Accepted Manuscript

Title: Microwave pyrolysis of textile dyeing sludge in a

continuously operated auger reactor: Char characterization
and analysis

Authors: Hedong Zhang, Zuopeng Gao, Wenya Ao, Jing Li,

Guangqing Liu, Jie Fu, Chunmei Ran, Xiao Mao, Qinhao
Kang, Yang Liu, Jianjun Dai

PII: S0304-3894(17)30214-5
DOI: http://dx.doi.org/doi:10.1016/j.jhazmat.2017.03.048
Reference: HAZMAT 18464

To appear in: Journal of Hazardous Materials

Received date: 9-1-2017

Revised date: 12-2-2017
Accepted date: 22-3-2017

Please cite this article as: Hedong Zhang, Zuopeng Gao, Wenya Ao, Jing Li,
Guangqing Liu, Jie Fu, Chunmei Ran, Xiao Mao, Qinhao Kang, Yang Liu,
Jianjun Dai, Microwave pyrolysis of textile dyeing sludge in a continuously
operated auger reactor: Char characterization and analysis, Journal of Hazardous
Materialshttp://dx.doi.org/10.1016/j.jhazmat.2017.03.048

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 Microwave pyrolysis of textile dyeing sludge in a continuously operated
auger reactor: Char characterization and analysis
Hedong Zhang, Zuopeng Gao, Wenya Ao, Jing Li*, Guangqing Liu, Jie Fu, Chunmei Ran, Xiao Mao,
Qinhao Kang, Yang Liu, Jianjun Dai*
College of Chemical Engineering, Beijing University of Chemical Technology
15 Beisanhua East Road, Chaoyang District, Beijing, China 100029

*Corresponding author: Tel: 1-7789383886; e-mail: crystaldlj@gmail.com

*Corresponding author: Tel/Fax: 86-010-64452091; e-mail: daijianjun@hotmail.com,

jjdai@mail.buct.edu.cn

Highlights

1. SC yield decreased with microwave power. The content of C, H and N in SC decreased with
temperature while S increased.
2. Both CaO and Fe increased the composition of H2, CH4 and CO, and decreased CO2 content.
CaO can absorb sulfur and CO2.
3. Maximum BET surface area of 91.9m2/g was observed for SC at 550oC
4. DS volume was reduced to ~60-66% after MWP
5. Leaching tests proved that heavy metals in SC don’t pose a threat to the environment

Abstract: Textile dyeing sludge (DS) contains toxic organic and inorganic substances, and needs

to be disposed by appropriate technologies. This paper investigated an auger pyrolyser under

microwave irradiation for treatment and disposal of DS. Microwave power, temperature, gas and

solid residence times, addition of catalysts were studied. The results showed that the char yield

gradually decreased with microwave power. The residence times of solid and gas have slight

1
effects on char yields in the temperature range of 450-750oC. Addition of CaO and Fe increased

char yield, decreased non-condensable gas yield and increased H2 content. CaO promoted

decomposition of DS and capture of CO2. In the meantime, CaO retained more sulfur in the solid

phase compared to MWP without addition of CaO. The content of C, H and N in DS and sludge

char (SC) decreased with temperature while S increased. The maximum BET

(Brunauer-Emmett-Teller) surface area of 91.9m2/g was observed for SC at 550oC, consistent

with Scanning Electron Microscopy (SEM) observations. X-Ray fluorescence (XRF) analysis

showed existence of some heavy metals, and leaching characteristics of heavy metals in the SC

meet the requirements of national standards in China and will not pose a threat to the

environments.

Keyword: Textile dyeing sludge; Microwave; Pyrolysis; Auger; Char

1 Introduction

There are 3830 wastewater treatment plants in total in China by September 2015, treating

162 million cubic meters wastewater each day. The discharge rate of industry sludge has been

increasing in the past decades in China, mainly due to rapid economy and industry development.

The discharge amount of wastewater from textile dyeing industries is about 2.1 billion tonnes

and about 21 million tonnes of sludge from dyeing industry is created each year in China [1].

Textile dyeing sludge (DS) has very complex chemical compositions, and usually contains more

toxic organic matter (e.g. perishable organics, parasites, microorganisms, dyeing agents,

additives, polycyclic aromatic hydrocarbons-PAH), and heavy metals (e.g. zinc, copper, lead,

2
chromium) than sewage sludge. Improper treatment and disposal of DS has caused serious

environmental problems.

Nowadays the treatment and disposal of DS makes use of technologies from sewage sludge

treatment. Traditional technologies treating and disposing sludge have their own limitations and

disadvantages, and cannot effectively and efficiently treat and dispose DS [2–5]. Pyrolysis and

gasification are important thermochemical conversion technologies and have been widely used

for various applications in industries. In recent years, pyrolysis and gasification were developed

to treat sludge of different sources and properties due mainly to their advantages such as fast

reaction rate, small footprint, high efficiency, reduced emissions under oxygen-deficient reaction

environment, flexibility to fuel properties, ease of control and scale-up. Both pyrolysis and

gasification are excellent candidates for processing various solid wastes and are more efficient

and cleaner in comparison with combustion [6–11].

