Novel Ebullated Bed Residue Hydrocracking Process

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Novel Ebullated Bed Residue Hydrocracking Process Jiankun Liu, Xiangchen Fang, and Tao Yang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b02937 • Publication Date (Web): 17 Mar 2017 Downloaded from http://pubs.acs.org on March 19, 2017

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Novel Ebullated Bed Residue Hydrocracking Process Jiankun Liu, Xiangchen Fang*, Tao Yang Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, P. R. China, 113001

ABSTRACT: Residue hydrocracking has been attracting more and more attention to refining industry in recent years, and one of the best approaches is ebullated bed residue hydrocracking (EBRH). STRONG® ebullated bed residue hydrocracking uses a new type of reactor, and a 50 KTA demonstration unit has been put into operation now. Crucial points of STRONG® residue hydrocracking are proposal physical and chemical properties of solid catalyst, flow mechanism, efficient separation of gas-liquid-solid in the reactor and reaction performance within various scale of pilot test. The results showed that STRONG® reactor with microspherical catalyst inside cancelled recycling pump inside and outside, overcame mass transfer difficulties, solved diffusion control problem, and created high catalyst efficiency to reduce catalyst consumption. To prevent catalyst from being entrained from the reactor, tri-phase separator was used and the amount of catalyst carried off were less than 1 µg/g.

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1. INTRODUCTION Heavy, sweet and sour crude oil have widened substantially in recent years. Conversion of heavy oil is still a major economic consideration for refiners around the world. While world demand on lighter fuels such as naphthas and middle distillates of crude oil is on the rise, quality of world crude is decreasing and extra heavy crudes and unconventional oil are alternative to conventional and sweeter oil. Heavy oil and bitumen resources and their worldwide distribution and composition of petroleum reserve worldwide are shown in Figure 1 and 2. Future refineries are dealing with conversion of nearly all residues to light and middle distillates through various separation and cracking processes. Optimum operation of such units depend on the knowledge of physical properties1 feedstocks and products. Meanwhile, driven by inferior crude oil supply, strict product and environmental protection specifications, all trends boost the importance of refining processes that are able to convert heavy petroleum fractions, such as vacuum residues, into lighter and more valuable clean products 2–5. Residue hydroprocess is gradually becoming a major upgrading process and being quickly developed. Residue hydrocracking has been attracting more and more attention to refining industry in decades, and one of the best approach is ebullated bed residue hydrocracking (EBRH)6. Ebullated bed hydrocracking process has been integrated in some refineries to upgrade heavy hydrocarbons (residues) from petroleum7. A homogeneous environment is created to hydrotreat and hydrocrack the problematic heavy feedstocks with a high amount of metals and asphaltenes. Hydrocarbon and hydrogen are fed upflow through a catalyst bed very flexible operation (high and low conversion modes); Operating factors of the process have been increased and maintenance costs has been reduced by periodic withdrawal or addition of

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catalyst to the reactor without interrupting the operation; Catalyst bed expansion is controlled by adjusting the circulating ebullating pump flow, catalyst bed expansion of 30-50% is desired, and it ensures ample free space between particles, allowing entrained solid to pass through the bed without accumulation or plugging; Good heat transfer leading to minimized overheating of the catalyst and less coke; Constant product properties are constantly maintained at a high level and isothermal operating conditions achieved. Ebullated bed has the folowing advantages: wide adaptability to feedstock due to reactants inside the reactor being continuously stirred and no blockage; low pressure drop and no increase with running time, avoiding shutdown of fixed bed caused by too high pressure drop; catalyst, feedstock and hydrogen inside the reactor being backmixed in the reactor, promote mass and heat transfer; ebullated bed reactor internal temperatures being basically the same, not only increasing catalyst activity, but also avoiding temperature runaway phenomenon of fixed bed process due to local overheating. Higher temperature in the reactor and full fluidized condition created the necessary conditions of processing pure vacuum residue directly, which is different from feedstock of fixed bed containing a certain amount of gas oil and provides more options for equipment investment and product structure optimization of general process of design in the refinery. Flexible operation and flexible adjustment reaction parameters according to the changes of feedstock and product, which is unlike all sorts of worries in fixed bed unit, such as once improper adjustment, causes the reaction sequence fail to run. The development of ebullated bed technology can enhance capability in treating inferior residue, so it has good application prospect and can bring economic and social benefits. The inlet gaseous hydrogen and liquid atmospheric/vacuum distillation tower bottoms mixture are

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heated separately and then fed into the plenum chamber below the grid (i.e., gas–liquid distributor plate) using a horse-shoe/shroud distributor assembly8. There are two ebullated bed technology licensers, namely IFP offer H-Oil and T-Star technology and CLG supplies LC-Fining technology9-10. The only one difference is the location of circulating pump, inner or outer the reactor11, 12, which can be seen in Figure 3. It is a fluidized-bed three-phase system with an excellent continuous mixing of liquid and catalyst particles. The inherent advantages of a good back-mixed bed are excellent temperature control and since bed plugging and channeling are eliminated, low and constant pressure drops over several years of continuous operation. Therefore, ebullated bed reactors have the unique characteristic of stirred reactor type operation with a fluidized catalyst. This results in the ability to handle exothermic reactions, solid-containing feedstock and a flexible operation while changing feedstocks or operating objectives. The catalyst used for the ebullated bed is typically a 0.8-1.0 mm diameter extrudates with nickel-molybdenum active metals. The catalyst used is held in a fluidized state through the upward lift of liquid reactants (feed oil plus recycle) and gas (hydrogen feed and recycle) which enter in the reactor plenum and are distributed across the bed through a distributor and grid plate. The height of the ebullated catalyst bed is controlled by the rate of liquid recycle flow. This liquid rate is adjusted by varying the speed of the ebullating pump (i.e., a canned centrifugal pump) which controls the flow of ebullating liquid obtained from the internal vapor/liquid separator inside the reactor. But others are more or less the same, such as both of them use cylindrical extrudates of 0.8-1.0 mm13. Continuous ebullation must be provided all along if this kind of particle is chosen, and cylinder attrition cannot be ignored. 4


