HEAVY AROMATIC SOLVENTS FOR CATALYST REACTIVATION

Abstract

Compositions and methods for restoring catalytic activity by dissolving soft coke with a solvent, one method including detecting soft coke deposition on a catalyst composition; preparing an aromatic bottoms composition with a Hildebrand solubility parameter of at least about 20 SI to remove the soft coke from the catalyst composition; and washing the catalyst composition with the aromatic bottoms composition until at least a portion of the soft coke deposition is removed.

Claims

1. A method for restoring catalytic activity by dissolving soft coke with a solvent, the method comprising the steps of: detecting soft coke deposition on a catalyst composition; preparing an aromatic bottoms composition with a Hildebrand solubility parameter of at least about 20 (SI) to remove the soft coke from the catalyst composition; and washing the catalyst composition with the aromatic bottoms composition until at least a portion of the soft coke deposition is removed.

2. The method according to claim 1, where the step of detecting soft coke deposition on the catalyst composition comprises detecting a pressure drop increase over a catalyst bed comprising the catalyst composition of at least about 1 bar.

3. The method according to claim 1, where the step of detecting soft coke deposition on the catalyst composition comprises detecting a radial temperature profile change in a reactor of at least about 1° C.

4. The method according to claim 1, where the aromatic bottoms composition comprises aromatic bottoms from an aromatic recovery complex.

5. The method according to claim 1, where the aromatic bottoms composition comprises aromatic bottoms from a xylene rerun column of an aromatic recovery complex.

6. The method according to claim 1, where the aromatic bottoms composition consists essentially of aromatic bottoms from a xylene rerun column of an aromatic recovery complex.

7. The method according to claim 1, where the aromatic bottoms composition consists of aromatic bottoms from a xylene rerun column of an aromatic recovery complex.

8. The method according to claim 1, further comprising the step of verifying the portion of the soft coke deposition is removed by testing the aromatic bottoms composition for an increase in organic molecule type.

9. The method according to claim 1, where soft coke deposition on the catalyst composition is formed in a hydrocracking or hydrogenation reactor.

10. The method according to claim 1, where soft coke deposition on the catalyst composition is formed from treatment of naphtha or residual oil.

11. The method according to claim 1, further comprising the step of reducing a reactor temperature by between about 100° C. and about 300° C. before the washing step.

12. The method according to claim 1, where the step of washing proceeds for at least about 6 hours.

13. The method according to claim 1, where the step of washing proceeds for at least about 12 hours.

14. The method according to claim 1, where the aromatic bottoms composition includes at least 50 wt. % C.sub.9+ aromatic hydrocarbons.

15. The method according to claim 1, where the aromatic bottoms composition exhibits a Hildebrand solubility parameter of at least about 21 (SI).

16. A method for hydrocracking a hydrocarbon feedstock to reduce soft coke deposition, the method comprising the steps of: hydrocracking the hydrocarbon feedstock in a reactor at a reaction temperature in a range of from about 300° C. to about 500° C., at a reaction pressure in the range of from about 50 bars to about 200 bars, at a hydrogen feed rate up to about 2500 standard liters per liter of hydrocarbon feed (SLt/Lt), and a hydrocarbon feed rate in the range of from about 0.25 h.sup.−1 to about 3.0 h.sup.−1 liquid hourly space velocity; detecting a pressure drop over a catalyst bed in the reactor; reducing the temperature of the reactor; reducing flow of the hydrocarbon feedstock; providing to the catalyst bed an aromatic bottoms composition with a Hildebrand solubility parameter of at least about 20 (SI) to remove soft coke from a catalyst composition in the catalyst bed; and re-starting hydrocracking of the hydrocarbon feedstock.

17. The method according to claim 16, where the step of detecting includes detecting a pressure drop of at least about 1 bar.

18. The method according to claim 16, where the step of reducing the temperature of the reactor includes reducing the temperature by at least about 100° C.