Microwave-assisted pyrolysis (MWP) is an emerging technology to treat and dispose sludge

thanks to its unique characteristics such as fast heating, selective heating, volumetric heating and

uniform heating. Microwave heating (MWH) is an energy transfer process without direct contact

with the heated materials, different from conventional heating (CH) methods such as conduction,

convection and radiation [12]. Potential applications of MWH are dependent on the dielectric

properties of target materials. Hence MWH is also referred to as dielectric heating [13]. MWH

reduces energy consumption and reaction time, and is more environmentally friendly compared

with CH [14].

DS is categorized into hazardous industry wastes, and ash content of DS is high and even up

to more than 60wt% (oven-dry basis) in terms of research works from the authors. DS from

3
different plants may have different compositions and properties, and needs to be analyzed

specifically, which add complexity to treatment and disposal of DS. The water content and

inorganic matter in sludge can absorb microwave and enhance sludge heating, improving

pyrolysis characteristics. Materials that can absorb microwave are called microwave absorbers

(MWAs) [11,15]. It would be desirable that the distribution of pyrolytic products can be

effectively regulated by MWAs and catalysts[3,16,17]. This paper characterized DS and

analyzed properties of DS and SC. The SC was generated from an auger pyrolyser of continuous

operation under MW irradiation. Many works in the literature focused on the production of

bio-oil, syngas and char from direct MWP of woody biomass, herbaceous biomass and sewage

sludge [10,18–24]. However, most of the research works on MWP employed fixed beds of batch

operation and MWP of DS has rarely been seen in previous studies. In fact, the coupling of

MWP and an auger reactor of continuous operation for treating and disposing DS has never been

reported from the literatures so far. Hence the current study is a significant contribution to both

MWP technologies of continuous operation, and DS treatment and disposal. The current study

focused on char characterization and analysis for MWP of DS in an auger pyrolyser, and

condensates and non-condensable gas will be investigated in the future work.

2 Materials and methods

2.1 Materials

The DS was from a printing and dyeing plant in Jiangsu province, located in southeastern

part of China. The collected DS was black in color and put in a barrel. After crushing, <1mm DS

solids were sieved and collected, then put in the drying oven (WHL-25AB, Taisite) at 105℃ for

12 hours. The dried DS sample was crushed and sieved, particles of <105μm was then collected

4
for proximate and ultimate analysis (Table 1). Calcium oxide (CaO)(AR, white Powder, purity

≥98.0%) was from Xilong Chemical Co., Ltd. in China. Iron powder (AR, purity ≥98.0%) was

acquired from Sinopharm Chemical Reagent Co., Ltd. in china. Pure ethanol (purity ≥99.7%)

was purchased from TianJin GuangFu Technology Development Co., Ltd. in China. Whereas

Beijing Chemical Plant provided sulfuric acid (H2SO4) (AR, 95%-98%) and nitric acid (AR,

65%-68%) for leaching tests of DS and SC. A bomb calorimeter (ZDHW-A9, Henan Sanbo

Instruments Co., LTD, China) was used to measure the lower heating value (LHV) of DS.

2.2 Experimental apparatus and procedure

This study used a two-mode microwave device (Huaye Microwave Technology, Ltd. China)

with the maximum MW power of 3kW and 2.45 GHz frequency. A schematic diagram of the

auger pyrolyser of continuous operation under MW irradiation (APCOMW) was shown in

Figure 1. The APCOMW mainly consisted of five units: feeding unit, a microwave-assisted

auger pyrolyzer (MWAP), char collection unit, pyrolysis gas cooling and cleanup unit, gas

analysis unit. The pyrolyser reactor (4cm ID, 40cm long) was made of quartz tube, inside which

there is an auger symmetrically placed at the tube centerline. Both ends of the quartz tube were

sealed tightly with a silica O-ring and a polytetrafluoroethylene sealer. An infrared pyrometer

was placed at the top of the quartz tube to control and measure the temperature of the sample

inside the quartz reactor. Temperature was controlled by adjusting the voltage through a

transformer, which is related to MW power. Hence MW power input was adjusted to ensure the

desired temperature of the reactor. A thermocouple (Type K, 0–1000oC) was also put at the top

of the quartz reactor to measure the outer surface temperature of the quartz tube to compare with

the results from the infrared pyrometer. Five resistance thermometers (PT100) were installed

5
before and after the quartz reactor for temperature measurement. Argon and nitrogen were routed

to MWAP from the feeding system to ensure inert gas environment of the auger pyrolyser. A

mass flow controller was employed to control and measure the mass flow rate of Argon, which

was used as the tracer gas to help calculate the flow rate of non-condensable gas. Whereas

nitrogen flow rate was measured by a rotameter. To prevent the magnetron from being damaged

by reflected microwaves, a ferrite circulator (Type: Y) was built between the microwave source

and the MWAP. Thus, the reflected microwaves were absorbed by the circulating water.

