02 Liquid fuels (transport, refining, quality, storage)

carbide. Both the iron oxide and carbide catalyst can selectively convert secondary alcohols to ketones and hydrogen. Fe:Os is reduced to FejOa during the conversion of secondary alcohols. Also both iron carbide and oxide catalysts dehydrogenate a primary alcohol. These results plus those of our earlier 14C-tracer studies suggest that dehydration of alcohols to produce olefins makes a minor contribution during Fischer-Tropsch synthesis with an iron catalyst at low and intermediate pressure conditions.

Kinetics of Fischer-Tropsch synthesis 00/01723 catalyst. (II). Model discrimination and parameter

over Fe-Cu-K estimation

Higher alcohol synthesis with Fischer-Tropsch 00/01718 elements Chen, X. Meitcw Zlturrdrrro. 1998. 21. (4). 22-28. (In Chinese)
This paper reviews several types of higher alcohol synthesis catalysts. which contained Fischer-Tropsch elements. All of the Fischer-Tropsch catalysts could produce appreciable quantities of higher alcohols from carbon monoxide hydrogenation under suitable conditions. A homogeneous distribution of the Fisher-Tropsch synthesis sites and the sites that adsorb carbon monoxide associatively was necessary for the formation of higher alcohols, hence, it was thought that the physical distribution of surface active centres were more vital than other factors.

Ma. W. N~rc~,er~rr,e ~r&m iClri/r. Ed 1. 1999. 50. (2). 167~ 173. (In Chinese) For the kinetics models ot Fischer-Tropsch synthesis (FTS) and water gas shift reaction (WGS) obtained in the previou% paper. the model discrimination and parameter estimation were performed on the hasis of kinetrc data measured hy using a fixed hed reactor. The results demonstrate that the best models for fitting the experimental data are the model of FTI which takes into account the effect of olefin readsorption on product distribution and the model of WGI. which is derived by assumption of CO? desorption step as the rate determining \tcp. The requirement of statistic test (F-test) are met hy the final models for FTS and WGS at a YSQ confidence level. The value of kinetic parameters for the final models agreed well with the data reported in literature.

Meeting requirements for automobile fuels in relation 00/01724 to the development of internal combustion engines
Kossowicz, L. ,Vrt//o-(;(~:. IYYY. 55. (I I. i2 41. (In Polish) Improvements in the refining of crude oils results in a better quality of liquid fuels that consume more energy with increased carbon dioxide emission. The hydrocracking and cracking rn the refineries renders the marketed fuels to synthetic furls.

00/01719 Hydrocarbon selectivity model for the gas-solid Fischer-Tropsch synthesis on precipitated iron catalysts
Laan, G. P. Ind. Wp. Chum. &r.. 1999. 38, (4), 1277--l 290. A continuous spinnmg basket reactor was used to study the kinetics of the gas-solid Fischer-Tropsch (FT) synthesis over a commercial Fe-Cu-K-SiO: catalyst. Experimental conditions were altered as follows: reactor prensurc of 0.8-3.2 MPa, Hz/CO feed ratio = 0.5-2.0 and a space velocity of 0.5-2.0 x IO- Nm kg;,\ s- at a constant temperature of 523 K. This paper also proposes a novel product distribution model for linear hydrocarbons. Deviations from conventional Anderson-Schulz-Flory distribution can be quantifiably described with an rr-olefin readsorption product distribution model. From the experimental observations. it was apparent that the following can be predicted from this new model; a relatively high yield of methane, relatively low yield of ethene and both the exponential decrease of the olefin-to-paraffin ratio and the change of the chain growth parameter with chain length. It combines a mechanistic model of olefin readsorption with kinetics of chain growth and termination on the same catalytic sites. The hydrocarbon formation is based on the surface carhide mechanism by CHz insertion. The olefin readsorption rate depends on the chain length because of increasing physisorption strength on the catalyst surface and increasing solubility in FT wax with increasing chain length. In the kinetic model, the interfacial concentrations of reactive olefins near the gas-wax and wax-catalyst surface are used. With optimization of three parameters the olefin readsorption product per experimental product distribution. distribution model proved to predict product selectivities accurately over the entire range of experimental conditions.

