JPS58215483A - Hydrocracking of heavy oil - Google Patents

Abstract

PURPOSE:To perform hydrocracking of heavy oil with a consistently high yield of low-sulfur light oil and a reduced amount of low value heavy components, by gasifying the residue of hydrocracking and recovering entrained solid substances in fine powder for use as cracking catalyst. CONSTITUTION:In the hydrocracking of petroleum heavy oil which employs hydrogen-containing gas and catalyst, the residue of hydrocracking is gasified with molten metal powder and solid substances formed from the metal bath together with the gas are separated from the gas for recovery. The solid substance in fine powder is used as it or after sulfation with elementary sulfur or sulfur-containing compd., as catalyst for the hydrocracking. The recovered solid substance which is a fine powder of scores of mu or smaller in size has a large surface area and a high activity. The activity is increased further when the molten metal bath consists of Fe, Mo, Cr, Ni, Co, Cu or V. The substance is recovered for use as metal for the bath.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for hydrocracking petroleum heavy oil using a hydrogen-containing gas and a catalyst, which can stably obtain low sulfur-containing needle light oil in high yield, and at the same time produce it. The purpose is to reduce pitch-like heavy components with low utility value as much as possible.

Hydrocracking of petroleum-based heavy oil aims to obtain light oil with low sulfur content by adding hydrogen to petroleum-based heavy oil. And desulfurization technology has become more popular in recent years due to the global trend towards heavier crude oil. The hydrocracking methods for petroleum heavy oil that have been developed so far include the cranking method, visgraking method, and coking method to lighten the vacuum residual oil, which is petroleum heavy oil. Yes, and as a desulfurization technology, Ni
Direct desulfurization technology using metals such as , Co, and M□ in a fixed bed or the so-called H-oin process using an ebullated bed have been proposed.

To explain specifically, for example, the visgraking method is 43
It performs thermal decomposition at a temperature of 0 to 480°C, and when used for Kafji vacuum residual oil, the gas content is 2%.

Naphtha (05~200°C) 9% 9 cracked light oil (2oo~
480"C) 88%2 cracked residual oil (480"C or more) 56
% yield is obtained. Also, at the same temperature of 480″C, in the Eureka process using superheated steam, about 60% of the vacuum residual oil is converted to light oil fraction and about 35% to pitch.
In both cases, the yield of the residual oil (pitch) fraction is high, and these residual oils contain a considerable amount of sulfur that is difficult to remove.
[11) ~ Under hydrogen pressure of 150 atm, 850 ~ 4 (1 (
A desulfurization rate of about 76 to 80 inches has been obtained with a residence time of 1 to 8 hours at a reaction temperature of about 1" (If), but heavy metals such as Ni and V It is applied to a limited number of types of heavy oil that contain few heavy metals, and will not be selected for the wide range of heavy oil treatment that is expected in the future. Using v1i Teng Song Touch llv: which was developed to deal with this problem.
In addition to the difficulty of operating the i-otn process, the catalyst is severely degraded due to powdering, etc., and the current state is that it has not yet reached the original target of 1.1.

This scabbard was done in view of the current situation.6
9. We propose a method for hydrocracking petroleum-based heavy oil that provides an inexpensive and highly active catalyst and is also easily recoverable and reusable.

That is, the present invention is directed to a method for hydrocracking petroleum heavy oil using a hydrogen-containing gas and a catalyst, in which the hydrocracking residue is gasified using a melt bath, and at that time, the residue is entrained in a metal bath. It is characterized by separating and recovering the fine powder solid produced from the gas and using it as a catalyst for hydrocracking.
Further, the recovered fine powder solid is sulfurized using elemental sulfur or a sulfur-containing compound and used as a catalyst for hydrocracking.

The hydrocracking residue is gasified by the metal bath gasification method, and the fine powder solids produced from the metal bath along with the gas can be self-sufficient within the hydrogenation system, so there is no cost, and the solids are blown away with the generated gas. Therefore, since it is a fine powder of several tens of microns or less, it does not need to be pulverized and has a high t1 specific surface area and high activity. For example, when the reaction residue is blown into a broad molten iron bath with a temperature of 1500 to 1600°C together with oxygen and water vapor, metal vapor is generated at the fire point of 2000°C or more formed by the oxygen jet, and some The metal vapor reacts with the sulfur content in the residue to produce iron sulfide, resulting in a highly active catalyst with a high specific surface area. In this case, the molten metal bath includes Fe, Mo, Cr, Ni, Co, Cu,
When using a metal bath consisting of at least one or two or more of V, Mu, Cr, Go, Cu,
When using a molten iron bath to which at least one of V and 11 or more of &412 is added, the hydrogenation activity is higher than that of iron, and the catalytic activity is further improved. An even greater advantage is that the finely divided solids can act as catalysts and 1. After working in the hydrogenation process, the reactant residue goes into the metal bath gasification process and is reused as a &,w4 source in the metal bath gasifier.

