You are on page 1of 21

Chemical Product and Process

Modeling
Volume 6, Issue 2

2011

Article 3

CAPE FORUM 2011

Modelling and Optimization of Crude Oil
Hydrotreating Process in Trickle Bed Reactor:
Energy Consumption and Recovery Issues
Aysar T. Jarullah, University of Bradford
Iqbal M. Mujtaba, University of Bradford
Alastair S. Wood, University of Bradford

Recommended Citation:
Jarullah, Aysar T.; Mujtaba, Iqbal M.; and Wood, Alastair S. (2011) "Modelling and
Optimization of Crude Oil Hydrotreating Process in Trickle Bed Reactor: Energy Consumption
and Recovery Issues," Chemical Product and Process Modeling: Vol. 6: Iss. 2, Article 3.
DOI: 10.2202/1934-2659.1600

Brought to you by | Hemeroteca de Estudios Económicos - Banco de la República
Authenticated
Download Date | 4/19/15 6:11 PM

Modelling and Optimization of Crude Oil
Hydrotreating Process in Trickle Bed Reactor:
Energy Consumption and Recovery Issues
Aysar T. Jarullah, Iqbal M. Mujtaba, and Alastair S. Wood

Abstract
Energy consumption is a very important consideration for reducing environmental impact and
maximizing the profitability of operations. Since high temperatures are employed in hydrotreating
(HDT) processes, hot effluents can be used to heat other cold process streams. The aim of the
present paper is to describe and analyze the heat integration (during hydrotreating of crude oil in
trickle bed reactor) of a hydrotreating plant’s process based upon experimental work.
In this work, crude oil is hydrotreated upon a commercial cobalt-molybdenum on alumina
catalyst presulfided at specified conditions. Detailed pilot plant experiments are conducted in a
continuous flow isothermal trickle bed reactor (TBR) in which the main hydrotreating reactions,
are hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs)
and hydrodemetallization (HDM). The latter includes hydrodevanadization (HDV) and
hydrodenickelation (HDNi). The reaction temperature, the hydrogen pressure, and the liquid
hourly space velocity (LHSV) are varied within certain ranges, with constant hydrogen to oil ratio
(H2/Oil).
Experimental information obtained from a pilot plant, together with kinetics and reactor
modeling tools,and a commercial process data are employed for heat integration process model.
The optimization problem to minimize the overall annual cost is formulated as a Non-Linear
Programming (NLP) problem, which is solved using Successive Quadratic Programming (SQP)
within gPROMS.
KEYWORDS: hydrotreating, trickle-bed reactor, integrated process, energy recovery

Brought to you by | Hemeroteca de Estudios Económicos - Banco de la República
Authenticated
Download Date | 4/19/15 6:11 PM

Union Carbide in the USA and Imperial Chemical Industries in the UK have both reported the results of numerous case investigations that reference 30% to 50% energy savings in comparison to conventional practice (Douglas. The primary human source of carbon dioxide in the atmosphere is from the burning of fossil fuels towards energy production and transport. dramatic cuts in all carbon dioxide emissions must be achieved. petrochemical complexes and gas units all generate big amounts of low grade heat. hot utility units are furnaces. the heat exchanger and finally end by utilizing utilities for supplying residual needs (Douglas. Due to the high cost of a pilot plant study. the separation system. Energy integration is a very beneficial tool and is a significant phase in estimating the cost of preliminary design. The utility includes hot and cold utility units.greenpeace. waste minimization and an efficient utilization of raw materials. turbines. 25% to 40% below 1990 levels by 2020. Thus.org). In order to make this jump successfully. However. Operation units. From an energy saving point view the significant field of energy use improvement are the heat exchange retrofit projects for maximizing the existing heat recovery (Khalfalla. boilers and motors 1 Brought to you by | Hemeroteca de Estudios Económicos . generators. 1988). and using it either as part of an operation integration scheme or to heat in domestic and industrial specifications by the installation of a hot water system. 2009). The estimation of the minimum cooling and heating requirements reveal important energy savings. there are opportunities for recovering some of this energy. Traditional design methods begin by designing the reactor. and 80% to 95% below 1990 levels by 2050 (www. process integration is an efficient design methodology. Introduction One of the tasks with which chemical engineers are continually addressing included is the scale up of laboratory experiments to full-scale production.: Optimization of Crude Oil Hydrotreating 1. 1988). energy conservation is significant in operation design.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM . a thorough understanding of the chemical kinetics and transport limitations is required. To avoid or reduce global warming. For instance.Jarullah et al. However. which addresses cases related to energy efficiency. Typically. Concentrations of carbon dioxide (CO2) in the atmosphere have increased from 270 ppm before the industrial age to 380 ppm by 2006: a 31% increase since 1870 and a 41% increase over preindustrial values. this step is starting to be surpassed in several instances via designing the full scale unit based on the process of a bench scale plant called a microplant. However. more efficient utilization of energy consumption results in the reduction of the negative effects of carbon dioxide emissions. oil refineries. This energy is usually rejected to the atmosphere utilizing either air or cooling water systems. where recovery of waste heat provides both financial and environmental benefits to process unit operators.

