Modernization of oil refining catalytic processes to produce fuels with enhanced environmental characteristics on the basis of existing refinery

equipment
M.I.Levinbuk, Moscow Oil and Gas University, Russia V.A.Khavkin, E.F.Kaminsky, All-Russia Refining Institute, Russia Abstract
Requirements for motor fuel characteristics will have changed dramatically by 2005-2007. Hence, construction of new grass-root secondary refining units is necessary, while the existing units have to be modernized substantially, which in turn requires extensive investments. However, there is a far much cheaper option. The philosophy of multifunctional reactors based on novel catalytic systems changes the feedstock conversion chemistry and allows existing refineries to produce fuels and petrochemicals with drastically improved qualities. We have succeeded in using old catalytic cracking and reforming technologies to produce hydrogen and reformulated gasoline (low in aromatics, benzene and olefins). We have also managed to increase the gasoline yield from vacuum gas-oil cracking.

Introduction
Catalytic cracking and reforming are currently the principal refinery processes. They produce required volumes and ensure necessary quality of components of commercial gasoline blends. The impending drastic changes in motor fuel properties in developed Western countries will mostly be attained through modernization of these two processes, and the most economic way to enhance these processes is development of fundamentally new catalysts, which have to make new reaction routes possible when processing the same feed. This will increase yields and favorably change the chemical composition of target products without significant modernization of process equipment, or make it feasible to process new feed types on existing units and, consequently, to obtain new valuable products.

Results and discussion New-generation reforming catalytic systems

One of the key issues connected with obtaining reformulated gasoline is modernization of catalytic reforming. Currently, this process is the main source of benzene and aromatics in commercial gasoline. Reforming faces contradictory challenges now: environmental legislation pushes for decreasing the proportion of benzene/aromatics, which can be quite precarious considering the impending ban on MTBE in commercial gasoline blends1. Therefore, the very philosophy of reforming should be changed: isomerization of n-C7-C9 paraffins into methylcyclopentane naphtenes should become the key process instead of n-hexane dehydrocyclization2, which would make it possible to decrease the aromatics proportion and increase the gasoline yield, without decreasing the reformate octane number. We have developed principally new catalysts that make this new approach feasible. When this new catalyst is loaded in one reactor vessel in a semi-regenerative or cyclic reformer, the reforming process is enhanced so dramatically that it virtually turns into a new, next-generation process called hydroisoforming. The properties of the new hydroisoforming catalyst for parallel reactions of n-heptane isomerization and benzene hydroisoforming to methylcyclopentane and cyclohexane, are illustrated by conversion of BTX reforming raffinate and its mixes with some individual hydrocarbons (Tab. 1).

New cracking catalytic systems

One of the main methods for FCC enhancement is to retrofit cracking units so that to apply the millisecond technology. This way the gasoline yield may be increased even if conventional catalysts are used. On the other side, considerable investments are necessary to adapt an FCC unit to this new technology, because the lift-reactor has to be substituted with a new millisecond reactor3. However, these expenses may be avoided if a new modification of Y zeolite, LAY-zeolite, is used4. This material allows the gasoline yield to be increased without changing the catalyst/feed contact time (i.e. there is no need to adapt reactors to the millisecond technology). Properties of the new catalyst were studied through a corrected MAT method (i.e.

under conditions that are closer to the real industrial environment); see Tab. 2 for comparison of product yields obtained through gas oil cracking over LAY-based and CRAY-based catalysts respectively (the latter is DA-250 Grace-Davison material) at a constant LHSV (16 h-1)2. It is obvious that the LAY-based catalyst ensures a higher gasoline yield than the conventional CRAY catalyst even though the contact time is longer. The LAY-based catalysts also decreases the olefin content in the gasoline fraction twofold, while the octane number even increases somewhat due to a higher proportion of iso-paraffins and aromatics. Table 1. Conversion of BTX reforming raffinate and raffinate mixed with benzene and n-C7H14 additives over the new isomerization catalyst at 320C Gas Hydrocarbon concentrations Feed/distillate yield a b c d e f g h i j (C1-C4) 1. raffinate 2.6 3.6 38.6 17.6 22.4 6.2 2.6 0.2 0.1 6.1 catalysate 5.9 4.3 4.2 37.5 16.4 24.2 5.5 2.3 0.4 5.3 2. raffinate+benzene 2.4 3.4 35.7 16.4 21.3 5.9 2.4 0.2 5.9 6.4 catalysate 5.2 4.0 4.3 35.4 15.4 22.9 5.2 5.9 2.3 4.6 3. raffinate + n-C7H14 2.1 3.0 31.8 14.7 19.0 21.3 2.1 0.2 0.1 5.7 catalysate 4.8 3.5 3.6 30.9 13.6 29.6 12.1 2.0 0.4 4.3 4. raffinate+benzene 2.1 3.0 30.9 14.1 17.4 19.0 2.1 0.2 6.1 5.1 + n-C7H14 5.4 3.4 3.2 31.7 13.1 27.3 10.1 5.5 2.0 3.7 catalysate a = i-C5H12; b = n-C5H12; c = i-C6H14; d = n-C6H14; e = i-C7H16; f = n- C7H16; g = methyl-cyclopentane; h = cyclohexane; i = benzene; j = C8 Table 2. Corrected micro-activity tests (MAT) of FCC catalyst samples: vacuum gas oil cracking at a constant LHSV (16 h-1) and 500C. Catalyst-to-feed weight ratio, 6.0 Catalyst-to-feed weight ratio, 9.0 Product yield, wt% Contact time, 37.5 s Contact time, 25 s Samples with 10 wt % RE-LAY DA-250 Gasoline Gas LCO HCO Coke Conversion 49.0 20.0 19.0 7.0 5.0 74.0 45.2 22.1 20.0 7.0 6.7 73.0

