Catalytic Pyrolysis of Herb Residues for the Preparation of Hydrogen

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Biofuels and Biomass

Catalytic Pyrolysis of Herb Residues for the Preparation of Hydrogen-rich Gas Baofeng Zhao, Ge Song, Weihong Zhou, Lei Chen, LaiZhi Sun, Shuangxia Yang, Haibin Guan, Di Zhu, Guanyi Chen, Weijing Ding, Jingwei Wang, and Huajian Yang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b02177 • Publication Date (Web): 20 Aug 2019 Downloaded from pubs.acs.org on August 21, 2019

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Catalytic Pyrolysis of Herb Residues for the Preparation of Hydrogen-rich Gas Baofeng Zhaoa,*, Ge Songa,b, Weihong Zhoub,c,*, Lei Chena, Laizhi Suna, Shuangxia Yanga, Haibin Guana, Di Zhua, Guanyi Chenc, Weijing Dinga,b, Jingwei Wanga, Huajian Yanga

Key Laboratory for Biomass Gasification Technology of Shandong Province, Energy Research Institute, Qilu University of Technology(Shandong Academy of Sciences), 19 Keyuan Road, Jinan 250014, China a

bSchool

of Civil Engineering, University of Science and Technology LiaoNing, 185 Qianshan Middle Road, Anshan 114051, China

c School

of Environmental Science and Engineering/State Key Lab of Engines, Tianjin University, 92 Weijin Road, Tianjin 300072, China

Corresponding Author E-mail:[email protected] Corresponding Author E-mail:[email protected]

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3242861_File000001_60932611.docxPrinted 8/20/2019 ACS Paragon Plus Environment

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Abstract: Thermochemical conversion technology for the resource utilization of biomass not only can treat wastes polluting the environment but also can efficiently generate hydrogen-rich gas for industrial applications. In this paper, the simulation calculation and experimental studies were employed to investigate the catalytic pyrolysis of herb residues for the preparation of hydrogen-rich gas. The results of TG-FTIR, kinetic, and thermodynamic studies showed that the catalytic pyrolysis of herb residues by 10 wt%Ni/CaO catalyst exhibited the lowest apparent activation energy compared with pyrolysis catalyzed with CaO or catalyst-free. Under the catalysis of 10 wt%Ni/CaO and the temperature range of 500~700 °C, the content of H2 in the catalytic pyrolysis gas products of herb residues was higher while the content of CO2 was lower. Furthermore, in the presence of 10 wt%Ni/CaO catalyst, the catalytic pyrolysis experiment of herb residues in a moving bed reactor was carried out at 500~700 °C. The results showed that the distribution of hydrogen-rich gas composition with increasing temperature was consistent with the thermodynamic simulation results. Specifically, with rising pyrolysis temperature, the H2 content increased initially and then decreased, which reached the highest ratio at 650 °C with an experimental value of 67.31 vol%.


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1 Introduction

Hydrogen plays an important role in the future energy structure because of its high calorific value, clean and pollution-free.1,2 Currently, hydrogen is mainly derived from fossil fuels such as coal, natural gas, petroleum by-products,3 but these raw materials are limited in reserves and can easily cause environmental pollution during exploitation. On the other hand, biomass is a renewable carbon source with wide distribution and large reserves. The production of hydrogenrich gas via biomass thermal conversion has the characteristics of high conversion efficiency, clean and pollution-free, which is a very promising technology for production of hydrogen.4 Herb residues are biomass waste produced after processing and purification of medicinal materials. Due to the rapid development of Chinese medicine industry, the annual discharge of herb residues reaches 10 million tons in China.5 Comparing with agricultural and forestry biomass waste, herb residues have the advantages of large output, easy collection, and uniform quality. It is highly suitable for utilization via biomass thermal conversion technology, which not only solves environmental pollution problems but also industrially produces hydrogen-rich gas to achieve significant environmental and economic benefits. The thermal conversion of herb residues tends to generate tar, as well as a relatively high content of CO2. It has been reported that the catalytic pyrolysis technology could prevent the generation of tar, adjust the gas composition, and increase the hydrogen yield.6-9 Guanyi Chen et al.10 studied the effect of La1xKxMnO3 catalyst on hydrogen production by catalytic pyrolysis of biomass. The results showed that the La1-xKxMnO3 perovskite catalyst with K substitution degree of 0.2 exhibited the best performance and could improve the H2 yield significantly. Blanco et al.11 employed the municipal solid waste as a raw material to carry out hydrogen production experiments by using a lab-made Ni/SiO2 catalyst. It was found that the Ni/SiO2 catalyst prepared by gel-sol method could improve the H2 yield significantly. Weijing Ding et al.12 studied the in-situ removal of CO2 by herb residues catalytic pyrolysis and found that the CaO catalyst could considerably reduce the CO2 content in gaseous products.