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Both of H-Oil and LC-Fining technology use circulating pump to supply efficient fluidization force to make particles fluidized. However, this will cause emergency, for example, serious explosion of H-Oil reactor in Bayway refinery in 1973 was caused by leakage of recycling pump14. In addition, there are other limitations when using cylindrical particles: attrition and erosion; low particles utilization; non-uniform of impurity sediment formation on catalyst. Vinod T. Sinha15 has studied in three phase fluidization, cylindrical extrudates of 1.6 mm diameter and L/D ratio of 3-6 are equivalent in expansion characteristics to polydisperse beads of median diameter 2 mm. Similarly, 1 mm diameter extrudates are equivalent to 1.3 mm median diameter beads. Fushun Research Institute of Petroleum and Petrochemicals (FRIPP)，SINOPEC has carried out systematic study of these two types of reactors, and compared and analyzed the advantages and disadvantages. Finally, a new ebullated bed reactor with novel tri-phase separator was created, and the technology was named STRONG® (SINOPEC Technology of Residue Oil New Generation). The microspherical catalyst used in the reactor is fluidized not by recycling pump, but only by gas and liquid which enter into the reactor. This requires that the tri-phase separator at the top of the reactor should have high separation efficiency and operational flexibility, which can ensure no catalyst entrainment. Furthermore, ebullated bed technology with novel tri-phase separator in the reactor has been researched and developed with independent intellectual property rights, which has unique advantages compared with them:

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(1) Improve the stability of the system by canceling high temperature and high pressure circulating pump, which affect operation and running with safety concerns. Canceling oil circulating pump can enhance the mixture of gas, liquid and solid in reaction zone, increase on-stream factor and the utilization of the reactor. (2) Improve the fluidization and ebullition by using microspherical catalyst. The catalyst in the reactor can be fluidized by gas-liquid flow, and fluidization effect of catalyst in the reactor can be controlled by adjusting gas and liquid flow rates, which can also increase the utilization of catalyst and improve on-stream addition and withdrawal of catalyst. Using microspherical catalyst solved diffusion control problem and high catalyst efficiency create the necessary conditions to reduce catalyst consumption. Pilot test were performed on various ebullated bed equipment in terms of reaction process performances and catalyst. Test of hydraulic and internal structure of the reactor were performed on 20 KTA semi-industrial cold model equipment. SINOPEC has organized research group to make an intensive study and development, and has constructed large scale cold model test equipment of 1 meter diameter, whole process pilot equipment of 4 liter, and applied for more than 160 patents. SINOPEC has completed 50 KTA ebullated bed industrial demonstration unit industrial operation test successfully in 2015. 2. BASIC PRINCIPLES Reactor with gas, liquid and solid plays an important role in STRONG® ebullated bed technology, which involves suitable selection, preparation technology of solid, flow pattern analysis of tri-phase fluidization reactor and principle and effect of tri-phase separator.

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2.1. Separation of gas-liquid-solid. As is shown in Figure 4, gas-liquid mass transfer and liquid diffusion in catalyst particle pores in gas-liquid-solid fluidization system is very important, especially in residue reaction system, coke and metal from feedstock will deposit onto the surface and into the pores of catalyst. In order to overcome mass transfer difficulties, increasing gas hold-up ratio, decreasing gas bubble size and catalyst particle size are preferred. Decreasing particle size of catalyst can increase surface area of the catalyst, decrease internal diffusion distance and increase adsorption rate. In gas-liquid-solid fluidization system, as continuous phase, liquid is the keypoint of making solid expanded. The choice of particle depends on critical fluidization velocity and terminal velocity of particle. Critical fluidization velocity can be observed and determined by inflexion point of bed pressure drops. The terminal velocity can be calculated by Stokes law Correlations and its semi-empirical formula with concrete parameters such as pore volume of particle (Eq. (1-2)). Fluidization velocity of particles with different diameter are shown in Figure 5.

ut =

g ( ρ s − ρ L )d p

2

18µ

(1)

where ut is the settling velocity; g is acceleration due to gravity; ρ s and ρ L are respectively the density of particle and liquid; d p is the diameter of particle; and µ is dynamic viscosity.

ut =

3 gd p

ρ Lψ

( ρ s − ρ L )(1 − ε 0 )

(2)

ψ is the resistance settlement coefficient which is caculated by ψ = 8.8 / R 0.64 , ε is the pore e 0 volume of particle.

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2.2. Preparation technology of microspherical catalyst. Based upon the characteristics of STRONG® process, FRIPP has worked on the development and preparation of microspherical catalyst. Carrier of active component of catalysts used in this work are Al2O3, active component are Mo-Ni. Aiming at the problems existing in the present preparation technology and the development of ebullated bed process technology features, three methods of preparation were selected to carry out the preparation process of catalyst16, as shown in Table 1. Method I, II, III are referred to oil-drop method, oil-ammonia column shaping and rotational forming, respectively. The results can be seen in Table 1, preparation method I of spherical carrier prepared by low yield, particle size distribution and diffusion; according to method III, the yield is higher, but it is difficult to obtain fine particles prepared by microspherical carrier; method II, high yield, fine particle size, particle size distribution is relatively concentrated, and the distribution range is easy to adjust the size. In this study, preparation method II was confirmed. Catalyst attrition index in fluidized bed was tested in measuring abrasion tester developed by FRIPP, as is shown in Table 2. Abrasion index refers to the sample weight abrasion rate per unit time, the smaller the value is, the better abrasion resistance is. Table 2 shows that the microspherical catalyst has good abrasion resistance compared with reference reagent by method I. More than two years of operation showed that catalyst strength met the requirements. Catalyst preparation process improvement and optimization design could realize large scale production of microspherical catalyst and production efficiency, achieve equal production

