CN102666793B - Hydrogenation of solid carbonaceous materials using mixed catalysts - Google Patents

Hydrogenation of solid carbonaceous materials using mixed catalysts Download PDF

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CN102666793B
CN102666793B CN201080053101.5A CN201080053101A CN102666793B CN 102666793 B CN102666793 B CN 102666793B CN 201080053101 A CN201080053101 A CN 201080053101A CN 102666793 B CN102666793 B CN 102666793B
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catalyzer
coal
carbonaceous material
copper
mixture
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CN102666793A (en
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A·E·库伯曼
韩今依
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Chevron USA Inc
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Chevron USA Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This invention encompasses systems and methods for converting solid carbonaceous material to a liquid product, comprising maintaining a solid carbonaceous material in the presence of at least one active source of copper and at least one active source of a second metal at a reaction temperature of greater than 350C and at a pressure in the range of 300 to 5000 psig for a time sufficient to form a liquid product.

Description

Make spent mixed catalyst by solid carbonaceous substance hydrogenation
Technical field
The present invention relates to for carbonaceous material being carried out pre-treatment, by carbonaceous material liquefaction and the system and method improving carbonaceous material liquefaction efficiency.
Background technology
A lot of work has been made for many years about the method being obtained liquids and gases product by solid carbonaceous substance such as coal.Known method comprises catalyzed reaction and uncatalyzed reaction two kinds.In catalysis process, hydrocarbonaceous material carries out pulp with solvent and catalyzer typically, and makes it react under the temperature and pressure raised under molecular hydrogen exists.
Such as, United States Patent (USP) 5,246,570 describe a kind of coal liquefaction method, wherein the mixture of coal, catalysts and solvents are heated rapidly to the temperature of 600-750 Fahrenheit degree in preheater, react under then making its gelatin liquefaction condition in liquefaction reaction.United States Patent (USP) 5,573,556 describe a kind of method carbonaceous material being converted into the product of normally liquid, the method comprises comprising carbonaceous material, be heated to containing the slurry of hydrocarbon solvent and catalyst precursor and be enough to make described catalyst precursor be converted into the temperature of corresponding catalyst, and is incorporated in fluidized zone by this slurry.United States Patent (USP) 5,783,065 describes a kind of coal liquefaction method, and the method comprises the catalyst soakage coal particle with having hydrogenation or hydrogenolysis activity; At at least about the temperature of 400 DEG C, the coal particle of dipping is incorporated in the turbulent flow of hydrogen-containing gas in the very short time; The temperature being significantly less than 400 DEG C is quenched to making the temperature of product.
Such ordinary method is that the liquid of the carbonaceous material improving hydrocracking and/or the quality of gas recovery ratio and the liquid obtained by such method and/or gaseous product leave a lot of leeway.Therefore, still need the system and method for the improvement for carbonaceous material hydrocracking, and the feed material of improvement for such system and method.
Summary of the invention
The present invention relates to a kind of method solid carbonaceous substance being converted into product liquid, the method makes solid carbonaceous substance be greater than the time maintaining under the pressure under the temperature of reaction of 350 DEG C with at 300-5000psig and be enough to form product liquid under being included at least one copper activity source and the existence of at least one second metal active source.
On the one hand, the method comprises the composition in preparation solid carbonaceous substance, at least one hydrocarbonaceous liquid, at least one copper activity source and at least one second metal active source; Said composition is delivered to hydroconversion reactions district and described solid carbonaceous substance is enough to described solid carbonaceous substance to be converted into boiling point at least partially at C being greater than to maintain under the pressure under the temperature of reaction of 350 DEG C with at 300-5000psig 5to the time of the product liquid in the temperature ranges of 650 DEG C.
In other side, the step preparing described composition comprises the mixture prepared and comprise at least one copper activity source and at least one second metal active source; This mixture and coal are merged with the coal particle formed containing catalyzer; Hydrocarbonaceous liquid carrying is fed to this coal particle containing catalyzer to prepare described composition.
On the other hand, the dry described coal containing catalyzer before the method preparing described composition is also included in and described composition delivered to the step in hydroconversion reactions district.
