WO2013077727A1 - Method of producing graphene, carbon nano-dendrites, nano-hexacones and nanostructured materials using waste tyres - Google Patents

Method of producing graphene, carbon nano-dendrites, nano-hexacones and nanostructured materials using waste tyres Download PDF

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Publication number
WO2013077727A1
WO2013077727A1 PCT/MY2012/000286 MY2012000286W WO2013077727A1 WO 2013077727 A1 WO2013077727 A1 WO 2013077727A1 MY 2012000286 W MY2012000286 W MY 2012000286W WO 2013077727 A1 WO2013077727 A1 WO 2013077727A1
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Prior art keywords
particulates
tyres
producing carbon
carbon nanomaterials
nano
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PCT/MY2012/000286
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French (fr)
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WO2013077727A4 (en
Inventor
Ehab Salim Ahmed MAHAL
Shaimaa Sultan Aboo AL-MUTLAQ
Rosiyah YAHYA
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Universiti Malaya
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Priority to LU92256A priority Critical patent/LU92256B1/en
Publication of WO2013077727A1 publication Critical patent/WO2013077727A1/en
Publication of WO2013077727A4 publication Critical patent/WO2013077727A4/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor

Definitions

  • This invention relates to a method of producing carbon nanomaterials using rubber tyres.
  • the carbon nanomaterials comprise graphene, carbon nanodendrites, nanohexacones and other carbon nanostructures which have considerable range of potential uses such as in nanotechnology.
  • Nanotechnology advancement provides greater potentials for improving performance and extended capabilities of products in various industrial sectors including electronics, optics, catalysts, and sorbents.
  • US Patent No. 7,604,791 disclosed a recycling method system for waste and a method of producing carbon materials such as inert carbon, carbon nanotubes, and activated carbon by utilizing such waste.
  • the carbon nanotubes and activated carbon can be produced in a large amount by the activation treatment of the obtained inert carbon by continuous production with high-temperature gas or the like.
  • waste such as scrap tires, rubber, vinyl, plastic, and other petroleum- and resin- based high molecular compounds are adopted in the cited invention for the conversion of waste into carbon materials, said compounds have to be treated by the complex recycling method prior to the carbon material production which render the process cumbersome, as well as time and cost consuming.
  • US Patent Application No. 1 1/395,100 disclosed a process for generating adsorbent nanoporous material which involves heating a carbonaceous source in a controlled atmosphere until an exothermic reaction is achieved, to generate the hydrocarbon gases and a substantially solid porous char mass.
  • the hydrocarbon gases can be re-circulated into the controlled atmosphere with a mixture of steam and air to substantially increase the temperature therein.
  • nanoscaled size pores may be imparted to the porous char mass, and with continued exposure to the increased temperature, the porous char may be converted into adsorbent nanoporous material.
  • the drawback of the cited invention is the generated hydrocarbon has to be directed out of the reactor and is temporarily stored before being re-directed back into the reactor, which is bulky and causes difficulty during the process of generating the adsorbent nanoporous material.
  • the present invention relates to a method of producing carbon nanomaterials using tyres, characterized by the steps of: thermal decomposition of the tyre to produce coal; grinding the coal to obtain particulates; mixing the particulates with transition metal-based catalyst; and heating the particulates to produce carbon nanomaterials; wherein said carbon nanomaterials comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles, and nanorods, or combination thereof.
  • the present invention also relates to a method of producing carbon nanomaterials using tyres, characterized by the steps of: mixing tyre pieces with transition metal-based catalyst; and heating the mixture for 30-90 minutes at 800-1200°C to obtain graphene and carbon nanoparticles.
  • Fig.1 is a diagram illustrates a process flow of a method of producing carbon nanomaterials using tyres, according to the present invention
  • Fig.2 shows Field Emission Scanning Electron Microscopy (FESEM) image of fused carbon nanospheres according to the embodiment described in Example 1 ;
  • Fig.3 shows FESEM image of the carbon nanorods according to the embodiment described in Example 1 ;
  • Fig. 4 shows Transmission Electron Microscopy (TEM) image of the fused carbon nanospheres according to the embodiment described in Example 1 ;
  • Fig.5 shows TEM image of the carbon nanorods according to the embodiment described in Example 1 ;
  • Fig.6 shows Raman spectroscopy of the result according to the embodiment described in Example 1 ;
  • Fig.7 shows FESEM image of the carbon nano-hexacones according to the embodiment described in Example 2;
  • Fig.8 shows FESEM magnified image of the carbon nano-hexacones according to the embodiment described in Example 2;
  • Fig. 9 shows TEM image of the carbon nano-hexacones according to the embodiment described in Example 2.
  • Fig.10 shows magnified TEM image of the carbon nano-hexacones according to the embodiment described in Example 2;
  • Fig.1 1 shows Raman spectroscopy of the carbon nano-hexacones according to the embodiment described in Example 2;
  • Fig.12 shows FESEM image of the graphene layers according to the embodiment described in Example 3.
