Next Article in Journal
Carbon Functionalized Material Derived from Byproduct of Plasma Tar-Cracking Unit on Biomass Gasifier Collected Using Standard Impinger Method
Next Article in Special Issue
Preparation and Emulsifying Properties of Carbon-Based Pickering Emulsifier
Previous Article in Journal
Test and Simulation Analysis of Soybean Seed Throwing Process
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Processes
Volume 10
Issue 9
10.3390/pr10091732
processes-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Study on High Temperature Pyrolysis Light Cycle Oil to Acetylene and Carbon Black

by
Zekun Li
1,
Qimin Yuan
1,
Jinlian Tang
1,
Xiaoqiao Zhang
1,
Shaobin Huang
2 and
Jianhong Gong
1,*
1
Sinopec Research Institute of Petroleum Processing Co., Ltd., Beijing 100083, China
2
Sinopec Jiujiang Company, Jiujiang 332000, China
*
Author to whom correspondence should be addressed.
Processes 2022, 10(9), 1732; https://doi.org/10.3390/pr10091732
Submission received: 26 July 2022 / Revised: 18 August 2022 / Accepted: 24 August 2022 / Published: 1 September 2022
(This article belongs to the Special Issue Research on Thermal and Catalytic Reaction Mechanism in Petrochemical Process)
Browse Figures
Review Reports Versions Notes

Abstract

:
The reaction performance of producing acetylene by light cycle oil (LCO) high temperature pyrolysis was investigated with a self-made electromagnetic induction heating device. The results showed that the reaction temperature and residence time were the main factors restricting the production of acetylene during LCO high temperature cracking. When the reaction temperature was 1800 °C and the residence time was 8.24 ms, the yield of acetylene reached 7.90%. At the same time, the comparative study of different raw materials shows that Yangzhou heavy cycle oil (YZHCO) with a higher content of chain alkanes, cycloalkanes, and tetrahydro-naphthalene aromatics was beneficial to the formation of acetylene, and the highest yield of acetylene reached to 12.7%. The preliminary characterization of byproduct carbon black showed it had a good structure and could be used for lithium electron conductive agent.

1. Introduction

Recently, excessive oil refining capacity, as well as new economic situation promotes the transformation of oil refining to chemical industry, and fluid catalytic cracking (FCC) low-value products such as light cycle oil (LCO) also face new outlet problems [1,2,3]. Acetylene is the basic raw material for the production of several processes of organic synthesis in the chemical industry [4]. Acetylene can be used as the raw material in a series of chemical reactions, which produce ethylene, vinyl chloride, trichloroethylene, ethylene acetate, acrylonitrile, polyacrylonitrile, and other chemical products [5,6]. Acetylene can be produced from hydrocarbons or by the calcium carbide technique [7,8]. However, the traditional production process of acetylene, such as the carbide technique, has many problems, including high energy consumption and heavy pollution. Instead of the calcium carbide method, one-step transformation from raw materials to acetylene is possible using thermal plasma with its special characteristics of high temperature, high enthalpy, and high reactivity [9,10]. A considerable amount of research and pilot plant trials have been carried out since the 1960s to testify the applicability of plasma pyrolysis [11,12,13,14,15,16,17,18,19,20,21,22,23] including MW reactors of Hüels and DuPont, respectively. However, the reactor performance is sensitive to reactor geometry and operating conditions, while the scaling-up of such processes, accompanied with the elevating power, also meets the challenge due to the duration and lifetime of the plasma electrode [6]. Currently, thermal plasma pyrolysis of methane to acetylene has still not been carried out in practice. Electromagnetic induction heating is a kind of direct contact heating technology [24] that directly absorbs electromagnetic energy into thermal energy through a ferromagnetic field. At present, it involves many application fields, such as magnetic hyperthermia [25], catalytic [26], organic synthetic [27], etc. Meanwhile, electromagnetic induction heating can eliminate the problems of slow heating/cooling rate, uneven heating, difficult temperature control, and low energy efficiency that are brought about by the traditional contact heating method. The catalytic process that is based on electromagnetic induction heating technology has the following advantages: high direct heating energy efficiency, body phase heating makes the heating more uniform, can realize instantaneous heating on/off, and the reactor setting is simple and safer.
Meanwhile, carbon black has now developed into one of the indispensable and important products in the modern national economy, and the global consumption is increasing year by year [28]. Among them, conductive carbon black shows high electrical conductivity or anti-static capability, which are aggregated nanoparticles with a developed chain branch structure [28]. Specifically, it is characterized by a high specific surface area, high structure, high purity, and excellent conductivity. Its “three high excellent” characteristics make the application of conductive carbon black wider than ordinary carbon black. On one hand, conductive carbon black are excellent fillers to achieve high conductivity or antistatic for polymer materials, widely used in electromagnetic wave shielding materials, power cable shielding line, oil pipe, and anti-static electronic component packaging materials; on the other hand, they are widely used in areas of aerospace communications, energy conservation, environmental protection, transportation, and energy. At present, the application of the conductive carbon black in the new energy vehicles becomes more and more interesting. The main research object of development of new energy vehicles are the electric vehicles that are powered by lithium batteries. Conductive carbon black is an indispensable conductive agent in batteries and its performance is directly related to the core technology implementation of the battery. Therefore, the fierce market competition of conductive carbon black means that all countries have invested a lot of manpower and material resources in the development of batteries, especially for conductive carbon black.
In fact, to the best of our knowledge, few literature has reported research on using LCO as a raw material for high temperature lysis to make acetylene and carbon black. Therefore, this research is using LCO to produce acetylene and conductive carbon black. It not only opens up a new way for oil utilization, but also provides a new idea for the transformation of oil refining to chemical industry.
In this paper, producing acetylene and conductive carbon from LCO via high temperature pyrolysis on a self-made electromagnetic induction heating device was reported. The influence of the reaction temperature, residence time, and composition of feedstock were investigated in detail. What is more, the by-products of carbon black were characterized and their electrochemical properties were tested.

