NL2029863B1 - A process for devulcanizing tyre rubber particles - Google Patents
A process for devulcanizing tyre rubber particles Download PDFInfo
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- NL2029863B1 NL2029863B1 NL2029863A NL2029863A NL2029863B1 NL 2029863 B1 NL2029863 B1 NL 2029863B1 NL 2029863 A NL2029863 A NL 2029863A NL 2029863 A NL2029863 A NL 2029863A NL 2029863 B1 NL2029863 B1 NL 2029863B1
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- rubber
- rubber tire
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- tire particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B17/0404—Disintegrating plastics, e.g. by milling to powder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/08—Depolymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B2017/0424—Specific disintegrating techniques; devices therefor
- B29B2017/0428—Jets of high pressure fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2030/00—Pneumatic or solid tyres or parts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L17/00—Compositions of reclaimed rubber
Abstract
The present invention relates to a process for devulcanizing tyre rubber particles. The present invention also relates to devulcanized tyre rubber particles having a sticky and popcorn like surface structure. An object of the present invention to provide a method for producing devulcanized rubber to be as a viable substitute to virgin rubber.
Description
Title: A process for devulcanizing tyre rubber particles
The present invention relates to a process for devulcanizing tyre rubber particles.
In a general rubber devulcanization, the process for devulcanizing involves cleaving of the monosulfidic, disulfidic and polysulfidic crosslinks (C-S or S-S bonds) existing in a vulcanized rubber. Vulcanized rubber comprises networks of hydrocarbon chains (C-C) linked together through C-S and S-S bonds and can be said to be made of a network of polymer macromolecules. A vulcanized rubber network can be thought of as many long and entangled hydrocarbon chains wherein the chains themselves are linked together by C-S and S-S bonds. Consequently, the vulcanized rubber networks contain chemical bonds of carbon to carbon (C-C), chemical bonds of carbon to sulfur (C-S) and chemical bonds of sulfur to sulfur (S-S), each having different bond energies where C-C > C-S > S-S thus providing opportunities for selective bond cleavage.
CN105150409 relates to a continuous green devulcanizing and regenerating technology for waste rubber, wherein rubber particles are fed into a screw rubber regenerator through a feeder for being subjected to screw extrusion-shearing pure mechanical action, so that sulfur-containing molecular chains are selectively broken.
The regenerated rubber enters filter equipment for filtering large particles, impurities and the like after being subjected to preliminary cooling; and finally, particle-shaped regenerated rubber is packed and stored after being waxed, cooled and dried.
US 2017/009044 relates to an apparatus for producing devulcanized rubber comprising: a devulcanization tank in which the reaction between vulcanized rubber particles and a chemical composition is carried out, at least one mass stirrer positioned in the devulcanization tank in which the mass stirrer rotates in circular motion to generate impact forces; at least one rotating shaft positioned in the devulcanization tank in which the rotating shaft has at least one axial blade and at least one radial blade to facilitate impact forces generation; and a blanket of cooling fluid enveloping the devulcanization tank to control the temperature, wherein the impact forces generated from the mass stirrer, the axial blade and the radial blade of the rotating shaft cause the vulcanized rubber particles to react with the chemical composition for producing devulcanized rubber. The chemical composition comprises of at least an accelerator, at least an inorganic activator and at least an organic activator.
US 6,387,966 relates to a method of de-vulcanizing waste rubber made of a network of polymer macromolecules from which metal has already been removed, comprising the steps of: turning the waste rubber into particles of waste rubber, simultaneously adding a modifying composition to the particles of waste rubber while the particles of waste rubber are being poured into an area between rollers of a first roll mill that crushes the particles, thereby creating modified crushed particles, pouring the modified crushed particles of waste rubber into an area between rollers of the second roll mill that crushes the modified crushed particles of waste rubber, repeating pouring the modified crushed particles of waste rubber into an area between rollers of eight further roll mills for method producing de-vulcanized rubber.
US6133413 relates to a method of manufacturing devulcanized rubber comprising rubber with sulfur crosslinks thereof severed and carbon black particles of 100 nm or less in diameter comprising the steps of pulverizing vulcanized rubber selected from the group consisting of EPDM (ethylene-propylene-diene terpolymer) rubber, natural rubber, styrene-butadiene rubber and butyl rubber containing carbon black, heating the pulverized vulcanized rubber containing carbon black, applying a shearing pressure in the pressure range of 10 to 50 kg/cm? while heating the pulverized vulcanized rubber containing carbon black, whereby sulfur crosslinking bonds in the vulcanized rubber are cut while main chains of the rubber are not cut, thereby preparing said devulcanized rubber.
