Effect of acid catalysts on scrap tyre pyrolysis under fast heating conditions

Abstract A study has been carried out on the effect of acid catalysts prepared based on HZSM-5, HY and HBeta zeolites on the distribution of volatile products (gas, non-aromatic C5–C10 fraction, aromatic C 10 − and tar), in the pyrolysis of tyre material carried out in a fast heating microreactor. The results have been compared with those of thermal pyrolysis. The strategies of using the catalyst in situ and reforming the volatiles generated in thermal pyrolysis have also been compared. The use of a catalyst in situ lowers the pyrolysis temperature by 50 K (to 723 K) and produces a significant increase in the yield of gases and light aromatic C 10 − , at the expense of a decrease in the yield of non-aromatic C 10 − . The yield of tar increases only slightly. The shape selectivity of each zeolite has a significant effect and, consequently, HY zeolite leads to the formation of heavier structures that make up the tar and to aromatic C 10 − , which is favoured by hydrogen transfer capacity. HZSM-5 is more efficient for the formation of gases, although it contributes only to decreasing the molecular weight of aromatic C 10 − fraction. HBeta zeolite catalyst has an intermediate behaviour. Reforming pyrolysis volatiles at 723 K using a HZSM-5 zeolite catalyst efficiently increases (from 2 to 20 wt%) the yield of gases, with a high yield of ethene and propene. The yields of BTX fraction are also very high (around 11.5 wt%).

[1]  C. Roy,et al.  Rheological properties of bitumen modified with pyrolytic carbon black , 1996 .

[2]  C. Roy,et al.  Characterization of pyrolytic light naphtha from vacuum pyrolysis of used tyres comparison with petroleum naphtha , 1995 .

[3]  Liang-cai,et al.  Pyrolysis of waste tyres with zeolite USY and ZSM-5 catalysts , 2007 .

[4]  J. Bilbao,et al.  Kinetic description of the catalytic pyrolysis of biomass in a conical spouted bed reactor , 2005 .

[5]  M. Arabiourrutia,et al.  Kinetics of scrap tyre pyrolysis under fast heating conditions , 2005 .

[6]  J. Bilbao,et al.  Relationship between surface acidity and activity of catalysts in the transformation of methanol into hydrocarbons , 1996 .

[7]  G. S. Miguel,et al.  Thermal and catalytic conversion of used tyre rubber and its polymeric constituents using Py-GC/MS , 2006 .

[8]  M. Arabiourrutia,et al.  Product distribution obtained in the pyrolysis of tyres in a conical spouted bed reactor , 2007 .

[9]  A. Marcilla,et al.  Catalytic flash pyrolysis of HDPE in a fluidized bed reactor for recovery of fuel-like hydrocarbons , 2007 .

[10]  Akbar A. Merchant,et al.  Pyrolysis of scrap tires and conversion of chars to activated carbon , 1993 .

[11]  Weidong Cao,et al.  Study on properties of recycled tire rubber modified asphalt mixtures using dry process , 2007 .

[12]  J. Bilbao,et al.  Catalyst Equilibration for Transformation of Methanol into Hydrocarbons by Reaction−Regeneration Cycles , 1996 .

[13]  Paul T. Williams,et al.  Influence of Process Conditions on the Rate of Activation of Chars Derived from Pyrolysis of Used Tires , 1999 .

[14]  Shen Bo-xiong,et al.  Pyrolysis of waste tyres: The influence of USY catalyst/tyre ratio on products , 2007 .

[15]  I. Joekes,et al.  Use of tire rubber particles as addition to cement paste , 2000 .

[16]  C. Roy,et al.  Surface morphology and chemistry of commercial carbon black and carbon black from vacuum pyrolysis of used tyres , 1996 .

[17]  Paul T. Williams,et al.  Fluidised bed catalytic pyrolysis of scrap tyres: Influence of catalyst: tyre ratio and catalyst temperature , 2002, Waste management & research : the journal of the International Solid Wastes and Public Cleansing Association, ISWA.

[18]  Javier Bilbao,et al.  Pyrolysis of sawdust in a conical spouted‐bed reactor with a HZSM‐5 catalyst , 2000 .

[19]  Ramón Murillo,et al.  The application of thermal processes to valorise waste tyre , 2006 .

[20]  Javier Bilbao,et al.  Catalytic pyrolysis of high density polyethylene in a conical spouted bed reactor , 2007 .

[21]  Paul T. Williams,et al.  Catalytic pyrolysis of tyres: influence of catalyst temperature , 2002 .

[22]  G. Lopez,et al.  Product distribution modelling in the thermal pyrolysis of high density polyethylene. , 2007, Journal of hazardous materials.

[23]  Christian Roy,et al.  A new method for DTA measurement of enthalpy change during the pyrolysis of rubbers , 1996 .

[24]  U. Henriksen,et al.  Devolatilization characteristics of large particles of tyre rubber under combustion conditions , 2006 .

[25]  Ali Akbar Yousefi,et al.  Effect of used-tire-derived pyrolytic oil residue on the properties of polymer-modified asphalts , 2000 .

[26]  G. S. Miguel,et al.  Porosity and surface characteristics of activated carbons produced from waste tyre rubber , 2002 .

[27]  A. Corma,et al.  Influence of Zeolite Composition and Structure on Hydrogen Transfer Reactions from Hydrocarbons and from Hydrogen , 1996 .

[28]  A. Marcilla,et al.  Catalytic pyrolysis of LDPE over H-beta and HZSM-5 zeolites in dynamic conditions: Study of the evolution of the process , 2007 .

[29]  Chunfei Wu,et al.  Pyrolysis of scrap tyres with zeolite USY. , 2006, Journal of hazardous materials.

[30]  J. M. Arandes,et al.  Effect of HZSM-5 Zeolite Addition to a Fluid Catalytic Cracking Catalyst. Study in a Laboratory Reactor Operating under Industrial Conditions , 2000 .

[31]  J. M. Arandes,et al.  Isotherms of chemical adsorption of bases on solid catalysts for acidity measurement , 1994 .

[32]  A. Marcilla,et al.  Effect of the temperature in the nature and extension of the primary and secondary reactions in the thermal and HZSM-5 catalytic pyrolysis of HDPE , 2007 .

[33]  D. Leung,et al.  Pyrolysis of tire powder: influence of operation variables on the composition and yields of gaseous product , 2002 .

[34]  A. Marcilla,et al.  Study of the influence of the characteristics of different acid solids in the catalytic pyrolysis of different polymers , 2006 .