. The oligomers could further

decompose into furan, oxygenates, char, gas and levoglucosan.

6

Figure 2.4. The speculative chemical pathways for the direct conversion of the

cellulose molecules [15]

The levoglucosan is formed in the liquid state and become volatile afterwards. The

secondary decomposition of levoglucosan could happen gradually in the

residence time of volatile to form pyrans and oxygenates. The secondary

decomposition of levoglucosan has been proven to increase the char yield in

pyrolysis which is obviously undesired [16]. Because the possibility of secondary

reaction of levoglucosan is related with the reaction time, the residence time of

pyrolysis vapor in the hot zone should be as short as possible to decrease the char

yield.

7

Fast pyrolysis of hemicellulose

Figure 2.5. The speculative chemical pathways of the hemicellulose [17]

As show in the Figure 2,1(b), hemicellulose, as the second most abundant

compound in lignocellulosic biomass, is usually seem as a complex polysaccharide.

The general formula of hemicellulose is identified as (C5H8O4) m and the

polymerization degree is between 50-200 [18]. Pushkaraj R. et al studied the

hemicellulose pyrolysis process by identified the products from hemicellulose

pyrolysis. Figure 2.5 shows that the pyrolysis products of hemicellulose is different

from the pyrolysis of cellulose. Hemicellulose extracted and purified from

switchgrass was used as the feedstock and 16 kinds of product were identified in

their research. Small oxygenates generated from decomposition of hemicellulose,

the main products were identified as water, methanol, acids, furans and some

other small molecule [17].

Fast pyrolysis of lignin Lignin is another necessary component of the cell walls in plants, since it is one of

the main structure provide strength to support the plant. Lignin has a three-

dimensional structure which is different from cellulose and hemicellulose, it has a

lot of branches and polyphenolic substance. The Figure 2.6 shows the three main

monomers which connected with each other to form lignin. In soft wood, guaiacyl

lignin is the most common type [19].

8

Figure 2.6. The monomers of lignin [19]

Lignin is quite stable, and it has high resistance to chemical, physical and microbial

reaction because of its three-dimensional structure. Which means it is hard to

convert lignin into liquid bio-oil when pyrolysis [18]. B.-h. Hwang et al. claimed

the lignin pyrolysis start with the thermal crack of big molecule of lignin from

200℃ . The β-O-4 linkage break down firstly, followed by the generation of

guaiacol, dimethoxyphenol, dimethoxyacetophenone and trimethoxy-

acetophenone [20]. The aromatization reaction happens until the temperature

goes to 300℃ to form aromatics. Until 370℃, the C-C linkage between lignin unit

start break down [18]. Lignin is the main source of char and heavy tar during

pyrolysis.

Fast pyrolysis of biomass in H2 Usually, pyrolysis experiments are carried out under nitrogen atmosphere, D.

Meier et al. and J. Dilcio Rocha et al. claimed that during the pyrolysis under

hydrogen atmosphere, the char formation is less than inert atmosphere, but the

composition of liquid and gas didn’t show significant difference between

hydrogen case and inert atmosphere. With the hydrotreating catalyst, the

distribution of the pyrolysis product shows a meaningful change, bio-oil yield

increased, and the molecule size decreased, more oxygen was removed by

hydrodeoxygenation reaction [21] [22].

The reason for using catalyst The composition of bio-oil has been studied by many people. From Figure 2.7,

we can see most of the products are oxygenates. The distribution could influence

9

the bio-oil properties.

Figure 2.7. Chemical composition of bio-oil (categorized by derivates of

cellulose, hemicellulose and lignin) [7]

Table 2.2 shows the difference of properties between pyrolytic bio-oil and diesel.

The bio-oil produced from fast pyrolysis is unstable and has high viscosity, acidity

and low heat value because of its high oxygen content, which results in its low

value as liquid fuel. The most favorable liquid fuel in transportation sector is the

hydrocarbon fuel. For better usage of bio-oil, the oxygen removal is necessary.

Catalytic fast pyrolysis has been proven to be one of the most efficient ways to

remove the oxygen in bio-oil (another way is hydrotreating under reductive

atmosphere and high pressure with directed catalyst).