  • Fig.13 shows FESEM image of the carbon nano-donuts according to the embodiment described in Example 3;
  • Fig.14 shows magnified FESEM image of the carbon nano-donuts according to the embodiment described in Example 3;
  • Fig.15 shows TEM image of the carbon nano-donuts according to the embodiment described in Example 3.
  • Fig.16 shows TEM image of the graphene according to the embodiment described in Example 3.
  • Fig.17 shows TEM image of the graphene according to the embodiment described in Example 3.
  • Fig.18 shows TEM image of the nano-donuts according to the embodiment described in Example 3.
  • Fig.19 shows Raman spectroscopy of the result according to the embodiment described in Example 3.
  • Fig.20 shows FESEM image of the carbon nano-hexacones according to the embodiment described in Example 4.
  • Fig.21 shows FESEM magnified image of the carbon nano-hexacones according to the embodiment described in Example 4;
  • Fig.22 shows FESEM magnified image of the carbon nano-hexacones according to the embodiment described in Example 4;
  • Fig.23 shows FESEM image of the carbon nanoparticles according to the embodiment described in Example 4.
  • Fig.24 shows TEM image of the carbon nanoparticles according to the embodiment described in Example 4.
  • Fig.25 shows TEM image of the carbon nano-hexacones according to the embodiment described in Example 4.
  • Fig.26 shows TEM image of the carbon nano-hexacones according to the embodiment described in Example 4.
  • Fig.28 shows FESEM image of the graphene and carbon nanoparticles according to the embodiment described in Example 5;
  • Fig.29 shows FESEM image of the graphene according to the embodiment described in Example 5;
  • Fig.30 shows FESEM image of the carbon nanoparticles and graphene according to the embodiment described in Example 5;
  • Fig.31 shows TEM image of the graphene layers according to the embodiment described in Example 5;
  • Fig.32 shows TEM image of the carbon nanoparticles according to the embodiment described in Example 5;
  • Fig.33 shows TEM image of the graphene and carbon nanoparticles according to the embodiment described in Example 5;
  • Fig.34 shows TEM image of the carbon nanoparticles and graphene according to the embodiment described in Example 5;
  • Fig.35 shows Raman spectroscopy of the result according to the embodiment described in Example 5;
  • Fig.36 shows FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
  • Fig.37 shows magnified FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
  • Fig.38 shows magnified FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
  • Fig.39 shows magnified FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
  • Fig.40 shows TEM image of the result according to the embodiment described in Example 6;
  • Fig.41 shows TEM image of the result according to the embodiment described in Example 6;
  • Fig.42 shows Raman spectroscopy of the result according to the embodiment described in Example 6;
  • Fig.43 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
  • Fig.44 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
  • Fig.45 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
  • Fig.46 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
  • Fig.47 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
  • Fig.48 shows FESEM image of the graphene according to the embodiment described in Example 7.
  • Fig.49 shows FESEM magnified image of the graphene according to the embodiment described in Example 7.
  • Fig.50 shows TEM image of the result according to the embodiment described in Example 7.
  • Fig.51 shows TEM image of the result according to the embodiment described in Example 7.
  • Fig.52 shows TEM image of the result according to the embodiment described in Example 7.
  • Fig.53 shows TEM image of the result according to the embodiment described in Example 7.
  • Fig.54 shows TEM image of the result according to the embodiment described in Example 7.
  • Fig.55 shows TEM image of the result according to the embodiment described in Example 7.
  • Fig.56 shows TEM image of the result according to the embodiment described in Example 7.
  • Fig.57 shows Raman spectroscopy of the result according to the embodiment described in Example 7; Detailed Description of the Invention
  • the present invention relates to a method of producing carbon nanomaterials using carbonaceous materials. More particularly, the present invention relates to a method of producing carbon nanomaterials using tyres, preferably waste rubber tyres, to promote the green environment by converting waste material into valuable material.
  • tyres preferably waste rubber tyres
  • the carbon nanomaterials comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles, and nanorods, or combination thereof.
  • the tyre is shredded and cut into pieces to the size of 1 -4cm 2 prior to thermal decomposition.
  • the step of thermal decomposition of the tyre is carried out for 2-4 hours at 400-800°C.
  • the method further comprises pre-treating the tyre by immersing said tyre in 30% (w/w) solution of zinc chloride, refluxing for 24 hours, and subsequently drying before thermal decomposition.
  • the particulates are mixed with the transition metal-based catalyst in a ratio of 2-5: 1 by weight of the particulates to the transition metal-based catalyst.
  • the transition metal-based catalyst is selected from a group consisting of chromium compound and iron compounds.
  • the chromium compound is mixed with the particulates in a ratio of 1 :2 by weight of the chromium compound to the particulates.
  • the chromium compound is chromium nitrate.
  • the particulates mixed with chromium compound are heated for 1 -3 hours at 400-800°C.
  • the iron compound is mixed with the particulates in a ratio of 1 :4-5 by weight of the iron compound to the particulates.
  • the iron compound is selected from ferrocene and ferric chloride.
  • the particulates mixed with ferrocene are heated for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C.
  • the particulates mixed with ferric chloride are heated for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the particulates mixed with ferric chloride are heated for 30-90 minutes at 500-700°C, followed by 1 -3 hours at 700-900°C.
