General Coal Enthalpy Model The general coal model for computing enthalpy in the Aspen Physical Property System is HCOALGEN. This model includes a number of different correlations for the following: + Heat of combustion + Heat of formation + Heat capacity You can select one of these correlations using an option code in the Methods | NC-Props form. (See Forms for Specifying Component Information in the help for the Properties Environment). Use option codes to specify a calculation method for properties. Each element in the option code vector is used in the calculation of a different property. ‘The table labeled HCOALGEN Option Codes (below) lists model option codes for HCOALGEN. The table is followed by a detailed description of the calculations used for each correlation. The correlations are described in the following section. The component attributes are defined Component Attributes in the help for the Properties Environment. About Note: The correlations used here may generate slightly different enthalpy for water are compared with steam tables or other methods typically used when water is in the MIXED substream. Small temperature differences may result when water is extracted from coal. Heat of Combustion Correlations The heat of combustion of coal in the HCOALGEN model is a gross calorific value. It is expressed in Btu/Ib of coal on a dry mineral-matter-free basis. ASTM Standard D5865-07a defines standard conditions for measuring gross calorific value. (Earlier ASTM Standard D-2015 used the same conditions.) Initial oxygen pressure is 20 to 40 atmospheres, Products are in the form of ash; liquid water; and gaseous CO,, SO, and NO, You can calculate net calorific value from gross calorific value by making a deduction for the latent heat of vaporization of water. Heat of combustion values are converted back to a dry, mineral-matter-containing basis with a correction for the heat of combustion of pyrite. The formula is: Adi = 1 — wns + 5400p The heat of combustion correlations were evaluated by the Institute of Gas Technology (IGT). They used data for 121 samples of coal from the Penn State Data Base (IGT, 1976) and 457 samples from a USGS report (Swanson, et al., 1976). These samples included a wide range of United States coal fields. The constant terms in the HCOALGEN correlations are bias corrections obtained from the IGT study. Boie Correlation: aim =| awe + anf + ashi + ays Parameter Name/Element Symbol Default BOIEC/1 ay 151.2 BOIEC/2 a) 499.77 BOIEC/3 5; 45.0BOIEC/4 ay -47.7 BOIEC/S ay, 27.0 BOTEC/6 25) Dulong Correlation: Ah =| ay 92% + ayo", + 2308" + ayeG + asw 9 |10? + asy Parameter Name/Element Symbol Default DLNGC/1 ay 145.44 DLNGC/2 a2; 620.28 DLNGC/3 a3, 40.5 DLNGC/4 4; -77.54 DLNGC/S as) -16.0 Grummel and Davis Correlation: ( 1+ anf) aaim= (art + arin + asn 4 + axsn6it)10” + a6; (-*d) Parameter Name/Element Symbol Default GMLDC/1 ax 0.3333 GMLDC/2 a2 654.3 GMLDC/3 a3; 0.125 GMLDC/4 as 0.125 GMLDC/S a5; 424.62 GMLDC/6 ag; -2.0 Mott and Spooner Correlation: ane aw" + awh" + 230% — ay" | 10? + ayy for wE% < 0.15 Ahi” =| ay wO" + anw" + a3w¥" -| ag. ay, for w8 < 0.15 meter Name/Element _ Symbol MTSPC/1 ay MTSPC/2 23) MTSPC/3 as;MTSPC/4 au 62.45 MTSPC/S 25 30.96 MTSPC/6 26 65.88 MTSPC/7 ay, -47.0 IGT Correlation: Ah =[ ay wd ,+ anwf , + a3,wG + ay ,|10? + asy Parameter Name/Element Symbol Default cIGTC/1 ay 178.11 cigTc/2 a3, 620,31 cIGTC/3 a3, 80.93 cieTc/4 au; 44.95 cIGTC/5 as, -5153.0 Revised IGT Correlation (Perry's, 7th ed., equation 27-7) aim _| d d d d 2. Adi =[aywd ,+ armed, + agw + aywd ,+ a5(w8 +08 jo Parameter Name/Element Symbol Default c1GT2/1 ay 146.58 c1GT2/2 22; 568.78 c1GT2/3 a3, 29.4 ciGT2/4 4; -6.58 c1GT2/5 as; -51.53 User Input Value of Heat Combustion Parameter Name/Element Symbol Default HCOMB Ang 0 Standard Heat of Formation Correlations ‘There are two standard heat of formation correlations for the HCOALGEN model: + Heat of combustion-based + Direct Heat of Combustion-Based Correlation: This is based on the assumption that combustion results in complete oxidation of all elements except sulfatic sulfur and ash, which are considered inert. Thenumerical coefficients are combinations of stoichiometric coefficients and heat of formation for CO,, H,0, HCI, and NO, at 298.15K: afi f= Ado - 1418 105 wf , + 3.278 x 10° wd , + 9.264 « 104 WE, = 2.418 x 104 WG j- 1.426 x 104 wg, 10? For example, the complete oxidation of hydrogen is based on the reaction #Xe) * 0.50{g) ~ #2010), since the stable phase of water at 298.15 K is Nauid, the heat of vaporization at 298.15 K is needed in the conversion. The numerical coefficient of “.! is calculated by 8.15, ~ MARS i ation(H20)) MVE) The complete oxidation of carbon is based on the reaction © * 9X€) > COA), and the numerical (assess (CO) coefficient of wes is calculated by: MWC) ‘The complete oxidation of sulfur (pyritic and organic sulfur) is based on the reaction (axzideaitgs (60) 5+ O48) ~ S02), and the numerical coefficient of WS. js calculated by: MIMS) ‘The complete oxidation of nitrogen is based on the reaction V+ 0X2) ~ NOX), and the numerical : sie) coefficient of "V.t is calculated by: MW) The complete oxidation