JPS6028492A - Hydrofining process - 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 provides a method for converting hydrocarbon-containing feed streams to metals, 0!
Carbonization aimed at removing yellow and potential coking components, as well as reducing the capping of heavy components contained in the feed stream and improving the life of the catalyst used in the refining process of the feed stream. The present invention relates to a method for treating a hydrogen-containing feed stream.

The meaning of the term "catalyst formulation" used here is:
The period of time during which a catalyst maintains acceptable activity. Typically, the catalyst must be replaced or regenerated when its activity drops to an unacceptable level. From both a process execution point of view and an economic point of view,
Long-lasting catalyst pairing is highly desirable.

It is well known that in addition to crude oil, extracts and/or liquefied products of coal and lignite, products from tar sands, products from shale oil, and others contain components that solidify the refining process. It is. For example, when fractionating a hydrocarbon-containing feed stream containing metals such as vanadium, nickel, and iron, these metals tend to undergo a-condensation in the heavy fractions, such as prefixed crude oil or residual oil. ing. In general, metals act as poisons for catalysts used in refining processes such as catalytic cracking, hydrogenation, or hydrodesulphurization, so inclusion of the full text would be helpful in refining these heavy fractions. becomes difficult.

The presence of other components such as sulfur and nitrogen is also believed to be detrimental to the ash system. The midstream hydrocarbon feed may also contain components that are easily converted to coke in refining processes such as catalytic cracking, hydrogenation, or aqueous desulfurization (referred to as Ramsbottom residual carbon). Therefore, it is desirable to remove components such as sulfur and nitrogen, as well as components that tend to form coke.

It is also desirable to reduce the amount of heavy components contained in heavy fractions such as prefixed crude oils and residual oils. The term heavy components is meant herein to mean fractions having a boiling range above about 1000'F.

By reducing the weight of such a fraction, a light fraction that is easy to purify and has high value can be obtained.

In a method commonly called hydrofining, removal of metals, sulfur, nitrogen and Ramsbottom residual carbon,
and catalysts are available that are effective in reducing the amount of heavy components (depending on the components contained in the hydrocarbon-containing feed stream, one or all of the above removals and content reductions may be achieved by hydrofining methods). ). However, it would be desirable to improve the lifetime of catalysts used for such removal or content reduction.

It is therefore an object of the present invention to remove components such as metals, sulfur, nitrogen and rum spot residual carbon from a hydrocarbon-containing feed stream and to reduce the amount of heavy components contained in the hydrocarbon-containing feed stream. It is an object of the present invention to provide a method for improving the life of a catalyst used in a hydrofining process. Such improvements provide substantial benefits. This is because it is possible to use a Type 1 medium for a long period of time without requiring regeneration or father exchange of the catalyst, and
This is because, in this case, it is recognized that the initial activity of the catalyst for removal and content loss reduction described above should be increased.

According to the invention, a hydrocarbon-containing feed stream containing metals, sulfur, nitrogen and/or Ramsbottom residual carbon is contacted with a solid catalyst composition comprising alumina, silica or silica-alumina. let

This catalyst composition includes groups VIB and VII of the periodic table.
At least one metal selected from Group B and Group V is also present in the form of an oxide or a oxide. Prior to contacting the hydrocarbon-containing feed stream with the catalyst composition, at least one decomposable molybdenum compound in a zero valence state is incorporated into the hydrocarbon-containing feed stream. A hydrocarbon-containing feed stream, which also includes molybdenum, is contacted with a catalyst composition in the presence of hydrogen under inning conditions. The concentrations of sulfur, nitrogen and Ramsbottom residual carbon are significantly reduced, as well as the presence of hydrocarbon components.By thus removing these components from the hydrocarbon-containing feed stream, catalytic cracking Refining operations on hydrocarbon-containing feed streams in refining processes such as devalorization, hydrogenation, and even hydrodevaluation are facilitated.The use of molybdenum increases the longevity of the catalyst.
Moreover, its initial activity is increased.

Addition of the molybdenum decomposable compound can be carried out when the catalyst composition is fresh or at any suitable time thereafter. The term "fresh catalyst" here means:
It refers to a fresh catalyst or a catalyst that has just been reactivated using known methods. If all conditions are constant, the activity of the first fresh catalyst generally declines as a function of time. By introducing estrous molybdenum compounds,
From the point of introduction, the rate of decay decreases and, in some cases, at least partially used or deactivated catalyst? The antiquity level improves dramatically from the point of introduction.

