Optimization of the

feedstock blend for the new Presented by: H--RC™ ebullated bed Dr. Dicho Stratiev LukOil - resid upgrading unit Wessel IJlstra Criterion - Amsterdam

at LukOil Neftochim Burgas, Co-authors: to maximize the conversion Dr. Ilshat Sharafutdinov LukOil - Burgas and yields of the on-site FCC Dr. Georgi Argirov LukOil – Burgas Dr. Magdalena Mitkova Burgas University unit Radoslava Nikolova Burgas University Dr. David E. Sherwood Jr. Criterion - Houston

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Always moving forward Program

- Introduction to LukOil Neftochim, Burgas and the new H-Oil-RC™ unit licensed by Axens - Study objectives for this presentation

- Introduction to ebullated bed pilot plant testing - Pilot plant test plan - Pilot plant test results

- Experimental and theoretical estimates FCC yields - Refinery scheduling

- Conclusions

3 «ЛУКОЙЛ Нефтохим Бургас» АД Always moving forward Process Diagram of LUKOIL Neftohim Burgas

Fuel gas AGFU CGFU B n-С4 LPG Naphtha Isomerization Hydrotreater Reformer L

SRU-2 SRU-3 E Naphtha

2015 SRU-4 N Premium gasoline HDS-1 HDS-2 D HDS-3 (A-95H) Alkylatio I

HDS-5 n Super Crude oil SMR FCC MTBE 1 700 N Gasoline AD-4 хил.т./г Pre- FCCU 6.5 MM t/y treate + 1.5 MM t/y r (А-98Н) Prime-G G Atm. Residue

Jet A-1 VDU-2 H-Oil residue hydrocracking Euro diesel AVD-1 SMR 2015 2015 Road VBU Bitumen

Fuel oil S<1% Bitumen unit

Sulphur - Existing units - New units - Units out of operation - Gasoline - VGO - C1-C4 gas - Heavy residue - Kerosene - - Н2S - 18 Always moving forward Program

Problem definition: • Commissioning of the new H-Oil-RC™ unit at LukOil Burgas will allow for rescheduling of the refinery to optimize product yields. • At start-up, not enough vacuum resid will be available to fully utilize the capacity of the new unit, but alternative heavy feed components (AR, VGO) can be rerouted to H-Oil-RC™ unit.

Study objectives:

Screen possible feed blends for the H-Oil-RC™ unit. • Use yields- and product quality results from H-Oil pilot-plant study to estimate/test FCC unit performance. • Use conclusions in site scheduling program to optimize refinery margins.

5 Introduction ebullated bed pilot plant testing

FRESH CATALYST PRODUCT LIQUID/GAS

Level instrument

EXPANDED CATALYST Example of a commercial LEVEL Ebullated Bed Reactor

LIQUID/GAS Defining characteristics: SETTLED CATALYST LIQUID LEVEL * Back-mixing of liquid and CATALYST/ catalyst LIQUID/GAS - Little temperature and concentration gradient - Uniform catalyst activity GRID PLATE WITH MULTIPLE * Continues catalyst replacement HYDROGEN and DISTRIBUTION CAPS - Stable performance of FEED OIL catalyst inventory

USED CATALYST

EBULLATION PUMP RECYCLE OIL Introduction to Ebullated Bed pilot plant testing

Criterion uses autoclave reactors equipped with Robinson-Mahoney type internals. Back-mixed (CSTR) kinetics are assumed to evaluate Ebullated Bed Catalyst Performance

• Fixed annular catalyst basket with baffles inside and outside the basket to prevent vortexing. • Rotating shaft with agitator, creating flow through the basket to the reactor wall for upward and downward deflection. • Liquid level controlled by overflow tube • Gas hold-up controlled by mixer speed • Multi-phase gradientless reactor.

From: http://www.autoclave-france.fr/english/cata.html Two of the four Criterion CSTR Pilot Plants located in the Houston R&D laboratory Test plan

• Three independent tests were done in the same Criterion pilot- plant at Shell Technology Center, Houston (STCH) to simulate the new H-Oil-RC™ unit at LukOil Burgas.

• Each test used one of 3 feed blends as specified and supplied by LukOil: A. 100% VR B. 75% VR + 25% heavy VGO C. 50% VR + 50% heavy AR (All feed blends were additionally blended with FCCUHCO + FCCU Slurry Oil [diluents], as specified and supplied by LukOil)

• Each test was done at equal conditions. The feed rates were kept constant, but, to allow for interpolation to the target conversion level, the evaluations were done at 2 different conversion levels. Test plan --- Feed Blends A, B and C (after diluent addition)

VR VR/VGO VR/AR Analysis Unit 100% 75%/25% 50%/50% (+diluents) (+diluents) (+diluents) Density kg/l 1.010 0.984 0.978 Sulphur wt-% 2.73 2.38 2.03 Nitrogen wt-% 0.4964 0.4051 0.3679 Carbon residue, MCR wt-% 16.0 11.0 11.0 Ni ppm 82 53 48 V ppm 258 175 143 SimDis 538 oC+ wt-% 82.1 65.5 58.6 565 oC+ wt-% 75.2 55.5 52.1 Test Results

• For each test, 2 (or 4) test-periods were selected for complete analysis (fractionation + product quality analysis).

• All samples of the VGO and VR products were shipped to LukOil Burgas for further evaluation by LukOil and Burgas University. Test Results

• Net 540°C+ conversion appears higher for vacuum resid only feed, compared to the lighter blends.