  • the particulates mixed with ferric chloride are heated for 30-90 minutes at 800- 200°C.
  • the present invention also relates to a method of producing carbon nanomaterials using tyres without any pre-treatment, characterized by the steps of:
  • the transition metal-based catalyst is ferric chloride.
  • the ferric chloride is mixed with the tyre pieces in a ratio of 1 :5 by weight.
  • Fig. l is a diagram shows a process flow of the method of producing carbon nanomaterials using tyres in accordance to the present invention.
  • the tyre can be any kind of tyre, such as tyre made of natural rubber, synthetic rubber and et cetera.
  • the tyre is shredded and cut into pieces prior to thermal decomposition.
  • the shredded size of the tyre can be various, preferably to the size of 1 -4cm 2 , to ease the thermal decomposition of the tyres.
  • the tyre Prior to the thermal decomposition step, the tyre may be pre-treated by immersing the tyre in 30% (w/w) solution of zinc chloride, refluxing for preferably 24 hours, following by drying the tyre for removing the remaining zinc chloride.
  • the tyre is then loaded into a first thermal unit for thermal decomposition of the tyre at 400-800°C for 2-4 hours to generate coal. Then, the coal obtained from the thermal decomposition was ground to produce particulates.
  • the particulates are mixed with the transition metal-based catalyst selected from chromium compound or iron compounds, in the ratio of 2-5: 1 by weight of the particulates to the transition metal-based catalyst.
  • the particulates may be sieved prior to mixing the particulates with the transition metal-based catalyst.
  • the particulates may be transferred to a second thermal unit for heating at a certain temperature on a certain period of time according to the different preferred embodiments of the present invention to produce the carbon nanomaterials which comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles and nanorods, or combination thereof. Still referring to Fig.
  • the second method of producing carbon nanomaterials using tyres as mentioned above does not involve the step of thermal decomposition of the shredded tyre and the grinding step comparing to the first method.
  • the similar end product including graphene and nanoparticles are still producible by using the second method of the present invention.
  • the transition metal-based catalyst is chosen as the catalyst due to the transition metal ions can change their oxidation states which therefore, become more effective as catalysts.
  • the waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm 2 . Then, the shredded tyre was loaded into a primary thermal unit (PTU) for thermal decomposition started from ambient temperature and maintained at 400-800°C for 2 hours to produce coal. The coal produced from the PTU was ground and sieved to obtain fine particulates. Then, the fine particulates were mixed with chromium nitrate as catalyst in a 2: 1 ratio by weight of the fine particulates to the chromium nitrate and loaded into a secondary thermal unit (STU). Thereafter, the run was started from ambient and maintained for 3 hours at 400-800°C for thermal cracking process.
  • PTU primary thermal unit
  • the waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm 2 . Then, the shredded tyre was loaded into PTU for thermal decomposition started from ambient temperature and maintained at 400-800°C for 2 hours to generate coal. The coal generated from the PTU was ground to obtain fine particulates. The sieving step was skipped in this embodiment. The fine particulates were then mixed with ferrocene as catalyst in a 4: 1 ratio by weight of the fine particulates to ferrocene and loaded into STU. Thereafter, the run was started from ambient temperature and maintained for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C. 75% of yield was obtained. The product was characterised using FESEM, TE and Raman Spectroscopy, which are showed in Figs. 7 - 1 1 . Nano-hexacones are produced in the preferred embodiment.
  • the waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm 2 . Then, the shredded tyre was loaded into PTU for thermal decomposition started from ambient temperature and maintained at 400-800°C for 2 hours to produce coal. The coal produced from the PTU was ground to obtain fine particulates. The sieving step was skipped in this embodiment. The fine particulates were then mixed with ferric chloride as catalyst in a 4: 1 ratio by weight of the fine particulates to ferric chloride and loaded into STU. Thereafter, the run was started from ambient temperature and maintained for 1 -3 hours at 500-700°C followed by 30-90 minutes at 700-900°C.
  • Waste tyre was shredded and immersed in a 30% (w/w) solution of zinc chloride and refluxed for 24 hours. Thereafter, the treated tyre was washed, dried and loaded into PTU for thermal decomposition. The thermal decomposition was started from ambient and maintained at 400-800°C for 2 hours to produce coal. Thereafter, the coal was ground to obtain fine particulates. The fine particulates were mixed in a 4: 1 ratio by weight of the fine particulates to ferric chloride. The run was started from ambient and maintained for 30-90 minutes at 500-700°C, followed by 1 -3 hours at 700-900°C respectively.
  • Waste tyres were used in this embodiment without any pre-treatments.
  • Shredded waste tyre was taken and mixed directly in a 5: 1 ratio by weight of the shredded tyre to ferric chloride, followed by loading into STU.
  • the run was started from ambient and maintained in the range of 800-1200°C for 30-90 minutes. 33% of yield was obtained.
  • the product was characterised using FESEM, TEM and Raman spectroscopy, which are showed in Figs. 28-35. Graphene and carbon nanoparticles were produced in the preferred embodiment.
  • the waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm 2 .
