CA2146410A1 - Delayed coking of bottoms product from a hydrotreatment process - Google Patents
Delayed coking of bottoms product from a hydrotreatment processInfo
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- CA2146410A1 CA2146410A1 CA002146410A CA2146410A CA2146410A1 CA 2146410 A1 CA2146410 A1 CA 2146410A1 CA 002146410 A CA002146410 A CA 002146410A CA 2146410 A CA2146410 A CA 2146410A CA 2146410 A1 CA2146410 A1 CA 2146410A1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A process wherein a sulfur- and metals-containing hydrocarbon feed is, in a hydroprocessing operation, contacted with hydrogen and a catalyst having 1.0 - 5.0 wt. % of an oxide of nickel or cobalt and 10.0 - 25.0 wt. % of an oxide of molybdenum supported on a porous alumina support and having a specified pore size distribution thereby forming a hydrotreated/hydrocracked product and finally subjecting the bottoms product recovered from the hydrotreated/hydrocracked product in a delayed coking process to yield coke, distillate and gas.
Description
21~6~10 DELAYED COKING OF BOTTOMS PRODUCT FROM A
HYDROTREATMENT PROCESS
(D# 92069-F) BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to a delayed coking process. More particularly, this invention relates to a process wherein a sulfur- and metals-containing hydrocarbon feed is, in a hydroprocessing operation, contacted with hydrogen and a catalyst having 1.0 -5.0 wt. % of an oxide of nickel or cobalt and 10.0 -25.0 wt. % of an oxide of molybdenum supported on a porous alumina support and having a specified pore size distribution thereby forming a hydrotreated/
hydrocracked product and finally subjecting the bottoms product recovered from the hydrotreated/hydrocracked product in a delayed coking process to yield coke, distillate and gas.
HYDROTREATMENT PROCESS
(D# 92069-F) BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to a delayed coking process. More particularly, this invention relates to a process wherein a sulfur- and metals-containing hydrocarbon feed is, in a hydroprocessing operation, contacted with hydrogen and a catalyst having 1.0 -5.0 wt. % of an oxide of nickel or cobalt and 10.0 -25.0 wt. % of an oxide of molybdenum supported on a porous alumina support and having a specified pore size distribution thereby forming a hydrotreated/
hydrocracked product and finally subjecting the bottoms product recovered from the hydrotreated/hydrocracked product in a delayed coking process to yield coke, distillate and gas.
2. Prior Art U.S. Pat. No. 4,941,964, incorporated herein by reference, discloses a process for the hydro-treatment of a sulfur- and metal-containing hydrocarbon feed which comprises contacting the feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed. The catalyst has a composition comprising 3.0 - 5.0 wt. % of an oxide of a Group VIII metal, 14.5 - 24.0 wt. % of an oxide of a Group VIB metal and 0 - 2.0 wt. ~ of an oxide of phosphorus supported on a porous alumina support, and the catalyst is further characterized by having a total surface area of 150 - 210 m /g and a total pore volume (TPV) of 0.50 - 0.75 cc/g with a pore diameter tistribution such that micropores having diameters of 100 - 160A constitute 70 - 85% of the total pore volume of the catalyst and macropores having diameters of greater than 250A constitute 5.5 - 22.0 % of the total pore volume of the catalyst.
U.S. Pat. No. 4,670,132 (Arias et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst comprising a high iron content bauxite with the addition of one or more of the following promoters: phosphorus, molybdenum, cobalt, nickel or tungsten. The bauxite catalysts typically contain 25 - 35 wt. % aluminum. The catalysts have certain characteristic features for the elemental components (including aluminum and where present, molybdenum) when the pellet exteriors aTe examined in the fresh oxide state using X-ray photoelectron spectroscopy (XPS). For those catalysts which contain molybdenum, the surface Mo/Al atomic ratios on the pellet exteriors are in the range of 0.03 to 0.09.
Arias is distinguished from the instant invention in that its catalyst requires a bauxite support whereas the catalyst of the instant invention does not. In addition, Arias requires a surface Mo/Al atomic ratio on the pellet exteriors in the range of 0.03 to 0.09 when the fresh oxide catalyst is examined by XPS
whereas the catalysts of the instant invention are characterized by ~l) bul~ Mo/Al atomic ratios of 0.06 -0.075 as measured by traditional techniques; (2) surface Mo/Al atomic ratios on the pellet exteriors of 0.20 - 0.55 as measured by XPS on the fresh oxide catalysts; (3) surface Mo/Al atomic ratios on the crushed catalyst pellets of 0.10 - 0.15 as measured by XPS on the fresh crushed oxide catalysts, and, (4) that the ratio of the surface Mo/Al atomic ratios 21~6410 of the pellet exteriors relative to the surface Mo/Al atomic ratios of the crushed catalyst pellets be less than 6Ø
U.S. Pat. No. 4,652,545 (Lindsley et al.), incorporated herein by reference, discloses a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing 0.5 - 5 ~ Ni or Co and 1.8 - 18 % Mo (calculated as the oxides) on a porous alumina support, having 15 - 30 ~ of the Ni or Co in an acid extractable form, and further characterized by having a TPV of 0.5 - 1.5 cc/g with a pore diameter distribution such that ti) at least 70 % TPV is in pores having 80 - 120A diameters, (ii) less than 0.03 cc/g of TPY (6% TPV) is in pores having diameters of less than 80A, and (iii) 0.05 - 0.1 cc/g of TPV
(3 - 20 % TPV) is in pores having diameters of greater than 120A. Lindsley et al. is distinguished from the instant invention in that although it teaches that having a proportion of nickel or cobalt contained in its catalyst in an acid extractable form is advantageous in terms of heavy oil hydroconversion.
Lindsley et al. does not teach or suggest that catalysts which have a prescribed molybdenum gradient are 21~6~10 advantageous in terms of heavy oil hydroconversion.
U.S. Pat. No. 4,588,709 (Morales et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst comprising 5 - 30 wt. % of a Group VIB element (e.g., molybdenum) and 1 - 5 wt. % of a Group VIII element (e.g., nickel). Morales et al.
indicate that the finished catalysts have average pore diameters of 150 to 300 Angstroms. The catalysts have certain characteristic features for the active components (Mo and Ni) when the pellet exteriors are examined in a sulfided state using X-ray photoelectron spectroscopy (XPS). Morales ('709) is distinguished from the instant invention in that its catalyst requires a large average pore diameter (150 to 300 Angstroms) whereas the catalyst of the instant invention has median pore diameters of 120 to 130 Angstroms. In addition, Morales ('709) requires certain characteristic XPS features of the pellet exteriors after presulfiding whereas the catalyst of the instant invention requires a specified molybdenum gradient as determined by measuring the molybdenum/
aluminum atomic ratios ~y XPS for the catalyst pellet 21q6~10 --exteriors and the pellets in a crushed form as measured on the fresh catalysts in an oxide state.
U.S. Pat. No. 4,579,649 (Morales et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing a Group VIB element (e.g., molybdenum), a Group VIII element (e.g., nickel) and phosphorus oxide on a porous alumina support. The catalyst has certain characteristic features for the three active components (Mo, Ni and P) when the pellet exteriors are examined in a sulfided state using X-ray photoelectron spectroscopy (XPS). Morales ('649) is distinguished from the instant invention in that its catalyst requires phosphorus whereas the catalyst of the instant invention does not.
In addition, Morales ('649) requires certain characteristic XPS features of the pellet exteriors after presulfiding whereas the catalysts of the instant invention require a specified molybdenum gradient as determined by measuring the molybdenum/
aluminum atomic ratios by XPS for the catalyst pellet exteriors and the pellets in a crushed form as measured on the fresh catalysts in an oxide state.
U.S. Pat. No. 4,520,128 (Morales et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing 5 - 30 wt. % of a Group S VIB element ~e.g., molybdenum), 0.1 - 8.0 wt. % of a Group VIII element ~e.g., nickel) and 5 - 30 wt. %
of a phosphorus oxide on a porous alumina support. The finished catalysts of Morales t'128) have mean pore diameters of 145 to 154 Angstroms. The catalyst has certain characteristic features for the three active components CMo, Ni and P) when the pellet exteriors are examined in a sulfided state using X-ray photo-electron spectroscopy ~XPS). Morales ('128) is distinguished from the instant invention in that its catalyst requires phosphorus whereas the catalyst of the instant invention does not. Morales ('128) also requires a large mean pore diameter (145 to 154 Angstroms) whereas the catalyst of the instant invention has median pore diameters of 120 to 130 Angstroms. In addition, Morales ('128) requires certain characteristic XPS features of the pellet exteriors after presulfiding whereas the catalysts of the instant invention require a specified molybdenum gradient as determined by measuring the molybdenum/
_ 7 _ aluminum atomic ratios by XPS for the catalyst pellet exteriors and the pellets in a crushed form as measured on the fresh catalysts in an oxide state.
A wide variety of delayed coking operations have been described in the art. In a typical delayed coking process a heavy liquid hydrocarbon fraction is converted to solid coke and lower boiling liquid and gaseous products. Generally, the coker feedstock is a residual petroleum based oil or a mixture of residual oil with other heavy fractions.
