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00221 Low temperature enhanced distillate fuels
02 Liquidfuels (derived liquidfuels) Hydrogen transfer reactions in solvent augmented 99/99219 coal llquafactlon Harrison, G. and Ross, A. B. Fuel, 1998, 77, (13) 1421-1425. Samples of Point of Ayr (POA) coal were dissolved in a solvent mixture of either hydrogenated tyre pyrolysis oil (HTPO) and HA0 or tyre pyrolysis oil (TPO) and hvdronenated anthracene oil (HAO). The addition of TPO caused ab ‘appaient deduction in percentage dissolution and introduced coking problems even at relatively moderate conditions. Analysis of the coal liquids by isotopic mass balance suggested the values of actual percentage dissolution calculated by ash balance were corrupted by coking of TPO. When a catalyst activated coal, produced by depositing-iron sulphide on POA coal, was used with TPO under various hydrogen overpressures, coking was reduced, with dissolution increasing with increasing hydrogen overpressure. Samples of HTPO were produced by hydrogenating TPO in either a spinninglfalling basket autoclave or a trickle bed reactor. The IITPO samples produced from the trickle bed reactor generally were not as effective in dissolving POA coal due to overproduction of saturates; however. the HTPO samoles from the autoclave contained a hieher proportion of >45O”C boiling point material, indicating underhydrog&ation of the TPO feed. Addition of HTPO from the autoclave caused coal dissolution to increase with increasing HTPO content and no coking was observed. Measurements of H-donor contents by a chemical test procedure using sulfur as a hydrogen acceptor, suggested that the increase was probably the result of the introduction of compounds more active towards initiating cleavage of bonds between aromatic centres, rather than differences in the total H-donor contents.
The lnveatlgatlon 99/00219 a plied to the dechlorlnatlon pPaatica
of the gas quench-method of oil recovered from waste
Miura, Y. er al. Hifachi Zosen Giho, 1998, 59, (l), 58-62. (In Japanese) The presence of polyvinyl chloride (PVC) in the liquefaction of waste plastics is undesirable because of the formation of Clz and HCI gases during thermal cracking. These gases in turn react with other organic compounds produced by the cracking of waste plastics and produce organic chlorides, i.e. impurities in the recovered oil. Then it produces HCI gas when the recovered oil is used as fuel oil. Therefore it is best to remove the Clz and HCI eases from the vaoour of the oreanic comoounds oroduced from waste plastics. We investigited two metgods to riduce the contamination of organic chlorides in the oil recovered from waste plastics. (1) Ca(OH)z reagent is supplied into the reactor vessel directly. (2) Vapours produced from waste plastics are quenched quickly by being sprayed cool water. In this paper the characteristics of these methods for repressionof organic
chloridesare compared. Llquefactlon of Yanzhou coal and TG analyala of 99lOO220 the heavy products Cui, H. et al. Proc. Annu. In?. Pirfsburgh Coal Conf.. 1997, 14, (18) 34-41. At 375-425”C and 7 MPa H, a Chinese bituminous coal, Yanzhou of Shandong province, was liquefied without a solvent. Heavy liquefaction products, a portion of toluene and trichloroenthylene solubles, were studied by thermogravimetric technique. Under most conditions, the overall liquefaction conversions increased by 100% when 1 wt% of the catalyst was added. The yields to toluene solubles were similar to that of trichloroethylene solubles. The heavy toluene solubles were subjected to TG/DTG analysis, and compared with petroleum derived highway asphalts and with a coal tar pitch. The results show that there is a big similarity between the TG patterns for the heavy toluene solubles and petroleum derived highway asphalts, but that there is a significant difference to those for coal tar pitch.
99IW221
Low temperature enhanced dlatlllate fuels
Chandler. J. E. U.S. US 5.755.834 (Cl. 44-386; ClOL1/18), 26 Mav 1998. US Appl. 608,991, 6 Mar 1996; 7‘ pp. Cont. of US Ser. No.608,991, abandoned. A method of enhancing the low temperature flow properties of fuels is described, comprising adding to the fuel a heated additive concentrate comprising: (A) at least one nitrogen-containing derivative of carboxylic acid, (B) an organic acid, and (C) at least one other flow improver, wherein the concentrate is heated to at least -35”.
Manufacture 99/00222 pyrolyala plant
blo-oils
from
wood
In
a
flash
Meier, D. et al. DGMK Tagungsber. 1998, 9802, 83-90. (In German) Wood chios were ovrolvsed at 475” in a continuously working fludized bed for flash pyrolysis’with.gas residence times of 1.2s. -The oil fraction of the pyrolysate was 70%, while gas and char held 15% each. The resulting oils were characterized by standard analysis methods. The thermal use as well as the use as raw material for chemical is discussed for the oils from flashpyrolysis of biomass.
