JPH0532976A - Coal extraction hydroconversion process involving solvent-enhanced carbon monoxide pretreatment - Google Patents

Abstract

(57) [Summary] [Purpose] Liquefaction of coal to obtain hydrocarbonaceous liquid with high selectivity,
It is to provide a method of manufacturing with a high conversion rate. (A) In a pretreatment zone, a mixture containing coal, carbon monoxide and an organic solvent is formed, and the mixture is exposed to a temperature and pressure effective to cause mild depolymerization of the coal; (b) removing gas from the coal mixture in the separation zone; (C) extracting the pretreated coal with an organic solvent in the extraction zone to obtain an extract containing a significant amount of soluble hydrocarbonaceous coal; d) The extract and the catalyst (the catalyst is a compound containing a metal sulfide, and the metal is a group VA or VIA of the periodic table of the elements,
A mixture of VIIA and VIIIA and mixtures thereof)); and then (e) the mixture of coal extract and catalyst in a hydroconversion zone in a hydroconversion condition. A method for producing a hydrocarbonaceous liquid by liquefying coal, which comprises reacting with hydrogen below to obtain a hydrocarbonaceous liquid product.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION This invention relates to a coal liquefaction process, and more particularly to a multi-stage process comprising a pretreatment stage, an extraction stage and a catalytic hydroconversion stage.