3 providing the necessary power. Art.d). HDAs and HDM. catalyst loading and catalyst presulfiding used in this study can be found in Jarullah et al. 2. 6 [2011]. 60. In the recovery system. Experimental Work Briefly. Table 1: Feedstock specifications Specific Gravity at 15. Iraqi crude oil was employed as a feed for the pilot plant hydrotreating studies.5 Nickel content 17 ppm DOI: 10.1 wt % Asphaltenes content 1.0 wt % Nitrogen content 0. 2009). The main focus of this paper is to maximize heat recovery within the crude oil hydrotreating process in a trickle bed reactor based. Cold water from external sources is employed as the cold utility.1600 Brought to you by | Hemeroteca de Estudios Económicos .7 cSt Pour point -36 °C Sulfur content 2. Vol.3 g of the fresh catalyst was charged to the HDT reactor and in situ activated by a solution of 0.5 hr-1.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 2 . reactor. The main properties of the feedstock and the catalyst used in this work are shown in Tables 1and 2. experimental runs. HDN. respectively. Iss. maintaining constant H2/Oil ratio at 250 L/L.5-1. upon experimental work and analysis the heat integration process. A commercial cobaltmolybdenum on alumina (Co-Mo/γ-Al2O3) catalyst was used for all experiments.2 wt % Vanadium content 26. The main hydrotreating reactions considered in this study are HDS. The experimental studies were carried out by varying the temperature (335-400 ºC). which provides the required cooling in the operations. (2011a. The temperature of the reactor was maintained at the desired value by utilizing independent temperature control of five zone electric furnaces that provide an isothermal temperature along the active reactor section.Chemical Product and Process Modeling.8558 Viscosity at 37. 2.2202/1934-2659. hydrotreating experiments were conducted in an isothermal pilot-plant continuous flow trickle bed reactor (TBR).c. the pressure 410 MPa and the liquid hourly space velocity (LHSV) 0. hot water and steam. The reactor tube was made from stainless steel with an inside diameter of 2 cm and a length of 65 cm.6 vol% of CS2 in commercial gas oil. which involves HDV and HDNi.8 °C 5.6 °C 0. the process streams exchange heat so as to reduce the cold and hot utility requirements. Further details of the experimental pilot plant. equipment and procedure.b. The heat exchangers are the only units in a heat recovery system (Khalfalla.

The objective is to calculate a retrofit design. Therefore. and the cooler adjusts the final temperature of the hot fluid to requirements of the next step of the process. heat recovery was not an issue in the pilot plant scale process.5 cm3/g 180 m2/g 4 mm 0. The exchangers. Energy Consumption and Recovery Issues Pilot plant trickle bed reactor experiments show that conversion in hydrotreating reactions is better at high reaction temperatures. which can reduce the energy consumption.1 wt % 0. However.Jarullah et al. In industrial processes.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM . Energy consumption for the pilot plant scale was negligible and natural cooling after the reaction was sufficient (no additional utility was required as the amounts reactants and products were small at pilot plant scale). The heater regulates the final temperature of the cold fluid to the required reaction temperature. this leads to the addition of a number of exchangers in the system. heaters and coolers used for heat integration and energy consumption in this study are shown in Figure 1.67 g/cm3 1. maximize energy recovery and consequently minimize capital investment. requiring capital investment.: Optimization of Crude Oil Hydrotreating Table 2: Catalyst commercial specifications (Co-Mo/-Al2O3) Chemical properties MoO3 NiO SiO2 Na2O Fe SO2 Al2O3 Physical properties Form Pore volume Surface area Mean particle length Bulk density Mean particle diameter 15 wt % 3 wt % 1. energy consumption will be a large issue and heat recovery must be taken into account. On the other hand. thus heat recovery was not taken into consideration.8 mm 3. Generally heat exchangers operate in series with a heater and a cooler. 3 Brought to you by | Hemeroteca de Estudios Económicos . scaling up a heat integrated hydrotreating process was considered for reducing overall energy consumption (hence reducing environmental effect).04 wt % 2 wt % Balance Extrude 0.07 wt % 0. especially when the type of reactions are exothermic.