Manufacture method of petroleum coke slurry 99/00223 Okada, K.er al. Jpn. Kokai Tokkyo Koho JI) 10 121,066 [98 121,066] (Cl. ClOL1/32), 12 May 1998, Appl. 96/281,075,23 Ott 1996; 8 pp. (In Japanese) For the manufacture of petroleum coke slurry for partial-oxidation gasification in a gasifier is a method which comprises mixing petroleum coke with 3-20 weight parts of inorganic minerals versus 1 weight part of ash content in the petroleum coke, by using fly ashes and their mp depressants of CaO and Fe ores. The Fe ores containing Fez03 as main
22
Fuel and Energy Abstracts
January 1999
component are obtained from the wastes discharged from the flotation refining of Cu. By pre-mixing water with bentonite to form expanded bentonite, adding the Fe ores after gelling for precipitation, prevention, and stirring-mixing to obtain low-viscosity Fe ore slurry, Fe ore slurry can be prepared.
99400224 Microscopic investigation of carbonaceous substances formed in coal llquefactlon reactors Okada, Y. et al. Nippon Enerugi Gakkaishi, 1998, 77, (5), 410-422. (In Japanese) Attention was given to coal particles and coal-derived particles that arc Hated and/or carbonized in the liquefaction reactors for the purpose of revealing the progress of coal liquefaction at the reaction fields, and tried an evaluation using microscopic technique. On the basis of microscopic textures and optical properties, carbonaceous substances in withdrawing from reactor bottom could be classified into five categories that include vitroplast, non-plastic and partially plastic coal particle, mesophase/ anisotropic semicoke, pyrolytic carbon like material and vitrinite remnant, and we clarified its microscopic compositions. Furthermore, the effects of operating conditions on the properties of carbonaceous substances from the principally reflectance of non-plastic coal particle were researched. Consequently, when the severity of operating conditions was raised, the properties of carbonaceous substances indicated that carbonization was superior to Hation under the atmosphere of initial liquefaction stage. As the reaction proceeds, Hation became predominant over carbonization. At high concentration coal/solvent slurry, it was confirmed that H availability tended to reduce for coal particles. However, this problem could be cleared by improvement in H donor ability of recycle solvent.
99iW225 A new process for catalytic llquefication of lowrank coal ualng dlaperaed Moss catalyst generated In-aifu with added HsO Song, C. et al. Proc. Annu. Int. Pittsburgh Coal Conf., 1997, 14, (8), 46-70. The effect of water in solvent-mediated runs was examined in addition to ‘dry’ tests, and a temperature-programmed liquefaction procedure was explored to take advantage of the synergetic effect between water and dispersed MO catalyst precursor at low temperatures for more efficient coal conversion. It was found that reaction using A’ITM with added water at 350°C followed by water removal and subsequent reaction at 400°C gave good coal conversion and oil yield. To understand the effect of water, model reactions of dinaphthyl ether, abbreviated as DNE, were also carried out using ATTM in the absence and presence of water. DNE conversion at 350°C was significantly enhanced by the addition of water to ATTM in the model reactions. The combination of one-step and two-step model tests revealed that at low temperature of 350°C the main role of water is to promote the formation of highly active MO sulfide catalyst. The liquefaction results coupled with model tests suggest that the presence of water results in substantially higher activity of the in-&u generated MO& catalyst for coal conversion at 350°C. Temperature-programming may be an effective strategy for developing a better liquefaction process using dispersed catalysts.
99100226 Process and plant for the production of methanol from a hydrocarbon feed Early, S. R. ef al. Eur. Pat. Appl. EP 849,245 (Cl. CO7C29/151), 24 Jun 1998, Appl. 96/309,421, 20 Dee 1996; 16 pp. For the production of methanol from a hydrocarbon feedstock a process comprises: (a) contacting a vapourous mixture of a hydrocarbon and steam in a steam-reforming zone with a catalyst effective for catalysis of at least one reforming reaction; (b) recovering from the reforming zone a synthesis gas mixture comprising carbon oxides and hydrogen; (c) supplying the synthesis gas mixture to a methanol synthesis zone charged with a methanol synthesis catalyst and maintained under methanol synthesis conditions; (d) recovering from the methanol synthesis zone a product gas mixture comprising methanol, carbon oxides and hydrogen; (e) supplying the product gas mixture to a methanol recovery zone maintained under methanol recovery conditions; (f) recovering from the methanol recovery zone a crude methanol product stream and a vaporous stream comprising carbon oxides and hydrogen; (g) separating the vaporous stream of step (f) into a first hydrogen-rich stream and a second carbon oxide-rich stream; (h) supplying the first hydrogen-rich stream to the steam-reforming zone as fuel; and (i) recycling the second carbon oxide-rich stream to the steamreforming zone to form part of the mixture of step (a).
