JPS6099194A - Hydrofining process for supply stream containing hydrocarbon - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrofining process for hydrocarbon-containing feed streams.

In one aspect, the invention relates to a method for removing metals from a hydrocarbon-containing feed stream. In other features, the present invention relates to a method for removing sulfur from a hydrocarbon-containing feed stream. In still another aspect, the present invention relates to a method for removing potentially cokingable components from a hydrocarbon-containing feed stream.

Crude oil, crude oil fractions and extracts of heavy crude oil and products from the extraction and/or liquefaction of coal and lignite, products from tar sands, products from rock oil and similar products are processed. It is well known that they contain certain ingredients that can cause problems. - By way of example, when these hydrocarbon-containing feed streams contain metals such as vanadium, nickel and iron, such metals are prefixed with crude oil (
(topped crude) and bottom oils. The presence of the metals mentioned above reduces the additional cost of these relatively heavy fractions since they generally act as catalyst poisons for catalysts used in processes such as catalytic cracking, hydrogenation or hydrodesulphurization. Makes machining difficult.

The presence of other components such as sulfur is also considered detrimental to the processability of hydrocarbon-containing feed streams. Also,
The hydrocarbon-containing feed stream contains components that are easily converted to coke in processes such as catalytic cracking, hydrogenation or hydrodesulfurization (Ramsbottom residual carbon).
It also contains carbon resiclue). Therefore, removal of components such as sulfur and components that tend to form coke is desirable.

The method of removing the above-mentioned components is generally referred to as hydrofining (depending on the components contained in the hydrocarbon feed stream, one or all of the above-mentioned components).
achieved by hydrofining method).

According to the invention, a hydrocarbon-containing feed stream containing metals, sulfur and/or Ramsbottom residual carbon is contacted with a suitable refractory inorganic material. A preferred decomposition selected from the group consisting of copper, zinc and Groups I-B, Vl-E, V-B, VI-B, ■-B and ■ of the periodic table. chemical compounds (hereinafter collectively referred to as “decomposable metals J (De
the refractory material in the hydrocarbon-containing feed stream prior to contacting the hydrocarbon-containing feed stream with the refractory material; Make a slurry with it. If said refractory material is not present in slurry form, a hydrocarbon-containing feed stream also containing decomposable metals is contacted with said refractory material in the presence of hydrogen under suitable hydrofining conditions. Hydrogen and suitable high profiling conditions also exist for the slurry process. After addition of decomposable metals or contact with refractory materials either in a slurry process, the concentration of metals, sulfur and rum spot residual carbon in the hydrocarbon-containing feed stream will be reduced. Removal of such components from a hydrocarbon-containing feed stream by such a method improves the processability of said hydrocarbon-containing feed stream in processes such as catalytic cracking, hydrogenation or additional hydrodesulfurization processes. .

Other objects and advantages of the invention will become apparent from the foregoing detailed description of the invention and the appended claims, as well as the following detailed description of the invention.

Any suitable refractory inorganic material for metal, sulfur and Ramsbottom residual carbon removal can be used in this noidorofining process. Suitable refractory inorganic materials include metal oxides, silica, metal silicates, chemically bonded metal oxides, metal phosphates, and mixtures of any two or more of these. Suitable refractory inorganic materials include alumina, silica, silica-alumina, aluminosilicates (e.g. zeolites and clays),
P2O5-alumina, B203-alumina, magnesium oxide, calcium oxide% lanthanum oxide, cerium oxide (Ce2O3, CeO2,), thorium dioxide, titanium dioxide (titania), titania-alumina, nizirconium, zinc phosphate, subaluminate, and zinc titanate. For fixed bed and moving bed applications, at least 95% by weight alumina, most preferably at least 9%
Refractory materials containing 7% by weight alumina are currently preferred.

Silica is the preferred refractory material for slurry or flow processes.

The refractory material can have any suitable surface area and pore volume. Generally, the surface area is from about 10 to about 5
00 m2/fi, preferably about 20 to about 300 m
2/g, while its pore volume is 0.1
~3. Oc! Ji, preferably about skin 6 to about 1.5CC
/g.

