JPH0525481A - Method for hydrogenation treatment of heavy hydrocarbon feeding raw material containing precipitable metal compound - Google Patents

Abstract

PURPOSE: To obtain a fuel with an appropriate quality for being used in jet and diesel engines without generating pollution problem by a method wherein a hydrocarbon feedstock such as crude oil shell is hydrogenation-treated in a specified system having an ebullition type catalyst bed reactor and a fixed bed catalytic reactor.

CONSTITUTION: A hydrocarbon feedstock (e.g. a crude oil shell) contg. a precipitable metal compd. is fed into a heater 12 from a line 10 and it is heated at most about 315.6°C to remove the precipitate formed and water from a line 13. The preheated oil is fed into an ebullated catalyst bed reactor 16 provided with an ebullition bed 16a for a particulate catalyst, wherein hydrogenation treatment is performed under a condition of 426.7-460.0°C and a hydrogen partial pressure of 126.55-210.92 Kg/cm². The steam effluent from a line 19 is fed with hydrogen into a fixed bed catalytic reactor (Ni-Mo catalyst) 30 through a heat separator 20 and flash processes 24 and 26 and hydrogenation treatment is performed under approximately the same temp. and pressure conditions as those in the reactor 16 to perform almost completely desulfurization and denitrification. The product is fed into a fractionating tower 36 through a cooler 32 and a phase separator 34 to obtain a fractionated refined oil.