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Biomass catalytic pyrolysis is a complex network system composed of a series of reactions. Although the interaction of each reaction affects the depth and progress of the pyrolysis, the overall apparent activation energy can be used to determine the difficulty degree of reaction. A kinetics Coats-Redfern method is an effective approach for calculating the pyrolysis activation energy of biomass. Can Yao et al.13 used Coats-Redfern method to determined that the pyrolysis activation energies of Chinese silver grass, corn stover, rice husk, and pine were 46.7, 29.3, 54.3, and 58.1 kJ mol-1, respectively. Vekes Balasundram et al.14 investigated the effect of Ni-Ce/Al2O3 on the pyrolysis of coconut shell and rice hull by Coats-Redfern method. It was found that the Ni-Ce/Al2O3 catalyst significantly reduced the apparent activation energy of pyrolysis of rice husk samples, which facilitated the initiation and progress of pyrolysis reaction. Currently, since there are few studies on the thermal conversion of herb residues for hydrogen production, the related mechanism remains unclear and needs further research. According to our previous studies,15,16 the Ni/CaO catalyst in the pyrolysis process of herb residues can not only catalyze tar crack but also absorb CO2, which can significantly improve the gas quality. Therefore, it is feasible to produce hydrogen-rich gas by herb residues catalytic pyrolysis with Ni/CaO catalyst. In this work, the simulation calculations combined with experimental studies were conducted to study the preparation of hydrogen-rich gas by herb residues pyrolysis, which provides experimental and theoretical support for the development of hydrogen production technology. 2 Materials and methods

2.1 Materials The biomass raw material used in this study is herb residues, which contains salvia miltiorrhiza and a small amount of Panax notoginseng. The results of the physical analysis indicated that the contents of herb residues included cellulose 46.38 wt%, hemicellulose 18.19 wt%, lignin 13.92 wt%, moisture 8.3 wt%, ash 3.3 wt%, volatile matters 74.8 wt%, and fixed carbon 14.2 wt%. The elemental ratios of C, H, N, O and S were 49.46, 5.41, 1.49, 43.3 and 0.34 wt%, respectively. According to our previous research,12,16 10% wtNi/CaO catalyst was prepared by isovolumetric impregnation method. Firstly, the CaO powder was placed in a muffle furnace and calcined at 700 ℃ for 4 hours. Then it was sufficiently stirred with an appropriate amount of [Ni(NO3) 2·6H2O] solution, after immersion for 6 hours, it was dried and


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calcined. Finally, it was reduced at 900 ℃ for 2 hours in a tube furnace under a 10 vol% H2 atmosphere. The mass ratio of catalyst (Ca) to (H) herb residues (Ca/H) was 0.65.

