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Methods to calculate hydrogen consumption during hydrocracking experiments in batch reactors Guillermo Felix, Alexander Quitian, Emmanuel Rodriguez, Jorge Ancheyta, and Fernando Trejo Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b01878 • Publication Date (Web): 19 Sep 2017 Downloaded from http://pubs.acs.org on September 24, 2017
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Methods to calculate hydrogen consumption during hydrocracking experiments in batch reactors Guillermo Félix1,2, Alexander Quitian2,3, Emmanuel Rodríguez1,2, Jorge Ancheyta2*, Fernando Trejo1. 1
Instituto Politécnico Nacional, Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria. Legaria 694, Col. Irrigación, Mexico City 11500 MEXICO 2
3
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, San Bartolo Atepehuacan, Mexico City, 07730, MEXICO Email:
[email protected] Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Coyoacán, Mexico City 04510 MEXICO ABSTRACT
Different approaches are described to quantify hydrogen consumption, gas production and mass balances in batch reactors for conducting hydrocracking experiments. The methods studied were by weight, by measuring the volume of gas loaded and unloaded from the reactor (with gas syringe and with gasometer), and by calculating the gas volume with an equation of state. All of the approaches proved to be adequate with low losses of mass. Experimental data of slurry-phase partial hydrocracking with mineral catalyst (molybdenite and hematite) conducted in reactors of different size were used to apply the various methods. The size of the reactor did not have a significant effect on the properties of the products, although a larger reactor size allows for a better precision in the measurement of the amount of feeds and products. Keywords: hydrogen consumption, hydrocracking, batch reactor, mass balance, equation of state. 1. Introduction From technical, economical, and environmental points of view the catalytic hydrocracking (HDC) has become one of the most important processes in the petroleum refining industry. HDC is a hydrogen addition process that increases the hydrogen/carbon ratio of a hydrocarbon feed to obtain fuels with reduced amounts of sulfur, nitrogen, metals, etc. [1]. Due to hydrogenation and hydrogenolysis reactions that take place HDC is a process that consumes great amount of hydrogen. In this process, hydrogen is used as a reactant to
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saturate and produce lower molecular weight compounds, also in parallel nitrogen and sulfur compounds are removed, thus producing high quality fuels [2,3]. Hydrogen is needed to perform the HDC reactions, which is mainly supplied by naphtha catalytic reforming units. Proper determination of hydrogen consumption becomes then an important issue during the development of experiments at any reaction scale. The consumption of hydrogen is calculated from mass balances using different approaches, and depends on feedstock and catalyst properties, conversion level, and impurities removal. For instance, a heavy feed requires more addition of hydrogen than a light feed to obtain products with improved quality and low impurities content [4]. Castañeda et al. [2] confirmed with a global hydrogen balance that hydrogen consumption depends on the nature of the feed, as well as the predominant type of reaction being carried out during HDC. This behavior is well-known since for instance heavy fractions contain higher concentrations of impurities than light fractions, and thus they require higher amounts of hydrogen to produce upgraded oils. Before industrial application catalysts and processes are studied at laboratory scale. Particularly, batch reactors are the most used setup in laboratory because of their efficient, cheap, and easy to operate characteristics. In this type of reactors, reactants and catalyst are loaded and brought to react as function of time, under specific conditions of stirring rate, pressure and temperature [5,6]. In the case of HDC tests in a batch reactor, a minimum value of 800 rpm of stirring rate has been reported in the literature to assure that reaction rate is not limited by external mass transfer [7]. The calculation of hydrogen consumption is a common task at commercial level, which is typical done by balance in the gas phase, i.e., the amount of hydrogen in the feed gas minus the amount of hydrogen in the product gas. This way for calculating hydrogen consumption at commercial level has been reported in the literature to be not the most accurate [2]. However, in batch reactors, where the conditions and handling of streams (gas and liquid) are more controlled, the calculation of hydrogen consumption can be done with the gas balance.