In other side, before the method is also included in and described composition delivered to hydroconversion reactions district, described composition carried out pre-treatment under the pretreatment temperature of 100-350 DEG C and continue time of 5-600 minute.
In other side, before pre-treatment step, period or afterwards, join in described solid carbonaceous substance by least one active sulphur source in the preparation of described composition, wherein the atomic ratio of sulphur and metal component is 1/1-10/1.
On the one hand, the second metal is iron.
To the of the present invention some embodiments comprising the above-mentioned aspect of the present invention be described in further detail as follows.Usually, unless otherwise indicated herein, each in these aspects can with other side and embodiment by various and be specifically combined into exercise and use.
Accompanying drawing briefly describes
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 describe the embodiment of solid carbonaceous substance being carried out the method transformed.
Describe in detail
Following term will be used in whole specification sheets, and unless otherwise indicated, following term will have following meanings.
Term " catalyst precursor " is for referring to by (such as vulcanizing agent and/or reductive agent are as hydrogen with one or more reagent herein, such as in hydrocarbon medium) there is chemical reaction and/or changed into the compound of catalyzer by other suitable process any (such as thermal treatment, multi-step thermal treatment, pressure treatment or their any combination), wherein catalyst precursor is decomposed into catalyzer at least partly.
Term " activated source " is for referring to as catalyzer or catalyst precursor herein or can being converted into the atom of element of catalyzer or catalyst precursor, molecule, complex compound or other form any.Activated source can be solution, slurry or particle form.When by when such as activated source is deposited in solid carbonaceous substance by plating, dipping, coating or brushing, the mixture of single-activity source or activated source can be deposited in the individual particles of solid carbonaceous substance.
Term " catalytic material " is used in reference to one or more active catalysts or catalyst precursor.The component of catalytic material can be slurry or particle form.Time in granular form, single or multiple catalysts can be there is in individual particles.Equally, when by such as plating, dipping, coating or when to brush depositing catalytic material in solid carbonaceous substance, can be deposited on forming the single catalyst of catalytic material or catalyst mixture or precursor mixture in the individual particles of solid carbonaceous substance.
Unless otherwise prescribed, coal performance disclosed herein is by drying ashless (daf) base, wherein uses ASTM 3173 to be used for ash content for moisture determination and ASTM3174 and quantizes.
" d " block elements refers to the element that the d subgrade of periodictable Atom is filled.Example comprises iron, molybdenum, nickel, manganese, vanadium, tungsten, cobalt, copper, titanium, chromium, platinum, palladium, cerium, zirconium, zinc and tin.
Group of the lanthanides (or lanthanum race, or be sometimes called rare earth metal) element refers to that periodictable Atom ordinal number is 15 kinds of elements of 57-71.
" oil-dispersing property " compound represents that compound scatters or is dispersed in oil and forms dispersion.In one embodiment, dispersible compounds is oil soluble, and it dissolves when mixing with oil.
For this disclosure, unless otherwise prescribed, catalyst composition is defined as the composition of the activated source joined in technique, and with hydrocracking during catalytic elements form have nothing to do.
The present invention relates to composition and the preparation manipulation of the copper containing catalyst of the sulfuration for the carbonaceous material hydrocracking by comprising coal, shale oil, vacuum residuum and biofuel raw material such as xylogen.The invention still further relates to hydrogenating conversion process solid carbonaceous substance being converted into product liquid under the catalyst composition comprising copper exists.In multiple embodiment, the invention still further relates to the method being carried out by carbonaceous material transforming, under the method is included in pretreatment temperature and under at least one copper activity source and at least one second metal active source exist, solid carbonaceous substance is carried out pre-treatment; In presence of hydrogen described pretreated material is heated to above the invert point of described pretreatment temperature; And make the substance reaction of this heating be enough to be formed by described solid carbonaceous substance the time of converted product.