An article written by Zhang X. X. et al: "Devulcanisation of natural rubber vulcanisate through solid state mechanochemical milling at ambient temperature”,
PLASTICS, RUBBER & COMPOSITES: MACROMOLECULAR ENGINEERING, volume 36, nr. 7-8, 19 October 2007 (2007-10-19), pages 370-376 relates to the devulcanisation of natural rubber vulcanisate. The experimental results indicate that gel fraction of the devulcanised natural rubber is substantially reduced, and the reduction of molecular weight of the sol part of devulcanized natural rubber is not significant.
An article written by Xu Xiaofei et al: "Batch grinding kinetics of scrap tire rubber particles in a fluidized-bed jet mill", POWDER TECHNOLOGY, ELSEVIER, BASEL (CH), volume 305, 11 October 2016 (2016-10-11), pages 389-395 relates to the study of batch grinding kinetics of scrap tire rubber articles in a fluidized -bed jet mill based on population balance modelling.
US 7 166 658 relates to a method of reducing vulcanized rubber, the method comprising the steps of heating the rubber, wherein the rubber includes synthetic rubber, in the presence of a solvent, wherein the solvent includes water to a temperature below a critical temperature of the solvent, providing a pressure that is at least equal to a saturated vapour pressure of the solvent at the temperature; and maintaining the temperature and the pressure for a time sufficient to devulcanize the rubber and produce a reaction product that is primarily a solid phase and includes rubber hydrocarbon.
CN 108 517 052 relates to a preparation method of reclaimed rubber.
The method includes steps of rubber cutting, crushing, desulfuration, secondary pulverization, hot-mixing, batch-off and packaging.
It is an object of the present invention to provide a method for producing devulcanized rubber to be as a viable substitute to virgin rubber.
It is another object of the present invention to provide a method for producing devulcanized rubber in large volume by establishing high scalability.
It is further an object of the present invention to provide a method for producing devulcanized rubber using a highly energy efficient technique at a controlled temperature and residence time range.
The present invention thus relates to a process for devulcanizing tyre rubber particles comprising the steps of: introducing tyre rubber particles to a mill; introducing a gaseous flow in the mill for generating a field of high turbulence, strong eddies and high energy impact between the tyre rubber particles which causes micronization and rupture of the tyre rubber particles due to extreme hysteresis and mechanical forces sufficient to at least partially devulcanize the tyre rubber particles; and fast dissipation of the heat generated into the gaseous flow.
The present inventors found that by such a method one or more of the objects have been achieved. In the present method the mill relies on extremely high gaseous flow throughput and velocities. The present inventors found that the heating and cooling of tyre rubber particles occur virtually instantaneously during the grinding.
Surprisingly for tyre rubber granulates this mechanism provides sufficient thermo- mechanical energy to cause devulcanization to occur within an extremely short timeframe (~1 second), thereby restricting undesirable oxidation and main chain (C-
C) scission.
Without being bound to any specific theory, the present inventors assume that the thermo-mechanical energy comes from the externally generated air flow that accelerates the tyre rubber particles to subsonic speeds. In the mill the particle to particle impacts are therefore extremely rapid and violent and much of the kinetic particle to particle impact energy is converted to particle heat by hysteresis. The effect of hysteresis in rubber particles is to transfer kinetic energy to its molecules, resulting in heating. Hysteresis occurs for every particle to particle impact.
The term tyre as used here includes all kind of tyres that are used on many types of vehicles, including cars, bicycles, motorcycles, buses, trucks, heavy equipment, and aircraft.
In the multi-chamber-like grinding zone of the mill, the gaseous flow generates a field of high turbulence and strong eddies which causes micronization and rupture of the tyre rubber particles. Within the grinding chamber, the tyre rubber particles are always kept in a free-flowing situation. The micronization and particle rupture produces enormous amounts of new particle surfaces and thermal energy, which is largely converted to heat by hysteresis. Excess heat is quickly carried away by the intense gaseous flow and turbulence resulting in only a very short exposure to heat for rubber granulate materials.
In an example tyre rubber particles having a particle size of 0.001 mm — 10 mm, preferably 2 — 8 mm, more preferably 2 — 5 mm are introduced in the mill. Such tyre rubber particles are obtained by shredding and crushing the waste rubber to make the relevant tyre rubber particles.