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To minimize internal mass transfer resistances, the HDC catalyst is crushed and sieved. For such a small size of catalyst the use of a basket is practically impossible and the catalyst is suspended in the liquid. At this condition, the reactor is considered to operate in slurry mode, and the catalyst has better contact with reactants due to high catalytic population in the reaction media. This high effectiveness of the crushed catalyst is the reason why some research has been done for the development of slurry-phase processes and catalysts for upgrading of heavy oils. The catalyst plays an important role in slurry phase hydrocracking of heavy oil. One of the main functions is to form active hydrogen from gaseous hydrogen preventing coke formation and promoting hydroconversion [8,9]. Either using supported catalyst or dispersed catalyst, mass balances have to be done with the available experimental information, from which the hydrogen consumption can be determined. Measuring the amount of liquid before and after the reaction is not a problem, however quantifying the amount of gases, particularly hydrogen, may be an issue. A few authors reported different values of hydrogen consumption for residue hydrocracking in batch reactors, which vary depending on the different catalysts and operating conditions used, as can be seen in Table 1 [10–14]. The main reason for this absence of hydrogen consumption data in batch reactors is because most of the research focuses on initial catalyst screening, whereby calculation of catalyst selectivity and activity, conversion, yields, removal of impurities (e.g., sulfur, nitrogen, etc.), changes in properties of the feed (e.g., API gravity, viscosity, etc.) are the main issues of importance, and not too much attention has been paid on other process parameters. Due to this, methods for calculating hydrogen consumption in laboratory batch reactors have not been reported in the literature. That is why the objective of this work is to describe and apply in detail four experimental approaches for measuring hydrogen consumption in hydrocracking reactions. In addition, laboratories are not equipped with the same facilities, so that having alternatives to calculate hydrogen consumption is of great importance for the researchers. 2. Methods for calculating hydrogen consumption The methods used to quantify the liquid and gas at the beginning and at the end of the reaction were: 1) by weight, 2) by measuring the volume of gas with a gas syringe, 3) by 3 ACS Paragon Plus Environment
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measuring the volume of gas with a gasometer, and 4) by calculating the volume of gas with an equation of state (EoS). In all cases, the mass balance closure (MBC) was calculated with the following equation:
=
100
(1)
where OM is the output mass and IM the input mass. Hydrogen consumption (HC) is calculated with the amount of hydrogen loaded to the reactor, WH0 (considering its purity, which in this case was > 99.9%), the mass of unloaded product gas (WPG) and the composition of gases after reaction using the following expression:
= − ∗
(2)
Where HPG is the weight composition of hydrogen in the product gas. Hydrogen consumption is usually reported in standard cubic feet per barrel (scf/bbl at 20°C and 1 atm). Using equation 2, it is possible to find the consumption of hydrogen in scf/bbl with the densities of hydrogen and heavy oil at standard conditions. 2.1. Hydrogen consumption by weight The first step is to weight by separate the reactor vessel (WRV0) and the reactor head (WRH0). The initial weight of the reactor is WRV0 + WRH0. The feed and the catalyst are then loaded to the reactor. The reactor is sealed and weighted again, firstly without hydrogen and subsequently with hydrogen at the initial operating pressure. Weighting is done with a Mettler Toledo scale model PBK989-B60 (60 kg capacity and accuracy of 0.1 g). The amount of hydrogen loaded to the reactor is calculated with: = −
(3)
Where WRFCH0 is the initial weight of the reactor plus feedstock, catalyst and hydrogen, and WRFC0 is the initial weight of the reactor plus only feedstock and catalyst (without hydrogen). Once the reaction has finished, the reactor is weighted before and after discharging of the product gas. The weight of product gas is calculated with Eq. 4. 4 ACS Paragon Plus Environment
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= −
(4)
Finally, after opening the reactor, the reactor vessel and the reactor head are weighted to calculate the weight of upgraded oil (WUO) by difference as shown in Eq. 5. = + − +
(5)
Where WRUOCPG is the weight of reactor plus upgraded oil, catalyst and product gas, WRUOC is the weight of reactor plus upgraded oil and catalyst (without product gas), WRVUO is the weight of reactor vessel plus upgraded oil, and WRHUO is the weight of the reactor head plus the upgraded oil. With these values, IM and OM can be calculated:
= +
= +
(6) (7)
Where WF0 is the weight of hydrocarbon feed at the beginning of the reaction. 2.2. Hydrogen consumption by measuring the volume of gas with a gas syringe Once the reactor has been sealed and initial operating pressure has been stablished with hydrogen, a gas syringe brand Hamilton (1.5 L capacity and precision of 10 mL) is connected to the reactor. A valve of the reactor is opened to full the gas syringe, and then the gas is released. This procedure is repeated until the pressure of the reactor reaches the atmospheric pressure. The total volume of gas (VG) is calculated with Eq. 8. Apart from the volume of gas measured with the gas syringe (VGS) it is necessary to add the hydrogen volume occupied within the reactor at temperature and pressure of measurement, due to the equilibrium of pressures (VEP).
= + = −
(8) (9)
Where VR is the volume of the reactor without internals and V0 is the volume of oil in the reactor.
