Processing Methods, Characteristics and Adsorption Behavior of Tires Derived Carbons: A Review Tawfik A. Saleh, V.K. Gupta PII: DOI: Reference:

S0001-8686(14)00201-2 doi: 10.1016/j.cis.2014.06.006 CIS 1453

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Advances in Colloid and Interface Science

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20 April 2014 4 June 2014 11 June 2014

Please cite this article as: Saleh Tawfik A., Gupta VK, Processing Methods, Characteristics and Adsorption Behavior of Tires Derived Carbons: A Review, Advances in Colloid and Interface Science (2014), doi: 10.1016/j.cis.2014.06.006

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ACCEPTED MANUSCRIPT Processing Methods, Characteristics and Adsorption Behavior of Tires Derived Carbons: A Review

Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

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Tawfik A. Saleh1 , V. K. Gupta2*

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Chemistry Department, Indian Institute of Technology Roorkee, Rooree-247667, India

*Corresponding Author; Email; [email protected]: Phone:+911332285801

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Abstract

The remarkable increase in the number of vehicles worldwide; and the lack of both

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technical and economical mechanisms of disposal make waste tires to be a serious source of pollution. One potential recycling process is pyrolysis followed by chemical activation

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process to produce porous activated carbons. Many researchers have recently proved the capability of such carbons as adsorbents to remove various types of pollutants including

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organic and inorganic species. This review attempts to compile relevant knowledge about the production methods of carbon from waste rubber tires. The effects of various process parameters including temperature and heating rate, on the pyrolysis stage; activation

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temperature and time, activation agent and activating gas are reviewed. This review

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highlights the use of waste-tires derived carbon to remove various types of pollutants like

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heavy metals, dye, pesticides and others from aqueous media.

Keywords: Porous activated carbons; waste rubber tires, sorption, pyrolysis

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Introduction ............................................................................................................................. 4 Waste tires generation problem ..................................................................................... 4

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Wastewaters Problem ..................................................................................................... 5

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Adsorbents for wastewater treatment ........................................................................... 5

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Contents

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Outlines

Preparation of carbon adsorbents from waste tires .................................................................. 6

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Characteristics ....................................................................................................................... 11

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Tires derived carbon for the adsorption of organic pollutants ............................................... 13

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Tires derived carbon for the adsorption of toxic metals ........................................................ 16

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Conclusions ........................................................................................................................... 17

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References ............................................................................................................................. 18

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ACCEPTED MANUSCRIPT 1. Introduction

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Since polymeric materials do not decompose easily, disposal of large amounts of waste rubber tires is a serious environmental problem. The disposal of waste rubber tires leading to environmental pollution, which is considered one of various problems humanity faces. Besides others, one approach to solve this problem is the recycle and the reuse of waste rubber tires. On the other hand, industrial developments have left their impression on the environmental society. Many industries produce wastewaters containing various types of pollutants. Therefore, saving fresh water to save the universe and to make the future of humankind safe is what we need now. A doubly effective solution for such environmental pollutions is to convert waste rubber tires into carbonaceous materials as adsorbents. From one side it represents a cleaning way to dispose the waste tires and in other side, an economic source of producing adsorbents.

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This paper review the global efforts and discussion toward the cost-effective utilization of waste rubber tires (hard-to dispose waste) as a precursor to produce activated carbons (pollution-cleaning adsorbent) for wastewater treatment. The review highlights the methods developed for the preparation of carbon from waste tires and their activation. It discusses the process for adsorption activities.

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1.1.Waste tires generation problem