Table 2.2 Characteristics of pyrolysis oil and diesel fuel (40℃ and 25% water) [23]

Physical property Pyrolysis oil Diesel fuel

Moisture content 20-30 wt% 0.1 wt%

pH 2.0-2.5 —

Density 1.2 kg/L 0.94 kg/ L

Elementary analysis (wt%)

C 55–58 85

H 5–7 11

O 35–40 1

N 0–0.2 0.3

Ash 0–0.2 0.1

HHV as produced 16–19 MJ/kg 40 MJ/ kg

10

Viscosity 40–100 cp 180 cp

Solids (char) (wt%) 0.1–0.5 1.0

Vacuum distillation residue Up to 50 wt%

1 wt%

Catalytic fast pyrolysis reaction on HZSM-5 The reactions of pyrolytic bio-oil over HZSM-5 has been studied in recent years

by the research community. Lignocellulose firstly thermal degrade into smaller

molecules as introduced before. These small molecules contact HZSM-5 and

diffuse into microporous to get further transformation. Different types of

lignocellulose derivates have different catalytic reactions and tend to lose oxygen

into different gas product. Table 2.3 shows the oxygen distribution of several main

products found in pyrolytic bio-oil after pyrolytic decomposition on HZSM-5 [23].

Dehydration reactions happen with alcohols at around 200℃ on HZSM-5, this

reaction generates olefins. Higher temperature (>350℃) will transform olefins to

alkanes then aromatics. Aldehydes are quite active and would result in the coke

deposition on catalyst these aldehydes group compounds are one of the main

reason of catalyst deactivation [24]. Acetone transform into isobutene firstly, then

at higher temperature it reacts on catalyst become heavier olefins, alkane and

finally become aromatics. The oxygen existing in forms of carboxylic acids and

esters could be removed by decarboxylation and dehydration reaction. Phenols,

as the most stable compounds under pyrolytic conditions, has quite low

conversion. Guaiacol, the most common lignin derivates is hard to convert even

the temperature reach 450℃.

Table 2.3. Formation of H2O, CO and CO2 for various organic species over a

HZSM-5 Zeolite

Oxygen in gas phase (%)

Feed compound H2O CO CO2

Methanol 100 0 0

Dimethyl ether 100 0 0

Guaiacol 96 3 1

Glyceril 92 7.5 0.5

Xylenol 93 6 1

Eugenol 89 9 2

Anisole 88 12 Trace

2,4-Dimethyl phenol 87 12 1

o-Cresol 80 17 3

Starch 78 20 2

Isoeugenol 77 19 4

Glucose 75 20 5

Dimethoxymethane 73 6 21

11

Xylose 60 35 5

Sucrose 56 36 8

n-Butyl formate 54 46 0

Diphenyl ether 46 46 8

Furfural 14-22 75-84 2.5-3.0

Methyl acetate 54 10 36

Acetic acid 50 4 46

3. Methodologies 3.1. Experimental facilities and procedures Before the pyrolysis tests, an efficient experimental plan should be made. Which

should include:

a) A suitable reactor for the pyrolytic tests.

b) Experimental parameters setup.

c) Chosen of feedstock and catalyst.

d) Preparation before the tests and option during the tests.

3.1.1. Pyrolysis reactor and procedures The whole reaction system is shown in Figure 3.1. Before test, the biomass need

to be dried in the drying oven for one night. Catalyst as shape of bed was set in

the furnace initially, biomass was hang on a hook at the top of furnace (the

temperature of top is stabilized by a recycling cool water as room temperature)

and will be inserted to sit on the catalyst bed when start the test. Firstly,

atmospheric carrier gas goes from top of the resistance furnace through the entire

system for 20minutes to remove all the air in the reactor, then start heat the

furnace for 2 hours until the temperature in the furnace is stable. A cooling system

connected with the outlet of furnace which was used for cooling the pyrolytic

vapor and collect the liquid product. For keeping vapor temperature until it meets

the cooling system from catalyst bed, a heating tape was employed to keep

temperature of the junction between cooling system and furnace at 330℃. The

cooling system followed by gas collection bottle which was filled with water

initially for water displacement method to measure the gas product volume, the

gas product push water to the water collection bottle. By weighing the water in

the water collection bottle, we can know how much gas was produced from the

pyrolysis reaction. The gas collected in gas collection bottle would be analyzed in

micro GC immediately after the pyrolysis test.

12

Figure 3.1. Experimental system of CFP tests

3.1.2. Experimental parameters set up

Reaction temperature The pyrolysis temperature was chosen as 450℃ because this temperature could

protect catalyst from deactivation of steam. Antonio de Lucas et al. claimed a

significant decrease on aromatic selectivity of HZSM-5 was observed under high

temperature [19].