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After the reaction, the volume of product gas at final pressure is measured by the same procedure. The weight of the initial hydrogen or of that the product gas are calculated with Eqs. 10 and 11 respectively. For these calculations, the gas composition is needed which is measured by the UOP539 method for refinery gases. = 2.016 $
% &'
() * +
,
= $( % *' , & '
+
(10) (11)
Where PA is the atmospheric pressure, ZH the hydrogen compressibility factor, R the universal gas constant, TR the room temperature, MWG the molecular weight of the product gas (which is calculated from gas composition), and ZG the gas compressibility factor calculated by an EoS based on gas composition. 2.3. Hydrogen consumption by measuring the volume of gas with a gasometer This method is similar to the previous one and is only different in the gas measurement instrument. A continuous gasometer brand Ritter is used that works by means of an inverted tipping bucket immersed in liquid. As the gas bubbles fill the bucket it tips and magnet activates a reed switch connected to a counting device (Figure 1). After sealing the reactor and loading it with hydrogen at the initial pressure, the gasometer is connected and the valve is opened slowly to allow the gas for passing through the gasometer. Once connected, the accumulated volume of the gasometer before and after the measurement is registered to calculate VG by difference. The pressure of the water column inside the gasometer must be also registered during the measurement for later calculations. After the reaction, the weight of product gas is calculated with Eq. 11, considering that in this case the pressure PA is the sum of the atmospheric pressure and the pressure corresponding to the height of the water column of the gasometer. The volume of product gas is measured by connecting the sealed reactor at the temperature of measurement and final pressure to the gasometer and this one to a gas chromatograph (Figure 2). 2.4. Hydrogen consumption by calculating the volume of gas with an EoS
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The measurement of the amount of hydrogen loaded to the reactor and the amount of gases unloaded from the reactor can also be calculated using an EoS with the composition of the gases, the hydrogen volume occupied within the reactor at temperature and pressure of measurement due to the equilibrium of pressures, and the initial and final conditions in the reactor (pressure and temperature). Among the various EoSs available in the literature to predict the thermodynamic properties of hydrogen-hydrocarbon systems, cubic EoSs are the most used in practice [15,16], which are shown in Tables 2 and 3 [17–21]. Grayson Streed EoS is the most recommended one for gaseous hydrocarbon mixtures containing hydrogen [22]. 3. Results and discussions 3.1. Experiments and initial calculations The experiments were carried out in two batch reactors (Figure 3) with different volumes (1 and 1.8 liters). For the slurry-phase hydrocracking tests a heavy crude oil with the properties reported in Table 4 was used. Two mineral catalysts were used (hematite and molybdenite) with particle size less than 5 µm, whose compositions are shown in Table 5.
As can be seen, the catalysts are
concentrated in iron or molybdenum, respectively. The two reactors were loaded with 200 g and 360 g of heavy crude oil according to their volumetric capacity, 1 and 1.8 liters respectively. The reactions were carried out at the same operating conditions: 380°C, 40 kg/cm2, 800 rpm and 4 hours. The concentration of catalyst used was 5000 ppm based on the active metal content [7,23]. It should be highlighted that the typical hydrocracking processes operate at high severity reaction conditions (particularly temperature and pressure). However, this work is focused on partial hydrocracking (partial conversion) aiming at achieving the API gravity and viscosity required for the transportation of crude oil. In the case of high severity hydrocracking, the objective is to convert most of the residue fraction to produce high amounts of distillates. The initial hydrogen pressure at which the reactors are pressurized at room temperature can be calculated using the equation of the corresponding states: 7 ACS Paragon Plus Environment
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= $ - , $ (
(+
&+. &+
,$
*+
*+.
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,
(11)
Where P0 is the initial hydrogen pressure at TR, PR the reaction pressure at reaction temperature (TRE), Z0 and ZR the compressibility factors at TR and TRE respectively, which are calculated using an EoS, and VR and VRE are the volume occupied by the gas in the reactor at TR and TRE respectively. Calculations at the studied conditions indicate that both ratios (Z0/ZR) and (VRE/VR) are close to unity, which is because at the operating and ambient conditions, pressures are lower than the critical pressure of hydrogen, and the temperatures are higher than the critical temperature of hydrogen. In the case of volume, the density changes are small because hydrocracking is conducted at moderate reactions conditions. For these reasons, the initial hydrogen pressure at which the reactors were pressurized at room temperature was calculated as: = $* + , *
+.
(12)
Table 6 shows the loaded hydrogen calculated with the different EoSs as function of the reactor capacity and the catalyst used. As can be seen, all of the EoS report approximately the same value since the pressure and temperature conditions are below the critical point of hydrogen. 3.2. Mass balance The gas composition (Table 7) produced in the slurry-phase hydrocracking is similar for both catalysts and they are composed mostly by light hydrocarbon gases (methane, ethane, propane and butane), hydrogen sulfide and hydrogen. Hydrogen is fed in excess with the purpose of reaching the initial pressure in the reactor, which was not totally consumed during the reaction. The amount of gas produced by the state equations as function of the type of reactor and catalyst are shown in Table 8. Similar results are obtained. So that, further calculation were done with the equation of Peng Robinson (PR).