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Polymers are classified into thermoplastics and thermosetting materials. When heated, molded and then cooled to obtain the desired shape, thermoplastics soften. Thus, they are readily recyclable by heating the resin above its processing temperature (reversible physical change for shaping). However, thermosetting materials such as rubbers on processing and molding are cross-linked, and cannot be softened or remolding by heating again. Therefore, their recycling or reshaping is not easy because their three-dimensional network must be broken down through the cleavage of crosslinks, or through the carbon– carbon linkage of the chain backbone. The fragmented products obtained by such cleavage are entirely different from the starting thermoset or even its precursor thermoplastics materials. Rubber tire is a mixture of various elastomers like natural, butadiene, styrene and butadiene with other additives like carbon black, sulfur and zinc oxide. Around 32% by weight of the waste tire is mainly constituted of carbon black. The carbon content is as high as 70-75 wt.% [2-4] (Williams et al. 1990; Ariyadejwanich, et al., 2003; Murillo et al., 2005, 2006; Rajalingam et al., 1993; Nevatia et al., 2002; Li et al., 2005; Castells et al., 2000; Mechant et al., 1993; Murillo et al., 2006; Gupta et al., 2012b). Because of the increase in the number of vehicles, there is a rabid increase worldwide in the waste rubber tires, which are considered a serious pollution problem in terms of waste disposal since they are non-biodegradable. The problem aggravates because the waste tire disposal represents major environmental issue throughout the world, since the same 4

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properties that make them desirable as tires, most notably durability, also makes their disposal and reprocessing difficult, they are also immune to biological degradation [Lehmann, et al., 1998]. Landfilling the waste tires is an uneconomical and nonenvironmental friendly strategy of disposal since it occupies large volumes and causes the destabilization of compacted landfill sites.

1.2.Wastewater Problem

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The rapid development of industry has led to severe problems of water pollution. Wastewater is considered a problem due to its increasing toxic threat to humans and the environment. Fresh water is considered an important and essential component of the universe. It plays a vital role in the proper functioning of the Earth’s ecosystem. However, safe drinking water is not available in many parts of the world. It is imperative for wastewater treatment for the removal of pollutants to provide good quality water. Rapid industrialization, modern methods of agricultural and domestic activities have resulted in the generation of large amount of wastewater containing diverse types of hazardous pollutants (Lehr, et al., 1980; UNESCO, 2003). According to United Nations World Water Development Report, some two million tons of waste are discharged to the water bodies per day including industrial wastes

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Organic, inorganic as well as microbial pollutants have been reported to thrive in such waste waters. Among these, some organic and inorganic pollutants are not biodegradable, and persist in the environment for a long time. Such pollutants are toxic, pose a serious threat to the environment (Celik, and Demirbas, 2005) and are harmful to human and animal life. Toxic organic pollutants include dyes, pesticides, polynuclear aromatic hydrocarbons, polychlorinated biphenyls, polybrominated diphenyl ethers, plasticizers, phenols and drug residues. Toxic inorganic or metal ions include arsenic, cadmium, selenium, mercury, antimony, lead, chromium and nickel. Now-a-days, water pollution is a serious issue because it affects our lives (Franklin, 1991) and is expected to get worse over the coming decades and thus has boosted the importance of Water technology.

1.3.Adsorbents for wastewater treatment Techniques for wastewater treatment include reverse osmosis, ion exchange, electrodialysis, and electrolysis (Parekh, 1988; McNulty, 1984). However, such methods have their own limitations such as low efficiency, sensitive operating conditions and further the disposal is a costly affair. In addition, continuous increase in the variety, amount and complexity of the toxic pollutants has made the conventional wastewater treatment methods ineffective. Another powerful technology is adsorption where a solute known as adsorbant is adhered to the surface of the adsorbent by means of physical, chemical, or electrostatic forces (Samuel and Osman, 1987). Since the types and cost of the adsorbents are key factors, lower cost adsorbents for large-scale use in water treatment are fast gaining momentum. Such adsorbents are usually waste generated in 5

ACCEPTED MANUSCRIPT abundance like agricultural wastes, various municipal and industrial by products and which either as such, or after their transformation into more active products.

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Carbon materials are extensively used as adsorbents for the advanced treatment of wastewaters. They have been used for the removal of organic and inorganic pollutants from aqueous media. In our reported work we have investigated the use of different materials and nanomaterials for water treatment (Gupta et al., 2010a; Gupta et al., 2011a; Gupta et al., 2011b; Gupta et al., 2012a; Gupta et al., 2012c; Jain et al., 2011 Saleh, 2011; Saleh and Gupta, 2011; Saleh and Gupta, 2012a; Saleh and Gupta, 2012b; Saleh and Gupta, 2012c; Saleh and Gupta, 2012d; Saleh et al., 2010; Saleh et al., 2011a; Saleh et al., 2011b; Gupta and Saleh, 2013; Gondal et al., 2012; Gupta et al., 2013; Gupta and Saleh, 2013).