Catalyst-type (Catalyst Formula)
In one embodiment, catalyzer composition represents to have general formula (R by element form p) i(M t) a(L u) b(S v) d(C w) e(H x) f(O y) g(N z) h.Refer to catalyst solid in this this formula, thus form catalyst pulp in oil.In this formula, M and L separately indication cycle table at least one " d " block elements, such as iron, molybdenum, nickel, manganese, vanadium, tungsten, cobalt, copper, titanium, chromium, platinum, palladium, cerium, zirconium, zinc and tin.M and L is different.R is optional, at least one lanthanon of its indication cycle table, such as La, Ce, Nd etc.In another embodiment, R is at least one alkaline-earth metal such as magnesium.
In this this formula external, p, t, u, v, w, x, y, z represent the total charge of various component (being respectively R, M, L, S, C, H, O and N); Pi+ta+ub+vd+we+xf+yg+zh=0; The subscript i that R has is 0-1; The value that M and L has subscript a and b, a and b is respectively 0-5, and (0<=b/a<=5); S represents that the value of subscript d is the sulphur of 0.5 (a+b) to 5 (a+b); C represents that subscript e has the carbon of the value of 0 to 11 (a+b); The hydrogen of H to be the value of f be 0 to 7 (a+b); O represents that the value of g is the oxygen of 0 to 5 (a+b); Represent that h has the nitrogen of the value of 0 to 2 (a+b) with N.
In multiple embodiment, M is iron, and L is copper (or vice versa).In the embodiment that some are such, catalyzer has formula (Fe zcu 1-z) a(S) d(C) e(H) f(O) g(N) h, wherein copper and the ratio of iron are that 9:1-1:9(is in wt.%).In the embodiment that some are such, copper is 1:5-5:1 with the ratio of iron; Or 1:10-1:5.
Pretreatment process
In multiple embodiment, the present invention relates to and carbonaceous material is carried out pretreated system and method, this system and method is used for making one or more catalyzer or catalyst precursor be distributed in carbonaceous material, in order to improve the transformation efficiency of carbonaceous material (such as natural solid carbonaceous material is as coal) to liquid and/or gaseous product, there is in order to preparation reactive carbonaceous material of raising, in order to improve the efficiency that carbonaceous material (such as coal) liquefies, this efficiency is such as measured by transformation efficiency and liquid yield, and/or in order to reduce the hydrogen consumption during carbonaceous material liquefaction.
In one embodiment, substantially do not occur during this pre-treatment of carbonaceous material is used in pre-treatment step carbonaceous material hydrocracking (be namely wherein less than about 20%, be less than about 10% or the carbonaceous material that is even less than about 1% transform) reaction conditions (or multiple condition is as temperature, pressure and/or combination of pre-treatment time length) implement or complete.Any suitable method or operational condition can be utilized to carry out pre-treatment carbonaceous material.In one embodiment, pretreatment compositions is heated to enough temperature to be distributed in carbonaceous material to make one or more catalyzer or catalyst precursor, and makes it maintain under this pretreatment temperature, control and/or keep time enough or sustained periods of time with the dispersion making one or more catalyzer or catalyst precursor be distributed in carbonaceous material to reach required degree, integration (integration) and/or homogeneity.In one embodiment, pretreatment compositions is heated to the temperature (such as about 150-300 DEG C or even about 180-220 DEG C) of about 100-350 DEG C.In the embodiment that some are such, described pre-treatment step carries out about 10-360 minute at the temperature of about 100-350 DEG C.
Preferably make pretreatment compositions maintain under pretreatment temperature, keep and/or control time enough or sustained periods of time to make carbonaceous material swelling and allow catalyzer or catalyst precursor to be distributed in carbonaceous material (such as completely dispersion and/or dispersed).In one embodiment, such as, pretreatment compositions maintained in suitable temperature, control and/or keep suitable time length to improve about 5% or about more than 25% to make carbonaceous material (or each carbonaceous material particle) total void volume compared with this carbonaceous material before pre-treatment.In one embodiment, thus, pretreatment compositions is maintained the time of 5-600 minute or 10-360 minute at pretreatment temperature.