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efficiency with extrusion strip method catalyst production process and meet requirements of million tons of industrial ebullated bed units. 2.3. Flow pattern analysis of tri-phase fluidization reactor. Suitable size of particles can be easily chosen, but the problem of gas-liquid-solid separation will be enlarged quickly. Before solving the problem of gas-liquid-solid separation, mixing and flow conditions are crucial to chemical reactions and the problem to study the reaction kinetics and reactor design or improvement must be considered. Mixing conditions in the reactor can be determined and described indirectly by residence time distribution (RTD), which is the basis of simplification of the problem, establishment of appropriate flow model and calculation of mass balance. As is seen in Figure 6, the test was carried out under the conditions of liquid velocity and different gas velocity, residence time distribution density function E(t) and variance σθ2 of various axial positions can be measured using pulse method and KCl solution tracer. Residence time distribution, mean residence time τ and variance σθ2 can be calculated and analyzed by injecting tracer into the bottom of the reactor and continuous detection of the liquid outlet and the electrolyte concentration with the time changing. According to the relationship curve of the known electrical conductivity and KCl solution concentration, E (t) was obtained17, and the residence time distribution curves were plotted, and mean residence time τ was calculated. ∞

τ=

∫ tc(t )d ∫ c(t )d 0 ∞

∞

σt

(3)

t

0

2

t

∫ t c(t )d = ∫ c(t )d 2

0

∞

−τ 2

(4)

t

0

σθ 2 =

t

σt2 τ2

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(5)

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Number of tanks can be got in Eq.(6)

N=

1

σθ 2

(6)

As is shown in Figure 7, one hand RTD is similar to the ideal well-mixed model. Liquid –gas –solid 1-5 of Figure 7 means five gas velocity conditions, from 14.1 mm·s-1, 18.3 mm·s-1, 22.0 mm·s-1, 24.6 mm·s-1, 35.2 mm·s-1. The density function E(t) curve is obvious, and the area under E(t) curve is unity. Both gas-liquid and gas-liquid-solid inside the reactor are stirred and mixed well, and is similar to 1-2 N tanks in series CSTR. On the other hand, this indicates that pseudo-homogeneous phase of solid and liquid is affected by gas weakly. Determination of RTD function under gas-liquid-solid condition shows that gas has increased mixing among three phases, enhanced fluidization and ebullition state, realized the mixing flow and no channeling, short circuit and dead time. With backmixing, the reaction will be self-sustaining because the heat generated by the reaction can raise fresh reactants to a temperature at which they will react.

2.4. New innovation of new tri-phase separator and its principle and effect. On the contrary, pseudo-homogeneous phase composed by solid and liquid add further problems to separate gas, liquid and solid. Separator must have such functions: gas, liquid and solid get into the separating zone and can be separated according to their velocity, density, viscosity and other character. We could separate one from it, and separate the other two phases; or separate all the three phases simultaneously, as is seen in Figure 8. The liquid velocity is normally much lower than the catalyst terminal velocity. Considering the liquid phase alone, the catalyst will not be entrained. After repeated experiments, the main reason is that large bubbles carrying particles out. Tri-phase separator is 10


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to solve the separation of rising bubbles, so that the catalyst is separated to return to the reaction zone. According to this principle, the structure of tri-phase separator is designed18, and the structure and size are studied and optimized. The basic principle is that the gas is separated from the reactor first and then liquid. So we divide the part with separator into three zones, as is seen in Figure 9: Gas separating zone S1: The raising part in the middle has some separating space and can separate gas which can flow in the upper side. Liquid-solid baffling zone S2: Liquid-solid flow along Liquid-solid separating zone S3: Particles can sedimentate in this zone and realize to be separated from liquid. In the raising part in the middle, gas has occupied some space, and thus the density of three phases is lower, and gas separated can flow from the upper side. The baffling zone of liquid-solid phase has higher density. So a natural cycle between S1 and S2 is formatted due to the driving force of the difference of density between inside and outside, which is beneficial to strengthening the flow and promoting the separation. At present, the structure of tri-phase separator has been greatly improved, and the relevant factors of tri-phase separator have been systematically studied, so that the separation efficiency of tri-phase separator has been improved, and the amount of catalyst is < 1µg/g.

3. PILOT TEST The diagram of ebullated-bed pilot plant, as shown in Figure 10, is that a mixture of feedstock and H2 is passed upwardly through a bed of catalyst particles so that the particles are forced into random motion as liquid and gas flow upwardly through the bed. In the upper

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portion of reactor, solid catalyst particles are separated from the mixture of gas-liquid-solid and drop back to the reactor. The effluent from reactor is fed to high temperature high pressure separator (HHS) in which liquid product is separated from gas. The separated liquid is fed to high temperature low pressure separator (HLS) to flash light component followed by stripping in a stripper, and then fed to product tank. Gas from HHS is fed to low temperature high pressure separator (LHS) to separate light distillate which is fed to product tank and then is recycled after washed in water-washing column. The feedstock for test is Iranian, Sadi Arab, Kuwait and other typical inferior vacuum residue. Effect of temperature, LHSV and H2/oil ratio on reaction performance has been tested. The element composition of feedstock and product were measured in accordance with ASTM D-5291 for nitrogen content and ASTM D-1552 for sulfur content. Conradson carbon content was measured according to ASTM D-189. The samples were analyzed for their SARA (saturates, aromatics, resins, and asphaltenes) composition in accordance with the procedure, described in ref 26. Distillation of feedstock and product were determined by high temperature simulated distillation, method ASTM D-7169. Density was measured according to ISO3838, and viscosity according to ASTM D445-86.

3.1. Effect of temperature on reaction performance. Under a given condition of pressure, H2/oil ratio and LHSV, the effect of temperature on nickel and vanadium removal (HD(Ni＋ V)) and HDS is investigated in a pilot plant. When other condition is given, the removal level of contaminant metals (HDM) and sulfur increase with the increment of reaction temperature. HDM is easier than HDS at the same temperature, which is almost twice of HDS.