In a typical delayed coking process, the residual oil is heated by exchanging heat with liquid products from the process and is fed into a fractionating tower wherein light end products are removed from the residual oil. The residual oil is then pumped from the bottom of the fractionating tower through a tube furnace where it is heated under pressure to coking temperature and discharged into a coking drum.
In the coking reaction the residual feedstock is thermally decomposed into solid coke, condensable liquid and gaseous hydrocarbons. The solid coke is 2146~10 recovered. Coke quality determines its use. High purity coke is used to manufacture electrodes for the aluminum and steel industry. Lower purity coke is used for fuel; its value calculated based on the sulfur and heavy metal impurities which are transferred from the feedstock to the coke.
The liquid and gaseous hydrocarbons are removed from the coke drum and returned to the fractionating tower where they are separated into the desired hydrocarbon fractions.
U.S. Pat. No. 4,332,671 to L. D. Boyer teaches a delayed coking process in which a heavy high-sulfur crude oil is first atmospheric distilled and then vacuum distilled to produce feedstock for delayed coking. Vapor and liquid products of delayed coking are subjected to hydrotreating to yield lower sulfur liquid and gas products.
U.S. Pat. No. 3,907,664 to H. R. Janssen et al. teaches a control system for a delayed coker fractionator. In particular, a coker fractionator overhead vapor fraction is condensed. .The uncondensed vapor is passed from the accumulator to gas recovery.
_g_ A portion of the condensed liquid is used to reflux the coker fractionator. The remaining portion of condensed liquid is passed to gas recovery.
U.S. Pat. No. 4,686,027 to J. A. Bonilla et al. teaches a delayed coker process. An overhead fraction from the coker fractionator is cooled, compressed and passed to an absorber/stripper. The vapor product of the absorber/stripped is a fuel gas stream. Fuel gas typically comprises methane and ethane.
The liquid product of the absorberlstripper is passed to a stabilizer which produces a C3/C4 overhead product and total naphtha as a bottoms product.
SUMMARY OF THE INVENTION
The instant invention is a delayed coking process in which a sulfur- and metals-containing hydrocarbon feedstock is treated in a catalytic hydro-processing operation thereby forming a hydrotreated/hydrocracked product from which there is recovered a bottoms product having a boiling point greater than 1000 F which in a final process step is subjected in a delayed coking operation to yield coke, distillate and gas.
DETAILED DESCRIPTION OF THE INVENTION
The process of the instant invention is a process for delayed coking of a bottoms product having a boiling point of 1000 F, which comprises:
a) hydroprocessing a sulfur- and metals-containing hydrocarbon feed in a hydroprocessing process which comprises contacting said feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed, where said catalyst has a composition comprising 1.0 - 5.0 weight 21~6410 percent of an oxide of nickel or cobalt and 10.0 - 25.0 weight percent of an oxide of molybdenum, all supported on a porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of less than 6.0, 15 - 30 ~ of the nickel or cobalt is in an acid extractable form, and said catalyst is further characterized by having a total surface area of 150 - 210 m /g, a total pore volume of 0.50 -0.75 cc/g, and a pore size distribution such that pores having d1ameters of less than lOOA constitute less than 25.0 %~ pores having diameters of 100 -160A constitute 70.0 - 85.0 % and pores having diameters of greater than 250A constitute 1.0 -15.0 % of the total pore volume of said catalyst thereby forming a hydrotreated-hydrocracked product containing a gaseous phase product and a liquid phase product, b) recovering from the liquid phase product a bottoms product having a boiling point greater than 1000 F, c) subjecting said bottoms product in a delayed coking process to yield coke, distillate and gas.
It is one feature of the catalyst composition employed in the hydroprocessing step of the instant invention that it has a specific molybdenum gradient (as herein defined) from the interior to the exterior of a given catalyst pellet. It is another feature of the catalyst composition that 15 -30 % of the nickel or cobalt contained in the catalyst is in an acid extractable form. It is yet another feature of the catalyst composition that it has a specified pore size distribution such that pores having diameters less than lOOA constitute less than 25.0 %, pores having diameters of 100 - 160A
constitute 70.0 - 85.0 %, and pores having diameters of greater than 250A constitute 1.0 - 15.0 % of the total pore volume of the catalyst. It is a feature of the method of the instant invention that the above-described catalyst is contacted with a hydrocarbon feedstock and hydrogen in the hydro-processing step in such a manner as to expose the catalyst to a uniform quality of feed and to maintain the catalyst at isothermal temperature.
The above-described catalyst is advantageous in the hydroprocessing step of this invention in that it has a high activity for hydroprocessing heavy hydrocarbon feedstocks including vacuum residua. The hydroprocessing method of this invention (i.e., step (a)) is advantageous in that it enables the attainment of improved levels of hydrodesulfurization when hydroprocessing heavy feedstock such as vacuum residua.
In one particularly preferred embodiment of the process of the instant invention, a sulfur- and metal-containing hydrocarbon feedstock is catalytically hydroprocessed with the above-described catalyst using the H-OIL process configuration. H-OIL is a proprietary ebullated bed process (co-owned by Hydrocarbon Research, Inc. and Texaco Development Corp.) for the catalytic hydrogenation of residua and heavy oils to produce upgraded distillate petroleum products and a bottoms product suitable as coker feed in the coking operation of the instant invention.
The ebullated bed system oper~tes under essentially isothermal conditions and allows for exposure of catalyst particles to a uniform quality of feed.
Petroleum feedstocks which may be treated by the above-described catalyst in the hydroprocessing step of the instant invention include naphthas, distillates, gas oils, petroleum cokes, residual oils and vacuum residua. A petroleum feedstock typical of those subject to catalytic hydroprocessing by the catalyst in the hydroprocessing step of the instant invention is an Arabian Medium/Heavy Vacuum Resid feedstock as set forth in Table I, below.
TABLE I
Typical Petroleum Feedstock ~Arabian Medium/Heavy Vacuum Resid) API Gravity 4.8 1000 F. +, vol % 87.5 1000 F. +, wt. % 88.5 Sulfur, wt. % 5.0 Total Nitrogen, wppm 4480 Hydrogen, wt. % 10.27 Carbon, wt % 84.26 Alcor MCR, wt. % 22.2 Kinematic Viscosity cSt @ 250 F 410 @ 300 F 117 Pour Point, F. 110 n-C5Insolubles, wt. % 28.4 n-C7Insolubles, wt. % 9.96 Toluene Insolubles, wt. %0.02 Asphaltenes, wt. % 9.94 Metals, wppm Ni Ccont'd.) 2146~10 TABLE I
(ConS ~ d . ) Fe 10 Cu 3 Na 49 Ch l o r i d e wppm The catalyst composition employed in the hydroprocessing step of the instant invention comprises 1.0 - 5.0 wt. %, preferably 2.5 - 3.5 wt. % of an oxide of nickel or cobalt, preferably NiO and 10.0 -25.0 wt. %, preferably 12.0 - 18.0 wt. % of an oxide of molybdenum, most preferably MoO3, all supported on a porous alumina support, most preferably a gamma-alumina support. Other oxide compounds which may be found in such a catalyst composition include SiO2 (present in less than 2.~ wt. %), S04 (present in less than 0.8 wt. %~, and Na20 (present in less than 0.1 wt. %~. The above-described alumina support may be purchased or prepared by methods well known to those skilled in the art. Similarly, the support material may be impregnated with the requisite amounts of the above-described oxides of nickel, cobalt, and molybdenum via conventional means known to those skilled in the art. The catalyst composition of the instant invention contains no bauxite and thus is distinguishable from bauxite-containing catalysts such as those described in U.S. Pat. No. 4,670,132.
A first necessary and essential feature of the catalyst composition is that 15 - 30 % of the nickel or cobalt present in the catalyst (relative to the total nickel or cobalt present in the catalyst) be acid extractable. As taught at Column 3, lines 7 - 35 of U.S. Pat. No. 4,652,545, it is the final calcination temperature during preparation of the catalyst which determines the percentage of free nickel oxide or cobalt oxide (which is acid extractable~ in the total catalyst composition.
Combined nickel or cobalt is not readily acid extractable. As taught at Column 3, lines 36 - 40 of U.S. Pat. No. 4,652,545, it is theorized that the above-described low proportion of acid extractable nickel or cobalt prevents the catalyst from being deactivated almost immediately with respect to hydroconversion activity.
A second necessary and essential feature of the catalyst composition is the specified pore size distribution of the catalyst. It is well known to those skilled in the art that the activity of a given catalyst is proportional to its surface area and active site density. Ordinarily, a catalyst with a large proportion of micropores (defined herein as pores with diameters less than 250A) will have a higher surface area and a corresponding higher intrinsic activity, whereas a catalyst having a large proportion of macropores (defined herein as pores with diameters greater than 250A) will have a lower surface area and a corresponding lower intrinsic activity. However, when hydroprocessing certain hydrocarbon feedstocks such as petroleum feedstocks, particularly vacuum resldua, the observed catalyst reaction rates for catalysts with a large proportion of small diameter pores are low due to diffusional limitations of the small pores, as well as pore blockage caused by accumulating carbon and metals as the catalyst ages.