  • the shredded tyre was loaded into PTU for thermal decomposition. The thermal decomposition was started from ambient and maintained at 400-800°C for 3 hours to produce coal. Thereafter, the produced coal was ground to obtain fine particulates. After grinding, the fine particulates were mixed in 4: 1 ratio by weight of the fine particulates to ferric chloride and loaded into STU. The run was started from the ambient and maintained in the range of 800-1200°C for 30-90 minutes.
  • the waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1-4cm 2 .
  • the shredded tyre was loaded into PTU for thermal decomposition. The thermal decomposition was started from ambient and maintained at 400-800°C for 3 hours to produce coal. Thereafter, the produced coal was ground to obtain fine particulates. After grinding, thefine particulates were mixed in a 4: 1 ratio by weight of the fine particulates to ferrocene. The run was started from ambient and maintained for 1 -3 hours at 500-700°C and 30-90 minutes at 700-900°C respectively.

Abstract

The present invention relates to a method of producing carbon nanomaterials using tyres, characterized by the steps of: thermal decomposition of the tyre to produce coal; grinding the coal to obtain particulates; mixing the particulates with transition metal–based catalyst; and heating the particulates to produce carbon nanomaterials; wherein said carbon nanomaterials comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles and nanorods, or combination thereof.

Description

METHOD OF PRODUCING GRAPHENE, CARBON NANO-DENDRITES, NANO-HEXACONES AND NANOSTRUCTURED MATERIALS USING WASTE
TYRES Background of the Invention Field of the Invention
This invention relates to a method of producing carbon nanomaterials using rubber tyres. The carbon nanomaterials comprise graphene, carbon nanodendrites, nanohexacones and other carbon nanostructures which have considerable range of potential uses such as in nanotechnology.
Description of Related Arts
Interest in the preparation and characterization of nanostructured materials has grown in recent years due to their distinctive properties and potential technological applications. Nanotechnology advancement provides greater potentials for improving performance and extended capabilities of products in various industrial sectors including electronics, optics, catalysts, and sorbents.
Currently, there is a numbers of method, such as chemical vapour deposition (CVD), arc discharge, laser ablation, thermal evaporation, electrochemistry, wet-chemistry, micro-emulsion, microwave-assisted synthesis and et cetera, have been developed to fabricate ' various nanomaterials. So far, a variety of nano-scaled functional inorganic, organic or inorganic-organic composite materials with different morphologies, such as nanowires, nanorods, nanotubes, nanospheres, nanobelts, nanosheets, nanowhiskers, nano-dendrites, nanocombs, and nanofeathers, have been prepared. However, it is still a challenge for chemists and material scientists to discover convenient, economical, less energy-consuming and environmentally friendly routes to fabricate nanocrystals with different morphologies by manipulation of reaction conditions. One of the major challenges on fabricating nanomaterials is to develop clear, inexpensive, safe and sustainable power resources. Alternative energy system is crucial in order to deal with the environmental threat of global warming and the exhaustion of fossil fuels. A number of energy conversion and storage technologies, such as fuel cells, has attracted interest of researchers in carbon nanostructured materials. These materials have a considerable range of potential uses, for example, in nano-electronics, fuel cells, hydrogen accumulators, reinforcing and membrane materials, thermal insulators, carriers for heterogeneous, electro-catalysts, lubricant additives, solar cells and lithium ion batteries whereby they can be developed to assistin reducing carbon emissions.
US Patent No. 7,604,791 disclosed a recycling method system for waste and a method of producing carbon materials such as inert carbon, carbon nanotubes, and activated carbon by utilizing such waste. The carbon nanotubes and activated carbon can be produced in a large amount by the activation treatment of the obtained inert carbon by continuous production with high-temperature gas or the like. Although waste such as scrap tires, rubber, vinyl, plastic, and other petroleum- and resin- based high molecular compounds are adopted in the cited invention for the conversion of waste into carbon materials, said compounds have to be treated by the complex recycling method prior to the carbon material production which render the process cumbersome, as well as time and cost consuming.
US Patent Application No. 1 1/395,100 disclosed a process for generating adsorbent nanoporous material which involves heating a carbonaceous source in a controlled atmosphere until an exothermic reaction is achieved, to generate the hydrocarbon gases and a substantially solid porous char mass. The hydrocarbon gases can be re-circulated into the controlled atmosphere with a mixture of steam and air to substantially increase the temperature therein. In the presence of increased temperature, nanoscaled size pores may be imparted to the porous char mass, and with continued exposure to the increased temperature, the porous char may be converted into adsorbent nanoporous material. The drawback of the cited invention is the generated hydrocarbon has to be directed out of the reactor and is temporarily stored before being re-directed back into the reactor, which is bulky and causes difficulty during the process of generating the adsorbent nanoporous material.
Accordingly, it can be seen in the prior arts that there exists a need to provide a simpler method of producing carbon nanomaterials using waste materials which has lower production cost yet utilising the environmental wasteto overcome the above-described problems in producing carbon nanomaterials as well as on the effort of reducing environmental waste by converting waste into valuable materials.
Summary of Invention
It is an objective of the present invention to providea method of producing carbon nanomaterials using low cost resources which is waste tyres.