One of the novel features of the present invention is the discovery that when a monodegradable metal is introduced into a hydrocarbon-containing feed stream, the promoting action of the refractory inorganic material described above is not required. The refractory inorganic substances used according to the invention will initially be substantially free of accelerating effects, in particular copper, zinc and mB, IVB, VB, VIB, VnB and the like of the periodic table. It will not contain any substantial concentration (about 1% by weight or more) of a transition metal selected from the 'im group. When used in long-term operations, substantial concentrations of decomposable metals accumulate on the refractory minerals. This discovery, which eliminates the need for accelerators for refractory inorganic materials, is another factor contributing to the cost reduction of the hydrofining process.

Any suitable hydrocarbon-containing feed stream can be hydrogen purified using the refractory materials according to the invention. Suitable hydrocarbon-containing feed streams include petroleum products, coal, pyrolysis products, products from the extraction and/or liquefaction of coal and lignite, products from tar sands, products from rock oil. , extremely severe (5 supercri) of heavy crude oil
tical ) extracts, and similar products. Suitable hydrocarbon feed streams include temperatures between about 205°C and about 568°C.
gas oils with a boiling point range of , prefixed crude oils and residual oils with a boiling point range above about 646°C. However, the present invention provides treatment for heavy feed streams such as heavy draft crude oil, extracts of heavy crude oil, resid oils, and other materials that are generally considered too heavy to distill. Especially oriented. These materials generally contain the highest concentrations of metals, sulfur and rum spot residual carbon.

It is believed that the use of the refractory material according to the present invention can reduce the concentration of any metal in the hydrocarbon-containing feed stream. However, the present invention is particularly applicable to the removal of vanadium, nickel, and iron.

The sulfur that can be removed using the refractory material according to the invention is generally contained in organic sulfur compounds. Examples of such organic sulfur compounds include sulfide P, disulfide, mercaptan, thiophene, benzylthiophene, dibenzylthiophene, and the like.

Any suitable decomposable compound can be introduced into the hydrocarbon-containing feed stream. Examples of suitable compounds include aliphatic, cycloaliphatic and aromatic carboxylates with 1 to 20 carbon atoms, diketones, carbonyls, cyclopentagenyl complexes, mercantides, dentates, carbamates, diteocarbamates and diketones. There is theophosphate. Any suitable decomposable metal can be used. Preferred decomposable metals are:
They are molybdenum, chromium, tungsten, manganese, nickel and cobalt. Molybdenum is carbonyl,
Acetate, acetylacetonate.

Particularly preferred decomposable metals can be introduced as octoates (2-ethylhexanoate), diteocarbamates, naphthinates or sothiophosphates. Molybdenum hexacarbonyl, molyzodene dithiocarbamate and molybdenum dithiophosphate are particularly preferred additives.

Any suitable concentration of the decomposable metal described above can be added to the hydrocarbon-containing feed stream. Generally, the concentration of the degradable metal is
In the range of about 1-6 o o ppm, preferably about 2-6 o o ppm
A sufficient amount of the decomposable metal is added to the hydrocarbon-containing feed stream to be in the range of about 1100 pp.

Concentrations higher than about 600111n should be avoided to prevent reactor blockage in fixed bed operations. It should be noted that one particular advantage of the present invention is that large sorptions are obtained even at very low concentrations of decomposable metals.

This substantially improves the economic viability of the method, which is the main objective of the invention.

After adding a decomposable metal to a hydrocarbon-containing feed stream over a period of time, one need only introduce the decomposable metal periodically to maintain the efficiency of the process. It can be combined with a hydrocarbon-containing feed stream in any suitable manner. Prior to introducing the decomposable metal into the hydrocarbon-containing feed stream, the decomposable metal may be mixed with the hydrocarbon-containing feed stream as a solid or liquid, or dissolved in a suitable solvent (preferably an oil). You may let them. Any suitable mixing time can be used. However, it is believed that simply injecting the decomposable metal into the hydrocarbon-containing feed stream is sufficient. No special mixing equipment or mixing times are required.

The pressure and temperature at which the decomposable metal is introduced into the hydrocarbon-containing feed stream is not considered critical. However, L
, temperatures as low as 450°C are recommended.

The hydrofining process of the present invention can be carried out in any apparatus that allows the refractory material described above to contact a hydrocarbon-containing feed stream and hydrogen under suitable hydrofining conditions. This hydrofining method has no restrictions on the use of special equipment. This hydrofining method may be fixed bed, moving bed or slurry or hydrovisbreaking.
g) can be carried out using fluidized bed operation, also called operation.

Fixed beds are currently preferred.