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However, activated carbon derived from waste rubber tires seems to be more promising to be applied for real applications. As adsorbent, activated carbon is a powerful adsorbent having a large surface area and pore volume that allows the removal of liquid phase pollutants (Merchant and Petrich, 1993). This carbonaceous adsorbent is rather similar to activated carbon and the only apparent physical difference is that carbon black has much less internal surface area (Knocke and Hemphill, 1981).

2. Preparation of carbon adsorbents from waste tires

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The major steps of producing activated carbons from waste rubber tires for water treatment are depicted in a schematic diagram in Figure 1. This section attempts to compile relevant knowledge about the production methods of carbon from waste rubber tires.

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Figure 1 Schematic diagram of the major steps of producing activated carbons from waste rubber tires for water treatment

Several methods (Table 1) have been developed for the waste rubber tire valorization, and the production of carbon from waste tires. Processes such as pyrolysis, gasification and combustion have been extensively studied for the energy recovery and for the production of materials such as activated carbon. Among these processes, pyrolysis is receiving renewed attention owing to the fact that it can be optimized to produce high value products. Experimental results showed that tire rubber started to decompose at 450 o C and this phase was essentially completed at 500–600 oC giving char yields in the range of 33–42% with very limited porosity development (San et al., 1998; Merchant and Petrich, 1992; Cunliffe and Williams, 1999). Carbon black obtained by untreated rubber tire pyrolysis may be heated in air, carbon dioxide or steam atmosphere to develop its surface area and porosity (Mechant and Petrich, 1993; Teng et al., 1995; Cunliffe, and Williams 1999; Lin, and Teng, 2002; San et al., 2003; Helleur et al, 2001; Ariyadejwanich et al., 2003; Zabaniotou et al., 2004; González et al., 2006; Suuberg et al., 2009; Suuberg et al., 2007; Betancur et al., 2009; Dodds et al., 1983) and hence to improve its adsorption behavior. Physical activation using carbon dioxide or steam, as oxidizing agents are the most commonly used processes in the production of tire carbons. The overall process usually consists of two 7

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steps: thermal pyrolysis at a relatively low temperature (typically 400–700 oC) in the presence of nitrogen or helium to break down the cross-linkage, and treatment with activating gas at 800–1000 oC for further development of the porosity of tire carbon (Edward et al., 2004; Rutland et. al., 1991; Richard et. al., 1991; Rana et. al., 2004; Nakagawa et. al., 2004; Huang et. al., 2003; Helleur et. al., 2001; Garcia et. al., 2007; Fei-Lian et. al., 2011; Min et. al., 2006)).

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Pyrolysis can be non-catalytic or catalytic process (Kar, 2011). Non-catalytic pyrolysis

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can be carried out under certain conditions such as a nitrogen flow of 100 mL/min and a heating rate of 10 oC/min, while the catalytic pyrolysis can be carried out at various

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catalyst-to-tire ratio (for example 0.05–0.25). The latter has slightly higher yield than the former. The potential catalytic support materials are the silica, copper nitrate, activated

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alumina, zeolite 4A and hydrothermal modified perlites, which were reported to improve specific surface area of pyrolytic char (Xie et al. 2004; Ates et al., 2005; Qu et al., 2006; Acosta et al., 2006). The basic catalysts such as MgO and CaCO3 over the products of the

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waste tire pyrolysis were reported to possess improvement effect on pyrolytic oil (Shah et

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al. 2008). Activated alumina catalyst has been reported to have a strong effect on pyrolysis product and conversion yield (Yorgun et al., 2008). An acidic (SiO2), basic

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(Al2O3) and the mixture of both in a 1:1 ratio were reported to effect the yield and composition of the derived oils obtained from waste tire catalytic pyrolysis (Shah et al. 2009).