It is also an objective of the present invention to provide a simple and cost effectivemethod for conversion of waste tyres into carbon nanomaterials by thermal process.
It is yet another objective of the present invention to provide a method of producing carbon nanomaterials including carbon nano-dendrites, nanohexacones, nanospheres, nanoparticles, nanorods, nano-donuts, as well as graphene using waste tyres.
Accordingly, these objectives may be achieved by following the teachings of the present invention. The present invention relates to a method of producing carbon nanomaterials using tyres, characterized by the steps of: thermal decomposition of the tyre to produce coal; grinding the coal to obtain particulates; mixing the particulates with transition metal-based catalyst; and heating the particulates to produce carbon nanomaterials; wherein said carbon nanomaterials comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles, and nanorods, or combination thereof.
The present invention also relates to a method of producing carbon nanomaterials using tyres, characterized by the steps of: mixing tyre pieces with transition metal-based catalyst; and heating the mixture for 30-90 minutes at 800-1200°C to obtain graphene and carbon nanoparticles.
Brief Description of the Drawings
The features of the invention will be more readily understood and appreciated from the following detailed description when read in conjunction with the accompanying drawings of the preferred embodiment of the present invention, in which:
Fig.1 is a diagram illustrates a process flow of a method of producing carbon nanomaterials using tyres, according to the present invention;
Fig.2 shows Field Emission Scanning Electron Microscopy (FESEM) image of fused carbon nanospheres according to the embodiment described in Example 1 ;
Fig.3 shows FESEM image of the carbon nanorods according to the embodiment described in Example 1 ;
Fig. 4 shows Transmission Electron Microscopy (TEM) image of the fused carbon nanospheres according to the embodiment described in Example 1 ;
Fig.5 shows TEM image of the carbon nanorods according to the embodiment described in Example 1 ;
Fig.6 shows Raman spectroscopy of the result according to the embodiment described in Example 1 ;
Fig.7 shows FESEM image of the carbon nano-hexacones according to the embodiment described in Example 2;
Fig.8 shows FESEM magnified image of the carbon nano-hexacones according to the embodiment described in Example 2;
Fig. 9 shows TEM image of the carbon nano-hexacones according to the embodiment described in Example 2;
Fig.10 shows magnified TEM image of the carbon nano-hexacones according to the embodiment described in Example 2;
Fig.1 1 shows Raman spectroscopy of the carbon nano-hexacones according to the embodiment described in Example 2;
Fig.12 shows FESEM image of the graphene layers according to the embodiment described in Example 3;
Fig.13 shows FESEM image of the carbon nano-donuts according to the embodiment described in Example 3;
Fig.14 shows magnified FESEM image of the carbon nano-donuts according to the embodiment described in Example 3;
Fig.15 shows TEM image of the carbon nano-donuts according to the embodiment described in Example 3;
Fig.16 shows TEM image of the graphene according to the embodiment described in Example 3;
Fig.17 shows TEM image of the graphene according to the embodiment described in Example 3;
Fig.18 shows TEM image of the nano-donuts according to the embodiment described in Example 3;
Fig.19 shows Raman spectroscopy of the result according to the embodiment described in Example 3;
Fig.20 shows FESEM image of the carbon nano-hexacones according to the embodiment described in Example 4;
Fig.21 shows FESEM magnified image of the carbon nano-hexacones according to the embodiment described in Example 4;
Fig.22 shows FESEM magnified image of the carbon nano-hexacones according to the embodiment described in Example 4;
Fig.23 shows FESEM image of the carbon nanoparticles according to the embodiment described in Example 4;
Fig.24 shows TEM image of the carbon nanoparticles according to the embodiment described in Example 4;
Fig.25 shows TEM image of the carbon nano-hexacones according to the embodiment described in Example 4;
Fig.26 shows TEM image of the carbon nano-hexacones according to the embodiment described in Example 4;
Fig.27 Raman spectroscopy of the result according to the embodiment described in Example 4;
Fig.28 shows FESEM image of the graphene and carbon nanoparticles according to the embodiment described in Example 5;
Fig.29 shows FESEM image of the graphene according to the embodiment described in Example 5;
Fig.30 shows FESEM image of the carbon nanoparticles and graphene according to the embodiment described in Example 5;
Fig.31 shows TEM image of the graphene layers according to the embodiment described in Example 5;
Fig.32 shows TEM image of the carbon nanoparticles according to the embodiment described in Example 5;
Fig.33 shows TEM image of the graphene and carbon nanoparticles according to the embodiment described in Example 5;
Fig.34 shows TEM image of the carbon nanoparticles and graphene according to the embodiment described in Example 5;
Fig.35 shows Raman spectroscopy of the result according to the embodiment described in Example 5;
Fig.36 shows FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
Fig.37 shows magnified FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
Fig.38 shows magnified FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
Fig.39 shows magnified FESEM image of the fused nanospheres and nanoparticles according to the embodiment described in Example 6;
Fig.40 shows TEM image of the result according to the embodiment described in Example 6;
Fig.41 shows TEM image of the result according to the embodiment described in Example 6;
Fig.42 shows Raman spectroscopy of the result according to the embodiment described in Example 6;
Fig.43 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
Fig.44 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
Fig.45 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
Fig.46 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
Fig.47 shows FESEM image of the carbon nano-dendrites according to the embodiment described in Example 7;
Fig.48 shows FESEM image of the graphene according to the embodiment described in Example 7;