Any suitable reaction time between the refractory material and the hydrocarbon-containing feed stream can be utilized. Generally, the reaction time is about 0
．． Preferably the reaction time will be within the range of about 0.4 to about 4 hours, to within the range of 1 to about 10 hours. Therefore, the flow rate of the hydrocarbon-containing feed stream is such that the time required for the mixture to pass through the reactor (residence time) is preferably about 0.
It should be within the range of 4 to about 4 hours. In fixed bed operations, the flow rate generally ranges from about 0.10 to about 10
Liquid hourly space velocity (LH8V, ) within the range of cc oil/aC refractory/hour, preferably between about 0.25 and about 2.5/CC/CCR.

In continuous slurry operation, oil and refractory materials are
Generally, they are premixed at a weight ratio within the range of about 100:1 to about 10:1. This mixture is then pumped into the reactor at a rate such that the residence time described above is achieved.

This hydrofining process can be performed at any suitable temperature. The temperature generally ranges from about 150° to about 5
It will be within the range of 50°C, preferably within the range of about 650° to about 450°C. Relatively high temperatures will improve metal removal rates, but temperatures that adversely affect hydrocarbon-containing feed streams, such as coking, should not be used and are not economical. Reasons should also be considered.

Lower temperatures are generally used for lighter feeds.

Any suitable hydrogen pressure can be used in this hydrofining process. The reaction pressure will generally be within the range of about atmospheric pressure to about 10,000 psig. Preferably, this pressure will be in the range of about 500 to about 3.000 psig. Although relatively high pressures tend to reduce coke formation, high pressure sand operations are economically disadvantageous.

Any suitable amount of hydrogen can be added to the hydrofining process described above. The amount of hydrogen used to contact the hydrocarbon-containing feedstock is generally in the range of about 100 to about 20,000 standard cubic feet per barrel of hydrocarbon-containing feedstream, more preferably in the range of about 100 to about 20,000 standard cubic feet per barrel of hydrocarbon-containing feedstream.
It will be in the range of about 1.000 to about 6.000 standard cubic feet per barrel.

Generally, the refractory material is used until a satisfactory level of metal removal cannot be achieved, which is believed to be the result of the refractory material becoming loaded with the metal to be removed. Although it is possible to remove metals from the refractory material by some type of leaching method, it is expensive, so it is generally possible to simply replace the used refractory material with a new It is considered to be a replacement for fire-resistant materials.

In the slurry process, the problem of the refractory material losing its activity can be avoided by recycling only part of the refractory material and adding fresh refractory material.

The length of time that the refractory material maintains metal removal activity will depend on the metal concentration in the hydrocarbon-containing feed stream being treated. It is believed that the refractory material can be used for a sufficiently long period of time until the oil accumulates 10-200% by weight, based on the weight of the refractory material, of metals, mostly Ni, V and Fe. Sign. The following example is presented to further illustrate the invention.

Example 1 This example describes the influence of the presence or absence of a decomposable molybdenum compound added when heavy oil is hydrotreated in a fixed bed. 26% by weight toluene and 74% by weight Venezuelan mongas pipeline oil.
A hydrocarbon feed consisting of Mongas pipeline oil) was pumped with a LAPP Model 211 (General Electric Co. model pump) into a metal mixing T-pipe where it was mixed with a controlled amount of hydrogen gas.oil/ The hydrogen mixture was placed in a stainless steel trickle peddler with a 0.25 inch outside diameter axial thermocouple well inside.
d) Pumped down into the reactor (28.5 inches long, 0.75 inches inside diameter). The upper layer of the reactor (6.5 inches below the oil/hydrogen inlet) K is a 50 cco low surface area (less than 1 m"/lI) α-alumina (alundum)
Lundum), Ohio.

Akron, Two-Tone Chemical Process (Sold by Norodacts)'fr:, 50cc in the middle layer
High surface alumina (Trilobe■ sold by American Cyanamid Company) SN
-5'548 alumina catalyst: 2.6 heavy f-chi Sing
, BET method, with a surface area of 144 m"/i as measured with N2 and a pore volume of 0.92 cr/9 as measured with a mercury porosimeter at 50 Kpsi Hg, from the pore volume and surface area. Calculated average pore diameter 170Xt
1), and a bottom layer of 50 cc of a-alumina. Triroso alumina was heated under hydrogen overnight before use.

This reaction tube is manufactured by Therm Craf.
t) (Winston-Salem, North Carolina) model 2116-zone furnace. Reactor temperature was typically measured at four points along the length of the reactor bed by thermocouples moving in axial thermocouple wells. The liquid product is collected in the receiver.