For economic reasons, some organizations prefer to carry out the hydrofining process without adding decomposable molybdenum compounds until the activity of the catalyst has declined below an unacceptable level. In some cases, catalyst activity is maintained by increasing the process temperature. The addition of decomposable molybdenum compounds occurs only after the activity of the catalyst has fallen to an unacceptable level and further increases in temperature would have deleterious consequences. As explained in detail in BuVll, the addition of the decomposable molybdenum compound at the above-mentioned point dramatically increases the activity of the catalyst.

Other objects and advantages of the present invention will become apparent from a reading of the claims and detailed description set forth above as well as the detailed description of the invention set forth below.

Removes metals, sulfur, nitrogen and rum spot residual carbon,
The catalyst composition used in the hydrofining method for reducing the concentration of 1.1 Tsukuda component includes a support and a co-catalyst. The support consists of alumina, silica or silica-alumina. What is considered a suitable support is Al2O2
,5in2,u2o3-8i02,AJ', 203-
T102, Al2O2-P2O3, Aj! 203-sn
o2 and /'J, 203-ZH□. Among these supports, Af of 0.5 is particularly preferred.

The co-catalyst includes at least one metal selected from the group consisting of metals from Group VIB, Group VnB, and Group XX of the periodic table. Cocatalysts are generally included in the catalyst composition in the form of oxides or compounds. Particularly suitable promoters include iron, cobalt, nickel, tungsten, molybdenum, chromium,
These are manganese, vanadium and platinum. Of these promoters, cobalt, nickel, molybdenum and tungsten are most preferred. A particularly preferred catalyst composition is Co
.

and MoO3 as a cocatalyst, or C! oo,
M, 03 containing IJiO and MoO3 as promoters.

Catalysts of this type are generally commercially available. The concentration of cobalt oxide in the yuzu catalyst is typically from about 0.5 to about 10% by weight, based on the weight of the total catalyst composition. The concentration of molybdenum oxide is generally from about 2 to about 25 weight percent, based on the weight of the total catalyst composition. The concentration of nickel oxide in the citrus catalyst is generally within the range of about 0.3 to about 10 percent, making up the total catalyst composition. The relevant performance of commercially available four-cypress catalysts, which have been found to be suitable, is shown in Table 1.

The catalyst composition may have any suitable surface area and pore volume. Generally, the surface area is about 2 to about 4
001 is preferably within the range of about 100 to about 300 m"/g, and the pore volume of the lees is 0.1 to 4.0, preferably about 1.0 m"/g.
50C/? It is.

Before using the catalyst for the first time, it is desirable to carry out a preliminary 4+tf conversion of the catalyst. Many presulfidation methods are known, and any conventional presulfidation method can be used. A preferred presulfurization method is the two-step method described below.

The catalyst is first treated with a mixture of hydrogen sulfide in hydrogen at a temperature of about 175° to about 225°C, preferably about 205°C. During the initial presulfidation step, the temperature within the catalyst composition increases. The initial preheating step is continued until this temperature increase within the catalyst substantially ceases or until hydrogen sulfide is detected in the effluent from the reactor. The mixture of hydrogen sulfide and hydrogen should contain about 5 to about 20% hydrogen sulfide, even about 10%.

The second step of the preferred preboiling process is from about 350° to about 40°
It consists of repeating the first step described above at a temperature of 0°C, preferably about 370.0°C, for about 2 to 6 hours.

It is also possible to presulfidize the catalyst using other mixtures containing valuable hydrogen. Furthermore, it is not necessary to use valued hydrogen. In commercial operations, sulfur-containing light oil naphtha is commonly used to presulfidize the catalyst.

As previously mentioned, the invention may be carried out when the catalyst is fresh, or the addition of molybdenum decomposable compounds may begin once the catalyst is partially deactivated. Addition of the decomposable molybdenum compound can be delayed until the catalyst is considered used.

Generally, "used catalyst" means a catalyst that has lost sufficient activity under effective purification conditions to produce a product that meets specifications, such as maximum metal content tolerances. . Taking metal removal as an example, a catalyst with less than 50% metal removal in the feed is generally considered to be obsolete.

In some cases, the used catalyst is defined by the metal loading (Kickel+vanadium). The allowable metal loading varies depending on the catalyst's gr1, but it is generally considered that a catalyst 'tt whose weight has increased by about 12% due to metal + vanadium) has been used.