Chemical Product and Process Modeling.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 4 . Due to high reaction products DOI: 10.E1.2202/1934-2659. the crude oil is fed into furnace F1 in order to preheat from TC1 to the reaction temperature (TR). Art. 3 Figure 1: Process of heat integrated reaction system As depicted in Figure 1. The second main feedstock. Iss.1600 Brought to you by | Hemeroteca de Estudios Económicos . Vol. After this. 6 [2011]. its temperature rises from TH1 to the reaction temperature (TR) by the furnace F1. The product stream leaving the reactor (hot stream) is cooled from TP1 to TP2 by contacting with the main crude oil feedstock in heat exchanger H. Then. which is hydrogen (cold stream) is fed into heat exchanger H.E1.E2 to preheat from TH0 to TH1. 2. the crude oil feedstock (cold stream) is pumped by P1 before preheating from TC0 to TC1 in heat exchanger H.

The main mass balance equations.. Alvarez et al.c. Other correlations for estimating gas and liquid properties and characteristics of the catalyst bed used at process conditions can be found in Jarullah et al.: Optimization of Crude Oil Hydrotreating temperature. 2007. 1995. 2009.E1) The products stream that leaves the reactor is used for preheating the crude oil feedstock from TC0 to TC1 through H. The heat duties for these streams are described as follows: Q1HE1  (VL c pL  L ) (TC1  TC 0 ) (1) Q2 HE1  (V L c pL  L  VG c Gp  G ) (TP 2  TP1 ) (2) Q2 HE1  Q1HE1 Q1HE1 AHE1  U HE1 Tlm1 T  T2 Tlm1  1  T  ln 1   T2  (3) T1  TP1  TC1 T2  TP 2  TC 0 (6) (7) (4) (5) 5 Brought to you by | Hemeroteca de Estudios Económicos .Jarullah et al. HDAs. 2004. a) Heat Exchanger (H. HDV and HDN) are presented in Table 3. the products stream is cooled again from TP2 to TP by in contact with hydrogen feed in heat exchanger H.E1 and at the same time is cooled from TP1 to TP2. Also.. Mederos and Ancheyta. Bhaskar et al. then its temperature is reduced from TP to the final product temperature (target temperature) TFP in cooler CO1 by using cold water at TW1. Chen et al. Rodriguez and Ancheyta. all the parameters required for the industrial trickle bed reactor are estimated based on the information presented in the literatures (Tarhan. 2004. HDN. Wauquier.. 1983. energy balance and reaction rate equations for all processes (HDS. (2011b. Model Equations The major focus of this paper is to minimize energy consumption and maximize heat recovery during crude oil hydrotreating.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM . 2010). 4.d).E2.

V and Ni in solid phase (j =HDS. N.2202/1934-2659. Vol.c. AHE1 is the heat transfer area of H. HDV and HDNi  EA j   K j  A 0j exp   RT  H2S  2761  K H 2 S  41769  8411 exp   RT  S nj i S mj H2 taken from Tarhan (1983) Q1HE1 and Q2HE1 are heat duties of H. 2.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 6 . 6 [2011].. HDAs. HDAs. HDN. VG is the volumetric flow rate of hydrogen (includes the main hydrogen feed plus quench feeds). H2S) in  dPi G RT L  Pi G   C iL  k i a L  gas phase dz ug Gases compounds (H2. HDN.1600 Brought to you by | Hemeroteca de Estudios Económicos .Chemical Product and Process Modeling. TC1 is the outlet temperature of the cold fluid. UHE1 is DOI: 10. cpG is the specific heat capacity of gas (involves all gases (reactants and products)). HDAs. Asph. HDV and HDNi) Energy balance equationa k iS   a C  C     r a C  C      a C  C     r L H2 S k HS 2 S L H 2S S S S H2 L i B j j S H 2S S i B B r HDS HDS j j l dT    H R  r j  B j G dz u g  G c p  g  u L  L c pL  l   Chemical reaction rates rHDS  K HDS HDS C  C  S n sul 1  K C  C  H 2S a S m H2 C HS 2 S  2 HDN. Iss. HDV and HDNi) H2S in solid phase k HS 2 S. 3 Table 3: Mass balances and reaction rate equations (Jarullah et al. TC0 is the inlet temperature of the cold fluid. cpL is the specific heat capacity of liquid. ρG is the gas density (includes all reacting gases). Asph. VL is the volumetric flow rate of crude oil. H2S) in liquid phase  hi  L G  P  dC i 1   k iL a L  i  C iL   k iS a S C iL  C iS  dz u l    hi  Liquid compounds (S.E1. TP2 is the outlet temperature of the hot products mixture. 2011b. HDV and HDNi rj  K j HDS . ρL is the liquid density. HDN.E1. TP1 is the inlet temperature of the hot products mixture. V and Ni) in liquid phase dC iL 1   k iS a S C iL  C iS dz uL H2 in solid phase (j =HDS.d) Mass balance equations Gases compounds (H2. HDAs. N. Art.