Catalyst to feed ratio Catalyst to feed ratio is chosen as 1 in our experiment. According to the review

done by Calvin Mukarakate et al. shown in Figure 3.2, oxygen content in oil is

related to biomass to catalyst ratio, and this value could be less than 20% when

the ratio is 1 [25]. In these tests, both biomass and catalyst was put as 10g.

H2/

N2

Furnace

Biomass Catalyst bed

Heating tape

water water

Gas collection

Water collection

Biomass basket holder

Washing bottle

Cooling bath filling

with liquid at -15℃

13

Figure. 3.2. Literature results for oxygen content in the bio-oil for CFP using

HZSM-5 vs. biomass-to-catalyst ratio [25]

Other parameters The flow rate was set as 130ml/min. Pyrolysis time was set as 25minutes for a

complete pyrolysis reaction.

3.2. Raw material The raw material used is an industrially available mixture of spruce and pine with

a particle size of 0.35-0.5mm provided by SCA (Svenska Cellulosa Aktiebolaget).

The composition of the biomass is shown in the following Table 3.1. The empirical

chemical formula of this biomass can be written as CH1.43O0.63.

Table 3.1. Composition of biomass used for fast pyrolysis experiments

Moisture [wt%] 9.80

Volatile Matter [wt%] 83.00

Ash [wt%] 0.31

Fixed Carbon [ wt%] 16.60

HHV [MJ/kg] 20.46

Ultimate Analysis[wt% db]

C 50.70

H 6.10

O 42.71

N 0.18

1

14

Metals[ppm]

Si 49.6 Pb 0.0523

Al 16.2 B 1.84

Ca 760 Cd 0.0556

Fe 23.8 Co 0.0228

K 390 Cu 0.626

Mg 106 Cr 0.14

Mn 95.6 Hg <0.01

Na 12.1 Mo 0.0106

P 31.6 Ni 0.059

Ti 0.659 V 0.0239

As <0.09 Zn 7.49

Ba 9.84

3.3. Catalyst preparation 500g ZSM-5 zeolite in ammonium state with SiO2/Al2O3 ratio of 30 was provided

by Alfa Aesar in NH4+ form. Catalyst acidity (SiO2/Al2O3 ratio) was chosen as 30

because it has been proved by many research that 30 gives the highest aromatic

hydrocarbon yields. Furthermore, the acidity of 30 could also limit the coke

formation which is the main result of deactivation of catalyst [26] [27] [28].

The method of catalyst preparation consists of calcination, pelletizing and sieving.

Firstly, the catalyst was put in the calcination oven with an air circulation, the

temperature in calcination oven was set as 5 degree/min from 120℃ to 550℃,

stay 15h at 550℃ and then 5 degrees/min to 120℃. After calcination, the catalyst

needs to be pelletized. The pelletizing could give catalyst an evenly density and

porosity. After pelletizing, the catalyst need to be crushed and sieved into the

certain particle size 0.125mm-0.180mm to make sure no catalyst will be blow

away by the gas flow.

Before tests, the catalyst will be placed on a platform made of steel mesh in the

reactor. It is important to shake and the reactor and check with light to make sure

the catalyst bed distribute evenly like shown in Figure 4.6.

(a) (b)

Figure 4.6. The catalyst bed shape before shake and check(a) before test and

Catalyst powder

Reactor

Steel mesh

15

after shake and check(b) before test

To increase the comparability of reference test which without catalyst inert sand

was employed with the same particle size and volume was add on the steel mesh

in reactor. The residence time of vapor go through the catalyst bed had been

calculated as about 1.7 seconds based on density of catalyst bed, density and

particle size of catalyst.

3,4. Products analysis and characterization

3.4.1. Gas analysis For gas analysis and online product detection, the Agilent 490 micro-GC has been

employed. This micro-GC consists of 4 columns and thermal conductivity

detectors. The calibration was done for CH4, C2H2, C2H4, C2H4, C2H6, CO, CO2, H2, N2

and O2.

3.4.2. Liquid analysis Liquid products were analysed with a GC/MS instrument(Agilent 7890A GC

coupled with Agilent 5975C MS). The column is VF-1701ms(0.25um) with 60m

length. The GC program was set as started holding time at 40℃ for 2 minutes,

then heat to 250℃ by 4℃/min heating rate. Followed by stable temperature for

30 minutes. The atom mass unit range was set from 45 to 450. Chemstation was

used incorporation with NIST11 to identify the peaks and calculate the peak area.

Also, the water content has been analyzed by using the water content analyzer

from Mettler Toledo AB. The method ASTM E203 was employed as the standard

method.