Any suitable hydrocarbon-containing feed stream can be used to carry out hydrofining using the catalyst composition according to the invention. Examples of suitable hydrocarbon-containing feed streams include petroleum products, coal pyrolysis products, coal and lignite extracts and/or liquefaction products, products from tar sands, gas oils such as mineral oils, about 343°C. Prefixed crude oil, which has a boiling point higher than that of crude oil, and residual oil are referred to as crude oil. however,
The present invention is particularly suited to negative feed streams that are generally considered too coarse to be distilled, such as icy prefixed crude oils and residual oils. These feedstocks generally contain highest concentrations of metals, sulfur, nitrogen and Ramsbottom residual carbon.

Although it is contemplated that by use of the above-described catalyst compositions according to the present invention, significant reductions in all metals present in hydrocarbon-containing feed streams may be achieved, the present invention removes vanadium, nickel, and iron. Especially suitable for.

The catalyst composition according to the invention can be used to remove (i)
Sulfur is commonly contained in organic yellow compounds. Examples of monosulfur compounds of this type include sulfides, disulfides, mercaptans, thiophenes, benzylthiophenes, dibenzylthiophenes, and the like.

Also generally contained in organic distillate compounds are carbonaceous residues that can be removed using the catalyst compositions according to the invention.

Examples of organic compounds in this building include amines, diamines,
Includes pyridine, quinoline, porphyrin, benzoquinoline, etc.

Although the catalyst composition described above is effective in removing metal, sulfur, nitrogenous, and Ramsbottom residual carbons, zero atoms of molybdenum are removed prior to contacting the catalyst composition with a hydrocarbon-containing feed stream. By introducing a suitable decomposable molybdenum compound in a sterile state into the scale-containing feed stream, the lifetime and efficiency of the catalyst composition is significantly improved by the present invention. As already mentioned, the addition of decomposable molybdenum compounds can begin when the catalyst is ripe, partially deactivated, or in used JPA, but in either case there are significant consequences. bring about. Examples of suitable molybdenum compounds include Mo(Co)6 (molybdenum hexacarbonyl), 07HBMO(Co)4 (
2+ 2 + 1-bicyclohebuta-2゜5-dienemolybdenumtetracarbonyl), [(C,H5)MO(C
o) 3) 2(cyclopentadienyl molysode 7 to 1 ``bot 3)' reimer, [(OHs)3C!aH3]M
o (glossy) 3 (mesitylene molybdenum tricarbonyl),
[OH305H4MO(Co)3]2 (methylcyclopentadienyl molybdenum tricarponyl dimer),
07H8MO(C!O)3 (cycloheptatriene molybdenum tricarbonyl) is opened. Molybdenum hexacarbonyl is a particularly preferred addition ★IJ.

Based on the test results described later, it is considered that molybdenum compounds in which molybdenum has a positive valence, especially tetravalence or higher, are ineffective in improving catalyst performance. Zero-valent molybdenum compounds, especially Mo(co)
6 is effective in improving catalyst performance.

Any suitable concentration of molybdenum additive can be added to the hydrocarbon-containing feed stream. Generally, the metal concentration is about 1 to about 60 ppm, more preferably about 2 ppm.
Sufficient amount of additive is added to the hydrocarbon-containing feed stream to provide a concentration within the range of about 30 ppm.

High concentrations above about 100 ppm, especially above about 360 ppm, should be avoided to prevent blockage of the reactor. One particular advantage of the present invention is that significant improvements are achieved at very low concentrations of molybdenum. This significantly improves the economics of the process.

It has been found that the efficiency of the process can be maintained by simply adding the additive periodically after the molybdenum additive has been added to the hydrocarbon-containing feed stream over a period of time.

The molybdenum compound and the hydrocarbon-containing feed stream can be combined by any suitable method. The molybdenum compound can be mixed with the hydrocarbon-containing feed stream as a solid or liquid, or it can be dissolved in a suitable solvent, preferably an oil, and then introduced into the hydrocarbon-containing feed stream. The mixing time may be any suitable time, but if the molybdenum compound is added to the hydrocarbon-containing feed stream
It seems that injection alone is sufficient. Specific mixing equipment and mixing periods are not specified.

It is believed that the pressure and temperature at which the molybdenum compound is introduced into the hydrocarbon-containing feed stream are not critical.

However, temperatures below 450°C are recommended.

