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44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Dicho Stratiev1, Ivelina Shishkova, Petya Dermatova

Lukoil Neftochim Bourgas R&D Department, 8104 Bourgas, Bulgaria, e-mail:

KEY WORDS: Atmospheric resid vacuum distillation, heavy vacuum gas oil, heat

Estimation of heat balance of the vacuum distillation column of atmospheric resid in the Lukoil Neftochim Bourgas identified the reason for a decrease in the heavy vacuum gas oil yield. The hypothesis of a leakage of the heavy vacuum gasoil draw tray was rejected and it was found that the hydraulic resistance in the heavy vacuum gas oil pump around did not allow an increase of its flow rate and taking away the heat required for condensation of heavy vacuum gas oil, contained in atmospheric residue.

Atmospheric residue vacuum distillation process economics is favored by heavy vacuum gas oil (HVGO) yield increase [1]. Therefore, all over the world many designs leading to reconstruction of atmospheric residue vacuum distillation columns in order to increase end boiling point resulting in HVGO yield growth are realized [2,3]. Two vacuum distillation columns for distillation of atmospheric residue produced via crude oil fractionation are included in Lukoil Neftochim Bourgas, Bulgaria crude oil processing scheme. The typical feed of these vacuum columns is atmospheric residue distilled from Ural crude oil (Table I). Within 2006 it has been established that at VD-2 (atmospheric residue vacuum distillation unit - 2) HVGO yield decreases as the unit rate increases. The principle process diagram of VD-2 unit is shown at Figure 1. The vacuum column consists of 4 structural Seltzer packing layers and includes four recycle refluxes, down recycle reflux (DRR); down sharp recycle reflux (DSRR), upper recycle reflux (URR) and upper sharp recycle reflux (USRR). The atmospheric residue is fractionated to light vacuum gas oil (LVGO)(side recovery), heavy vacuum gas oil (HVGO)(side recovery) and vacuum residue, and minimum quantity light diesel fraction (LDF) is drawn out from the column top. VD-2 is wet vacuum column since superheated steam is fed at the bottom to strip entrained lighter hydrocarbons from the vacuum residue. The vacuum column K-101 process parameters and material balance has been recorded as well as produced product physical-chemical parameters have been determined at different rates in order to identify the cause of HVGO yield decrease as the VD-2 rate is increased within April 2006 (Tables II-IV).

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Figure 1 Process diagram of VD-2

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Table I Density and TBP of atmospheric residue, obtained at Ural crude oil distillation (feed for VD-1 and VD-2 units)
Density, d420 TBP distillation range, OC IBP - 380 380-400 400-430 430-470 470-490 490-510 510-540 Over 540 0.934 % recovered 10.30 4.75 8.83 14.59 6.36 4.47 6.48 42.73 % recovered 10.30 15.05 23.88 38.47 44.83 49.30 55.78

Table II VD-2 unit vacuum distillation column process parameters

Parameters Rate, t/h Column K-101 inlet temperature, o C Temperature beneath 1st packing, o C Temperature beneath 2nd packing, o C Temperature beneath 3rd packing, o C Temperature beneath 4th packing, o C Bottom temperature, o C Top temperature, o C URR flow, m3/h USRR flow, m3/h DRR, m3/h DSRR, m3/h LVGO, t/h HVGO flow, m3/h (t/h) LDF, t/h Darken product, m3/h (t/h) URR temperature, o C USRR temperature, o C DRR temperature, o C DSRR temperature, o C Stripping steam quantity, kg/h Top residual pressure, mmHg Residual pressure at column feeding area, mmHg Residual pressure at the bottom, mmHg 13.04.2006 289 386 203 270 359 366 367 84 111 68 102 13 15 167 (135.5) 1,5 73 173 94 285 960 60.8 68.4 98.8 14.04.2006 274 386 196 268 355 368 366 90 114 70 104 13 167 (135.5) 1,5 73 173 94 285 960 47* 52.5* 148* 17.04.2006 282 382 194 257 338 364 364 90 113 70 102 12 167 (135.5) 1,5 7 (6) 73 173 94 285 960

* The residual pressure has been measured by absolute pressure gauge with accuracy of 1 mmHg

It is seen from these data that vacuum residue density at 13.04.2006 is lower (0.95) as compare to typical values of that product (about 1.0). The vacuum residue lower density supposes higher content of HVGO which

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

complies with HVGO lower recovery. When the unit rate has been decreased from 289 t/h to 274 t/h, it is established that HVGO recovery increases that corresponds to the higher density of vacuum residue sampled at lower rate. Obviously, the column rate has effect on the extent of deriving HVGO from vacuum residue. One of the primary suppositions for the HVGO low yield has been that HVGO product collective tray is leaky. Table III VD-2 products density data D420 Vacuum residue HBGO LVGO LDF