19. The method according to claim 16, where the aromatic bottoms composition liquid hourly space velocity is between about 0.1 h.sup.1 to about 10 h.sup.1.

20. The method according to claim 16, where the step of providing to the catalyst bed an aromatic bottoms composition comprises washing the catalyst bed with the aromatic bottoms composition for at least about 6 hours.

21. The method according to claim 16, where the aromatic bottoms composition comprises aromatic bottoms from an aromatic recovery complex.

22. The method according to claim 16, where the aromatic bottoms composition comprises aromatic bottoms from a xylene rerun column of an aromatic recovery complex.

23. The method according to claim 16, where the aromatic bottoms composition consists essentially of aromatic bottoms from a xylene rerun column of an aromatic recovery complex.

24. The method according to claim 16, where the aromatic bottoms composition consists of aromatic bottoms from a xylene rerun column of an aromatic recovery complex.

25. The method according to claim 16, further comprising the step of verifying soft coke removal by testing the aromatic bottoms composition for an increase in organic molecule type.

26. The method according to claim 16, where the aromatic bottoms composition includes at least 50 wt. % C.sub.9+ aromatic hydrocarbons.

27. The method according to claim 16, where the aromatic bottoms composition exhibits a Hildebrand solubility parameter of at least about 21 (SI).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] No drawings.

DETAILED DESCRIPTION

[0029] So that the manner in which the features and advantages of the embodiments of compositions and methods for soft coke removal may be understood in more detail, a more particular description of the embodiments of the present disclosure briefly summarized previously may be had by reference to the embodiments thereof, which are described as a part of this specification. It is to be noted, however, that the various embodiments are not to be considered limiting of the present disclosure's scope, as it may include other effective embodiments as well.

[0030] Embodiments disclosed here show that the aromatic bottoms stream from an aromatic recovery complex possesses a high solubility factor compared with straight run petroleum fractions. The Hildebrand solubility scale (described, for example, in “Standard Hildebrand values from Hansen.”, Journal of Paint Technology, Vol. 39, No. 505, February 1967) is an accepted scale used in the oil and gas industry to describe solvents.

[0031] The Hildebrand solubility parameter is derived in part from the cohesive energy density of the solvent, which in turn is derived from the heat of vaporization. When a liquid is heated to its boiling point, energy is added to the liquid, resulting in an increase in the temperature of the liquid. Once the liquid reaches its boiling point, however, the further addition of heat does not cause a further increase in temperature.

[0032] The energy that is added is entirely used to separate the molecules of the liquid and boil them away into a gas. If the amount of energy (in calories) added from the onset of boiling to the point when all the liquid has boiled away were measured, it will provide a direct indication of the amount of energy required to separate the liquid into a gas, and thus the amount of van der Waals forces that held the molecules of the liquid together. The amount of heat required to separate the molecules is instructive. A liquid with a low boiling point may require considerable energy to vaporize, while a liquid with a higher boiling point may vaporize quite readily, or vice versa. The energy required to vaporize the liquid is called the heat of vaporization. From the heat of vaporization, the cohesive energy density is calculated by Equation 1:

[00001]$\begin{array}{cc}C=\frac{\Delta .Math.H-R*T}{V.Math.m}.& \mathrm{Eq}..Math.1\end{array}$

[0033] In Equation 1, c is cohesive energy density, ΔH is heat of vaporization, R is the ideal gas constant, T is temperature, and Vm is molar volume. For cohesive energy density, c is represented in kcal cm.sup.−3, Vm is represented in cm.sup.3 mol.sup.−1, T is represented in Kelvin (K), ΔH is represented in kcal mol.sup.−1, and R is represented in kcal K.sup.−1 mol.sup.−1.

[0034] Hildebrand solubility proposes a solubility parameter, the square root of the cohesive energy density, as a numerical value indicating the solvency behavior of a specific solvent, shown by Equation 2.