Any apparatus in which contact of the catalyst composition with the hydrocarbon-containing feed vt and hydrogen under suitable hydrofining conditions can be used to carry out the hydrofining process of the present invention.

The hydrofining method is not limited to the use of specific equipment. Hydrofining processes can be carried out using fixed catalyst beds, fluidized catalyst beds or moving catalyst beds. Fixed catalyst beds are currently preferred.

Any suitable reaction time between the catalyst composition and the hydrocarbon-containing feed stream can be employed.

Generally, the reaction time is within the range of about 0.1 to about 10 hours. Preferably, the reaction time is within the range of about 0.6 to about 5 hours. Therefore, the hydrocarbon-containing feedstock flow meter should be proportioned such that the time it takes the mixture to pass through the reactor (residence time) is preferably about 0.3 to about 5 hours. . This generally means a liquid hourly space velocity (LH8V) in the range of about 0.10 to about 10 CC of oil per CC of catalyst per hour, preferably about 0.2 to about 3-Occ/cc/hr. It will be decorated.

The hydrofining method can be carried out at any suitable temperature. The temperature is generally about 150° to about 550°
°G, preferably within the range of about 650° to about 450°C. Elevated temperatures should not result in better metal removal or have adverse effects on hydrocarbon-containing feed streams such as coking, and economic considerations should be considered. be. Lower temperatures can generally be used for @sparrow feeds.

Any suitable hydrogen pressure can be used in the present hydrofining method. The reaction pressure is generally about 1 atm ~
In the range of approximately 10,000 psig. A preferred pressure range is about 500 to about 6+000 psig. If the pressure is increased, the coke production plate will be reduced, but high pressure operation is disadvantageous from an economical point of view.

Any suitable amount of hydrogen can be used in this hydrofining process. The availability of hydrogen in contact with the hydrocarbon-containing feed stream is generally from about 100 to about 20,000 standard cubic feet per barrel of hydrocarbon-containing feed stream, more preferably from about 1.0 to about 30 standard cubic feet per barrel of hydrocarbon-containing feed stream. Approximately 6.00
It is within a ridge of 0 cubic feet.

Generally, the 11 insect repellent composition is utilized until the addition of degradable molybdenum compounds no longer provides satisfactory metal removal. Although it is possible to remove metals from catalyst compositions using various leaching methods, these methods are expensive, and once the catalyst's ability to remove metals is compromised, the used catalyst can be easily removed. The catalyst should be replaced with fresh catalyst.

The time period during which the catalyst composition can retain its metal removal activity is:
It depends on the concentration of metals contained in the hydrocarbon-containing feed stream to be treated. 10 to 20 based on one batch of catalyst composition
It is contemplated that the catalyst composition can be used until 0% by weight of N1, ■ and Fe based metals accumulate on the catalyst composition from the oil.

Examples are provided below to further illustrate the invention.

Example 1 In this example, an automatically piloted experimental apparatus for researching the deginning and desulfurization of Tobitsukuda oil according to the present invention will be described. Oil enriched with decomposable molybdenum compounds or unenriched was pumped through a lower inlet tube into a 28.5 inch long, 0.75 inch diameter dropwise reactor. The oil pump used was a Whitey
) Model LP1 [1] (an old II tit pump with a diaphragm-sealed head; sold by Whitey Corp., Hylan V. Heights, Ohio). The tip of the oil inlet tube was in the catalyst bed (located approximately 6.5 inches below the top of the reactor). The catalyst bed was made of low surface area alpha-alumina (Alundum; surface area less than 1 m2/g; manufactured by Norton Chemical Process Products, Akron, Ohio).
Sold from ProcessProducts) 150
Upper layer consisting of CC, hydrofining catalyst 53c
It consisted of an intermediate layer made of c.c. and a lower layer made of α-alumina 5Qcc.

Water-based gas was introduced into the reactor through a tube that concentrically surrounded the oil introduction tube but whose tip stopped at the top of the reactor. Thermcraft (Winston, North Carolina - %A) Model 211
The reactor was heated in a 6-zone furnace. The temperature of the reactor was regulated at three different locations within the catalyst bed by six separate thermocouples embedded in axial thermocouple holes (0.25 inch outside diameter). The liquid oil product was collected and analyzed essentially daily. The water system was evacuated. Vanadium and nickel deposits were measured by plasma generation analysis.

The sulfur content was determined by X-ray fluorometry and the AS
Ramsbottom residual carbon measurements were carried out by TMD 524.

