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Method of fabricating brown coal briquets with humate conversion to humic acid
02 Liquid fuels (sources, properties,
Derived
solid fuels
Characterization of chars obtained from co03/00505 pyrolysis of coal and petroleum residues Suelves, I. et ul. Energy & Fuels, 2002, 16, (4), 878-886. Co-pyrolysis of coal and petroleum residue has been carried out in a bench scale unit in order to study the influence of the coal nature and the experimental conditions on the characteristics of the char obtained. Two coals of different rank, Samca (sub-bituminous) and Figaredo (bituminous), and a petroleum residue from the Maya crude have been used. Temperatures of 600, 650, and 7OO”C, pressures of 0.1,0.5, and 1 MPa, and mass ratios (Coal/PR) of 70/30 and 50/50 have been studied. A synergistic effect on char yields, which increases as temperature, pressure, and PR/coal ratio increase, is observed for both coals studied. Some relevant char characteristics of sulfur content, reactivity, and coking properties have been analysed in order to detect a final use fol the chars obtained. It is concluded that Samca/PR chars, especially for the 70/30 mixture, could be gasified to produce synthesis gas. Coal/PR ratio higher than 50/50, temperature lower than 7OO”C, and atmospheric pressure should be used in co-pyrolysis with Samca coal, to keep chars reactive enough to be gasified. Figaredo/PR chars, having a low sulfur content, good optical properties, and a lower reactivity could be used as a coke feedstock. 03/00506 Improving form coke briquette strength Plancher, H. et al. Fuel Prowssing Technology, 2002, 79, (2), 83 92. Formcoke technology, which involves briquetting of char, coke and/or raw coals with a binder material, permits the use of a wide range of coals as the feedstock. This technology aims to produce a fuel that possesses properties similar to those of conventional coke. In addition to a high calorific value and fixed carbon content, the major physical requirement is that the formcoke must retain its shape and form during shipping and storage, as well as exposure to heat in a furnace. The major objective of this study was to determine the conditions that could provide high compressive strengths [in excess of 2.8 x 10’ Pa (4000 psi)] for piston formcoke briquettes prepared without air-curing green briquettes in the FMCoke process. The effect of the thermal pretreatment of the binder on compressive strength of briquettes was examined. In addition, novel methods to promote stronger bonds at the binder/culcinute interface were explored. The addition of liquid phase oxidants (for example, hydrogen peroxide, among others) to coal tal binders was examined to promote in situ release of oxygen during curing under an inert environment. This release of oxygen, simulating the presence of air in the curing environment, was expected to promote stronger interfacial bonds between the binder and the calcinute. Modification of the bindericnlcinrrtc interface was also examined In through use of minor quantities of other types of additives. particular, the addition of phosphoric acid to the calcirlute delivered piston briquettes with compressive strength readily exceeding 2.X x IO’ Pa without recourse to air-curing. Curing in air. in fact, led to compressive strengths exceeding 5.5 y 10’ Pa. Manufacture of smokeless fuel from steam coal in 03/00507 the classic coking process Liberacki, J. Kurho. 2002, 47, (4), I3 I-1 34. (In Polish) Alterations during heating coal grained and in the form of lumps in the coking chamber have been discussed and compared. It has been proved that the use of coal lumps in size 20-80 mm instead of coal grained has an essential meaning for profitable running of coking process. It creates a change for obtaining smokeless fuel with high reactivity from coal which coking properties are low. Favourable running of coking process in the conditions of thermal waves moving lies in reversing the direction of the pyrolytic gases flow towards the coal charge due to what the coal lumps are heated more quickly and bitumens going through the temperature zone of the pre-plastic layer are exposed to destruction to a smaller extent. Method of fabricating brown coal briquets with 03/00508 humate conversion to humic acid Petrova, G. I. and Khudyakova, I. G. Russ. RU 2,173,697 (Cl. c‘lOL51 04), 20 Sep 2001, Appl. 99,122.190, 22 Ott 1999. (In Russian) In a method where brown coal is subiected to electrochemical treatment in aq. NaCl solution to form a &al-humate mixture, which is then partially dried and briquetted at 85-95”, the humates are converted into humic acids by treating the coal-humate mixture with hydrochloric acid to pH 4.0-4.5. The compressive strength of the briquets is increased by 10.6-21.8% when humic acids are the binder rather than humates. Milling and mixing animal meal with solid fuels to 03/00509 produce an enriched fuel Marechal, J. M. Fr. Demande FR 2,818,658 (Cl. ClOL9IIO). 2X Jun 2002, Appl. 2000/17,052. 19. (In French)