3.4.3. Catalyst characterization For better characterization of catalyst, BET (Brunauer–Emmett–Teller theory)

analysis and elemental analysis has been done with the calcined HZSM-5. The

surface area and acidity could be identified. As a microporous catalyst, enough

surface area is important to provide space for catalytic reaction. Acidity is another

essential property of HZSM-5. The BET method is basically extended from

Langmuir theory. It describes the phenomenon that gas molecules absorbed on

the multilayers.

Table 4.5 shows the elemental analysis of HZSM-5. According to BET result,

surface area of HZSM-5 used in this research has been determined as 402m²/g.

Table 4.5. Element analysis of HZSM-5

Element Concentration(mg/kg)

Si 340000

Al 21200

O 407414

16

3.5. Experimental plan Four cases have been set for the investigation. Case 2 under N2 atmosphere and

case 4 N2 with catalyst were reference tests to show the H2 carrier gas influence

on the pyrolysis of biomass. Case 1 was repeated 2 times, and other cases have 3

repetition tests.

Table 3.1 Four cases in this research

H2 N2 HZSM-5

Case 1 X

Case 2 X

Case 3 X X

Case 4 X X

4. Results and Discussion 4.1. Liquid analysis As shown in Figure 4.1, the liquid product from experiments has been separated

into oil phase(left), and aqueous phase(right) for each experiment by using a

separation funnel. this phenomenon occurs because the polar molecules easily

dissolve into water and the nonpolar molecules are insoluble in water which

generate the oil phase. The oil phase shows higher viscosity than the aqueous

phase. The oil phase is mainly lignin derivatives and the aqueous phase comes

from mainly the cellulose and hemicellulose pyrolysis [7].

Figure 4.1. Liquid product oil phase (left), aqueous phase (right). Sample was

taking from catalytic test under H2 atmosphere

17

Figure 4.2. Effect of atmosphere and catalyst on liquid product peak area

percentages in oil phase

Figure 4.2 shows the peak area percentage of different compounds in the oil

phase from each test. The oil phase product of catalytic tests gives a high aromatic

hydrocarbon yield of around 90% in both H2 and N2 atmosphere compared to

non-catalytic tests. HZSM-5 shows an excellent performance on aromatization

and deoxygenation. The peak area percentage of phenolics was higher in H2

catalytic test than the N2 catalytic test. Compared to catalytic tests, the non-

catalytic tests have a relatively high concentration on phenolics which could come

from the lignin. By comparing the two non-catalytic tests, H2 test gives about

5area% sugar yields (mainly D-Allose), simultaneously the N2 case show about

5area% furans yield (mainly furfural). Which could be explained the H2 atmosphere

tend to form sugar from the biomass fast pyrolysis.

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

H2 N2 H2 HZSM5 N2 HZSM5

Pea

k ar

ea p

erce

nta

ge

Aromatic hydrocarbons Phenolics Furans Overlab Ketones Sugars

18

Figure 4.3. Water content analysis of aqueous phase and oil phase

In Figure 4.3, the water content analysis result of aqueous phase and oil phase

from each test is shown. An interesting phenomenon need to be outlined is that

the presence of hydrogen in catalytic pyrolysis seems to increase the H2O

production. Different from the hydrotreating process, the oxygen shows the trend

that inhibited to be removed as H2O with the appearance of hydrogen during

catalytic pyrolysis. The elemental analysis of bio-oil cannot be done because of

the limitation of experiment scale which is so small to produce enough oil for

elemental analysis.

In Table 4.1, 4.2, 4.3, main compounds in liquid product from the different cases

have been listed. The compounds in aqueous phase of catalytic cases couldn’t be

detected, the reason is thought to be the high water content in that phase dilute

the compounds which result in they are below detection limit. The peak area of

non-catalytic tests aqueous phase is quite small, but still some peaks could be

detected, especially the sugar group (levoglucosan and D-Allose).

From Table 4.1, it can be found that higher concentration of monoaromatic

hydrocarbons(MAH) was produced in N2 than in H2. On the contrary, H2 with

HZSM-5 show a higher concentration on polyaromatic hydrocarbons(PAH).