2.2 Methods 2.2.1 TG-FTIR Experiment Thermogravimetric-Fourier Transform Infrared analyzer(TG-FTIR), integration of the Netzsch STA409PC thermogravimetric analyzer with the Brook TENSOR27 Fourier transform spectrometer, can accurately analyze the composition and release time of pyrolysis gas products, which is particularly suitable for the study of biomass pyrolysis mechanisms.17-19 In this experiment, the final pyrolysis temperature was set at 900 °C with a heating rate of 50 °C min-1. Herb residues with the weight of 10 mg were loaded into the thermogravimetric instrument. During the experiment, the gas products after pyrolysis were carried to the FTIR gas cell with a high purity nitrogen flow 70 ml/min. The FTIR measured and recorded the experimental data automatically and simultaneously. According to the different infrared wavenumbers, the characteristic peaks of each gas phase product were analyzed to determine their formation.20,21

2.2.2 Moving Bed Experiment The moving bed system was used for the catalytic pyrolysis experiment of herb residues. Figure.1 illustrates the technical flow of the system. The pyrolyzer consists of a stainless steel tube with a length of 1 m and a diameter of 0.05 m. The particle size of the herb residues is 30-40 mesh. The mixture of herb residues and 10 wt%Ni/CaO was loaded into the pyrolyzer by a quantitative feeder. The herb residues pyrolysis, CO2 absorption, and tar catalytic cracking occurred simultaneously in the pyrolyzer. The solid product char after the catalytic pyrolysis of herb residues fell directly into the char collector. After washed and dried, the volatile matters entered the gas analyzer, which monitored the gas composition and calorific value in real- time. The pyrolysis gas was collected in triplicate when the analyzer data was stable. The sample was analyzed by gas chromatography to confirm the composition of the product. (Figure.1)


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2.2.3 Kinetics and Thermodynamics The Coats-Redfern method was adopted to carry out kinetic calculation of the catalytic pyrolysis data of herb residues obtained by TG, which is usually used to determin the kinetic parameters of biomass pyrolysis. The kinetic reaction equation can be described as :22-24

Wherein, A, E, T, and t represent the pre-exponential factor, the apparent activation energy, temperature, and time, respectively. The conversion rate of the herb residue “α” can be expressed as:

Wherein, m0, m∞, and mt represent the initial mass, terminating mass, and time, respectively. According to the approximate expression of the CoatsRedfern equation, equation (1) can be integrated as follows:

Wherein, R is the ideal gas constant, g; β= dT/dt is the heating rate. For most biomass pyrolysis, E/2RT»1, (1-2RT / E) ≈ 1, so the above equation can be simplified to:

Therefore, the left side of the above equation was plotted against 1/T to obtain a straight line with a slope of -E/R and an intercept of ln(AR/βE).


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According to the Gibbs free energy minimization method,25-27 the thermodynamic simulation of the catalytic pyrolysis of herb residues was conducted by Matlab programming.28 In the calculation, temperature, pressure, and catalyst mass ratio are key parameters of the reaction system. Herb residues were input with C, H, O elements. The pyrolysis temperature was in the range of 500~700 °C and the pressure was 101.325 KPa, while the Ca/H was 0.65. The output products were simplified as 18 components including water, benzene, toluene, acetic acid, styrene, phenol, naphthalene, CaO, CaCO3, and Ca(OH)2, where the gas is in an ideal state while carbon (graphite) and CaCO3 were in solid states. 3 Results and discussion 3.1 TG/DTG Analysis Figure.2 shows TG/DTG curves of pyrolysis of herb residues at a heating rate of 50 °C min-1 under the conditions of catalystfree, CaO catalyst, or 10 wt%Ni/CaO catalyst. It can be seen that the process of herb residues catalytic pyrolysis is roughly divided into four stages (dehydration, transition, fast pyrolysis, carbonization stage). The first stage starts from the beginning to about 150 °C, in which the TG curve was slightly reduced with the observation of the first peak of DTG curve . This stage is considered the process of removing the surface water from the herb residues, which is usually called the dehydration process. The second stage is approximately from 150 to 250 °C. The TG curve slowly declined due to the removal of bound water in the raw material and prolysis of a small amount of hemicellulose. The third stage occurs between 250 and 600 °C. The TG curve exhibited a steep decline at this stage with the presence of a maximum peak in the DTG curve. This result indicated that a large amount of volatiles were precipitated, including non-condensable gases and condensable macromolecular. The forth stage is the slow pyrolysis process of carbon residues when temperature exceeded 600 °C. In this stage, the DTG curve of the herb residues pyrolysis with CaO and 10 wt%Ni/CaO catalyst shows a small weight loss peak. The reason is the release of CO2 from solid samples resulting from the decomposition of CaCO3 at high temperature.