recovery)
Fuels for cement kilns or boilers comprise petroleum coke, coal, or other solid fuel mixed with animal meal, optionally with other additives, which have been milled together to optimltm grain size and homogenization. The fuels may also be incinerated. 03/00510 Petroleum coke as a supplementary fuel for cyclone boilers: characteristics and test results Tillman, D. Proceedings of’the International Tclchnical Corlference on Coal Utilization & Fuel SJlstem.r, 2002. 1, (27), 489-501. Petroleum coke is periodically tested and used as a supplementary fuel for cyclone boilers. Its high heat content and low cost combine to make it an attractive fuel for power generation. In cyclone boiler firing, it also has environmental advantages. While it is high in sulfur content, it can be used to reduce NO, emissions along with such trace metal emissions as mercury and arsenic. Successful firing of petroleurn coke in cyclone boilers, however, requires considerable attention to fuel properties of the coal and the opportunity fuel including fuel structure and reactivity, and ash chemistries. This paper discusses selected properties of petroleum coke including traditional analyses plus ,>tructural characterization using liC NMR, drop tube reactor characterization for kinetics and volatility evaluation, and thermogravimetrlc analysis (TGA) for char oxidation kinetics. The paper then summarizes results of petroleum coke firing at the Paradise Fossil Plant of TV A, and Bailly Generating Station of Northern Indiana Public Service Company. Results presented include impacts of cofiring or1 boiler efficiency, NO, emissions, and the fate of selected trace metals lmcluding arsenic, mercury, nickel, and vanadium. It documents the overall benefits and issues associated with cofiring petroleum coke with coal in cyclone boilers as a significant opportunity fuel. 03/00511 Production research and pilot-plant operation of coke breeze briquette Liu, B. Mei Humgong, 2002, (l), 22 25. (In Chinese) The article introduces production research, pilot plant operation and manufacture process of coke breeze briquette made from cheap coke breeze and composite binder. which replace lump (coke used in gas generating furnace. 03/00512 Residua coke formation predictability maps Schabron, J. F. er ul. FM>/,2002, 81, (17). 2227-2240 The dispersed particle solution model of petroleum residua structure was used to develop predictors for pyrolytic coke formation. Coking indexes were developed in prior years that measure how near a pyrolysis system is to coke formation during the coke formation induction period. These have been demonstrated to be universally applicable for residua regardless of the source of the material. Coking onset is coincidental with the destruction of the ordered structure and the formation of a multi-phase system. The amount of coke initially formed appears to be a function of the free solvent volume of the original residua. In the current work, three-dimensional coke make predictability maps were developed at 400, 450 and 500°C for four residua with nominal H/C atomic ratios of 1.4. The maps relate residence time and free solvent volume to the amount of coke formed at a particular pyrolysis temperature. Coke formation reactions can be modelled with zero-order kinetics which occur in two stages. The first stage produces 22.5-27.0 wt% coke with activation energies ranging from 22 000 to 38 000 calimol. The second stage continues the reaction to completion, producing 58.1-63.6 wt% coke with activation energies ranging from 54 000 to 83 000 cal/mol. The activation c.:nergies correlate with the original residua free solvent volumes. The results provide a new tool for ranking residua, gauging proximity to cokeformation, and predicting initial coke make tendencie\.