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3.2. Effect of LHSV on reaction performance. Under a given condition of pressure, the effect of H2/oil ratio, mean reaction temperature and LHSV on HD(Ni＋V) and HDS are investigated in a pilot plant. The feedstock for test is Iranian atmospheric residue. When other condition is given, HDM and HDS decrease with the increment of LHSV, but the level of HDM decreases obviously as compared with HDS. The flow state of fluid in an ebullated-bed reactor is between completely back mixing flow and plug flow. The flow state of fluid is close to plug flow at lower LHSV. At this time, HDM and HDS can be attained effectively due to poorly back mixing of feedstock with product, only a small quantity of unconverted feedstock being mixed with the effluent from reactor, and long residence time. Conterwise, the flow state of fluid is close to completely back mixing with the increment of LHSV, which has negative impact on result, because the effluent from reactor contains a great deal of unconverted feedstock and residence time of feedstock in reactor is shortened at high LHSV.

3.3. Effect of H2/oil ratio on reaction performance. Under a given condition of pressure, LHSV and mean reaction temperature, the effect of H2/oil ratio on HD(Ni＋V) and HDS is investigated in a pilot plant. The changing trends of HDS and HDM approximate parabola with the increment of H2/oil ratio. The removal of impurities is higher in base+600 of H2/oil ratio. Gas holdup in reactor is too low to meet the demand for residue hydrocracking when H2/oil ratio is too low, and as a result, the removal of impurities isn’t effective. Gas holdup and H2 pressure increase with the increment of H2/oil ratio which are beneficial to residue hydrocracking. But when H2/oil ratio increases over base+600, gas holdup in reactor will gradually decrease and reduce contact time between feedstock and catalyst. The exorbitant H2/oil ratio will bring the change of flow state and has negative impact.

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3.4. Test on reaction performance of different feedstock adaptability. To test reaction performance of different feedstock adapbility, several kinds of high metal, high viscosity and high CCR feedstock were selected to carry out HDM with single reactor, HDM and HDS test with single stage in series, which are shown in Table 3 and Table 4. Reaction condition: temperature base and base +20、H2/oil ratio 900:1、pressure 15 MPa. The 500° C+ conversion was estimated by the relative equation19. As can be seen in Table 3, F3 is inferior and difficult to process compared with reference feedstock F4 or F2. It can be seen from Table 4 that feedstock F4: CCR removal, the corresponding reaction results of 500℃+ conversion, asphaltenes removal and HDV are better than that of feedstock F1, F2 and F3, and this phenomenon is more obvious under high temperature base+20. As can be seen from Table 4 and Table 5: sulfur in Feedstock F2 can be easily removed under temperature base, LHSV base, HDS reached 94.74%; sulfur in Feedstock F3 is difficult to be removed under temperature base, LHSV 0.5 base, HDS 72%. This is due to the two main sulfur structure, thiophene, and thioether of easier sulfur removal; thiophene exists in the aromatic ring in the conjugate effect and steric hindrance inhibited the removal of sulfur, which shows most of the sulfur in feedstock F2 exist in sulfide sulfur form, sulfur in F3 exists in heterocyclic aromatic ring structure, and is difficult to be removed. Comparison of HDV and HDNi of F2, F3 and F1 showed that under the same reaction conditions, HDV of the same feedstock is higher than HDNi; HDV of F1 and F2 are easier than that of F3, HDNi of F2 and F3 are more difficult than F1, and HDNi of F2 is the most difficult. It is considered that Ni and V are in the form of porphyrins of various types20,21, and that they

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are associated with the asphaltenes aggregates in a porphyrin-like form by strong noncovalent interactions22,23, in which porphyrins core of small molecule can be adsorbed or encapsulated in the asphaltenes molecule due to strong polarity. Porphyrins complexes structure difference between Ni and V is obvious: Ni2+ in porphyrins is located in the center, while V is located in the central position of circular plane upward projections of four side cone structure, where four nitrogen atoms located at four corners of the bottom, so the polarity of V porphyrins is stronger than Ni porphyrins24. Catalyst acid is easy to adsorb and remove strong polar compounds, so HDV is higher than HDNi. It is obvious that V in F2 exists in the form of small molecule porphyrins nucleus and porphyrins complexes, and porphyrins complexes is distributed in the relatively small molecular weight of light resin. Ni in F2 and F3 were mainly distributed in porphyrins complexes and non porphyrins complexes forms in asphaltenes and heavy resin, so it is difficult to remove. Reaction performance such as CCR, metal and sulphur removal of single reactor under temperature base and LHSV 0.5base is better than reactors in series with HDM and HDS temperature base+20 and LHSV base, which shows that residue hydrocracking should choose mode of operation with mild temperature, low LHSV and multi reactor in series.

3.5. Analysis of chemical structure of feedstock and products. As one component of residue, asphaltenes are a solubility class of petroleum crude oil that can destabilize and deposit in both upstream and downstream processes25. In order to characterize chemical structure during the process and analyze the properties of feedstock above and reaction performance further, chemical structure of feedstock and product was analyzed and calculated. The results are shown in Table 6-9. The samples were characterized by 13C nuclear magnetic resonance (NMR)

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for structural characterization26, 27. Number-average Molecular Weight (Mn) was measured according to ASTM D 2503-92. As can be seen from Table 6, aromatic ring content and degree of aromatic ring condensation of F2 and F3 are high, which are difficult to process. Comparison of chemical structure of Table 6-9 can be seen that aromatic carbon ratio, aromatic ring number and total ring number decrease, condensation degree parameters of aromatic ring increase, aromatic ring condensation degree reduce, and properties of products are greatly improved by single reactor hydrodemetalization(HDM), single stage of HDM and desulfurization reaction. Comparison of chemical structure can be seen in Table 8-9: for the same feedstock, aromatic carbon ratio and total ring number, aromatic ring number, aromatic ring condensation parameters in product of single reactor hydrodemetallization under temperature base and LHSV 0.5base is similar to single reactor hydrodemetallization under temperature base+20 and LHSV base, which can also explain mode of operation with mild temperature, low LHSV and multi reactor in series is an ideal scheme for residue hydroprocessing.