Before each test, put 300-800g DS into the feeding hopper, then closed the feeding port of

the hopper. N2 of 0.12m3/h was used to purge MWAP for 10 min to ensure the reactor system

was filled with inert gas. Kept N2 and Ar at certain flow rates, respectively, then turned on the

MW switch. When the desired temperature was achieved, started the auger at certain rotational

speed. Run the experiments continuously for 20-60 min. SC was received by a container below

the MWAP. After cooling, the condensates were collected by four cooling bottles downstream

the MWAP. The non-condensable gas, after washing by deionized water and alcohol in two

washing bottles, was directed to a GC or collected by the sample gas bags every 2 min. After the

test, shut off the MW and auger switch, kept N2 of 0.02m3/h flowing through the reactor until the

reactor temperature <350oC. SC and condensates were weighed and characterized. Whereas gas

samples were analyzed by a GC. This study employed temperature of 350oC, 450oC, 550oC,

650oC, 750oC, the corresponding SCs were named as SC350, SC450, SC550, SC650, SC750.

Whereas SC650-1, SC650-2, SC650-3, SC650-4, SC650-5 were used to represent the SC

generated at different operation parameters (e.g. different auger speeds, additions of CaO and Fe)

as shown in Table 2.

6
 2.3 Analytical methods

Proximate and ultimate analyses of the raw DS and SC were shown in Table 1. Elemental

analysis (CHNS analyzer, VARIO EL cube, Germany), SEM (Scanning electron microscopy,

HITACH S4700, Japan), BET surface area analysis (Kubo-X100, BJBuilder, Beijing, China),

XRF (X-Ray fluorescence, Lab Centre XRF-1800, SHIMADZU) and ICP-MS (inductively

coupled plasma mass spectrometry, 7700 Series ICP-MS, Agilent Technologies) were employed

to analyzed DS and SC. Leaching characteristics of heavy metals in DS and SC were

investigated. The mixing solution of concentrated sulfuric acid and nitric acid at 1:2 mass ratio

was added to deionized water to make extractants of pH=3.21. 20 g DS, SC450, SC650 were

added to 200ml extractants in a beaker, which was placed on the magnetic stirrers at 650 rpm for

6h to enhance mixing. An ultrasonic oscillating device was employed to further promote mixing

for 20min. Repeat the procedure twice from magnetic stirrers to the ultrasonic oscillating device.

After filtration, the supernatant was taken for ICP-MS analysis.

3 Results and discussion

The MW power, heating time and reactor temperature were pretested and recorded before

experimental research. It was shown that the reactor temperature was almost linearly

proportional to heating time and the reactor temperature reached ~820oC at 2100W (Figure 2a).

The reactor temperature was obtained from the infrared pyrometer reading. Figure 2b showed

the relationship between the total inert gas flow rate and inert gas residence times at room

temperature in the MW auger pyrolyzer. Figure 2c showed the relationship between auger

speeds and mass flow rates of DS. Whereas Figure 2d exhibited the solids residence times

corresponding to specified auger speeds.

7
 3.1 Effects of temperature on product yields

Figure 3a showed that gas yield increased as reactor temperature increased and SC yield

decreased with temperature increasing. The yield of condensates exhibited a different trend,

which increased with temperature in the temperature range of 450-650oC and reached maximum

at 650oC, then the condensates yield decreased as temperature increased. Volatiles were released

when DS entered the hot reaction zone. Higher reactor temperature increased the heating rate of

DS, generating more pyrolysis oil due to faster pyrolysis. Increasing temperature up to 750oC,

pyrolysis oil was reformed and cracked inside the hot reaction zone, reducing pyrolysis oil and

increasing non-condensable gas yield. From previous literature, 450-650oC is the temperature

range beneficial for oil production, depending on different feedstock types and properties,

reactor types and operating conditions. When temperature reached 550oC, most of the volatiles

were released. Hence the SC yield curve between 550-650oC became flatter than that between

450-550oC. When temperature increased from 650oC to 750oC, inorganic matter (e.g. ammonium

salts and carbonates) became to decompose. Moreover, the gas velocity inside the MW auger

pyrolyser increased as temperature increased because the inert gas flow rate was set constant at

room temperature upstream the pyrolyzer and pyrolysis gas released from DS and SC also

increased with temperature. It indicated larger entrainments of fines to downstream, which was

proved by the darker condensates collected in the cooling bottles. Hence the curve after 650oC

became steeper than that in the temperature range of 550-650oC, indicating the higher mass loss

rate and decomposition of inorganics above 650oC.