Fig.49 shows FESEM magnified image of the graphene according to the embodiment described in Example 7;
Fig.50 shows TEM image of the result according to the embodiment described in Example 7;
Fig.51 shows TEM image of the result according to the embodiment described in Example 7;
Fig.52 shows TEM image of the result according to the embodiment described in Example 7;
Fig.53 shows TEM image of the result according to the embodiment described in Example 7;
Fig.54 shows TEM image of the result according to the embodiment described in Example 7;
Fig.55 shows TEM image of the result according to the embodiment described in Example 7;
Fig.56 shows TEM image of the result according to the embodiment described in Example 7; and
Fig.57 shows Raman spectroscopy of the result according to the embodiment described in Example 7; Detailed Description of the Invention
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting but merely as a basis for claims. It should be understood that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the invention is to cover all modification, equivalents and alternatives falling within the scope of the present invention as defined by the appended claims. As used throughout this application, the word "may" is used in a permissive sense (i.e., meaning having the potential to), rather than the mandatory sense (i.e., meaning must). Similarly, the words "include," "including," and "includes" mean including, but not limited to. Further, the words "a" or "an" mean "at least one" and the word "plurality" means one or more, unless otherwise mentioned. Where the abbreviations of technical terms are used, these indicate the commonly accepted meanings as known in the technical field. For ease of reference, common reference numerals will be used throughout the figures when referring to the same or similar features common to the figures. The present invention will now be described with reference to Figs. 1 -57.
The present invention relates to a method of producing carbon nanomaterials using carbonaceous materials. More particularly, the present invention relates to a method of producing carbon nanomaterials using tyres, preferably waste rubber tyres, to promote the green environment by converting waste material into valuable material.
Said method of producing carbon nanomaterials using tyres is characterized by the steps of:
thermal decomposition of the tyre to produce coal;
grinding the coal to obtain particulates;
mixing the particulates with transition metal-based catalyst; and
heating the particulates to produce carbon nanomaterials; wherein the carbon nanomaterials comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles, and nanorods, or combination thereof. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the tyre is shredded and cut into pieces to the size of 1 -4cm2 prior to thermal decomposition.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the step of thermal decomposition of the tyre is carried out for 2-4 hours at 400-800°C.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the method further comprises pre-treating the tyre by immersing said tyre in 30% (w/w) solution of zinc chloride, refluxing for 24 hours, and subsequently drying before thermal decomposition.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the particulates are mixed with the transition metal-based catalyst in a ratio of 2-5: 1 by weight of the particulates to the transition metal-based catalyst.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the transition metal-based catalyst is selected from a group consisting of chromium compound and iron compounds.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the chromium compound is mixed with the particulates in a ratio of 1 :2 by weight of the chromium compound to the particulates. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the chromium compound is chromium nitrate. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the particulates mixed with chromium compound are heated for 1 -3 hours at 400-800°C. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the iron compound is mixed with the particulates in a ratio of 1 :4-5 by weight of the iron compound to the particulates.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the iron compound is selected from ferrocene and ferric chloride.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the particulates mixed with ferrocene are heated for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the particulates mixed with ferric chloride are heated for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the particulates mixed with ferric chloride are heated for 30-90 minutes at 500-700°C, followed by 1 -3 hours at 700-900°C.
In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the particulates mixed with ferric chloride are heated for 30-90 minutes at 800- 200°C.
The present invention also relates to a method of producing carbon nanomaterials using tyres without any pre-treatment, characterized by the steps of:
mixing tyres pieces with transition metal-based catalyst; and
heating the mixture for 30-90 minutes at 800-1200°C to obtain graphene and carbon nanoparticles. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the transition metal-based catalyst is ferric chloride. In a preferred embodiment of the method of producing carbon nanomaterials using tyres, the ferric chloride is mixed with the tyre pieces in a ratio of 1 :5 by weight.
Depicted in Fig. l is a diagram shows a process flow of the method of producing carbon nanomaterials using tyres in accordance to the present invention. The tyre can be any kind of tyre, such as tyre made of natural rubber, synthetic rubber and et cetera. The tyre is shredded and cut into pieces prior to thermal decomposition. The shredded size of the tyre can be various, preferably to the size of 1 -4cm2, to ease the thermal decomposition of the tyres. Prior to the thermal decomposition step, the tyre may be pre-treated by immersing the tyre in 30% (w/w) solution of zinc chloride, refluxing for preferably 24 hours, following by drying the tyre for removing the remaining zinc chloride. The tyre is then loaded into a first thermal unit for thermal decomposition of the tyre at 400-800°C for 2-4 hours to generate coal. Then, the coal obtained from the thermal decomposition was ground to produce particulates.