4. DEMO PILOT TEST 50 KTA industrial demonstration unit has finished all the researching test, involving thermal inspection, catalyst loading, reactor pressurization, catalyst sulfiding, residue switching, conversion test, on-line addition and withdrawn, emergency relief, shutdown catalyst unloading and spent catalyst handling, and has finished normal shutdown. Residue hydrocracking conversion test was carried on under different conditions on industrial demonstration unit. STRONG® technology could process the feedstock with metal content (Ni + V) 210.8 µg/g, sulfur content 6.0%, and carbon residue content 23.73%, HDCCR

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could reach 83.5%, HDS could reach 87.6%, HDM could reach 97.3% and conversion could reach 78.6%. Carbon residue content was 4.36%, sulfur content was 0.83% and metal content (Ni + V) was 6.35 µg/g in whole fraction of product. The emergency pressure relief system is composed of two parts: Manual emergency pressure relief system; uniform emergency pressure relief system. Smooth operation and no liquid level rising in flash tank and hot high pressure separator of manual pressure relief and uniform discharge pressure test showed that no catalyst entrained in gas phase and verified that the relief pressure system is safe and reliable, as is seen in Figure 11. In the pressure relief process, the temperature of upper part of the reactor was significantly reduced, which shows that the emergency pressure relief is effective to suppress the excess temperature condition. The on-line addition process is divided into two parts, which are transportation from storage tank to addition tank and from addition tank to reactor. The on-line withdrawn process is divided into two parts, which are transportation from reactor to withdrawn tank and from withdrawn tank to withdrawn storage tank. Convenient and reliable on-stream addition and withdrawal of catalyst system and control scheme has been confirmed. The catalyst addition and withdrawal test under different working conditions proved that it has no influence on unit operation. The significance of industrial demonstration unit operation: First, STRONG® ebullated bed technology whole process was gotten through; Second, ebullated bed reactor and internals with independent intellectual property rights was fully confirmed in wide operating conditions, more stable system and no high temperature and high pressure circulating pump system compared to existing technology; Third, controlling depressurization, emergency relief

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pressure, reduction impact of fluctuations operation proved STRONG® ebullated bed technology with high safety and system reliability; Fourth, production process of microspherical catalyst is simple and catalyst performance is stable with high strength and low attrition, reflecting microspherical catalyst advantage in residue processing; Fifth, convenient and reliable on-stream addition and withdrawal of catalyst system and control scheme has been confirmed.

5. Application field Taking ebullated bed as the core of refinery processing, combination process of ebullated bed with fixed-bed, FCC and coking can improve the utilization of heavy oil resources significantly, increase production of high value-added products significantly, thus improve economic efficiency greatly. For feedstock of Ni+V < 200 µg/g and CCR < 20 µg/g, combination process of ebullated bed with fixed bed and FCC is suitable to process, as is seen in Figure 12. It is possible to improve the property of fixed bed feedstock significantly28, reduce the content of impurities substantially, and improve fixed bed operation greatly within ebullated bed ahead. The advantages of combination process are low pressure drop of ebullated bed reactor and no increase with running time; wide adaptability to feedstock because reactants inside the reactor are continuous stirred; higher temperature in the reactor and full fluidized condition enhances asphaltenes removal; and high viscosity vacuum residue is processed directly. Meanwhile, it can enlarge the range of heavy oil feedstock and prolong the operating cycle. Combination process can improve the utilization of heavy oil resources significantly, form the new situation of ebullated bed integrated with fixed bed as the core of refinery processing, and improve the

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overall economic benefits greatly with a good prospect of application. Pilot test data shows that combination of ebullated bed and fixed bed can realize stable operation and hydrotreated oil can be directly used as feedstock of FCC, so as to realize efficient conversion of residue. Combination of ebullated bed and fixed bed has better profitability and can realize stable operation of three years, which can match with downstream process and realize the synchronous startup and shutdown by analyzing technical characteristics and technical economy and comparing with fixed bed process alone. For feedstock of 200 µg/g < Ni+V < 300 µg/g and 20 µg/g < CCR < 25 µg/g, combination of ebullated bed with FCC is suitable to process, as is seen in Figure 13. After hydrotreated by ebullated bed, hydrotreated atmospheric residue can be used as the feedstock of FCC29, which is one of the means for the efficient conversion of inferior residue, and the yield of light oil is more than 63%, meanwhile the yield of high value-added products is more than 78%, based on the characteristics of inferior residue. It is fully proved that the process of ebullated bed integrated with FCC is entirely feasible, with high quality of product, high yield of liquid product, good economic returns and comprehensive utilization ratio. Meanwhile, it is possible to improve the property of FCC feedstock significantly, reduce the content of impurities substantially, and improve FCC operation greatly, which is more important to increase gasoline yield in China. The process has combined the characteristics of ebullated bed and FCC, exerted each advantage fully, altered the circumstances of FCC as the core of refinery processing in the past simply, and formed the new situation of ebullated bed as the core of refinery conversion. The combined process has expanded the source of feedstock for the

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heavy oil processing, improved the utilization of heavy oil resources significantly, and improved overall economic benefits greatly with a good prospect of application. For feedstock of Ni+V > 300 µg/g and CCR > 25 µg/g, combination process of ebullated bed with coking is suitable for inferior residue processing, as is seen in Figure 14. Impurity of the product from inferior residue feedstock is significantly reduced after ebullated bed residue hydroprocessed30. Compared with coking process, combination of ebullated bed and coking can achieve efficient conversion of residue, process inferior residue feedstock, increase the total liquid volume by more than 13%, reduce sulfur content in coke and improve the ability to increase production of high value-added products significantly, thus improve economic efficiency greatly. Meanwhile, the combination has obvious advantages of improving stability, wide adaptability of feedstock and flexible process, which is the preferred option to improve crude oil resource utilization.