The lowest char yield was 63.87wt% at 750oC from the tests, slightly higher than ash

content of DS (i.e. 60.75wt%). It indicated that ~92wt% organics in DS was converted to

8
condensates and non-condensable gas at 750oC. SC was a MWA, absorbing MW once it was

generated in the auger pyrolyser and increasing the pyrolyser temperature [25,26]. SC can also

act as catalysts, catalyzing pyrolysis of DS and reducing tar content [27]. Large ash content led

to low heating value of DS, which needs to consume additional energy to keep high enough

temperature for pyrolysis, gasification or combustion. However, MWP of DS is efficient

technique to treat and dispose DS mainly due to good MW absorbing capacity of SC, fast heating,

volumetric heating and uniform heating characteristics. Moreover, DS volume was reduced to

~60-66v% after MWP, which is beneficial to save areas to dispose SC compared with direct DS

landfilling.

3.2 Effects of gas residence time on MWP of DS

Figure 3b showed that char yield slightly decreased as inert gas flow rates (i.e. Ar and N2)

increased, which was, at least partly, caused by reduced secondary pyrolysis when inert gas flow

rate increased. Larger gas flow rate led to shorter residence time of vapor in the MW auger

pyrolyser, secondary pyrolysis between the vapor and the char was inhibited. Hence the amount

of char generated by secondary pyrolysis was reduced, leading to lower char yield compared to

that with smaller inert gas flow rate. Another possible reason is that higher inert gas flow rate led

to more particle entrainments with the pyrolysis gas to downstream and slightly reduced the char

yield, which was observed from darker color of the collected condensates in the gas cooling and

cleanup unit. For higher inert gas flow rates, more vapor in the pyrolyser was entrained to the

washing bottles and may not be captured by the cooling bottles downstream the auger pyrolyser.

The washing liquids in the two washing bottles were alcohol and de-ionized water, respectively.

The washed condensates by the washing liquids were not counted for the calculations of

9
condensates yield, leading to reduced condensates yield. Hence the liquid yield slightly

decreased.

3.3 Effects of auger speeds on MWP of DS

Figure 3c showed the product yields at different auger speeds. When auger speeds were

adjusted from 0.5 rpm to 9 rpm, char yield was almost constant. Reducing auger speeds from 5

rpm to 2.5 rpm, the DS/SC residence time in the auger pyrolyser increased from 3.3 min to 6.6

min. Carbon and nitrogen contents in SC decreased as solid residence time increased as shown in

Table 2 (SC650 and SC650-5), mainly due to release of carbon and nitrogen containing organics

to vapor phase after longer exposure at pyrolysis temperature. Whereas hydrogen content and

sulfur content in SC showed the opposite. For 2.5rpm at 650oC (i.e. SC650-5), the pyrolysis gas

residence time in the MW auger pyrolyser was longer than that for 5 rpm at 650oC (i.e. SC650)

as shown in Table 2. Hence there might be more vapor entrained to char collector with SC for

SC650-5, leading to higher hydrogen content in the SC650-5. It was proved by LHV of SC650-5,

which was slightly higher than those of SC650 and SC550. For the case of CaO addition,

hydrogen and nitrogen contents in SC decreased as solid residence time increased because more

hydrogen and nitrogen containing organics were released when the lower auger speed (i.e.

2.5rpm) was used (e.g. SC650-1 and SC650-4 in Table 2). Whereas, carbon and sulfur contents

showed a different trend, which increased as solid residence time increased, mainly because of

formation of secondary pyrolysis char and sulfur capture by CaO absorbents at lower auger

speed or longer solid residence time. Sulfur capture by CaO absorbents has been reported in

conventional pyrolysis and gasification processes from previous literatures [28,29]. Moreover,

CaO can also act as MWAs and catalysts in MWP of biomass and other solid wastes [18,20].

10
 3.4 Effects of CaO and Fe on char yield and gas compositions

CaO and Fe were used as MWAs and catalysts. As mentioned above, CaO was also a good

absorbent for in-situ CO2 capture. When CaO content increased from 20wt% to 30wt% (e.g.

SC650-1 and SC650-2 in Figure 3d), the SC yield increased from 66.6wt% to 78.18wt%. It may

be mainly caused by formation of CaCO3 due to reactions between CO2 and CaO [28–30], which

was proved by reduced gas yield for SC650-2 (30wt% CaO). It was reported that CaO also

promoted decomposition of organics in biomass and sludge [28,30]. 20wt% Fe in the DS (i.e.

SC650-3) increased SC yield by 4% compared to that without addition Fe catalyst (i.e. SC650).

Compared to SC650-1 (20wt% CaO), 20wt% addition of Fe (i.e. SC650-3) increased SC yield

and decreased yields of non-condensable gas and condensates, mainly thanks to sorption of CO2

by CaO. Excessive CaO addition (e.g. SC650-2) may absorb more CO2 and enhance secondary

pyrolysis, leading to higher SC yield and lower gas and liquid yields compared to SC650-1(20wt%

CaO) and SC650-3(20wt% Fe) as shown in Figure 3.