which is cooled at the same time from TP2 to TP in H.E1 and ∆Tlm1 is the log mean temperature difference for H.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM . AHE2 is the heat transfer area of H. cpH2 is the specific heat capacity of hydrogen. TH1 is the outlet temperature of the cold fluid.E1.E2 by contact with the products stream that leaves H.E2 are: Q1HE 2  (VH 2 c Hp 2  G ) (TH 1  TH 0 ) (8) Q2 HE 2  (VL c  L  VG c  G ) (TP  TP 2 ) (9) L p G p Q2 HE 2  Q1HE 2 Q1HE 2 AHE 2  U HE 2 Tlm 2 T  T4 Tlm 2  3  T  ln 3   T4  (10) T3  TP 2  TH 1 T4  TP  TH 0 (13) (14) (11) (12) Q1HE2 and Q2HE2 are heat duties of H.E2 and ∆Tlm2 is the log mean temperature difference for H.Jarullah et al. UHE2 is the overall heat transfer coefficient for H. TP is the outlet temperature of the hot products mixture.E2.E2) The main hydrogen feedstock is heated from TH0 to TH1 in H.E1. c) Cooler (CO1) The product stream that leaves H.E2. The model equations for H.E2. VH2 is the volumetric flow rate of hydrogen (without quench feeds).: Optimization of Crude Oil Hydrotreating the overall heat transfer coefficient for H. The model equations for CO1 are shown below: Q1CO1  mW cp w (TW 2  TW 1 ) (15) Q2CO1  (VL c  L  VG c  G ) (TFP  TP ) (16) Q2CO1  Q1CO1 (17) L p G p 7 Brought to you by | Hemeroteca de Estudios Económicos .E2. b) Heat Exchanger (H. TH0 is the inlet temperature of the cold fluid.E2 is cooled from TP to the final product temperature TFP in the cooler by using water at TW1. TP2 is the inlet temperature of the hot products mixture.

TFP is the final products temperature. UCO1 is the overall heat transfer coefficient for CO1. DOI: 10. 3 Q1CO1 U CO1 Tlmc T  T6  5  T  ln 5   T6  ACO1  (18) Tlmc (19) T5  TP  TW 2 T6  TFP  TW 1 (20) (21) Q1CO1 and Q2 CO1 are heat duties of CO1. ∆Tlmc is the log mean temperature difference for CO1.1600 Brought to you by | Hemeroteca de Estudios Económicos . ACO1 is the heat transfer area of CO1. TW1 and TW2 are the inlet and outlet temperature of the cooled water.Chemical Product and Process Modeling. gas compressibility factor) are estimated at average temperature (Tav) for each equipment using the following equation: Tav  Tin  Tout 2 (26) Tin and Tout are the inlet and outlet temperatures for item of each equipment. cpw is the heat capacity of water and mw is the mass flow rate of cooling water. crude oil and hydrogen are fed into furnace F1 separately in order to preheat from TC1 to the reaction temperature (TR) for crude oil and from TH1 to TR for hydrogen. The total heat transfer area (At) is given in the following equation: At  AHE1  AHE 2  ACO1 (22) d) Furnace (F1) The main feedstocks.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 8 . The heat equations for F1 can be written as follows: QH 2  (VH 2 c Hp 2  G ) (TR  TH 1 ) (23) QCrude  (VL c Lp  L ) (TR  TC1 ) (24) QF  QH 2  QCrude (25) Note. Iss. heat capacity of gas and liquid. all the physical properties of gases and liquid (such as gas and liquid density.2202/1934-2659. 2. 6 [2011]. Vol. Art.

and between inlet and outlet crude oil in the furnace within 100-130°C. the optimization problem can be presented as: Min Ct TP2. Subject to process constraints and linear bounds on all decision variables. u(z). inlet water temperature(TW1). v) = 0 TP2L ≤ TP2 ≤ TP2U TH1L ≤ TH1 ≤ TH1U TW2 L ≤ TW2 ≤ TW2 U ∆TF L ≤ ∆TF ≤ ∆TFU ∆TW L ≤ ∆TW ≤ ∆TW U TR = TR* TFP = TFP* (model. which can be calculated using the following expression: 9 Brought to you by | Hemeroteca de Estudios Económicos . respectively. that the best temperature difference between inlet and outlet water in the cooler is within 5-20°C. Optimization Problem Formulation The optimization problem can be stated as follows: Given Optimize inlet temperature of crude oil (TC0) and hydrogen (TH0). Note. TR* is the required reaction temperature (which is 400°C) and TFP* is the target final temperature of product (which is 26°C). volumetric flow rate of liquid (VL) and gas (VH2 and VG). U and L are the upper and lower bounds. TW2 s.: Optimization of Crude Oil Hydrotreating 5. equality constraints) (inequality constraints) (inequality constraints) (inequality constraints) (inequality constraints) (inequality constraints) (equality constraints) (equality constraints) ∆TW and ∆TF are the temperature differences between the inlet and outlet temperatures of water in the cooler and liquid crude oil in the furnace. which are quite practical. TP2. in practice. TH1.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM .1 Cost Function The objective function is the overall annual process cost (Ct). reaction temperature (TR). Mathematically. TH1. outlet temperature of products mixture (TP1).t f(x(z). TW2 So as to minimize the total annual cost of the process (Ct).Jarullah et al. 5.