The pre-treatment of carbonaceous material can be carried out under any suitable atmosphere.In one embodiment, the pre-treatment of carbonaceous material is carried out under an inert atmosphere.In another embodiment, pre-treatment in reducing atmosphere, such as, is carried out under hydrogen and/or synthetic gas (" syn-gas ") pressure.In some embodiments, such as, at normal atmosphere to about 500psig, such as, under the pressure of about 100-450psig or about 200-350psig, pre-treatment is carried out.In other embodiments, under the pressure that pre-treatment limits at hydroconversion process, such as, under the pressure of about 300-5000psig as 500-3500psig, about 1000-3000psig or even about 1500-2600psig, carry out under reducing atmosphere.Any suitable synthetic gas can be used thus, such as, comprise the 1:1-2:1 mixture of hydrogen and carbon monoxide, and the optional synthetic gas also containing carbonic acid gas, methane and/or other component.
In one embodiment, such pre-treatment is carried out or is completed under being enough at least part of catalyzer or catalyst precursor to be deposited to the condition in solid carbonaceous substance between pre-treatment period.In the embodiment that some are such, one or more catalyzer or catalyst precursor and liquid contact with solid carbonaceous substance.
Comprise carbonaceous material, the pretreatment compositions of one or more catalyzer or catalyst precursor and hydrocarbonaceous liquid can be prepared in any suitable way.In one embodiment, carbonaceous material, catalyzer or catalyst precursor and hydrocarbonaceous liquid are simply mixed to form pretreatment compositions, and make this pretreatment compositions stand pretreatment condition.In another embodiment, under hydrocarbonaceous liquid exists, carbonaceous material is contacted with catalyzer or catalyst precursor, and make this pretreatment compositions stand pretreatment condition.In another embodiment, under one or more catalyzer or catalyst precursor and the existence of hydrocarbonaceous liquid, carbonaceous material is ground to produce the pretreatment compositions of slurry form; And make this pretreatment compositions stand pretreatment condition.In another embodiment, under hydrocarbonaceous liquid exists, carbonaceous material is ground to produce slurry; One or more catalyst precursors are joined in this slurry to form pretreatment compositions; Pretreatment condition is stood with making this pretreatment compositions.In other embodiments, preprocessing process start add catalyzer or catalyst precursor.In another embodiment, in whole preprocessing process, catalyzer or catalyst precursor is added at set intervals.In other embodiments, during pre-processing at least part of catalyzer or catalyst precursor are deposited on carbonaceous material.
After the pre-treatment of carbonaceous material, the catalyzer of carbonaceous material and dispersion or catalyst precursor, optionally together with hydrocarbonaceous liquid, form the charging of the improvement being used for hydroconversion process.The charging of this improvement can be used for any suitable hydroconversion process to prepare liquid and/or gaseous product.
Carbonaceous material
Carbonaceous material can be any suitable solid carbonaceous substance, such as any natural solid or be generally the carbonaceous material of solid.Particularly, such as carbonaceous material can be that coal is as hard coal, bituminous coals, secondary bituminous coals, brown coal or their any composition or mixture.Carbonaceous material can also be any containing heteroatomic solid carbonaceous substance or charging, and any heavy hydrocarbonaceous feed, such as coal, coke, mud coal, shale oil and/or similar substance are as any solid carbonaceous substance containing relatively high ratio of carbon-hydrogen or their composition or mixture.In some embodiments, carbonaceous material is have the particle of any suitable dimension or the form of fine particle at least partially.Such as, be the form that median size is less than the particle of about 0.5 inch at least about the carbonaceous material of 50 % by weight.In multiple embodiment, the form of the carbonaceous material being at least greater than 70 % by weight to be median size the be particle of about 0.1-0.4 inch.In one embodiment, the carbonaceous material being greater than about 80 % by weight is the form that mean diameter is less than the particle of about 0.25 inch.In another embodiment, the carbonaceous material being greater than 80wt% is mean diameter is 50 microns-500 microns, the form of the particle of such as 100 microns.Such particle can being formed in any suitable way such as by grinding carbonaceous material at least partially.In one embodiment, under one or more catalyzer or catalyst precursor and the existence of hydrocarbonaceous liquid, carbonaceous material is ground at least partially.In another embodiment, under hydrocarbonaceous liquid exists, grind the slurry of formation at least partially of carbonaceous material, and this slurry is mixed with one or more catalyzer or catalyst precursor by (such as subsequently).In other embodiments, under inertia or reducing atmosphere such as hydrogen, nitrogen, helium, argon gas, synthetic gas or their any composition or mixture, carbonaceous material is ground.Any method or equipment can be used to grind carbonaceous material, such as beater grinder, ball mill (such as wet-type ball mill, conical bell mill, rubber roll milling train), rod mill, or their combination.