[00002]$\begin{array}{cc}\delta ={\left[\frac{\Delta .Math.H-R*T}{V.Math.m}\right]}^{1/2}.& \mathrm{Eq}..Math.2\end{array}$

[0035] In Equation 2, δ is represented in (calories per cm.sup.3).sup.1/2 (common form) or MPa.sup.1/2 (SI). Common form is derived from cohesive energy densities in calories/cc, and standard international units (SI units), are derived from cohesive pressures. The SI unit for expressing pressure is the pascal, and SI Hildebrand solubility parameters are expressed in mega-pascals (1 mega-pascal or mpa=1 million pascals). SI parameters are about twice the value of standard parameters. Since Hildebrand solubility parameters are not readily available, solubility parameters for kerosene, light gas oil, and an aromatic bottoms stream were calculated here, with the results shown in Table 1. Values for individual organic solvents are also shown in Table 1.

TABLE-US-00001 TABLE 1 Hildebrand solubility parameters of solvents. Solvent δ = MPa.sup.1/2 (SI) Heptane 15.3 n-Dodecane 16.0 Benzene 18.7 Kerosene 16.3 Light gas oil 15.7 Heavy Aromatic Bottoms (full range) 20.7 Heavy Aromatic Bottoms 180° C.+ 21.2

[0036] As seen in Table 1, heptane, a paraffinic solvent with a carbon number of 7, exhibits a Hildebrand solubility parameter (HSB) of 15.3 and n-dodecane, a paraffinic solvent with carbon number of 12, exhibits a HSB value of 16. Benzene, a mono-aromatic solvent with a carbon number of 6, exhibits a HSB value of 18.7. Kerosene's HSB is 16.3, showing that it is composed of paraffinic and aromatic components. Light gas oil is more paraffinic in nature based on the HSB compared with the kerosene fraction. The aromatic bottoms stream, whether its full range stream as-received from an aromatic recovery complex, or the fraction boiling above 180° C., exhibits greater HSB values in the range of 20.7-21.7. Based on the HSB values, the aromatic bottoms stream (ABS) obtained from an aromatic recovery complex is a powerful solvent for soft coke and mixtures of coke. Examples described further here demonstrate that this solvent removes soft coke formed on catalysts.

[0037] In some embodiments, coke is formed in an integrated hydrocracking process for producing cracked hydrocarbons from a hydrocarbon feedstock. The process can include hydrocracking the feedstock in a reactor to produce hydrocracking reactions at a reaction temperature in the range of from about 300° C. to about 500° C.; at a reaction pressure in the range of from about 50 bars to about 200 bars; at a hydrogen feed rate up to about 2500 standard liters per liter of hydrocarbon feed (SLt/Lt); and at a hydrocarbon feed rate liquid hourly space velocity (LHSV) in the range of from about 0.25 h.sup.−1 to 3.0 h.sup.−1.

[0038] A method to recover catalyst activity and regenerate the catalyst using a solvent can include observing a reaction pressure drop during a hydrocracking or hydrotreating operation in a unit prior to washing of the catalyst bed; shutting-down the unit by reducing all bed temperatures to below a set limit; stopping the hydrocracking or hydrotreating hydrocarbon feedstock flow to the unit; charging a wash solvent to reduce the pressure drop in the unit under hydrogen flow; and starting the unit back up to return to the operating conditions. In some embodiments, a pressure drop in a reactor is about 1 bar, or about 2 bars, or more than 3 bars before shutting down reactor operations for catalyst regeneration by addition of heavy aromatic bottoms solvent. In some embodiments, the reactor temperature is lowered by at least about 10° C., 100° C., or at least about 200° C., or at least about 300° C.