Iss. 2005): ACC  CC  i (1  i ) n (1  i ) n  1 (28) n is number of years and i is the fractional interest per year. 2005).Banco de la República Authenticated Download Date | 4/19/15 6:11 PM (33) (34) (35) 10 .82 C Comp ($)   (517. Smith.9 DR LR (2. the following equation is used (Smith. i = 5% (Smith. Vol. Quintero and Villamil. $) = Reactor Cost (CR) + Compressor Cost (CComp) + Heat Exchanger Cost (CHE) + Pump Cost (CP) + Furnace Cost (CF) (29) The operating cost is calculated as shown below: Operating Cost ($/yr) = Heating Cost (CH) + Compression Cost (CCmpr) + Pumping Cost (CPU) + Cooling Cost (CCol) (30) The capital costs of equipment can be estimated using the following equations (Douglas. Capital Cost (CC.1600 Brought to you by | Hemeroteca de Estudios Económicos . 6 [2011].066 0. 1988.802 C R ($)    101. Art. 2.03  10 5   Pin Qin  out hp     Pin        1   DOI: 10. 2009): a) Reactor Cost (CR) M &S 1.18  FC )  280  FC  Fm F p (31) (32) b) Compressor Cost (CComp) M &S 0.5)(bhp) (2.2202/1934-2659. 3 Ct ($/yr) = Annualized Capital Cost ($/yr) + Operating Cost ($/yr) (27) To calculate the annualized capital cost (ACC) from capital cost (CC).Chemical Product and Process Modeling. n = 10 years.11  Fd ) 280   hp bhp  ise  P  3. 2005.

and design type. 2010)). QF is the heat duty of the furnace.78 At (2.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM . DR is the reactor diameter and FC. Fp.27  FC ) 280   FC  Fd  Fm  F p (42) (43) M&S is the Marshall and Swift index for cost escalation (M&S = 1468. LR is the reactor length. 1988). γ is the specific heat ratio.84  10 FC  P   280   4  FC  Fm F p FT 0. 11 Brought to you by | Hemeroteca de Estudios Económicos . ηise ranges between 70-90% (here it is assumed to be 80%) (Douglas.: Optimization of Crude Oil Hydrotreating  cp H 2   H  1 2 cv    H2  cp   H  2  cv  (36) cv G  cp G  R (37) c) Heat Exchanger Cost (CHE) M &S 0.ise is isentropic efficiency. Qin is the volumetric flow rate at compressor suction. FT and Fd are the dimensionless factors that are functions of the construction material. cvG is the specific heat capacity at constant volume and Pin and Pout are the pressure in the compressor inlet and outlet. bhp is the brake horsepower required in the compressor motor.6 (chemical engineering.29  FC ) 280   FC  ( Fd  F p ) Fm (38) (39) d) Pump Cost (CP) Q  M &S 3 C P ($)    9. Qp is the pump power. respectively.52  10 QF (1. hp is the compressor horsepower.Jarullah et al.55 (40) (41) e) Furnace Cost (CF) M &S 3 0. operating pressure and temperature.85 C F ($)    5. Fm.65 C HE ($)    210.

2202/1934-2659.341hp  kWh  1day  1yr  (45) c) Pumping Cost (CPU)  0.. 3 The operating cost is calculated using the following expressions: a) Heating Cost (CH)  0. which is 0. 6. nickel and asphaltene) at reaction temperature 400 ºC. 2009).062$  24h  340day    C Cmpr ($ / yr )       0.9  1.5 hr-1 and hydrogen pressure 10 MPa. 2005) are listed in Table 4.062$  24h  340day   C PU ($ / yr )  QP (kW )     kWh  1day  1yr  (46) d) Cooling Cost (CCol)   kg   f $  24h  340day   C Col ($ / yr )   mw    w     h   kg  1day  1yr  (47) fw is the price of cooling water. 2009).062$  24h  340day   C H ($ / yr )  QF (kW )     kWh  1day  1yr  (44) b) Compression Cost (CCmpr)  bhp(hp)  1kW  0. it has been found that the crude oil hydrotreatment process (from experimental data) achieved maximum conversion of the impurities (sulfur. Sinnott. 2. The values of constant parameters with factors and coefficients used in this work (Douglas.1600 Brought to you by | Hemeroteca de Estudios Económicos .Chemical Product and Process Modeling. The compression cost is based upon a motor efficiency of 90% (Bouton and Luyben.. Iss. 6 [2011]. 2005. Vol. Smith. liquid hourly space velocity (LHSV) 0. The reactor is assumed to operate for 340 days/yr.0305 $ per ton (Khalfallah. 2011a).062$/kWh (Alvarez et al.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 12 . Art. These conditions are utilized as a typical operating condition for the industrial trickle bed reactor (TBR). nitrogen. 1988. 2008) and an average power price of 0. In our previous study (Jarullah et al. vanadium. DOI: 10. Results and Discussion The industrial trickle bed reactor (TBR) in this study has a processing capacity of 10000 bbl/day.

