Ind. Eng. Chem. Res.

2002, 41, 1419-1424


KINETICS, CATALYSIS, AND REACTION ENGINEERING Steam Cracking of Naphtha in Packed Bed Reactors
Jafar Towfighi,*,† Heinz Zimmermann,‡ Ramin Karimzadeh,† and Mohammad M. Akbarnejad§
Chemical Engineering Department, Tarbiat Modares University, P.O. Box. 14115-111, Tehran, Iran, LINDE AG, Process Engineering and Contracting Division, Dr.-Carl-von-Linde-Str. 6-14, D-82049 Hoellriegelskreuth, Germany, and Research Institute of Petroleum Industry, National Iranian Oil Company, Tehran, Iran

Thermal steam cracking of naphtha in packed bed reactors has been compared with cracking in an empty tube. A laboratory-scale packed bed reactor has been used to investigate the effects of inert and catalytic active materials on the steam cracking of naphtha. Different sizes of ceramic materials as inert materials have been tested at various reactor temperatures. The results show that lower molecular weight products, such as hydrogen, methane, and ethylene, have been increased by steam cracking in packed bed reactors compared to a conventional approach in an empty tube. Steam cracking of naphtha over six different catalysts consisting of mixtures of alumina and metal oxides, such as CaO, TiO2, SrO, MgO, Cr2O3, and MnO, has been tested, and the results are compared with those for a ceramic packed bed reactor. It could be demonstrated that the catalysts used do not improve the yields of ethylene and propylene as main products. However, the same catalysts have shown significant gasification activity, indicated by the increased yield of H2, CO, and CO2 with a reduction of the yields of ethylene, propylene, and other cracking products. Among those catalysts, it has been found that calcium aluminate (12CaO‚7Al2O3) selectively gasifies aromatics produced during the cracking reactions without any reduction of ethylene and propylene.
1. Introduction Light olefins, ethylene and propylene, are produced commercially via steam cracking of various hydrocarbons, such as ethane, naphtha, and gas oil. These low molecular weight olefins are among the most important base chemicals for the petrochemical industry. Modern steam cracking plants today typically are the center of petrochemical complexes producing 500 0001 000 000 tons per year of ethylene, the main petrochemical building block. Ethylene yield on a weight basis is typically 30% with naphtha feedstock and goes down to 25% for gas oil feedstock. The cracking reactions inside the coils are endothermic, and the temperature is increased from 600 °C at the inlet of the cracking coil to 820-870 °C at the outlet. Under these conditions the feedstock is converted in a free radical mechanism to the products. To improve the yield of light olefins and to decrease the process temperatures, the application of catalysts could be an option. However, the use of packed bed catalysts in commercial coils has pressure drop limitations. Higher pressures are required for processing the feed over a packed catalyst bed, reducing the yield of lower molecules in steam cracking. Several research groups have tried to overcome the disadvantages of the technology by using catalysts in steam cracking, but so far no commercial application has been achieved, though some of the results are promising.
† ‡

Tarbiat Modares University. LINDE AG. § National Iranian Oil Company.

Chernykh et al.1 proposed a promoted vanadium catalyst on a low surface alumina carrier. With this catalyst, the yield of ethylene in the pyrolysis of gasoline at 780 °C, at a steam-to-feed ratio of 1:1, and at a residence time of 0.15 s is 40 wt %. This yield is approximately 5-10 wt % higher than the yield of ethylene in conventional steam cracking of naphtha in commercial reactors. The calcium aluminate catalyst T12 was investigated by Kikuchi et al.2 under various conditions of temperatures, pressures, steam ratios, residence times, and feedstocks to produce olefins. In this work the conditions to produce olefins using a catalyst have been optimized, but there is no comparison between the yields of products with and without a catalyst. Benzene, toluene, 1-methylnaphthalene, and n-heptane were studied over the temperature range 550-950 °C, by passing a low concentration of the compounds through 5.5 cm deep packed beds of calcium oxide.3 It was shown that calcium oxide significantly increased the rate of pyrolysis of the aromatics, reducing the temperature for a given percentage conversion by around 150 °C. In contrast, CaO decreased the comparable temperature for n-heptane by 40 °C. Lemonidou et al.4,5 proposed several types of catalysts consisting of different phases of calcium aluminate and other complexes of various metal oxides such as Mg, Mn, Ti, In, and Zr which have been tested in steam cracking of n-hexane. The selectivity ratio, defined as the weight of the target product (ethylene or propylene) to the weight of reacted n-hexane, is 10-18% higher than the