COPYRIGHT: (C)1993,JPO

Description

Description: FIELD OF THE INVENTION The present invention treats hydrocarbon feedstocks containing precipitating impurities deposited during normal preheat treatment, especially crude oil shale containing precipitating metal compounds. For producing catalytic hydrotreating fuel suitable for jet and diesel engines. BACKGROUND OF THE INVENTION When crude oil shale is catalytically hydrotreated to produce an improved light oil product, the preheater flow path is typically from the oil shale at temperatures above about 204.4 ° C (400 ° F). It is known to be contaminated by the fine particulate deposits of This deposit causes a high pressure drop,
Blocking the flow path creates a very troublesome and undesirable problem. A particular problem encountered during the hydrotreating of oil shale feedstocks is about 204 preheater channels.
Repeated fouling by particulate deposits at temperatures of 400 ° F. (4 ° C.) and fixed catalyst bed reactors by very fine particulate deposits with high iron content, which results in high pressure drops. The result is inadequate oil conversion. These deposits are primarily compounds which are difficult to filter in liquid feed streams at ambient temperatures, especially those containing iron and arsenic compounds. To this end, solutions have been attempted to avoid or prevent the pollution problems in crude oil shale processing when the oil shale is subjected to continuous catalytic processing to produce upgraded fuel products. Multi-stage catalytic processing of heavy petroleum crude oil and resid is known. For example, U.S. Pat.
bullated) A method for desulfurizing petroleum residue feedstocks using a catalyst bed hydrogenation reactor to reduce hydrogen consumption and increase catalyst life is described. U.S. Pat. Nos. 3,773,673 and 3,887,973 describe similar catalytic conversion processes for petroleum residues. U.S. Pat. No. 3,874,555 describes a process for hydrotreating heavy crude oils and residual oils which employs a series of boiling catalyst bed or fixed bed reactors, and a small reactor size catalyst in the second reactor. Have been described. US Pat. No. 4,046,670 discloses an anti-clogging age agent containing an iron oxide-containing inorganic material.
nt) is added to the feed stream and the heavy petroleum is pyrolyzed in a tubular furnace. US Patent 418159
No. 6 describes treating oil shale retort effluents to lower the pour point, and cooling such effluents to produce a liquid phase at a critical temperature in the range of 315.6 to 426.7 ° C (600 to 800 ° F). Treatment of oil shale retort effluent to reduce contaminants such as soluble arsenic and iron by maintaining for ~ 120 minutes is described. In addition, US patent
No. 4158622 describes a two stage hydrogenation process for hydrocarbons containing particulates such as oil shale using a boiling catalytic bed reactor in which the vapor portion is passed through a fixed bed reactor for further hydrotreatment. ing. In this case, it is necessary to avoid fouling of the channels and the catalyst bed and to obtain good operating conditions in order to treat the crude oil shale containing the precipitable inorganic materials and compounds. DISCLOSURE OF THE INVENTION The present invention is directed to hydrocarbon feedstocks containing precipitating compounds that cause channel fouling problems, and hydrotreating such hydrocarbon feedstocks such as crude oil shale to jet and diesel engines. It is to provide a method of producing an improved fuel suitable for use. To carry out the hydrotreating of the present invention, the hydrocarbon feedstock is first heated directly to a low, moderate temperature which results in any precipitation of inorganic compounds, such as about 204.4 to 315.6 ° C (400 to 600 ° F). And then passed to the first stage-boiling catalyst bed reaction step for the first hydrotreatment. In the present invention, the product effluent liquid from this boiling catalyst bed reaction process is separated into phases and its vapor portion is generally operated under more severe conditions, i.e. higher temperature and pressure conditions, or lower space velocities. Alternatively, it is passed through a hydrotreating step of two or more fixed catalyst beds. Also, in practicing the present invention, the feedstock, eg, crude oil shale, is at least about 176.7 ° C.
Includes preheating to a temperature of (350 ° F) to separate deposits and water. However, in this case temperatures which cause deposits and contamination in the preheater flow path should be avoided. The preheated feed stream is then passed through a first stage hydrocracking operation using a boiling catalyst bed reactor with hydrogen to further heat the feed stream via the heat of hydrogenation to deposit a precipitated solid on the catalyst. .. Recycled hydrogen stream and / or about 343.3 ° C
(About 650 ° F) +, such as a heavy recycle oil fraction, should be heated to a temperature sufficient to provide additional heating to a reaction temperature of about 398.9 ° C (about 750 ° F) or higher in a boiling catalyst bed reactor. It can be heated. The reaction conditions are 426.7-460.0 ° C (800-86