75 0.688 0.c.0 Heat Exchanger 6.0 Pump 3.147 0. order (n) order (m) energy (EA) (J/mol) (mol/cm3)-m 1.0 Compressor 0. HDAs.00 TC0 °C 70.. Such kinetic parameters (summarized in Table 5) used for HDS.189 Cpw W/m2 K 250 UHE1 W/m2 K 113 UHE2 2 W/m K 400 UCO1 Dimensionless Factors Fm Fp Fd FT 3.15 1.0 1.5 2.sec).045×108 HDNi Note: these parameters are used in the model equations presented in Table 3.00 TW1 kJ/kg K 4.56134×108 HDAs 1.10 2026.0 0.0 0.1 Kinetic Parameters Estimation The optimal set of kinetic parameters for crude oil hydrotreating reactions (involve HDS.93 0.0 0.75 0.672 0.6337 46181. HDV and HDNi have been developed accurately among all results for all reactions with average absolute error less than 5%.0 1.625 1. 13 Brought to you by | Hemeroteca de Estudios Económicos .(cm3/g.9 0.c. 2011b.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM .: Optimization of Crude Oil Hydrotreating Table 4: Values of constant parameters.23 HDS 1. HDN. factors and coefficients used in this work Parameter Unit Value °C 28. HDAs. which can be confidently applied for reactor design.Jarullah et al.452 0.251 0.0 1.0 0.4709 50264.67 3.0 Reactor 0.d).00 TH0 °C 406. These kinetic parameters were validated against pilot plant experiments reported elsewhere (Jarullah et al. HDV and HDNi) have been evaluated based upon minimizing the sum of squared error between experimental and estimated results.0 0.85×107 HDN 1.02 TP1 °C 20.3555 71775. operation and control.d) Reactions Reaction Hydrogen Activation Pre-exponential factor (A0) (mol/cm3)1-n.3 1.6 126566 HDV 1. Table 5: Kinetic parameters of hydroprocessing reactions (Jarullah et al.0 Furnace 1.. HDN.5667 37678.3068 104481 2. 2011b.

0 64. 3 Table 6: Results of optimization problem for heat integration process Variables Without heat With heat Decision Optimized integration integration variable type value At (m2) 475.2%.57 TH1 (C) CS (%) ------55.2 ------------CS = Cost saving.207 202. It has been observed that the energy consumption and heat recovery is considered a big issue that should be taken into account in industrial operations particularly when the type of reactions are exothermic. which is a coupled function of capital and operating costs including design parameters. The results also show that the minimum energy requirement was reduced by 64.3 ------------ES (%) 0. Also. the amount of cooling water required for reaching the final product temperature is greater than that with heat integration due to the heat recovery. 2.00 TW2 (C) mw (kg/hr) 711873.00 ∆TW (C) QHE1 (kJ) ------784918598.5 110.2.2 Optimization Results The optimization results.3148 1033. 7. Iss. QHE = Heat duty of exchanger1. which are summarized in Table 6.2202/1934-2659.99 TP2 (C) Ct ($/yr) 9744870.2%. Art. ES = Energy saving. 6. and consequently the cost of the cold utility in addition to capital cost of cooler will decrease.4 26. show that the minimum total cost (Ct) and cooling water amounts with heat integration of the hydrotreating process are less than those without the heat integration at specified variables.9 272716.76 40. which has the added benefit of significantly reducing environmental impact.25 ∆TF (C) QC (kJ) 1431379037 548357040 20. Conclusions Heat integration and energy consumption in a hydrotreating process were investigated.9 ------------Qr (kJ) ------889872376. the recovery of which is very significant for maximizing profitability of process.1600 Brought to you by | Hemeroteca de Estudios Económicos . the CO2 emissions will be reduced by 64. Therefore.56 400.8 496317300. Qt = Total heating.Chemical Product and Process Modeling.00 TFP (C) QHE2 (kJ) ------104953777. QC = Heat duty of cooler. The cost saving is around 56% in comparison with the cost obtained without heat integration to achieve the reaction temperature (400°C) and to reduce the final product temperature up to 26°C.00 TR (C) Qt (kJ) 1386189676. Optimal DOI: 10. Qr = Heat recovery.8 4310909. Vol.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 14 .8 200. 6 [2011]. Optimization problem was formulated in order to optimize some of the design and operating parameters of integrated process while minimizing an objective function.