Both CaO and Fe significantly increased contents of H2, CH4 and CO, and decreased CO2

content in the non-condensable gas as shown in Figure 4, which indicated their catalysis effects

and CO2 absorption by CaO. Moreover, CO2 might be reduced to CO or C due to presence of Fe

in DS and SC. Addition of CaO significantly reduced the contents of carbon, nitrogen, hydrogen

and increased sulfur content in the SC as shown in Table 2. It was mainly because CaO

promoted pyrolysis of carbon, hydrogen and nitrogen containing organics in DS and CaO also

capture more sulfur in the solid phase at the same operation conditions (e.g. pyrolysis

temperature, auger speed and inert gas flow rate). As CaO changed from 20wt% to 30wt%, the

contents of carbon, hydrogen and nitrogen all decreased, indicating the catalytic effects of CaO

11
on pyrolysis as shown in Table 2. However, sulfur content of SC decreased as CaO content

changed from 20wt% to 30wt%. Hence 20% CaO may reach maximum sulfur capture capacity at

650oC, and increased CaO to DS ratios were not much useful to promote further sulfur capture.

However, Fe addition reduced sulfur content in SC, indicating catalysis effects of Fe on

decomposition of sulfur containing organics as shown in Table 2.

3.5 Proximate and ultimate analyses of SC

The ultimate analyses of SC were conducted. Figure 5 showed that carbon content

decreased and carbon conversion increased as reactor temperature increased. The same trends

were found for nitrogen and hydrogen.

The carbon content in DS is 15.53wt% based on elemental analysis. After MWP of DS, the

carbon content in the SC decreased to 12.16~14.55wt%. The hydrogen content in the SC was

0.63~1.42wt%, far less than that in the DS (i.e. 3.44wt%), indicating most of hydrogen in the DS

went to condensates and non-condensable gas phase. Nitrogen content decreased from 1.94wt%

to 1.18wt% when temperature increased from 450oC to 750oC. All the nitrogen contents

corresponding to different pyrolysis temperature in the SC were much lower than that in the DS

(i.e. 2.43wt%). However, sulfur content increased with temperature, indicating that sulfur may

exist in the inorganic form in DS and/or organic sulfur may be captured by CaO absorbents in

the SC. Considering the SC yields at different temperatures, it can be concluded that carbon,

hydrogen and nitrogen are easier to be pyrolyzed, and end up in aqueous and gaseous products

compared to sulfur. Higher temperature led to higher conversion of carbon, hydrogen and

nitrogen to condensates and non-condensable gas. However, relatively more sulfur stayed in the

solid phase as temperature increased. There are some organic compounds containing amino and

12
nitro functional groups in the DS. Hetero-aromatic compounds, such as aniline and pyridine,

were found in the condensates from MWP of DS in terms of GC-MS analysis. For the

non-condensable gas analysis, sulfur-, nitrogen- and chlorine-containing gases were detected,

such as NH3, H2S and HCl, respectively.

The heating value of DS is low due to its high ash content. Hence DS needs additional

energy to conduct drying and pyrolysis. Water and SC/ash are good MWAs and can absorb MW

energy efficiently, which improves the energy efficiency for disposing DS. Moreover, MWH has

advantages over conventional heating methods such as fast, uniform and volumetric heating, and

can easily kill parasites and pathogens, and efficiently convert organics in DS to useful gas,

liquid and solid products.

3.6 SEM analyses of DS and SC

In order to obtain high resolution images, and the surface topography and composition of

DS and SC, SEM imaging was conducted on the samples of DS and SC from different pyrolysis

temperature as shown in Figure 6. The surface of DS was relatively smooth without many

protrusions. However, the surfaces of SC450, SC550, SC650, SC650-1 and SC750 were slightly

fluffy, and there were asperities and more pores on their surfaces, increasing the surface areas.

The surface characteristics were closely related to the release of volatiles during pyrolysis. The

heating rate of MWP was much faster than that of conventional pyrolysis because DS had higher

ash content, and inorganics in DS and SC acted as MWAs. SC was a good MWA and would

increase the heating rate once it was formed in the MW auger pyrolyser. Moreover, volumetric

and uniform heating characteristics of MWP were also beneficial to obtain better surface

properties and pore structures. It should be noted that C550 exhibited more irregular protrusions

13
and better pore structures in comparison with others except SC650-1 from the SEM images.

550oC looked like the best temperature to provide good surface characteristics and pore

structures of SC. Lower temperature (e.g. SC450) may not be able to release all the volatiles

inside the pores during pyrolysis, and the pore structures and surface properties may not be fully

developed. Higher temperature (e.g. SC650, SC750) may cause sintering of inorganics and block

the pores. The infrared pyrometer only controlled and measured the average SC temperature

inside the MW auger pyrolyser, and there might be hotspots inside the SC particles, leading to

sintering of some inorganics. It looked like that addition of CaO significantly increased the

number of surface protrusions, and improved the surface topography and pore structure as shown

in SC650-1 image in Figure 6.