0 ° F) temperature, 126.55 to 210.92kg / cm ² (1800 to 3000)
using spatial velocity of the hydrogen partial pressure and _{0.7 ~3V f / h r / V} r of psig). As mentioned above, the first catalytic hydrogenation step in a boiling catalyst bed reactor is followed by a heavy feedstock such as oil shale in a forward flow fixed bed catalytic hydrotreatment operating at extremes of temperature and pressure. Was further processed to find the unexpected fact that a very high quality product was produced despite the presence of high partial pressures of H ₂ S and NH ₃ . The extreme conditions used are 410.0 ° C
Temperatures above (780 ° F) and 126.55 kg / cm ² (1800 psi)
g) Hydrogen partial pressure above. This temperature is 265.6 ° C (510 °
F) It is possible to achieve some hydrotreating of liquid products of this operation with boiling points below that meet military specifications for JP-4 jet and diesel fuels. This hydrotreatment also facilitates denitrification of the product. The operating conditions for treating a crude oil shale having a nitrogen content of about 1.27 wt% and a sulfur content of 0.75 wt% are fuel oil production with a nitrogen content of 4 ppm or less and a sulfur content of 0.01 wt% or less. Meet the JP-4 fuel standard. The present invention will now be described with reference to the accompanying drawings.
The figure shows a flow sheet of a two-step catalytic reaction process in which the hydrocarbon feed stream upstream of the boiling catalyst bed hydrogenation step is directly heated and then further catalytically hydrotreated in a fixed bed reactor. As shown in FIG. 1, the crude oil shale feedstock from line 10 is fed to a heater 12 in a low calorific unit gas (Btu ga
s) using an ordinary heat source such as 176.7-204.4 ° C (350
~ 400 ° F) and about 315.6 ° C (about 600 ° F)
Heat to a low temperature containing an inorganic compound precipitate as follows. Precipitate and water are removed from line 13. Preheated oil is introduced through line 14 into boiling catalyst bed reactor 16 along with hydrogen from line 15. Fresh catalyst is added to reactor 16 along with feedstock via line 14a, or fresh catalyst is added to the reactor via line 17. The spent catalyst is removed from line 18 as shown in the drawing. Generally, the reaction conditions are a temperature of 440.5 to 460 ° C (825 to 860 ° F), 140.61 to 1
82.80 kg / cm ² (2000 to 2600 psig) hydrogen partial pressure and 0.7
To liquid hourly space velocity in the range of _{~1.5 V f / h r / V} r. The reactor has a boiling bed 16a of granular catalyst. Suitable catalysts are cobalt-molybdenum or nickel-molybdenum supported on commonly available alumina supports at 0.076 to 1.524 m.
It has a particle size in the range of m (0.003 to 0.060 inches). The catalyst and solids are withdrawn from reactor 16 via line 18 or with the non-volatile products from thermal separator 20. Reactor effluent stream from line 19 to heat separator 20
The vapor stream from this separator 20 is passed through line 21 to hydrotreating zone 30. The liquid in the heat separator 20 is sent from the line 22 to the two-stage flashing steps 24 and 26 to be sequentially flashed at low pressure, and the combined steam produced is passed from the line 23 to the vapor product line 27. A portion of the residual liquid from the final flash step 26 is recycled to the reactor for further decomposition from line 28 and the remaining liquid is burned as fuel from line 28a or discarded. The product hydrocarbon-containing stream is introduced directly from line 27 into the cocurrent fixed bed catalytic hydrotreating zone 30 with hydrogen at about the same high temperature and pressure conditions as in reactor 16. 426.7 to 440.6 ° C (800 to 825 ° F), 126.
In 55~175.77kg / cm ² (1800 ~2500psig) hydrogen partial pressure and _{0.8 ~1.5 V f / h r /} V preferred hydrotreating zone 30 is to operate in extreme hydrotreating space velocity _r of The steam product is further decomposed and almost completely desulfurized and denitrogenated. As a catalyst, 1.524-3.175 mm (0.060-0.
A nickel-molybdenum catalyst supported on an alumina support having a particle size of 125 inches) is suitable. The reaction temperature increases in the catalyst bed due to the exothermic reaction. Hydroprocessing area
30 can be formed from a series of two or more catalyst beds. The temperature rise in the catalyst bed is controlled by introducing cooling hydrogen gas between the catalyst beds indicated by 30a. The product from hydrotreating zone 30 is sent via line 31 to cooler 32 for cooling and phase separation in separator 34. The liquid portion produced is decompressed at 35 and the fractional column 36 fractionates fuel gas from line 37, naphtha from line 37a, jet fuel from line 38, and diesel fuel product from line 38a, respectively. The naphtha produced is suitable for catalytic reforming to produce gasoline. Fractionation tower 36 to 343.
Heavy liquid fractions such as 3 ° C (650 ° F) + are sent through line 39 to heater 51 to heat above 426.7 ° C (800 ° F) and recirculate to reactor 16 for further processing. To do. The effluent vapor stream from phase separator 34 is sent via line 33 to separation step 40 for separation and removal of contaminants such as C ₁ -C ₃ gases, H ₂ S and NH ₃ from line 42. .. Hydrogen is pressurized by a pressurizer 44 via line 41 and sent to a heater 45 via line 15 at 454.4 to 537.8 ° C (850 to 1000 ° F).