(Figure.2)


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3.2 Kinetic Analysis Table.1 illustrates the kinetic parameters of herb residues pyrolysis with catalyst-free, CaO catalyst, and 10 wt%Ni/CaO catalyst. The results showed that the correlation coefficients of the three samples were above 95% when the reaction order was 1. In addition, it was found that the activation energies of the three samples were 45.47, 38.51, and 36.66 kJ mol-1, respectively. When the catalyst was added, the pyrolysis activation energy was significantly reduced. It is noted that of the 10 wt%Ni/CaO catalyst was the lowest. These results demonstrated that the catalyst could reduce the apparent activation energy of the herb residues pyrolysis, resulting in facilitation of pyrolysis reaction. In particular, the catalytic ability of 10 wt%Ni/CaO was better than that of CaO.

(Table.1)

3.3FTIR and Thermodynamic Simulation Analysis FTIR analysis can give the CH4, CO and CO2 escape processes in spite of H2 during the herb residues pyrolysis with 10 wt%Ni/CaO from 30 to 900 °C, shown in Figure.3. It can be seen that the catalytic pyrolysis of herb residues was divided into four stages. The first stage range from 30 to 250 °C. According to the TG-DTG analysis results, this stage is a process consisting of dehydration and pyrolysis of a small amount of hemicellulose. Therefore, the yeild of each gas component was low at this stage. The second stage is in the temperature range of 250~500 °C. The first peak of CO2 appeared, accompaning with the release of a large amount of CH4 and gradually increase in the release of CO, indicating that the methanation reaction mainly occur at this stage. The third stage is 500~700 °C. At this stage, the yeild of CH4 declined, whereas the yield of CO slightly increased. Although CO2 exhibited a slowly rising trend, the total yield of CO2 was low, illustrating that the absorption of CO2 by CaO is optimal compared to other stages. The temperature of the final stage exceeds 700 °C. The yield of CO2 reached the maximum peak. In the meantime, the yield of CH4 almost remained constant while the yield of CO increased and reached the peak value. This result could be attributed to the decomposition reaction of calcium carbonate at this stage, which releases a large amount of CO2, promoting the C-CO2 reaction.


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According to the above analysis, the variation of CH4, CO and CO2 yield may lead to the significant change of H2 content in third stage. Therefore, the thermodynamics simulation of the herb residues catalytic pyrolysis was carried out in the temperature range of 500~700 ℃. Figure.4(a) shows the variation of gas yields with increase of temperature, which are consistent with the results of FTIR analysis. The changes of gas contents are shown in Figure.4(b), indicating that the content of CH4 declined, CO content gradually increased, while that of CO2 changed slightly remaining low value. Specifically, with the increasing pyrolysis temperature, the H2 content increased initially and then decreased, which reached the highest ratio at 650 ℃with an maximum value of 77.35 vol%. Therefore, it is concluded that the optimum temperature range is 500~700 ℃ for hydrogen-rich gas by catalytic pyrolysis of herb residues.

(Figure.3) (Figure.4)

3.4 Catalytic Pyrolysis Experiment In a Moving Bed System The catalytic pyrolysis experiment for the preparation of hydrogen in a moving bed system was carried out under the 10 wt%Ni/CaO catalyst and the temperature range of 500~700 °C. The gaseous product distribution was investigated, and verified by thermodynamic simulation results, which are shown in Figure.5. The comparison of the two results indicates that both experiment and simulation of variation trends of each component are very similar. The H2 content increased and then decreased, which reached the highest value at 650 °C with an experimental value of 67.31 vol%. The CO2 content remained almost constant in the beginning and then increased significantly after 650 °C, indicating that the reaction (1) is one of the main reactions before 650 °C. CaO can effectively absorb CO2, and promote the reaction (2) to the forward direction, resulting in a increase of H2 content. Inversely, it is declined due to the reverse of the reaction (1) when temperature exceeded 650 °C. .In addition, the content of CH4 continuously declined. The CO content increased slowly and then rose significantly above 650 °C, because the reaction (3) occurred mainly at high temperature.15 It can be concluded that the in-situ CO2 removal by 10