3.7 Specific surface area and porous properties

BET surface areas increased with pyrolysis temperature and reached maximum at 550oC

(91.9m2/g) as shown in Table 3. Release of volatiles was beneficial to generate good pore

structures inside the particles, depending on the texture and composition of DS. There may be

volatiles trapped inside the pores of the particle at lower temperature than 550oC. Higher

temperature may cause almost complete release of volatiles and larger carbon conversion into

vapor and gas phases, as well as sintering of inorganics [31]. The latter may block the pores. The

yield of condensates reach maximum at 650oC, secondary pyrolysis may occur between the

pyrolysis oil and the char, forming secondary char and block the pores [32]. Many researchers

have conducted research on surface areas of char [33,34], which is closely related to pyrolysis

temperature, particle sizes, feedstocks types and properties, and additives.

3.8 Major metal and non-metal contents in DS and SC

14
 XRF was conducted for DS and SC as shown in Table 4. The major metal elements in the

DS and SC were Al, Fe, Ca, Mg, Zn, Na, K, Mn, Cu, Sn, Cr, Pb, etc. Whereas, non-metal

elements were mainly Si, S, P, Cl, Br, etc. Al is the most abundant elements in DS, probably

because the aluminum additives were used for wastewater treatment. The next most abundant

elements were Fe and Si. The contents of Al, Si, Mg in the SC increased with pyrolysis

temperature increasing, which indicated that these elements may be present in inorganic forms

and lesser of them were released into vapor phase in comparison with organics and other

elements. Fe, S, P, Cl, Zn, Br etc. were detected by GC-MS in condensates which were collected

downstream the MW auger pyrolyser, indicating splitting of the metal and non-metal compounds

in DS to the solid and liquid products.

At 450oC, the contents of heavy metals such as Zn, Cu, Cr, Pb, Ni etc.in SC450 were higher

than those in DS. The content of Sn in SC450 is slightly lower than that in DS. As temperature

increased, the contents of these heavy metals in the SC decreased although there were some

variations, indicating larger loss of these heavy metals in the SC at higher temperature. The lost

heavy metals from the SC were expected to be entrained to aqueous and gaseous products.

However, most of the heavy metals listed above stayed in the SC (~80-96wt%), depending on

different types of heavy metals.

3.9 Leaching characteristics of heavy metals

There are some heavy metals in DS, which may pose a threat to the environments if not

properly treated and disposed. The heavy metals based on the decreasing order of contents in DS

leachate were Zn>As>Cu>Ni>Pb>Hg>Cd as shown in Table 5. Zn has the highest concentration

among the heavy metals in both DS and SC leachates, which may be related to the zinc-plating

15
pipes used in the wastewater treatment plants in China [35]. The content of Cd is the lowest one

in DS and SC.

The heavy metals were mostly kept in the SC during the MWP of DS, and were further

enriched at certain degrees as pyrolysis temperature increased, especially Zn. The Zn content in

DS leachate is ~35 times as large as those in SC450 and SC650 leachates, respectively,

indicating more concentrated metal contents in SC and easier leaching from SC to aqueous phase

compared to DS. There were also some heavy metals vaporized, and entrained to downstream

and ended up in aqueous phase condensates during MWP of DS. It is still an active research area

about stabilization of heavy metals in the SC, preventing pollutions of these heavy metals to the

soil and water sources.

Table 5 showed the contents of the heavy metals in the leachates from leaching tests for DS,

SC450 and SC650. It was evident that all the heavy metals contents were lower than those from

the national standards (Sludge pollutants control standards for agricultural uses-GB4282-84,

China), and MWP of DS doesn’t pose any threat to the environments in terms of heavy metal

contents in SC. However, considerable amounts of heavy metals were collected in condensates,

which will be further investigated in the future work.

4 Conclusions

The MWP of DS using the auger pyrolyser of continuous operation was conducted. The SC

yield decreased as temperature increased and reached minimum of 63.87wt% at 750oC from the

current study. The yield of condensates increased from 450oC to 650oC, and reached maximum

at 650oC, then decreased as temperature increased. However, the non-condensable gas yield

increased when temperature increased from 450oC to 750oC. From elemental analysis, the

16
contents of carbon, hydrogen and nitrogen in the SC were always lower than those in the DS.

