Zeolite pyrolysis

Zeolite-bentonite hybrid catalysts for the pyrolysis of woody biomass... 

Hybrid catalysts consisting of a zeolite (ZSM-5 or Beta) and bentonite as a binder were prepared and characterized by XRD, pyridine FTIR and nitrogen adsorption. The hybrid catalysts exhibited similar properties as the combined starting materials. Catalytic pyrolysis over pure ZSM-5 and Beta as well as hybrid catalysts has been successfully carried out in a dual-fluidized bed reactor. De-oxygenation of the produced bio-oil over the different zeolitic materials was increased compared to non-catalytic pyrolysis over quartz sand. 

The highly oxygenated bio oil can be de-oxygenated, and thereby upgraded, over acidic zeolite catalysts through the formation of mainly water at low temperatures and C02 and CO at higher temperatures [1-3], Successful catalytic pyrolysis of woody biomass over Beta zeolites has been performed in a fluidized bed reactor in [4]. A drawback in the use of pure zeolitic materials has been the mechanical strength of the pelletized zeolite particles in the fluidized bed. 

The objective of this work is to synthesize and characterize zeolite-bentonite hybrid catalysts and perform test reactions in the pyrolysis of woody biomass in a dual-fluidized bed reactor. The aim is to produce catalytic materials which have good mechanical strength and are still able to de-oxygenate the pyrolysis oil. 

Testing of the catalyst was performed in the dual-fluidized bed reactor, where in the first reactor pyrolysis of the biomass and in the second upgrading of the pyrolysis vapours through catalytic de-oxygenation occurred. The bed material in the pyrolysis section was 40 g of quartz sand with a particle size distribution of 100 - 150 pm. The particle size of the catalyst was 250 - 355 pm. The amount of zeolite used in each experiment was 1.75 g. The biomass raw material used in the experiments was pine... 

Pyrolysis and catalytic de-oxygenation of pine wood biomass was successfully carried out in a dual-fluidized bed reactor. Hybrid catalysts consisting of zeolites Beta and ZSM-5 and bentonite were used. Pure zeolites Beta and ZSM-5 and also pure bentonite were tested as bed materials in the fluidized bed reactor. 

In this work the methanol and methyl iodide conversion and their co-reaction are investigated on Fe-Beta zeolite without any oxygen. Partly Fe-ion-exchanged Beta-300 i.e. Fe-H-Beta-300 (shortly Fe-Beta-300) zeolite keeps the light acidity to a certain extent, however the presence of Fe ions (as transition metal, Fe is an excellent Lewis acid) can modify the reaction pathway. This Fe-Beta-300 has been tested already by low temperature peat pyrolysis [6], At present, the adsorption as well as desorption of methanol are followed-up by radiodetectors using ( -radioisotopic labeling [4, 7]. The... 

D. Fabbri, C. Torri, and V. Baravelli, Effect of zeolites and nanopowder metal oxides on the distribution of chiral anhydro sugars evolved from pyrolysis of cellulose An analytical study, J. Anal. Appl. Pyrolysis, 80 (2007) 24-29. 

Enciforming [National Chemical reforming] A petroleum reforming process that converts pyrolysis gasoline to mixtures of propane, butane, and aromatic hydrocarbons, thereby obviating the usual hydrogenation and solvent extraction processes. The catalyst is a ZSM-5-type zeolite containing both iron and a platinum metal. Developed by the National Chemical Laboratory, Pune, India, since 1988, but not yet commercialized. 

Deoxygenation reactions are catalyzed by acids and the most studied are solid acids such as zeolites and days. Atutxa et al. [61] used a conical spouted bed reactor containing HZSM-5 and Lapas et al. [62] used ZSM-5 and USY zeolites in a circulating fluid bed to study catalytic pyrolysis (400-500 °C). They both observed excessive coke formation on the catalyst, and, compared with non-catalytic pyrolysis, a substantial increase in gaseous products (mainly C02 and CO) and water and a corresponding decrease in the organic liquid and char yield. The obtained liquid product was less corrosive and more stable than pyrolysis oil. 