It was filtered with a glass filter and analyzed once. Vanadium and nickel in oil were determined by Zolaz strawberry luminescence analysis.
ission analysis),
Sulfur content was determined by X-ray fluorescence spectroscopy. The hydrogen gas was released.

Degradable molybdenum compounds, if used, were added to the toluene-oil feed. This mixture is then heated at about 40°C for about 2
Stir for hours.

In a 41 ft control experiment, the feed had Mo(IV) octoate M00 (07H15002) 2 s (containing about 8% MOt- by weight, sold by Chefart Chemical Co., Cincinnati, Ohio) dissolved in the feed.
8i invention experiments and MO(V) naphthinate, Mo
(CxoH2002)s (available from ON Pharmaceuticals, Plainville, New York)) are shown in Table 1.

The reactor source temperature was 400° C. and the hydrogen pressure was approximately 1.000 psig in all experiments.

The data in Table 1 show that there is a clear demetalization and desulfurization effect when molybdenum compounds are present in the feed (Experiments 2, 6) versus a control experiment without molybdenum in the feed (Experiment 1). Advantages have been shown.

Based on the performance of molybdenum as demonstrated in this and the following examples, it appears that other decomposable metals mentioned herein will have certain similar beneficial effects. These other metals are generally effective as hydrogenation components; these metals tend to widen the gap between metal and sulfur-containing molecules, which aids in metal and sulfur removal. It is considered.

Example ■ This example demonstrates the effect of a small amount (16IIP) of molybdenum in another heavy oil feed (prefix, 650 sub++Arabian heavy crude) in a long-term hydrodemetallization and hydrodesulfurization experiment. explain. These experiments were performed essentially as described in Example I, with the following exceptions: (a) The demetallizing agent was a mixture of Mc(Co) (from Aldrisohy Chemical Co., Milwaukee, Wis.). (1+) oil pumps with diaphragm shield heads sold by Whittey Co., Highland Heights, Ohio.
(c) Hydrogen gas was introduced into the reactor through a tube concentrically surrounding the oil guide tube, which was a Mol5'mol LP10 reciprocating pump. (d) Axial thermocouple well (
(e) When using degradable molybdenum compounds, the temperature of the catalyst bed was measured at three locations by three separate thermocouples embedded in a 55-gallon capacity steel drum. Fill the drum with feed oil at a temperature of about 160'F.

The oil and additives were circulated for approximately 2 days with a circulation pump for thorough mixing. The reactor temperature was approximately 407°C (765°C) for all experiments.
6F), its H2 pressure is 2250 in Experiments 4 and 5.
psig, 2oo in experiment 6.

The % H2 feed rate in psig was 4800 standard cubic feet per barrel ('5OFB). The refractory material was Triroso alumina sold by American Cyanamid Company. Related experimental data are shown in Table ①.

The data in Table 1 clearly demonstrate the demetalization and desulfurization benefits of small amounts of Mo (as molyzodene hexacarbonyl) in the feed. Excess amount of Mo'' (approximately 2000 ppm) was not advantageous as the fixed bed became plugged after approximately 1 day as evidenced in experiment 6.

The amount of Ramsbottom residual carbon (not shown in Part ■) is
In the product of control experiment 4 (9.1 to 10.6 wt. % Ramsbottom C), more in the hydrotreated product of inventive experiment 5 (8.
4-9.6% by weight Ramsbottom C) was generally lower. The raw feed had a Ramsbottom carbon content of approximately 11.6 parts by weight.

EXAMPLE nt In this example, a small amount of Mo(Co)6 in the feed was carried out essentially as described in Example 11, except that katalco alumina was used. The effect on hydrodemetalization and hydrodeflow is explained. Catalco alumina is 181ff
It has a surface area of 1"15" and an average pore diameter of about 231 A (calculated) and is available from Catalco, Inc., Chicago, IL. The refractory material was heated under hydrogen overnight. The process conditions were the same as those described in Example 2. The results are summarized in Table 2.

The data in Table ■ shows the small amount of Mo in Arabian heavy crude oil.
(as Mo(Co)) clearly shows that it has a clear beneficial effect on the removal of nickel and vanadium, especially after about 7 days.

