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MILOS Shells ultimate flexible FCC technology in delivering diesel/propylene

NPRA Annual Meeting, San Diego, CA, March 9-11, 2008: Paper AM-08-54 Presenter: Mart Nieskens - Global Manager Cat Cracking Shell Global Solutions (US), Houston, TX

SUMMARY
This paper presents a novel Process option developed by Shell Global Solutions that aims at producing more diesel with improved quality and more propylene from Fluid Catalytic Cracker (FCC) Units. After a unit revamp, the propylene production can be more than doubled, or the LCO-yield increased by more than 20%, with a cetane increase of more than 7 points. The hardware components in this new technology are already individually proven. Hence, a revamp to an existing FCCU does not constitute a significant risk. The key element of MILOS is a separate riser to produce the additional propylene, with its own optimal process conditions, while the existing FCC riser is used for "normal" cracking or for enhanced LCOmake. This process option has a wide flexibility with respect to products, ranging from the normal product slate to maximized propylene or diesel, which can be achieved through operational measures.

1 Introduction - historical perspective


Since the first FCC Unit was started up in 1942, it has played a central role in the Refining Industry to provide the refinery with generous amounts of gasoline with a relatively high octane number to be blended into the mogas pool. In recent years however, several factors led refiners to reconsider the future role of FCC:  The demand for gasoline is being replaced by diesel. This trend is evident in Europe and Asia-Pacific; it is now becoming visible in the US as well.  Worldwide stricter specifications on sulphur in gasoline makes cat-cracked gasoline a difficult contributor to the gasoline pool. Alternatively, the refiner will consider other, potentially more profitable uses of CC-gasoline.  The demand for propylene is growing so rapidly that the traditional source for propylene steam cracking - cannot keep up with the demand. From the available technologies to bridge the gap, FCC is by far the best placed one. The Refining Industry needs a redefinition of the FCC process to enable the following Process objectives to be satisfied:  Lower gasoline yield;

NPRA paper on MILOS final to NPRA Mar081.doc

 Higher LCO yield, with better product quality characteristics (lower density and higher Cetane number);  Higher propylene yield;  Flexibility to switch seamlessly between these different production modes and conventional FCC operation. The MILOS process (MILOS being an acronym for: MIddle distillate and Lower Olefins Selective process) was created to achieve these process objectives. Patent applications have been filed (Reference [4]).

2 Process Background of MILOS


Recycling cat-cracked gasoline to the bottom of the riser (where the temperature is typically in the range of 1250-1320 F) has been widely practiced in the refining industry with the objective of increasing propylene yield. This has the desired effect of producing more propylene, but with significant penalties of producing large amounts of coke, dry gas, butylenes, LCO+ and it would produce little iso-butane. To confirm this, experiments were conducted in which light and heavy cat cracked gasoline were recycled in the Shell Global Solutions large FCC riser pilot plant. The most favourable condition for the production of propylene was found when light CC gasoline was injected below the VGO feed such that the residence time for cracking pure light CC gasoline was approximately 0.5 to 1 second prior to the VGO injection point. However, it had a large impact on VGO conversion, which dropped at constant coke rate. As a result the net LCO+ flow rate at riser exit increased significantly. Such large increases in LCO+ material were also observed in all other tests. Additionally, injecting light CC gasoline with or above the VGO feed yielded a net decrease in propylene yields due to quenching in that section of the riser reactor. For heavy gasoline, the results were even more disappointing in all cases. The flaw of this option is that it is impossible to achieve optimal conditions for both feeds (both the recycled gasoline and the VGO) in one single riser.

3 The MILOS Process Concept

The MILOS concept consists of adding a separate riser to the FCC unit, in which gasoline or other suitable streams are cracked under process conditions tailored specifically to maximize

NPRA paper on MILOS final to NPRA Mar081.doc

propylene yield, to maintain or increase the iso-butane yield (which is desirable for the alkylation plant) without producing excessive amounts of dry gas, coke and butylenes. The ideal temperature is relatively low (1050-1150 F) in order to minimize thermal reactions. At still lower temperatures, high gasoline conversions cannot be easily obtained. The catalyst used is the same as in a conventional cat cracker with ZSM-5 added to boost the propylene yield. Typical yields obtained by cracking cat cracked gasoline in a MILOS riser are 15.5 %wt propylene, 7.5 %wt dry gas and 5%wt iso-butane.