According to the invention: (a) coal, carbon monoxide and an organic solvent in a pretreatment zone
To produce a mixture containing
Exposed to temperatures and pressures effective to cause coalescence; (b) removing gas from the coal mixture in the separation zone; (c) extracting pretreated coal with organic solvent in the extraction zone.
Extract containing a significant amount of soluble hydrocarbonaceous coal
Obtaining; (d) the extract and the catalyst (wherein the catalyst contains metal sulfide)
Compound (the above-mentioned metals are VA group, VIA group of the periodic table of elements,
Group VIIA and Group VIIIA and mixtures thereof
A subsequent mixture of)))
Then (e) the mixture of coal extract and catalyst in a hydroconversion zone
Reacts with hydrogen under coal hydroconversion conditions at
A method for producing oil by liquefying coal is proposed, which is characterized by obtaining a liquid product.
Be served. According to another embodiment of the invention, (a) a mixture comprising coal, an organic solvent and carbon monoxide is added to
88 ° C to 371 ° C (550 ° F to 70 ° F) and
35-352kg / cm ^Two (500-5000psi)
Carbon monoxide partial pressure over a period of at least 10 minutes
Exposing; (b) removing gas from the coal mixture; (c) extracting the pretreated coal with an organic solvent in an extraction zone.
Extract containing a significant amount of soluble hydrocarbonaceous coal
Obtaining; (d) The above extract, organic solvent (preferably derived from coal)
Derived) and a catalyst (the catalyst contains a metal sulfide compound).
, Having an average particle size of 0.02 to 2 microns), preferred
Or conversion products of organic oil-soluble metal-containing compounds (above
Metals are group VA, group VIA, group VIIA and the periodic table of elements.
And Group VIIIA and mixtures thereof
Is produced) in a hydroconversion zone and then (e) this mixture is subjected to coal hydroconversion in a hydroconversion zone.
Hydrocarbons by reacting with gas containing molecular hydrogen under certain conditions
A method for producing oil by liquefying coal is proposed, which is characterized by obtaining a liquid product.
Be served. The method of the present invention will be described with reference to the following detailed description and drawings.
More clearly understood. The method of the present invention is generally applied to coal.
The coal liquid (ie oil or normally liquid hydrocarbonaceous product
It is applicable to hydroconversion to The method is before
It includes a physical stage, an extraction stage, and a catalytic hydroconversion stage. Previous
During the treatment stage, the coal feedstock is melted at high temperature and high pressure
Of carbon monoxide (or syngas containing carbon monoxide
Gas mixture such as). At the extraction stage,
Pretreated coal is available on-site or following pretreatment
Extracted with machine solvent and before subsequent quality improvement by catalyst
A substantially ashless hydrocarbonaceous extract (typically 1% by weight)
% Ash). Stones before subsequent hydroconversion
Separation of this extract from the char ash residue significantly increases catalyst recovery.
Easy to. Even loading of catalyst (wt%) is good for quality
Improved raw made possible in the upper zone or hydroconversion zone
Provides product condition and product quality. For details, see
Coal's hydroconversion process provides high liquid to gas selectivity.
Can be given. Also, the extraction stage has a constant conversion rate.
Produces a hydrogen-rich fraction that requires less hydrogen,
Low in hydrogen due to oxidation or combustion and free of catalyst
Defective ash residue results. This residue is 1g more than raw coal
It contains a small amount of hydrogen. The term "coal" is
Such as green coal, subbituminous coal, lignite, peat and mixtures thereof.
, Solid carbonaceous, including all grades below anthracite
Used herein to refer to a substance. Abituminous coal
And lower grades of coal are particularly preferred. Raw material of this method
Is a coal that was first reduced to granules or a mold-milled form
Is. Coal is crushed appropriately in an ordinary ball mill or
10 micron to 1/4 inch (0.6c
m) particle size range, typically about 8 mesh
Obtain particles of (Tyler). Preprocessing According to that method, lignite, sublimate dispersed in an organic solvent
Feedstocks such as charcoal, subbituminous coal, or bituminous coal are being pretreated
Exposed to carbon monoxide. Coal is relatively pre-treated
It can be reacted at a mild temperature. Limited amount of volatile hydrocarbons
A liquid is produced. However, the coal is depolymerized,
Equilibrium water and oxygen content is reduced. After such pretreatment
In addition to improving the properties of coal,
Shows increased reactivity due to the treatment of Especially pretreatment
Noted the value of coal as a feedstock for coal hydroconversion
Increase. The severity of coal hydroconversion reduction can be reduced,
Increase liquid yield, reduce gas production, reduce hydrogen consumption
However, the intensity of hydroconversion is maintained to maximize the conversion rate.
It is economically more advantageous to have. After pretreatment of coal
To a very high daf weight% (anhydrous ashless weight%) conversion
Reach During the pretreatment, a coal depolymerization reaction occurs. Depolymerization
Is detected by the increased solubility of coal in different solvents.
Be done. The ability of the pretreatment to depolymerize the coal depends on the bond breaking activity.
Properties, or thermal bond breaking to high molecular weight products
Due to removal of potential cross-linking sources that cause repolymerization
Was. During pretreatment, coal in the form of particles is
Dispersed in the solvent, this solvent transports carbon monoxide to the coal material.
Available for use. Generally, in addition to organic solvents, internal water
The presence of (bulkwater) has the advantage of pretreatment
Coal volatiles and improved reaction during hydroconversion
However, coal particles are not
Is preferably dispersed in a single liquid phase containing an organic solvent such as
Good To prepare for the hydrogenation of coal materials, some water
Are required for the pretreatment reaction system. However, no water
Equilibrium moisture content of coal as it is (also called "physical water")
Water) and / or chemical water in coal (“chemical water” is pretreated)
Water that is made available in the conditions of coal minerals
Can include water of hydration therein). one
One of the proposed reaction mechanisms is that during the pretreatment, carbon monoxide
Reacts with water in the coal matrix to form reactive intermediates (this
Hydrogenate coal to produce carbon dioxide)
Is Rukoto. In fact, the method is not
Liquid phase is not required.
It's not necessary in the meantime. Typically, about 30% by weight of water
It may be present as water in the as-received coal,
Is insufficient to form an aqueous phase during pretreatment. example
For example, a large amount of water may be present in lignite, which is preferable.
No, but generally not harmful to pretreatment. But Naga
, When both organic solvent and water are present in intermediate amounts.
In some cases, the hydroconversion reactivity of coal may be a problem.
The main advantage of this method is that additional water is required during the pretreatment.
Not by liquid water filtration from pretreated coal
Separation is not required after it leaves the pretreatment reactor
That is. Separation of water from pretreated coal for filtration
Properly performed in the gas phase by intermediate gas separation regardless of
Be done. The weight ratio of organic solvent to dry coal is 4: 1 to 1: 1
It is suitable and about 3: 1 to 1.5: 1 is preferred. Under conditions
The water to dry coal ratio is less than about 0.5: 1,
The dry coal inlet ratio is less than about 1: 1. ("Entry conditions"
Compared to the term "under conditions" was evaporated into water vapor
Excludes water and water lost through water-gas shift reactions
It ) Coal during pretreatment should be used for final use in the liquefaction stage.
Be slurried in a suitable process-derived hydrocarbon solvent.
And are preferred. An example of solvent is 204 ℃ up to VGO solvent +
(40 ° F +) Distillate (including VGO solvent) and circulating fluid
It is a residual liquid. Pretreatment temperature has a significant effect on coal quality.
Have. 288 to 371 ° C (550 to 700 ° F)
The ambient temperature is important and is 316-357 ° C (600-6
75 ° F) is preferred and 316-343 ° C (600-6
50 ° F.) is most preferred. Conditions of another important pretreatment method
Is supplied to the pressure of carbon monoxide (CO) and coal.
That is the amount that is given. Generally, the partial pressure of CO (P _co ) Is increased
With the addition, the properties of the coal are gradually improved. Suitable
Range is 35-105 kg / cm at ambient temperature ^Two (500
~ 1500 psi) (initial), preferably about 60-70
kg / cm ^Two (850 to 1000 psi). Well
Also, the weight of the coal or CO supplied to the "treatment"
As the quantity% increases, the properties of coal gradually improve.
It The preferred treatment range is 40-100% by weight (dry coal
By weight), preferably about 60-90 wt% CO.
Total pressure under conditions (H _Two O vapor, CO _Two , H _Two , CO, and
C ₁ ~ C _Four Is included) is P _co And about 12 depending on temperature
7 to 316 kg / cm ^Two (1800-4500ps
i), preferably about 197-316 kg / cm ^Two (28
The preferred range is 0-4500 psi, which is
Determine the solvent partial pressure. Generally during residence in the pretreatment zone
Coal quality improves as the time increases. 343 ° C (6
The preferred residence time at 50 ° F is about 10 minutes to 5 hours
From the economical point of view, the range of 20 to 2 hours is preferable.
Is. Effective mixing in pretreatment reactor and CO and coal
Good contact between is desirable. This is a mechanical stirrer and /