The catalyst utilized in this invention has a limited macroporosity sufficient to overcome the diffusion limitations for hydroprocessing of the largest molecules but not so much as to allow poisoning of the catalyst pellet interiors.
The catalyst of the instant invention is characterized by having a total surface area of 150 -210 m2/g, preferably 170 - 205 m2/g, and a TPV of 0.50 - 0.75 cc/g, preferably 0.60 - 0.70 m2/g, with a pore size distribution such that micropores having diameters of 100 - 160A constitute 70 - 85%, preferably 70 - 80 % of the catalyst, and macropores 2146~10 having diameters of greater than 250A constitute 1.0 -15.0 %, preferably 4.0 - 14.0 % TPV of the catalyst.
In such a catalyst, it is particularly preferred that the pore volume of micropores having diameters less than lOOA, be limited to less than 25.0 ~ TPV, preferably 5.0 - 20.0 % TPV, most preferably 9.0 -17.0 % TPV of the catalyst. The catalyst of the instant invention has a median pore diameter of 120 -130A, and thus is distinguishable from larger average micropore diameter catalysts such as those disclosed in U.S. Pat. Nos. 4,588,709 and 4,520,128.
A third necessary and essential feature of the catalyst composition is that the above-described oxide of molybdenum, preferably MoO3 is distributed on the above-described porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of less than 6Ø As used in this description and in the appended claims, the phrase "molybdenum gradient" means that the ratio of a given catalyst pellet exterior molybdenum/aluminum atomic ratio to a given catalyst pellet interior molybdenum/
aluminum atomic ratio has a value of less than 6.0, preferably 1.5 - 5.0, the atomic ratios being 21~6410 measured by X-ray photoelectron spectroscopy (XPS), sometimes referred to as Electron Spectroscopy for Chemical Analysis (ESCA). It is theorized that the molybdenum gradient is strongly affected by the impregnation of molybdenum on the catalyst support and the subsequent drying of the catalyst during its preparation. ESCA data on both catalyst pellet exteriors and interiors were obtained on an ESCALAB
MKII instrument available from V. G. Scientific Ltd., 1~ which uses a 1253.6 electron volt magnesium X-ray source. Atomic percentage values were calculated from the peak areas of the molybdenum 3p3/2 and aluminum 2p3/2-1/2 signal5 using the sensitivity factors supplied by Y. G. Scientific Ltd. The value of 74.7 electron volts for aluminum was used as a reference binding energy.
The catalyst employed in hydroprocessing step (a) of this invention is more completely described in Sherwood, Jr., et al., U.S. Patent No.
5,047,142 which is incorporated herein by reference in its entirety.
In the hydroprocessing step of the instant invention the above-described catalyst is contacted 21~6410 with hydrogen and a sulfur- and metal-containing hydrocarbon feedstock by any means which insures that the catalyst is maintained at isothermal conditions and exposed to a uniform quality of feed. Preferred means for achieving such contact include contacting the feed with hydrogen and the prescribed catalyst in a single continuous stirred tank reactor or single ebullated bed reactor, or in a series of 2 - 5 continuous stirred tank or ebullated bed reactors, with ebullated bed reactors being particularly preferred. This hydroprocessing process is particularly effective in achieving high levels of desulfurization with vacuum re~idua feedstocks.
lS In the delayed coking process of this invention, the feedstock which is a bottoms product is pumped at about 150 to 500 psig into a fired tube furnace where it is heated to about 850 F. to 975 F.
and then discharged into a vertically oriented coking drum through an inlet in the bottom head. The pressure in the drum is maintained at 20 psig to 80 psig and the drum is insulated to reduce heat loss, so that the coking reaction temperature remains preferably between about 825 F. and 950 F. The hot 21~6410 feedstock thermally cracks over a period of several hours, producing hydrocarbon vapors which rise through the reaction mass and are removed from the top of the coke drum and passed to a coker fractionator. In the coker fractionator, the vapors are fractionally distilled to yield condensable liquids and gases.
The material which does not vaporize and remains in the vessel is a thermal tar. As the coking reaction continues, the coke drum fills with thermal tar which is converted over time at these coking reaction conditions to coke. At the end of the coking cycle, the coke is removed from the drum by cutting with a high impact water jet. The cut coke is washed to a coke pit and coke dewatering pad. The coke may be broken into lumps and may be calcined at a temperature of 2000 F. to 3000 F. prior to sampling and analysis for grading.
Premium grade coke, referred to in the art as needle grade coke, is used to make steel and for specialty alloy applications. This p~oduct has a co-efficient of thermal expansion of 0.5 x 10 7 to 5 x m/cm/C., an ash content of O.OOl to n.o2 wt. %, volatiles of about 3 to 6 wt. % and sulfur of about 21~6~10 0.1 to 1 wt. %.
Aluminum grade coke, referred to in the art as anode grade coke, is used in the manufacturing of aluminum. This product has a density of about 0.75 to 0.90 gm/cc, an ash content of about 0.05 to 0.3 wt. %, volatiles of about 7 to 11 wt. % and sulfur of about 0.5 to 2.5 wt. %.
Fuel grade coke typically has an ash content of about 0.1 to 2 wt. %, volatiles of about 8 to 20 wt. % and sulfur of about 1 to 7 wt. %.
Usually in the delayed coking operation of this invention coking is conducted at temperatures ranging from about 825 F. to 950 F. and at pressures ranging from atmospheric up to about 80 psig.
Preferably, the coking operation is conducted at a temperature of about 845 F. to about 865 F. and at a pressure ranging from 0 psig to 20 psig.
Surprisingly, in the process of this invention a substantial increase in the more valuable liquid products from the coking operation is achieved while at the same time the yield of the lower value coke produced is reduced. Particularly advantageous 21~6~10 is the increase in the 400 - 650 F. liquid product (i.e., the diesel fraction) from the coking step.
A further advantage of the process of the instant invention is that a reduction of the total sulfur content of the coker liquids and solid coke is achieved.
-EXAMPLES
In Example 1 and Example 2 (Comparative) H-OIL bottoms products (i.e., a 1000 F.~ product) were taken from a nominal 5 BBL/Day two-stage H-OIL
pilot hydroprocessing unit runs in which an 85 wt. %/
15 wt. % mixture of virgin vacuum resid/fluid catalytically cracked (FCC) heavy cycle gas oil was fed to the H-OIL unit. The feedstock (i.e., the H-OIL
bottoms products utilized in the delayed coking operation of Examples 1 and 2) were produced from an Arabian-Medium/Arabian-Heavy mixture crude source. A
summary of the operating conditions for the H-OIL
unit is listed in Table I and the catalyst properties of the catalysts employed are set out in Table II.
- 2146~10 TABLE I
OPERATING CONDITIONS
(HYDROPROCESSING UNIT) Example 1 2 Catalyst Catalyst A* Catalyst B**
Run Number 912249 912214 Date on Test 06/29/91 05/18/91 Hours on Test 12 12 Number of Stages 2 2 Oper. Conditions Average Reactor Temperature, F 782 786 LHSVTotal Voil/Hr/
V reactor 0.383 0.384 LHSVFF ~ voil/Hr/
V reactor 0.326 0.323 CDSV, B/D/Lb 0.089 0.056 Average Catalyst Age, Bbl/Lb 3.017 3.667 H2 Partial Pressure Inlet, psia 2179 2159 Outlet, psia 1948 1946 Throughput Ratio Vol (FF~VBR)/Vol (FF) 1.17 1.18 Gas Rates, SCFB Total/Hydrogen Total/Hydrogen Make-up Gas 4893/3379 4465/4068 Rx Feed Gas 4203/3848 4019/3661 Quench Gas 520/488 507/448 Hydrogen Purge Gas 316/289 274/250 (Cont'd.) - 21g6410 TABLE I
(Cont'd.) Example 1 2 Run Number 912249 912214 Reactor Conditions*** RXl/RX2 RXl/RX2 Avg. rx. Temp., F 776/789 782/790 LHSVTotal ,V/Hr/V 0.77/0.77 0.77/0.77 FF 1 / / 0.65/0165 0.65/0.65 CDSV, B/D/Lb 0.12/0.14 0.10/0.11 Superficial Gas Velocity, Ft/sec .057/.065 .055/.062 Cat. Age, BBl/Lb 7.19/7.48 7.06/7.46 Conversion 1000+ F Conv., Vl.% 57.2 56.8 1000+ Conv., wt% 57.0 56.3 Desulfurization wt % 92.8 81.6 Denitrogenation wt% 69.9 34.9 MCR Reduction, wt% 49.4 51.7 Demetallization wt~ 67.4 74.4 Nickel removal, wt% 64.4 39.8 Vanadium, wt% 25.4 15.7 1000- F in FF, vol% 33.3 34.1 Calc. H2 cons., (Cont'd.) TABLE I
(Cont'd.) * Catalyst of the instant invention.
* Catalyst B - HDS-1443B, a commercially available H-OIL
catalyst sold for use in hydroprocessing resid oils by Criterion Catalyst Corp.