Zhang et al. claimed that one type of precursor of aromatization during fast

pyrolysis are compounds which contains the methoxy- functional group [29]. By

comparing the H2 and N2 non-catalytic tests, there is no significant difference on

methoxy- containing compounds (such as guaiacol) peak area percentage

between the two atmospheres. Since change of atmosphere doesn’t show

difference on aromatization precursor peak area percentage, it means the reason

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

Aqueous phase Oil phase

Wat

er c

on

ten

t

H2 N2 H2 HZSM5 N2 HZSM5

19

which result in a higher PAH peak in oil phase is not only the existence of H2, but

also the co-operation between H2 and HZSM-5 tend to produce more PAH than

MAH from biomass pyrolysis. According to Table 4.2, H2 has no influence on non-

catalytic cases oil phase composition compared to N2.

Table 4.1. GC/MS identified compounds in oil phase of catalytic cases (Peak

Area %)

Compound H2 HZSM5 N2 HZSM5

Peak area percentage

Standard deviation

Peak area percentage

Standard deviation

Monoaromatic Hydrocarbons Benzene 2,76% 0,64% 6,28% 0,79% Toluene 15,00% 0,41% 23,84% 2,88%

Ethylbenzene 0,82% 0,04% 0,99% 0,11% p-Xylene 15,59% 0,80% 18,57% 0,70% Benzene, 1,3-dimethyl- 4,30% 0,22% 4,79% 0,03% Benzene, 1-ethyl-3-methyl- 0,54% 0,03% 0,52% 0,02% Benzene, 1-ethyl-2-methyl- 0,41% 0,01% 0,43% 0,01% Mesitylene 0,53% 0,04% 0,44% 0,05% Benzene, 1,2,4-trimethyl- 2,91% 0,10% 2,81% 0,24% Benzene, 1,2,3-trimethyl- 0,24% 0,02% 0,00% 0,00% Indane 1,14% 0,05% 1,08% 0,02% Benzene, 1-propynyl- 0,67% 0,01% 0,69% 0,12% 2-Methylindene 0,84% 0,05% 0,73% 0,01% 1H-Indene, 2,3-dihydro-4,7-dimethyl- 0,11% 0,11% 0,00% 0,00% Benzene, (1-methyl-2-cyclopropen-1-yl)- 0,41% 0,04% 0,19% 0,19%

Polyaromatic Hydrocarbons Naphthalene 10,30% 0,27% 7,53% 0,24% Naphthalene, 2-methyl- 14,89% 0,73% 11,36% 0,45% Naphthalene, 1-methyl- 5,08% 0,21% 3,61% 0,25% Naphthalene, 2-ethyl- 0,98% 0,10% 0,75% 0,07% Naphthalene, dimethyl- & trimethy- 13,79% 0,81% 7,62% 1,23% Fluorene 0,11% 0,11% 0,00% 0,00% Anthracene 0,24% 0,00% 0,00% 0,00% Phenanthrene 1,04% 0,00% 0,53% 0,06% Phenanthrene, 2-methyl- 1,23% 0,10% 0,63% 0,08%

Phenolics Phenol, 2-methyl- 0,63% 0,05% 0,22% 0,22% Phenol, 2-methoxy- 2,05% 0,15% 1,07% 0,33% Creosol 3,50% 0,66% 2,36% 0,73% Phenol, 4-ethyl-2-methoxy- 1,60% 0,37% 0,98% 0,25%

20

2-Methoxy-4-vinylphenol 1,35% 0,27% 0,37% 0,37%

Eugenol 0,39% 0,10% 0,00% 0,00% Phenol, 2-methoxy-4-propyl- 0,34% 0,10% 0,00% 0,00% trans-Isoeugenol 2,10% 0,60% 0,22% 0,22%

Table 4.2. GC/MS identified compounds in oil phase of non-catalytic cases (Peak

Area %)

Compound H2 N2

Phenolics Phenol, 2-methoxy- 14.53% 12.78%

Phenol, 2-methyl- 2.02% 1.54%

p-Cresol 3.51% 0.00%

Creosol 25.20% 24.17%

Phenol, dimethyl- 0.00% 2.43%

Phenol, 4-ethyl-2-methoxy- 10.05% 11.51%

2-Methoxy-4-vinylphenol 9.83% 9.11%

Eugenol 2.93% 3.34%

Phenol, 2-methoxy-4-propyl- 2.93% 3.52%

trans-Isoeugenol 2.82% 3.30%

Phenol, 2-methoxy-4-(1-propenyl)- 17.42% 18.22%

Others D-Allose 3.96% 0.00%

Furfural 0.00% 3.18%

2-Cyclopenten-1-one, 2-hydroxy-3-methyl- 4.81% 3.84%

Table 4.3. GC/MS identified compounds in aqueous phase of non-catalytic cases

(Peak Area %)