02
LIQUID Sources,
FUELS
properties,
recovery
03/00513 13C NMR research on the kerogens of Jurassic source rocks of the northern edge of the Qaidam Basin Peng, L. et al. Shi_vozrXuehao, 2002, 23, (2), 34-37. IIn Chinese) The northern edge of the Qaidam Basin is one of the three hydrocarbon bearing areas in the basin. Its source rocks are Early and Middle Jurassic coal measures. The organic matter types of the source rocks are mainly type III, and type 11 Kerogen; the type I1 Fuel and Energy Abstracts
May 2003
137
Derived
solid fuels
Characterization of chars obtained from co03/00505 pyrolysis of coal and petroleum residues Suelves, I. et ul. Energy & Fuels, 2002, 16, (4), 878-886. Co-pyrolysis of coal and petroleum residue has been carried out in a bench scale unit in order to study the influence of the coal nature and the experimental conditions on the characteristics of the char obtained. Two coals of different rank, Samca (sub-bituminous) and Figaredo (bituminous), and a petroleum residue from the Maya crude have been used. Temperatures of 600, 650, and 7OO”C, pressures of 0.1,0.5, and 1 MPa, and mass ratios (Coal/PR) of 70/30 and 50/50 have been studied. A synergistic effect on char yields, which increases as temperature, pressure, and PR/coal ratio increase, is observed for both coals studied. Some relevant char characteristics of sulfur content, reactivity, and coking properties have been analysed in order to detect a final use fol the chars obtained. It is concluded that Samca/PR chars, especially for the 70/30 mixture, could be gasified to produce synthesis gas. Coal/PR ratio higher than 50/50, temperature lower than 7OO”C, and atmospheric pressure should be used in co-pyrolysis with Samca coal, to keep chars reactive enough to be gasified. Figaredo/PR chars, having a low sulfur content, good optical properties, and a lower reactivity could be used as a coke feedstock. 03/00506 Improving form coke briquette strength Plancher, H. et al. Fuel Prowssing Technology, 2002, 79, (2), 83 92. Formcoke technology, which involves briquetting of char, coke and/or raw coals with a binder material, permits the use of a wide range of coals as the feedstock. This technology aims to produce a fuel that possesses properties similar to those of conventional coke. In addition to a high calorific value and fixed carbon content, the major physical requirement is that the formcoke must retain its shape and form during shipping and storage, as well as exposure to heat in a furnace. The major objective of this study was to determine the conditions that could provide high compressive strengths [in excess of 2.8 x 10’ Pa (4000 psi)] for piston formcoke briquettes prepared without air-curing green briquettes in the FMCoke process. The effect of the thermal pretreatment of the binder on compressive strength of briquettes was examined. In addition, novel methods to promote stronger bonds at the binder/culcinute interface were explored. The addition of liquid phase oxidants (for example, hydrogen peroxide, among others) to coal tal binders was examined to promote in situ release of oxygen during curing under an inert environment. This release of oxygen, simulating the presence of air in the curing environment, was expected to promote stronger interfacial bonds between the binder and the calcinute. Modification of the bindericnlcinrrtc interface was also examined In through use of minor quantities of other types of additives. particular, the addition of phosphoric acid to the calcirlute delivered piston briquettes with compressive strength readily exceeding 2.X x IO’ Pa without recourse to air-curing. Curing in air. in fact, led to compressive strengths exceeding 5.5 y 10’ Pa. Manufacture of smokeless fuel from steam coal in 03/00507 the classic coking process Liberacki, J. Kurho. 2002, 47, (4), I3 I-1 34. (In Polish) Alterations during heating coal grained and in the form of lumps in the coking chamber have been discussed and compared. It has been proved that the use of coal lumps in size 20-80 mm instead of coal grained has an essential meaning for profitable running of coking process. It creates a change for obtaining smokeless fuel with high reactivity from coal which coking properties are low. Favourable running of coking process in the conditions of thermal waves moving lies in reversing the direction of the pyrolytic gases flow towards the coal charge due to what the coal lumps are heated more quickly and bitumens going through the temperature zone of the pre-plastic layer are exposed to destruction to a smaller extent. Method of fabricating brown coal briquets with 03/00508 humate conversion to humic acid Petrova, G. I. and Khudyakova, I. G. Russ. RU 2,173,697 (Cl. c‘lOL51 04), 20 Sep 2001, Appl. 99,122.190, 22 Ott 1999. (In Russian) In a method where brown coal is subiected to electrochemical treatment in aq. NaCl solution to form a &al-humate mixture, which is then partially dried and briquetted at 85-95”, the humates are converted into humic acids by treating the coal-humate mixture with hydrochloric acid to pH 4.0-4.5. The compressive strength of the briquets is increased by 10.6-21.8% when humic acids are the binder rather than humates. Milling and mixing animal meal with solid fuels to 03/00509 produce an enriched fuel Marechal, J. M. Fr. Demande FR 2,818,658 (Cl. ClOL9IIO). 2X Jun 2002, Appl. 2000/17,052. 19. (In French)