2. Experimental

2.1. Feedstock

The LCO that were obtained from Yanshan petrochemical refinery SINOPEC were used in this research as the main feedstock. Meanwhile, a hydrated LCO from Shijiazhuang refining branch SINOPEC (HLCO) and a heavy cycle oil (HCO) from Yangzhou branch SINOPEC were chosen as comparative feedstocks. The basic composition and main properties of these three oil samples are shown in Table 1. As can be seen from Table 1 that Yanshan LCO has a carbon content of 89.07% and a hydrogen content of 9.17%, and the content of aromatics is 82.6%. Moreover, single and double cyclic aromatic hydrocarbons are mainly aromatics, with a mass fraction of 28.1% and 54.4%, respectively.

2.2. Experimental Apparatus and Procedure

2.2.1. High Temperature Cracking Reaction Performance

The high temperature cracking reaction was implemented with one self-made electromagnetic induction heating device, as shown in Figure 1. This apparatus is comprised of a feed injection system, a reactor, and a product recovery system. A high frequency electromagnetic induction was used to supply high temperature for the reaction which could offer a temperature as high as 2000 °C. The electromagnetic induction heating principle is mainly in the heated metal material around a set of induction coils, when the coils flows through a frequency current, they will produce the same frequency of alternating magnetic flux and induction potential in the material, thus produce an induction current, generate heat, and heat the material. This technology has the advantages of fast heating speed and controllable temperature and is increasingly applied in the study of high temperature reactions.
1—Nitrogen; 2—feedstock; 3—feeding pump; 4—moisture mete; 5—High frequency induction heating power; 6—cooling system; 7—K type thermocouple; 8—Ice bath; 9—Gas-solid separator; 10—reactor; 11—Induction coil
According to the literature [29,30,31], when the temperature rises above 1500 K, the Gibbs function of acetylene becomes the lowest among the low-molecular-weight hydrocarbons. That is to say, when the reaction system is heated up to an extremely high temperature rapidly, acetylene is the most stable species among the hydrocarbons in the gas phase and will be the main gas component in principle. Therefore, the reaction temperature and residence time are the key factors in determining the yield of acetylene. Different from traditional reactors, a self-made electromagnetic induction heating device provides an extremely high temperature and short residue time which matches the requirements of acetylene generation. In the test, the investigation range of reaction temperatures is from 750 to 1800 °C, and the carrier gas flow of nitrogen is from 0.3 to 8 L/min to reach an optimum residence time. The different reaction temperature and nitrogen flow result in different residence times. When the temperature is from 750 to 950 °C and the nitrogen flow is 0.3 L/min, the residence time is about 600 ms. The reaction temperature is from 1100 to 1400 °C and the nitrogen flow is 4 L/min, the residence time is 50 ms. When we continue to increase the reaction temperature from 1500 to 1800 °C and nitrogen flow to 8 L/min, the residence time of 10 ms could be obtained. During the experiment, the residence time is defined as the time that the reaction material passes through the reactor. It is dependent on the reactor length divided by the average line speed.