00101725 Mossbauer study of precipitated Fischer-Tropsch catalyst

unpromoted

iron

Zhang, Y. Prr~pr. Am. Clrrm SW. D~I, PC,/ C/ww.. 1999. 44, (I ). 100-102. The Mosshauer study results on the content and type of iron phases in COactivated and ayngas-active precipitated unpromoted iron-based FischerTropsch catalysts in a slurry-phase C STR at high conversion levels. Following carbon monoxide activation but hefore the active FischerTropsch reaction. the distribution of iron phases wa\ 04% k-FeiCZ-FclO,: during active Fischer-Tropsch reaction, the \-FciC2 was oxidized to Fe>O,. until no dctectahle carbide phase was ohserved after 4.53 hours onstream. Observation\ were made of a strong correlation hctwcen iron carbide content and Fischer-Tropsch actrvity.

00101726

Natural gas to hydrocarbon

liquids

Wilson, G. R. and Carr, N. L. Inr. .J. N~~r/r~rr~<,rhr>n E/r,e.. IYYX. 3. (4). 43. 45 47. Palladron Publications Ltd. Using the syncrude technological process the Fischer-Tropsch synthesis of high-quality diesel fuel and naphtha from natural gas was described, The procedure involves: the separation of air and autothermal reforming of natural gas to prepare 2.0: I (Hz-CO) synthesis gas. (2) a two-stage F-T reaction rn a slurry huhhle column reactor using promoted cobalt catalysts, and (3) mild wax hydrocraking to recover LPG. naphtha. and middle distillate. l-he system has also heen set up for additional purposes including the co-production trf electric power for plant requirements or for export to outside network\.

00101720

Indirect

coal liquefaction

- where do we stand? 00101727 Novel activation of ColSiO, catalysts alkoxide method for Fischer-Tropsch synthesis prepared by
Okahe. K. Pr~pr. .4111.Chem. So< ., Dil,. PC/. Clmi.. I YYY. 44. (I ). 9%96. Small amounts of noble metals such as rhenium and iridium can be used in the promotion process of silica-supported cobalt catalysts. After the Fischer-Tropsch catalysts have undergone reduction and activation (in HZ at 773 K) they can be used in the production of transportable liquids from remote natural gas fields. The catalysts were prepared hy the alkoxide method. in which Co(NOx): is dissolved in ethylene glycnl. mixed with tetra-Et orthosilicatr and hydrtrlysed to form a glassy gel that was dried and calcincd prior to imprcgnatron with the noble metal. The cxpcrimcntal results indicate that the nohlc mcta-promoted catalysts had turnover frequencies (TOF) that wcrc two-three time\ greater than the TOF of conventional catalysts prepared hy impregnation.

Davis, B. H. Pwpr. - Am. Chcni. sm ., D;IK Per. Chcvn.. 1999. 44. (I ). 20-24. The recent developments in the commercialization of the Fischer-Tropsch synthesis are reviewed. The main emphasis of this paper is the reduction of such as the separation of gas using costs in syngas manufacturing, membranes and in the conversion of remote natural gas feedstocks into pipeline-transportable liquids and upgrading of petroleum residues to fuels and power. The recent announced corporate agreements between petroleum, natural gas, and energy companies; co-operative projects; and novel technology in reactor management and catalyst design are the main topics under discussion.

00/01721 Isotopic Tropsch synthesis

tracer study of the mechanism

for Fischer-

Shi, B. and Davis, B. H. Prep. - Am Chow. Sock., Dir. Per. C /wm, I Y9Y. 44. (I), 106-l IO. This paper provides additional evidence to support the impact of hydrocarbon accumulation in a slurry-phase Fischer-Tropsch (F-T) JC-labelled reactants, typically ethylene and ethanol reactor. In the study, were added to the process and the C was observed as it was incorporated into the chain growth in the F-T reaction. In addition, the role of initiation of chain growth was defined as it is related to the above added reactants. Both alkenes and alkanes in the lower carbon-number fractions exhibited the same constant radioactivityimol. as would be required if both compared classes were formed by a common reaction mechanism. The higher carbonnumber alkenes also exhibited a constant radioactivityimol. whereas the alkanes did not, which was consistent with these products being diluted with alkanes produced prior to the period when the tracer is added. The products formed by the isotopically labelled compound, that act as chain initiators were diluted by the accumulated alkanes.