Monagas pipeline oil or Arabic heavy oil was used as raw material as undiluted heavy oil. In all demetalization experiments, the reactor temperature was approximately 407°0
(765'F) and the liquid hourly space velocity (LH3V) of the oil feed is approximately 1. OCC/Catalyst CC/hr, the total pressure was about 2250 psig, and the hydrogen feed rate was about 4800 S(!F/1) bl (standard cubic feet of water system per barrel of oil).

To mix a degradable molybdenum compound, typically solid MO(Co) or liquid molybdenum octoate, with the feed, place the desired amount of the compound in a 55 gallon steel drum and place the desired amount of the compound at about 16"F. A drum is filled with feedstock oil having a temperature of supply to

Example ■ In this example, the degradable molybdenum compound MO(Co) 6 [Aldrich Ch.
We will discuss the effects of ``Sold from ``Emical Co.''''.

The hydrofining catalyst used was a fresh, commercial cocatalyst desulfurization catalyst (Catalyst D in Table ■) from Vershaw Chemical Co., Beachwood, Ohio.
Met. This catalyst is 178m2/,! Surface area of i' (11411 constant by BET method using N2 gas), 14
0A Taira J! ;J pore diameter and 0.682 CC/f
1 total pore volume [both manufactured by American Instrument Co., Silver Spring, Maryland]
Catalog number 5 of N Engineering Nettrument Co.
-7125-13, the Af203 support was preferred. This catalyst contains 0.92 wt% Co (as cobalt oxide), 0.92 wt% N1 (as nickel oxide) and 7.3 wt% MO (as molybdenum oxide).
It contained.

Catalyst preparation (pitting) was carried out as follows: In a tubular reactor equipped with a heating device, a bottom layer of 8-inch high alundum, a middle layer of catalyst silica 7-8 inches high, and a 11-inch high After purging the reactor with the chlorine, the catalyst was heated to about 400'F for 1 hour in a stream of hydrogen.While maintaining the reactor temperature at about 400'F, catalytic hydrogen (0.46 scf) and hydrogen sulfide (
0-049 scf min) for approximately 2 hours. The catalyst was then heated in a mixture of hydrogen and sulfurized water system to a temperature of about 700F for about 1 hour. The reactor temperature was then increased to 700F.
for 2 hours, during which time the catalyst was constantly exposed to a mixture of hydrogen and hydrogen sulfide. The catalyst was then cooled to ambient temperature conditions in a mixture of hydrogen and hydrogen sulfide and finally purged with nitrogen.

The heavy oil feed contained approximately 87 ppm Ni, 6 ppm Ni
■ of m, 42 ppm Fe, 11.41-jJi*
,,% Ramsbottom residual carbon and 2.72 ilt%
It was a Mona gas pipeline oil containing S. Purohis conditions (as described in Example 1. In Experiment 1, 17 ppm of Mo [as Mo(co)6]
A raw material oil to which was added was used. 58 cities of Mo(Co)6
The content was gradually reduced over the course of the day to a final content of 4 ppm.

The molybdenum content in the produced oil varies irregularly1ji) L
However, in most measurements the molybdenum content in the product oil was less than 1 ppm. The data are shown in Cloth H. In Control Experiment 2, the same feedstock oil and catalyst were used, but no MO(00)s was added to the oil. The soot fruits are shown in Table 1■.

■) Experiment according to the present invention; LH8V of oil feed is 0.96
~1.08 CC,/catalyst cc/hr; temperature is approximately 765'
F (407°C); pressure was approximately 2250 psig; hydrogen feed rate was approximately 4800 BCf/barrel oil; catalyst was presulfided catalyst D0 2) The product oil also contained some MO; The No content of 19 samples was < 1.0 ppm; the No content of 6 samples was 1-9 ppm; the No content of 3 samples was > 20 ppm (these 6
analysis of individual samples is considered to be incorrect).

The metals (N1
+■) removal, sulfur removal and Ramsbottom residual coal purple removal data are shown graphically in Figures 1.2 and 6. From these drawings, Mo (co) ++
MO(
It is clear that when CCI) 6 is present (Experiment 1), the activity (for metal, sulfur and Ramsbottom residual carbon removal) of the cocatalyst-containing catalyst is surprisingly maintained much longer. I understand.

Furthermore, the initial removal effect on these impurities was also slightly better in Experiment 1.