Compound H2 N2

Acetic acid 9.10% 3.42%

Phenolics Phenol, 2-methoxy- 7.75% 3.69%

Creosol 9.40% 4.58%

trans-Isoeugenol 2.93% 2.65%

Apocynin 0.00% 2.37%

Sugars .beta.-D-Glucopyranose, 1,6-anhydro- 5.87% 8.74%

D-Allose 52.43% 68.69%

4.2. Gas analysis Gas analysis has been done with Micro-GC. As shown in Figure 4.4 and 4.5, more

gas was produced in the catalytic tests which shows the HZSM-5 cracking of

21

pyrolytic vapors, more cracking reaction happened on HZSM-5 than the inert

sand. It has been found that H2 as carrier gas has the effect on producing more

CO and CO2, which refer to more oxygen been removed as CO and CO2. This

correspond to the water content analysis which could be concluded the H2

atmosphere inhibit the trend of oxygen distribute into H2O, and increase the

chance removing oxygen as CO and CO2.

By looking at Figure 4.5, for yields of C2H4, C2H6 and C3H6, H2 cases present a higher

result than N2 cases. However, no obvious difference on C3H8 yield has been found

between all? different cases.

Figure 4.4. Effect of atmosphere and catalyst on main gas product (mole/10g

biomass)

0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

0.045

CH4 CO CO2

mo

le

H2 N2 H2 HZSM5 N2 HZSM5

22

Figure 4.5. Effect of atmosphere and catalyst on other gas product (mole/10g

biomass)

4.3. Coke characterization The catalyst was collected after pyrolysis for thermogravimetric analysis. Figure

4.6 shows the coke deposition to catalyst ratio. It has been found that H2 has

slightly higher coke deposition than N2 as carrier gas. This correlates with the

results shown in section 4.1, the H2 catalytic reaction produce more PAH. Due to

the big molecule size of PAH, the microporous on HZSM-5 could be blocked by

these big molecules. Which means catalytic pyrolysis under H2 atmosphere might

has a higher risk on catalyst deactivation [7].

Figure 4.6. Mass of coke deposition to catalyst ratio

0

0.0002

0.0004

0.0006

0.0008

0.001

0.0012

0.0014

0.0016

H2 C2H4 C2H6 C3H6 C3H8

mo

le

H2 N2 H2 HZSM5 N2 HZSM5

0%

2%

4%

6%

8%

10%

12%

coke

dep

osi

tio

n t

o c

atal

yst

ratio

H2 HZSM5

N2 HZSM5

23

4.4. Mass balance and product distribution The distribution of three types of product is shown in the Figure 4.7. The standard

deviation of gas, oil and aqueous phase was presented by char yield. According

to Figure 4.7, atmosphere and catalyst affects product yields on various aspects.

The char yield slightly increased from H2 to N2 in both catalytic and non-catalytic

case, this might prove the H2 can help the decomposition of biomass. The reason

could be hydrogen has better efficiency on heat transfer than the nitrogen

because of its higher thermal conductivity, a faster pyrolysis process could

decrease the char yield [11] [30]. By comparing the results with and without

catalyst, catalytic cases show a higher gas yield and lower liquids yield which

shows the HZSM-5 help the bio-oil cracking into smaller molecules and generate

more gas. By comparing the oil phase and liquid phase yields, catalytic cases

present lower yields than non-catalytic cases because of the oxygen removal as

CO and CO2 into gas phase by catalytic cracking reaction. Simultaneously, H2

atmosphere shows the influence of increasing of oil phase yield and decreasing

of aqueous phase compared with N2 atmosphere.

Figure 4.7. Effect of atmosphere and catalyst on product yields

All the products and feedstock have been scaled. Figure 4.8 shows the results of

calculatingthe mass of products divided by the feedstock to get the ratio. In this

Figure, hydrogen atmosphere wasn’t considered as one of the feedstock because

it will finally collected in the gas bottle mixed with other product which means it

is impossible to separate the produced H2 and calculate how much H2 was

consumed. On the other hand, in non-catalytic cases, the coke deposition on inert

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

50%

Char Gas phase Oil phase Aqueous phase

Yie

lds

H2 N2 H2 HZSM-5 N2 HZSM-5

24

sand bed hasn’t been measured, this result in their product to feedstock ratios are

relatively lower than ratios of catalytic tests. Besides this, the amount of H2

produced under H2 atmosphere is impossible to measured and the mass of H2 in

gas product is relatively low in the N2 cases because of its low molecule weight,

therefore the H2 was excluded from the gas product in Figure 4.8. The reason of

total ratio for N2 HZSM-5 case higher than 100% might because some system error

such as the catalyst absorb moisture between scaling and test, and this could be

also happened in the hydrogen case. By assume the system error was similar

between H2 case and N2 case, the test under H2 always show a higher product to

feedstock ratio than under N2 in both with and without catalyst cases, which means

there was some H2 react with biomass or biomass derivates and goes into product.