10.1021/ie010636e CCC: $22.00 © 2002 American Chemical Society Published on Web 02/16/2002

The residence time in all experiments is 0. 2.61 3.87 3. mm value 6. The work reported in the present paper is aimed at determining the reasons for the increase of light components in the product of steam cracking of naphtha through a packed bed reactor. Steam cracking of naphtha has been studied over 12CaO‚7Al2O3 catalyst in a fixed bed reactor in the temperature range 700-850 °C. 2. The gases are analyzed in gas chromatographs to determine H2. ethylene.37 2.8 Mukhopadhyay et al. No.86 2. g/min steam-to-naphtha ratio. Naphtha Specification.09 7. The best results of selectivity ratio were obtained with a calcium aluminate catalyst at the CaO-to-Al2O3 molar ratio 12:7.0 ( 0. addition of the catalysts significantly increased the production of methane. Reactor Specifications. some investigators found that the ethylene yield was affected by the active sites of the catalysts while others found that this was due to the surface of packed bed materials.5 0.6 found that the use of MgO for catalytic steam cracking increases the conversion of n-heptane.61 0. The reactor is placed in a vertical furnace heated by three equal zones.8 g/min for an empty tube. 41. CO2 and C4components.79 10. different packings.23 s increased by 7 wt % compared to those for an empty tube under identical conditions.7. and propylene.11 investigated vanadium oxide.7 (g/g).94 1. The skin temperature profile of the reactor is measured with chromel-alumel thermocouples. n-paraffins iso-paraffins naphthenes aromatics olefins 3 4 5 6 7 8 9 10 11 12 total 0.23 0.02 28. The gas product is sampled at point Figure 1. Table 3 lists the dimensions of the inert materials used in the experiments.95 7. g/g residence time.2. Taralas also studied the catalytic steam cracking of n-heptane using dolomites (CaMg(CO3)2) and NiMo/ Al2O3. the naphtha flow rate is changed from 6. Experiments 2.3.18 0.37 3. To maintain a constant residence time in all experiments. 6.82 9. the inert. The same naphtha feedstock was used in all experiments.05 21.3 0.1 g/min for packed bed reactors to 7.5 Table 2.28 0.07 4 6. The liquid and gas phases are analyzed separately with a PONA column to determine the C5+ components.08 0. Talaras et al. Schematic of the experiemental setup. All the experiments were carried out under the same operating conditions as shown in Table 1. Thermal steam cracking of naphtha is performed in a vertical tube of length 120 cm and inside diameter 1.12 4. The only effect that has been observed was the suppression of coking activity by a catalyst containing potassium.59 0.6 770-890 150 4. The products leaving the reactor are cooled in an ice-cooled water condenser. The mixed stream is routed through a preheater and then enters the reactor at approximately 400 °C.7 0. The effect of inert materials and the catalytic effect on the distribution of products were investigated in a bench scale steam cracking unit. CO. Compared to thermal pyrolysis. reducing the temperature required for a given conversion by approximately 50 °C.57 0. A screen is welded inside the tube to hold approximately 150 cm3 of the ceramic or catalytic active materials.1420 Ind. The specification of the naphtha feed is shown in Table 2. He showed that the conversion of n-heptane is constant over NiMo catalyst and decreases over dolomite.05 5. s maximum skin temperature. Vol. Naphtha and water are pumped to two separate vaporizers and mixed at the outlet of the vaporizers as shown in Figure 1. at a steam-to-feed ratio of 1:1.35 0. potassium containing catalysts.91 0. A list of . 2002 selectivity ratio over R-alumina.9 reported that yields of ethylene and propylene in steam cracking of naphtha over 12CaO‚7Al2O3 at 780 °C. The selectivity ratio over R-alumina is already 7% higher than the ratio achieved in an empty tube. Bench scale unit experiments including empty tube tests. and inert packings such as quartz and alumina materials. Eng.14 2. Conversion of naphtha increased in the presence of the catalyst.1.17 3. The experiments can be classified into three categories according to the use of an empty tube. The maximum skin temperature is set between 770 and 890 °C in the experiments.10 Golombok et al. Chem.8 0.9 cm. Three different sizes of cylindrical ceramic materials were used to determine the effect of inert inserts and also the effect of the surface of the inert packings on the results of the steam cracking of naphtha.12 1. In these experiments it was shown that the improvements of yields over the inert materials are in a similar range as those with catalysts. magnesium oxide. Operating Conditions for Steam Cracking of Naphtha parameter naphtha flow rate.09 0.6 1.74 5. Ceramic material of a cylindrical shape is used as inert material packing. or ceramic materials and the catalysts.65 0.1 41.36 0. Specification of Naphtha Feed (All Components Are in wt %) carbon no. Six catalysts consisting of mixtures of alumina with different metal oxides have been prepared. and different catalysts are described below. where steam and heavier hydrocarbons are condensed. Packing Material Specifications. 2. Res. Table 1.1-7. cm3 catalyst size.91 12. and at a residence time of 0. °C packing material volume.6 s at a steam/ hydrocarbon ratio of 0.. The authors have shown that increased light olefin yields during catalytic steam cracking are mainly due to a surface/volume effect and are not due to a catalytic effect. In summary.34 2.55 0. and the liquid product is sampled at points 2 and 3 as shown in Figure 1.57 0.06 2.