And is recycled directly to the reactor 16. C ₁ from separation step 40 along with some natural gas replenished from line 49
C ₃ gas is sent via line 49 to step 50 for reforming, where it produces the additional hydrogen required for the process and this additional hydrogen stream is delivered via line 46. An important feature of the process of the invention for improving the quality of hydrocarbon feedstocks such as oil shale is (a)
Limiting the preheating of such feedstock and supplying additional heat by heating hydrogen and clean recycle heavy liquid fractions, thereby preventing sedimentation of deposits in the preheater channel; (b ) Inorganic compounds are precipitated on the catalyst in ebullated bed reactors; and (c) the final liquid fuel product can be produced in a catalytic hydrotreating step operating under extreme conditions. The clean recycle heavy product cut and hydrogen are heated separately using the first heater to provide the required heat to the boiling bed catalytic reaction. These process steps and other features of the process can be applied to the treatment of heavy oils and tar sands bituminous material, and preferably to the treatment of crude oil shale to refined fuel oil products. Next, the present invention will be described by way of example, but the present invention is not limited thereto. Example 1 In this example, the quality improvement procedure was carried out using 1.6% by weight of nitrogen, 20
Performed with a crude oil shale containing ppm arsenic, 60 ppm iron and about 0.06 wt% ash impurities. The oil shale was preheated to about 371.1 ° C (700 ° F) in a tubular exchanger and passed with hydrogen through a forward flow catalytic reactor with a fixed bed of commonly available nickel catalyst particles for hydrotreatment. .. The pressure drop across the preheater tube increased to about 0.70 to 14.16 kg / cm ² (about 10 to 200 psig) over 12 days, so the operation was interrupted and replaced with the preheater coil. The material deposited on this coil and on the top of the reactor bed was analyzed to be about 38 wt% oil and 62 wt% ash containing 2 wt% carbon, 45 wt% iron and 6.3 wt% arsenic. I confirmed that. Example 2 In this example, another quality enhancement operation was performed using the same crude oil shale feed as described in Example 1. However, the feedstock is fed in a tubular heat exchanger at about 232.2 ° C (about 450 ° C).
It was heated to F) and then passed through the bottom of a countercurrent reactor with a boiling bed of commonly available cobalt-molybdenum catalyst extruded particles. Also, recirculate hydrogen gas to 496.1 ~ 510.
Heat to 1 ° C (925 to 950 ° F) and heat to heavy (343.3 ° C (65
0 ° F)) + recirculating oil 426.7 to 438.6 ℃ (800 to 825
It was heated to ° F) and introduced at the bottom of the reactor. The reaction conditions are a temperature of 439.6 to 454.4 ° C (825 to 850 ° F), 140.
It was maintained at a space velocity of the hydrogen partial pressure and about _{1.2 V f / h r / V} r of ^{61~182.80kg / cm 2 (2000 ~2600psig)} . The effluent stream was removed from the top of the reactor and passed through another process step to recover the product oil. Most of the iron and arsenic impurities were deposited on the catalyst particles in the reactor and were removed along with the spent catalyst. For this reason, it has been established that the drawbacks due to the accumulation of said contaminants from the oil shale, which raises the pressure drop and causes operating problems in the process, can be avoided and that it can be operated continuously for a long time. Example 3 The preheated effluent stream from the boiling catalyst bed reactor of Example 1 having a nitrogen content of about 0.9% by weight was passed through a second stage fixed bed catalytic reactor for further processing. Oil at 426.7 to 438.6 ° C (80
0 to 825 ° F) and 126.55 to 140.61 kg / cm ² (1
800 V to 2000 psig) hydrogen partial pressure inlet conditions, about 1.0 V _f
/ H _r / V _r nickel at a space velocity of - molybdenum was hydrotreated through on a suitable hydrotreating catalyst supported on an alumina carrier. Hydrotreated oil products have enhanced AP
I Specific gravity, nitrogen content below about 4ppm and about 0.01wt%
It has the following sulfur content and has been found suitable as a high quality fuel in jet and diesel energy use. Although the preferred examples of the present invention have been described above, the present invention can be variously modified without departing from the description of the present specification and claims.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a float sheet of a two-step catalytic reaction process for carrying out the method of the present invention. [Explanation of symbols] 16 Boiling catalyst bed reactor 16a Boiling catalyst bed 20 Thermal separator 24, 26 Two-stage flash process 30 Hydrotreating zone 30a Catalyst bed 32 Cooler 34, 40 Separator 36 Fractionation tower 44 Addition Pressure device 45 Heater 51 Heater