Note that this method can be applied to Mo, W, Ni, Cu, Cr.
This is particularly advantageous when using catalysts containing expensive metals such as.

That is, M is expensive but has high activity. .

After catalysts containing W, Ni, Cr, etc. act as catalysts in the liquefaction system, they enter the metal bath gasifier together with their residue, are decomposed, and are recovered and used as metals in the metal bath.

A part of it vaporizes at the flash point or comes flying as droplets, so if it is collected, it can be reused as a highly active catalyst.

As a result, the catalyst containing valuable metals can be utilized in its infancy.

To summarize the advantages of using fine powder solids produced from a metal bath gasifier as a catalyst for hydrocracking heavy oil,
It can be self-sufficient within the system, resulting in low costs.■ It is a fine powder, so there is no grinding cost.■ It is reduced at high temperatures, contains sulfur, and has a high specific surface area, so it is highly active as a catalyst for hydrocracking. Yes, ■After use, it is collected in a metal furnace and can be reused, so Moe W* N1
Catalysts containing highly active and expensive metals such as 1Cu can be used.

- Also, in order to further increase the catalytic activity, Fe, MO.

Since Ni, W, etc. all produce catalytic activity in the form of sulfides, it is desirable to increase the S content of fine powder solids. The method is to add elemental sulfur or a sulfur-containing compound together with the fine powder solids in the hydrogenation step, or to react the fine powder solids with elemental sulfur or a sulfur-containing compound, presulfurize the mixture, and then catalyze the reaction. It can be used as

Here, the sulfur-containing compound refers to hydrogen sulfide, carbonyl sulfide, carbon dioxide, mercaptan, etc., and it does not matter whether it is gaseous or liquid.

If it is in a gaseous state, it may be diluted with water, carbon oxide, nitrogen, or the like. Therefore, as a source of sulfur-containing compounds, it is naturally possible to use hydrogen gas containing hydrogen sulfide, which is produced from the process 1: for irrigation after liquefaction.

Pre-sulfurization method and 1. For example, there is a method in which a finely powdered solid and elemental sulfur are mixed at a ratio of 1:1 and maintained at a temperature of 800"C or less in an atmosphere of water and air. Note that mS as a catalyst for finely powdered solids )Rlmk'' Although not particularly limited, heavy oil (1,8 to I (about 1 wt% may be sufficient) whether used alone or pre-sulfurized.
When finely divided solids are mixed with elemental sulfur or sulfur-containing compounds in the hydrocracking process, the ratio of sulfur to finely divided solids may be approximately 0.1 to 2. Also, when pre-sulfurized C fine powder solid is used, the density ratio of sulfur to fine powder solid may be about 0.1 to 2.

The drawings show a flow for implementing the invention.

Pre-treatment f1 "At step 1, mix coal-based heavy oil and fine powder 1i', which is a catalyst, to prepare a slurry. At this time, add elemental sulfur or sulfur-containing compounds to FA/J11. The reaction temperature for hydrogenolysis in the hydrogenation step may be 800 to 500°C, and the hydrogen reaction pressure may be approximately 50 to 200 kg/cII.The separation step is generally performed using a distillation column. However, separation from the catalyst may be performed using a solid-liquid separation device such as centrifugation, gravity sedimentation, or critical extraction.In a metal bath gasifier, the reaction residue is blown together with oxygen and water vapor. In order to collect fine powder solids from the gas generated at this time, dry dust collection methods such as bag filters and cyclones, and wet dust collection methods such as venturi scrubbers can be used. C
070%.

Although it contains about 26% H2 and a small amount of CO□, it can be sufficiently used as hydrogen gas for the hydrocracking of heavy oil if the hydrogen gas concentration is increased by the -carbon oxide conversion reaction. In addition, in order to produce hydrogen gas, not only the reaction residue but also raw material heavy oil, coal, etc. may be blown into the iron bath gasifier.

Next, embodiments of this invention will be described.

〔Example〕

Hydrogenation experiments were conducted using petroleum heavy oil having the properties shown in Table 1 as a raw material and using the equipment and operating conditions shown in F ii+,l.

Table 1 Elemental analysis of the crude oil Iiiijj (wt%)
Equipment used and conditions> (1) Heavy oil water hydrolysis 1 & reaction time: 11Tr I7! I button: 41st 1° () pressure Crab reaction water water pressure 190 kg 10j catalyst added 1.5 ts catalyst for 10j catalyst added oil: Reduction 11 - reaction residue remaining at the bottom of the distillation tower (9
Page) The residue was blown into two types of metal bath gasifiers, A and B shown in Table 2, and a fine powder solid was recovered from the generated gas using a bag filter.

The composition of this catalyst is shown in Table 7.

In addition, the fine powder generated from bath A For solids, pre-sulfurization is performed. It was.

(2) Vacuum distillation column (separation process) 10β scale, 588°C (1000'F) in terms of normal pressure
The reaction residue was gasified in a metal bath gasifier.

(3) In a 6-ton metal bath gasifier, the above reaction residue was blown in from the top of the bath along with oxygen and steam. The pressure of oxygen is 11 kf/ctj.

Ryu ii 7. I N rr// Hr, water vapor temperature: 800″C9 pressure: 12 kg/c++I, flow rate: 1.1
It was 5 kp/Hr. The composition of the metal bath is shown in Table 2. The temperature of the metal bath was 1550°C.

Table 2 Metal bath composition After hydrogenation, vacuum distillation, and gasification were repeated using the IZ method, and continuous operation was carried out, a steady state was reached.
The result was

1 Precise distillation rr J, S, If you take the mass balance of water percentage decomposition, Table 8 VC shows ↓? It became

Table 8: Balance of 2 items However, the remaining pitch does not contain any catalyst.

From Table 8, it can be seen that the residual pitch yield is significantly lower than that of the conventional Eureka process.

Also, among the oil yields, gas oil with a b-p of 200 to 480°C is particularly common. It can be seen that if the catalyst is sulfided, its effectiveness is greatly reduced. Naphtha yield includes Mo, Ni
It can be seen that in the case of bathing, it increases to nearly 20%.

Table 4 also summarizes the sulfur content of each oil.

thtr I Q101 L! lj l l n) Table 4 Generation 1'llll (I) Ql, yellow content m (w
t%) It is clear from Section 46 that more than 5.14% of the sulfur in the raw material is lost, which is very low in the produced oil, especially when using the catalyst produced from the Mu-Nl-containing bath. Remarkable. In addition, the removed sulfur migrates into the gas as (2S), so the desulfurization rate of the sulfur that migrated into the gas is very high at 60% and 885%, and the 1a liquid of the existing c. The desulfurization rate was again as high as or higher than desulfurization.
+) (All nickel was removed, and the removed vanadium and nickel were transferred to the slag in the molten metal bath, indicating that the method of the present invention is superior as a metal removal method.

2 The generated gas hydrocracker was operated continuously for 24 hours, and the decomposition residue (residual pitch) obtained by distillation under reduced pressure was gasified in a metal bath. The results are shown in Table 5.

Table 5 Generated Gas Company (page 14) 8 Gas Composition Him1 Generated Gas 0) The average composition is as shown in Table 6.

Table 6: Gas composition (val!%) From Table 6, it can be seen that if the concentration of hydrogen gas is increased by the -carbon oxide conversion reaction, it can be sufficiently used as water*gas for water decomposition. In addition, 1.9 per unit of heavy oil, 2.
It is theoretically possible to produce 5% blisters, and the above-mentioned B.
Considering the result of H, the supply of hydrogen gas is the working oil. In addition, when there is a shortage of hydrogen gas, the t211 profit I
&I Gasify quality oil, coal, etc. and tJ! All you have to do is build one
．． 4 ml of catalyst: The composition of the metal bath is approximately 5 ml.
0P/N door contained fine powder solids, and after 24 hours of hydrogenation experiment, it was 195y for A and 175y for B.
A finely powdered solid of y is obtained, which can be recycled as a catalyst for subsequent hydrocracking. The composition of the catalyst was as shown in Table 7.

Table 7 Catalyst Composition (H) As explained above, the present invention is an excellent method for obtaining light oil and naphtha with a low sulfur content at a high yield. When this invention was applied to the heavy residue after distilling tar obtained by carbonizing coal, similar results were obtained. Therefore, the present invention is applicable to all heavy oils, regardless of whether they are petroleum-based or coal-based.