5 2. Configuration and Composition of Inert Materials Configuration of Inert Materials no.69 2.66 Table 4. gas temperature.9 bulk density. pressure.57 magnesium 0.08 0.35 length.95 Dout. °C 1200 1200 1200 950 950 950 surface area. and measurements of the surface area is shown in Table 4. The product distribution is a function of feedstock. 2002 1421 Table 3. Catalyst Composition and Properties no. and residence time.7 10.95 6.10 Composition of Chemical Elements of Inert Materials aluminum iron potassium titanium 13.11 who attributes enhanced ethylene production to the surface-to-volume ratio increase. The yields of ethylene and propylene are compared in Figures 4 and Figure 2. Yield of C5+ in steam cracking of naphtha in an empty tube and in a ceramic packed bed reactor. Eng. A different result was achieved with the C5+ products as shown in Figure 3. No. mm 0. The mixture was moulded into cylinders and placed in a desiccator for aging. Figure 2 shows that ethylene yields in a packed bed reactor are higher than in an empty tube over a wide range of severities. However.8 3.2 4. the particles were placed into a furnace and the temperature was gradually increased to achieve complete dehydration of the mouldings and burn off the organic binder. After aging for 24 h. As shown above.01 9. g/cm3 1. the specific surface area of inert materials does not affect the product yields over a wide range. 41.14 0. 1 2 3 elements wt % shape cylindrical cylindrical cylindrical silicon 34.9 3. In an empty tube. To determine the effect of the specific surface area of packing material inside the reactor. was used for correlation. cm2/cm3 17.2 2. Figure 3. Steam cracking of naphtha was tested in different ranges of skin temperature between 770 and 890 °C in an empty tube and a ceramic packed bed reactor. The method of catalyst preparation is the same as that described by Lemonidou. The temperature was then raised at a rate of 250 °C/h until it reached the sintering temperature.Ind. mm 3. 6. the gas is mainly heated by contact with the walls . Results and Discussion 3. Yield of C2H4 in steam cracking of naphtha in an empty tube and in a ceramic packed bed reactor. The sample was calcined at the sintering temperature for 48 h to complete the solid reaction between the two oxides and to increase the crushing strength of the sintered product. mm 2 5. calcination temperatures. since temperature measurements in this range are not very precise. The lower concentration of C5+ in packed bed reactors leads to the assumption that the packing material in the reactor improves the conversion of feed to lower hydrocarbon molecules in naphtha steam cracking reactions.25 0. 1 2 3 4 5 6 catalyst composition 12CaO‚7Al2O3 MgO‚Al2O3 SrO‚Al2O3 MnO‚Al2O3 TiO2‚Al2O3 Cr2O3‚Al2O3 calcination temp. the severity. m2/g 1. Vol. 3. Chem. Inert Material Effect.41 5. 5 at different surface-to-volume ratios of packings and different severities. different sizes of ceramic materials have been tested. Yield of C2H4 in the ceramic packed bed reactor at different surfaces of the packings.31 oxygen 48.26 specific area.7 5.93 0. and then small amounts of distilled water and binding agent were added to facilitate moulding.1.2 catalysts. Res. Figures 2 and 3 show the comparison of the results of the products obtained in a packed bed reactor of 5 mm diameter ceramic with an empty tube at different severities. defined as propylene/ethylene ratio. These results do not agree with those presented by Golombok.90 Din.. Figure 4.5 1. Only the gas temperature was considered variable in the experiments.4 The required amounts of the metal oxide and alumina were mixed.66 1. steam ratio.