2.2.2. Products Analysis and Characterization

An Agilent 7890 gas chromatograph was used to analyze the gas products and the volume percentage of H2, N2, and C1 to C6 hydrocarbons were determined. The concentrations of gaseous hydrocarbons such as CH4, C2H2, C2H4, C2H6, and so on, are analyzed by GC-Hydrogen flame ionization detector (FID) with a capillary column (HP-plot Al2O3, Alient Crop). H2, CO, and CO2 are determined by a GC-thermal conductivity detector (TCD) with a packed column.
The mean particle size, the aggregate structure, and voids morphology of carbon blacks that were obtained from LCO high temperature cracking are analyzed by scanning electron microscopy (SEM, Hitachi 8020, 5.5 kV) and transmission electron microscopy (TEM, Tecnai G2 F20).

2.2.3. Electrochemical Measurement

Typically, 89 wt% LFP, 7 wt% polyvinylidene fluoride, and 4 wt% conductive additives were mixed in N-methyl-2- pyrrolidinone to obtain a slurry. The slurry was coated on an aluminum foil, followed by drying at 100 °C for 12 h to remove the solvent. The dried foil was cut into electrode disk. For the fabrication of the half-cell, the lithium metal foil was used as reference/counter electrodes in half cells, and 1 M LiPF6 dissolved in a mixture of ethylene carbonate and dimethyl carbonate was used as electrolyte. The electrode behaviors of as-obtained electrode samples were tested on a charge/discharge tester (Neware, Ratnagiri, India).

3. Results and Discussion

3.1. Effect of Temperature

Figure 2 illustrates the effect of temperature on the yields of the main gaseous products. As can be seen from Figure 2, the yield of the main products of Yanshan LCO changes with the reaction temperature in the range of 750 to 1800 °C. In the low temperature section, the yields of hydrogen and acetylene increase with the increasing reaction temperature. Among them, the yield of hydrogen increases significantly, while the yield of acetylene changes little with the temperature changes and remains at a low level. When the temperature continued to rise, the yield of acetylene continued to increase gradually from 2.27% to 4.18%, which was significantly higher than that in the low temperature section. The hydrogen yield first increased and then decreased with the increasing temperature, from 4.01% to 7.54%. When the temperature was higher than 1300 °C, the hydrogen yield decreased with the increase of temperature, from 7.54% to 6.58%. In the high temperature section, the acetylene yield continued to increase, which was significantly higher than that in the low temperature section and medium temperature section, from 6.24% to 7.90%; at the same time, with the increase of the reaction temperature, the yield of hydrogen decreased from 6.34% to 4.61%. Thermodynamic research show that the reaction temperature is the main driving force for the formation of acetylene, and the Gibbs energy of acetylene decreases with the increase of temperature. When the temperature is higher than 1200 °C, acetylene becomes a stable hydrocarbon [30]. Therefore, in the low temperature section which is far from the optimal equilibrium temperature for the formation of acetylene, the yield of acetylene has been maintained at a low level. In the medium reaction temperature and high reaction temperature, the yield of acetylene increases with the raising of the reaction temperature. The reaction will be carried out in the direction to produce acetylene, and the yield of acetylene increases and the yield of hydrogen decreases.

3.2. Effect of Residence Time

The residence time is an important factor affecting the distribution of high temperature cleavage products. Klass [31] found in the lysis of high temperature (from 800 to 1400 °C) that the distribution and composition of cleavage products were affected by the residence time. A different distribution of products is obtained from different combinations of reaction temperatures and residence times. The final product of hydrocarbon cracking is carbon and hydrogen. It can shorten the residence time of the product in the high temperature area and improve the yield of the target product by regulating the carrying gas flow.
Figure 3a depicts the performance of Yanshan LCO at a reaction temperature of 1300 °C and a residence time ranging from 24 to 48 ms. As can be seen from Figure 3a, at the reaction temperature of 1300 °C, the acetylene yield increases rapidly from 3.36% to 5.05% at a residence time from 48 ms to 24 ms, respectively; the hydrogen yield decreases from 7.54% to 6.51%. Figure 3b depicts the cleavage performance of the LCO at residence times from 8 to 12 ms and a reaction temperature of 1800 °C. As can be seen from Figure 3b, with an increasing reaction temperature and shorter residence time, the acetylene yield still increases rapidly from 5.54% at 12 ms to 7.90% at 8 ms; the hydrogen yield continues to decrease from 6.59% to 4.35%.
The acetylene Gibbs free energy decreases with increasing temperature, when the temperature is above 1500 K, the Gibbs free energy of acetylene starts to be lower than the other hydrocarbons, when the temperature is about 3000 K, the equilibrium concentration of acetylene in the product will reach the maximum [32,33]. The reaction to generate acetylene is a millisecond reaction. Theoretically, the final product is carbon and hydrogen if the reaction time is enough long. Therefore, emergency cooling is implemented to terminate the further cracking of acetylene to improve the yield of acetylene. Hydrogen is the by-product of LCO cracking, and the yield of hydrogen reduces when the residence time reduces as it promotes the balance towards acetylene generation and the inhibition of hydrogen production.