Although we did not measure the removal of nitrogen, it is well known that catalysts are effective for denitrification, and in view of the improvement effect on desulfurization, the addition of Mo(Co)6 also has a denitrification effect. I'm sure it's true.

Another critical parameter (Table II and IT [K not shown) is the amount of undesirable heavy components (fractions with a boiling range above 1000°F).

Figure 4 shows that the amount of undesirable heavy components in the product was significantly lower in experiment 1 (with MO(CO)6 in the feed) compared to control experiment 2 (possibly due to hydrogenation). (due to advanced decomposition).

Example ■ The test described in this example uses Arabic heavy crude oil (approx.
ppm N1,100 ppm V, 6 ppm Fe
, 2*0 as MO(Co)6 for 3.98 wt% S and 11.5 wt% Ramsbottom residual carbon content.
00 ppm of MO was added and the hydrogenation was carried out essentially following the procedure described in Example 2. LH3V of oil is 1.04
〜1゜09CC/cc of catalyst is 7 o'clock and the pressure is 2.0
0 [] psig, hydrogen supply rate i, 5 sc
f 7 hours, the temperature was 765°F' (4079C), and the catalyst was fresh presulfided catalyst.

This experiment (Experiment 6) had to be stopped after about 20 hours. This is because the reactor bed became clogged, which reduced the feed flow rate and caused the pressure to rise abnormally. After cooling, the reactor was opened and compressed air was blown out to remove the plugs formed in the catalyst bed (apparently consisting of metal and coke).

In another similar experiment (Experiment 4), 990 p
360 ppm Mo was added to the oil as pm Mo(Co)6. In this experiment, the reactor bed plugged after 48 hours. These experiments were carried out at a high level of M.

(more than 360 ppm) should not be used.

Relatively low concentrations of molybdenum, above about 100 ppm, are also believed to exhibit deleterious plugging effects.

Example IV - This example describes the demetalization effect of MO(Co)60 at various temperatures on the Arabian heavy crude oil described in Example 2. The LH8V of the oil was varied at each temperature to achieve 92-93% sulfur removal. The hydrogen supply rate is 4,800 scf/1 barrel of oil,
The pressure was 2,250 psig and the catalyst was fresh presulfided catalyst.

Experiment 5 according to the invention [1 as MO(CO)6 in the feed
5 ppm MO addition] and control experiment 6 [M
o (co) 6 was not added] are shown in Table IV.

Table IV 737? 535 93 93 76 -- -740
325 - - - 939384750 499
93 98 82 - - -751 478 - -
-939578753 550 - - - 9295
79765 810 92 99.7 90 - -
- The data in Table 1 shows that at temperatures of about 767° to 740'F, there is no difference in metal removal efficiency at the same sulfur removal level, but in the temperature range of 750° to 765'F, the present invention This shows that the removal rate of Ni and V in Experiment 5 was significantly superior.

Example V Arabian heavy crude oil (approximately 30 ppm nickel and 1
(containing 0.02 ppm vanadium) was hydrogenated using the procedure described in Example ①. LH8V of oil is 1. [ ],
The pressure was 2,250 psig and the hydrogen feed rate was 1
There were 4,800 standard cubic feet to the barrel and the temperature was 765°p (407°C).

In Run 7, no hydrocarbon feed molybdenum was added. In experiment 8, molybdenum octoate (
IV) was added for 19 days. During the next 8 days, molybdenum (IV) octoate, which had been heat treated to 635° F. in Monagas pipeline oil for 4 hours under constant hydrogen pressure of 980 psig in a stirred autoclave, was added. In the final stage of the experiment, molybdenum hexacarbonyl was added. In Run 9, molybdenum hexacarbonyl was added to the hydrocarbon feed for 46 days, after which time the molybdenum introduction was stopped. The results of Experiment 7 are shown in Table ■, the results of Experiment 8 are shown in Table ■, and the results of Experiment 9 are shown in Table ■.