[0039] In some embodiments, the step of detecting soft coke deposition on the catalyst composition comprises detecting a radial temperature profile change in a reactor of at least about 1° C. Reactor temperature measure includes two types: radial and axial. Radial temperature measure includes horizontal temperature location across the diameter of a reactor, and axial temperature measure includes vertical temperature location along the reactor height. These temperature measures are generally applicable for all type of reactors, but most common for fixed-bed reactors. Thermocouples can be located, therefore, at multiple locations horizontally across the diameter of a fixed bed and at multiple locations vertically through the height of a fixed bed. If there is a change in temperature between two thermocouples, it is commonly an indication of coking proximate that thermocouple in the reactor, for example in a fixed bed of catalyst.

[0040] In some embodiments, the hydrogen to oil ratio is at least 3 times hydrogen consumption. In some embodiments, where solvent washing is carried out at temperatures below about 250° C., hydrogen application is not required. In embodiments where hydrogen application with solvent washing is required, hydrogen can be provided via a recycle gas containing hydrogen sulfide, which is used to maintain certain catalysts in a sulfide state.

[0041] In some embodiments, heavy aromatic bottoms solvent liquid hourly space velocity is between about 0.1 h.sup.−1 to about 10 h.sup.−1, between about 0.5 h.sup.−1 to about 5 h.sup.−1, or between about 1 h.sup.−1 to about 3 h.sup.−1. In some embodiments, a solvent wash proceeds for at least about 6 hours or at least about 12 hours or at least about 24 hours. In some embodiments, the solvent comprises more than about 50 wt. %, more than about 70 wt. %, more than about 90 wt. %, or more than about 95 wt. % aromatic C.sub.9+ (C.sub.9 and greater) aromatic hydrocarbons.

[0042] In some embodiments, when solvent washing is completed, the feedstock is switched from aromatic solvent to hydrocracking feedstock and the temperature of the hydrocracking reactor is increased to the operating temperature by at least about 10° C., or at least about 100° C.

[0043] Advantages include utilizing aromatic rich streams to recover hydrotreating in addition to or alternative to hydrocracking catalyst activity by removing soft coke or any polymeric material deposited on the catalyst, including mixtures of soft coke with other materials such as hard coke precursors. Reactor pressure drop increase is a common problem in many hydrocarbon conversion processes, and embodiments disclosed here enable the operations to recover the catalyst activity. Aromatic recovery complex bottoms are applied as a solvent to recover hydrocracking and hydrotreating catalyst activity by washing deposited heavy hydrocarbons on catalyst surfaces. Experiments are discussed as follows.

[0044] Example 1. A hydrocracking pilot plant test was conducted using an aromatic rich cracking feedstock having the following properties: density 0.9195 g/cc, 2.56 wt. % sulfur, 499 ppmw nitrogen, and simulated distillation data shown in Table 2.

TABLE-US-00002 TABLE 2 Simulated distillation data for Example 1 hydrocarbon feedstock. Initial boiling point 239° C.  5 wt. % 314° C. 10 wt. % 345° C. 30 wt. % 423° C. 50 wt. % 444° C. 70 wt. % 491° C. 90 wt. % 526° C. 95 wt. % 534° C. Final boiling point 545° C.

[0045] A hydrocracking test was run at 120 bar, 390° C., LHSV of 0.426 hr.sup.−1, and H.sub.2 to oil ratio of 1000 standard liters of hydrogen per liter of oil. The test was run for 30 days. Afterward, catalyst bed temperature was reduced to 205° C. at a rate of 10° C. per hour in the presence of the same feed while maintaining the pressure of 120 bar. The aromatic rich cracking feedstock was then switched to an aromatic solvent comprising heavy aromatic bottoms having the following properties: density at 0.8825 g/cc and simulated distillation data according to Table 3.

TABLE-US-00003 TABLE 3 Simulated distillation data for Example 1 heavy aromatic solvent. Initial Boiling Point 153° C.  5 wt. % 163° C. 10 wt. % 164° C. 30 wt. % 166° C. 50 wt. % 172° C. 70 wt. % 174° C. 90 wt. % 187° C. 95 wt. % 195° C. Final boiling point 208° C.