16 0.04 15. Figure 9 shows that the yields of C5+ hydrocarbons are reduced over the 12CaO‚7Al2O3 and SrO‚Al2O3 catalysts in comparison with the yields of C5+ over the ceramic particles.87 1.71 MnO‚Al2O3 1.38 4.37 4. 12CaO‚7Al2O3 has the strongest effect on the rate of the gasification reactions.35 15. and H2 are produced in the highest amount over a 7CaO‚12Al2O3 catalyst.61 26.22 0.07 Figure 5. it has been found that the aromatics yield is lower. CO2.13 MgO‚Al2O3 1.87 14. and CO2 are also observed in steam re-forming of hydrocarbons such as naphtha cracking across metal catalyst supported on a metal oxide. and H2 in steam cracking of naphtha over the metal oxide catalysts are increased dramatically compared to the yields of CO.60 2.66 4.33 4.22 15. 2002 Table 5.46 4.72 2.83 1.13 0. and it is assumed that these components are preferentially gasified over the . MgO.16 3.80 2.10 0.54 0.13 Cr2O3‚Al2O3 1.36 0. Yield of H2 in a ceramic packed bed reactor and over different metal oxide catalysts. although ethylene does not participate in the gasification reactions over this catalyst and thus is not decreased.43 0. and MnO. has been tested at different skin temperatures. and the yields of products are shown in Table 5. The catalysts 12CaO‚7Al2O3.85 13.71 2.28 14. SrO‚Al2O3.34 4. TiO2. and H2. CO2.87 14. and H2 in a ceramic packed bed reactor. The components CO.2.51 26.54 28. Among the C5+ hydrocarbons.42 0.56 28.29 29.57 4. 6. CO2. The absorbed radiative heat of the ceramic particle is transferred to the gas surrounding the particle. Vol.53 27.26 2.30 3. Res. Yield of C3H6 in the ceramic packed bed reactor at different surfaces of the packings. 3. MnO‚Al2O3. The experiments carried out show that the yield of ethylene as a main product of steam cracking of naphtha does not change for some of the catalysts and for some catalysts it decreases compared to that for a packed bed reactor with inert material.55 27.. Catalytic Effects.55 0.69 0.27 0.77 0.25 3. and the heat is transferred from the wall to the gas by a convective mechanism. Chem. such as CaO.19 0.55 0. Figure 6.1-10 Figure 6 compares the yield of ethylene over the metal oxide catalysts with the yield of ethylene in a ceramic packed bed reactor at different cracking severities.53 28.57 0.58 27.32 2.53 0.73 0. packings act as a heat sink to absorb the radiative heat from the reactor wall and then transfer the heat into the cracked gas by a convective mechanism.85 14.80 0.66 0. but the catalysts MgO‚Al2O3. This result is in contradiction to results published by others. It could be concluded that the used catalyst acts as a steam re-forming catalyst.75 0.20 3.36 27.90 12.07 0. Cr2O3. The metal oxide catalyts improve the gasification of the mixture of steam and hydrocarbons and increase the yields of CO.57 24. CO2.91 14.30 14.38 4. In a packed bed reactor.11 12CaO‚7Al2O3 1.73 4. H2. and Cr2O3‚Al2O3 do not affect the yield of ethylene.86 0.44 30.38 TiO2‚Al2O3 1.49 27.65 0. CO2. No.36 16.71 0. Yields of Products of Steam Cracking of Naphtha over Ceramic Packing and Different Catalysts under Identical Conditions (Skin Temperature ) 830 °C) product wt % over the following ceramic H2 CH4 C2H2 C2H4 C2H6 C3H4 C3H6 C3H8 C4H6 C4H8 C4H10 C5+ COx 1. and H2.12 Figure 7.30 0.02 1. Eng. Thus.88 14.51 28.67 0.58 2. Figures 7 and 8 show that the yields of CO. CO.41 SrO‚Al2O3 1.38 4. Steam cracking of naphtha over six different catalysts consisting of mixtures of alumina and metal oxides.1422 Ind. It can be concluded that the 12CaO‚7Al2O3 and SrO‚Al2O3 catalysts facilitate the gasification of some of the components of the C5+ hydrocarbons and increase the yield of CO. SrO.38 0.61 0.18 0.26 0. among these catalysts.28 0. Yield of C2H4 in a ceramic packed bed reactor and over different metal oxide catalysts.35 4. and Ti2O3‚Al2O3 reduce the yield of ethylene. 41.08 15.