The residual carbon (not shown in Table 2) was higher in the hydrotreated product of Inventive Run 8 (10.2-10.6 wt. % Rum Spotom C) than in the product of Control Run 7 ( 9,6
˜10.0 wt% Ram Spotom C) was lower. The Ramsbottom carbon content of the raw feed is between 11.5 and 11
．． It was 8% by weight.

Example ■ In this example, undiluted, undesalted Mongas heavy crude oil was hydrotreated over catarrhal alumina essentially by the method of Example Ill. In particular, mechanical problems during invention run 120 caused errors in feed rates and demetallization results. These experimental data for a period of 2 to 17 days, summarized in Table 1V, therefore demonstrate the advantage of MO in the feed during hydroprocessing using catarrhal alumina as the refractory material. It wasn't clearly shown.

Example V In this example, molybutene hexacarbonyl dissolved in undiluted Mongas heavy crude oil (containing about 2.6% by weight sulfur and about 11.3% by weight Ramsbottom carbon) was The effect on the aqueous bed demetalization of the above crude oil in a fixed catalyst bed containing a solid refractory material other than alumina will be explained. Experiments 16-17 were carried out at 765°F (407°C), 2250°C essentially by the method described in Example
Performed with p8ig R2 and 4B OO5cpBH2.

The following refractory materials were used: (1) SIO2, surface area (BgT, Hg used), sold by Davison Chemical Division, R1 Grace, Inc., Valves 1 Sore, Maryland 16
2"Z'/P, pore volume (using Hg) 0.74ee
15'.

(11) MgO1 Surface H (BET
(using Hg) 54 m2/l, pore volume (using Hg) 0.4
1 CCl &-.

Qll) Al (No3
)・AlP produced by the reaction of 9H20, H3PO4 and NH3 and baked at 700°F' for 2 hours.
O4゜θ■) U.S. Patent Specification No. 4. ! Zn2Ti prepared by the method described in Example I of No. 171,728
04 (zinc titanate), surface area (BET, using Hg) 2
4.2m”/P, pore volume (using Hg) 0.36CC
/J.

M Zn sold by Harsha Chemical Co. (a subsidiary of Garfoil Co., Ltd.), Cleveland, Ohio
(AlO2)2 (zinc aluminate), surface area 40m27
f/-1 pore volume 0.33cc/fi"& 1 ru.

Relevant experimental data are summarized in Table V. These data indicate that the supports presented above are generally nearly as effective as alumina in removing nickel and vanadium in the presence of dissolved Mo(Co)a. I understand. Although no baseline experiments were performed, it is believed that in all cases the addition of molybdenum hexa\carbonyl resulted in a small (approximately 10%) improvement.

The amount of sulfur in the product (shown in light V) is
The range was approximately 2.1-2.4% by weight in all experiments. The amount of Ramsbottom carbon in the product (Mo) ranged from about 9.0 to 10.8% by weight in all cases. C
o) Demonstrates the unsuitability of 6 (dissolved in a prefixed Arabian heavy oil feed) as a demetallizing and desulphurizing agent. The above-mentioned heavy oil (containing Mo).

Two types of low surface area materials near random A1203 (Example 1
The hydrogenation process was carried out essentially according to the method of Example (2), in which the hydrogenation treatment was carried out in a fixed bed of l/x a II x l/a # stainless steel chips. As shown in the data in Table 1, the reactor clogged after a few days.

EXAMPLE In this example, Triroso alumina from American Cyanamid (see Example 1) and Molyvan 807 (approximately 4 .6
Hondo California heavy prefixed crude oil (650°F+) (supe
(extracted with n-pentane)
Hydrogenation treatment of extract will be explained.

Inventive experiment 66, 66.5 pounds of bond extract was combined with 7
．． 5 g of molypan and then heated to 700-750°F + 12250 p essentially by the method of Example 1.
Hydrotreated at sig Hz and 48005CFB Hz. The experimental results summarized in Table 1 demonstrate the beneficial influence of dissolved molybdenum dithiocarbamate compounds on the extent of hydrodemetalization of the bond extraction feed.

Example 1 In this example, a slurry type hydrofining method (hydrovis breaking) will be explained.

Approximately 1,109 pipeline grade mongas heavy oil (392
1) I) A clause containing 100 ppm of N1 plus, if desired, variable amounts of a degradable molyzodene compound and a refractory material in a 300 cc autoclave (Pennsylvania Tithe, E. (supplied by Autoclape Engineers, Inc.).