3.3. Effect of Feedstock’s Composition

In order to study the influence of raw material composition on LCO high temperature cracking, Yanshan LCO (YSLCO), Shijiazhuang hydrogenation LCO (SJZHLCO), Yangzhou HCO (YZHCO) with different properties and compositions were studied under the same reaction conditions (reaction temperature of 1400 °C, residence time of 22 ms, feed rate of 0.3 g/min). The results are shown in Figure 4. As can be seen from Figure 4, the hydrogen yield of SJZHLCO was the highest among the three raw materials, with 7.12%. The acetylene yield of YZHCO was highest at 12.70%.
The composition of the raw materials in Table 1 showed that the C and H compositions of YSLCO, SJZHLCO, and YZHCO are different. The oxygen content of three raw materials is very low. The literature shows that the higher oxygen content will affect the production of acetylene [32]. Therefore, the influence of the oxygen content in the raw material is not considered for this study. It can be shown that the raw material with high hydrogen content favors the production of acetylene. Further comparison of the hydrocarbon composition of the three raw materials showed that YZHCO contained a higher content of chain alkanes which was beneficial to producing acetylene. Therefore, from the perspective of acetylene production, it may be possible to saturate the raw materials via hydrogen high temperature cracking reaction or hydrogenation-high temperature cracking reaction, so as to improve the acetylene yield.

3.4. Proposed Mechanism of LCO High Temperature Pyrolysis

According to composition analysis of LCO, toluene, naphthalene, and tetrahydronaphthalene were selected as model compounds to study the cracking performance of LCO during high temperature cracking reactions. The cracking behavior at different reaction temperatures was presented in Table 2.
It can be seen from Table 2 that the product distribution of several model compounds varied remarkably at different reaction temperatures. At the reaction temperature of 800 °C, neither toluene nor naphthalene undergo any lysis reactions, just a very small amount of methane and benzene were produced. Meanwhile, the reaction of tetrahydronaphthalene was obvious, methane, hydrogen, and ethylene were detected in the products. It shows that both toluene and naphthalene were difficult to crack at 800 °C, and just a small amount of toluene or naphthalene was cracked to form methane and benzene. This is due to the stable structure of the benzene ring and the temperature of 800 °C is not high enough to cause the open-ring cleavage reaction. In contrast, tetrahydronaphthalene is easier to crack due to its saturated ring. Thus, the yield of methane, ethylene, and hydrogen in product is higher. When the reaction temperature increases to 1100 °C, the yield of lysis products of the three model compounds increased, especially the yield of methane, hydrogen, and benzene during the use of toluene and naphthalene as feedstocks. At this temperature, toluene underwent a more intense demethylation reaction and dehydrogenation reaction, increasing the methane and benzene yields. It is still difficult to open naphthalene at this temperature, and the dehydrogenation reaction may be primary. As the reaction temperature continued increased to 1400 °C, more acetylene and hydrogen appeared and some methane and a small amount of ethylene were generated when using toluene and naphthalene as a feedstock, indicating that the open ring cracking reaction of the benzene occurred. A lower acetylene and higher hydrogen content of naphthalene than those of toluene seems to indicate that naphthalene is more difficult to crack than toluene. As for tetralin, the yield of acetylene and hydrogen gas was the highest compared with the other two model compounds. Therefore, it can be seen that tetrahydronaphthalene has the best lysis performance.
Therefore, the high temperature cracking process of LCO can be summarized in Figure 5. It involves chain alkane, single cyclic aromatics, polycyclic aromatics, and tetrahydronaphthalene aromatics cracking. The chemical reactions of LCO high temperature cracking mainly involve the cracking of C-H, C-C, C=H, and C=C bonds. The intensities of these bonds influence the product distribution. The main products of this process are CH4, C2H4, C2H2, H2, and carbon black. The specific target product content could be obtained through optimized reaction conditions.