Whereas the sulfur contents in the SC was mostly higher than that in the DS. It indicated that

most of sulfur in the DS was in inorganic forms and/or sulfur in the organics was captured and

ended up in the SC. However, Fe addition reduced sulfur content in SC, indicating catalysis

effects of Fe on decomposition of sulfur containing organics. Addition of CaO promoted

decomposition of DS and capture of CO2. In the meantime, CaO changed products yields and

retained more sulfur in the solid phase compared to MWP without addition of CaO. BET surface

areas reached maximum of 91.9m2/g at 550oC, consistent with SEM observation. Addition of

CaO improved surface characteristics of SC based on SEM analysis. XRF analysis showed

existence of some heavy metals, and leaching characteristics of heavy metal s in the SC meet the

requirements of national standards in China and will not pose a threat to the environments. DS

volume was reduced to ~60-66v% after MWP. Hence MWP showed great promises for treatment

and disposal of DS.

17
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Figure 1. Experimental apparatus for the microwave pyrolysis of dyeing sludge

21
 (a) (b)
800 60

Inert gas residence time (s)

Room temperature
Temperature (℃) 700
50
600
500 40
400
30 y= 1/0.1382x
300 200W 400W
200 600W 800W 20
1100W 1400W
100 1700W 2100W 10
0
0 400 800 1200 1600 2000 2400 0.04 0.08 0.12 0.16 0.20
(c) Time (s) (d) 3
Inert gas flow rate (m /h)
280 2.7
260
Solid residence time (s)

2.4

Mass flow rate (kg/h)

240
220 2.1
-0.962
200 y= 749.25x 1.8
180
160 1.5
140 1.2
120
0.9
100
3 4 5 6 7 3 4 5 6 7
Auger speed (rpm) Auger speed (rpm)

Figure 2. Relationship between (a) reactor temperature and MW heating times without DS; (b) Inert
gas (N2+Ar) flow rates and residence times in the auger pyrolyser at room temperature (20oC); (c)
solid residence times and auger speeds;(d) Dry DS mass flow rates and auger speeds.

22
 (a) (b)
80
70
70
60

Yield (wt.%)
Solid 60
50 Solid
Yield (%)
Liquid
40 Gas Liquid
Gas
30 20
20
10
0 10
450 550 650 750 0.04 0.08 0.12 0.16
(c) Temperature (℃) (d) 3
Gas flow rate (m /h)
80 no catalyst, 2.5rpm
70
70 no catalyst, 5rpm
20wt% CaO, 2.5rpm
60 20wt% CaO, 5rpm
Yield (wt.%)

60

Yield (%)
Solid 30wt% CaO, 5rpm
50
Liquid 20wt% Fe, 5rpm
Gas 40
20 30
20
10 10
0 2 4 6 8 10 0
Solid Liquid Gas
Auger speed (rpm)

Figure 3. Relationship between (a) pyrolysis products distribution (at 5 rpm and inter gas flow
rate=0.16m3/h); (b) Inert gas flow rates and yields (at 5 rpm and 650℃); (c) Auger speeds and yields
(inert gas flow rate=0.16m3/h and 650℃); (d) Catalysts effects on gas, liquid and solid products yields
(650oC and inter gas flow rate=0.16m3/h);

23
 (a) 70
450 550
60
650 750
Gas Content (%) 50
40
30
20
10
0
CO2 CO CH4 H2
(b)
60 no catalyst 20% Fe
20% CaO 30% CaO
Gas Content (%)

50
40
30
20
10
0
CO2 CO CH4 H2
Product Gas

Figure 4. Gas content of different pyrolysis condition:(a) at 5 rpm and inert gas flow rate=0.16m3/h; (b) at
5 rpm, 650℃ and inert gas flow rate=0.16m3/h

24
 16

Percentage (wt%)
14 DS
12 SC450
10 SC550
8 SC650
6 SC750
4
2
0
C H N S
Element
6
5
LHV (MJ/kg)

4
3
2
1
0
DS SC450 SC550 SC650 SC750
Sample

Figure 5. Ultimate analysis and LHV of DS and SC (5rpm)

25
 (A) DS (B) SC450

(C) SC550 (D) SC650

(E) SC750 (F) SC650-1

Figure 6. SEM of DS and SC (auger speed=5rpm, inert gas flow rate=0.016m3/h)

26
 Table 1. Proximate and ultimate analyses of DS
a
Proximate analysis (wt%) Elemental analysis b (wt%) LHV(MJ/kg)
Moisture Ash Volatile Fixed Carbon C H N S Oc
c

1.37 60.75 36.53 1.35 15.53 3.44 2.43 1.38 16.47 5.99
a
Air Dry basis
b
Oven Dry basis
c
Calculate by deference

27
 Table 2. Main process parameters and ultimate analysis of DS and SC a (wt%)

Auger Inert gas flow Total gas flow Gas residence

Sample Catalysts b 3 c 3
C H N S
speed(rpm) rate(N2+Ar) (m /h) rate (m /h) timed (s)