99iOO227 Results of the demonatratlon experiment hydrogenation of pyrolysis oils from blomaaaea
for
Kaiser, M. DGMK Tagungsber., 1998, 9802, 359-366. (In German) In an IGOR aooaratus desiened for liouid ohase hvdroeenation of coals. the hydrogenat& of oils fro’m biomass& to;k place and-the experimental conditions, yields, and product qualities are reported. The bio-oils have a high water content as well as a high oxygen content of the anhydrous oil. The IGOR Process was able to produce oils suitable for heatina and as motor gasoline. The composition of the products can be optimized by recycling the intermediate products and by changing the process parameters, particularly the temperature of the condenser.
The lnveatlgatlon 99/00219 a plied to the dechlorlnatlon pPaatica
of the gas quench-method of oil recovered from waste
Miura, Y. er al. Hifachi Zosen Giho, 1998, 59, (l), 58-62. (In Japanese) The presence of polyvinyl chloride (PVC) in the liquefaction of waste plastics is undesirable because of the formation of Clz and HCI gases during thermal cracking. These gases in turn react with other organic compounds produced by the cracking of waste plastics and produce organic chlorides, i.e. impurities in the recovered oil. Then it produces HCI gas when the recovered oil is used as fuel oil. Therefore it is best to remove the Clz and HCI eases from the vaoour of the oreanic comoounds oroduced from waste plastics. We investigited two metgods to riduce the contamination of organic chlorides in the oil recovered from waste plastics. (1) Ca(OH)z reagent is supplied into the reactor vessel directly. (2) Vapours produced from waste plastics are quenched quickly by being sprayed cool water. In this paper the characteristics of these methods for repressionof organic
chloridesare compared. Llquefactlon of Yanzhou coal and TG analyala of 99lOO220 the heavy products Cui, H. et al. Proc. Annu. In?. Pirfsburgh Coal Conf.. 1997, 14, (18) 34-41. At 375-425”C and 7 MPa H, a Chinese bituminous coal, Yanzhou of Shandong province, was liquefied without a solvent. Heavy liquefaction products, a portion of toluene and trichloroenthylene solubles, were studied by thermogravimetric technique. Under most conditions, the overall liquefaction conversions increased by 100% when 1 wt% of the catalyst was added. The yields to toluene solubles were similar to that of trichloroethylene solubles. The heavy toluene solubles were subjected to TG/DTG analysis, and compared with petroleum derived highway asphalts and with a coal tar pitch. The results show that there is a big similarity between the TG patterns for the heavy toluene solubles and petroleum derived highway asphalts, but that there is a significant difference to those for coal tar pitch.
99IW221
Low temperature enhanced dlatlllate fuels
Chandler. J. E. U.S. US 5.755.834 (Cl. 44-386; ClOL1/18), 26 Mav 1998. US Appl. 608,991, 6 Mar 1996; 7‘ pp. Cont. of US Ser. No.608,991, abandoned. A method of enhancing the low temperature flow properties of fuels is described, comprising adding to the fuel a heated additive concentrate comprising: (A) at least one nitrogen-containing derivative of carboxylic acid, (B) an organic acid, and (C) at least one other flow improver, wherein the concentrate is heated to at least -35”.
Manufacture 99/00222 pyrolyala plant
blo-oils
from
wood
In
a
flash
Meier, D. et al. DGMK Tagungsber. 1998, 9802, 83-90. (In German) Wood chios were ovrolvsed at 475” in a continuously working fludized bed for flash pyrolysis’with.gas residence times of 1.2s. -The oil fraction of the pyrolysate was 70%, while gas and char held 15% each. The resulting oils were characterized by standard analysis methods. The thermal use as well as the use as raw material for chemical is discussed for the oils from flashpyrolysis of biomass.
Manufacture method of petroleum coke slurry 99/00223 Okada, K.er al. Jpn. Kokai Tokkyo Koho JI) 10 121,066 [98 121,066] (Cl. ClOL1/32), 12 May 1998, Appl. 96/281,075,23 Ott 1996; 8 pp. (In Japanese) For the manufacture of petroleum coke slurry for partial-oxidation gasification in a gasifier is a method which comprises mixing petroleum coke with 3-20 weight parts of inorganic minerals versus 1 weight part of ash content in the petroleum coke, by using fly ashes and their mp depressants of CaO and Fe ores. The Fe ores containing Fez03 as main
22
Fuel and Energy Abstracts
January 1999
component are obtained from the wastes discharged from the flotation refining of Cu. By pre-mixing water with bentonite to form expanded bentonite, adding the Fe ores after gelling for precipitation, prevention, and stirring-mixing to obtain low-viscosity Fe ore slurry, Fe ore slurry can be prepared.