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Tables 9 and 10 show the mass balance results with the four methods. All approaches report quite similar values. IM and OM for each reactor were calculated or measured by different ways to demonstrate that any of the four methods can be used. The easiest method to calculate the mass balance is by using an EoS because it only requires the gas composition. In all cases, the mass balance closure was higher than 99.7%. 3.3. Hydrogen consumption The amount of hydrogen measured or calculated at the beginning of the reaction with the different methods is shown in Figure 4. All values are similar with all methods for both catalysts and reactors. On the other hand, the mass of unloaded product gas showed a slight variation with the different methods as can be seen in Figure 5. This difference can be attributed to different factors, such as gas composition which can affect the calculation of the EoS, the precision of the gasometer, variations of pressure during measurement of amount of gas which makes it less accurate. It is noted that the amount of unloaded product gas is greater using molybdenite catalyst than with hematite catalyst, which is due to a higher production of hydrogen sulfide. The results of hydrogen consumption are reported in Figure 6. The values are higher for molybdenite mineral catalyst which has higher hydrogenation capacity than the hematite mineral catalyst. It is also observed that hydrogen consumption resulted to be independent on the reactor size, which means that both reactors were operated at identical reaction conditions. However, using bigger size reactor causes higher accuracy in terms of weighting of liquid samples. Conversion of vacuum residue (Figure 7) was higher in experiments with molybdenite, which causes the API gravity to be also higher (Tables 6 and 7). These results are consistent with those obtained in previous studies [23]. The reactor size does not affect the conversion of vacuum residue due to the same reason explained above. 3.4. Final remark Hydrogen consumption determined in batch reactor may be different than that determined in continuous reactor. However, the values of hydrogen consumption in batch reactor are not calculated for extrapolation purposes, but to provide more information to the catalyst 9 ACS Paragon Plus Environment
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screening step for having more elements for better selection of catalysts. Knowing the hydrogen consumptions at batch reactor scale for different catalysts, feeds and reaction conditions are useful data for deciding which catalyst, apart from exhibiting better activity and selectivity, performs better in terms of hydrogen requirements. Conclusion Hydrogen consumption during hydrocracking experiments in batch reactor was calculated with four different methods: by weight, by measuring the volume of gases (with gas syringe and with gasometer) and by calculating the gas volume with an EoS. Similar results were obtained with the four approaches in terms of mass balance, product gas composition, hydrogen consumption and properties of upgraded oil. The size of the reactor did not affect the hydrocracking reaction since almost the same values were observed for 1 and 1.8 liters reactor capacity, which means that both reactors operated at identical conditions. Molybdenite resulted to show higher hydrogenation capacity than hematite, which as expected, causes higher conversion and hydrogen consumption. Any of the proposed approaches can be used to determine hydrogen consumption, which depend mainly on the available experimental infrastructure. Using at least two methods is highly recommended to have accurate results. Acknowledgments Authors thank to Mexican Institute of Petroleum (IMP) for the economic support provided. G. Felix, A. Quitian and E. Rodríguez also thank to Consejo Nacional de Ciencia y Tecnología (CONACYT) for the PhD Scholarship. References [1]
[2]
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[21] E.W. Lemmon, M.L. Huber, J.W. Leachman, Revised standardized equation for hydrogen gas densities for fuel consumption applications., J. Res. Natl. Inst. Stand. Technol. 113 (2008) 341–50. doi:10.6028/jres.113.028. [22] H.G. Grayson, C.W. Streed, Vapor-liquid equilibria for high temperatur, high pressure hydrogen-hydrocarbon systems, in: 6th World Pet. Congr., World Petroleum Congress, Frankfurt am Main, Germany, 1963: pp. 169–181. [23] A. Quitian, J. Ancheyta, Partial upgrading of heavy crude oil by slurry-phase hydrocracking with analytical grade and ore catalysts, Energy & Fuels. 30 (2016) 10117–10125. doi:10.1021/acs.energyfuels.6b01648.
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Table 1. Hydrogen consumption reported in the literature for hydrocracking reactions in batch reactors Hydrogen consumption* Operating conditions, Autor Feed (scf/bbl) P (MPa), T (°C), t (h) Du et al. [10]
181-290
Karamay vacuum residue
P=8 T=400-430 t=1
Rezaei et al. [11]
195-650
Cold Lake vacuum residue
P=5.5 T=415 t=1
240-1000
Khafji atmospheric residue
P=15.2 T=400 t=6
Marques et al. [13]
168-237
Safaniya vacuum residue
P=9.5 T=370 t=2
Del Bianco et al. [14]
192-3210
Belaym vacuum residue
P=9 T=410-450 t=0.25-4
Miki et al. [12]
*With differents types of catalysts
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Table 2. Equations of state and their parameters PVT
EoS =
Redlich Kwong (RK)
National Institute of Standards and Technology (NIST) Grayson-Streed
/0 2/3 − − /1 √0 + /1
/0