Most importantly, biomass pyrolysis will be carried out at remote locations, and in distributed manner. Thus, the catalysts should be cheap and simple to use. Acidic clays, silica aluminas and H-FAU type zeolites are relatively cheap and robust materials, can be mixed easily with heat carriers, and used for pyrolysis. Efficient contact between the solids (catalyst and biomass) to maximize catalytic action is one of the challenges that need to be overcome. 

Gayubo, A.G., Aguayo, A.T., Atutxa, A., Aguado, R., Bilbao, J., Transformation of oxygenate components of biomass pyrolysis oil on a HZSM-5 zeolite. 

Home, P.A., Williams, P.T., The effect of zeolite ZSM-5 catalyst deactivation during the upgrading of biomass-derived pyrolysis vapours, J. Anal. Appl. Pyrolysis, 1995, 34, 65. 

Membranes with extremely small pores ( < 2.5 nm diameter) can be made by pyrolysis of polymeric precursors or by modification methods listed above. Molecular sieve carbon or silica membranes with pore diameters of 1 nm have been made by controlled pyrolysis of certain thermoset polymers (e.g. Koresh, Jacob and Soffer 1983) or silicone rubbers (Lee and Khang 1986), respectively. There is, however, very little information in the published literature. Molecular sieve dimensions can also be obtained by modifying the pore system of an already formed membrane structure. It has been claimed that zeolitic membranes can be prepared by reaction of alumina membranes with silica and alkali followed by hydrothermal treatment (Suzuki 1987). Very small pores are also obtained by hydrolysis of organometallic silicium compounds in alumina membranes followed by heat treatment (Uhlhom, Keizer and Burggraaf 1989). Finally, oxides or metals can be precipitated or adsorbed from solutions or by gas phase deposition within the pores of an already formed membrane to modify the chemical nature of the membrane or to decrease the effective pore size. In the last case a high concentration of the precipitated material in the pore system is necessary. The above-mentioned methods have been reported very recently (1987-1989) and the results are not yet substantiated very well. 

Several zeolites were used both in original and calcined form. The volatile products of pyrolysis either analyzed directly by GC/MS or after passing over the respective zeolites. 

The pyrolysis gas chromatogram of ABS at 550°C changes considerably when the pyrolysis products are passed over zeolite catalysts. The specific activity towards certain reactions, e.g., cycliza-tion, aromatization, or chain cleavage is somewhat dependent on the nature of the individual zeolite. In general, enhanced benzene, toluene, ethylbenzene at the cost of dimer, trimer formation is observed. Nitrogen containing compounds do not appear in the pyrolysis oil after catalytic conversion. However, the product gas is rich in nitriles (132). 

The presence of zeolite catalysts increases the amount of gaseous hydrocarbons produced during pyrolysis but decreases the amount of pyrolysis oil. Further, significant quantities of coke were formed on the surface of the catalysts in the course of pyrolysis. The catalysts reduced the yield of e.g., as styrene and cumene, in favor of naphthalene. The zeolite catalysts, especially Y-Zeolite, were found to be very effective in removing volatile organo bromine compounds. However, they were less effective in removing antimony bromide from the highly volatile products of pyrolysis (133). 

W.J. Hall and P.T. Williams, Removal of organobromine compounds from the pyrolysis oils of flame retarded plastics using zeolite catalysts, J. Anal. Appl. Pyrolysis, 81(2) 139-147, March 2008. 

Material balances for the pyrolysis products from HIPS equipped with flame retardants have been given (53). The pyrolysis experiments were performed to some extent in the presence of zeolite catalysts. The zeolites were added in order to remove organic bromine from the products of pyrolysis. In addition to their potential of destroying toxic brominated flame retardants, zeolites have been believed to be suitable to upgrade the pyrolysis products. 

The zeolite catalysts are very effective in removing volatile organic bromine. However, they are not very effective in removing antimony bromide from the volatile pyrolysis products. Actually, the zeolites cause a dramatic increase of the formation of hydrogen by a factor of 10. In addition, zeolite catalysts were found to reduce the formation of some valuable pyrolysis products, such as styrene and cumene, but other products, such as naphthalene were formed instead (53). 

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