3.1 Other feedstocks in a MILOS riser


In addition to cat cracked gasoline, several other feedstocks were tested in the Shell Global Solutions FCC pilot plant to establish optimal process conditions for producing propylene. A C4 raffinate stream (~85% C4 olefins, 15% C4 paraffins) was processed under MILOS conditions. Propylene and ethylene yields were 15 %wt. and 4.4 %wt respectively. Dry gas make was relatively low (~ 4-5 %wt. excluding ethylene). Yields of heavy liquid products were very low (< 1 %wt.). This product distribution is significantly better than cracking a raffinate in an ethylene cracker. It is interesting to note that even though the feed consisted of 100% C4s, the products contained C4+ material (gasoline and LCO). These molecules are formed by recombination reactions of carbenium radicals. We also explored the feasibility of running some unconventional feeds (paraffinic resid feed, hydrowax, rapeseed oil and palm oil) under MILOS conditions. Conversions were over 90 %wt. and propylene yields were very high (~ 20-23 %wt.). While these unconventional feeds had very high conversions, they also produced more dry gas than conventional naphthas at similar severity. From the point of view of maximizing propylene, these are excellent feeds for a MILOS riser. The optimum operating conditions for various feedstocks were different owing to differences in their crackability.

4 Case studies
A number of case studies are presented here to demonstrate aspects of implementing MILOS in existing FCC units. One case focuses on a diesel-mode implementation; another one involves offsite feeds to the MILOS riser (coker naphtha and butadiene unit raffinate). Finally, we consider modifications of the product work-up section in case of a MILOS revamp to an existing FCC unit.

4.1 Diesel-mode case study


The base-case is a Shell Global Solutions designed long residue unit, processing long residue with Conradson Carbon content of 3.2%wt. Shells rigorous heat-balanced Catalytic Cracking Process model was used. This model was tuned to the actual operating conditions of the specific FCC unit, including realistic unit constraints and feed properties.

NPRA paper on MILOS final to NPRA Mar081.doc

The base-case (case #1) represents the average operating condition and average feed properties of the unit over the recent years. Besides this case, the following cases were explored:  Cases #2 and #3: the maximum diesel and the maximum propylene cases based on the conventional FCC-unit without the addition of a separate MILOS riser.  Case #4: a MILOS riser is added to the FCC unit to achieve maximum diesel and propylene  Case #5: a sensitivity case with the same MILOS-FCC unit, maximising propylene only. The results of the case studies are presented in Table 1.
Case number Case #1 Base #2 FCC only Diesel mode #3 FCC only Propylene mode #4 FCC Diesel mode + MILOS #5 FCC Propylene mode + MILOS

Case description

Existing FCC revamp Existing FCC revamp Typical operating Existing unit operated Existing unit operated with addition of with addition of conditions and to produce maximum to produce maximum MILOS technology. MILOS technology. feedstock properties LCO propylene FCC is operating in FCC is operating in in recent years diesel mode propylene mode t/d
o

Fresh feed rate to FCC riser

10000 N/A Base 0 25.9

10000 N/A -19 0 31.0

10000 N/A +5 10 24.9

10000 2500 -30 10 33.3

10000 2500 +5 10 24.8

Recycle of light cat crack gasoline to MILOS t/d FCC riser outlet temperature ZSM-5 additive in catalyst inventory LCO Cetane Index Overall yield C2 minus Ethylene Total C3 Propylene Propane Total C4 i-Butane n-Butane Total C4 Olefins i-Butylenes Light cat crack gasoline (C5 - 142 degC) LCO (221 - 370 degC) HCO (370 - 425 degC) SO (425 degC+) Coke Gasoline/Cycle Oil ratio %wt %wt %wt %wt %wt %wt %wt %wt %wt %wt %wt %wt %wt %wt %wt wt C %wt -