DS - - 15.53 3.44 2.43 1.38

SC450 - 5 0.16 0.81 2.94 14.55 1.42 1.94 1.53
SC550 - 5 0.16 1.07 2.21 13.41 1.27 1.53 1.71
SC650 - 5 0.16 1.23 1.93 13.32 0.72 1.34 1.92
SC750 - 5 0.16 1.38 1.72 12.16 0.63 1.18 1.96
SC650-1 20wt%CaO 5 0.16 0.94 2.53 9.57 1.03 0.81 3.68
SC650-2 30wt%CaO 5 0.16 0.86 2.76 8.23 0.66 0.58 2.71
SC650-3 20wt%Fe 5 0.16 1.02 2.32 11.63 0.87 1.05 0.87
SC650-4 20wt%CaO 2.5 0.16 0.94 2.53 10.57 0.82 0.79 3.73
SC650-5 - 2.5 0.16 0.99 2.52 12.12 1.23 1.32 3.3
a
Oven-dry basis
b
The volumetric flow rate ratio of N2 to Ar=3:1. The volumetric flow rate is based on room temperature
(i.e. 20oC)
c
Equal to inert gas volumetric flow rate plus pyrolysis gas volumetric flow rate at pyrolysis temperature
d
At corresponding pyrolysis temperature

28
 Table 3. Porous properties of DS and SC

Sample name SBET (m2/g)a Smic (m2/g)b SP(m2/g)c Vt(cc/g)d Vmic(cc/g)e VP(cc/g)f DP(nm)g

DS 65.59 59.06 71.83 0.106 0.021 0.110 3.24

SC350 62.14 52.31 73.86 0.105 0.019 0.111 3.37

SC450 90.38 72.99 104.42 0.158 0.026 0.167 3.5

SC550 91.90 81.42 105.12 0.181 0.029 0.189 3.94

SC650 73.76 75.32 85.26 0.177 0.027 0.184 4.8

SC750 60.58 64.07 62.29 0.118 0.023 0.119 3.89

a
BET specific surface area
b
Micropore specific surface area
c
BJH desorption cumulative specific surface area
d
Single point total pore volume
e
Micropore volume
f
BJH desorption cumulative total pore volume
g
Single point average pore diameter

29
 Table 4. Ash characterization of DS and SC (wt%)

Mass fraction (%)

Compounds
DS C450 C550 C650 C750 C650-1 C650-2

Al2O3 38.46 38.11 38.55 38.86 41.31 21.71 17.19

Fe2O3 16.38 18.93 14.87 15.60 14.19 12.54 11.92

SiO2 15.42 15.05 16.17 16.82 16.92 6.58 5.18

CaO 7.80 8.06 8.22 8.43 7.66 40.43 50.25

SO3 7.61 5.54 6.23 5.86 5.85 9.31 8.11

P2O5 5.34 4.75 4.97 4.96 5.19 2.18 1.76

TiO2 1.90 2.05 1.81 1.88 1.74 1.49 1.45

MgO 1.71 1.83 2.29 2.56 2.32 1.10 1.10

Cl 1.43 1.14 1.21 1.16 1.17 1.06 1.02

ZnO 1.11 1.41 0.97 1.01 0.91 0.71 0.69

Na2O 1.02 1.03 1.04 1.08 1.13 0.52 0.31

K2O 0.38 0.40 0.38 0.40 0.37 0.19 0.17

MnO 0.35 0.39 0.32 0.34 0.31 0.27 0.27

CuO 0.30 0.37 0.26 0.27 0.24 0.20 0.18

SnO2 0.29 0.24 0.22 0.25 0.25 0.13 0.11

Cr2O3 0.144 0.16 0.14 0.15 0.13 0.12 0.11

ZrO2 0.10 0.14 0.09 0.09 0.08 0.06 0.05

Br 0.08 1.00 0.06 0.07 0.06 0.04 0.03

I 0.05 0.06 - 0.05 0.05 - -

PbO 0.05 0.07 0.04 0.04 0.04 0.02 0.04

NiO 0.04 0.10 0.04 0.04 0.04 0.03 0.03

SrO 0.04 0.06 0.04 0.04 0.03 0.04 0.04

Ga2O3 0.01 0.02 0.01 0.01 0.01 - -

Rb2O - 0.02 0.01 0.01 0.01 - -

NbO - - 0.01 0.01 0.01 - -

30
 Table 5. DS and SC leachate concentrations of heavy metals (mg/kg)

Sample Ni Cu Zn As Cd Hg Pb Cr

DS 1.419×10-2 1.989×10-2 8.057×10-2 3.918×10-2 2.200×10-4 2.090×10-3 1.052×10-2 -

SC450 9.484×10-2 4.259×10-2 2.876 7.710×10-2 5.000×10-5 4.927×10-2 1.054×10-2 -

SC650 2.545×10-2 1.433×10-1 2.841 7.667×10-2 3.400×10-4 5.283×10-2 6.483×10-2 -

GB4282-84a 100 250 500 75 5 5 300 600

a
《Sludge pollutants control standards for agricultural uses》(GB4282-84)

31