92 1.85 9. No. 6. Yields of CO and CO2 and Aromatics in Steam Cracking of Naphtha in a Ceramic Packed Bed Reactor (All Components Are in wt %) T.48 4.14 Figure 8.09 3.19 1.33 styrene 0. Weight of Elementary Carbon of Reacted Aromatics and Produced CO and CO2 in Gasification Reactions of Steam Cracking of Naphtha over 12CaO‚7Al2O3 Catalyst T.58 4. As a result.7 ethyl benzene 0.076 0. A stoichiometric relationship between the reacted amount of aromatics and the produced amount of CO and CO2 in the gasification reactions over the 12CaO‚7Al2O3 catalyst can be shown by calculation of the carbon weight balance.33 0.03 styrene 0.6 7. From the results discussed above.66 3. Eng.26 1. Tables 6 and 7 show the yields of CO.59 1.189 CO2 0.26 Figure 9.45 7. This trend shows that the gasification rate of benzene over the catalyst increases at high temperature or low severity.04 0.77 1.88 3. The amounts of the reacted aromatics in the gasification reactions over the 12CaO‚ 7Al2O3 catalyst are equal to the yield of aromatic components in the inert ceramic packed bed reactor minus the yield of the aromatic components over the 12CaO‚7Al2O3 catalyst. The composition data in Tables 6 and 7 show the reduction of aromatic weight percent between inert materials and catalyst.43 0. The yield of benzene is decreased noticeably across the 12CaO‚ 7Al2O3 catalyst at lower severities.07 1.96 6.5 1.84 1.88 for ceramic material to 7.022 0.18 1.03 weight of carbon in the produced CO and CO2 (g) 0.82 3.Ind.57 0.034 0.038 0.71 1.38 2.985 4.6 toluene 2.89 1.813 6.39 8.38 0. Table 8.16 C9 aromatics 2.1 1.37 1.071 0.26 3.64 2.18 3.57 1. Figure 10 compares the yield of benzene over the 12CaO‚7Al2O3 catalyst with the yield of benzene over the inert particles.33 0. the amounts of the produced CO and CO2 in the gasification reactions over the 12CaO‚7Al2O3 catalyst are equal to the yield of the CO and CO2 produced over the 12CaO‚7Al2O3 catalyst minus the yield of the CO and CO2 in the inert ceramic packed bed reactor.122 0.4 ethyl benzene 0.87 1.43 1. The weights of elementary carbon in the reacted aromatic components are approximately equal to the weights of elementary carbon of the CO and CO2 produced in the gasification reactions at the temperatures 800.24 1.11 C9 aromatics 1. Yields of CO and CO2 and Aromatics in Steam Cracking of Naphtha over 12CaO‚7Al2O3 Catalyst (All Components Are in wt %) T.307 0. For example.83 2.572 CO2 0. CO2.931 1. and 860 °C as shown in Table 8.55 0.23 C9/C10 aromatics 0.06 C9/C10 aromatics 0. Res. Figure 10..26 0.68 Table 7.22 0.036 benzene 2.79 4.022 0.60 0. Vol.042 0.64 4.48 0.44 0.69 toluene 2.52 1.1 1. °C 770 800 830 860 890 CO 0. °C 770 800 830 860 890 CO 0. and the aromatic components in a ceramic packed bed reactor and over the 12CaO‚7Al2O3 catalyst at different maximum temperatures of the reactor. . the weight percent of benzene at 860 °C reduces from 8.16 0.26 1.4 xylene 1.869 benzene 2.33 0.33 1. Yield of CO + CO2 in a ceramic packed bed reactor and over different metal oxide catalysts.44 1.59 0.85 for catalyst. 830.94 0. Yield of C5+ in a ceramic packed bed reactor and over different metal oxide catalysts.56 0. 12CaO‚7Al2O3 catalyst.88 10. °C 770 800 830 860 890 weight of carbon in the reacted aromatics (g) 0.149 0. 2002 1423 Table 6.035 0.58 2. Yield of benzene in a ceramic packed bed reactor and over the 12CaO‚7Al2O3 catalyst.62 0. Chem. it can be concluded that aromatics are the preferred species that are gasified by a 12CaO‚7Al2O3 catalyst.43 0. The difference between the yield of benzene in catalyst and the ceramic material is more pronouced at low severity. 41.48 xylene 1.59 0.74 1.54 1.24 1.24 1.