Cracking of heavy and polycyclic aromatic hydrocarbons is prevented at atmospheric pressure for thermodynamic reasons. This obstacle can be overcome if catalytic cracking (realized through the carbeniumion mechanism) is combined with partial oxidation of hydrocarbons. Such a process can be realized if cracking catalyst is doped with transition metals following a special technique. These metals bind oxygen during regeneration. The oxygen is then consumed for partial feed oxidation in the reactor. We designated this new catalyst as "reagent catalyst". Tab. 3 demonstrates how the reagent catalyst improves the performance of old TCC cracking units; its properties are compared with that of an Engelhard TCC catalyst. Table 3. Yields of vacuum gas-oil cracking products over reagent catalyst and Emcat-Extra TCC catalyst Reagent catalyst Emcat-Extra Gas 7.8 8.3 CO + CO2 0.45 0.18 Gasoline 38.9 33.5 Light gas-oil 29.0 27.0 Heavy gas-oil 19.3 27.3 Coke 4.0 3.9 Oxygen-containing hydrocarbons 1.0 Gasoline MON + 3.0 base Gasoline RON + 5.5 base Light gas-oil cetane number + 3.0 base

New hydrogen units based on obsolete cracking units.

The above-described reagent catalysts also catalyze methane decomposition into hydrogen and carbon with a 60-70 wt % conversion at 750C5. This property of reagent catalysts can be used to produce hydrogen from methane on old TCC units (Tab. 4). This is an alternative to steam reforming. Table 4. Calculated material and heat balance for vacuum gas-oil and methane cracking (the reactor/regeneration sections of a TCC unit; the operation conditions of the regenerator vessel were not changed) Cracking conditions in the reactor/regenerator sections of TCC units Parameters Vacuum gas-oil Methane feed 1400 1. Coke burning in the regenerator, kg/h 1400 35.0 2. Feed flowrate, t/h 2.7 60 3. Catalyst circulation rate, t/h 120 1.4 4. Catalyst/feed weight ratio 30 50 5. Feed cracking heat, kcal/kg 3100 60 6. Feed conversion, wt % 70 460 7. Cracking temperature, C 580 5.9 8. Gas flowrate at the exit from the reactor, m3/s 2.1 9. Target product yield, t/h 12.2 (gasoline) 1.7 (hydrogen) 10. Temperature of feed preheating, C 480 600

Zeolites with positively charged framework

Zeolites with positively charged framework is one more promising development direction in catalysis. These materials can be used at old industrial units (Tab. 5). These new zeolites can eliminate the induction period observed in catalytic cracking of paraffins, because they split the hydride ion from a paraffin molecule better than traditional zeolites with a negatively charged framework. This effect ensures a higher conversion of cracking feed and a higher yield of target products. Table 5. Basic Directions of development of new zeolites Characteristics Zeolites with a negative Zeolites without framework charge framework charge 1. Types of adjacent AIO2(-) and SiO2(0) AIO2(-) and PO2(+) tetrahedrons 2. Zeolite trademarks A, X, Y, ZSM, MCM, etc. AIPO4-5, AIPO4-8, VPI5 3. Surface type Acidic Neutral 4. Principal type of Carbenium-ion mechanism Used as a supporting reaction with (acidic catalysis) material hydrocarbons / R R+ (carbenium ion), reaction over zeolite application

Zeolites with a positive framework charge PO2(+)and SiO2(0) Supposed to be named Alice Basic Carbanion mechanism (base catalysis) R R- (carbanion), a reaction over molecular sieves

Conclusion
The above-described new catalytic systems create economic opportunities for existing refining processes and units to enhance performance without expensive retrofits, and allow refiners to improve the quality and yield of target products.

References
1. Kauwff D.A., Bartholic D.B., Hydrocarbon Engineering, 1996, vol. 1, p.51 2. Levinbuk M.I., Pavlov M.L., Kustov L.M., Appl. Catal. A, 1998, vol.172, p. 177 3. Levinbuk M.I., Pavlov M.L., Kustov L.M., et al., Industrial Application of Zeolites, Congress in Brugge, Belgium, 2000, p.157 4. Marxusen C.S., Oil and Gas J., 2001, Feb. 26, p.20 5. Levinbuk M.I., Usachev N.Y., Natural Gas Conversion V, Taormina, Italy, 1998, p.391.