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Michael See Chebebenatsk             United States New Jersey             08534 Pennington Dublin Road             26 (72) Inventor Alfredos G. Komori             United States Pennsylvania             19067 Yardley University             Live 1128

Claims (1)

Claims 1. (a) Preheat a hydrocarbon feedstock containing a precipitable metal compound to a temperature below the precipitation temperature of such metal compound, and heat this feedstock into a reaction zone having a boiling catalyst bed. (B) the reaction zone is at a temperature of 426.7 to 460.0 ° C (800 to 860 ° F) and 126.55 to 210.92 kg / cm ² (1800 to 3000 psi).
g) hydrocracking and treating the feedstock while maintaining the hydrogen partial pressure to deposit the precipitable metal compounds on the catalyst particles; (c) the effluent vapor fraction from the reaction zone from 410.0 to 440.6.
℃ (780 ~ 825 ° F) and 126.55 ~ 210.92 kg / c
Further hydrotreating in a fixed bed catalytic reactor maintained at a hydrogen partial pressure of m ² (1800-3000 psig); (d) recovering a hydrogen-containing gas stream, a hydrocarbon liquid product stream and a heavy hydrocarbon liquid stream; (e) purifying the hydrogen-containing gas stream,
Reheat to a temperature of 4.5 to 537.8 ° C (850 to 1000 ° F),
The heated hydrogen stream is introduced into the boiling catalyst bed reaction zone to maintain the temperature of the reaction zone; and (f) the heavy hydrocarbon liquid stream is fed at 426.7-454.5 ° C (800
A hydrocarbon feedstock containing a precipitable metal compound, characterized in that it is reheated to a temperature of ~ 850 ° F) and this heated liquid stream is introduced into the boiling catalyst bed reaction zone to maintain the reaction temperature in this reaction zone. Hydrotreating method. 2. Crude oil shale as the hydrocarbon feedstock,
The method of claim 1 wherein said feedstock is preheated to a temperature not exceeding about 315.6 ° C (about 600 ° F). 3. The method according to claim 1, wherein the pollutant material precipitated and deposited on the catalyst in the step (b) is removed from the boiling catalyst bed reaction zone together with the used catalyst and replaced with a new catalyst. 4. The first reaction zone of the boiling catalyst bed is 440.6-460.0 ℃ (825-
860 ° F) temperature, 126.55 ~ 196.86 kg / cm ² (1800 ~ 28)
Hydrogen partial pressure and _{0.5 ~3V f / h r / V} r The method of Claims claim 1 wherein maintaining the space velocity of 00psig). 5. The method according to claim 1, wherein the catalyst used in the hydrotreating step (e) of the fixed bed reaction zone is a nickel-molybdenum catalyst supported on an alumina carrier. 6. In a method for hydrocracking and hydrotreating a heavy crude oil shale containing contaminants that precipitate at temperatures below the reaction temperature, (a) said hydrocarbon feed stream at 204.4 to 315.6 ° C (400
Preheated to a temperature of ~ 600 ° F) and introducing this heated feed stream with heated hydrogen into a first reaction zone having a boiling catalyst bed; (b) said feed stream in said boiling catalyst bed first reaction zone 426.7 to 460.0 ° C (800 to 860 ° F) and 12
Reacting at a hydrogen partial pressure of 6.55-210.92 kg / cm ² (1800-3000 psig) to deposit the precipitable material on the catalyst in the catalyst bed; (c) arsenic and iron contaminants precipitated from the first reaction zone. (D) replacing the used catalyst with fresh catalyst by removing the used catalyst containing; and (d) further hydrotreating the first reaction zone effluent at 415.6-443.3 ° C (780-830 ° F). Through a second reaction zone having a fixed contact bed maintained at a temperature of (e) recovering a hydrogen-containing gas stream, a hydrotreated oil shale liquid product stream and a heavy hydrocarbon liquid stream; (f) containing hydrogen The gas stream is purified and this hydrogen gas stream is
Reheat to a temperature of 850 to 1000 ° F. to 537.8 ° C. and introduce the heated hydrogen gas stream into the boiling catalyst bed reaction zone to maintain the temperature in the reaction zone; and (g) the heavy carbonization Hydrogen liquid stream at 426.7-454.4 ° C (800
Reheat to ~ 850 ° F) and introduce this heated liquid stream into the boiling catalyst bed reaction zone to maintain the reaction temperature in this reaction zone and hydrogenate heavy crude oil shale containing pollutants. Method for cracking and hydrotreating.