** where RXl is the first-stage reactor and RX2 is the second-stage reactor.
HSV = liquid hourly space velocity as calculated by taking the volume of feed oil charged to the hydroprocessing unit per hour divided by the volume of the hydroprocessing unit reactors.
FF = fresh feed or in this case 1000 F~ residuum feed.
DSV = catalyst daily space velocity as calculated by the average number of barrels of total feed oil per day per pound of catalyst in the hydroprocessing unit reactors.
21~6410 TABLE II
CATALYST PROPERTIES
Catalyst Type Catalyst A Catalyst B
CHEMICAL PROPS.
Mo, wt% dry 10.5 8.77 Ni, wt% dry 2.5 2.42 SiJ wt% dry 1.1 0.1 S, wt% dIy 0.07 0.14 Na, wt% dry 0.04 0.04 PHYSICAL PROPS.
Avg. LengthJ in. 0.148 0.146 DiameterJ in. 0.037 0.0398 Length Distribution < 0.5 mm, wt% 0.0 -< 1.0 mm, wt% 0.0 0.0 < 1.6 mm, wt% 0.0 0.0 < 2.5 mm, wt% 6.6 40.71 > 15 mm, wt% 0.0 0.0 Compacted Bulk3 Density, lb/ft 40.8 36.1 Crush Strngth, lb/mm 1.8 1.5 Hg Pore Vol.J cc/g 0.64 0.74 (Cont'd.) TABLE II
(Cont'd.) Catalyst Type Catalyst A Catalyst B
PORE SIZE
DISTRIBUTION, cc/g (% TPV) <100A 0.05 (8.5) 0.42 (56.8) 100-250A 0.54 (84.2) 0.08 (10.8) >250A 0.05 (7.3) 0.24 (32.4) 250-500A 0.02 (3.9) 0.03 (4.1) 500-1500A 0.02 (2.5) 0.06 (8.1) 1500-4000A 0.005 (0,7) 0.08 (10.8) > 4000A 0.001 (0.2) 0.07 (9.5) Drum Attrition (#30 US Sieve), wt% 0.4 0.6 In Example 1 and Comparative Example 2 2500 gram samples of the 1000 F. bottoms product recovered from the product of the hydroprocessing operation were coked in glass flasks in which the temperature was raised incrementally to a maximum of 850 F. and maintained at that temperature until coking was complete after which high vacuum was applied at the end of the run, the liquid produced in the coking reaction was withdrawn and the coke recovered.
The liquids were fractionated in HYPERCAL ~
high efficiency glass columns. The fractions measured were dry gas, butanes, pentanes, to 400 F naphtha, 400 F to 650 F light gas oil (diesel) and 650 F +
heavy gas oil.
The properties of the coker feedstocks employed in Example 1 and in Comparative Example 2 are shown in Table III and the properties of the products recovered from the delayed coking operation in Examples 1 and 2 are set out in Table IY.
TABLE III
COKER FEEDSTOCK PROPERTIES
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST A CATALYST B
FEEDSTOCK catalyst type API GRAVITY, 0 4.6 2.9 SULFUR, WT% 2.08 2.72 NITROGEN, WPPM 4650 5272 CARBON, WT% 86.93 86.47 HYDROGEN, WT% 10.20 10.12 NITROGEN, WT% 0.40 0.49 CARBON RESIDUE, Wl~18.28 28.49 ASPHALTENES, WT~ 15.44 17.39 H/C RATIO, atomic 1.41 1.40 K.VIS. cSt, 212 F 2179 3477 PENTANE INSOL. WT% 34.66 36.79 HEPTANE INSOL. WT% 15.66 17.61 TOLUENE INSOL. WT% O.22 0.22 ICAP METALS, WPPM
Ni 42.8 47.7 V 58.5 58.6 (Cont'd.) 2146gl O
TABLE III
(Cont'd.) H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST A CATALYST B
Fe 2.7 7.5 Mo < 1 <1 Cr < 1 ~1 Total metals 104 115 TABLE IV
COKER PRODUCT QUALITIES
COKER NAPHTHA
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST ACATALYST B
FEEDSTOCK/catalyst type SULFUR, WT% Ø07 O.ll NITROGEN, WPPM 145 155 BASIC N2, WPPM 116 229 BROMINE NUMBER 3.1 5.7 RON (CLEAR) 40 44 MON (CLEAR) 46 44 CARBON (WT%) 84.26 83.42 HYDROGEN (WTS) 15.29 15.44 NITROGEN (WT~) 0.07 0.09 (Cont'd.) - ` 2146410 TABLE IV
(Cont'd.) COKER DIESEL
EXAMPLE H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST A CATALYST B
FEEDSTOCK/catalyst type SULFUR, WT% 0.74 1.03 NITROGEN, WPPM 720 739 ABSORBTIVITY @285 F 4.06 3.48 FIA AROMATICS, WT% 51.9 50.4 FIA OLEFINS, WT%5.3 4.3 FLASH POINT, F 188 174 ANILINE POINT, F119 119 CLOUD POINT, F -6 -6 POUR POINT, F -27 -13 BROMINE NUMBER 2.4 3.5 BAS. NITROGEN, WPPM 444 489 KINEMATIC VISCOSITY
@ 40 C, cSt 2.73 2.63 @ 70 C, cSt 4.28 4.15 CARBON, WT% 86.62 86.36 HYDROGEN, WT%13.03 13.36 NITROGEN, WT% 0.10 0.11 (Cont'd.) TABLE IV
(Cont'd.) COKER HEAVY GAS OIL
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST ACATALYST B
FEEDSTOCK~catalyst type SULFUR, WT% 2.79 1.67 NITROGEN, WPPM5876 520D
WATSON AROMATICS, WT% 90.5 76.7 ANILINE POINT, F145 142 POUR POINT, F 80 64 BASIC N2, WPPM 473 650 KINEMATIC VISCOSITY
50 C, cSt 33 46 77 C, cSt 11 15 100 C, cSt 6 7 CARBON, WT% 87.19 86.85 HYDROGEN, WT~11.42 11.37 NITROGEN, WT% 0.08 0.2 REFRACTIVE INDEX, 70 C 1.5295 1.5393 (Cont'd.
TABLE IV
(Cont'd.) SOLID COKE
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST ACATALYST B
FEEDSTOCK/catalyst type SULFUR, WT~ 2.98 3.92 MOISTURE, WT% 0.04 0.07 VOLATILE
CARBONACEOUS
MATERIAL, WT% 13.54 14.17 ICAP METALS, WPPM
IRON ll 25 CHROMIUM
COEFPICIENT OF
THERMAL EXPANSION
(m/cm/C) 6.1 x 104.7 x 107 21~6~10 Yield and material balance data from Examples 1 and 2 are presented in Table V which follows. These data show that with the process of this invention a substantial increase in the total coker liquid product resulted while at the same time the amount of less valuable coke formed was reduced by 27% and the amount of less valuable heavy gas oil was reduced by 29%. An improvement of 67% of the more valuable diesel fraction was achieved. In addition, the amount of sulfur removed from the coker feed in non-dry gas stream (i.e., the C4~ product) during the coking step increased to 26.8% in Example 1 as compared to only 17.3% in Example 2.
21~6~10 TABLE V
Catalyst A Catalyst B
Coker Yields (wt% FF) Dry Gas 8.81 5.77 Total C4 0.63 2.29 Total C5 0.12 1.15 C6-400 F (naphtha) 15.95 11.11 400-650 F (diesel) 30.17 18.11 650 F+ liquid 17.52 24.71 Coke 26.89 36.84 Total 100.09 99.98 % Desulfurization of feed to non-dry gas products 26.79 17.30
U.S. Pat. No. 4,670,132 (Arias et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst comprising a high iron content bauxite with the addition of one or more of the following promoters: phosphorus, molybdenum, cobalt, nickel or tungsten. The bauxite catalysts typically contain 25 - 35 wt. % aluminum. The catalysts have certain characteristic features for the elemental components (including aluminum and where present, molybdenum) when the pellet exteriors aTe examined in the fresh oxide state using X-ray photoelectron spectroscopy (XPS). For those catalysts which contain molybdenum, the surface Mo/Al atomic ratios on the pellet exteriors are in the range of 0.03 to 0.09.
Arias is distinguished from the instant invention in that its catalyst requires a bauxite support whereas the catalyst of the instant invention does not. In addition, Arias requires a surface Mo/Al atomic ratio on the pellet exteriors in the range of 0.03 to 0.09 when the fresh oxide catalyst is examined by XPS
whereas the catalysts of the instant invention are characterized by ~l) bul~ Mo/Al atomic ratios of 0.06 -0.075 as measured by traditional techniques; (2) surface Mo/Al atomic ratios on the pellet exteriors of 0.20 - 0.55 as measured by XPS on the fresh oxide catalysts; (3) surface Mo/Al atomic ratios on the crushed catalyst pellets of 0.10 - 0.15 as measured by XPS on the fresh crushed oxide catalysts, and, (4) that the ratio of the surface Mo/Al atomic ratios 21~6410 of the pellet exteriors relative to the surface Mo/Al atomic ratios of the crushed catalyst pellets be less than 6Ø
U.S. Pat. No. 4,652,545 (Lindsley et al.), incorporated herein by reference, discloses a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing 0.5 - 5 ~ Ni or Co and 1.8 - 18 % Mo (calculated as the oxides) on a porous alumina support, having 15 - 30 ~ of the Ni or Co in an acid extractable form, and further characterized by having a TPV of 0.5 - 1.5 cc/g with a pore diameter distribution such that ti) at least 70 % TPV is in pores having 80 - 120A diameters, (ii) less than 0.03 cc/g of TPY (6% TPV) is in pores having diameters of less than 80A, and (iii) 0.05 - 0.1 cc/g of TPV
(3 - 20 % TPV) is in pores having diameters of greater than 120A. Lindsley et al. is distinguished from the instant invention in that although it teaches that having a proportion of nickel or cobalt contained in its catalyst in an acid extractable form is advantageous in terms of heavy oil hydroconversion.