The reactor contents were stirred at about 100 Or, p, m, pressurized with about 1000 psig of hydrogen gas, and heated at about 4101 °C for about 2.0 hours. The reactor was then cooled, vented, and its contents analyzed. The results of a representative experiment are summarized in Table ■. These experiments demonstrate the advantageous results of adding dissolved molybdenum to the slurry process.

1) Amorphous Hi-8il sold by PPG Industries, Inc., Pennsylvania.
Me8il silica: surface area of 160 m2/&-
It has an average viscosity of 0,022 microns.

11) Approximately 50% by weight of molybdenum (■) ditridecyl dithiocarbate and 50% by weight of aromatic oil (specific gravity 0.9
Molipane [F] 807 contains about 4.6% MO by weight. This material is sold as an antioxidant and anti-wear additive by Panderbilt, R.T., Norwalk, Conn.

1i1) R is a 2-ethylhexyl group, M02
Molybdenum sulfide (■) of S202 (P82(OR)2)
It is a mixture of about 80% by weight dithiophosphate and about 20% by weight aromatic oil (see note (11)), sold by R.T. Vanderbilt.

1v) This result seems erroneous.

EXAMPLE ■ Two continuous slurry-type hydrodemetallization (hydrvissilyking) experiments were conducted using a truly prefixed (650'F+) heavy crude oil. In experiment 47, the above crude oil was
．． pumped at a rate of 7 lb/hr, about 0.05 lb/hr (3.0% by weight) Hi-8il silica, about 2°6 x 10-' lb/hr MO(Co),
Mo as (150 ppm MO) and about 288
1scf/barrel H2 gas approximately 1/4 I>1'
Mixed in stainless steel pipes. This oil/gas mixture is heated in an electric furnace into a coil (60 feet long, 1/2 inch diameter).
4 inches) and pumped into the heated reactor (4 inches diameter, 26 inches long) through a guide tube extending near the bottom of the reactor. The product is approximately 8
The drain tube is evacuated such that the average residence time of the oil/gas mixture is approximately 90 minutes at reaction conditions of 00'F/11000 psi N2. This product passes through a pressure drop pulp into a series of phase separators and coolers.

All liquid fractions were combined and analyzed for metals. Experiment 47
About 51% by weight of V and about 27% by weight of Ni were removed.

780'F, 100pp10 as Mo(Co)a
A second test (Run 4) using 0 pp and 6.0 wt% 5102 was conducted in the continuous ST IJ-operation described above.
In 8), about 51% by weight of V and about 23% by weight of N1 were removed.

As a control, no experiments were performed without the addition of MO.

However, it is thought that such an experiment without the addition of MO would yield significantly worse results than those shown above.

Reasonable modifications and improvements to the present invention are possible within the scope of the claims.

Agent Akira AsamuraContinued from page 1Priority claim 0198 group May 21st [phase] United States (U.S.
) ■ 612539 @ Inventor Nidward Loren United States Ophras Sugeryu, The -, Spruce 224 Second 0 Inventor Ot

Claims (9)