4.3 1.1 8.2 5.2 3.1 10.2 3.2 1.2 5.8 1.3 34.7 11.2 15.8 3.4 4.5 7.6 2.9

3.2 0.8 6.3 4.0 2.3 8.6 2.8 0.9 4.9 1.1 32.8 12.4 18.9 4.4 6.7 6.8 2.4

4.4 1.2 12.2 8.2 4.0 13.7 3.8 1.5 8.4 2.9 30.3 9.4 14.7 3.4 4.4 7.5 2.7

4.7 1.9 13.7 9.8 4.0 16.0 5.5 1.7 8.9 2.9 14.4 12.0 19.3 4.5 7.5 7.9 1.4

6.3 2.4 17.1 11.9 5.1 17.8 5.6 2.0 10.2 3.5 16.1 10.8 15.2 3.5 4.5 8.8 1.8

Heavy cat crack gasoline (142 - 221 degC) %wt

Table 1: Diesel revamp case study results

The comparison between the base case FCCU (Case #1) versus the diesel mode FCCU(Case #2) or propylene mode FCCU (Case #3) is straightforward. If we operate the unit in diesel mode (case #2), the LCO yield is boosted by more than 3%wt (Table 2) and the cetane index is increased by 5 points. However, propylene yield suffers a reduction of 1.2%wt. Valuable LPG (total C3s and C4s) is also suffering a reduction of 3.5%wt. On the other hand, if we operate the unit in propylene mode (case #3), the propylene yield is boosted by 3%wt, and the LPG (total C3s and C4s) is also increased by 9%wt. (The increase in butylenes in the cases #3, 4 and 5 is a direct result of ZSM-5 addition). However, cetane index of LCO suffers a big hit of about 6 points reduction. LCO yield is slightly reduced by 1%wt.

NPRA paper on MILOS final to NPRA Mar081.doc

The situation above is a typical dilemma faced by FCC that is supplying a diesel and propylene driven market. The diesel mode and propylene mode represent the opposite extreme ends of operation and depending on market forces, the operator swings from one mode to the other. Some operators might choose to operate in the middle of the two modes and not make either maximum propylene or maximum diesel in terms of quantity and quality. However, after revamp with MILOS, the operator can produce more propylene than the standalone FCC propylene mode and more LCO than the standalone FCC diesel mode, with even higher cetane index, all achieved at the same time.

Case number Case

#1 Base

#2 FCC only diesel mode 0.8

#3 FCC only propylene mode 1.2

#4 FCC diesel mode + MILOS 1.9

Remarks

Ethylene yield

% wt

1.1

Propylene yield

% wt

5.2

4.0

8.2

9.8

LCO yield

% wt

15.8

18.9

14.7

19.3

LCO Cetane Index

pt

25.9

31.0

24.9

33.3

MILOS revamp almost doubles the ethylene compared to the base case. The revamp even boosts the ethylene to about 160% of maximum achievable on FCC standalone. MILOS revamp almost doubles the propylene make compared to the base case. The revamp even boosts the propylene make by 1.6%wt higher than maximum achievable on FCC standalone. MILOS revamp increases the LCO make by 22% compared to the base case. The revamp slightly increases the LCO make compared to the maximum achievable on FCC standalone. MILOS revamp increases the LCO Cetane Index by more than 7 points compared to the base case. The revamp even boosts the property by at least 2 points higher than maximum achievable on FCC standalone.

Table 2: Advantage of Diesel MILOS-FCC revamp

It is clear from the results above that a revamp with MILOS (Case #4) on a conventional FCC unit brings the benefits of maximising propylene make, maximising LCO make and increasing LCO Cetane quality, all at the same time. This is achieved by allowing the FCC to operate in diesel mode to achieve the desired high LCO yield and high LCO Cetane. Directing the cooler MILOS spent cat (cooler relative to regen temperature) to the FCC riser also plays an important role in improving the LCO yield and quality. On the other hand, the MILOS riser is focusing on maximising propylene by cracking recycled light cat-cracked gasoline. With the same FCC & MILOS unit, we have studied a sensitivity case to see if the propylene make can be boosted further. In this study, the conventional FCC is operated towards maximum propylene make instead of operated in diesel mode (Table 3).

NPRA paper on MILOS final to NPRA Mar081.doc

Case number Case

#1 Base

#3 FCC only propylene mode 1.2

#4 FCC diesel mode + MILOS 1.9

#5 FCC propylene mode + MILOS 2.4

Remarks

Ethylene yield

%wt

1.1

Propylene yield

%wt

5.2

8.2

9.8

11.9

LCO yield

%wt

15.8

14.7

19.3

15.2

LCO Cetane Index

pt

25.9

24.9

33.3

24.8

Operating the FCC + MILOS in fullforce propylene mode also increases the ethylene make to almost 2.2 times compared to the base case, and about 2 times compared to the standalone FCC propylene mode (case #3). Operating the FCC + MILOS in fullforce propylene mode increases the propylene make to almost 2.3 times compared to the base case, almost 1.5 times compared to the standalone FCC propylene mode (case #3). LCO yield and Cetane Index will be less ideal than base case. But if compared to the FCC standalone max propylene mode, the LCO yield and Cetane are comparable, even slightly better.