Lindsley et al. does not teach or suggest that catalysts which have a prescribed molybdenum gradient are 21~6~10 advantageous in terms of heavy oil hydroconversion.
U.S. Pat. No. 4,588,709 (Morales et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst comprising 5 - 30 wt. % of a Group VIB element (e.g., molybdenum) and 1 - 5 wt. % of a Group VIII element (e.g., nickel). Morales et al.
indicate that the finished catalysts have average pore diameters of 150 to 300 Angstroms. The catalysts have certain characteristic features for the active components (Mo and Ni) when the pellet exteriors are examined in a sulfided state using X-ray photoelectron spectroscopy (XPS). Morales ('709) is distinguished from the instant invention in that its catalyst requires a large average pore diameter (150 to 300 Angstroms) whereas the catalyst of the instant invention has median pore diameters of 120 to 130 Angstroms. In addition, Morales ('709) requires certain characteristic XPS features of the pellet exteriors after presulfiding whereas the catalyst of the instant invention requires a specified molybdenum gradient as determined by measuring the molybdenum/
aluminum atomic ratios ~y XPS for the catalyst pellet 21q6~10 --exteriors and the pellets in a crushed form as measured on the fresh catalysts in an oxide state.
U.S. Pat. No. 4,579,649 (Morales et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing a Group VIB element (e.g., molybdenum), a Group VIII element (e.g., nickel) and phosphorus oxide on a porous alumina support. The catalyst has certain characteristic features for the three active components (Mo, Ni and P) when the pellet exteriors are examined in a sulfided state using X-ray photoelectron spectroscopy (XPS). Morales ('649) is distinguished from the instant invention in that its catalyst requires phosphorus whereas the catalyst of the instant invention does not.
In addition, Morales ('649) requires certain characteristic XPS features of the pellet exteriors after presulfiding whereas the catalysts of the instant invention require a specified molybdenum gradient as determined by measuring the molybdenum/
aluminum atomic ratios by XPS for the catalyst pellet exteriors and the pellets in a crushed form as measured on the fresh catalysts in an oxide state.
U.S. Pat. No. 4,520,128 (Morales et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing 5 - 30 wt. % of a Group S VIB element ~e.g., molybdenum), 0.1 - 8.0 wt. % of a Group VIII element ~e.g., nickel) and 5 - 30 wt. %
of a phosphorus oxide on a porous alumina support. The finished catalysts of Morales t'128) have mean pore diameters of 145 to 154 Angstroms. The catalyst has certain characteristic features for the three active components CMo, Ni and P) when the pellet exteriors are examined in a sulfided state using X-ray photo-electron spectroscopy ~XPS). Morales ('128) is distinguished from the instant invention in that its catalyst requires phosphorus whereas the catalyst of the instant invention does not. Morales ('128) also requires a large mean pore diameter (145 to 154 Angstroms) whereas the catalyst of the instant invention has median pore diameters of 120 to 130 Angstroms. In addition, Morales ('128) requires certain characteristic XPS features of the pellet exteriors after presulfiding whereas the catalysts of the instant invention require a specified molybdenum gradient as determined by measuring the molybdenum/
_ 7 _ aluminum atomic ratios by XPS for the catalyst pellet exteriors and the pellets in a crushed form as measured on the fresh catalysts in an oxide state.
A wide variety of delayed coking operations have been described in the art. In a typical delayed coking process a heavy liquid hydrocarbon fraction is converted to solid coke and lower boiling liquid and gaseous products. Generally, the coker feedstock is a residual petroleum based oil or a mixture of residual oil with other heavy fractions.
In a typical delayed coking process, the residual oil is heated by exchanging heat with liquid products from the process and is fed into a fractionating tower wherein light end products are removed from the residual oil. The residual oil is then pumped from the bottom of the fractionating tower through a tube furnace where it is heated under pressure to coking temperature and discharged into a coking drum.
In the coking reaction the residual feedstock is thermally decomposed into solid coke, condensable liquid and gaseous hydrocarbons. The solid coke is 2146~10 recovered. Coke quality determines its use. High purity coke is used to manufacture electrodes for the aluminum and steel industry. Lower purity coke is used for fuel; its value calculated based on the sulfur and heavy metal impurities which are transferred from the feedstock to the coke.
The liquid and gaseous hydrocarbons are removed from the coke drum and returned to the fractionating tower where they are separated into the desired hydrocarbon fractions.
U.S. Pat. No. 4,332,671 to L. D. Boyer teaches a delayed coking process in which a heavy high-sulfur crude oil is first atmospheric distilled and then vacuum distilled to produce feedstock for delayed coking. Vapor and liquid products of delayed coking are subjected to hydrotreating to yield lower sulfur liquid and gas products.
U.S. Pat. No. 3,907,664 to H. R. Janssen et al. teaches a control system for a delayed coker fractionator. In particular, a coker fractionator overhead vapor fraction is condensed. .The uncondensed vapor is passed from the accumulator to gas recovery.
_g_ A portion of the condensed liquid is used to reflux the coker fractionator. The remaining portion of condensed liquid is passed to gas recovery.
U.S. Pat. No. 4,686,027 to J. A. Bonilla et al. teaches a delayed coker process. An overhead fraction from the coker fractionator is cooled, compressed and passed to an absorber/stripper. The vapor product of the absorber/stripped is a fuel gas stream. Fuel gas typically comprises methane and ethane.
The liquid product of the absorberlstripper is passed to a stabilizer which produces a C3/C4 overhead product and total naphtha as a bottoms product.
SUMMARY OF THE INVENTION
The instant invention is a delayed coking process in which a sulfur- and metals-containing hydrocarbon feedstock is treated in a catalytic hydro-processing operation thereby forming a hydrotreated/hydrocracked product from which there is recovered a bottoms product having a boiling point greater than 1000 F which in a final process step is subjected in a delayed coking operation to yield coke, distillate and gas.
DETAILED DESCRIPTION OF THE INVENTION
The process of the instant invention is a process for delayed coking of a bottoms product having a boiling point of 1000 F, which comprises:
a) hydroprocessing a sulfur- and metals-containing hydrocarbon feed in a hydroprocessing process which comprises contacting said feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed, where said catalyst has a composition comprising 1.0 - 5.0 weight 21~6410 percent of an oxide of nickel or cobalt and 10.0 - 25.0 weight percent of an oxide of molybdenum, all supported on a porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of less than 6.0, 15 - 30 ~ of the nickel or cobalt is in an acid extractable form, and said catalyst is further characterized by having a total surface area of 150 - 210 m /g, a total pore volume of 0.50 -0.75 cc/g, and a pore size distribution such that pores having d1ameters of less than lOOA constitute less than 25.0 %~ pores having diameters of 100 -160A constitute 70.0 - 85.0 % and pores having diameters of greater than 250A constitute 1.0 -15.0 % of the total pore volume of said catalyst thereby forming a hydrotreated-hydrocracked product containing a gaseous phase product and a liquid phase product, b) recovering from the liquid phase product a bottoms product having a boiling point greater than 1000 F, c) subjecting said bottoms product in a delayed coking process to yield coke, distillate and gas.
It is one feature of the catalyst composition employed in the hydroprocessing step of the instant invention that it has a specific molybdenum gradient (as herein defined) from the interior to the exterior of a given catalyst pellet. It is another feature of the catalyst composition that 15 -30 % of the nickel or cobalt contained in the catalyst is in an acid extractable form. It is yet another feature of the catalyst composition that it has a specified pore size distribution such that pores having diameters less than lOOA constitute less than 25.0 %, pores having diameters of 100 - 160A
constitute 70.0 - 85.0 %, and pores having diameters of greater than 250A constitute 1.0 - 15.0 % of the total pore volume of the catalyst. It is a feature of the method of the instant invention that the above-described catalyst is contacted with a hydrocarbon feedstock and hydrogen in the hydro-processing step in such a manner as to expose the catalyst to a uniform quality of feed and to maintain the catalyst at isothermal temperature.
The above-described catalyst is advantageous in the hydroprocessing step of this invention in that it has a high activity for hydroprocessing heavy hydrocarbon feedstocks including vacuum residua. The hydroprocessing method of this invention (i.e., step (a)) is advantageous in that it enables the attainment of improved levels of hydrodesulfurization when hydroprocessing heavy feedstock such as vacuum residua.