Thereafter, the particulates are mixed with the transition metal-based catalyst selected from chromium compound or iron compounds, in the ratio of 2-5: 1 by weight of the particulates to the transition metal-based catalyst. Optionally, the particulates may be sieved prior to mixing the particulates with the transition metal-based catalyst. Subsequently, the particulates may be transferred to a second thermal unit for heating at a certain temperature on a certain period of time according to the different preferred embodiments of the present invention to produce the carbon nanomaterials which comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles and nanorods, or combination thereof. Still referring to Fig. 1 , the second method of producing carbon nanomaterials using tyres as mentioned above does not involve the step of thermal decomposition of the shredded tyre and the grinding step comparing to the first method. However, the similar end product including graphene and nanoparticles are still producible by using the second method of the present invention.
In the preferred embodiment, the transition metal-based catalyst is chosen as the catalyst due to the transition metal ions can change their oxidation states which therefore, become more effective as catalysts.
Below are examples of the method of producing carbon nanomaterials using waste tyres in respect to multiple preferred embodiments of the present invention from which the advantages of the present invention may be more readily understood. It is to be understood that the following examples are for illustrative purpose only and should not be construed to limit the present invention in any way.
Example 1
The waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm2. Then, the shredded tyre was loaded into a primary thermal unit (PTU) for thermal decomposition started from ambient temperature and maintained at 400-800°C for 2 hours to produce coal. The coal produced from the PTU was ground and sieved to obtain fine particulates. Then, the fine particulates were mixed with chromium nitrate as catalyst in a 2: 1 ratio by weight of the fine particulates to the chromium nitrate and loaded into a secondary thermal unit (STU). Thereafter, the run was started from ambient and maintained for 3 hours at 400-800°C for thermal cracking process.
25% of yield was obtained. The product was characterised using Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM) and Raman Spectroscopy, which are showed in Figs. 2-6. Fused carbon nanospheres and carbon nanorods were produced in the preferred embodiment. Example 2
The waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm2. Then, the shredded tyre was loaded into PTU for thermal decomposition started from ambient temperature and maintained at 400-800°C for 2 hours to generate coal. The coal generated from the PTU was ground to obtain fine particulates. The sieving step was skipped in this embodiment. The fine particulates were then mixed with ferrocene as catalyst in a 4: 1 ratio by weight of the fine particulates to ferrocene and loaded into STU. Thereafter, the run was started from ambient temperature and maintained for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C. 75% of yield was obtained. The product was characterised using FESEM, TE and Raman Spectroscopy, which are showed in Figs. 7 - 1 1 . Nano-hexacones are produced in the preferred embodiment.
Example 3
The waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm2. Then, the shredded tyre was loaded into PTU for thermal decomposition started from ambient temperature and maintained at 400-800°C for 2 hours to produce coal. The coal produced from the PTU was ground to obtain fine particulates. The sieving step was skipped in this embodiment. The fine particulates were then mixed with ferric chloride as catalyst in a 4: 1 ratio by weight of the fine particulates to ferric chloride and loaded into STU. Thereafter, the run was started from ambient temperature and maintained for 1 -3 hours at 500-700°C followed by 30-90 minutes at 700-900°C.
85% of yield was obtained. The product was characterised using FESEM, TEM and Raman Spectroscopy, which are showed in Figs. 12 - 19. Graphene, carbon nano-donuts and carbon nanorods were produced in the preferred embodiment. Example 4
Pre-treatment of the waste tyres was performed to examine the effect on the resulted products. Waste tyre was shredded and immersed in a 30% (w/w) solution of zinc chloride and refluxed for 24 hours. Thereafter, the treated tyre was washed, dried and loaded into PTU for thermal decomposition. The thermal decomposition was started from ambient and maintained at 400-800°C for 2 hours to produce coal. Thereafter, the coal was ground to obtain fine particulates. The fine particulates were mixed in a 4: 1 ratio by weight of the fine particulates to ferric chloride. The run was started from ambient and maintained for 30-90 minutes at 500-700°C, followed by 1 -3 hours at 700-900°C respectively.
79% of yield was obtained. The product was characterised using FESEM, TEM and Raman spectroscopy, which are showed in Figs. 20 - 27. Carbon nano-hexacones and fused carbon nanoparticles were produced in the preferred embodiment.
Example 5
Waste tyres were used in this embodiment without any pre-treatments. Shredded waste tyre was taken and mixed directly in a 5: 1 ratio by weight of the shredded tyre to ferric chloride, followed by loading into STU. The run was started from ambient and maintained in the range of 800-1200°C for 30-90 minutes. 33% of yield was obtained. The product was characterised using FESEM, TEM and Raman spectroscopy, which are showed in Figs. 28-35. Graphene and carbon nanoparticles were produced in the preferred embodiment.
Example 6
The waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1 -4cm2. The shredded tyre was loaded into PTU for thermal decomposition. The thermal decomposition was started from ambient and maintained at 400-800°C for 3 hours to produce coal. Thereafter, the produced coal was ground to obtain fine particulates. After grinding, the fine particulates were mixed in 4: 1 ratio by weight of the fine particulates to ferric chloride and loaded into STU. The run was started from the ambient and maintained in the range of 800-1200°C for 30-90 minutes.