[0046] The pressure was reduced to 30 bar with the same H.sub.2 to oil ratio. The bed temperature was raised to 310° C. and ran for 18 hours. Pressure can be reduced quickly to about 30 bars, for example at a rate of about 30 bars or less per hour. The product catalyst was collected for analysis.

[0047] Example 2. Aromatic recovery complex bottoms samples before and after the solvent washing were analyzed using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Table 4 shows the species in the wash solvent before and after the washing. Description of species are as follows: HC denotes hydrocarbon molecules detected; N denotes the molecules containing one nitrogen atom; S denotes the molecules containing one sulfur atom; S2 denotes the molecules containing two sulfur atoms; and S3 denotes the molecules containing three sulfur atoms. As seen, the solvent contains more species after the wash, so it can be concluded that the solvent removed adsorbed species on the catalyst surface, including soft coke in addition to or alternative to hard coke precursors.

[0048] Tested catalysts included a mixture of hydrocracking pretreat catalyst and hydrocracking catalysts. The pretreat catalysts desulfurize, denitrogenize, and hydrocrack feedstock in the range of 20-50 wt. %, and the hydrocracking catalyst is for cracking of the unconverted fraction. Pretreat catalysts can include alumina, silica, titania or combinations thereof, optionally further including Ni, Co, Mo, and/or W as active phase metals. Hydrocracking catalysts can contain non-zeolitic supports such as alumina, silica, titania, or combination thereof. Suitable zeolitic catalyst for treatment can include about 1 wt. % to about 80 wt. % zeolite, and one or more non-crystalline binder such as alumina, silica, titania or combination thereof, optionally further including Ni, Co, Mo, and/or W as active phase metals. Solvent washing described here can be applied to hydrocracking catalysts and also all hydrotreating catalysts, from stages including naphtha treatment to residual oil treatment.

[0049] Generally the term residual oil includes atmospheric residue from atmospheric columns boiling at and above about 370° C. and vacuum residue. When the atmospheric residue is sent to vacuum distillation column, vacuum gas oils boiling in the range of about 370-565° C. are recovered, and the bottoms include the vacuum residue, which boils above about 565° C.

[0050] The increase in number of molecule types exhibits that the molecules, including soft coke in addition to or alternative to hard coke precursors, were desorbed from the catalyst surfaces. The FT-ICR-MS data shows that these molecular species have high double bond equivalent (DBE) values, indicative of aromaticity of the molecules. The solvent washing over catalyst does not cause reactivity of the solvent, because hydrogenation of aromatic components and cracking of the solvent was not observed. FT-ICR-MS data indicates solvent washing to remove chem-adsorbed species without reaction of the solvent itself

TABLE-US-00004 TABLE 4 Number of molecule types before and after solvent washing of catalyst. Species Before After Difference HC 330 480 150 N 1 5 4 S 1 75 74 S2 1 1 0 S3 0 2 2

[0051] A low value heavy aromatic stream was utilized to wash catalyst in a hydrocracking unit that was fouled by organic deposition. In some embodiments a heavy aromatic solvent for soft coke washing and removal comprises C.sub.9+, C.sub.10+, or C.sub.11+ heavy aromatic compounds, depending on if C.sub.9+ in addition to or alternative to C.sub.10+ compounds have been separated out of a mixed aromatic bottoms product. In embodiments disclosed here, aromatic bottoms compositions are used to remove soft coke comprising multiple aromatic ring compounds and are not necessarily used to remove polymerization products.

[0052] The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise. The term “about” when used with respect to a value or range refers to values including plus and minus 5% of the given value or range.

[0053] In the drawings and specification, there have been disclosed example embodiments of the present disclosure, and although specific terms are employed, the terms are used in a descriptive sense only and not for purposes of limitation. The embodiments of the present disclosure have been described in considerable detail with specific reference to these illustrated embodiments. It will be apparent, however, that various modifications and changes can be made within the spirit and scope of the disclosure as described in the foregoing specification, and such modifications and changes are to be considered equivalents and part of this disclosure.