In one particularly preferred embodiment of the process of the instant invention, a sulfur- and metal-containing hydrocarbon feedstock is catalytically hydroprocessed with the above-described catalyst using the H-OIL process configuration. H-OIL is a proprietary ebullated bed process (co-owned by Hydrocarbon Research, Inc. and Texaco Development Corp.) for the catalytic hydrogenation of residua and heavy oils to produce upgraded distillate petroleum products and a bottoms product suitable as coker feed in the coking operation of the instant invention.
The ebullated bed system oper~tes under essentially isothermal conditions and allows for exposure of catalyst particles to a uniform quality of feed.
Petroleum feedstocks which may be treated by the above-described catalyst in the hydroprocessing step of the instant invention include naphthas, distillates, gas oils, petroleum cokes, residual oils and vacuum residua. A petroleum feedstock typical of those subject to catalytic hydroprocessing by the catalyst in the hydroprocessing step of the instant invention is an Arabian Medium/Heavy Vacuum Resid feedstock as set forth in Table I, below.
TABLE I
Typical Petroleum Feedstock ~Arabian Medium/Heavy Vacuum Resid) API Gravity 4.8 1000 F. +, vol % 87.5 1000 F. +, wt. % 88.5 Sulfur, wt. % 5.0 Total Nitrogen, wppm 4480 Hydrogen, wt. % 10.27 Carbon, wt % 84.26 Alcor MCR, wt. % 22.2 Kinematic Viscosity cSt @ 250 F 410 @ 300 F 117 Pour Point, F. 110 n-C5Insolubles, wt. % 28.4 n-C7Insolubles, wt. % 9.96 Toluene Insolubles, wt. %0.02 Asphaltenes, wt. % 9.94 Metals, wppm Ni Ccont'd.) 2146~10 TABLE I
(ConS ~ d . ) Fe 10 Cu 3 Na 49 Ch l o r i d e wppm The catalyst composition employed in the hydroprocessing step of the instant invention comprises 1.0 - 5.0 wt. %, preferably 2.5 - 3.5 wt. % of an oxide of nickel or cobalt, preferably NiO and 10.0 -25.0 wt. %, preferably 12.0 - 18.0 wt. % of an oxide of molybdenum, most preferably MoO3, all supported on a porous alumina support, most preferably a gamma-alumina support. Other oxide compounds which may be found in such a catalyst composition include SiO2 (present in less than 2.~ wt. %), S04 (present in less than 0.8 wt. %~, and Na20 (present in less than 0.1 wt. %~. The above-described alumina support may be purchased or prepared by methods well known to those skilled in the art. Similarly, the support material may be impregnated with the requisite amounts of the above-described oxides of nickel, cobalt, and molybdenum via conventional means known to those skilled in the art. The catalyst composition of the instant invention contains no bauxite and thus is distinguishable from bauxite-containing catalysts such as those described in U.S. Pat. No. 4,670,132.
A first necessary and essential feature of the catalyst composition is that 15 - 30 % of the nickel or cobalt present in the catalyst (relative to the total nickel or cobalt present in the catalyst) be acid extractable. As taught at Column 3, lines 7 - 35 of U.S. Pat. No. 4,652,545, it is the final calcination temperature during preparation of the catalyst which determines the percentage of free nickel oxide or cobalt oxide (which is acid extractable~ in the total catalyst composition.
Combined nickel or cobalt is not readily acid extractable. As taught at Column 3, lines 36 - 40 of U.S. Pat. No. 4,652,545, it is theorized that the above-described low proportion of acid extractable nickel or cobalt prevents the catalyst from being deactivated almost immediately with respect to hydroconversion activity.
A second necessary and essential feature of the catalyst composition is the specified pore size distribution of the catalyst. It is well known to those skilled in the art that the activity of a given catalyst is proportional to its surface area and active site density. Ordinarily, a catalyst with a large proportion of micropores (defined herein as pores with diameters less than 250A) will have a higher surface area and a corresponding higher intrinsic activity, whereas a catalyst having a large proportion of macropores (defined herein as pores with diameters greater than 250A) will have a lower surface area and a corresponding lower intrinsic activity. However, when hydroprocessing certain hydrocarbon feedstocks such as petroleum feedstocks, particularly vacuum resldua, the observed catalyst reaction rates for catalysts with a large proportion of small diameter pores are low due to diffusional limitations of the small pores, as well as pore blockage caused by accumulating carbon and metals as the catalyst ages.
The catalyst utilized in this invention has a limited macroporosity sufficient to overcome the diffusion limitations for hydroprocessing of the largest molecules but not so much as to allow poisoning of the catalyst pellet interiors.
The catalyst of the instant invention is characterized by having a total surface area of 150 -210 m2/g, preferably 170 - 205 m2/g, and a TPV of 0.50 - 0.75 cc/g, preferably 0.60 - 0.70 m2/g, with a pore size distribution such that micropores having diameters of 100 - 160A constitute 70 - 85%, preferably 70 - 80 % of the catalyst, and macropores 2146~10 having diameters of greater than 250A constitute 1.0 -15.0 %, preferably 4.0 - 14.0 % TPV of the catalyst.
In such a catalyst, it is particularly preferred that the pore volume of micropores having diameters less than lOOA, be limited to less than 25.0 ~ TPV, preferably 5.0 - 20.0 % TPV, most preferably 9.0 -17.0 % TPV of the catalyst. The catalyst of the instant invention has a median pore diameter of 120 -130A, and thus is distinguishable from larger average micropore diameter catalysts such as those disclosed in U.S. Pat. Nos. 4,588,709 and 4,520,128.
A third necessary and essential feature of the catalyst composition is that the above-described oxide of molybdenum, preferably MoO3 is distributed on the above-described porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of less than 6Ø As used in this description and in the appended claims, the phrase "molybdenum gradient" means that the ratio of a given catalyst pellet exterior molybdenum/aluminum atomic ratio to a given catalyst pellet interior molybdenum/
aluminum atomic ratio has a value of less than 6.0, preferably 1.5 - 5.0, the atomic ratios being 21~6410 measured by X-ray photoelectron spectroscopy (XPS), sometimes referred to as Electron Spectroscopy for Chemical Analysis (ESCA). It is theorized that the molybdenum gradient is strongly affected by the impregnation of molybdenum on the catalyst support and the subsequent drying of the catalyst during its preparation. ESCA data on both catalyst pellet exteriors and interiors were obtained on an ESCALAB
MKII instrument available from V. G. Scientific Ltd., 1~ which uses a 1253.6 electron volt magnesium X-ray source. Atomic percentage values were calculated from the peak areas of the molybdenum 3p3/2 and aluminum 2p3/2-1/2 signal5 using the sensitivity factors supplied by Y. G. Scientific Ltd. The value of 74.7 electron volts for aluminum was used as a reference binding energy.
The catalyst employed in hydroprocessing step (a) of this invention is more completely described in Sherwood, Jr., et al., U.S. Patent No.
5,047,142 which is incorporated herein by reference in its entirety.
In the hydroprocessing step of the instant invention the above-described catalyst is contacted 21~6410 with hydrogen and a sulfur- and metal-containing hydrocarbon feedstock by any means which insures that the catalyst is maintained at isothermal conditions and exposed to a uniform quality of feed. Preferred means for achieving such contact include contacting the feed with hydrogen and the prescribed catalyst in a single continuous stirred tank reactor or single ebullated bed reactor, or in a series of 2 - 5 continuous stirred tank or ebullated bed reactors, with ebullated bed reactors being particularly preferred. This hydroprocessing process is particularly effective in achieving high levels of desulfurization with vacuum re~idua feedstocks.
lS In the delayed coking process of this invention, the feedstock which is a bottoms product is pumped at about 150 to 500 psig into a fired tube furnace where it is heated to about 850 F. to 975 F.
and then discharged into a vertically oriented coking drum through an inlet in the bottom head. The pressure in the drum is maintained at 20 psig to 80 psig and the drum is insulated to reduce heat loss, so that the coking reaction temperature remains preferably between about 825 F. and 950 F. The hot 21~6410 feedstock thermally cracks over a period of several hours, producing hydrocarbon vapors which rise through the reaction mass and are removed from the top of the coke drum and passed to a coker fractionator. In the coker fractionator, the vapors are fractionally distilled to yield condensable liquids and gases.
The material which does not vaporize and remains in the vessel is a thermal tar. As the coking reaction continues, the coke drum fills with thermal tar which is converted over time at these coking reaction conditions to coke. At the end of the coking cycle, the coke is removed from the drum by cutting with a high impact water jet. The cut coke is washed to a coke pit and coke dewatering pad. The coke may be broken into lumps and may be calcined at a temperature of 2000 F. to 3000 F. prior to sampling and analysis for grading.
Premium grade coke, referred to in the art as needle grade coke, is used to make steel and for specialty alloy applications. This p~oduct has a co-efficient of thermal expansion of 0.5 x 10 7 to 5 x m/cm/C., an ash content of O.OOl to n.o2 wt. %, volatiles of about 3 to 6 wt. % and sulfur of about 21~6~10 0.1 to 1 wt. %.