Table 3: Sensitivity study

It is clear that with this MILOS-FCC configuration (Case #5), the propylene yield can be further boosted if the operator is ready to accept the same level of LCO yield and quality as they are getting during the conventional FCC propylene mode operation. The propylene yield can be increased to almost 1.5 times compared to the standalone FCC propylene mode operation. Concluding The revamp of a conventional FCC unit to a Diesel MILOS-FCC is a very attractive option to refiners, especially for those units located in Europe or other region where both diesel and propylene demand are expected to grow rapidly. A conventional FCC, maximising propylene and maximising diesel represent two opposite ends of operation modes and the operator cannot achieve the purpose of maximising both propylene and diesel at the same time. However, with a Diesel-mode MILOS-FCC, we bring the best of both worlds together. The Diesel-mode MILOS-FCC discussed in this case study can almost double propylene make, boost the LCO yield by more than 20%, and boost its cetane index by more than 7 points compared to the base case; all achieved at the same time.

4.2 MILOS Offsite Feed Case


In addition to recycling cat cracked gasoline, the propylene-driven refiner could consider cracking other materials to propylene in the MILOS configuration. This approach can be applied in complex refineries or petrochemical complexes where lower valued by-product streams may be advantageous feeds for the MILOS configuration. The yields for two lower

NPRA paper on MILOS final to NPRA Mar081.doc

value streams we have evaluated for cracking in MILOS, coker naphtha and butadiene unit raffinate, are shown below (Table 4):
Coker Naphtha wt% C2minus Propane Propylene Isobutane Total C4 Olefins N-Butane Isobutylene Total C5 C6-310F, Lt. Naphtha 310-450F, Hy. Naphtha 450-650F, LCO 650-750F, HCO 750F+, CLO Coke 4.3 1.4 12.6 2.8 9.7 1.7 3.5 14.0 38.8 11.1 2.0 0.3 0.2 1.2 Butadiene Unit Raffinate wt% 8.2 4.1 15.8 14.3 20.1 15.3 7.5 6.3 7.6 2.0 0.9 0.2 0.2 5.1

Table 4: Yields for cracking coker naphtha and raffinate in a MILOS riser. Yields are expressed as weight % on intake of naphtha feed to the MILOS riser.

Depending on location economics, the above streams or other similar streams could be considered for feed to MILOS. To assess any candidate streams, the MILOS yields would be established via pilot plant testing designed to simulate MILOS operating conditions. In the MILOS installation, the MILOS riser would be operated at the desired severity to deliver optimum propylene yields while minimizing coke make. To further evaluate the suitability of offsite streams for MILOS feed, the expected yields should be used in conjunction with a site master plan or hydrocarbon utilization plan. Such reviews can establish the true alternate economic value by uncovering additional benefits to rerouting hydrocarbon streams. For example, if the existing coker naphtha routing is to naphtha hydrotreating, the coker naphtha is penalized for additional hydrogen consumption to saturate olefins and for accelerated catalyst usage due to the effects of antifoam injection at the coker. Routing the material to MILOS eliminates both problems, to the benefit of the refinery operator.

4.3 Workup Section Revamp Considerations


In any revamp situation involving a large increase in LPG, a range of options for the revamp of the work-up section can be considered within the mechanical and process constraints of the existing plant. Some of these options are:  Application of tower packing or advanced Shell Calming SectionTM trays to increase column capacity. The use of Shell Global Solutions ConSepTM trays can even double the capacity of columns in light ends service.  Increasing Main Fractionator pressure to increase capacity, within R&R limits.

NPRA paper on MILOS final to NPRA Mar081.doc

      

Decreasing pressure in the Debutaniser to improve relative volatility and column capacity. Application of a heat pump to the PP Splitter, if this is not already present. Reconfiguring the Gas Plant. Additional columns in parallel or series, especially Absorber and PP-Splitter. Use of a pre-flash or quench tower to reduce the load on the CCU main fractionator. Integration of the MILOS CCU with an existing Olefins Plant cold-side operation. Shifting base CCU operating mode from gasoline to diesel.

The optimisation of changes will depend on many factors, including implementation time, maintenance issues, accessibility, capital and operating costs, upstream and downstream issues and resources. By using MILOS pilot plant yields, the distillation design can be developed with a high degree of certainty. The optimum approach will not only depend on capital cost, but also on the impact of the required project shutdown or turnaround and future inspection and maintenance turnarounds.

5 Comparison of MILOS with DCC


In this section, MILOS is compared with Deep Catalytic Cracking (DCC). DCC is a commercially proven technology licensed by the Shaw Group (Stone & Webster). DCC is capable of producing significant amounts of light olefins. Several DCC units are in commercial operation. DCC yield data were collected from the open literature, pertaining to two different feeds:  Feed consisting of a VGO blend with 50% Arabian Light VGO and 50% Brent VGO [1];  Daqing VGO feed [2]. As the feed properties for the DCC feeds were not reported, we estimated the hydrogen contents from assay data for feeds/crude sources. Table 5 below compares yields of the DCC cases with pilot plant data for MILOS using a typical VGO feed.