80.0

75.0

70.0 Target Conversion

65.0

60.0

55.0

50.0[wt%] conversion C °

45.0

40.0 Net 540 Net

35.0 406 408 Operating410 412 temperature414 416 [°C]418 420 Test Results

• For each of the feed blends the yield pattern was determined. • This example is for the100% VR feed.

37.0

32.0 VGO

27.0

22.0

17.0 Target Conversion

12.0

7.0[wt%] yields Product

2.0 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 Net 540°C+ conversion [wt%] Test Results

• The yield patterns can be directly compared for the different feed blends. • Lighter feed blends, containing more VGO, give higher VGO yields at equal 540°C+ conversion.

47.0

42.0 75/25 VR/VGO 37.0

32.0 100% VR

27.0 VGO yields [wt%] yields VGO

22.0 Target 17.0 Conversion

12.0 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 Net 540°C+ conversion [wt%] Test Results

• Lighter feed blends, containing more diesel, result in higher diesel yields at equal 540°C+ conversion.

37.0

32.0

27.0

22.0

17.0

12.0 Target

Conversion Diesel yields [wt%] yields Diesel 7.0

2.0 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 Net 540°C+ conversion [wt%] Test Results

• Hydrogenation performance and product quality data were interpolated to the target 540°C+ conversion level.

Feed blend VR VR/VGO VR/AR Blending ratio 100 75/25 50/50 540°C+ Conversion Base Same Same Sulfur in unconverted resid wt% Base -0.2 -0.2 HDS wt% Base +4 +4 HDN wt% Base +5 Same HDMCR wt% Base +5 +6 HDMetals wt% Base +4 +2 Always moving forward H-Oil-RC™ products from 3 different feed blends were separated and analyzed for product quality

H-Oil-RC(TM) Product Density Feed blends 100% VR 75/25 VR/VGO 50/50 VR/AR

Diesel VGO VR

H-Oil-RC(TM) Product Sulfur Feed blends 100% VR 75/25 VR/VGO 50/50 VR/AR

Diesel VGO VR

H-Oil-RC(TM) Product Nitrogen Feed blends 100% VR

75/25 VR/VGO

50/50 VR/AR Diesel VGO 17 Always moving forward Specific properties of the H-Oil-RC™ products, needed for predicting the FCC unit performance were analyzed in the LukOil laboratory

FCC feed specific properties for VGO product

Feed blends 100% VR 75/25 VR/VGO 50/50 VR/AR Kw Saturates light middle heavy Resins Aromatics

Specific properties for the unconverted product

Feed blends 100% VR 75/25 VR/VGO 50/50 VR/AR

Kw Saturates Aromatics Resins Asphaltenes

18 Always moving forward H-Oil-RC™ pilot-plant products were used as feed for Micro Laboratory FCC pilot units

VGO product

100% VR

75/25 VR/HVGO

50/50 VR/AR

drygas LPG gasoline LCO HCO Coke conversion

FCC yield patterns simulated at max gasoline yield, when using H-Oil-RC™ VGO products neat from different feed blends

19 Always moving forward In addition, Micro Laboratory FCC simulations were performed for blends of H-Oil-RC™ products with straight-run HVGO

VGO blends

100% SR HVGO

50% SR HVGO + 50% H-Oil VGO (100% VR)

50% SR HVGO + 50% H-Oil VGO (75/25 VR/HVGO)

drygas LPG gasoline LCO HCO Coke conversion

FCC yield patterns simulated at max gasoline yield, when using blends of SR HVGO and H-Oil-RC™ VGO products

Compared to the blend 50%/50% blend with VGO product from 100% VR run, the 50%/50% blend with VGO product from the 75%/25% VR/VGO run gave ~+4% gasoline + LPG at the expense of ~-4% cycle . 20 Always moving forward Simulated LUKOIL Neftohim Burgas Constrained FCCU yields

50%/50% 50%/50% 90%/10% HTVGO/ HTVGO/ HTVGO/ H-Oil-RC™ H-Oil-RC™ VGO Product Yields, VGO VGO (75%/25% wt.% (100%VR) VR/HVGO) dry gas 2.5 3.30 2.8 PPF 8.7 7.48 8.1 BBF 13.4 11.80 12.4 Cracked Naphtha 52.4 49.00 51.0 LCO 9.9 11.48 10.9 HCO 5.3 6.70 5.5 Slurry 3.9 5.85 5.2 Coke 4.0 4.40 4.1 Conversion 81.0 76.0 78.4

21 Always moving forward Yield- and product property data were used in the refinery’s LP-model to evaluate the profitability

Base + 7.5% Base + 5% Base

100% VR 75/25 50/50 VR/AR VR/HVGO When the H-Oil-RC™ unit capacity is not fully utilized, processing SR HVGO in the unit appears

very favorable for overall refinery profitability 22 Always moving forward Conclusions

• LukOil, Burgas is starting up it’s new H-Oil-RC™ unit. Initially, not enough VR will be available to fully utilize the unit capacity.

• Criterion’s pilot-plants were used to simulate the new H-Oil-RC™ unit of LukOil Burgas, processing 3 different feed blends.

• Products of the pilot-plant studies were analyzed and used for FCC simulations and micro FCC conversion tests.

• The FCC laboratory yields, simulated on the basis of LukOil derived correlations and properties of VGO products from H-Oil-RC™ pilot-plant tests, revealed an opportunity for an FCC conversion increase between about 5 and 10%.

• Applying predicted commercial yields and product property data in the refinery’s LP model showed a clear profitability advantage to use the remaining unit capacity for co-processing of SR HVGO.

Burgas University 23 Always moving forward Thanks for your attention

Burgas University

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