Method of carbonization chemical treatment with steam activation was employed for the production of carbon from waste rubber tires. The waste rubber tires are cleaned, thoroughly washed with deionized water, and then dried in an oven at 120 oC for 4 h. This is followed by heating to approximately 800oC for 6 h, then, treatment with hydrogen peroxide solution for 24 h to oxidize adhering organic impurities. This is followed by washing the materials with deionized water and dried in vacuum oven. Activation step is conducted at 900oC for 2 h (N2 flow rate = 225 mL min-1). The sample then to be saved in desiccators. Several chemicals like nitric acid and hydrogen peroxide were used for the chemical activation (Saleh et.al., 2014; Saleh et al., 2013 Saadi et al., 2013).

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Tanthapanic hakoon et al. 2005 Ariyadejwan ich et al. 2003 San Miguel et al. 2002 Lin and Teng 2002 Helleur et al. 2001 Cunliffe and Williams 1999 Ariyadejwan ich et al. 2003

Limited air CO2 Steam + N2



910



H2SO4 24 h



1011







996





8

CO2

350

240.1

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Demineralization agent 10% HCl for 2 h

850

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Steam



755

31.4



850

3

1177

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Demineralization agent 1 M HCl 24 h

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925

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1070

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-

900



Steam



602

57



500, -

900

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Steam

485

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74.1



500, -

935

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640

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PH2O was 0.46 atm Total pore volume was 2.19 cc/g Heating rate was 5 LC/ Min Particle size of tyre rubber (mm) p-anisidine > p-chloro aniline (Gupta et al., 2012). Two types of activated carbons from tire char (with or without sulphuric acid treatment) were produced via carbon dioxide activation with BET surface areas in the range 59–1118 m2/g. The adsorption capacities were in the range of 0.45–0.71 mmol/g (untreated) and 0.62–0.84 mmol/g (acid-treated) for Acid Blue 25 (Mui et al., 2010). The composition, structure, and adsorption behavior of activated carbons derived from tire rubber activated by KOH was reported for the adsorption of methylene blue (Yang et al., 2011). The data were fitted well by Langmuir equation, indicating monolayer coverage on the carbon (Yang et al., 2011).

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ACCEPTED MANUSCRIPT 5. Tires derived carbon for the adsorption of toxic metals

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Batch adsorption system and column system are used to study the adsorption of toxic metals on the tires derived carbons. Rubber tires derived carbon was investigated for the removal of copper ions from aqueous solutions with optimization of the experimental conditions like pH ranging from 1.5 to 7.0, contact time ranging from 6 to 96 h and initial metal concentration ranging from 1 mg/L to 50 mg/L. Adsorption of Cu(II) is pHdependent with pH 6.0 as optimium value. Models like Langmuir and Freundlich were applied to describe the isotherms and isotherm constants for the removal of Cu(II) from aqueous solutions. The data was reported to well fit the Langmuir model (Calisir et al., 2009).

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Carbon adsorbent was prepared by thermal treatment of rubber tire and activated using nitric acid and hydrogen peroxide oxidizing agents. It was reported to be a potential adsorbent for the removal of lead ions from wastewaters. The carbon was reported to be effective in a 4 to 7 pH range with a highest uptake at pH 5 - 6. Density functional theory calculations were performed at the B3LYP/6-31G(d) level adopting a functionalized pyrene molecule as a model to further explanation the chemistry behind the adsorption process. The binding energy of lead ion toward carboxylic acid, carbonyl, and hydroxyl groups was calculated and reported to be in the range between 310–340 kcal/mol. It was concluded that adsorption of the lead ion toward the carbonyl groups in relatively all cases shows more stable binding compared to the sorption toward other groups. It was reported that the adsorption process is to be indicative of a chemisorptions (Saleh , et al., 2013). Carbon developed by physical activation from waste tire rubber, was used as adsorbent for assessing its removal capacity of lead and nickel ions from aqueous solutions. A welldeveloped mesoporous structure in RTAC was conducive for its enhanced batch adsorption capacity of the studied metal ions removal in comparison to a microporous commercial carbon (CAC). Uptake trend of RTAC for Pb2+ > Ni2+ revealed the adsorbate properties of electronegativity and ionic radii to play a contributory role. Effect of various operating parameters along with equilibrium, kinetic and thermodynamic studies reveal the efficacy of the RTAC for lead and nickel removal. The adsorption equilibrium data obeyed the Langmuir model and the kinetic data were well described by the pseudosecond-order model. A physical electrostatic adsorbate–adsorbent interaction is revealed from pHPZC studies and from D–R model constants. The adsorption process is believed to proceed by an initial surface adsorption followed by intraparticle diffusion (Gupta et al., 2012). Carbonaceous adsorbents were treated thermally at 400-900 oC for 2 h in N2 and at 850 o C for 2 h in steam. Concentrated NaOH, HCl, H2SO4, HNO3 and H2O2 solutions were also used for chemical treatment. Carbon was also treated with ozone at 25 oC for 1 h and 16