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wt%Ni/CaO catalyst breaks the equilibrium of gaseous reaction in herb residues catalytic prolysis, leading to the forward-going tendency in hydrogen yield.

(Figure.5)

4 Conclusion

TG-FTIR experiments, kinetic and thermodynamic results showed that the addition of 10 wt%Ni/CaO catalyst could significantly reduce the apparent activation energy of pyrolysis of herb residues for the preparation of hydrogenrich gas. 10 wt%Ni/CaO catalyst and 500~700 °C temperature range are determined to be the optimal operating parameters for hydrogen-rich gas from herb residues. Under these conditions, the catalytic pyrolysis experiment are carried out in a moving bed system, which indicate that the hydrogen content reach the maximum at 650 °C with an experimental value of 67.31 vol%. It will provide solution of industrial waste pollution and promote the hydrogen production technology from biomass.


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Acknowledgments This work was supported by National Key R&D Program of China (2018YEE0106400), Natural Science Foundation of Shandong Province of China (ZR2019MEE069, ZR2019MB061, ZR2016YL010 and ZR2016YL012), Shandong Provincial Key Research and Development Plan (2018GGX104028 and 2018GGX104026).

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Figure.1 Moving bed pyrolysis system

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-12

60 0

200

400

600

800

-16 1000

Temperature(℃)

(c)

Figure.2 TG/DTG curve of herb residue pyrolysis under a heating rate of 50 °C/min. (a) no catalyst, (b) addition of CaO catalyst, (c) addition of 10 wt%Ni/CaO.

Table.1 Calculation Results of Coats-Redfern Model for herb residues


17

Energy & Fuels

Sample

Fitting equation

R2

none CaO 10% wtNi/CaO

Y=-5468.70753X-4.42615 Y=-4631.5766X-6.14584 Y=-4409.84706X-6.50544

0.99090 0.97755 0.98049

E，kJ mol-1 45.47 38.51 36.66

A, min-1 3.27×103 4.96×102 3.29×102

0.25

CH4 0.20

Absorbance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 25

CO CO2

0.15

0.10

0.05

0.00

200

400

600

800

1000

Temperature (ºC)

Figure.3 temperature

The

absorbance

variation

of

gases


with

increasing

18

Page 19 of 25

0.9 0.8 0.7

gases yield (mol)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

0.6 0.5

CH4

0.4

CO CO2

0.3 0.2 0.1 0.0

500

550

600

650

700

Temperature (℃)

(a)


19

Energy & Fuels

80 70

Gas Concentration(vol.%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 25

60

H2

50

CH4 CO CO2

40 30 20 10 0

500

550

600

650

700

Temperature(℃)

(b) Figure.4 The variation of gases with increasing temperature (a) Gas yields, (b) Gas contents.


20

Page 21 of 25

80

simulation experiment

75


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

70

65

60

55

50

45

550

600

650

700

Temperature(℃)

(a)


21

Energy & Fuels

40


35


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 25

30 25 20 15 10 5 550

600

650

700

Temperature(℃)

(b)


22

Page 23 of 25

30

simulation experiment 25


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

20

15

10

5

0

550

600

650

700

Temperature(℃)

(c)


23

Energy & Fuels

8


7


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 25

6

5

4

3

2 550

600

650

700

Temperature(℃)

(d) Figure.5 Effect of temperature on the distribution of non-condensable gas products. (a) H2, (b) CH4, (c) CO, (d) CO2.


24

Page 25 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels


25

Catalytic Pyrolysis of Herb Residues for the Preparation of Hydrogen

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