The entire product distribution and feedstock is presented in Appendix.

Figure 4.8. Products to feedstock ratio

4.5. Comparison with ideal yield of liquid hydrocarbon fuel By assuming only three type products, CH1.2(the empirical chemical formula of

gasoline), CO2 and H2O, was produced from the process. Based on the elemental

balance, the maximum hydrocarbon yield could be calculated ideally based on

elemental balance.

Without H2: CH1.43O0.63 = 0.99423CH1.2 + 0.00577CO2 +0.61846H2O 1

With H2: CH1.43O0.63 + 0.515H2 = CH1.2 + 0.63H2O 2

In without eq. 1, the idea yield of CH1.2 (the liquid hydrocarbon) could reach 33.85%

weight percentage. For H2 addition case eq. 2, this value could increase to 44%.

Figure 5.1 show the comparison of ideal yield of liquid hydrocarbon and the real

oil phase yield in this project (seem as pure hydrocarbon cause its low oxygen

content and low water content).

0%

20%

40%

60%

80%

100%

120%

H2 H2 HZSM-5 N2 N2 HZSM-5

Pro

du

ct t

o f

eed

sto

ck r

atio

Char Organic compounds in Oil phase

Organic compounds in aqueous phase Water

Gas Coke deposition

25

Suchithra Thangalazhy-Gopakumar et al. claimed that no significant change was

found by change catalytic pyrolysis atmosphere from He to H2 [8]. Because they

used Pyroprobe model 5200 as the reactor which is a kind of small scale reactor,

so the product distribution information couldn’t be monitored very well. Therefore,

they claimed no significant change was found by changing atmosphere.

Figure 5.1. The ideal liquid hydrocarbon yield and the oil phase yield in this

project

During the entire work, moisture absorbed by biomass and catalyst between scale

and experiment could be an error which can increase the feedstock into the

system. As we see in Figure 4.8, the N2 catalytic case shows a higher output than

feedstock, which require the moisture influence should be taken into

consideration in the further work. A TGA test could help to understand how much

moisture could be absorbed by biomass and catalyst.

The GC-MS used in this work is not calibrated which means the only provided

information about compounds is the peak area. The peak area percentage has

limitation on quantitative analysis because it is different with concentration.

The pressure in gas collection bottle is slightly higher than atmospheric pressure,

which could result in less calculated gas yield than the real gas yield. This pressure

difference should be measured in the further work.

4.6. Discussion on environmental feasibility Growing demand of liquid hydrocarbon fuel in transportation sector is creating

pressure and competition, especially on timber resources and land crops. In 2016,

the biofuel was accounted for 19% of all the fuel consumed in the transportation

sector in Sweden, most of the biofuel comes from the hydrotreated vegetable oil.

But the additional land for growing energy crop to produce vegetable oil could

cause a negative impact on food production and animal habitats.

This technique is a promising way to produce liquid hydrocarbon fuel from

Yield in this

project

Yield in this

project

Ideal yield Ideal yield

0%

10%

20%

30%

40%

50%

60%

Without H2 With H2

Yie

lds

26

lignocellulosic biomass, which is widely existed in agricultural waste, forestry waste

and so on. It could help not only to ease the energy shortage problem, but also

to gain better usage of lignocellulosic waste.

5. Conclusions The conclusion could be divided into two parts.

a) Effects of H2 in non-catalytic fast pyrolysis process

b) Effects of H2 in catalytic fast pyrolysis

Effect of H2 in non-catalytic process The presence of H2 decrease the char yield slightly from the case which use N2 as

carrier gas. Simultaneously H2 atmosphere also show a higher oil phase yield and

lower water phase yield. More CO and CO2 generated with the H2 atmosphere,

higher water production in the N2 atmosphere, which proved that H2 as carrier gas

preferably remove oxygen as CO and CO2. In the oil phase, D-Allose peak only

existed in oil produced with H2, comparatively furfural with similar peak area of D-

Allose only existed in oil phase produced with N2. Which could be concluded sugar

was preferably generated under H2 atmosphere. The product to feedstock ratio of

H2 case is higher than N2 case which proved H2 as carrier gas was consumed during

the pyrolysis.