3.5. Characterization of the by-Product Carbon Black

Carbon black is a special kind of porous carbon with a well-developed pore channel structure. The SEM images of carbon blacks that were obtained from LCO pyrolysis are shown in Figure 6.
As shown in Figure 6, carbon black particles are agglomerated or chain clustered together with a spherical appearance and smooth surface. Different reaction temperatures result in different aggregation forms. Carbon black particles that formed at 1200 °C have a relatively larger size, with a not uniform and dispersed composition, and the chains are not developed. When the reaction temperature is 1400 °C, the particles are smaller and less uniform, forming a branched chain structure. Compared to the particles that were obtained at 1400 °C, the carbon black particles that were generated at 1800 °C are much smaller and more homogeneous. They are almost spherical, mainly clustered together in a chain shape, with a more developed spatial structure and larger surface area. The above SEM analysis results show that the increasing reaction temperature helps to reduce the particle size of carbon black particles and improve the spatial structure development degree. The higher reaction temperature accelerates the rupture of bonds and gasification reaction. The generated carbon black particles have no time to reunite into large particles under a shorter residence time. Therefore, a smaller particle size and lower gathered concentration of chain carbon black products are formed.
The transmission electron microscopy (TEM, Tecnai G2 F20) test of carbon black was conducted using the field emission transmission electron microscope that was manufactured by FEI Company. Figure 7 shows the TEM images of carbon black that were obtained from different temperatures. It could be found that carbon black are almost spherical solid ball particles. Some spherical particles are connected head by head into chain aggregates, and some overlapped together to form aggregates. Comparing the TEM images of different temperatures, it could be seen that the carbon black particles have different aggregation forms due to their reaction conditions, although their particle size is generally less than 100 nm. The carbon black that is generated at 1200 °C is a poor structure. The particle size is large and uneven with a particle size between 50 and 100 nm, most of the particles gather together, and the chain is not developed. In fact, the particle size and chain development degree of carbon black particles are important factors affecting the performance of carbon black. At 1400 °C, the particle are about 50 nm and are more uniform and almost ellipsoid. At 1800 °C, the carbon black particles had a smaller particle size, from about 20 nm to 40 nm. The structural characteristics are similar to the carbon black particles that were generated by 1400 °C, but with more linear chains, less end to end overlap, and a larger specific surface. It can be seen that the reaction temperature will directly affect the structure of carbon black. Improving the reaction temperature is conducive to the cracking of small-size carbon black particles and improving the development degree of the spatial structure of carbon black particles, so as to improve the reinforcing performance of carbon black.

3.6. Electrochemical Tests of the by-Product Carbon Black

In recent years, carbon black is usually employed as the conductive additive for electrochemical energy-storage devices, such as lithium-ion batteries [34,35], super capacitor [36], and lithium sulfur battery [37], due to the extremely high conductivity, excellent chemical stability, and strong mechanical strength. The as-prepared high temperature carbon black (HCB) is employed as the conductive additive for LiFePO4 (LFP) cathode. For comparison, the commercial carbon black (CB) is used as the counterpart. Therefore, the corresponding electrode samples are labeled as LFP/HCB and LFP/CB. Their rate capabilities are shown in Figure 8a.
As shown in Figure 8a, the LFP/HCB electrode can deliver reversible capacities of 155 and 148 mAh/g at 0.5 and 2 C, respectively. Besides, the LFP/HCB electrode affords higher capacities than that of LFP/CB under all the applied current densities (0.5 to 2 C), demonstrating the better electrical conductivity behavior of HCB. In charge and discharge profiles, the voltage platform of LFP/HCB electrode still retains at around 3.4 V (Figure 8b), even when the current density increases from 0.5 to 2 C. Therefore, the HCB that was obtain from research could be utilized as potential conductive carbon black.

4. Conclusions

The high temperature cracking performance of LCO was investigated with the self-made electromagnetic induction heating device. The extraordinary high temperature and short residence time are beneficial to the generation of acetylene during LCO cracking. When the reaction temperature is 1800 °C, the residence time is 8.24 ms, and the acetylene yield reaches 7.90%. The hydrogen yield increases with the increasing reaction temperature, the highest hydrogen yield that was obtained reaches 7.54% at reaction temperature of 1300 °C and a residence time of 48 ms. Meanwhile, the cracking properties of different raw materials indicate that the properties and composition of the raw material will affect the distribution of the products. YZHCO with a high content of chain alkanes, cycloalkanes, and tetrahydronaphthalene are more likely to crack to acetylene. The analysis of the cracking mechanism during LCO high temperature cracking by model compounds illustrates the specific target product could be obtained through optimized reaction conditions and feedstock for an ideal reaction path. The characterization of carbon black expounds that the obtained carbon black products have good electrochemical properties and can be further utilized as conductive agents for lithium batteries.