6. CONCLUSIONS Residue hydroprocessing technology is effective to lighten heavy oil widely. With the aggravation of more inferior crude oil, ebullated bed hydroprocessing technology has been widely concerned and applied. Ebullated bed hydroprocessing technology can bring operational flexibility and economic benefit for the enterprise. One key of STRONG® ebullated bed technology is the choice and preparation of microspherical catalyst. The other is its unique reactor. The tri-phase separator prevented the catalyst from being entrained from the reactor effectively, and the amount of catalyst carried off was less than 1 µg/g. Meanwhile, STRONG® reactor with microspherical catalyst inside cancelled recycling pump inside and outside, overcame mass transfer difficulties, solved

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Energy & Fuels

diffusion control problem, and high catalyst efficiency create necessary conditions to reduce catalyst consumption. Effect of temperature, LHSV on reaction performance and chemical structure during the process are checked from pilot test, and results shows that residue hydrocracking should choose ideal mode of operation with mild temperature, low LHSV and multi reactor in series. ®

After nearly half a century of research and development, STRONG ebullated bed technology has completed laboratory, pilot and industrial enlarging test successfully, and 2 MMTA process package programming has been compiled. Complete conversion of inferior ®

residue can be achieved by combination of STRONG ebullated bed with fixed bed, FCC, coking, solvent deasphalting or others, which will provide technical support for refining enterprises.

■ AUTHOR INFORMATION Corresponding Author *E-mail: [email protected].

Notes The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS This work was financially supported by Research Program of SINOPEC and Natural Science Science Foundation (6162780020).

■ Nomenclature ut

settling velocity

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g

acceleration due to gravity

ρs

density of particle

ρL

density of liquid

dp

diameter of particle

µ ψ

dynamic viscosity resistance settlement coefficient

ε0

pore volume of particle

U min

minimum fluidization velocity

Re RTD t E (t) c(t)

Reynolds number residence time distribution time residence time distribution density function concentration of KCl with time 2 σθ dimensionless variance 2 σt variance τ mean residence time N number of tanks CSTR continuous stirred-tank reactors fA aromaticity Mn number-average molecular weight fP fraction of paraffinic carbon RT total ring number RA aromatic ring number RN naphthenic ring number δ chemical shift HAU unsubstituted hydrogen of aromatic carbon CA carbon arocmatiity HAU /CA degree of aromatic ring condensation S sulfur N nitrogen Fe iron Ni nickel V vanadium Ca calcium Na sodium LHSV liquid hourly space velocity HD(Ni＋V) nickel and vanadium removal HDV vanadium removal HDNi nickel removal

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Energy & Fuels

HDS HDM CCR HDCCR HDAS NMR FCC

hydrodesulfurization hydrodemetalization Conradson carbon residue Conradson carbon residue removal asphaltenes removal nuclear magnetic resonance fluid catalytic cracking

■ REFERENCES

(1) Riazi, M. R. Characteristics of heavy fractions for design and operation of upgrading related processes. AIChE Annual Meeting, 2013. (2) M.S. Rana, V. Sámano, J. Ancheyta, J.A.I. Diaz, A review of recent advances on process technologies for upgrading of heavy oils and residua, Fuel 2007, 86, 1216–1231. (3) A.Y. Huc (Ed.), Heavy Crude Oils: From Geology to Upgrading, Editions Technip, Paris, 2011, ISBN 978-2-7108-0890-9. (4) H. Toulhoat, P. Raybaud (Eds.), Catalysis by Transition Metal Sulphides: From Molecular Theory to Industrial Application, Editions Technip, Paris, 2013, ISBN978-2-7108-0991-3. R.J. (5) Luís Pereira de Oliveira, Jan J. Verstraete, Max Kolb, Simulating vacuum residue hydroconversion by means of Monte-Carlo techniques, Catalysis Today 2014, 220– 222, 208– 220. (6) Farshid, D.; Murphy, J.; Reynolds, B. Process for upgrading heavy oil using a reactor with a novel reactor separation system. US, 7431822, 2008. (7) F. Ortega García, E. Mar-Juárez, and P. Schacht Hernández, Controlling Sediments in the Ebullated Bed Hydrocracking Process, Energy Fuels 2012, 26, 2948−2952. (8) Pjonteka, D.; McKnightb, C. A.; Wiens, J.; Macchi, A. Ebullated bed fluid dynamics relevant to industrial hydroprocessing. Chemical Engineering Science 2015, 126, 730-744.

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(9) K. M. Sundaram, U. Mukherjee, M. Baldassari, Thermodynamic Model of Sediment Deposition in the LC-FINING Process, Energy & Fuels 2008, 22, 3226–3236. (10) R. S. Ruiz, F. Alonso, and J. Ancheyta, Minimum Fluidization Velocity and Bed Expansion Characteristics of Hydrotreating Catalysts in Ebullated-Bed Systems, Energy & Fuels 2004, 18, 1149-1155. (11) McKnight, C. A.; Hackman, L. P.; Grace, J. R.; Macchi, A.; Kiel, D.; Tyler, J. Fluid dynamic studies in support of an industrial three-phase fluidized bed hydro-processor. Can. J. Chem. Eng. 2003, 81, 338-350. (12) Elia, M.; Schweitzer, J. M.; Lopez-Garcia, C. IFP Energies Nouvelles, Solaize/F; U. Ehrenstein, IRPHE, Marseille/F Modelling ebullated bed reactor for residue hydroprocessing. (13) Eccles, R. M. Residue hydroprocessing using ebullated-bed reactors. Fuel Process. Technol. 1993, 35, 21-38. (14) Fang, X. Hydroprocessing. Beijing: China Petrochemical Press, 2006. (15) Sinha, V. T.; Butensky, M. S.; Hyman, D. Comparison of cylinders and spheres in three-phase fluidization. Ind. Eng. Chem. Process Des. Dev. 1986, 25, 324-324. (16) Sun, S.; Wang, G.; Fang, X.; Zhu, H.; Liu, J.; Yang, G. Development of catalyst for STRONG ebullated-bed residue hydrotreating process. Petroleum Refinery Engineering 2011, 26-30. (17) Levenspiel, O. Chemical Reaction Engineering (3rd ed.). John Wiley & Sons 1999. (18) Fang, X. World resid hydrotreating technology development state and its evaluation. Chem. Ind. Eng. Prog. 2011, 30, 95-104. (19) Stratiev, D.; Dinkov, R.; Shishkova, I.; Sharafutdinov, I.; Ivanova, N.; Mitkova, M. What is behind the high values of hot filtration test of the ebullated bed residue H-oil hydrocracker residual oils. Energy