In an example the temperature of the tyre rubber particles in the mill increases to at least 250 DegC, preferably at least 300 DegC, and to a temperature of at most 350 DegC. If the temperature of the tyre rubber particles in the mill is below the under limit of 250 DegC, the process of devulcanizing the tyre rubber particles will not take place sufficiently. If the temperature of the tyre rubber particles is above the higher limit of 350 DegC the thermo-mechanical energy will cause undesirable scission of the hydrocarbon main chain (C-C bonds) to occur.
In an example the residence time of the tyre rubber particles in the mill is less than 2 seconds, preferably less than 1 second. A residence time of the tyre rubber particles in the mill longer than 2 seconds will result in an excessive exposure to thermo-mechanical forces capable of inducing high degrees of C-C scission and 5 oxidation of the product, which is undesirable.
During the process for devulcanizing tyre rubber particles volatiles originally present in the tyre rubber particles may be released and accumulate in the mill.
Therefore, the volatiles are preferably removed from a vent.
In an example the gaseous flow is chosen from the group of air and inert gas, such as nitrogen.
The present invention also relates to devulcanized tyre rubber particles having a sticky and popcorn like surface structure resulting in a material that has flow characteristics somewhere between a powder and a friable solid.
The devulcanized tyre rubber particles can be used as a viable substitute to virgin rubber in different types of applications, such as in tyres and general rubber goods such as conveyor belts, sheeting, extrusion profiles and moulded products. The devulcanized tyre rubber particles can also be used as a highly dispersible modifier and as a replacement or partial replacement of bitumen binders in asphalt to enhance the visco-elastic, durability and sound-deadening performance of pavements and road surfaces.
For the purpose of facilitating an understanding of the invention, there is illustrated in the accompanying drawings the preferred embodiments from an inspection of which when considered in connection with the following description, the invention, its construction and operation and many of its advantages would be readily understood and appreciated.
Figure 1 shows a picture of untreated tyre rubber.
Figure 2 shows a picture of a devulcanized tyre rubber.
The devulcanized tyre rubber was characterized by Soxhlet extraction in toluene, according to Eq. (1). The insoluble fraction, or gel fraction of the rubber can be separated from the soluble fraction with this extraction technique. Extraction was for 18 h followed by drying the samples for 12 h at 80 °C to remove the solvent.
Sol Fraction (3%) = (1 — Mr «1433
Myf where Mi and Mf stand for the mass of rubber before and after the extraction, respectively.
The cross-link density of untreated tyre rubber and the devulcanized sample was determined via swelling tests according to ASTM D 297-15. The cross-link density value was calculated using the Flory-Rehner Eq. (2) after equilibrium swelling (72h followed by drying to constant mass at 80 °C) in toluene. vy = —in{l — Vp) + Ve + g Vr] (2) [Vi (V5 — Vr)}/2] where De is cross-link density (mol/cm3); V, is the molar volume of the solvent (for toluene: 106.13 cm3/mol); Xx; is the rubber-solvent interaction parameter (0.39), and Vr is the volume fraction of rubber in the swollen sample, which can be determined with the Ellis and Welding Eq. (3). = (3)
Vm
Fr ì ix where ms is the mass of the swollen rubber sample (g), mr is the mass of the dry rubber sample (9}, ps is the density of the solvent, toluene (0.8669 g/cm3) and p- is the density of the rubber sample (1.20 g/cm?). The degree of devulcanization was calculated with
Eq. (4)
EO EN
Devi) = (1! ~ 2) 108 (4)
Vif where uf is the cross-link density of the devulcanized sample and vi is the cross-link density of untreated tyre rubber.
A rubber granulate having a particle size of as 2-5 mm produced from EOL {end-of-life} whole truck and bus tyres was used as raw material. The natural rubber content of the rubber granulate was between 40 and 45 wt.% and the total hydrocarbon content of the rubber granulate was between 80 and 65 wt.%. The raw material was 99% free from steel and textile and its moisture content was < 1 wt. %.
The mill used was a Jaeckering Ultra-Rotor Model “UR la S” (manufactured by
Altenburger Maschinen Jäckering GmbH (DE)) fitted with a 18kW main motor, an 11kW fan motor, an air inlet temperature of 20 DegC. An airflow of at least 30,000 and at most 90,000 parts by volume of atmospheric air for one part by volume of tyre rubber particles and a residence time of the ground material of a maximum of 1.2 s was introduced in the mill for generating a field of high turbulence, strong eddies and high energy impact between the tyre rubber particles. Particle to particle impact speeds are dramatically increased to around the speed of sound. This air flow causes micronization and rupture of the tyre rubber particles resulting in thermo-mechanically devulcanized tyre rubber particles. During the devulcanization process the temperature of the tyre rubber particles exceeded the melting temperature of the few remaining textile fibres (predominantly polyamide and polyester types), where polyester fibres melt at around 295 DegC. The outlet temperature of the air was 125
DegC.