Author Contributions

Conceptualization, J.G. and Z.L.; methodology, Q.Y.; validation., J.T. and X.Z.; formal analysis, X.Z.; data curation, S.H.; writing—original draft preparation, Z.L.; writing—review and editing, Z.L. and X.Z.; supervision, J.G. and Q.Y.; project administration, J.G. and Z.L.; funding acquisition, J.G. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Informed consent was obtained from all subjects involved in the study.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Acknowledgments

The financial support from Sinopec Research Institute of Petroleum Processing, China (118004-1 and ST22004) is greatly acknowledged.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Vasiliki, D.; Stella, B.; Dimitrios, K. LCO upgrading via distillation and hydroprocessing technology. Energy Fuels 2019, 33, 1023–1028. [Google Scholar]
  2. Jin, N.; Wang, G.; Yao, L.B.; Hu, M.; Gao, J.S. Synergistic process for FCC light cycle oil efficient conversion to produce high-octane number gasoline. Ind. Eng. Chem. Res. 2016, 55, 5108–5115. [Google Scholar] [CrossRef]
  3. Georgina, C.L.; Vega Merino, P.M.; Hernández, P.S. Light cycle oil upgrading to high quality fuels and petrochemicals: A review. Ind. Eng. Chem. Res. 2018, 57, 7315–7321. [Google Scholar]
  4. Holmen, A. Direct conversion of methane to fuels and chemicals. Catal. Today. 2009, 142, 2–8. [Google Scholar] [CrossRef]
  5. Schobert, H. Production of acetylene and acetylene-based chemicals from coal. Chem. Rev. 2014, 114, 1743–1760. [Google Scholar] [CrossRef]
  6. Su, B.G.; Fang, J.W.; Wen, G.D.; Ma, J.; Xing, H.B.; Ren, Q.L. Development and process of pyrolysis of light alkanes to acetylene by thermal plasma. Chem. React. Eng. Technol. 2013, 29, 230–237. [Google Scholar]
  7. Chen, J.Q.; Cheng, Y.; Xiong, X.Y.; Wu, C.N.; Jin, Y. Research progress of coal pyrolysis to acetylene in thermal plasma reactor. Chem. Ind. Eng. 2009, 28, 361–367. [Google Scholar]
  8. Cheng, Y.; Li, T.Y.; Jin, Y. State-of-the-art development of research and applications of chemical conversion processes at ultra-high temperature in thermal plasma reactors. Chem. Ind. Eng. Prog. 2016, 35, 1676–1686. [Google Scholar]
  9. Cheng, Y.; Yan, B.H.; Li, T.Y.; Li, X.; Guo, C.Y. Experimental study on coal tar pyrolysis in thermal plasma. Plasma. Chem. Plasma. Process. 2015, 35, 401–413. [Google Scholar] [CrossRef]
  10. Wu, C.N.; Chen, J.Q.; Cheng, Y. Thermodynamic analysis of coal pyrolysis to acetylene in hydrogen plasma reactor. Fuel Process. Technol. 2010, 91, 823–830. [Google Scholar] [CrossRef]
  11. Tian, Y.L. The study of methane pyrolysis to acetylene in arc plasma. In Key Laboratory of Coal Science and Technology; Taiyuan University of Technology: Taiyuan, China, 2007. [Google Scholar]
  12. Heinz, G. How Hüels makes acetylene by DC arc. HydroCarb. Process. Pet. Refin. 1962, 41, 159–164. [Google Scholar]
  13. Haworth, J.W.; Grant, W.J. Acetylene Form Hydrocarbons. In Introduction to Petroleum Chemicals; Pergamon Press: Oxford, UK, 1961. [Google Scholar]
  14. Leutner, H.W. Producing acetylene in a plasma jet. Ind. Eng. Chem. 1961, 53, 341–342. [Google Scholar] [CrossRef]
  15. Anderson, J.E.; Case, L.K. Pyrolysis of methane in DC arc plasma. Ind. Eng. Chem. Process. Des. Dev. 1962, 54, 161–167. [Google Scholar] [CrossRef]
  16. Holmes, J.M. Evaluation of DuPont Arc Process for Acetylene and Vinyl Chloride Monomer Production; ORNL-TM-2725; Oak Ridge National Laboratory: Oak Ridge, TN, USA, 1969. [Google Scholar]
  17. Gehrmann, K.; Schmidt, H. Pyrolysis of Hydrocarbons Using a Hydrogen Plasma. In Proceedings of the 8th World Petroleum Congress, Moscow, Russia, 13 June 1971. [Google Scholar]
  18. Vursel, F.; Polak, L. Plasma chemical processing. In Reactions under Plasma Conditions; Venugopalan, M., Ed.; Wiley: New York, NY, USA, 1971. [Google Scholar]