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Fuels 2016, DOI: 10.1021/acs.energyfuels.6b01241. (20) Goulon, J.; Retournard, A.; Friant, P.; Ginet-Goulon, C.; Berte, C.; Muller, J. F.; Poncet, J. L.; Guilard, R.; Escalier, J. C. Structural characterization by x-ray adsorption spectroscopy (EXAFS/XANES) of the vanadium chemical environment in Boscan asphaltenes. Chem. Soc. Dalton Trans. 1984, 6, 1095-1103. (21) Jacobsen, A. C.; Cooper, B. H.; Hannerup, P. N. Catalysts for hydrotreating of heavy oil fractions. Proc. 12th Petrol. World Congr. 1987, 4, 97-107. (22) Sakanishi, K.; Yamashita, N.; Witehurst, D. D.; Mochida, I. Depolymerization and demetallization treatments of asphaltene in vacuum residue. Preprint. Am. Chem. Soc. Div. Petrol. Chem. 1997, 42, 373-377. (23) Ancheyta, J.; Rana, M. S.; Furimsky, E. Hydroprocessing of heavy petroleum feeds: tutorial. Catal. Today 2005, 109, 3-15. (24) Ali, M. F.; Abbas, S. Fuel Process. Technol., 2006, 87, 573. (25) Michael P. Hoepfner, Vipawee Limsakoune, Varun Chuenmeechao, Tabish Maqbool and H. Scott Fogler, A Fundamental Study of Asphaltene Deposition, Energy Fuels 2013, 27, 725−735. (26) Joao Marques, Simon Maget, and Jan J. Verstraete, Improvement of Ebullated-Bed Effluent Stability at HighConversion Operation, Energy Fuels 2011, 25, 3867–3874. (27) Isabelle Merdrignac, Anne-Agathe Quoineaud, and Thierry Gauthier, Evolution of Asphaltene Structure during Hydroconversion Conditions, Energy & Fuels 2006, 20, 2028-2036. (28) YANG, T.; LIU, J.; GENG, X. Study on residue hydrotreating technology of integration of

ebullated bed and fixed bed. Petroleum Refinery Engineering 2015, 5, 35-39. (29) LIU, J.; YANG, T.; JIANG, L.; FANG, X. Study on the process of ebullated bed integreted with FCC. 2013, 10, 104-107.

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(30) LIU, J.; YANG, T.; FANG, X.; JIANG, L. Study on the combined process of ebullated bed residue hydroprocessing and coking. Acta Petrolei Sinica 2015, 3, 663-669.

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Energy & Fuels

Table 1. Study of Different Preparation Methods of Carrier Carrier

Method

Distribution (%)

Yield/% 0.5 mm

Z-1

Ⅰ

55.6

3.4

48.1

48.5

Z-2

Ⅱ

85.2

6.7

93.1

0.2

Z-3

Ⅲ

90.5

0

0

100

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Table 2. Comparison of Catalyst Attrition Strength Carrier

STRONG®

Reference reagent

Shape

Microsphere

Microsphere

Diameter (mm)

0.4～0.5

0.4～0.5

Abrasion index (%)

0.62

2.64

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Table 3. Feedstock Property Feedstock

F1

F2

F3

F4

Density (20℃) (g.cm-3)

1.0102

1.0215

1.0144

0.9780

Viscosity (100℃) (mPa.s)

926

1889

1705

108

S (%)

3.31

5.22

2.70

2.81

N (%)

0.4977

0.5427

0.5068

0.3529

CCR (%)

19.67

23.83

21.60

12.55

℃

High temp sim dist, ASTM D-7169, wt % IBP

356

399

443

345

10

526

520

537

414

30

581

583

613

538

50

630

641

703

610

70

692

714

/

710

Saturates

16.70

19.31

19.85

34.72

Aromatics

47.82

47.23

48.44

45.46

Resins

33.19

27.91

23.97

17.78

2.28

5.55

7.75

2.03

Fe

13.84

16.68

26.85

6.54

Ni

61.36

53.63

43.32

28.5

V

171.50

162.30

143.90

85.18

Ca

4.88

2.07

7.81

2.81

Na

3.67

1.04

1.28

0.86

Ni+V

232.86

215.93

187.22

113.68

255.25

235.72

223.16

123.89

SARA Composition, wt %

Asphaltenes -1

Metal (µg.g )

Metal (µg.g-1)

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Table 4. Reaction Performance of Different Feedstock in Single Reactor Feedstock

F1

F2

F3

F4

Temperature (℃)

base

base +20

base

base +20

base

base +20

base

base +20

LHSV

base

base

base

base

base

base

base

base

HDS (%)

58.31

67.07

94.74

97.37

20.51

50.04

45.59

68.22

HDCCR (%)

32.84

40.77

42.06

49.99

12.34

27.74

33.16

55.72

+

16.91

34.01

9.78

22.02

8.75

26.51

20.73

51.02

Saturates

32.96

38.73

30.36

43.61

23.67

31.64

42.89

49.58

Aromatics

43.83

40.72

41.08

31.86

47.66

46.35

44.18

41.70

Resins

22.30

19.90

23.59

20.42

23.74

18.97

12.31

8.51

Asphaltenes

0.91

0.65

4.97

4.15

4.93

3.04

0.62

0.20

HDAS (%)

60.89

72.06

12.24

26.72

37.66

61.56

70.07

90.34

HDNi (%)

74.01

76.34

3.81

11.97

25.55

50.96

70.19

89.00

HDV (%)

90.71

94.77

96.32

98.25

29.58

68.06

94.41

99.42

500℃ conversion (%) SARA composition (%)

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Energy & Fuels

Table 5. Reaction Performance of Different Feedstock in Reactor in Series F1

F2

F3

Temperature

base/base

base+20/base+20

base/base

base+20/base+20

base/base

base+20/base+20

(℃) LHSV (h-1)

0.5base

0.5 base

0.5 base

0.5 base

0.5 base

0.5 base

HDS (%)

71.00

79.46

96.06

98.28

63.64

72.00

HCCR (%)