Or fixed baffles (which produce high turbulence),
Is a properly designed inlet gas sparge (these are small
Can be achieved. Pretreatment of coal of the present invention
The reason is that the normal structure and destructuring that can withstand the above conditions of pretreatment.
Appropriately carried out in the reactor of Zain. Coal slurry and
A stream having a carbon monoxide inlet pipe and a product outlet pipe
A cylindrical container made of stainless steel is preferred. Pretreatment reactor
Circulation of solvent phase compounds into the liquid can provide certain advantages
Is a feature of. Circulation has low molecular weight contained in the circulating solution
Organic solvents such as alcohol, phenol, and
Rubonic acid) can help dissolve coal. Some kind
Soluble acids or metal salts of acids or bases, especially pretreatment
All of the products made in the reaction system have a certain temperature and temperature.
Pretreatment of coal by improving coal solubility with pressure and pressure.
It can act as a promoter to accelerate the process. Most preferred
The preferred accelerator is sodium formate or calcium formate.
It Other preferred accelerators are ammonium sulfide or
Is ammonium hydrogen sulfide or hydrogen sulfide. Accelerator
Is 0.5 to 50% by weight in the water system, preferably 0.5 to 1
0% by weight, most preferably 1-5% by weight (based on dry coal
And then) should be present in an amount. As shown below
In addition, these accelerators are sprayed on coal crushed in an aqueous solution.
You can During pretreatment, coal is subjected to extraction and
, Soluble carbonaceous material was pretreated with organic solvent
Extracted from coal. If necessary, add additional solvent or
Solvent can be added subsequent to the pretreatment and coal can be further extracted.
Can be hung. The extracted material is sedimented and filtered or its
Separated from the ash-containing residue by other means. Coal particles
The extraction of the components of a coal material actually
And separate according to the molecular weight. Generally, its component is hydrogen
The higher the content or the lower the molecular weight, the more soluble it is in the solvent
Is big. Due to the high hydrogen content of the extracted material, its
Higher conversion and higher selectivity of the subsequent hydroconversion were obtained.
It On the other hand, the residue has less hydrogen than the coal supplied for pretreatment.
It is insufficient. Due to extraction and separation, coal feedstock
It can be divided into two fractions. First fraction (ash residue
0-40% daf (anhydrous ashless) pretreated coal
It is preferred to include quality. Second fraction (including coal extract
Substantially free of ash (less than 2% by weight, preferably
Less than 1 wt% ash)) before 60-100% daf
It is preferred to include treated coal material. For example, typical
In the case of natural Wyoming coal, the coal to be pretreated is
The fraction containing the extract with an H / C ratio of 0.82 is 0.9
Fraction containing H / C ratio of 7 and containing residue is 0.77
Has an H / C ratio of (has an ash content greater than 25%
). Fractions containing ash are sent to the partial oxidation unit and integrated
It is preferred to supply carbon monoxide and hydrogen to the process. stone
Another fraction containing charcoal extract and solvent was conducted to the hydroconversion zone.
Where the coal extract is converted to a lighter product.
Be done. If necessary, some or all of the extraction solvent may be an extract.
May be removed by distillation before being sent to the hydroconversion stage
However, it is more convenient to send the solvent to the extraction. Also,
Additional solvent or circulating solvent is mixed with the coal slurry and water
It may be sent to the digest conversion band. Actually 343 ° C +
(650 ° F +) extraction solvent and 343 ° C + (650 ° F
F +) hydroconversion product is 343 ° C + (650 ° F)
+) Disappeared, resulting in a net of 343 ° C .- (650 °
F-) to the extent required to produce the product
It is fed to the nitration conversion reactor. Extraction of sufficient VGO
Sent separately from the purpose of. As mentioned above, the extract is substantially
Rich in hydrogen and the residue is less than the coal fed to the pretreatment
Hydrogen is reduced. This method treats high ash coal
Even if the hydrocarbonaceous material sent to the hydroconversion zone is
Other hydroconversion processes in that the stream is substantially ash free
Give an advantage over. The amount of ash should be less than about 1% by weight.
Is preferred, with less than 0.1% being most preferred.
Good In addition, hydroconversion feedstock (pretreated coal
(Including extracts from these) is rich in hydrogen and is unfractionated and pretreated.
Hydrogenation with better liquid / gas selectivity than coal
It can be easily converted in the conversion step. Another advantage is less total material
To be sent to the reactor. What if the ash and its
This is because other useless substances are removed beforehand. That
Therefore, additional reactor volume results in high conversion due to long residence time
Available to get rate. Yet another advantage of this method is that
Ash coal extracts are easier to handle than solid-liquid mixtures
Is. For example, separation can usually be done by simple distillation.
It When comparing the coal supplied to the pretreatment as a standard
In this case, the process is much less carbonized during the continuous hydroconversion.
Even if the hydrogen substance is sent to the quality improvement process, other
More desirable liquid products (and
Less gas), i.e. more naphtha and distillate
It Extraction and liquid-solid separation of coal is carried out on coal (pretreated
The worst 15% to 25% of the daf)
To be sent selectively to the storage and the rest almost completely converted.
Bring That is, the initial coal material undergoing hydroconversion
Approximately 75% to 85%, and in fact 100% can be converted.
More distillate and vacuum gas oil (VGO) are obtained by this method
It is thought to be done. Up to 25% of initial coal is hydrogenated
Separation of solid residue without extraction, even if not subjected to conversion
Based on the coal fed to the pretreatment than if not
As a liquid at 538 ℃-(1000 ℃ F-)
It is possible to obtain the conversion rate. Furthermore, this high liquid conversion
Rates are possible with low hydrogen consumption during the hydroconversion process
Is. The conditions of the method are that the carbon content of the ash-containing residue is
H _Two And process requirements for obtaining CO from partial oxidation
Is set to meet. Partial oxidation of coal after pretreatment
Typical splits of 30% to 70% and 70% to hydroconversion are common
To achieve this goal. If the carbon content is low,
The residue may be oxidized and also burned due to heat
May be. As mentioned above, additional extraction of coal solubles
Can be done in a separate extraction stage after pretreatment, or
It can only be done on the fly. Hydroconversion Pretreatment of coal, extraction, and liquid-solid separation followed by stone
Extracted components of charcoal undergo hydroconversion to produce lighter products
To generate. Solvents used in the hydroconversion step of the invention
(This may include pretreatment organic solvent)
Approximately 1/2 to about 2% by weight of donation (donata)
ble) Hydrogen may be included. The preferred solvent is coal
Derived liquid and coal distillates or mixtures thereof,
For example, about 177 ° C (350 ° F) to about 566 ° C (10
50 ° F., more preferably about 343 ° C. (650
° F) to about 538 ° C (1000 ° F) atmospheric pressure boiling
Includes a mixture of compounds having dots. Preferred solvent is reduced pressure
It is light oil (VGO). What makes it the most extracted
The boiling range is high.
Reactor pressure with little or no extraction even
This is because I will proceed with. Also it is a good choice
It What makes it relatively less valuable as a product?
And can be sent to partial oxidation without costly loss
(Typically less than about 10% of VGO is
It can be lost by partial oxidation without financial concern). Invited from coal
The guided VGO is about 343-538 ° C (650-100
Boiling in the range of 0 ° F. Other suitable solvents are
Fragrance compounds such as alkylbenzene, alkylnaphtha
Ren, alkylated polycyclic aromatic compounds, heteroaromatized
Compound, unhydrogenated or hydrogenated creosote oil, petroleum supply
Tetralin intermediate product stream from catalytic cracking of raw materials,
Oil, or virgin petroleum streams, such as vacuum gas oil or
Include residual oil and the like and mixtures thereof. Catalyst is normal support
(A fixed bed) metal sulfide containing catalyst
And are preferred. The catalyst used in the hydroconversion step is
Well dispersed micron or submicron size
It is preferable to include particles. The catalyst is a compound containing metal sulfide
It is preferable that it is a thing. The catalyst is an organic oil-soluble metal
Most preferably it is produced from a precursor that is a compound
Yes. The precursor is an oil-soluble metal compound or solvent in the mixing zone.
And typically after extraction to produce a mixture of coal
Is added to the solvent before quality improvement. Under process conditions
Suitable oil-soluble metal compounds that can be converted to active catalysts are:
(1) Halide, oxyhalide, hydrated oxidation
A heteropoly acid (eg, phosphomolybdic acid, molybdenum)
An inorganic metal compound such as (dosilicic acid); (2) two or more
Acyclic and cycloaliphatic aliphatic carboxylic acids containing carbon atoms
(For example, naphthenic acid); aromatic carboxylic acid (for example,
Toluic acid); Sulfonic acid (eg, toluene sulfone
Acid); sulfinic acid; mercaptan, xanthogenic acid;
Such as phenol, di- and polyhydroxy aromatic compounds
Metal salts of organic acids; (3) metal chelates (eg 1,
3-diketone, ethylenediamine, ethylenediamine