Table V (Experiment 7) 1 0 1325 38 71 2 D 1430 44 67 3 0 1430 44 67 6 0 1530 45 66 7 0 1530 45 66 9 0 1428 42 68 10 0 1427 41 69 11 0 1427 41 69 13 0 1428 42 68 14 0 132 (S 39 70 15 0 1428 42 68 16 0 1528 4.5 67 19 0 1328 41 69 20 0 17 Ro3 50 62 21 0 1428 42 68 22 0 1429 43 67 23 0 1428 42 68 25 0 1 Ro 26 39 70 26 0 919 28 79 27 0 1427 41 69 29 0 1326 39 70 30 0 1528 4 Ro 67 31 0 1528 43 67 32 [] 1527 42 68 Table ■ (Experiment 8) 3 23 16 29 45 66 4 23 16 28 44 67 7 23 13 25 6B 71 8 23 14 27 41 69 10 23 15 29 .44 6712 23 1
22 23 16 28 44 67 24 23 17 30 47 64 26 23 16 26 42 68 28 23 1628 44 67 29M0 source switched to MO(Co)6 30 16 14 23 37 72 31 16 13 18 31 77 32 16 12 17 29 78 35 16 13 18 31 77 37 1 6 12. 17 29 7839 16 1
2 17 29 78 42 16 12 17 29 78 43 16' 13 18 31' 77 Looking at Tables V and ■, it can be seen that the % removal of nickel + vanadium remains fairly constant.

In Experiment 8, no improvement was observed when untreated or hydrotreated molyzodene octoate was added. However, when we switched from molybdenum to molybdenum hexacarbonyl at 29 days, a significant improvement was observed (Table)
'', the characteristics of the invention were demonstrated in the first 46 days, and 9. However, when the total molybdenum addition was stopped at day 44, the metal removal effect did not immediately decrease, but rather remained essentially constant over the remaining 21 days of the experiment. From this it is clear that after adding molybdenum to the feed over a period of time, periodic additions of molybdenum compounds can be used.

It is unclear which stands will continue to have a beneficial effect, or which stands will have to have K4O added before periodic additions are possible. However, after 43 days, M
o The ability to stop the deployment and M for at least 21 days.
It is clear that it is not necessary to redirect O.

Example ■ In this example, new yL "
A similar catalyst, carried out essentially according to the procedure of Example I, is also shown to have approximately the same degree of initial demetalization activity in a relatively short experiment. The feed was Monagas crude oil (no molybdenum compounds dissolved). Relevant process parameters and analysis results are shown in Table II.

-ζ79 Table vllll 101゜51 425 Unsulfurized catalyst D 4゜611 1
．． 51 425 Presulfurization catalyst D 2.010 1.0
0 425 Unsulfurized broad medium D 3.011 1.00 4
25 Pre-sulfurized catalyst D2.610 1.51400 Unsulfurized catalyst D 2.0111°50 400 Pre-sulfurized catalyst D1°910 1.01 400 Unsulfurized catalyst D 3
．． 011 1.02 400 Presulfurization catalyst D2.51
0 0.48 4[]0 Unvalued catalyst D 6.011
0.46 400 Presulfidation f'l [D 6.01) Change the conditions at the end of each specified experimental time and then
275 3ro 2 29 99 125 6265 2
20 285 34 91 125 5657 275
332 25 81 106 6865 220 2
85 17 40 57 8057 275 332
44 164 208 3765 220 285 4
5 175 220 2357 275 332 39
134 173 4865 220 285 42
132 174 3957 275 332 27 8
8 115 6565 220 285 19 64
83 '71 The wheat experiment was continued as it was.

As shown in Table VII■, pre-sulfurized catalysts are not necessarily superior in performance to unsulfurized catalysts, but given that pre-sulfided treatment improves performance during long-term operations, Pre-sulfurization treatment should be performed.

Example ■1 This example essentially follows Example ■, except that the amount of catalyst is 10 CC, and by adding MO(Co)6 to the feed, substantially used sulfurized catalyst is removed. will be updated. The feed is approximately 28-65 p.
N1 of pm, V of about 101-113 ppm, about 6.0-
It was a supercritical monogas oil extract containing 6.2% by weight S and about 5.0% by weight Ramsbottom residual carbon. The LH8V of the feed is about 5° Q cc/cc 7 hours of catalyst, the pressure is about 2,250 psig, the hydrogen feed rate is about 1 p00 Dscf of N2 per barrel of oil,
And the reactor temperature was about 7751 (416°C). No JJO(Co)6 was added to the feed during the first 600 hour run period, after which Mo(Co)6 was added.

K: i8i results are shown in Table ■.

The data listed in the table shows the indigo metal removal activity of the catalyst that is essentially used, that is, deactivated, after MO addition for about 120 hours (5 days) [(Nj + V) removal rate after 586 hours:
21%] was dramatically increased [(old+■) removal rate of about 87%]. ) At the time of starting the addition of 0, the metal (old+■) loading amount of the deactivated catalyst was approximately 54ffi.
% (i.e., the weight of fresh catalyst had increased by 64% due to metal build-up). At the end of the experimental sweep, the metal (old + ■) load was approximately 44
% by weight. No significant influence on the desulfurization effect was observed due to the addition of MO(Co)+1.