13.04.2006 0.9502 0.9136 0.882

14.04.2006 0.9984 0.9096 0.882 0.856

Table IV Distillation data of LVGO, HVGO and LDF sampled at 3.04.2006 Distillation, % v/v IBP 5 10 20 30 40 50 60 70 80 90 95 98 Recover up 3600, % v/v HVGO, ASTM D-1160 254 362 380 394 407 417 432 444 459 474 497 518 LVGO, ASTM D-86 279 291 298 306 315 323 332 340 349 361 LDF, ASTM D-86 147 184 196 219 234 248 261 275 291 308 345 354 363



In order to check this supposition material and heat balances of sections from which LVGO and HVGO are drawn out has been calculated (Tables V and VI).

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Table V Material and heat balance calculations of the LVGO sampling loop 1st packing material balance Vapor quantity at 1st packing inlet Vin Vin = LVGO + USRR + steam + LDF = 15 + 54 + 0.96 + 1.5 = 71.5 t/h (1) Vapor quantity at 1st packing outlet Vout Vout = steam + LDF = 0.96 + 1.5 (2) Liquid quantity leaving 1 packing Lout Lout = USRR 1st packing heat balance LVGO vapor enthalpy 106 kcal/kg* Superheated steam enthalpy 675 kcal/kg LDF enthalpy - 91 kcal/kg* LVGO liquid enthalpy 16.74 kcal/kg* LVGO specific heat capacity 0.5 kcal/kg0C* Inlet heat quantity - Qin Qin = 15 000 106 + 54 000 106 + 960 675 + 1500 91 = 8 098 300 kcal/h (3) Heat quantity released from 1st packing with vapors Qvapour out Qvapour out = 1500 91 + 960 675 = 784 300 kcal/h (4) Heat quantity released with USRR, LVGO and URR - Qliquidout
Qliquidout = 54 000 X 16.74+15000 X16.74 + 95000 X 0.5 X (203-73) = 7 329 825 kcal/h

(5) According the heat balance Qin = Qvapour out + Qliquidout Qvapour out + Qliquidout = 7 329 825 + 784 300 = 8 114 125 kcal/h (6) Difference between total Qvapour out + Qliquidout and Qin is 15 825 kcal/h and 0,19% of Qin. Hence, there is no rupture of the collective tray from which LVGO is drawn out. *Enthalpy and the specific heat capacity values are calculated by the help of software simulator ChemCad and use of the Lee-Kesler model, that is suitable for hydrocarbon systems [4]

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Table VI HVGO and LVGO drawing out loop material and heat balance calculations 3rd packing material balance 3rd packing inlet vapor quantity Vin is:
Vin = HVGO + DSRR + LVGO + steam + LDF = = 135.5 + 9.8 + 15 + + 0.96 + 1.5 = 216.7 = 162.7 t/h.

(7) Vapor quantity, computed by software simulator Chemcad at column feeding rate of 289 t/h atmospheric residue has been 165t/h. The phase equilibrium constants have been computed according to Chao-Seader model [5] The vapor quantity computed by equation 7 and by Chemcad is in good compliance. 3rd packing heat balance LVGO specific heat capacity 0.433 kcal/kg0C* 3rd packing inlet heat - Qin is: Qin = 32.64 X 106 kcal/h (Computed by use of ChemCad simulator)

Heat quantity, released by DRR QHVGO is: QHVGO = 86 400 X 0,433 x (359-94) = 9 913 968 kcal/h (8) Heat quantity, released by URR QLVGO is: QLVGO = 95 000 X 0.500 X (203-73) = 6 175 000 kcal/h (9) Heat quantity, released by LVGO QLVGO is: QLVGOprod = 251 049 kcal/h Heat quantity, released by HVGO QHVGOprod is: QHVGOprod = 17 X 106 kcal/h Total released heat quantity Qout is: Qout = QHVGOprod + QLVGOprod + QLVGO + QHVGO = =17 X 106 + 251 049 + 6 175 000 + 9 913 968 = 33.3 X 106 kcal/h (10) Difference between Qin and Qout, is 0,66.106 kcal/h and is 2%, therefore it is considered as negligible. Hence, the tray from which HVGO is drawn out is not leaky and can not be considered as cause for HVGO low yield. *The specific heat capacity values are calculated by the help of software simulator ChemCad and use of the Lee-Kesler model [3].