of chlorine is based on the reaction ©!X8) + #20()) — 2HCI(g) + 0.5 * OXg), : (2anSes (4c - aH, (H120)) and the numerical coefficient of “C/.t is calculated by MIV(Cly) Direct Correlation: The heat of formation of coal is normally small, relative to its heat of combustion. An error of 1% in the heat of combustion produces about a 50% error when it is used to calculate the heat of formation. For this reason, the following direct correlation was developed, using data from the Penn State Data Base. It has a standard deviation of 112.5 Btu/Ib, which is close to the limit, due to measurement in the heat of combustion: Apr? =| ay Zt + anf + aspofh , + ayaw¥, + aspv¥|10? sags [arkwd + whe.) + axoety 1 f + euler wfe,) + orf) 10 4 afm) + aro(t) P+ aya wibe i) (Wels whe.) 104 + a, +ai34Ro,3 Where R,, is reflectance, specified as element 1 of component attribute COALMISC, and: Parameter Name/Element Symbol DefaultHFC/1 ay 1810.123 HFC/2 22, -502.222 HFC/3 a5; 329.1087 HFC/4 24; 121.766 HFC/S as; 542,393 HFC/6 a; 1601.573 HFC/7 a7 424.25 HFC/8 En -525,199 HFC/9 a5; -11,4805 HFC/10 10; 31.585 HFC/11 a 13,5256 HFC/12, ayy 15 HFC/13 any -685.846 HEC/14 aw -22.494 HFC/15 a5) -64836.19 Heat Capacity Kirov Correlations The Kirov correlation (1965) considered coal to be a mixture of moisture, ash, fixed carbon, and primary and secondary volatile matter, Secondary volatile matter is any volatile matter up to 10% on a dry, ash-free basis; the remaining volatile matter is primary. The correlation developed by Kirov treats the heat capacity as a weighted sum of the heat capacities of the constituents: i ‘Component index i = Constituent index j = 1,2, ...,nen Where the values of j represent: 1 Moisture 2 Fixed carbon 3 Primary volatile matter 4 Secondary volatile matter 5 Ash Wy = Mass fraction of jth constituent on dry basis This correlation calculates heat capacity in cal/gram-C using temperature in C. The parameters must be specified in appropriate units for this conversion. Ps meter Name/Element Symbol DefaultcCPIC/1 a CP1C/2 cPic/3 aia cPic/4 cPic/s cP1c/6 cPic/7 cPic/s cPic/a cPic/i0 cpic/it cic/i2 cic/13 cPIC/i4 CPIC/15 43 cPic/i6 a4 CP1C/17 cPic/i8 cPic/19 a3 cP1C/20 aise Cubic Temperature Equation The cubic temperature equation is: d_ 2 3 p= ay ant + age + agit Parameter Name/Element _Symbol cp2c/1 ay cp2c/2 ay cp2c/3 a5, cp2c/4 a 1.0 Default 0.438 -7.576 x 10-3 8.793 x 10-5 -2.587 x 10-7 ‘The default values of the parameters were developed by Gomez, Gayle, and Taylor (1965). They used selected data from three lignites and a subbituminous B coal, over a temperature range from 32.7 to 176.8°C. This correlation calculates heat capacity in cal/gram-C using temperature in C, The parameters must be specified in appropriate units for this conversion.HCOALGEN Option Codes Option Option Calculation Parameter Component Code Code Method Names Attributes Number _Valuet 1 Heat of Combustion 1 Boie BOIEC ULTANAL correlation SULFANAL PROXANAL 2 Dutong DLNGC ULTANAL correlation SULFANAL PROXANAL 3 Grummel and GMLDC ULTANAL Davis SULFANAL correlat PROXANAL 4 Mott and MTSPC ULTANAL Spooner SULFANAL correlation PROXANAL 5 IGT ciGTc ULTANAL correlation PROXANAL 6 User input HCOMB ULTANAL value PROXANAL 7 Revised IGT CIGT2 ULTANAL correla PROXANAL Option Option Calculation Parameter Component Code Code Method Names Attributes Number Value! 2 Standard Heat of Formation 1 Heat-of- - ULTANAL combustion- SULFANAL based correlation 2 Direct HFC ULTANAL correlation SULFANAL PROXANAL COALMISC Option Option Calculation Parameter Component Code Code Method Names Attributes Number _Valuet 3 Heat Capaci 1 Kirov cpic PROXANAL correlation 2 Cubic cp2c =temperature equation Option Option Calculation Parameter Component Code Code Method Names Attributes Number Value’ 4 Enthalpy Basis 1 Elements in — - their standard — - states at 298.15K and 1 atm 2 Component at — - 298.15 K * Default = 1 for each option code Older Enthalpy Models Three other versions of the correlation also exist. HCJ1BOIE is similar to HCOALGEN with the first, second, and fourth option codes set to 1. That is, it always uses the Boie correlation for heat of combustion, the heat-of-combustion-based heat of formation correlation, and elements as enthalpy basis. The option code of HCJ1BOIE is equivalent to the third option code of HCOALGEN, selecting the heat capacity equation. HCOAL-R8 and HBOIE-R8 are old versions of HCOALGEN and HCJ1BOIE, respectively. They do not perform the dry/wet basis conversions correctly, They are preserved for upward compatibility only and are not recommended for use in any new simulations. References Gomez, M., J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965, IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data Book, Section PMa. 44.1, 1976. Kirov, N.Y., "Specific Heats and Total Heat Contents of Coals and Related Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965), pp. 29, 33. Swanson, V.E. et al., Collection, Chemical Analysis and Evaluation of Coal Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76-468. R. H. Perry and D. W. Green, eds., Perry's Chemical Engineers" Handbook, 7th ed., McGraw-Hill (1997), p. 27-5.