NPRA paper on MILOS final to NPRA Mar081.doc

Feed

H-content of feed Products (%wt on feed): C2minus excl. ethylene (Methane in C2 minus) Ethylene Propane Propylene Butanes Butylenes Naphtha (C5 450 F) LCO HCO/slurry Coke

DCC case #1 (Reference [1]) 50 % Arab Light VGO & 50 % Brent VGO 12.4 % (est.)

DCC case #2 (Reference [2]) Daqing VGO

MILOS VGO

13.4 % (est.)

12.3 % (meas.)

4.9 (4.4) 5.4 3.0 17.0 4.9 11.4 29.5 10.4 5.8 6.6

7.2 (1.2) 5.7 3.2 20.4 3.0 15.9 20.2 7.9 7.3 9.4

2.3 3.1 2.1 17.1 5.8 12.6 28.2 15.8 8.0 5.0

Table 5: Comparison of DCC yields with MILOS yields

The feed qualities of the MILOS and the DCC case #1 being similar in terms of hydrogen content, we can compare the two technologies on a similar-feed basis. Unfortunately, the DCC yields for feed #1 do not add up to 100% and the original reference (web page) is no longer available. We can still say the following when comparing the MILOS and the DCC case #1 data:  MILOS and DCC#1 are similar in propylene yield.  Coke and dry-gas yields are significantly lower for MILOS. This enables MILOS to revamp FCCUs with minor hardware modifications, or to build grass roots units with smaller equipment and lower compression costs.  The estimated propylene purity [propylene/totalC3] is higher for MILOS (89.1% vs 85%). This will benefit separation equipment and energy requirements. The DCC case #2 data refer to a very paraffinic, high-quality VGO feed. The high H-content of this feed gives rise to high yields for ethylene and propylene. As the H-content in the MILOS case is lower, MILOS gives somewhat less propylene than DCC (17.1 vs 20.4%), as expected. The other yield data (coke and dry-gas yields, propylene purity) show that the relative advantages of MILOS are also valid for this case. In commercial practice, there are substantial benefits in the application of MILOS:

NPRA paper on MILOS final to NPRA Mar081.doc

 As the reactor pressure in MILOS is higher (>2 barg versus < 1.0 barg for DCC [3] ) the MILOS system has smaller vessels and a smaller wet gas compressor.  MILOS equipment is smaller due to a lower steam-to-oil ratio (<10% for MILOS versus 20 30% wt [3] for DCC).  MILOS capacity is similar to the capacity of a world-scale FCC unit (200+ MB/day feed). This is substantially more than commercially proven with DCC (18 MB/day of feed [3]).  By fine-tuning operating conditions, MILOS is flexible in processing external feeds from the refinery or chemical plants. Although DCC can also process feeds from steam crackers [2], it is less flexible.  As MILOS is integrated in an FCCU, MILOS is very flexible in operation mode; it can even be reverted on the run to regular FCC operation if this is required. DCC does not have this flexibility. A DCC implementation requires much more significant changes to an existing FCC unit.  MILOS uses the same commercially available and proven catalysts as conventional FCC. DCC uses a proprietary catalyst.  In case of a minimum capital approach to revamp, the fresh feed capacity of a DCC unit is likely to be significantly reduced. This need not be the case for MILOS. Summarizing - MILOS has unique features to meet the goal of higher propylene yields and operating flexibility. In the comparison above, we did not even discuss the MILOS-flexibility in providing more diesel. It has been shown that MILOS has significant advantages over DCC.

6 References
1. A Review of Short Residence Time Cracking Processes, Craig Hulet et al, International Journal of Chemical Reactor Engineering Volume 3 (2005), page 19. 2. Deep Catalytic Cracking, Maximize Olefin Production, Lark Chapin and Warren Letzsch, NPRA Annual Meeting, AM-94-43, March 20-22, 1994. 3. Deep Catalytic Cracking, The New Light Olefin Generator, Warren S. Letzsch, Handbook of Petroleum Refining Processes 3rd Edition, Chapter 3.2. 4. US2006/0231461A1 W.Mo, F.H.H.Khouw and G.A.Hadjigeorge Method and Apparatus for making a Middle Distillate Product and Lower Olefins from a Hydrocarbon Feedstock; US2006/0178546A1; US2006/0191820A1.

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