Processes leading to increase 00/01728 under hydrous pyrolysis conditions

Barth,

of alkyl chain lengths

T. and Hansen. B. G. Prep! .T~orp .4/rr. C/11.111. sot DilV F-d 44. (2). 397 400. The alkyt chain generation in classical hydrous pyrolysis of simple compounds will he presented. Information will also he included on the reproduction of a series of organic acids found in waters in the vicinity of oil and also contribute to the long-chain hydrocarbon compounds that are found in the petroleum phases. A discussion will also he included on the applicability of the Frscher-Trrrpsch mechanism for the polymerization step.

C lmr.. 199 ).

00101729

Product control in Fischer-Tropsch

synthesis

00101722 Kinetics of Fischer-Tropsch synthesis over Fe-Cu-K catalyst. (I). Kinetic model on the basis of mechanism Ma, W. H~rcrxong XIU~UI~ lChOl. Ed.). 1999. 50. (2). I59%166. (in Chinese)
On the basis of the carbide mechanism a kinetics model of Fischer-Tropsch was derived in which the readsorption of olefins was considered. The chain growth factor in the derived models was no longer a constant, hence the new model is ideal for interpreting non-ideal Anderson-Schulz-Flory distribution on an iron-based catalyst.

Tsubaki. N. and Fujimoto, K. I;trc,l. Prw. 7 c~~lmol.. 2000. 63. (2-3). I73 I X6 High quality liquid furls for diesel engine arc normal paraffins with C,,,C2,,. The most promising method to make them from other carbon resources is the Fischer-Tropsch synthesis (F-T) which gives wide range of product distribution. Higher paraffins can he cracked with a conventronal method to diesel fraction while lighter ones cannot. The authors have developed a new F-T process that makes wax products selectively with reduced gaseous products. Efficient transportation of reactants and products to the inside of catalyst hed and pellet. quick heat-transfer and in situ wax extraction from catalyst hy supcrcriticat fluid were accomplished. The procrr\ is operated under supcrcritical conditions of light paraffins and

198

Fuel and Energy Abstracts July 2000

02 Liquid fuels (transport,

refining,

quality,

storage)

in the presence of small amounts assumed to he the seed of carbon promote the wax formation.

of 1-olefins.
chain

The propagation

added I-olefins are of C, monomer to

00101730

Production of fuels from petroleum refining wastes

lower energy requirements. The product from the NCE process never had a solvent with a concentration low enough for the process to he self-sufficient in the solvent, when the flow-sheet contained one product recovery unit. However, with multiple recovery units, self-sufficiency was obtained. It appears that the NCE process is feasible and has many attractive features,
00/01735 Stability and handling of Sasol semi-synthetic jet fuel Roets, P. Proc. Irrt. Cork/: Srrrh. Hur~tll. Liy. FIW/.Y. 6th 1097. 1998, 2. 7X9804. Various methods, employing hydrogen treatment and polymerization can he used to produce jet fuel with very high thermal stability. negligible levels of sulfur and aromatics. In the 1980s research was carried out on both shale- and coal-derived jet fuel and from the results, two drawbacks to the potential commercial use of these fuels were identified. These were the fuel poor lubricity properties and the shrinkage of seals previously wetted s by crude oil-derived fuels. Additional concerns expressed at the time were the fuel additive response and its capacitance, or dielectric constant. when s used in density correlations. In order to produce a more acceptable fuel for use in commercial aircraft operating out of Johanneshurg international airport, Sasol will blend a synthetic jet fuel component with crude oilderived jet fuel to increase the blend aromatic content. The properties of s the synthetic jet fuel component and the semi-synthetic jet fuel blend are discussed in this paper. Finally biocide additive efficacy in the synthetic fuels was detected.