45.45

60.80

48.57

62.83

33.94

50.17

500℃+

25.65

51.65

14.51

37.52

17.88

42.71

Saturates

41.01

44.55

38.93

53.36

28.13

36.77

Aromatics

39.21

36.49

37.36

27.82

46.49

45.44

Resins

19.34

18.72

20.69

16.80

22.41

15.84

Asphaltenes

0.49

0.24

3.02

2.02

2.97

1.95

HDAS (%)

78.94

90.00

46.67

65.42

62.44

75.34

HDNi (%)

83.65

89.70

5.75

40.41

50.16

70.71

HDV (%)

98.68

99.78

97.85

99.17

75.75

86.70

Conversion SARA Composition

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Table 6. Chemical Structure of Feedstocks Feedstock

F1

F2

F3

F4

H/C

1.43

1.42

1.47

1.52

Mn, g/mol

940

1463

1298

742

fA

0.33

0.33

0.31

0.28

fN

0.14

0.11

0.10

0.16

fP

0.53

0.56

0.59

0.56

RT

9.04

13.92

11.11

6.29

RA

5.86

10.13

8.09

3.55

RN

3.18

3.79

3.02

2.74

RA/RN

1.85

2.67

2.67

1.29

δ

0.57

0.53

0.47

0.54

HAU/CA

0.59

0.53

0.54

0.60

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Energy & Fuels

Table 7. Uncertainty analysis and repeatability of measurements about Chemical Structure of Feedstocks Feedstock

F1

Arithmetic mean

Summation

Square root

Standard deviation

value

value H/C

1.43

1.43

0.0003789

4.21*10-5

0.006488

Mn, g/mol

940

940

324.9

36.1

6.008 -5

0.004972

fA

0.33

0.33

0.0002225

2.47*10

fN

0.14

0.14

9.21*10-5

1.02*10-5

0.003198

-6

0.003019

fP

0.53

0.53

8.2025*10

-5

9.11*10

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Table 8. Chemical Structure of Feedstocks and Hydrometal Products Feedstock

F1

F2

F3

F4

Temperature/℃

base

base+20

base

base+20

base

base+20

base

base+20

H/C

1.54

1.56

1.54

1.59

1.53

1.57

1.58

1.65

Mn

672

542

1137

976

828

608

545

423

fA

0.27

0.27

0.28

0.25

0.29

0.27

0.26

0.22

fN

0.16

0.17

0.09

0.10

0.10

0.14

0.17

0.20

fP

0.57

0.56

0.63

0.66

0.61

0.59

0.57

0.58

RT

5.51

4.32

8.69

6.70

6.44

4.60

4.18

2.95

RA

2.97

2.13

6.15

4.45

4.40

2.60

2.00

0.93

RN

2.54

2.19

2.53

2.25

2.04

2.00

2.18

2.01

RA/RN

1.17

0.97

2.43

1.98

2.15

1.30

0.92

0.46

δ

0.53

0.50

0.46

0.45

0.36

0.36

0.44

0.47

HAU/CA

0.65

0.71

0.58

0.63

0.57

0.61

0.65

0.81

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Energy & Fuels

Table 9. Chemical Structure of Hydrometal and Hydrodesulfurization Products Feedstock

F1

F2

F3

Temperature

base/base

base+20/base+20

base/base

base+20/base+20

base/base

base+20/base+20

(℃) LHSV

0.5base

0.5 base

0.5 base

0.5 base

0.5 base

0.5 base

-1 (h H/C)

1.57

1.61

1.60

1.69

1.60

1.67

Mn

543

376

1050

672

562

475

fA

0.26

0.25

0.24

0.20

0.26

0.22

fN

0.17

0.22

0.10

0.11

0.14

0.14

fP

0.57

0.53

0.67

0.68

0.61

0.64

RT

4.31

2.91

7.15

3.73

3.97

2.82

RA

2.03

0.90

4.70

1.89

2.10

1.19

RN

2.28

2.01

2.45

1.84

1.87

1.62

RA/RN

0.89

0.45

1.91

1.02

1.12

0.74

δ

0.52

0.49

0.49

0.45

0.36

0.37

HAU/CA

0.72

0.84

0.63

0.79

0.66

0.83

35


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(a) Heavy oil Resources 3.3 Trillion Bbl In place

(b) Bitumen Resources 2.6 Trillion Bbl In place

Figure 1. Heavy oil and bitumen resources and their worldwide distribution.

36


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Energy & Fuels

Figure 2. Composition of petroleum reserve worldwide.

37


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(a) LC-Finer

Page 38 of 49

(b) H-Oil

Figure 3. Schematic of the LC-Finer and H-Oil hydroprocessor.

38


Page 39 of 49

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Energy & Fuels

Figure 4. Deposition diagram of coke and metal onto the surface and the pores of catalyst

39


Energy & Fuels

120

Umin Ut

100 Velocity,mm/s

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 40 of 49

80 60 40 20 0 0

0.1

0.2

0.3 0.4 Diameter,mm

0.5

0.6

Figure 5. Fluidization velocity of particles with different diameter of particles.

40


0.7

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Energy & Fuels

Figure 6. Diagram of cold-model experimental apparatus. 1 feed-tank 2 feed-pump 3 gas-balloon 4 liquid-flow meter 5 ejection-nozzle 6 spinner-flow meter 7 reactor 8 liquid-storage 9 gas-storage 10 solvent-inlet 11 detector

41


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 7. Gas-liquid-solid and gas-liquid-solid E (t) function.

42


Page 42 of 49

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Energy & Fuels

Figure 8. Reactor with a tri-phase separator.

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Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 9. Structure of tri-phase separator.

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Energy & Fuels

Figure 10. Reactor with a tri-phase separator.

45


Energy & Fuels

16

7Bar/min 5Bar/min 12

P/MPa

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 46 of 49

8

4

0 0

4

8

12

Time/min

Figure 11. The emergency pressure relief system.

46


16

20

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Energy & Fuels

Figure 12. Combination process of ebullated bed with fixed bed and FCC.

47


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 13. Combination process of ebullated bed with FCC.

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Energy & Fuels

Figure 14. Combination process of ebullated bed with coking.

49


Novel Ebullated Bed Residue Hydrocracking Process

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