Table: Soxhlet extraction results of devulcanization experiment (107% mol/cm?) (%) enor wT rubber sample
From the Table one will conclude that the treatment of the tyre rubber particles in the mill has resulted in a devulcanization grade of 64.9 %.
From the difference between Figure 1 and Figure 2 it is clear that the devulcanized sample (Figure 2) has a sticky and popcorn like surface structure. Such a structure is characteristic for the cleavage of the monosulfidic, disulfidic and polysulfidic crosslinks existing in a vulcanized rubber.
Claims (7)
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6133413A (en) | 1995-12-19 | 2000-10-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of manufacturing devulcanized rubber using high temperature and shearing pressure |
US6387966B1 (en) | 2001-05-21 | 2002-05-14 | Vadim Goldshtein | Method and composition for devulcanization of waste rubber |
US7166658B2 (en) * | 2003-04-22 | 2007-01-23 | Sorbecon Consultants Inc. | Rubber reduction |
CN105150409A (en) | 2015-09-24 | 2015-12-16 | 安徽世界村新材料有限公司 | Intelligent modularized continuous green devulcanizing and regenerating complete technology for waste rubber |
US20170009044A1 (en) | 2012-09-12 | 2017-01-12 | Sekhar Research Innovations Sdn. Bhd. | Method for producing devulcanized rubber and an apparatus therefor |
CN108517052A (en) * | 2018-04-24 | 2018-09-11 | 德昌金锋橡胶有限公司 | A kind of tyre reclaim preparation method |
-
2021
- 2021-11-23 NL NL2029863A patent/NL2029863B1/en active
Patent Citations (6)
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US6133413A (en) | 1995-12-19 | 2000-10-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of manufacturing devulcanized rubber using high temperature and shearing pressure |
US6387966B1 (en) | 2001-05-21 | 2002-05-14 | Vadim Goldshtein | Method and composition for devulcanization of waste rubber |
US7166658B2 (en) * | 2003-04-22 | 2007-01-23 | Sorbecon Consultants Inc. | Rubber reduction |
US20170009044A1 (en) | 2012-09-12 | 2017-01-12 | Sekhar Research Innovations Sdn. Bhd. | Method for producing devulcanized rubber and an apparatus therefor |
CN105150409A (en) | 2015-09-24 | 2015-12-16 | 安徽世界村新材料有限公司 | Intelligent modularized continuous green devulcanizing and regenerating complete technology for waste rubber |
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Non-Patent Citations (3)
Title |
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"Sustainable Catalysis : Without Metals or Other Endangered Elements, Part 2", 1 January 2018, ROYAL SOCIETY OF CHEMISTRY, Cambridge, ISBN: 978-1-78262-641-1, ISSN: 1757-7047, article ADHIKARI JAIDEEP ET AL: "CHAPTER 1. Grinding of Waste Rubber : Challenges and Developments", pages: 1 - 23, XP055926495, DOI: 10.1039/9781788013482-00001 * |
XU XIAOFEI ET AL: "Batch grinding kinetics of scrap tire rubber particles in a fluidized-bed jet mill", POWDER TECHNOLOGY, ELSEVIER, BASEL (CH), vol. 305, 11 October 2016 (2016-10-11), pages 389 - 395, XP029834837, ISSN: 0032-5910, Retrieved from the Internet <URL:https://www.sciencedirect.com/science/article/pii/S0032591016306994> [retrieved on 20220531], DOI: 10.1016/J.POWTEC.2016.10.019 * |
ZHANG X. X. ET AL: "Devulcanisation of natural rubber vulcanisate through solid state mechanochemical milling at ambient temperature", PLASTICS, RUBBER & COMPOSITES: MACROMOLECULAR ENGINEERING, vol. 36, no. 7-8, 19 October 2007 (2007-10-19), GB, pages 370 - 376, XP055913317, ISSN: 1465-8011, Retrieved from the Internet <URL:http://dx.doi.org/10.1179/174328907X237584> [retrieved on 20220531], DOI: 10.1179/174328907X237584 * |
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