1993. T.. Longwell. Can. G. Res.. J. Res. (6) Taralas. Can. 31. D. 1998. 1080. M. New Catalysts for the Conversion of Methane to Synthesis Gas. Effect of potassium carbonate Impregnation. Res. G.. Literature Cited (1) Chernykh.. Germany. T. M. Chem. 69. 1985. 2000. T. 54. 4. 39. Catal.. A. R. V. The surface area of packed bed materials has no considerable effect on the product yields in the range of investigated surface areas. S. Anton Kirzinger and Mr. Catalyst Evaluation and Kinetic Study for Ethylene Production. 32. Eng.. M. Appl. Sjostrom. (7) Taralas. Conclusions Yields of light molecular weight products.. A. I. Vol. (5) Lemonidou. A. (12) Claridge. 2002 (2) Kikuchi.. 414. E. (10) Basu. The authors would like to thank Dr. A. L.. Eng. 1991. K. (3) Ellig.. Hirschberg. Eng. Brungs. June. A. Chem. V. Sov.. Eng. Eng. Ishida. C. I. V. J. Preparation and Evaluation of Catalysts for the Production of Ethylene via Steam Cracking. 2001 IE010636E . N. D. 285. Vassilatos. 54. A. L. 1914. Eng. Chem. Sakamoto.. Catalytic Pyrolysis of Naphtha. V. Mead. Ind. The catalytic active metal oxides used do not increase the ethylene yield compared to those for ceramic materials in steam cracking of naphtha. Chem. G. Acknowledgment This work has been performed with the financial support of Linde AG. 1983. 85. (8) Taralas. 119. 524. J. Alvarez. K. 2001 Accepted December 7. Catalytic Steam Pyrolysis of a Selected Saturated Hydrocarbon on Calcined Mineral Particles. Barabanov. 1989. 24. Josef Freisinger for assistance with the setup of the equipment and analysis of the products and the companies of Suedchemie and KataLeuna for preparation of the catalysts. G. Grotenberg. P. York. E. Kornegoor. such as hydrogen.. Process Des.. J. R. Kunzru. Chem. K. Eng.. Ind. The calcium aluminate catalyst (12CaO‚7Al2O3) selectively gasifies aromatic components without affecting the yield of ethylene in catalytic steam cracking of naphtha. S. W. Sloan... (4) Lemonidou. J. 76. Ind. 180. 1998. Chem.. Ind.. Res. (9) Mukhopadhyay. Peters. Dierickx. Eng. Chem. Pyatiletov. J. I. T. Received for review July 27. Vasalos. J. No. A. Mukhina. Pyrolysis of Volatile Aromatic Hydrocarbons and n-Heptane over Calcium Oxide and Quartz. Chem. I. N. 6. Vasalos.. MgO and Calcined Dolomites. D. Dev. J.. Catalytic Pyrolysis of Straight-Run Gasoline on a Promoted Vanadium Catalyst. D. Ind. Brink. A. Nikonov. B. Catal.. 1985. Surface-Enhanced Light Olefin Yields during Steam Cracking.. M. Res. Tsang.. 1992. A. Chem.. Kunzru. J. S.. 1996. A. Eng.. C. 1989. Motorina. Rudyk.. Tomita. Eng. Ind. 35. I. Chem. Catal. Prog. 28. 2001 Revised manuscript received November 26. 2121. (11) Golombok.1424 Ind. Res. M. 15 (4). C. Zhagfarov. ethylene. methane.. Catalytic Steam Cracking of n-Heptane with Special Reference to the Effect of Calcined Dolomites. and propylene. B. W. Chem... 41. Adelson. Thermal and ¨ ¨ Catalytic Cracking of n-Heptane in the Presence of CaO.. Lal. P. Bertolacini.. F. L. R. 1413. 146.. 1093. Green. A New Catalytic Cracking Process. P.. are increased over packed inert materials in steam cracking of naphtha. J. Ind. Catalytic Pyrolysis of Naphtha on Calcium Aluminate Catalysts. P.

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