69% of yield was obtained. The product was characterised using FESEM, TEM and Raman spectroscopy, which are showed in Figs. 36-42. Free and fused carbon nanospheres, and nanoparticles were produced in the preferred embodiment.
Example 7
The waste tyre sidewall was shredded into pieces using commercial electrical handsaw. The shredded pieces were further cut into smaller pieces to the size of 1-4cm2. The shredded tyre was loaded into PTU for thermal decomposition. The thermal decomposition was started from ambient and maintained at 400-800°C for 3 hours to produce coal. Thereafter, the produced coal was ground to obtain fine particulates. After grinding, thefine particulates were mixed in a 4: 1 ratio by weight of the fine particulates to ferrocene. The run was started from ambient and maintained for 1 -3 hours at 500-700°C and 30-90 minutes at 700-900°C respectively.
70% of yield was obtained. The product was characterised using FESEM, TEM and Raman spectroscopy, which are showed in Figs. 43-57. Carbon nano-dendrites and graphene were produced in the preferred embodiment.
Although the present invention has been described with reference to specific embodiments, also shown in the appended figures, it will be apparent for those skilled in the art that many variations and modifications can be done within the scope of the invention as described in the specification and defined in the following claims.

Claims

Claims
I/We claim:
A method of producing carbon nanomaterials using tyres, characterized by the steps of:
thermal decomposition of the tyre to produce coal;
grinding the coal to obtain particulates;
mixing the fine particulates with transition metal-based catalyst; and heating the fine particulates to produce carbon nanomaterials; wherein the carbon nanomaterials comprises graphene, carbon nanostructures including nano-dendrites, nano-hexacones, nanospheres, nano-donuts, nanoparticles and nanorods, or combination thereof.
A method of producing carbon nanomaterials using tyres according to claim 1 , wherein the tyres are waste tyres.
A method of producing carbon nanomaterials using tyres according to claim 1 , wherein the tyres is shredded and cut into pieces to the size of 1-4cm2 prior to thermal decomposition.
A method of producing carbon nanomaterials using tyres according to claim 1 , wherein the step of thermal decomposition of the tyre is carried out for 2-4 hours at 400-800°C.
A method of producing carbon nanomaterials using tyres according to claim 1 , wherein the method further comprises pre-treating the tyre by immersing said tyre in 30% (w/w) solution of zinc chloride, refluxing for 24 hours, and subsequently drying before thermal decomposition. 6. A method of producing carbon nanomaterials using tyres according to claim 1 , wherein the fine particulates are mixed with the transition metal-based catalyst in a ratio of 2-5:1 by weight of the particulates to the transition metal-based catalyst.
A method of producing carbon nanomateriais using tyres according to claim 1 , wherein the transition metal-based catalyst is selected from a group consisting of chromium compound and iron compound.
A method of producing carbon nanomateriais using tyres according to claim 7, wherein the chromium compound is mixed with the particulates in a ratio of 1 :2 by weight of the chromium compound to the particulates.
A method of producing carbon nanomateriais using tyres according to claim 7, wherein the chromium compound is chromium nitrate.
A method of producing carbon nanomateriais using tyres according to claim 1 and claim 8, wherein the particulates mixed with chromium compound are heated for 1 -3 hours at 400-800°C.
A method of producing carbon nanomateriais using tyres according to claim 7, wherein the iron compound is mixed with the particulates in a ratio of 1 :4-5 by weight of the iron compound to the particulates.
A method of producing carbon nanomateriais using tyres according to claim 7, wherein the iron compound is selected from ferrocene and ferric chloride.
A method of producing carbon nanomateriais using tyres according to claim 1 , claim 1 1 and claim 12, wherein the particulates mixed with ferrocene are heated for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C.
A method of producing carbon nanomateriais using tyres according to claim 1 , claim 1 1 and claim 2, wherein the particulates mixed with ferric chloride are heated for 1 -3 hours at 500-700°C, followed by 30-90 minutes at 700-900°C.
A method of producing carbon nanomaterials using tyres according to claim 1 , claim 1 1 and claim 12, wherein the particulates mixed with ferric chloride are heated for 30-90 minutes at 500-700°C, followed by 1 -3 hours at 700-900°C.
A method of producing carbon nanomaterials using tyres according to claim 1 , claim 1 1 and claim 12, wherein the particulates mixed with ferric chloride are heated for 30-90 minutes at 800-1200°C.
A method of producing carbon nanomaterials using tyres without any pre-treatment, characterized by the steps of:
mixing waste tyre pieces with transition metal-based catalyst; and heating the mixture for 30-90 minutes at 800-1200°C to obtain graphene and carbon nanoparticles.
A method of producing carbon nanomaterials using tyres according to claim 17, wherein the transition metal-based catalyst is ferric chloride.
A method of producing carbon nanomaterials using tyres according to claim17 and claim 18, wherein the ferric chloride is mixed with the tyre pieces in a ratio of 1 :5 by weight.
PCT/MY2012/000286 2011-11-24 2012-11-23 Method of producing graphene, carbon nano-dendrites, nano-hexacones and nanostructured materials using waste tyres WO2013077727A1 (en)

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