99400224 Microscopic investigation of carbonaceous substances formed in coal llquefactlon reactors Okada, Y. et al. Nippon Enerugi Gakkaishi, 1998, 77, (5), 410-422. (In Japanese) Attention was given to coal particles and coal-derived particles that arc Hated and/or carbonized in the liquefaction reactors for the purpose of revealing the progress of coal liquefaction at the reaction fields, and tried an evaluation using microscopic technique. On the basis of microscopic textures and optical properties, carbonaceous substances in withdrawing from reactor bottom could be classified into five categories that include vitroplast, non-plastic and partially plastic coal particle, mesophase/ anisotropic semicoke, pyrolytic carbon like material and vitrinite remnant, and we clarified its microscopic compositions. Furthermore, the effects of operating conditions on the properties of carbonaceous substances from the principally reflectance of non-plastic coal particle were researched. Consequently, when the severity of operating conditions was raised, the properties of carbonaceous substances indicated that carbonization was superior to Hation under the atmosphere of initial liquefaction stage. As the reaction proceeds, Hation became predominant over carbonization. At high concentration coal/solvent slurry, it was confirmed that H availability tended to reduce for coal particles. However, this problem could be cleared by improvement in H donor ability of recycle solvent.
99iW225 A new process for catalytic llquefication of lowrank coal ualng dlaperaed Moss catalyst generated In-aifu with added HsO Song, C. et al. Proc. Annu. Int. Pittsburgh Coal Conf., 1997, 14, (8), 46-70. The effect of water in solvent-mediated runs was examined in addition to ‘dry’ tests, and a temperature-programmed liquefaction procedure was explored to take advantage of the synergetic effect between water and dispersed MO catalyst precursor at low temperatures for more efficient coal conversion. It was found that reaction using A’ITM with added water at 350°C followed by water removal and subsequent reaction at 400°C gave good coal conversion and oil yield. To understand the effect of water, model reactions of dinaphthyl ether, abbreviated as DNE, were also carried out using ATTM in the absence and presence of water. DNE conversion at 350°C was significantly enhanced by the addition of water to ATTM in the model reactions. The combination of one-step and two-step model tests revealed that at low temperature of 350°C the main role of water is to promote the formation of highly active MO sulfide catalyst. The liquefaction results coupled with model tests suggest that the presence of water results in substantially higher activity of the in-&u generated MO& catalyst for coal conversion at 350°C. Temperature-programming may be an effective strategy for developing a better liquefaction process using dispersed catalysts.
99100226 Process and plant for the production of methanol from a hydrocarbon feed Early, S. R. ef al. Eur. Pat. Appl. EP 849,245 (Cl. CO7C29/151), 24 Jun 1998, Appl. 96/309,421, 20 Dee 1996; 16 pp. For the production of methanol from a hydrocarbon feedstock a process comprises: (a) contacting a vapourous mixture of a hydrocarbon and steam in a steam-reforming zone with a catalyst effective for catalysis of at least one reforming reaction; (b) recovering from the reforming zone a synthesis gas mixture comprising carbon oxides and hydrogen; (c) supplying the synthesis gas mixture to a methanol synthesis zone charged with a methanol synthesis catalyst and maintained under methanol synthesis conditions; (d) recovering from the methanol synthesis zone a product gas mixture comprising methanol, carbon oxides and hydrogen; (e) supplying the product gas mixture to a methanol recovery zone maintained under methanol recovery conditions; (f) recovering from the methanol recovery zone a crude methanol product stream and a vaporous stream comprising carbon oxides and hydrogen; (g) separating the vaporous stream of step (f) into a first hydrogen-rich stream and a second carbon oxide-rich stream; (h) supplying the first hydrogen-rich stream to the steam-reforming zone as fuel; and (i) recycling the second carbon oxide-rich stream to the steamreforming zone to form part of the mixture of step (a).
99iOO227 Results of the demonatratlon experiment hydrogenation of pyrolysis oils from blomaaaea
for
Kaiser, M. DGMK Tagungsber., 1998, 9802, 359-366. (In German) In an IGOR aooaratus desiened for liouid ohase hvdroeenation of coals. the hydrogenat& of oils fro’m biomass& to;k place and-the experimental conditions, yields, and product qualities are reported. The bio-oils have a high water content as well as a high oxygen content of the anhydrous oil. The IGOR Process was able to produce oils suitable for heatina and as motor gasoline. The composition of the products can be optimized by recycling the intermediate products and by changing the process parameters, particularly the temperature of the condenser.