Effects of H2 in catalytic fast pyrolysis In catalytic tests, H2 test shows lower char yield, aqueous phase yield, water

production, and higher oil phase yield, gas production, CO and CO2 production.

Higher PAH and lower MAH peak area percentage was found in H2 case compare

to N2 case which could be due to the corporation of H2 and HZSM-5. More coke

deposition on catalyst was found with H2 atmosphere.

Thus, it can be concluded that H2 as carrier gas has the influence on both chemical

composition and yields of product in HZSM-5 catalytic pyrolysis of biomass. And

some of the influence is caused by co-operation of H2 and the HZSM-5 catalyst.

6. Further work on H2 effect on CFP process The elemental analysis of bio-oil and char need to be done for better

understanding of H2 effect on CFP process.

For more feasibility study on the industrial scale production with H2 atmosphere.

The energy balance need to be calculated, and more fuel properties of bio-oil

should be also taken in account.

27

7. Acknowledgement I would like to thank my supervisors, Docent Weihong Yang and PhD student

Henry Persson. Thanks for giving me this chance to work in this fantastic project

and help me solve the problem I met during the project.

I would also like to thank my closest friend Rikard Svanberg, he gave me a lot of

suggestions during my work.

All the members in my group taught me a lot during the past several months for

helping me get used to this new field of study, thank you for all of you!

28

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30

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31

Appendix. Basic result from four cases tests

In this figure, all basic information of product yields from different tests was shown.

H2

H2 zsm5

N2

N2 zsm5

2017/3/23

2017/

5/22

Aver

age

ST

DE

V

2017/

3/24

2017

/5/9

2017/6

/14

Aver

age

ST

DE

V

2017/3

/31

2017/

4/19

2017/

5/18

Ave

rage

ST

DE

V

2017/

4/13

2017/

5/10

2017/

5/19

Ave

rage

ST

DE

V

char 25,78%

24,83

%

25,3

0%

0,47

%

24,79

%

25,3

5%

25,38

%

25,1

7%

0,11

%

25,31

%

25,93

%

26,08

%

25,7

7%

0,33

%

25,77

%

26,12

%

25,49

%

25,7

9%

0,31

%

gas

No water

collection

18,65

%

18,6

5%

0,00

% -

24,7

1%

30,27

%

24,7

1%

0,00

%

12,35

% 9,39%

14,70

%

12,1

5%

2,17

%

14,60

%

21,47

%

20,73

%

18,9

3%

4,33

%

Liquid 58,17%

58,78

%

58,4

8%

0,30

%

49,45

%

51,9

6%

42,93

%

50,7

1%

0,00

%

59,17

%

58,59

%

58,03

%

58,8

8%

0,48

%

56,05

%

41,94

%

52,33

%

54,1

9%

2,63

%

Oil

phase -

13,70

%

13,7

0%

0,00

%

11,1

1% 7,65%

11,1

1%

0,00

%

11,04

%

11,0

4%

0,00

%

9,90

%

7,15

%

9,68

%

9,79

%

0,16

%

Aqueou

s phase -

45,08

%

45,0

8%

0,00

%

40,8

5%

35,28

%

40,8

5%

0,00

%

46,99

%

46,9

9%

0,00

%

46,15

%

34,79

%

42,65

%

44,4

0%

2,48

%

Out/In -

102,2

6%

102,

26%

0,00

% -

102,

02%

98,58

%

102,

02%

0,00

%

96,79

%

93,91

%

98,82

%

95,3

5%

2,09

%

96,42

%

89,53

%

98,56

%

97,4

9%

1,51

%

Recalc

ulation

Oil

phase

12,24

%

12,2

4%

0,00

%

10,8

0% 7,57%

10,8

0%

0,00

%

9,68

%

9,68

%

0,00

%

9,50

%

7,05

%

9,43

%

9,46

%

0,05

%

TGA mass loss/ dry catalyst

7,80

%

8,51

%

10,18

%

7,36

%

10,57

%

5,72

%

H2

loss(g)

0,080

6002

0,09

2116

0,0959

50175

H2 loss(g)/H2 Input

CO(g)

0,667

4944

1,07

3641

1,4784

66774

0,4152

86023

0,008

18301

0,508

9387

0,011

3738

1,012

7921

0,954

7373

CO2(g)

1,201

7675

1,21

2196

1,3816

58687

0,7410

52004

0,735

4672

0,862

718

1,065

954

0,964

7507

0,945

2801

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