recovery)
Fuels for cement kilns or boilers comprise petroleum coke, coal, or other solid fuel mixed with animal meal, optionally with other additives, which have been milled together to optimltm grain size and homogenization. The fuels may also be incinerated. 03/00510 Petroleum coke as a supplementary fuel for cyclone boilers: characteristics and test results Tillman, D. Proceedings of’the International Tclchnical Corlference on Coal Utilization & Fuel SJlstem.r, 2002. 1, (27), 489-501. Petroleum coke is periodically tested and used as a supplementary fuel for cyclone boilers. Its high heat content and low cost combine to make it an attractive fuel for power generation. In cyclone boiler firing, it also has environmental advantages. While it is high in sulfur content, it can be used to reduce NO, emissions along with such trace metal emissions as mercury and arsenic. Successful firing of petroleurn coke in cyclone boilers, however, requires considerable attention to fuel properties of the coal and the opportunity fuel including fuel structure and reactivity, and ash chemistries. This paper discusses selected properties of petroleum coke including traditional analyses plus ,>tructural characterization using liC NMR, drop tube reactor characterization for kinetics and volatility evaluation, and thermogravimetrlc analysis (TGA) for char oxidation kinetics. The paper then summarizes results of petroleum coke firing at the Paradise Fossil Plant of TV A, and Bailly Generating Station of Northern Indiana Public Service Company. Results presented include impacts of cofiring or1 boiler efficiency, NO, emissions, and the fate of selected trace metals lmcluding arsenic, mercury, nickel, and vanadium. It documents the overall benefits and issues associated with cofiring petroleum coke with coal in cyclone boilers as a significant opportunity fuel. 03/00511 Production research and pilot-plant operation of coke breeze briquette Liu, B. Mei Humgong, 2002, (l), 22 25. (In Chinese) The article introduces production research, pilot plant operation and manufacture process of coke breeze briquette made from cheap coke breeze and composite binder. which replace lump (coke used in gas generating furnace. 03/00512 Residua coke formation predictability maps Schabron, J. F. er ul. FM>/,2002, 81, (17). 2227-2240 The dispersed particle solution model of petroleum residua structure was used to develop predictors for pyrolytic coke formation. Coking indexes were developed in prior years that measure how near a pyrolysis system is to coke formation during the coke formation induction period. These have been demonstrated to be universally applicable for residua regardless of the source of the material. Coking onset is coincidental with the destruction of the ordered structure and the formation of a multi-phase system. The amount of coke initially formed appears to be a function of the free solvent volume of the original residua. In the current work, three-dimensional coke make predictability maps were developed at 400, 450 and 500°C for four residua with nominal H/C atomic ratios of 1.4. The maps relate residence time and free solvent volume to the amount of coke formed at a particular pyrolysis temperature. Coke formation reactions can be modelled with zero-order kinetics which occur in two stages. The first stage produces 22.5-27.0 wt% coke with activation energies ranging from 22 000 to 38 000 calimol. The second stage continues the reaction to completion, producing 58.1-63.6 wt% coke with activation energies ranging from 54 000 to 83 000 cal/mol. The activation c.:nergies correlate with the original residua free solvent volumes. The results provide a new tool for ranking residua, gauging proximity to cokeformation, and predicting initial coke make tendencie\.
02
LIQUID Sources,
FUELS
properties,
recovery
03/00513 13C NMR research on the kerogens of Jurassic source rocks of the northern edge of the Qaidam Basin Peng, L. et al. Shi_vozrXuehao, 2002, 23, (2), 34-37. IIn Chinese) The northern edge of the Qaidam Basin is one of the three hydrocarbon bearing areas in the basin. Its source rocks are Early and Middle Jurassic coal measures. The organic matter types of the source rocks are mainly type III, and type 11 Kerogen; the type I1 Fuel and Energy Abstracts
May 2003
137