[Claims] (1) Hydrofining of said hydrocarbon-containing feed stream comprising contacting said hydrocarbon-containing feed stream with hydrogen and a refractory inorganic material suitable for Hi-V rofining under suitable hydrofining conditions. In the inning process, the hydrocarbon-containing feed stream contains copper, zinc or
1- Group B, Group 1v-n, Group V-B, Group VI'-B
introducing at least one decomposable compound of a metal of Groups I to B or Group II, provided that said refractory inorganic substance is first brought into contact with said hydrocarbon-containing feed stream. Copper, zinc, and Group 1[-'B, Group 1V-B, Group V-B, Group Vl-B, Group ■-B of the periodic table]
The concentration of the transition metal selected from Groups 1 and 2 in the refractory inorganic material is about 1% based on the weight of the refractory inorganic material.
% by weight. (2) The decomposable metal compound has 1 to 20 carbon atoms.
aliphatic, cycloaliphatic or aromatic carboxylates with
The method according to claim 1, wherein the dithiocarbamate or dithiophosphate. (3) The degradable compound is carbonyl, acetate, acetylacetonate, octoate (2-ethyl
hexanoate), natutanate, dithiocarbamate, or dithiophosphate.
The method described in section. (4) Claim 1, wherein the metal in the decomposable compound is copper or a metal of Group V-B, Group Vl-B, Group ■-B, or Group ■ of the periodic table. 3. The method according to any one of items 3 to 3. (5) The metal in the decomposable compound is molybdenum. 5. The method according to claim 4, wherein chromium, tungsten, manganese, and nickel are cobalt. (6) The method according to claim 5, wherein the metal in the decomposable metal compound is molybdenum. (7) The method according to claim 6, wherein the decomposable compound is molybdenum hexacarbonyl, molybdenum dithiocarbamate, or molybdenum dithiophosphate. (8) adding a sufficient amount of said degradable compound such that the concentration of said metal in said degradable compound in said hydrocarbon feed stream is within the range of about 1 to about 600 min. Claim 1 added to a hydrocarbon-containing feed stream
7. The method according to any one of 7. (9) adding a sufficient amount of said degradable compound such that the concentration of said metal in said degradable compound in said hydrocarbon feed stream is within the range of about 2 to about 100 min. 9. A method according to claim 8, wherein the method is added to a hydrocarbon-containing feed stream. αq The fire-resistant inorganic material is about 10 to about 500 m”
/11 and about 0.1 to about 3.0 CC/I
Claims 1 to 1 have a pore volume within the range of i.
9. The method according to any one of Section 9. Makiriki The above-mentioned fire-resistant inorganic material is about 20 to about 600 r
Surface area within the range of rL2/I and about 0.6 to about 1.50C
Claim 1 having a pore volume within the range of /g.
The method described in item 0. Obu The refractory inorganic substance is silica, metal oxide,
12. A method according to any one of claims 1 to 11, which is a metal silicate, a chemically bonded metal oxide, a metal phosphate or a mixture of any two or more thereof. o3 The refractory inorganic substance is alumina or silica. Silica-alumina, aluminosilicate, p2o, -alumina% B203-alumina, magnesium oxide. Calcium oxide, lanthanum oxide, cerium oxide. Thorium dioxide, titanium dioxide, titania-alumina,
Zirconium dioxide, aluminum phosphate, magnesium phosphate, calcium phosphate, cerium phosphate, thorium phosphate,
13. The method according to claim 12, wherein zirconium phosphate, phosphoric acid 1[[, zinc aluminate or zinc titanate. 14. The method of claim 13, wherein the refractory metal oxide contains about 95 parts by weight alumina based on the weight of the refractory metal oxide. 14. The method of claim 13, wherein the refractory metal oxide contains about 97 g of alumina, based on the weight of the refractory metal oxide. 17. The method of claim 16, wherein the refractory inorganic material is zinc titanate. 17. The method of claim 16, wherein the refractory inorganic material is an aluminate subsalt. 0 barrels The preferred hydrofining conditions include a reaction time between the refractory inorganic material and the hydrocarbon-containing feed stream in the range of about 0.1 to about 10 hours at 150°C.
Temperature within the range of ~550℃, approximately atmospheric pressure ~10+00℃
0 p8ig, and from about 100 to about 2 o per barrel of said hydrocarbon-containing feed stream, o o o
18. A method according to any one of claims 1 to 17, comprising a hydrogen flow rate in the range of standard cubic feet. (b) The preferred hydrofining conditions include a reaction time between the refractory inorganic material and the hydrocarbon-containing feed stream ranging from about 0.64 to about 4 hours at 650°C.
Temperatures within the range of ~450°C, approximately 500°C to approximately 3,000°C
psig, and a hydrogen flow rate within the range of about 1.000 to about 6,000 standard cubic feet per barrel of said hydrocarbon-containing feed stream. . 4. Any one of claims 1 to 19, wherein the hydrofining method is a demetalization method, and the hydrocarbon-containing feed stream contains one or more metals.
The method described in section. 21. The method of claim 20, wherein the metals Qυ consist of nickel and vanadium. ■ The above hydrofining method is a desulfurization method,
Process according to any one of claims 1 to 19, wherein the hydrocarbon-containing feed stream contains one or more organic sulfur compounds. 23. The method of claim 22, comprising nosulfide, mercaptan, thiophene, pencilthiophene and dibenzylthiophene. (c) The hydrofining method is a method for removing Ramsbottom residual carbon, and the hydrocarbon-containing feed stream contains Ramsbottom residual carbon. The method described in Section 1. (c) introducing the decomposable compound and the refractory material into the hydrocarbon-containing feed stream to form a slurry, and contacting the slurry with hydrogen in a reactor under suitable hydrofining conditions; Claims 1 to 24
A method according to any one of Sections.