Starzak, M. Pol. PL 174,.572 (Cl. CiOGl/OO), 31 Aug 1998, Appl. 304,548, 2 Aug 1994. 3. (In Polish) Production of fuels from petroleum refining waste residues, hy neutralization of their acid content, using lime and chalk and emulsification of hydrocarbons by using nonionic and/or anionic emulsifiers is examined in this paper. Lime is added as a powder in the presence of ethanolamine and 4S-50% sodium hydroxide solution (at a ratio of 1 : (0.1-3)) (10-300) wt parts/l00 wt parts lime. Chalk is used at a lime/chalk ratio of l:(O.l-3). Then, the emulsifier (l-5% aqueous solution) lo-70 wt parts/l00 wt parts residue is added. Optionally, less than 2000 wt parts fuel oil is added to 100 wt parts residue. The resultant temperature of the fuel is stable and remains the same during storage and transportation. The calorific value is greater than 25 MJikg. and viscosity at 80 is 100 mm-/s.

00/01731

Production of lubricant base oils

Richter, F. Eur. Pat. Appl. EP 921.184 (Cl. CIOMI 11106) 9 Jun 1999, ZA Appl. 1998/9,528, 19 Ott 1998:. 14. The process of lubricant base oil production involves hydrotreating a feedstock comprising a Fischer-Tropsch wax and a petroleum-based waxy distillate. A range of hydrogenated products are produced during this procedure and waxy products can he recovered from them.

00101736 Status and prospects of gas-to-liquids processes

Senden, M. M. G. and Punt, A. D. Pwpr. - .4n1. C/tori. Sot.. Dir. PC,/ Chen1.. 1999, 44. (1). 10-12. The Shell middle distillate synthesis process, which uses the FischerTropsch process in the conversion of natural gas into middle distillate is characterized.

00/01732

Refining and blending of aviation turbine fuels

White, R. D. Drug Chern. Fbosicol, 1999. 22, (I). 143-153. Aviation turbine fuels (jet fuels) are similar to other petroleum products that have a boiling range of 300-550 F. Kerosene and number one grades of fuel oil. gas turbine oil and diesel fuel share many similar physical and chemical properties with jet fuel. The extrapolation of toxicology data on one material should provide information on the other products due to their similarity. Refineries in the USA manufacture jet fuel to meet industry standard specifications. Civilian aircraft primarily use Jet A or Jet A-l fuel as defined by ASTM D 1655. Military aircraft use JP-5 or JP-8 fuel as defined by MIL-T-5624R or MIL-T-83133D respectively. The f.p. and flash point are the principle differences between the finished fuels. Common refinery processes that produce jet fuel include distillation, caustic treatment, hydrocracking and hydrotreating. Each of these refining processes may be the final stage in the production of jet fuel. Occasionally, the blending of two or more of these refinery process streams are required to produce jet fuel that meets the desired specifications. Chemical additives allowed for use in jet fuel are also defined in the product specifications. In order to meet the specific storage or flight condition requirements of the customer, the customer has to put additives into the fuel as opposed to the refinery doing it on production. OOlO1733

OOlO1737 Steady-state and dynamic behavior of the fixed-bed catalytic reactor for Fischer-Tropsch synthesis
Liu, Q. Sh;roir Htrtrgoiig Coo&ig .Yvrviw Xw/xw. I YY9. I?. ( I ). I4 2 1 (In Chinese) A two-dimensional heterogeneous model is used to simulate a FischerTropsch synthesis fixed-bed reactors. The numerical calculation methods of the model equations are also analysed and the method to solve the FischerTropsch synthesis fixed-bed reactor model equations is detected. The purposes of this paper is to assess the steady state and dynamic behaviour of the F-T fixed-bed catalytic reactor. The operation conditions of the reactor steady state hehaviour are investigated. Reactor dynamic behaviour for step changes in the feed temperature. fluid rate and the wall temperature are also studied.

OW01738 The effect of boron on the catalyst reducibility and actlvlty of Co/T102 Fischer-Tropsch catalysts
Li, J. and Coville, N. J. A&. Corrrl.. A. 1999. 181. (I). 201 -208. The techniques DRIFTS, XRD, LRS TGA and a fixed bed flow reactor were used to investigate the effect of boron (as H2BOJ) on the CO hydrogenation ability of Co/TiOz catalysts. The introduction of boron (O.OZlS%) into a 10 wt% CofliOa catalyst decreased the Co30s crystallite size (26-16 nm) in the oxidic catalysts (calcined at 300C) and decreased the uptake of hydrogen (0.35-0.9 mL/g cat) in the reduced catalyst. The presence of boron made the reduction of the Co/TiO: catalyst more difficult. The CO conversion and overall hydrogenation rate decreased with decreasing ease of reducibility and decreasing cobalt dispersion caused by boron. Turnover frequency (approximately 20x IO-? s-- however. ), remained constant throughout and was independent of the extent of reduction and dispersion of the catalysts. This provides further evidence of the structure-insensitivity of supported Co Fischer-Tropsch catalysts. The addition of small amounts of boron (~0.1%) do, however, result in an increase in o less CHI production and an increase in the olefiniparaffin ratio.