With traacetic acid, dithiocarbamate, xanthate, etc.
Chelates) such as organometallic compounds; (4) Aliphatic amino
Amines, aromatic amines, and quaternary ammonium compounds
Includes metal salts of organic amines. Oil-soluble metal compound metal
The ingredients are Sargent-Welch Scientific
Ku-Kampanyi (Sargent-Welch Sci
Entity Company (copyright 1979)
VA of the Periodic Table of the Elements according to the table published by
Group consisting of Group VIA, Group VIA, Group VIIA and Group VIIIA
Selected from: vanadium, niobium, tantalum, black
Aluminum, molybdenum, tungsten, manganese, rhenium,
Iron, cobalt, nickel and precious metals (platinum, iridium
Aluminum, palladium, osmium, ruthenium and rhodium
Is included). Preferred metal composition of oil-soluble metal compounds
Molybdenum, vanadium, chromium, nickel and
It is selected from the group consisting of cobalt. Oil-soluble metal compound
The metal components of molybdenum, nickel and cobalt are
Most preferably, it is selected from the group consisting of Metal preferred
Some compounds are acyclic (linear or branched) aliphatic carvone.
Acid salt, alicyclic aliphatic carboxylic acid salt, heteropoly acid,
Hydrated oxides, carbonyl compounds, phenolates and organics
Contains amine salts. A more preferred type of metal compound is hetero
A polyacid, such as phosphomolybdic acid (PMA).
Other preferred metal compounds are metal naphthenates such as
It is a salt of an alicyclic aliphatic carboxylic acid. Preferred compounds are
Molybdenum naphthenate, vanadium naphthenate, black
Romnaphthenate, and molybdenum-, cobalt-, or
Or nickel-dibutyldithiocarbamate or sodium
It is Iodine may be used as a catalyst
Yes. Gold in the hydrocarbonaceous matrix produced during the process
Preferred catalyst particles containing metal sulphide are homogeneous in the feedstock.
Dispersed in. Due to their tiny size, normal touch
Expanded bed or solid of media particles
Typically per cubic centimeter of oil than is possible in a fixed bed
There are several times more of these catalyst particles. High degree of catalyst dispersion
And easy access to active catalytic sites, good reactivity of the reaction
Give control. Such a catalyst can be used in a few p
Since it is effective with pm (weight basis) metal,
Economically viable to use without recovery
Noh. Most of the catalysts, along with the retentate recycle stream, are used to improve quality.
Return to Oki. Only a small amount of "make-up" catalyst is added
Need. The catalyst loading is in the range of several ppm to several weight%.
Flexibility in the enclosure (this is the pumping in the slurry reactor).
Limited by the binding of sending). High catalyst loading is due to gas
To low boiling liquids with better selectivity to liquids than
Increase conversion and reduce heteroatom content. The catalyst is
May be used in rally mode and is substantially
May also be used with the ashless extract. The conditions are
As diesel or gasoline for automobiles (or it
Slightly saturated / hydrocracking suitable for conversion to
It may be modified to produce the desired product. 34
Mild water in the range of 3 to 427 ° C (650 to 800 ° F)
It is preferred that the nitriding conversion temperature is used. 100-5
Approximately 1000 ppm catalyst in the range of 000 ppm
The filling amount is suitable for the hydroconversion reaction system of this method. Oil soluble gold
Genus-containing compound supplement (not including additional amount from circulation)
As a metallic element, based on the weight of dry coal in the mixture.
Calculated about 10-5000 wppm, preferably about 25
~ 950 wppm, more preferably about 50-700 wp
pm, most preferably about 50-400 wppm
Is added in a sufficient amount. Catalyst replenishment rate for coal
It is preferably about 30-500 ppm. The rest
Circulate unconverted coal extract or residual liquor with normal catalyst
Supplied by However, the cost of the catalytic
To some extent by increasing operating costs and manufacturing costs
However, the important advantage of high catalyst loading is that the final product is almost
Is to be manufactured. High catalyst loading is 1-10
%, Preferably 1-5% by weight (number of 1%
The value corresponds to 10,000 ppm). Almost final generation
Object means a liquid characterized by a low heteroatomic weight.
At high catalyst loadings, the typical product is about 5 ppm
Full nitrogen, less than 194 ppm sulfur, 1300 ppm not
Have full oxygen and a hydrogen to carbon ratio of at least about 1.7
It The significance of getting nearly the final product is that it is the second
Reactors for quality improvement (eg hydrotreating, hydrodenitrification
Elementary, or hydrodenitrogenation) (this is usually the total process cost
Hydrogen, which is the bulk of the
Consuming a significant amount of) can be omitted. Touch
The amount of medium is about 0 to 1500 ppm nitrogen, 200 to 40
Sulfur content of 0 ppm, and about 1300 to 15,000 pp
to obtain a nearly final product characterized by m oxygen.
Fluid catalytic cracking (this does not require a high pressure hydrogen atmosphere)
To be suitable as a feedstock for
You can Of nitrogen, sulfur and oxygen in coal extracts
Suitably at least 50% by weight, preferably at least
Removal by using a high catalyst loading of about 90% by weight.
To be left. The relative morphology of the catalyst slurry during hydroconversion
The advantages obtained by using high catalyst loadings are:
Achieved without the need for difficult catalyst recovery or recycling processes
To be done. What happens, as a result of the previous extraction stage, hydrogen
The ash conversion zone is very low in ash,
This is because there is almost no residual liquid. Without the extraction stage,
The catalyst is lost. What is necessary is to prevent the accumulation of ash.
The result is that some of the residual liquid is mixed with a proportional amount of catalyst.
Because it will be leaked to. As a general rule, the catalyst is the residual liquid first.
, But there is currently no economical way to do this.
Yes. In this method, almost 100% of the catalyst circulates without difficulty.
obtain. Higher catalyst loadings will yield near final product
And this is part or all of the secondary quality improvement process.
Can be omitted, which means that economic efficiency can be greatly improved.
It Convert catalyst precursor to active catalyst in coal-solvent slurry
Various methods can be used to replace. Good
After dissolving the soluble precursor to obtain a good dispersion
Is usually good to produce. Precursor or oil soluble gold
One method of producing catalysts from genus compounds is hydroconversion
Prior to the reaction, metal compounds, coal extraction in a premix unit
The mixture of the product and the solvent is about 3 in the presence of hydrogen-containing gas.
5.2 to about 352 kg / cm ^Two Gauge pressure (500-50
316 ° C (600 °) at pressures in the range of 00 psig
F) -heat to a temperature in the range of 449 ° C (840 ° F)
That is. H _Two S, CS _Two (Liquid) or elemental sulfur
A sulfur-containing reagent such as yellow should be introduced. Containing hydrogen
The gas can be pure hydrogen, but generally some
Hydrogen streams containing other gas contaminants, such as reformie
Is a hydrogen-containing stream produced from the effluent gas by the Hung process. Touch
Another method of producing the medium is to add the catalyst precursor to the pretreatment step.
Is to add. This is because the subsequent extraction is "presso
The "presoak" option (ie filtration
It does not take effect). Filtered catalyst particles
Remove the child. H _Two S of sulfur for activating the catalyst
Hydrogen sulfide, when used as a source, is a hydrogen-containing gas mixture
It is preferred to make up about 1/2 to about 10 mol% of the product.
It Hydrogen sulphide is mixed with hydrogen gas in the inlet pipe and the preheater
May be heated up to the reaction temperature in the or circulating gas
It may be part of the flow. High-sulfur coal provides an additional source of sulfur
May not be needed. The treatment of the catalyst precursor is
About 5 minutes, depending on the composition and the particular catalyst precursor used
To a period of about 2 hours, preferably about 10 minutes to about 1 hour
Suitably, it is carried out over a period of time in the range.
In the presence of reducing gas (hydrogen or carbon monoxide) or reduction
Such heat treatment in the presence of gas and hydrogen sulfide
A metal-containing sulfide catalyst corresponding to a metal compound (this is a
It also acts as a king inhibitor). Catalyst precursor
Catalysts for the use of body or oil soluble metal compounds in the present process
Another method of converting to metal compounds, coal extracts and
The mixture of agents is subjected to coal hydroconversion conditions in a hydroconversion zone.
It is to react with a hydrogen-containing gas by itself. Oil-soluble
Metal compound (catalyst precursor) of the solvent and coal extract
It is preferably added to the catalyst produced in a mixture of solvents.
However, the dispersion may not be good as described above.
However, it is also possible to add the already formed catalyst to the solvent.
Noh. In any case, catalyst, solvent, and coal extraction
The mixture of products is sent to the hydroconversion zone described below.
Be done. The coal hydroconversion zone is approximately 343-510 ° C (6
50-950 ° F), preferably about 343-454 ° C
(650-850 ° F), more preferably about 385-4
Temperatures in the range of 27 ° C (725-800 ° F), and about 3
5.2 kg / cm ^Two Gauge pressure (500 psig) to about 3
52 kg / cm ^Two Gauge pressure (5000 psig), preferred
About 84.4 kg / cm ^Two Gauge pressure (1200ps
ig) ~ about 211 kg / cm ^Two Gauge pressure (3000ps
The hydrogen partial pressure in the range of (ig) is maintained. Hourly reactor capacity
Defined as the volume of coal and solvent feedstock per product
The space velocity (V / H / V) depends on the desired conversion level.
Can vary widely. Suitable space velocities are every 0.1 to 10
Volume of feedstock per reactor volume, preferably about
0.25-6V / H / V, more preferably about 0.5-2
It can be a wide range of V / H / V. From the hydroconversion stage
343 ° C + (650 ° F +) residual liquid of
Loss of conversion due to reaction of residual liquid at 343 ° C + (65 ° F +)
Partially circulated back to the hydroconversion zone to increase
You may Purged 538 ° C + (1000 ° F
The residual liquid of +) is, for example, partially oxidized together with the residue from the extraction.
Vaporized by hydrogen to produce hydrogen, carbon monoxide and heat
Is preferred. Suitable for residual liquid circulation to hydroconversion zone
Solvent: Coal Extract: 538 ° C + (1000 ° F) residue
The liquid weight ratio ranges from about 2.5: 1: 0 to about 0.5: 1: 2.
It is inside the enclosure. Lowering the solvent to solids ratio is more
Improve the thermal efficiency of the method. What is the size of the reactor
Reduced or even higher for a given coal throughput
This is because it makes sense. Typical process solvent boiling
Range is 232-343 ° C (450-650 ° F) IB
From P to about 538 ° C. (1000 ° F.) FBI.
According to the embodiment considered to be the best method, the hydroconversion
The range of process conditions recommended for the stages is shown in Table 1 below.
To be summarized daf coal based on wt% various greater than 90%
The conversion to product can be obtained. However,
As mentioned above, high catalyst loadings lead to corresponding gas yields.
Significant improvements with reduction, e.g. good liquid selectivity and
And conversion can be given. Low hydroconversion temperature is usually low
Provides coal extract reactivity. However, good transfer
Conversion reaction enabling conversion and good liquid selectivity
At low temperatures due to high catalyst loading and / or coal
Can be obtained if is first pretreated as above
Wear. The method of the invention may be a batch-type method, or
It may be performed as a continuous method. Preferably final
For improving the quality of the field to obtain a product, for example transportation fuel
There is a unit device. Description of the drawings Referring to FIG. 1, finely pulverized coal is mixed by a pipe 1,
Introduced to the science zone 3, where coal is fed into the pipes 6 and 5, respectively.
It is mixed with the introduced carbon monoxide and the organic solvent.
This coal mixture is exposed to high temperature and high pressure conditions as described above.
Exposed. Gas remaining or generated in the pretreatment zone
Gas, typically CO _Two , CO, H _Two O, H _Two And C
₁ ~ C _Four The hydrocarbons are removed by the pipe 15. Preprocessing
Following, the coal enters extraction zone 4. (as mentioned above,
In another embodiment, coal extraction is carried out simultaneously in pretreatment zone 3.
May be done in. ) Extraction is carried out in a step-wise unit
Good. While the coal is being passed through the extraction zone 4, or
Additional solvent introduced through line 22 after passing through it
May be done. Under that condition, about 1: 1 to 5: 1, preferably
Is sufficient to obtain a total solvent to coal weight ratio of about 2: 1.
Different solvents may be introduced into the extraction zone. Residence time of coal
Is in the range of about 10 minutes to 2 hours, preferably about 20 minutes.
It The preferred temperature is 93-343 ° C (200-650 °).
F), preferably 177 to 343 ° C (350 to 650 °)
F), most preferably 260-343 ° C (500-65 ° C)
0 ° F). Typically from evaporating the solvent
35.2kg / cm to prevent ^Two (500 psi)
Pressure can be maintained in the extraction zone. However, some
Solvents, especially process distillates such as coal distillates or VGO
The solvent transfer can be kept under very low pressure. 70% by weight or less
It is preferred that the above anhydrous ashless treated coal is extracted.
A suitable range is 70-100%, preferably 80-100.
%. In the extraction zone, the coal mixture is stirred, which
Hydrocarbonaceous material is extracted from coal material by
Leaving a solid coal residue that is dissolved in and contains insolubles and ash.
Converting coal material into a soluble form is difficult to process
Minimize or eliminate retrograde reactions that result in residual liquid
It Then the mixture of solvent, extract and residue is separated first
It is passed through zone 16 where the mixture is soluble in all solvents.
Hydrocarbonaceous product components of (substantially all
The liquid or solvent phase in the pipe 18 containing the melt and the extraction zone
All solvent-insoluble hydrocarbonaceous substances (stone
The solids in the pipe 20 containing substantially all the ash from the charcoal)
It is separated into a containing phase. Separation by filtration means or centrifugation
This can be easily done by using a container. Solvent insoluble matter
The containing phase is typically solid and its replenishment is
It depends on the composition of the particular coal produced. Second separation zone 24
Among them, some or all of the solvent is soluble in the solvent due to fractionation.
It can be separated from hydrocarbonaceous products. Solvent-soluble charcoal water
Elementary products generally have an initial boiling point well above the boiling point of the solvent.
As it has, it is conveniently separated from the solvent in the distillation column.
Be separated. Separated solvent mixed with pretreated coal
The extraction zone (or pretreatment zone) by the pipe 26
Can be circulated back to. The coal extraction phase is introduced into the mixing zone 17.
(Similarly, in FIG. 2, the coal extract in the pipe 100 is
Rally mixer 108), where additional melt
The agent and the residual liquid are extracted by the pipe 21 (124 in FIG. 2).
Added to. Furthermore, the solvent recovered from the downstream side is pipe 1
9 (128 in FIG. 2). Catalyst precursor
The solvent containing is introduced into the mixing zone 17 through the pipe 23.
In FIG. 2, the solvent stream 104 and the catalyst precursor 102 are mixed with the catalyst.
It is introduced to the combined band 106. The components in the mixing zone are closely packed
Mix to produce a uniform mixture. Oil-soluble metal catalyst
A mixture of precursor, solvent, and coal extract is shown in Figure 2.
Is introduced into the preheating zone 114 as described above. Hydrogen and necessary
The gas mixture containing hydrogen sulfide is supplied through the pipe 112.
Will be introduced in the band. Preheating zone is about 316-371 ℃
Temperatures in the range of (600-700 ° F) and about 141-1
76 kg / cm ^Two Pressure (2000-2500 psi)
Is preferably maintained at. Then the coal extract and
And the catalyst slurry is hydroconversion zone 29 of FIG.
Will be introduced in 116). Hydroconversion reactor desired
Any temperature and pressure that can withstand the hydroconversion conditions
It may be a vessel or a reactor. Typically multiple stages
There are floor hydroconversion reactors (not shown), each
The reaction zone conditions maximize the desired equilibrium limit and reaction rate.
And set to obtain the best profile of the product.
Is determined. The feedstock to the hydroconversion zone is typically
Solvent to coal extract weight ratio of 0.5: 1 to 1: 1.
A make-up solvent may be introduced if desired. Solvent is hydrogenated
It is preferred to be sent to the conversion zone and circulated after hydroconversion.
Good 1: 1: 1 solvent to coal extract to hydroconversion zone
Residual liquid circulation to the area is preferred. The yield of lighter liquids
As much as possible, 343 ° C + (650
It is preferred to circulate the ° F +) liquid. Total hydrogenation
The product of the conversion process is the basic process (the basic process is the pretreatment stage and / or
Is a comprehensive method that does not include coal extraction and separation)
Be improved. For example, 5 regarding the basic method of catalytic hydrogen conversion
Typical conversion to 38 ° C- (1000 ° F-) product
Is based on the DAF weight% of the initial coal feed
It was 75%. Typical product (Wyoming Amber)
From charcoal) is about 14% C ₁ ~ C _Four Gas and 43.69%
C ₅ ~ 538 ° C- (1000 ° F-) liquid (12%
Naphtha, 29% distillate and 9% 538 ° C- (100
VGO) in the boiling range of 0 ° F-). Hydrogen consumption
The cost was about 5.3% on daf-fed coal. Comparison
In addition, by adding carbon monoxide in the pretreatment stage,
Gas production and hydrogen consumption are reduced, and naphtha in the product is reduced.
And the amount of distillate increases. Separate the coal extract as well
This further reduces gas production and hydrogen consumption,
Further increase in the amount of fluff and distillate. Pretreatment process and extraction
The increased amount of naphtha produced by the use of the release process is
Therefore, it is particularly remarkable. Referring again to FIG. 1, hydrogen-containing gas
Is introduced directly into the hydroconversion reactor 29, or temperature controlled.
Introduced via pipe 31 in front of the reactor for your control
It Hydrogen-containing gas suitable for introduction into the hydroconversion zone
The mixture is raw syngas, ie, about 5 to about 50 mol% water.
Elemental, preferably about 10 to 30 mol% carbon monoxide
Including gas. Another suitable hydrogen-containing gas is natural gas
Obtained from boom reforming. Pure hydrogen is available
It is also suitable when possible. Required for hydroconversion
Some of the hydrogen that is provided by the partial oxidation unit device 33
It is preferable. The rest of the hydrogen is normal coal partial oxidation or
Can be produced by natural gas reforming. like this
In this method, the coal or coal fraction is
Partial oxidation reactor, essentially a vaporizer, in the form of small droplets
Pumped to an oxygen (e.g., oxygen pump)
(From runt) and steam. Amount of oxygen
Is CO _Two Oxidation of coal material up to
To be adjusted. Some CO _Two Is always made
Heat for the process (which is net and endothermic)
give. These reactions are as follows.

[Chemical 1] The resulting mixture of CO and H ₂ (known as “syngas”) is removed from the acid gas in the separator 35, followed by a prismatic membrane unit 41 (Monsanto Corporation (M.
(registered trademark of Onsanto Corporation). H ₂ is separated and removed by the pipe 43, and CO in the pipe 6 is used in the pretreatment process. In addition, some of the gas from the partial oxidation unit is Ni
CO ₂ is passed through the catalyst and contacted with additional water in reactor 39 to shift CO according to the water gas shift reaction described below.
And generate additional H ₂ needed for the plant.

[Chemical 2] Following acid gas removal in separator 37, H ₂ is obtained in line 47. Hydrogen in lines 43 and 47 may be used in the hydroconversion reaction zone. Returning to hydroconversion zone 29 in FIG. 1, the effluent in line 49 contains light gas, oil product, bottoms, and catalyst slurried together. The effluent is passed through a separation zone 51 (including atmospheric pipestill), from which gas is removed overhead by line 53. Gas typically comprises a _C 1 -C ₄ hydrocarbons, _{H 2,} and acid gases. C ₁ -C ₄ gas may be used for example as fuel for preheating the coal. H ₂ may be recycled to the coal hydroconversion zone by lines 53 and 31, or may be used to enhance the liquid product. The gas may first be scrubbed by conventional methods to remove undesired amounts of hydrogen sulfide, ammonia, water and carbon dioxide. The slurried effluent from the hydroconversion zone 29 is a hydrocarbonaceous oil (boiling at atmospheric pressure of less than about 343 ° C. (650 ° F.)) in zone 51 by conventional means such as distillation. The first stream containing the pipe 57 sent to the separation zone 61 and the heavy liquid (about 343 ° C. + (65
It is separated into a second stream containing a slurry of atmospheric pressure above 0 ° F +)), solvent, and catalyst. The slurry is divided between circulation lines 21 and 55 at a ratio determined by the desired solids purge rate and / or the desired amount of solvent replenishment. In line 21, the slurry is circulated directly back to the mixing zone 17 for reuse in the hydroconversion zone. This is desirable for increasing conversion and circulating the catalyst. Piping 5
In 5, the slurry is conveyed to a vacuum separator 59 where heavy solvent (343 ° C. (650 ° F.) to 538 ° C. (1000 ° C.
The atmospheric boiling point of ° F) is separated from the residue by vacuum distillation. The heavy solvent is circulated through the pipe 19 to the mixing zone 17 or the extraction zone 4. The residue may be sent to any catalyst recovery zone (not shown) or may be disposed of in an environmentally acceptable manner. Since the solid residue is substantially ashless, the catalyst recovery zone can readily yield a catalyst for reuse in, for example, the mixing zone 17.
The hydrocarbonaceous oil produced in the hydroconversion zone is removed from the separation zone 51 by the pipe 57 and passed to the fractionation zone 61, where distillates in various boiling ranges can be obtained.
Depending on the catalyst loading in the hydroconversion zone, these fractions can be sent to a quality improvement zone (not shown) where the treatment with hydrogen in the presence of a hydrotreating catalyst can be piped if necessary. The final product occurs in 67. In another embodiment of the invention, at least a portion of the oil product is circulated to the extraction zone 4 by line 21 to provide a light solvent for the extraction process. A variety of process options for treating the liquid effluent removed from the hydroconversion reactor 29 are possible and appreciated by those skilled in the art. For example, in FIG.
, A preferred embodiment for treating a liquid product is shown. The liquid effluent 118 from the hydroconversion reactor 116 is fractionated in atmospheric pressure fractionator 120 to a 343 ° C- (650 ° F-) crude product in line 122. A portion of the atmospheric residue is circulated in the recycle stream 124 in the desired ratio with the coal extract and catalyst. Atmospheric residual liquid that is not needed for circulation to hydroconversion is in residual liquid separator 130 in line 126.
To be used as a solvent for additional 343 ° C +
(650 ° F +) Collect liquid. The separator 130 may be a vacuum distillation column, a solvent extraction unit device, or the like. The residual vacuum bottoms in line 132 may be used separately or as a blend with coal as a feed to a partial oxidation unit, a hybrid boiler, or a conventional boiler for process heat or hydrogen. The circulating atmospheric bottoms stream contains active, well-dispersed microcatalyst. Make-up catalyst is needed to maintain catalyst concentration due to loss of catalyst purged with residual liquid. In another embodiment, the fractionator following the hydroconversion zone treats the effluent as a light liquid or naphtha, C
_{5 to} 204 ° C (400 ° F), 204 to 343 ° C (4
Distillate and 343-538 at 0-650 ° F)
It can be used to separate into solvents at ° C (650-1000 ° F). The solvent is preferably recycled to the hydroconversion reactor and / or the extraction reactor, and the bottoms from the fractionator can be recycled to the hydroconversion reactor, sent to the partial oxidation unit or purged. The following example illustrates a preferred embodiment of the method and certain advantages. This example is not intended to limit the broad scope of the invention. Other advantages and embodiments of the present invention will be apparent to those skilled in the art from the description provided herein.

EXAMPLES Example 1 The following is a prospective process design for practicing the present invention. Please refer to FIG. Pipe 201 as-is coal
Is introduced into the crushing zone 203 by means of which the coal is circulated in a conventional ball or rod mill to a diameter of about 0.64 cm (1
Crush into particles smaller than / 4 inch). If the as-received coal is very damp, the coal may be dried in a conventional gas sweep dryer to prevent agglomeration during crushing. Following the shredding zone 203, it is optional to spray the coal with a chemical accelerator solution introduced by piping 204 to facilitate subsequent pretreatment steps. The crushed coal is then treated in a hot oil grinding zone 205 with solvent (also referred to as "hot oil") at a solvent to dry coal ratio of about 1.5: 1 at a temperature of about 107 ° C (225 ° F). Mix. This grinding step can be carried out in a conventional hot oil ball mill and reduces the coal slurry to a paint-like consistency with coal particles of about -100 to -200 mesh. The temperature of the hot oil solvent is such that it maintains a pumpable viscosity. The coal slurry then enters a tank 207 for mixing and / or holdup, after which it is pressurized by pump 209. Pressurized coal slurry is heat exchanger 2
Pass 11 and 213. (The heat exchanger in FIG. 3 is designated by reference symbols A, B, C, etc. to indicate where the heat sink and cold sink are heat exchanged to optimize the thermal efficiency of the process.)
Carbon monoxide is mixed with the coal slurry via line 215,
The coal slurry is further raised in temperature by furnace 217 and then enters pretreatment zone 219 for a residence time of about 90 minutes. The pretreatment zone is 246 kg / cm ² (3500 ps)
i) pressure and 316 ° C. (600 ° F.) temperature.
357 the pretreated coal in the heat exchanger 221 or furnace
Further heated to a temperature of 675 (F), 183 kg /
Flash tank 2 with a pressure of cm ² (2600 psi)
Enter 23. Cooling the gas effluent from the flash tank in a heat exchanger 225 and a cold water exchanger 227 to a temperature of 43 ° C. (110 ° F.) and collecting the condensate in tank 229;
There are two immiscible liquid phases. That is, the pipe 228
An aqueous phase (pipe 2) containing a light solvent phase therein (which can be sent to atmospheric pipestills) and soluble organics (which can be extracted and sold for use in various products).
30) occurs. The CO ₂ to remove non-condensable gas from the tank 229 is treated in an acid gas cleaning zone 231 may be recycled to the pretreatment zone 219 residual CO, or water -
The gas shift reaction may be purged to produce plant hydrogen. The liquid effluent containing the solvent to coal extract in a weight ratio of 1.8: 1 is flushed to the flash tank 223 via line 235.
And is introduced into a liquid-solid separation zone 224 where the solid residue is disposed of by line 226 and preferably sent to the partial oxidation unit. The separated liquid (coal extract) phase containing the soluble matter of coal is taken out by the pipe 228 and mixed with the solvent atmospheric residual liquid circulating product in the pipe 236. The catalyst for the hydroconversion reaction is introduced into the coal extract through the pipe 237. The coal extract and catalyst slurries were then placed at 357 ° C (6
75 ° F) and 179 kg / cm ² (2550p
Enter the mixing zone 239 at pressure si). A small amount of hydrogen may be added to the mixing zone to prevent retrograde reaction. The mixed coal extract and catalyst slurry receive the molecular hydrogen gas from the process gas in the pipe 269, and the process gas is supplied to the pipe 2
It is supplied by 65 and heated by the furnace 263 and the heat exchanger 267. The process gas is heated to help raise the temperature of the total mixture and meet the hydroconversion conditions. The mixture of coal extract, solvent, process gas and catalyst enters the hydroconversion zone 241 where it is at a ratio of solvent to treated coal extract to recycle bottom of 1.8: 1: 0.5. 90-12
Expose to a temperature of 427 ° C. (800 ° F.) and a pressure of 178 kg / cm ² (2500 psig) for a period of 0 minutes. One or a series of hydroconversion reactors may be used. The effluent from the reactor 241 is a gas-liquid separator 24.
3 and the liquid separated therein is fed to the atmospheric pipestill 2
Send to 77. The gas from the gas-liquid separator 243 is cooled to 343 ° C. in the heat exchangers 245 and 247.
Enter heat separator 249 at a temperature of (650 ° F.). The condensed liquid phase is taken out from the heat separator 249 through the pipe 273 and sent to the atmospheric pipe still 277. After passing through the heat exchangers 251 and 253 and the cold water exchanger 255, the non-condensed gas is sent to the cold separator 257 through the pipe 250, where the non-condensed gas is cleaned with acid gas in the zone 259, and then the pipe 2
Remove by 60. The gas stream can then be split to create a recycle stream containing hydrogen (not shown) and a purge stream for hydrogen recovery. The condensate from the cold separator 257 is taken out through the pipe 275, passed through the heat exchanger 261, and then sent to the atmospheric pipe still 277. Atmospheric pressure pipe still 277 (this is hydroconversion reactor 241 and separator 22)
9 receives liquid product from 9) produces overhead gas stream 281 and product stream 279, which may be sent to a hydrotreating zone (not shown) for final processing. A part of the residual liquid from the atmospheric pressure pipe still is piped 28
3 to the bottoms recycle stream 236, which is mixed with the coal effluent and catalyst prior to hydroconversion, as described above. Another portion of the bottoms is sent to a vacuum pipestill 285 where a further product stream 287 for hydrotreatment is produced. The residual liquid stream 293 from the vacuum pipestill is sent to the partial oxidation unit as a feedstock to produce some of the required CO and H ₂ . Decompression pipe still 285 is 343-53
A distillate having a boiling point of 8 ° C (650-1000 ° F) is produced, which distillate forms a VGO (vacuum gas oil) recycle stream. After passing through heat exchanger 288, VGO is circulated through pipe 291 for mixing with the coal entering hot oil grinding zone 205 as described above.

[Brief description of drawings]

FIG. 1 is a process flow diagram for explaining the present invention in which coal is treated in an organic solvent in the presence of carbon monoxide and then converted into a valuable liquid.

FIG. 2 is a process flow diagram illustrating a method for upgrading the liquid effluent of a hydroconversion reactor.

FIG. 3 is a process flow diagram of an exemplary method of the present method.

[Explanation of symbols]

3 ... Mixing, pretreatment zone 4 ... Extraction band 16 ... First separation zone 17 ... Mixed zone 24 ... Second separation zone 29, 116 ... Hydrogenation conversion zone 33 ... Partial oxidation unit 35, 37 ... Separator 61 ... Separation band 114 ... Preheating zone

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Stephen Dave It Reynolds             United States Bayton, Louisiana               Rouge Yu Shin Crea Drive             1089

Claims (16)

[Claims] 1. A slurry of hydrous coal in an organic solvent in a pretreatment zone (a) (ratio of water to dry coal under conditions of 0.5:
Less than 1) and the slurry at 288 ° C-3
Exposure to an effective amount of carbon monoxide at temperatures of 71 ° C. (550 ° F. to 700 ° F. and high pressure) causes depolymerization and hydrogenation of coal, thereby increasing the solubility of coal in solvents and (B) the pretreated coal slurry in two phases, an organic solvent phase containing a significant amount of soluble hydrocarbonaceous material extracted from the coal, and from the coal. Separating into a second solid residue phase containing substantially all of the inorganic ash; (c) the extract and catalyst (wherein the catalyst is a compound containing a metal sulfide (wherein the metal is a group VA, VIA of the Periodic Table of the Elements)). ,
Forming a substantially ashless mixture (comprising dispersed particles of groups VIIA and VIIIA and mixtures thereof)); and (d) substantially ashless coal extract and catalyst. A method for producing a hydrocarbonaceous liquid by hydroconversion of coal, which comprises reacting the mixture of 1) with a hydrogen-containing gas under a coal hydroconversion condition in a hydroconversion zone to obtain a hydrocarbonaceous liquid. 2. Subsequent to the pretreatment of step (a), the pretreated coal slurry is further extracted in an extraction zone prior to the separation of the coal material of step (b) into a solid phase and a liquid phase. The method according to Item 1. 3. The hydroconversion zone is between 343 and 510.
The process of claim 1 wherein the pretreatment zone is at a temperature of 316-357 ° C (600-675 ° F). 4. The method according to claim 1, wherein the catalyst is a conversion product of an organic oil-soluble metal compound. 5. The coal extract of step (b) is separated from the residue containing coal solids containing ash, and the residue obtained is subjected to partial oxidation, thereby producing carbon monoxide for step (a),
The method of claim 4, wherein hydrogen is produced for step (d). 6. The method of claim 1 wherein a portion of the first crushed as-received coal bypasses step (a) and undergoes partial oxidation. 7. The method further comprising introducing the hydrocarbonaceous liquid produced in step (d) into a fractionation zone, wherein at least two fractions are obtained, whereby at least one fraction is in a hydroconversion zone. The method of claim 1, wherein the method is circulating. 8. The solvent stream is recycled to the pretreatment zone.
The method described in. 9. A process according to claim 1 wherein an additional organic solvent is mixed with the coal extract prior to hydroconversion and the catalyst is recycled to the hydroconversion zone. 10. The organic solvent is about 227-343 ° C. (44
Distillate boiling about 0-650 ° F) or about 3
The process according to claim 1, which is a vacuum gas oil or a mixture thereof boiling in the range of 43 to 538 ° C (650 to 1000 ° F). 11. The method of claim 4, wherein the oil soluble metal compound comprises phosphomolybdic acid. 12. The method of claim 1, wherein the hydrogen-containing gas of step (d) comprises about 1-10 mol% hydrogen sulfide. 13. The oil-soluble metal compound is converted under hydroconversion conditions in a hydroconversion zone in the presence of a hydrogen-containing gas, whereby in the hydroconversion zone in the mixture as described above. The method of claim 4, wherein the catalyst of claim 1 is produced in situ. 14. The solvent and coal extract in a ratio of about 1: 1.
The method of claim 1, wherein the solvent to coal weight ratio in the range of ˜2: 1 is mixed in step (b). 15. The method of claim 1 wherein an effective amount of catalyst is used in step (d) to convert the extract into a near final product. 16. Nearly final product is 0-1500 pp
m nitrogen content, 200-400 ppm sulfur content, 1300
16. The method of claim 15, characterized by an oxygen content of ˜15,000 and a hydrogen to carbon ratio of at least about 1.7.