76% and the energy saving is 64. cm-1 Annualized capital cost. $ Overall annual process cost.K Pumping cost. Nomenclature aL Gas–liquid interfacial area. $/yr Heat transfer area of CO1. $ CH CHE C iL Heating cost.: Optimization of Crude Oil Hydrotreating minimum energy requirements. (mol/cm3)1-n(cm3/g.Jarullah et al.K Reactor diameter. $ Concentration of i compound in the liquid phase.2% in comparison to the process without heat integration. J/mol hi Henry’s coefficient. J/g. MPa. J/g. $/yr Heat capacity of water.cm3/mol hp Compressor horsepower cp 15 Brought to you by | Hemeroteca de Estudios Económicos . This saving in the energy consumption provides better minimum energy requirement. m2 Pre-exponential factor for reaction j.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM .E2.E1. cm Activation energy for j process. m2 Total heat transfer area. $/yr Capital cost of the reactor.K Specific heat capacity at constant volume. mol/cm3 CP CPU CR Ct cpw cv DR EA j Pump cost.sec)(mol/cm3)-m Hydrpdeasphaltenezation Hydrodemetalization Hydrodenitrogenation Hydrodenickelation Hydrodesulfurization Hydrotreating Hydrodevanadization Furnace cost. cm-1 aS ACC ACO1 AHE1 AHE2 At A0 j HDAs HDM HDN HDNi HDS HDT HDV CF Liquid–solid interfacial area. m2 Heat transfer area of H. J/g. hence reducing environmental effect and maximum heat recovery. $ Specific heat capacity. mol/cm3 C iS Concentration of i compound in the solid phase. $/yr Heat exchanger cost. The results show that the cost saving are 55. heat recovery and cost saving were obtained utilizing optimization process. m2 Heat transfer area of H.

Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 16 . 6 [2011].E1. Iss. g/sec Heat duties of H.2202/1934-2659. K Outlet temperature of the cold fluid from H. K Overall heat transfer coefficient for CO1. K TH0 TH1 TP TP1 TP2 TR Tw1 Tw2 UCO1 UHE1 Inlet temperature of the cold fluid to H.E1. Art. K Outlet temperature of the hot products mixture from H. cm/sec k iS liquid–solid mass transfer coefficient for i compound.E1. cm Order of reaction of hydrogen in reaction j mw nj M&S N Ni P1 Pi G Pin Pout q Qi Qin Qp rj R S T TBRs TC0 TC1 TFP Mass flow rate of cooling water. J/sec Volumetric flow rate at compressor section. cm3/mol k iL Gas–liquid mass transfer coefficient for i compound. cm/sec DOI: 10. Ib/ft3 Quench mass flow rate. Vol. K Outlet temperature of the cold fluid from H.K Sulfur Temperature Trickle Bed Reactors Inlet temperature of the cold fluid to H.sec)(mol/cm3)-m K H 2S Adsorption equilibrium constant of H2S. (mol/cm3)1-n(cm3/g. K Outlet water temperature from CO1.Chemical Product and Process Modeling. W/m2 K UHE2 Overall heat transfer coefficient for H. g/sec Order of reaction of i compound in reaction j Marshall and Swift index for cost escalation Nitrogen Nickel Pumps1 Partial pressure. kW Chemical reaction rate of j reaction per unit mass of catalyst. 3 Kj Reaction rate constant for j reaction.1600 Brought to you by | Hemeroteca de Estudios Económicos . C1 and F1.sec-1 Universal gas constant. K Outlet temperature of the hot products mixture from H.2.E1. cm/sec Velocity of the liquid. ft3/min Power pump.E2.E1. W/m2 K Overall heat transfer coefficient for H. K Inlet reactor temperature. J/mol. MPa Inlet pressure.E1. K Inlet temperature of the hot products mixture to H. mol/g. K Outlet product temperature from CO1. cm/sec LR mj Length of reactor bed. K Inlet water temperature to CO1.E2. 2. Ib/ft3 Outlet pressure. W/m2 K ug uL Velocity of the gas.E2. CO1.E2.