Selective production of Cs hydrocarbons from syngas In a dual reactor using Co-Ni/ZrO, and S04*-Er02 catalysts
Malyala, R. V. I/it/. E/IR. Cheni. Rc\.. 1999. 38. (4). 1323-1334. A sulfated zirconia (Sod -/Zr02) solid acid catalyst in a dual fixed-bed microreaction system, was used to modify the product stream from the Fischer-Tropsch (FT) reaction over Co-Ni/ZrO? catalyst. Although the operating conditions for the first reactor containing the FT catalyst was fixed at 523 K and I atm, the effects of operating variables, such as a second *-/ZrO, catalyst ratio. and weight reactor temperature. the Co-Ni/ZrOz:S04 hourly space velocity (WHSV) on the steady-state-product distribution were analysed. A high selectivity (33 wt%) to total CJ hydrocarbons was achieved when the second reactor was operated at 423 K. with a catalyst ratio of l:l.5 and at a WHSV of 15 hh in comparison . to a maximum selectivity of 14 wt% obtained using a single reactor with a Co-NiiZrOz catalyst, this selectivity was substantially higher. Catalyst characterization using temperature-programmed desorption of NH3 and H-MAS NMR demonstrated that this high selectivity toward total Cq hydrocarbons was a result of catalyst. However, the rapid catalyst the strong acidity of the SO 4*-/ZrOa deactivation was attributed to coke deposition on the SOn--lZrOl catalyst. External and intraparticle mass transfer effects were negligible under these experimental conditions. Based on the product distribution in a dualreaction system, a reaction pathway was proposed. 00101734

OOlO1739 The influence of conveying distance on low velocity pneumatic conveying of fly ash
Agarwal, V. K. Powder Hand. Prow.u. 1999. Ii. (I). 57-60. In order to convey fly ash through a 130 metres long pipeline over a wide variety of conveying conditions, an extensive experimental investigation was performed. A pressure minimum point emerged at very low conveying velocities. The full hatch of material could not be conveyed through the pipeline at these velocities. An analysis of the low velocity results for the conveying of the fly ash is included to illustrate the relationships obtained, and to demonstrate that the optimum conveying air velocity is not always the lowest achievable velocity with fly ash.

Separation of Fischer-Tropsch wax from Catalyst using near-critical fluid extraction: Analysis of process feasibility
Biales, J. M. Oier,er F~ l,cl.v.1999. 13. (3). 667-677. An analysis of the technical feasibility of a near-critical fluid extraction (NCE) process for the recovery of heavy normal paraffins from a FischerTropsch slurry reactor. Process simulations were performed using the ASPEN PLUS program, considering 100 individual compounds from CL to n-hexane, n-heptane, and n-octane C,,,,,. Four light solvents: n-pentane, were evaluated. These four compounds are major products of the F-T reaction. Most of the analysis was concentrated in two regions: (1) high solvent/product ratios (ca. 20/l), such that product could he recovered by temperature-retrograde condensation; and, (2) low solvent/product ratios (approximately 311). The latter region appeared to require higher extraction but had several attractive temperatures and higher slurry flow-rates, features such as lower vapour flow-rates. lower solvent makeup rates and

OWO1740 Thermodynamic analysis of phase states of products of Fischer-Tropsch synthesis

Ermakova, A. Z/i. Prikl. Khim. l.S.-P~~t~rhr,~). 1998. 71, (I I). 1776-1782 (In RussiaN) The phase transition states of Fischer-Tropsch synthesis products are thermodynamically analysed in this paper. The Redlich-Kwong-Soave equation of state is used for the basis of the study. It is used to calculate the Gibbs energy, entropy and enthalpy of phase transitions. which are necessary for designing the reactor.

Fuel and Energy Abstracts

July 2000

199