Aluminum grade coke, referred to in the art as anode grade coke, is used in the manufacturing of aluminum. This product has a density of about 0.75 to 0.90 gm/cc, an ash content of about 0.05 to 0.3 wt. %, volatiles of about 7 to 11 wt. % and sulfur of about 0.5 to 2.5 wt. %.
Fuel grade coke typically has an ash content of about 0.1 to 2 wt. %, volatiles of about 8 to 20 wt. % and sulfur of about 1 to 7 wt. %.
Usually in the delayed coking operation of this invention coking is conducted at temperatures ranging from about 825 F. to 950 F. and at pressures ranging from atmospheric up to about 80 psig.
Preferably, the coking operation is conducted at a temperature of about 845 F. to about 865 F. and at a pressure ranging from 0 psig to 20 psig.
Surprisingly, in the process of this invention a substantial increase in the more valuable liquid products from the coking operation is achieved while at the same time the yield of the lower value coke produced is reduced. Particularly advantageous 21~6~10 is the increase in the 400 - 650 F. liquid product (i.e., the diesel fraction) from the coking step.
A further advantage of the process of the instant invention is that a reduction of the total sulfur content of the coker liquids and solid coke is achieved.
-EXAMPLES
In Example 1 and Example 2 (Comparative) H-OIL bottoms products (i.e., a 1000 F.~ product) were taken from a nominal 5 BBL/Day two-stage H-OIL
pilot hydroprocessing unit runs in which an 85 wt. %/
15 wt. % mixture of virgin vacuum resid/fluid catalytically cracked (FCC) heavy cycle gas oil was fed to the H-OIL unit. The feedstock (i.e., the H-OIL
bottoms products utilized in the delayed coking operation of Examples 1 and 2) were produced from an Arabian-Medium/Arabian-Heavy mixture crude source. A
summary of the operating conditions for the H-OIL
unit is listed in Table I and the catalyst properties of the catalysts employed are set out in Table II.
- 2146~10 TABLE I
OPERATING CONDITIONS
(HYDROPROCESSING UNIT) Example 1 2 Catalyst Catalyst A* Catalyst B**
Run Number 912249 912214 Date on Test 06/29/91 05/18/91 Hours on Test 12 12 Number of Stages 2 2 Oper. Conditions Average Reactor Temperature, F 782 786 LHSVTotal Voil/Hr/
V reactor 0.383 0.384 LHSVFF ~ voil/Hr/
V reactor 0.326 0.323 CDSV, B/D/Lb 0.089 0.056 Average Catalyst Age, Bbl/Lb 3.017 3.667 H2 Partial Pressure Inlet, psia 2179 2159 Outlet, psia 1948 1946 Throughput Ratio Vol (FF~VBR)/Vol (FF) 1.17 1.18 Gas Rates, SCFB Total/Hydrogen Total/Hydrogen Make-up Gas 4893/3379 4465/4068 Rx Feed Gas 4203/3848 4019/3661 Quench Gas 520/488 507/448 Hydrogen Purge Gas 316/289 274/250 (Cont'd.) - 21g6410 TABLE I
(Cont'd.) Example 1 2 Run Number 912249 912214 Reactor Conditions*** RXl/RX2 RXl/RX2 Avg. rx. Temp., F 776/789 782/790 LHSVTotal ,V/Hr/V 0.77/0.77 0.77/0.77 FF 1 / / 0.65/0165 0.65/0.65 CDSV, B/D/Lb 0.12/0.14 0.10/0.11 Superficial Gas Velocity, Ft/sec .057/.065 .055/.062 Cat. Age, BBl/Lb 7.19/7.48 7.06/7.46 Conversion 1000+ F Conv., Vl.% 57.2 56.8 1000+ Conv., wt% 57.0 56.3 Desulfurization wt % 92.8 81.6 Denitrogenation wt% 69.9 34.9 MCR Reduction, wt% 49.4 51.7 Demetallization wt~ 67.4 74.4 Nickel removal, wt% 64.4 39.8 Vanadium, wt% 25.4 15.7 1000- F in FF, vol% 33.3 34.1 Calc. H2 cons., (Cont'd.) TABLE I
(Cont'd.) * Catalyst of the instant invention.
* Catalyst B - HDS-1443B, a commercially available H-OIL
catalyst sold for use in hydroprocessing resid oils by Criterion Catalyst Corp.
** where RXl is the first-stage reactor and RX2 is the second-stage reactor.
HSV = liquid hourly space velocity as calculated by taking the volume of feed oil charged to the hydroprocessing unit per hour divided by the volume of the hydroprocessing unit reactors.
FF = fresh feed or in this case 1000 F~ residuum feed.
DSV = catalyst daily space velocity as calculated by the average number of barrels of total feed oil per day per pound of catalyst in the hydroprocessing unit reactors.
21~6410 TABLE II
CATALYST PROPERTIES
Catalyst Type Catalyst A Catalyst B
CHEMICAL PROPS.
Mo, wt% dry 10.5 8.77 Ni, wt% dry 2.5 2.42 SiJ wt% dry 1.1 0.1 S, wt% dIy 0.07 0.14 Na, wt% dry 0.04 0.04 PHYSICAL PROPS.
Avg. LengthJ in. 0.148 0.146 DiameterJ in. 0.037 0.0398 Length Distribution < 0.5 mm, wt% 0.0 -< 1.0 mm, wt% 0.0 0.0 < 1.6 mm, wt% 0.0 0.0 < 2.5 mm, wt% 6.6 40.71 > 15 mm, wt% 0.0 0.0 Compacted Bulk3 Density, lb/ft 40.8 36.1 Crush Strngth, lb/mm 1.8 1.5 Hg Pore Vol.J cc/g 0.64 0.74 (Cont'd.) TABLE II
(Cont'd.) Catalyst Type Catalyst A Catalyst B
PORE SIZE
DISTRIBUTION, cc/g (% TPV) <100A 0.05 (8.5) 0.42 (56.8) 100-250A 0.54 (84.2) 0.08 (10.8) >250A 0.05 (7.3) 0.24 (32.4) 250-500A 0.02 (3.9) 0.03 (4.1) 500-1500A 0.02 (2.5) 0.06 (8.1) 1500-4000A 0.005 (0,7) 0.08 (10.8) > 4000A 0.001 (0.2) 0.07 (9.5) Drum Attrition (#30 US Sieve), wt% 0.4 0.6 In Example 1 and Comparative Example 2 2500 gram samples of the 1000 F. bottoms product recovered from the product of the hydroprocessing operation were coked in glass flasks in which the temperature was raised incrementally to a maximum of 850 F. and maintained at that temperature until coking was complete after which high vacuum was applied at the end of the run, the liquid produced in the coking reaction was withdrawn and the coke recovered.
The liquids were fractionated in HYPERCAL ~
high efficiency glass columns. The fractions measured were dry gas, butanes, pentanes, to 400 F naphtha, 400 F to 650 F light gas oil (diesel) and 650 F +
heavy gas oil.
The properties of the coker feedstocks employed in Example 1 and in Comparative Example 2 are shown in Table III and the properties of the products recovered from the delayed coking operation in Examples 1 and 2 are set out in Table IY.
TABLE III
COKER FEEDSTOCK PROPERTIES
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST A CATALYST B
FEEDSTOCK catalyst type API GRAVITY, 0 4.6 2.9 SULFUR, WT% 2.08 2.72 NITROGEN, WPPM 4650 5272 CARBON, WT% 86.93 86.47 HYDROGEN, WT% 10.20 10.12 NITROGEN, WT% 0.40 0.49 CARBON RESIDUE, Wl~18.28 28.49 ASPHALTENES, WT~ 15.44 17.39 H/C RATIO, atomic 1.41 1.40 K.VIS. cSt, 212 F 2179 3477 PENTANE INSOL. WT% 34.66 36.79 HEPTANE INSOL. WT% 15.66 17.61 TOLUENE INSOL. WT% O.22 0.22 ICAP METALS, WPPM
Ni 42.8 47.7 V 58.5 58.6 (Cont'd.) 2146gl O
TABLE III
(Cont'd.) H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST A CATALYST B
Fe 2.7 7.5 Mo < 1 <1 Cr < 1 ~1 Total metals 104 115 TABLE IV
COKER PRODUCT QUALITIES
COKER NAPHTHA
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST ACATALYST B
FEEDSTOCK/catalyst type SULFUR, WT% Ø07 O.ll NITROGEN, WPPM 145 155 BASIC N2, WPPM 116 229 BROMINE NUMBER 3.1 5.7 RON (CLEAR) 40 44 MON (CLEAR) 46 44 CARBON (WT%) 84.26 83.42 HYDROGEN (WTS) 15.29 15.44 NITROGEN (WT~) 0.07 0.09 (Cont'd.) - ` 2146410 TABLE IV
(Cont'd.) COKER DIESEL
EXAMPLE H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST A CATALYST B
FEEDSTOCK/catalyst type SULFUR, WT% 0.74 1.03 NITROGEN, WPPM 720 739 ABSORBTIVITY @285 F 4.06 3.48 FIA AROMATICS, WT% 51.9 50.4 FIA OLEFINS, WT%5.3 4.3 FLASH POINT, F 188 174 ANILINE POINT, F119 119 CLOUD POINT, F -6 -6 POUR POINT, F -27 -13 BROMINE NUMBER 2.4 3.5 BAS. NITROGEN, WPPM 444 489 KINEMATIC VISCOSITY
@ 40 C, cSt 2.73 2.63 @ 70 C, cSt 4.28 4.15 CARBON, WT% 86.62 86.36 HYDROGEN, WT%13.03 13.36 NITROGEN, WT% 0.10 0.11 (Cont'd.) TABLE IV
(Cont'd.) COKER HEAVY GAS OIL
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST ACATALYST B
FEEDSTOCK~catalyst type SULFUR, WT% 2.79 1.67 NITROGEN, WPPM5876 520D
WATSON AROMATICS, WT% 90.5 76.7 ANILINE POINT, F145 142 POUR POINT, F 80 64 BASIC N2, WPPM 473 650 KINEMATIC VISCOSITY
50 C, cSt 33 46 77 C, cSt 11 15 100 C, cSt 6 7 CARBON, WT% 87.19 86.85 HYDROGEN, WT~11.42 11.37 NITROGEN, WT% 0.08 0.2 REFRACTIVE INDEX, 70 C 1.5295 1.5393 (Cont'd.