Banco de la República Authenticated Download Date | 4/19/15 6:11 PM . cm3/sec Axial position along the catalyst bed. cm3/sec Volumetric flow rate of hydrogen. cm Greek letters ∆HR Overall heat of reaction.: Optimization of Crude Oil Hydrotreating V VG VH2 VL z Vanadium Volumetric flow rate of gas. J/mol Bulk density of the catalyst particles. g/cm3 B L G j Liquid density at process conditions. g/cm3 Gas density.Jarullah et al. g/cm3 Catalyst effectiveness factor for j reaction ise g l  Isentropic efficiency ∆Tlm log mean temperature difference Gas phase fraction Liquid phase fraction Specific heat ratio Superscripts G H2 L Gas phase Hydrogen Liquid phase or gas-liquid interface S Solid phase or liquid-solid interface Subscripts B F g Bulk Furnace Gas G H2 Gases Hydrogen H2S Hydrogen sulphide L Liquid R sul Reactor Sulfur 17 Brought to you by | Hemeroteca de Estudios Económicos . cm3/sec Volumetric flow rate of crude oil.

6 [2011]. Optimum Economic Design and Control of a Gas Permeation Membrane Coupled with the Hydrotreating (HAD) Process. (2007). Li. J. Energy and Fuels. Fuel.. (2011a). Modelling and optimization of Oxidative Desulfurization Process for Model Sulfur Compounds and Heavy Gas Oil. Res. Wood A.T. K. 66.. Eng. M. Chen.S. pp 6654.. Ind. Eng. pp 2165. Chemical Engineering Science. A. Jarullah.2202/1934-2659. 90. H. F. and Balu.F.S. University of Bradford. Kinetic Model Development and Simulation of Simultaneous Hydrodenitrogentaion and Hyhdrodemetallization of Crude Oil in a Trickle-Bed Reactor.T... 2010]. Ind. Mujtaba. Bouton. pp 1228. Eng. H.R. H. Applied Catalysis A: General.T. I. Valavarasu.. Conceptual Design Chemical Processes.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM 18 . Iss. Art. Ind. I. Economic Indicators. A. Xu. Sairam. (2010). (1988).. (2004). G. 2. Vol. Submitted to Chemical Engineering Science. 43. Zheng. Chem. J.. pp 3100. Wood A.. A and Ancheyta.M. 47. Wood A. Hydrodeasphaltenization of Crude Oil in a Trickle Bed Reactor: Kinetic Model Development and Process Simulation. McGraw.A. Mujtaba. B. DOI: 10. Khalfhallah. and Luyben. A. Mujtaba.D. PhD Thesis. P. 35... Douglas. Jarullah. Mathematical modeling and simulation of hydrotreating reactors: Cocurrent versus countercurrent operations... Effect of Liquid Quenching on Hydroprocessing of Heavy Crude Oils in a Fixed-Bed Reactor System. pp 773. G. Jarullah. and Villamil. pp 1221.M.com [Accessed January 16. V. (2009). Y.R.che.S. Wood A.Chemical Product and Process Modeling.. Res. Liu. Chem. (2008).M. Quintero. I. 25. and Ancheyta. Kinetic parameter estimation and simulation of trickle-bed reactor for hydrodesulfurization of crude oil. New York. Bhaskar.. Res.S. Res. 48. (2009). Mederos. Eng..S. W. (2010). pp 8. Mujtaba. On the Multiplicities of a Catalytic Distillation Column for the Deep Hydrodesulfurization of Light Gas Oil. International Journal of Hydrogen Energy. Three-Phase Reactor Model to Simulate the Performance of Pilot-Plant and Industrial Trickle-Bed Reactors Sustaining Hydrotreating Reactions. Ind. and Bie. 332.S. Chemical Engineering. Improvement of the Middle Distillate Yields during Crude Oil Hydrotreatment in a Trickle-Bed Reactor. J. www. (2009). A. Study on real-gas equations of high pressure hydrogen. K. J. Jarullah. 3 References Alvarez. (2011b). pp 859. (2011c). L. I.T. Chem. pp 1259. 48. Balaraman.L..1600 Brought to you by | Hemeroteca de Estudios Económicos .M..Hill. (2011d). Chem.M. A.

(2005). M.Jarullah et al. (2004). pp 789. and the Hydrogenation of Aromatics (HDA) in a Vacuum Gas Oil Hydrotreater. and Ancheyta. (2005). Wauquier. Paris. Elsevier Butterworth-Heinemann.: Optimization of Crude Oil Hydrotreating Rodriguez. (1995).M. Modeling of Hydrodesulfurization (HDS).A.P. Volume 6: Chemical Engineering Design. Sinnott. Chemical Engineering. Editions Technip. Crude Oil: Petroleum Products. R.Banco de la República Authenticated Download Date | 4/19/15 6:11 PM . 18. Smith. Catalytic Reactor Design. John Wiley & Sons. UK. Energy Fuels.K. J. (1983). R. McGraw-Hill. Tarhan. Process Flowsheets. 19 Brought to you by | Hemeroteca de Estudios Económicos . Hydrodenitrogenation (HDN). Chemical Process Design and Integration. O. J. 4th ed. UK. New York.