  19. Plotczyk, W.W. Effect of Quenching Temperature of the Reaction on the Synthesis of Acetylene in Hydrogen Plasma Jet. In Proceedings of the Sixth International Symposium on Plasma Chemistry, Montreal, QC, Canada, 24–28 July1983; pp. 300–305. [Google Scholar]
  20. Plotczyk, W.W. Thermodynamic Models of Acetylene Synthesis in an Argon Plasma Jet. In Proceedings of the Seventh International Symposium on Plasma Chemistry, Eindhoven, The Netherlands, 1–5 July 1985; pp. 280–285. [Google Scholar]
  21. Show, D.K. Varner to make carbon black. Eur Rubber J. 1994, 9, 30–31. [Google Scholar]
  22. Zhang, X.F.; Zeng, D.Q. The plasma method for acetylene production from natural gas. Nat. Gas. Chem. Ind. 1998, 23, 39–43. [Google Scholar]
  23. Tao, X.M.; Dai, W.; Chen, Q.; Yin, Y.X.; Dai, X.Y. Laboratory test for conversion of natural gas to acetylene plasma jet. Nat. Gas. Ind. 2006, 26, 131–134. [Google Scholar]
  24. Lucia, O.; Maussion, P.; Dede, E.J. Induction heating technology and its applications: Past developments, current technology, and future challenges. IEEE Trans. Ind. Electron. 2014, 61, 2509–2520. [Google Scholar] [CrossRef]
  25. Hedayatanasab, Z.; Abnisa, F.; Daud, W.M.A.W. Review on magnetic nanoparticles for magnetic nanofluid hyperthermia application. Mater. Des. 2017, 123, 174–196. [Google Scholar] [CrossRef]
  26. Leclercq, J.; Giraud, F.; Bianchi, D. Novel inductively heated catalytic system for fast VOCs abatement, application to IPA in air. Appl. Catal. B-Environ. 2014, 146, 131–137. [Google Scholar] [CrossRef]
  27. Ceylan, S.; Friese, C.; Lammel, C. Inductive heating for organic synthesis by using functionalized magnetic nanoparticles inside microreactors. Angew. Chem. Int. Ed. Engl. 2008, 47, 8950–8953. [Google Scholar] [CrossRef]
  28. Ahmad, Z. Investigating the performance of carbon black/Tin selenide composite as the counter electrode in dye sensitized solar cells. J. Electron. Mater. 2021, 50, 1544–1551. [Google Scholar]
  29. Butala, S.J.M.; Medina, J.C.; Taylor, T.Q. Mechanisms and kinetics of reactions leading to natural gas formation during coal maturation. Energy Fuels 2000, 14, 235–259. [Google Scholar] [CrossRef]
  30. Plooster, M.N.; Reed, T.B. Carbon-hydrogen-acetylene equilibriumat high temperatures. Chem. Phys. 1959, 31, 66–72. [Google Scholar]
  31. Klass, D.L. High Temperature Pyrolysis of Biomass. In Energy from Biomass & Wastes XV; Mracel Dekker Institute of Gas Technology: New York, NY, USA, 1991; pp. 877–894. [Google Scholar]
  32. Li, T.Y.; Rehmet, C.; Cheng, Y.; Jin, Y.; Cheng, Y. Experimental comparison of methane pyrolysis in thermal plasma. Plasma Chem. Plasma Process. 2017, 37, 1033–1049. [Google Scholar] [CrossRef]
  33. Yu, H.; Yin, Y.X.; Dai, X.Y. Numerical simulation of methane conversion to acetylene in plasmajet reactor. J. Chem. Ind. Eng. 2006, 57, 2319–2326. [Google Scholar]
  34. Mo, R.; Rooney, D.; Sun, K.; Yang, H.Y. 3D nitrogen-doped grapheme foam with encapsulated germanium/nitrogen-doped grapheme yolk-shell nano-architecture for high-performance flexible Li-ion battery. Nat. Commun. 2017, 8, 13949. [Google Scholar] [CrossRef]
  35. Li, Z.; Xu, Z.; Tan, X.; Wang, H.; Holt, C.M.B.; Stephenson, T.; Olsen, B.C.; Mitlin, D. Mesoporous nitrogen-rich carbons derived from protein for ultra-high capacity battery anodes and supercapacitors. Energy Environ. Sci. 2013, 6, 871–878. [Google Scholar] [CrossRef]
  36. Zhou, J.; Lian, J.; Hou, L.; Zhang, J.; Gou, H.; Xia, M.; Zhao, Y.; Strobel, T.A.; Tao, L.; Gao, F. Ultrahigh volumetric capacitance and cyclic stability of fluorine and nitrogen co-doped carbon microspheres. Nat. Commun. 2015, 6, 8503. [Google Scholar] [CrossRef]