TABLE IV
(Cont'd.) SOLID COKE
H-OIL BOTTOMS H-OIL BOTTOMS
PRODUCT PRODUCT
CATALYST ACATALYST B
FEEDSTOCK/catalyst type SULFUR, WT~ 2.98 3.92 MOISTURE, WT% 0.04 0.07 VOLATILE
CARBONACEOUS
MATERIAL, WT% 13.54 14.17 ICAP METALS, WPPM
IRON ll 25 CHROMIUM
COEFPICIENT OF
THERMAL EXPANSION
(m/cm/C) 6.1 x 104.7 x 107 21~6~10 Yield and material balance data from Examples 1 and 2 are presented in Table V which follows. These data show that with the process of this invention a substantial increase in the total coker liquid product resulted while at the same time the amount of less valuable coke formed was reduced by 27% and the amount of less valuable heavy gas oil was reduced by 29%. An improvement of 67% of the more valuable diesel fraction was achieved. In addition, the amount of sulfur removed from the coker feed in non-dry gas stream (i.e., the C4~ product) during the coking step increased to 26.8% in Example 1 as compared to only 17.3% in Example 2.
21~6~10 TABLE V
Catalyst A Catalyst B
Coker Yields (wt% FF) Dry Gas 8.81 5.77 Total C4 0.63 2.29 Total C5 0.12 1.15 C6-400 F (naphtha) 15.95 11.11 400-650 F (diesel) 30.17 18.11 650 F+ liquid 17.52 24.71 Coke 26.89 36.84 Total 100.09 99.98 % Desulfurization of feed to non-dry gas products 26.79 17.30
Claims (10)
1. A process for delayed coking of a bottoms product having a boiling point of 1000° F+
which comprises:
a) hydroprocessing a sulfur- and metals-containing hydrocarbon feed in a process which comprises contacting said feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed, where said catalyst has a composition comprising 1.0 - 5.0 weight percent of an oxide of nickel or cobalt and 10.0 to 25.0 weight percent of an oxide of molybdenum, all supported on a porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of less than 6.0, 15 - 30% of the nickel or cobalt is in acid extractable form, and said catalyst is further characterized by having a total surface area of 150 - 210 m2/g, a total pore volume of 0.50 - 0.75 cc/g, and a pore size distribution such that pores having diameters of less than 100.ANG.
constitute less than 25.0%, pores having diameters of 100 - 160.ANG. constitute 70.0 - 85.0% and pores having diameters of greater than 250.ANG. constitute 1.0 - 15.0%
of the total pore volume of said catalyst thereby forming a hydrotreated/hydrocracked product containing a gaseous phase product and a liquid phase product.
b) recovering from the liquid phase product a bottoms product having a boiling point greater than 1000° F, c) subjecting said bottoms product in a delayed coking process to yield coke, distillate and gas.
which comprises:
a) hydroprocessing a sulfur- and metals-containing hydrocarbon feed in a process which comprises contacting said feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed, where said catalyst has a composition comprising 1.0 - 5.0 weight percent of an oxide of nickel or cobalt and 10.0 to 25.0 weight percent of an oxide of molybdenum, all supported on a porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of less than 6.0, 15 - 30% of the nickel or cobalt is in acid extractable form, and said catalyst is further characterized by having a total surface area of 150 - 210 m2/g, a total pore volume of 0.50 - 0.75 cc/g, and a pore size distribution such that pores having diameters of less than 100.ANG.
constitute less than 25.0%, pores having diameters of 100 - 160.ANG. constitute 70.0 - 85.0% and pores having diameters of greater than 250.ANG. constitute 1.0 - 15.0%
of the total pore volume of said catalyst thereby forming a hydrotreated/hydrocracked product containing a gaseous phase product and a liquid phase product.
b) recovering from the liquid phase product a bottoms product having a boiling point greater than 1000° F, c) subjecting said bottoms product in a delayed coking process to yield coke, distillate and gas.
2. The process of Claim 1 wherein the catalyst of step (a) comprises 2.5 - 3.5 wt. % NiO
and 12.0 - 18.0 wt. % Mo03 supported on a porous alumina support.
and 12.0 - 18.0 wt. % Mo03 supported on a porous alumina support.
3. The process of Claim 1 wherein the catalyst of step (a) has a molybdenum gradient value of 1.5 - 5Ø
4. The process of Claim 1 wherein the catalyst of step (a) has a composition comprising 2.5 - 3.5 weight percent Ni0 and 12.0 - 18.0 weight percent Mo03, all supported on a porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of 1.5 - 5.0, 15 - 30%
of the nickel is in an acid extractable form, and said catalyst is further characterized by having a total surface area of 170 - 205 m2/g, a total pore volume of 0.60 - 0.70 cc/g, and a pore size distribution such that pores having diameters of less than 100.ANG.
constitute less than 25.0%, pores having diameters of 100 - 160.ANG. constitute 70.0 - 80.0% and pores having diameters of greater than 250.ANG. constitute 4.0 - 14.0%
of the total pore volume of said catalyst.
of the nickel is in an acid extractable form, and said catalyst is further characterized by having a total surface area of 170 - 205 m2/g, a total pore volume of 0.60 - 0.70 cc/g, and a pore size distribution such that pores having diameters of less than 100.ANG.
constitute less than 25.0%, pores having diameters of 100 - 160.ANG. constitute 70.0 - 80.0% and pores having diameters of greater than 250.ANG. constitute 4.0 - 14.0%
of the total pore volume of said catalyst.
5. The process of Claim 1 wherein in step (a) the feed is contacted with the catalyst in a single continuous stirred tank reactor.
6. The process of Claim 1 wherein in step (a) the feed is contacted with the catalyst in a single ebullated bed reactor.
7. The process of Claim 1 wherein in step (a) the feed is contacted with the catalyst in a series of 2-5 ebullated bed reactors.
8. The process of Claim 1 wherein in step (a) the feed is contacted with the catalyst in a series of 2-5 continuous stirred tank reactors.
9. The process of Claim 1 wherein in step (c) the delayed coking is conducted at a temperature ranging from 825° F to about 950° F
and at a pressure ranging from atmospheric up to about 80 psig.
and at a pressure ranging from atmospheric up to about 80 psig.
10. The process of Claim 1 wherein in step (c) the delayed coking is conducted at a temperature of about 845° F to about 865° F.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26267494A | 1994-06-20 | 1994-06-20 | |
| US08/262,674 | 1994-06-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2146410A1 true CA2146410A1 (en) | 1995-12-21 |
Family
ID=22998518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002146410A Abandoned CA2146410A1 (en) | 1994-06-20 | 1995-04-05 | Delayed coking of bottoms product from a hydrotreatment process |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0892566A (en) |
| CA (1) | CA2146410A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111420669A (en) * | 2020-04-21 | 2020-07-17 | 上海静好化工有限公司 | Dry gas impurity removal catalyst for refinery plant |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2805276B1 (en) * | 2000-02-23 | 2004-10-22 | Inst Francais Du Petrole | PROCESS FOR CONVERTING HYDROCARBONS ON A CATALYST WITH CONTROLLED ACIDITY |
| ES2438529T3 (en) | 2002-12-02 | 2014-01-17 | Avery Dennison Corporation | Procedure for labeling fabrics and heat transfer label very suitable for use in said procedure |
| WO2017019744A1 (en) * | 2015-07-27 | 2017-02-02 | Saudi Arabian Oil Company | Integrated ebullated-bed hydroprocessing, fixed bed hydroprocessing and coking process for whole crude oil conversion into hydrotreated distillates and petroleum green coke |
-
1995
- 1995-04-05 CA CA002146410A patent/CA2146410A1/en not_active Abandoned
- 1995-06-19 JP JP7175442A patent/JPH0892566A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111420669A (en) * | 2020-04-21 | 2020-07-17 | 上海静好化工有限公司 | Dry gas impurity removal catalyst for refinery plant |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0892566A (en) | 1996-04-09 |
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