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Material and heat balances calculations show complete compliance between calculated and real USRR and DSRR flows. That means that supposition for LVGO and HVGO collective trays rupture is not true. Hence, crux for HVGO low yield and 360oC minus fraction low content in LVGO (up to 360oC distilled 79 -80%) is another. An experiment has been carried out on 14.04.2006 that consists of following: The DSRR quantity has been decreased from 13 to 0 m3/h and hence, DRR quantity increases from 102 to 104 m3/hv i.e. DRO + DSRR total flow decreases from 115 to 104 m3/h. At that H-105 pump pressure along the compressed line increases from 0.9 MPa to 0.95 MPa. That means that along the DRR line resistance exists and impedes DRR flow increase. Another experiment has been carried out on 17.04.2006 that consists of following: The DSRR flow has been increased from 12 to 21 m3/h and at that DRR flow decreases from 102 to 100 m3/h i.e. total flow increases from 112 to 121 m3/h. That once again shows that the reason for impossibility to increase DRR flow is not due to the H-105 pump capacity but to the resistance along DRR line. Because of that reason DRR possesses restricted resource for heat withdrawing out and for condensation of higher HVGO quantities. That is why as the K-101 rate is increased the HVGO drawing out decreases since it is not possible to keep high feed evaporation degree. On 17.04.2006 as the inlet temperature has been increased from 382 to 386oC the packing temperatures increase by about 10oC, HVGO drawing out does not increase but LVGO drawing out increases and vacuum residue drawing out decreases. The LVGO drawing out growth is due to the increase content of high boiling components in this fraction. If the yield of component distilled to 360oC is of 80% order in this fraction the last can not be used as feed for motor diesel fuel with sulfur content of 50 ppm production. It is established from carried out investigations by the research laboratory that among all middle distillate fractions produced from Ural crude oil processing at Lukoil Neftochim Bourgas-AD LVGD from VD is the most difficult to be hydrotreated [6]. That is why the smallest quality fraction worsening makes impossible production of diesel fuel with 50 ppm sulfur content when this fraction is included in the feed for hydrotreatment. The conclusion may be derived from carried out investigation that crux for the unsatisfactory operation of VD-2 K-101 column at high rate is due to the insufficient resource for heat withdrawing out by DRR. This explains why at low rates HVGO drawing out and LVGO quality are satisfactory. It has been established that DRR distribution device is damaged and part of it is broken and partially obstruct the line connecting DRR with distribution device within the VD-2 unit plan overhaul. Obviously because of this cause it has been impossible to increase DRR flow. As the DRR distribution device has been rehabilitated it becomes possible to increase its flow and at parameters of vacuum column shown in Table 1, at column rate of 288 t/h and all other equal conditions the DRR flow has been increase from 102 to 140 m3/h and as a result HVGO quantity increases from 135.5 t/h to 141 t/h.

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

CONCLUSIONS It is established that the narrow point of VD-2 vacuum column K-101 operation at high rate is restricted heat withdrawing by DRR. Because of that reason at high rates of order over 260 t/h the heat that may be withdrawn by DRR is insufficient for condensation of the all 360 -540 oC fraction quantity contained in atmospheric residue. At high rates the operation personnel is forced to keep lower atmospheric residue evaporation degree since otherwise that HVGO part that could not condensate because of restriction for heat withdrawing by DRR and could not be drawn as HVGO product, will be drawn as LVGO and may even be drawn as LDF because of considerable temperatures increase along the column height. This explains low HVGO drawing out and why part of it remains in the vacuum residue. The removal of hydraulic resistance along the DRR line within the plan overhaul allows HVGO drawing out increase of 2%.

REFERENCE 1. S. W. Golden, G. R. Martin, Improve HVGO quality and cutpoint, Hydrocarbon Processing, November, 69 74,1991. 2. N. P. Lieberman, E. T. Lieberman, Design, Installation Pitfalls Appear In Vac Tower Retrofit, Oil&Gas Journal, Aug 26, 57-59, 1991. 3. S. W. Golden, A. W. Sloley, Simple methods solve vacuum column problems using plant data, Oil&Gas Journal, Sept. 14, 74-79, 1992. 4. B. I. Lee, M. G. Kesler, AIChE J.,21,510, 1975. 5. K. C. Chao, J. D. Seader, A General Correlation of Vapor-Liquid Equilibria in Hydrocarbon Mixtures, AIChE Journal, No4,7, 1961. 6. D. Dobrev, D. Stratiev, G. Argirov, T. Tzingov, A. Ivanov, Investigation on middle distillates ultra low hydrodesulphurization at Lukoil Neftochim Bourgas, Oxidation Communication, No3, 668-677, 2007.