  37. Zhang, T.; Zhang, F.; Zhang, L.; Lu, Y.; Zhang, Y.; Yang, X.; Ma, Y.; Huang, Y. High energy density Li-ion capacitor assembled with all graphene-based electrodes. Carbon 2015, 92, 106–118. [Google Scholar] [CrossRef]
Processes 10 01732 g001 550
Figure 1. Schematic of electromagnetic induction high frequency high temperature cracking device.
Figure 1. Schematic of electromagnetic induction high frequency high temperature cracking device.
Processes 10 01732 g001
Processes 10 01732 g002 550
Figure 2. Influence of temperature on the yields of H2 and C2H2.
Figure 2. Influence of temperature on the yields of H2 and C2H2.
Processes 10 01732 g002
Processes 10 01732 g003 550
Figure 3. Influence of residence time on the yields of H2 and C2H2. (a) residence time 24~48 ms. (b) residence time 8~12 ms.
Figure 3. Influence of residence time on the yields of H2 and C2H2. (a) residence time 24~48 ms. (b) residence time 8~12 ms.
Processes 10 01732 g003
Processes 10 01732 g004 550
Figure 4. The main product yields of three feedstocks.
Figure 4. The main product yields of three feedstocks.
Processes 10 01732 g004
Processes 10 01732 g005 550
Figure 5. Reactions during LCO high temperature cracking.
Figure 5. Reactions during LCO high temperature cracking.
Processes 10 01732 g005
Processes 10 01732 g006 550
Figure 6. SEM images of carbon black.
Figure 6. SEM images of carbon black.
Processes 10 01732 g006
Processes 10 01732 g007 550
Figure 7. TEM images of carbon black.
Figure 7. TEM images of carbon black.
Processes 10 01732 g007
Processes 10 01732 g008 550
Figure 8. The electrochemical tests of carbon black. (a) Cycling stability. (b) Galvanostatic charge/discharge curves.
Figure 8. The electrochemical tests of carbon black. (a) Cycling stability. (b) Galvanostatic charge/discharge curves.
Processes 10 01732 g008
Table
Table 1. Properties of the experimental feedstocks.
Table 1. Properties of the experimental feedstocks.
FeedstocksYanshan LCOShijiazhuang HLCOYangzhou HCOMethods
ρ20, (kg·m−3)948.6888.7894.7ISO12185
w(C), %89.0789.0887.09ASTM D5291-0656
w(H), %9.1710.9211.85ASTM D5291-0656
w(S), %0.54109 (1)0.34ASTM D5453-0689
w(N), %0.0360.90 (1)0.27ASTM D4629
Composition of hydrocarbons, w%ASTM D2425
Chain alkane hydrocarbons13.312.553.5
Cycloalkanes4.119.68.3
Aromatics82.667.938.2
Monocyclic aromatics28.156.43.4
Indane/tetrahydronaphthalene10.135.41.8
Bicyclic aromatics54.410.58.0
Tricyclic aromatic hydrocarbons0.11.026.8
(1) unit of mg·L−1.
Table
Table 2. The main gas product distribution of the model compounds at different temperatures.
Table 2. The main gas product distribution of the model compounds at different temperatures.
Temperature/°CMain Gas ProductsTolueneNaphthaleneTetrahydronaphthalene
Quality Yields/%
800CH40.030.054.15
H20.000.002.09
C2H40.000.033.48
C2H20.000.000.03
C2H60.200.180.16
1100CH42.711.456.84
H21.502.195.20
C2H40.180.096.66
C2H20.050.041.70
C2H63.894.343.87
1400CH42.440.591.59
H25.445.977.86
C2H40.270.192.84
C2H25.704.625.91
C2H62.513.031.11
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Li, Z.; Yuan, Q.; Tang, J.; Zhang, X.; Huang, S.; Gong, J. Study on High Temperature Pyrolysis Light Cycle Oil to Acetylene and Carbon Black. Processes 2022, 10, 1732. https://doi.org/10.3390/pr10091732

AMA Style

Li Z, Yuan Q, Tang J, Zhang X, Huang S, Gong J. Study on High Temperature Pyrolysis Light Cycle Oil to Acetylene and Carbon Black. Processes. 2022; 10(9):1732. https://doi.org/10.3390/pr10091732

Chicago/Turabian Style

Li, Zekun, Qimin Yuan, Jinlian Tang, Xiaoqiao Zhang, Shaobin Huang, and Jianhong Gong. 2022. "Study on High Temperature Pyrolysis Light Cycle Oil to Acetylene and Carbon Black" Processes 10, no. 9: 1732. https://doi.org/10.3390/pr10091732

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop