JPS598785A - Solvent extraction for coal with heavy oil - 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 method for converting carbonaceous materials such as coal into liquid products.2. Two more details.

A mixture of liquefied coal and liquefied coal is converted into a liquid product by solvent extraction of coal using a heptane-free fraction of a heavy hydrocarbon-based liquid and a hydrocarbon-based circulating stream. This relates to the method of collection.

Solid carbonaceous materials such as coal, lignate, and oil shells are useful resources as raw materials for the production of liquid carbonized water products commonly obtained from petroleum.The source of solid carbonaceous materials is petroleum. Since they are relatively more abundant than other sources, it is economically desirable to use these solids as an alternative or supplementary energy source to petroleum.

Several methods are known in the art for converting coal into useful liquid products. Recently, a pressure hydrogenation method and a solvent extraction method have been developed, and the present invention belongs to the latter. In solvent extraction methods known in the art, finely ground coal or other carbonaceous material is contacted with its liquid electrolyte, conveniently a dross, usually in the presence of hydrogen gas. Following this contact, the liquid solvent and a portion of the liquefied solids are separated from the remaining solid material by filtration, centrifugation, or other operations. In another conventional process, the solid material is typically separated from the solvent by fractional distillation (by fractional distillation). 5 The solvent extracted material gold is further converted into useful products.

Prior literature related to the present invention is US Pat. No. 3,705,092
No. 2, a method for extracting coal with a heavy hydrocarbon liquid while simultaneously improving the quality of the hydrocarbon liquid is taught. The present invention was completed in recognition of the fact that the conventional process can be improved by recycling at least a portion of the reaction zone effluent.
Ru.

A typical prior art of coal hydroconversion technology is found in US Pat. No. 4,077,867.

One of the problems with solvent extraction methods for liquefying solid carbonaceous materials is that the solvation that occurs is non-selective. Although this solvent extraction method is designed to extract the most valuable hydrogen-rich components from carbonaceous materials, the solvents that are effective in extracting these components will also dissolve undesirable components, including asphaltenes. It's lenient. Asphaltenes are non-distillable commercially available carbon compounds, approximately 7wt.
It contains less than % hydrogen. Asphaltene is insoluble in normal hepta. Asphaltenes are present not only in the products of solvent extraction of carbonaceous materials such as coal, but also in VC in crude oil and in atmospheric residue oils, viscosity oil visbreaker effluents, etc. It also exists within. These liquid hydrocarbon bulk asphaltene components are inherently of low value, and it is undesirable for them to be present in the entire treatment of more valuable substrate oils. Therefore, it is desirable to reduce asphalt/key content in hydrocarbon oils that are subject to various treatments, and '-! Converting the asphaltenes to distillable hydrocarbons allows at least a portion of the two reaction zone effluents to be recycled.

The purpose of the present invention is to convert solid hydrocarbon substances into valuable liquid products and at the same time to convert solid hydrocarbon oils into high quality hydrocarbon oils. The purpose is to devise effective ways to improve. More specifically, the purpose of the present invention is to solvent extract valuable liquids from solid carbonaceous materials, and at the same time extract a portion of pure hydrocarbon oil QP9.
``It is possible to convert an undesirable substance into a more desirable substance.
We aim to provide this effective method. The present invention is specifically directed to techniques for solvent extraction of valuable components in solid carbonaceous materials while simultaneously reducing asphaltenes in heavy hydrocarbon oils.

As already stated, one object of the present invention is achieved by using a 1MX asqualtene-containing hydrocarbon liquid as a solvent in a solvent extraction process of solid carbonaceous materials. Thus - by way of example, the present invention provides a method for producing hydrogen-rich hydrocarbon products from petroleum and coal containing asphalte, which method comprises IVB of the periodic table.
Asphaltene? The oil and coal contained at a temperature of about 128 ~
Approximately 510°C1 Pressure approximately 3450 to approximately 68950 kPa
liquefy at least a portion of the coal and reduce the asphaltene content of the petroleum by deashing at least the top km of the reaction zone effluent to be used in said reaction zone. The method consists of obtaining a liquid circulation stream containing an unsupported metal catalyst.

In a preferred embodiment of the invention, finely ground coal is introduced into a solvent extraction zone where the coal is extracted in the presence of hydrogen gas and a finely divided unsupported metal catalyst.

A portion of the coal contacts the crude oil and liquid circulation stream at a temperature and pressure that liquefies it.

In a preferred embodiment, the crude oil used as the solvent is one in which at least 8096 has a boiling point of about 343.3°C or higher and 50% has a boiling point of about 538"C or higher.

In a general embodiment of the invention, a mixture of a heavy hydrocarbon oil solvent, coal, a liquid recycle stream and a finely divided unsupported metal catalyst comprises:
In the presence of hydrogen gas, the solid desired components are exposed to sufficient temperature and pressure to liquefy. The solvent extraction and hydrocarbon conversion of the present invention can be carried out in either batch or continuous reactors. Conditions for solvent extraction and hydrocarbon conversion are approximately 128~
Temperature tW of approximately 510”C and approximately 3450 to approximately 68950kP
a-gauge pressure, and the hydrogen gas is present at said pressure.

The method of the present invention uses coal and static hydrocarbon oil.

It is commonly used for hydroconversion to more valuable hydrocarbon products. Here, 105 coal refers to normally homogeneous carbonaceous materials, including all grades of coal such as lignite, anthracite, bituminous coal, semi-bituminous coal, and mixtures thereof.

Heavy hydrocarbon inner edges are utilized in solvent extraction.

A heavy hydrocarbon that is liquid under solvent extraction conditions.

This substance contains asphaltene, which is different from normal hebutane, and 80% of it boils at about 343.3°C or higher.
50% boils above about 538°C.

The liquid hydrocarbon bath medium and the coal may be mixed at any ratio of about 1 to about 5 parts solvent to 1 part coal. ratio is preferred.

In a preferred embodiment of the invention, the coal is a bituminous coal with a high volatile content. The volatile content of typical charcoal is about 20φ or more without moisture or ash.

The coal is subjected to extraction and conversion conditions in a finely ground state. The finely pulverized state refers to a state in which, for example, coal particles pass through a Tyler sieve of about 200 mesh or finer (e).

The dead carbonized ice water bath medium used in the preferred embodiment of the invention is heavy whole crude oil. Typical examples of preferred solvents
Well, the API specific gravity is about 10, and it contains normal hemobutane.
This is Cold Lake crude oil, where i is about 8. In a preferred embodiment, the crude oil used as a solvent is
(containing oil, at least 80% of crude oil)
It rises above 3433°C and boils above 50% 01538°C.

In a preferred embodiment of the present invention, water A is also a mixture of solvent, coal and liquid circulating stream in the presence of gas.

Coal is exposed to light temperatures and pressures to liquefy the desired components. Solvent extraction methods can be carried out in batch or continuous reactors. The solvent extraction conditions were an eccentricity of about 128 to about 510'C and a temperature of about 3450 to about 6-8950 K.
Pa gauge pressure k Hydrogen gas is present at the above pressure.

The mixture of solvent, coal and liquid circulating stream Q) is preferably treated in a continuous reactor at a flow value of from about 0.5 to about 10 (JJ liquid bending velocity). The rate is constant in units of feed/units of reactor per hour.Hydrogen gas is approximately 888.8 to approximately 3555 m1 per 1113 m of mixture of solvent, coal and liquid recycle stream. The reactor effluent is recycled to the reactor and just enough hydrogen gas is added to the reactor to maintain the overall pressure within the desired range.

It takes a light minute to liquefy the H↑ desired acid component of coal.

After the reactants are exposed to solvent extraction conditions, the contents of the reactor are evacuated. Gas is then separated from the reaction zone effluent. The slurry thus obtained is deashed with a solvent under conditions that allow separation of the petroleum oil and the heavy lime phase.

] The IL shell phase is the same boiling point as the polymer needle material, the unconverted QI coal and the catalyst, and virtually all the V mineral deposits. Part of this excitement is reflected in the reactions of people in the reaction zone.

In an unspecified preferred embodiment, 1 part of crude oil per 1 part of coal with 1 part of crude oil solvent and 1 part of coal is used.
', 1(U) 11j Mixed at a ratio of 8. The liquid flow obtained later is circulated into the extraction zone at a ratio of 1 part of the extraction zone effluent to 1 part of the coal.
This mixture of Sutsukuda and liquid recycle stream is the feed to the 11 anti-Ib zone or extraction zone in which the solvent extraction takes place. The solvent extraction conditions in a preferred example are as follows:
The temperature is about 454°C and the hydrogen gas pressure is about 20,680kPa gauge. The feed to the reaction zone passes continuously through the reaction zone with sufficient flow to maintain a liquid hourly space velocity of approximately 50 liquid hourly space velocity based on the volume of fresh feed. Approximately 2666 m3 per I11' is recycled from one reaction zone effluent to the reaction zone.About 7 Qw of coal without bath medium extraction conditions CJ, moisture and ash needles.
t% should be maintained so that it is converted to liquid egitract.

Once the feed to the reaction zone has been subjected to the solvent extraction conditions described above, it is collected as an effluent from the reaction zone. While the supply 9 is exposed to 1 unextracted 1 coal, 1 coal becomes XJ70% tL M and becomes a hydrocarbon cable forming mouth valued at 7)/l muff 1□ -\ of butane-insoluble crude oil. A portion is converted into a storage room for normal hezotane VCtJ bath.

After removal of gaseous components in the normal phase, the reaction zone effluent is subjected to vinegar separation to separate solids from the liquid product. A portion of the solids containing the liquid stream is recycled to the inlet of the reaction zone;
Mixed with fresh feed.

The hydrocarbon volume C'i recovered by the process of the present invention constitutes synthetic petroleum gold, which can be processed in the same manner as conventional petroleum crudes. According to the method of the present invention, the quality of both the component derived from the solid and the component derived from the solvent is reduced, and the asphaldene content of both is reduced.

Does the fact that petroleum has less asphaltenes, especially those derived from solids, mean that its hydrocarbons are easier to process than those obtained by conventional extraction methods?
means.

A suitable liquid recycle stream can be provided in whole or in part by the extraction zone effluent. A preferred liquid recycle stream is prepared as follows. First, the extraction zone effluent is removed in a gaseous state (component D) and then the desired hydrocarbon is removed by solvent separation using a soft, low-molecular-weight short hydrocarbon bath medium. , substantially all the ash, unconverted coal, asphaltenes and soft molecular hydrocarbons, and 7
If a fine unsupported metal catalyst is present, it is suitable as a liquid circulating flow! It is possible to obtain the ii M style.

The solvent separation method described above is correct! i, similar to the solvent deasphalting method well known in the art. Suitable solvents for hydrocarbons include ethane, sol, ethane, and ethane.

isobutane, pentane, isopentane, neopentane,
Hexane, isohbutane, heptane, and these monofin fibers are light hydrogen ash particles that surround 16+a i. The prior art teaches the use of aromatic hydrocarbon systems for the purpose of improving the bath medium.

A thin non-supported metal catalyst with periodic extension 601νB.

VB, VIB, VI[B and [VIt&(QW search i
Selected from a mixture of 1 and 1 and 1 and 1 and 1 and 1. It can be prepared by any suitable method for fine non-reciprocal contact.

Catalyst or &:1 Its precursor may be an oil-soluble metal compound.

It may be a thin metal or an oil-soluble metal compound that is easily suspended in hydrocarbon oil.

Fine, unsupported metal catalysts generally contain between about 10 wppm and about 4 wt of elemental mass based on the coal flap in the mixture.
%exist.

Suitable metal compounds that can be converted into active catalysts under process conditions include slag, oxides, hydrous oxides, and sulfides.

Included are all inorganic compounds such as thiosalts, heteropolyacids, isopolyacids, halides, oxyhalides, etc., all groups of oxyhalides, metal salts of organic amines, inorganic and organic metal complexes, and all organic compounds. Ru.

Although various methods are available for forming fine catalysts, the preferred method for forming fine catalysts entirely from metal compounds is to inject a mixture of metal compounds, coal, and petroleum into a water-based gas mixture. and heating to a temperature in the range of about 3156°C to about 4267°C at a pressure of about 3447 to about 34470 kPa gauge. Preferably, the in-situ hydrogen S' collapse gas also contains hydrogen sulfide. The hydrogen sulfide is present in an amount of from about 1 to about 90 moles, preferably from about 1 to about 30 moles, of the gaseous mixture.

The above-described method of converting a metal compound over a fine metal catalyst can be carried out in its own catalyst preparation step or method, or in the hydroconversion zone or reaction zone itself.

The following examples illustrate the process of the present invention useful in producing hydrogen-rich hydrocarbon products from lime and asphaltene-containing petroleum. However, one embodiment of the present invention is not limited to this embodiment e.

EXAMPLE In this example, a rocker autoclave with a capacity of 1800 cc was used to perform the experiment in a single batch type. Explain the results obtained.

Fine coal with properties shown in Table 1 (Illinois Yang 6) 1
00g/6: No. 1 with the properties shown in Table ■tζ? The mixture was placed in an autoclave together with 2 t) of Scann atmospheric distillation residue oil and 22.1 g of hexacarbonyl.

Then autoclave (i=(m-hydrogen/hydrogen (10/
90) The mixture was pressurized to approximately 7583 kPa gauge, and further pressurized to approximately 10341 kPa gauge with pure hydrogen. The autoclave was heated to about 390'C and held at a pressure of about 17235 kPa gauge for 1 hour. Washed with toluene [2] All contents of the autoclave were cooled and collected. After flushing the toluene, the product was solvent separated with 4 volumes of isopentane. The isopentane soluble content was collected, and the isopentane was removed by flushing. The weight of the isopentane soluble portion excluding the bath medium was 185.8 g. Breaks down fine unsupported metal catalysts and produces 56 pieces
．． 3 g of isopentane insoluble matter was circulated into the autoclave together with 100 g of coal and 200.7 g (DH?Scan atmospheric distillation IA residue oil). Heating of the autoclave and external pressure were repeated in the same manner as above. Washing with toluene was performed again. The autoclave contents were cooled and collected. After flushing with toluene, the product was solvent separated with 4 volumes of isopentane. The isopentane soluble content was collected and the isopentane was removed by flushing. Pentane I'l (am) was 98.4 g.The insoluble content of isopentane, which contains fine unsupported total area catalyst and has a diameter of 118.4 g, is 100 g of coal and 198.1 g.
The mixture was returned to an autoclave together with g of Boscan atmospheric distillation residue oil. In the same way as above, apply force (1 heat).

Repeat the pressurization and separation operations. V1189.7g of isopentane soluble product that does not disturb the heating medium,
The isopentane-insoluble portion of the pheasant elm was 178.7 g. This isopentane-insoluble matter (178.7 g) was supplied to an autoclave together with 1100 g of coal and 188.1 g of Mescan atmospheric distillation residue. The autoclave was operated in the same manner as described above to yield 164.1 g of isopentane soluble product and 186.7 g of isopentane insoluble product. This isopentane-insoluble product was extracted with a bath medium using toluene, and 1307 g of a toluene-soluble substance useful as an interstitial fuel oil was obtained.
51.1 g of toluene-insoluble material containing unconverted coal, mineral matter and catalytic gold was obtained.

The contents of the above four autoclave experiments are shown in Table ■, and the results of the toluene extraction of impentane insoluble matter are shown.
Show K.

Table 1 Properties of two coals (Illinois m6) Carbon, wt% 70.05 Hydrogen, wt
5.88 oxygen, wt%
9.01 sulfur, wt% 2
,68 nitrogen, vit% 1.20
Atsushi, wt% 902 Moisture (water), wt rice cake 2.15 (margin 9 below Table Til:, r? Scan residual oil property specific gravity, A, P
I at 15.5℃ 5.5 Distillation characteristics Initial boiling point 1i' 6935%
769 10% 804 30% 977 End point Component (volume) % above 977 end point 305 Carbon, w
t% 82.8 water cable, wt≠
10.6 nitrogen, wt%
08 Sulfur, wt%
56 hebutane non-bath amount, wt 俤
1904 Vanadium, I)I)m
1500 nickel, ppm
130 Table 1: Summary of batch autoclave experiments Feed Coal, g 100 100 Z
oo 100 Zescan residual oil, g 200
200.7 198.1 188. IMo(CO),
, g 22.1 - - - Circulating fluid, g -56,3117,317
7,9 isopentane solubles, g 185.8
98.4 189.7 164.1 Carbon, “wt%
86.22 84.03 Water purple, wt
% 11.44 10.78 oxygen,
wt chi 0.17
0.10 sulfur, wt%
2.77 3.17 Nitrogen, wt%
0.43 0.56 nickel, ppm
2.7 1.8 no 9〃mu, I) p
m <1
18 Insoluble matter, wt (0,010,3&lV
: Toluene extraction sample of isopentane force, g
186.7 Recovery phase, g
130.7 51.1 Carbon, wt%
84.74 31.60 hydrogen, wt staff
7.66 3.04 Tough element, wt% 2
73- Sulfur, wt% 2.36 14.1
Nitrogen, WIs 1.43
-Morizode/, wt folds
670 vanadium, wt chi
1.73 nickel, wt kesa
015 iron, wt%
68 As is clear from the foregoing, the process of the present invention is suitable for producing hydrogen-rich hydrocarbon products from asphaltene-containing petroleum and coal.

Claims (1)

[Scope of Claims] 1(a) Contains asphaltene and heavy oil, and contains at least 8
0% of crude oil and coal having a boiling point of about 3433"C or above are mixed. Φ) In this mixture, the metals are the elements of groups IV, VB and VIB of the periodic table, and the elements of groups VIB, ■B and ■, and these n A temperature flatus of about 128 to about 510"C1 hydrogen pressure of about 3450 to about 68950 kPa in one reaction zone together with the liquid circulation stream described below containing an unsupported fine metal catalyst selected from mixtures and mixtures.
At least a portion of the coal is subjected to conversion to avoid total liquefaction and to reduce the asphaltene content of the crude oil. (C) separating the gas from the resulting reaction zone effluent; (d) At least a portion of the reaction zone effluent is then deashed with a relatively low molecular weight hydrocarbon bath medium to remove substantially all of the ash, unconverted coal, asphaltenes, and unsupported fines. A heavy liquid phase containing catalyst is separated from the effluent. (e) A process for producing an ice water-enriched hydrocarbon product from a carbonaceous material, comprising feeding at least a portion of this heavy liquid phase to a reaction zone for use as a liquid recycle stream in step Φ). . 2. 50% of crude oil containing asphaltenes is about 53
8. The method of claim 1, wherein the boiling point exceeds 8'C. 3. The method according to claim 1, wherein the fine unsupported metal catalyst comprises molybdenum. 4. The method as recited in claim 1, wherein the fine unsupported metal catalyst comprises vanadium. 5. The method according to item 1, wherein the ratio of crude oil containing all asphaltenes to coal is from about 1:1 to about 5; 6. The method of claim 1, wherein the liquid flow chamber in the reaction zone has a liquid hourly space velocity of about 0.5 to about 10. 7. 2. The process of claim 1, wherein the reaction zone hydrogen circulation t is from about 888.8 to about 3555 standard mWms based on the reaction zone acid feed.