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with air at 250 oC for 1 and 24 h. When carbon was heat-treated, in particular in steam, developments in porosity were reported. Carbon prepared using oxidizing agents such as O3 and H2O2, associated with a lack of available or accessible surface active sites for oxidation process. Thermal and chemical treatments were reported to increase the adsorption of cadmium ions in aqueous solution. The adsorption process of cadmium ions is fast and the data fit better to a pseudo-second order kinetic equation (AlexandreFranco, et al., 2011).

6. Conclusions

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During the last two decays, many researchers reported on the production of activated carbons from waste rubber and their application for the adsorption of pollutants from wastewaters. This review highlights the methods for utilization of waste tires (hard-to dispose waste) as a precursor in the production of activated carbons (pollution-cleaning adsorbent). The review attempted to highlight the production methods and conditions of conversion and activation. It also represented the feasibility of their applications as sorbents for the removal of pollutants via adsorption process.

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The production of activated carbon as adsorbent from waste tire rubber has been studied and reported in various literatures, with differences in the porosity of the final products. The variability could be attributed mainly to differences in the pyrolysis and activation conditions employed but also to the characteristics of the rubber feed including particle size and composition

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It can be stated that the activated carbon produced from waste rubber tires are effective adsorbents for organic and inorganic removal from wastewaters. These adsorbents require a treatment process to enhance their efficacy for pollutants removal. The most important factor that affects adsorption is the surface activation, active sites and porosity. The pH of the solution is also an important factor, where a high pH value is preferred for cationic pollutants adsorption while a low pH value is preferred for anionic pollutants adsorption. The producing porous-carbon from waste rubber tires is considered a doubly effective solution for environmental pollutions; that is a cleaning way to dispose the waste tires and an economic source of carbonaceous materials. However, cost comparison between the commercial carbon and porous-carbon sorbents produced from waste rubber tires is an important need in order to evaluate their utility in adsorption process from the economic point of view. Acknowledgments T. Saleh acknowledges the support of Chemistry department, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia. V K Gupta is thankful to Department of Science and Technology (DST) Govt. of India for funding this work. 17

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Figure 1 Major steps for water treatment and recycling by adsorption using carbon produced from waste rubber tires

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Figure 2. Schematic diagram of the main steps in producing carbons from waste rubber tires

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Graphical Abstract

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ACCEPTED MANUSCRIPT Table 1 Summary of production of tire carbons activated under different conditions

Tanthapanic hakoon et al. 2005 Ariyadejwan ich et al. 2003 San Miguel et al. 2002 Lin and Teng 2002 Helleur et al. 2001 Cunliffe and Williams 1999 [20] Ariyadejwan ich et al. 2003 [35]a

Limited air CO2 Steam + N2



910



H2SO4 24 h



1011







996





8

CO2

350

240.1

78

Demineralization agent 10% HCl for 2 h

850

3

Steam



755

31.4



850

3

1177

31.4

Demineralization agent 1 M HCl 24 h

-

925

9

1070

44



-

900



Steam



602

57



500, -

900

2

Steam

485

272

74.1



500, -

935

6

Steam



640

35



7.9

PH2O was 0.46 atm Total pore volume was 2.19 cc/g Heating rate was 5 LC/ Min Particle size of tyre rubber (mm)

Processing methods, characteristics and adsorption behavior of tire derived carbons: a review.

The remarkable increase in the number of vehicles worldwide; and the lack of both technical and economical mechanisms of disposal make waste tires to ...
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