(1st fi shellfish)

[Brief explanation of drawings]

The drawing shows the equipment flow for carrying out the method of this invention. Applicant: Sumitomo Gosei Koushiba Co., Ltd. (page 16) Continued from page 10 Inventor: Takuo Kano Sumitomo Metal Industries, Ltd., 1-3-2 Marunouchi, Chiyoda-ku, Tokyo0 Inventor: Tamio Shirafuji Higashi, Osaka City 5-15 Kitahama, Sumitomo Metal Industries, Ltd. Voluntary procedure amendment April 26, 1982! Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Display of the case 1982 Patent Application No. 99646 2 Name of the invention Hydrocracking method for heavy oil 3 Relationship with the person making the amendment case Applicant: Ukewazume #Higashi-ku, Osaka City 5-16 Kitahama (211) Sumitomo Metal Industries Co., Ltd. 4 Agent Ginza Building (561-53) 3-3-12 Ginza, Chuo-ku, Tokyo
86.0274) (7390) Patent attorney press 1) Yoshihisa 8. Contents of amendment As shown in the attached sheet, 10 the claims of the present application are amended as follows. [In the hydrocracking method of petroleum-based or coal-based heavy oil using a hydrogen-containing gas and a catalyst, the hydrocracking residue f is gasified using a molten metal bath, and at that time, it is generated from the metal bath along with tf gas. A method for producing heavy oil, which is characterized in that a fine powder solid is separated and recovered from a gas, and the fine powder solid is sulfurized as it is using I, elemental sulfur, a sulfur-containing compound, etc., and used as a catalyst for hydrocracking. Hydrocracking method. ” 2. Change “petroleum-based heavy oil” to “petroleum-based heavy oil” in lines 14 and 15 of η 1 of the same specification W.
Corrected to ``oil-based oil, 6 IJ, and coal-based municipal oil.'' 8, same specification 1] fvAI page 19 line “Petroleum heavy oil...
..."oil amount or coal yarn salt quality 411" and same 19
Correct the line “petroleum-based heavy oil” to “stone 7111 thread or coal-based heavy oil”. 5. On page 9, line 1 of the same specification, "coal-based heavy oil" is amended to "coal-based or petroleum-based heavy oil." 6. Change "[Example]" to "[Example 1]" on page 9, line 1 of the same specification.
]” and corrected it. 7. On page 14 of the same specification, line 8, insert the following sentence next to "It was gasified." [However, when the fine powder solid produced from the iron bath (A) is used as a catalyst, the residual pitch after hydrogenolysis is gasified in the iron bath, and the fine powder solid produced from the MO, N1 alloy bath (B) is The remaining pitch after hydrogenolysis when using the above as a catalyst was deoxidized in a Mo-containing and Ni-containing alloy bath, respectively. ”8,
In Table 5 on page 14 of the same specification, Mo and Ni alloy baths (B
) remaining pitch amount "1.52 kfJ rl, 48 kfJ, which is obtained by gasifying the remaining pitch of the same < (B), but month i
Correct r8.5Nm'J to [8°41Nml. 9. The following sentence (Example 2) is inserted next to Table 7 on page 16 of the same specification. [Example 2] Tar obtained by carbonizing coal was distilled to obtain heavy oil (road tar) shown in Table 8. However, solvent extraction was performed by centrifugation. 1-2.1% of fine powder solids generated from iron bath gasifier when gasifying coal-based heavy oil residues
After adding 1.2% of 111-sulfur, hydrogenolysis was carried out under the reaction conditions shown in [1-A]. The fine powder solid contains 85% iron and 20% carbon. -(-Table 9) After hydrogenolysis, the gas was rapidly cooled to room temperature, and the gas was sampled.
After gas analysis, the solid-liquid mixture was distilled to determine the mass balance. The results are shown in Table 10. Note that the hydrogen gas consumption was 2 wt% raw material heavy ura. From Table 1θ and Table 1O, the boiling point of coal-based heavy oil is 450°.
It can be seen that the pitch components of C or higher are significantly reduced by hydrogenation. 10, page 16, lines 14-20 of the same specification, ``As explained above......applicable.'' is amended as follows. "As explained above, this invention is an excellent H method that can obtain light oil with a low sulfur content of 1 and naphtha in high yield. Therefore, this invention can be applied to both oil-based and coal-based
Applicable to all heavy oils. ” 1. The drawings attached to the same specification have been amended as shown in the attached sheet (heavy petroleum oil →
petroleum-based or coal-based heavy oil). Attached documents 11 (1) Ura IE drawing 1 copy 61

Claims (1)

[Claims] In a method for hydrocracking petroleum heavy oil using a hydrogen-containing gas and a catalyst, the hydrocracking residue is gasified using a molten metal bath, and at that time, the residue is generated from the metal bath along with the gas. The fine powder solid is separated and recovered from the gas, and the fine powder solid is used as it is or as elemental sulfur. A method for hydrocracking heavy oil, characterized by sulfurizing it using a sulfur-containing compound or the like and using it as a catalyst for hydrocracking.