Appropriate changes and modifications to the invention are possible within the scope of the following claims.

[Brief explanation of drawings]

The drawings are graphs comparing experiments according to the present invention and control experiments. The results for the reduction of the amount of components are shown respectively. 10 20 30 40 50 60 较葲 Physique FICr, 3 10 20 30 40 50 60 ・Lid extraction θ叡 FIcr, 4

Claims (1)

Claims: (1) removing one or more impurities selected from metals, sulfur, nitrogen, and Ramsbottom residual carbon from a hydrocarbon-containing feed stream; In a hydrofining method for reducing precipitation of hydrocarbon components, under hydrofining conditions, an alumina, silica or silica-alumina support;
contacting hydrogen with said feed stream and a catalyst composition comprising a cocatalyst containing a metal of groups VIB, VIIB or Vm of the periodic table; Prior to contacting the hydrogen-containing feed stream with the catalyst composition, the lifetime of the catalyst composition under the hydrofining conditions is increased by incorporating a decomposable compound of molybdenum into the hydrocarbon-containing feed stream. wherein the molybdenum in the degradable compound is in a zero valence state and the concentration of molybdenum in the hydrocarbon-containing feed stream is from about 1 to about 60 ppm.
A sufficient amount of said decomposable compound of molybdenum is added to said hydrocarbon-containing feed stream to be within the range of . (2) The method of claim (1), wherein said catalyst composition comprises alumira, cobalt and molybdenum. (3) The method of claim (2), wherein the catalyst composition further comprises nickel. (4) Claims (1) to (3) wherein the molybdenum decomposable compound is molybdenum hexacarbonyl.
). (5) adding a degradable compound of said molybdenum to said hydrocarbon-containing feed stream in an amount sufficient to provide a concentration of molybdenum in said hydrocarbon-containing feed stream within the range of about 2 to about 30 ppm;
Claims (1) to (4) in addition to the containing feed stream
The method according to any one of the above. (6) Hydrofining conditions are approximately 0.1 to approximately 1
The reaction time between said catalyst composition and said hydrocarbon-containing feed stream is within the range of 150° to about 55°C.
Temperature within the range of 0°C, approximately 1 atm to approximately 10,000 pθ
1 g and a hydrogen feed rate within the range of about 100 to about 20,000 standard cubic feet per barrel of said hydrocarbon-containing feed stream.
1) The method according to any one of (5). (7) The above appropriate hydrofining conditions are approximately 0
．． Reaction time between the catalyst composition and the hydrocarbon-containing feed stream in the range of 4 to about 4 hours, 650° to about 45
Temperature within the range of 0℃, about 500 to about: 5+000 p8
: from about 1.000 to about 6.0 Lg per barrel of said hydrocarbon-containing feed stream. Claim (6) consisting of a hydrogen supply rate of D OD standard cubic feet.
). (8) A process according to any one of claims (1) to (7), wherein the addition of said molybdenum decomposable compound to said hydrocarbon-containing feed stream is periodically interrupted. (9) Any one of claims (1) to (8), wherein the hydrofining process of the previous MU2 is a demetalization process and said hydrocarbon-containing feed stream contains metals.
The method described in section. (101 the metals are nickel and vanadium,
The method according to claim (9). (11) The hydrofining process is a desulfurization process and the hydrocarbon-containing feed stream includes an organic sulfur compound. t12+ The method according to claim OJ), wherein the organic sulfur compound consists of sulfide, disulfide, mercaptan, thiophene, benzylthiophene and/or dibenzylthiophene. 9. A process according to any one of claims 1 to 8, wherein the inning process is a denitrification process and the hydrocarbon-bearing feed stream contains nitrogenous compounds. (141) The method according to claim (13), wherein the organic nitrogen compound is an amine, a diamine, a pyridine, a quinoline, a porphyrin, and/or a benzoquinoline. The method of any one of claims 1 to 8, wherein the method is a method for removing carbon and wherein the hydrocarbon-containing feed stream comprises rum spot residual carbon. Claims (1) to (8), wherein said hydrofining method is a method for reducing the amount of M-loaded hydrocarbon components contained in said hydrocarbon-containing feed stream.
The method according to any one of the above.