Hydrocarbonaceous liquid
Hydrocarbonaceous liquid can be any suitable liquid (such as solvent or thinner) liquefied for carbonaceous material (such as solid carbonaceous substance is as coal) known in the art.In one embodiment, hydrocarbonaceous liquid is hydrogen donor solvent, such as, in hydrocracking condition, play any compound of hydrogen donor effect.Hydrocarbonaceous liquid can have any suitable hydrogen supply capacity (hydrogendonatability), such as, measured the hydrogen supply capacity being greater than about 1.0wt% by NMR.
In one embodiment, hydrocarbonaceous liquid comprises the derivative solvent of coal, or its cut.In another embodiment, hydrocarbonaceous liquid comprises the aromatic substance of hydrogenation, naphthenic hydrocarbon, aldehydes matter or similar compound, or their composition or mixture.In another embodiment, hydrocarbonaceous liquid comprises one or more aromatic substance, and such as one or more alkyl replace aromatic substance.Known during liquefying the solvent of hydrogen supply comprise such as dihydronaphthalene, C 10-C 12naphthane, six hydrogen fluorenes, dihydro-, tetrahydrochysene-, six hydrogen-and octahydro be luxuriant and rich with fragrance, C 12-C 13acenaphthene, tetrahydrochysene-, six hydrogen-and decahydro pyrene (decahydropyrene), two-, four-and octahydro anthracene, and other derivative of the aromatic substance of fractional saturation.They stand conventional hydro reactor by the in the future overhead product stream of arrogant steam distillation method and are prepared.Effective especially mixed solvent comprises initial boiling point for about 343 DEG C (650 °F) and full boiling point is the heavy gas oil fraction (so-called vacuum gas oil, or VGO) of about 538 DEG C (1000 °F).This stream comprises aromatic substance, the aromatic substance of hydrogenation, naphthene, aldehydes matter and similar compound.If use the solvent without the hydrogen that can supply, then hydrogen can be originated by another kind and be added.
The boiling point of solvent is generally the temperature being greater than 300 DEG C, such as the temperature of 450-900 or 650-850 °F.In one embodiment, fluid catalytic cracking (FCC) the type process oil fraction (FCC type technical oil (500 °F+cut)) of hydrocarbonaceous liquid to be boiling point be about 500 °F or higher temperature.In another embodiment, hydrocarbonaceous liquid is boiling point at the FCC type technical oil (" FCC type technical oil (500 °F-cut) ") of about 500 °F or lower temperature.In another embodiment, hydrocarbonaceous liquid is the FCC oil of hydrotreatment.In another embodiment, hydrocarbonaceous liquid is tetralin (1,2,3,4-tetralin).In another embodiment, hydrocarbonaceous liquid comprises the compound that one or more atmospheric boiling points are about 350-850 °F.
Can use the ratio of any suitable hydrocarbonaceous liquid and carbonaceous material (such as carbonaceous particles or even coal particle) in the context of the present invention, such as, be expressed as about 1:10-with the weight of this mixture and be about 10:1, as 1:6-is about 6:1, or about 1:2-is about 2:1.In one embodiment, the ratio of the hydrocarbonaceous liquid used in preprocessing process and carbonaceous material is about 1:1 for about 0.75:1-.
Catalyst precursor
The method that solid carbonaceous substance carries out transforming is included in catalyst composition and there is lower this carbonaceous material of heating.In multiple embodiment, the method that solid carbonaceous substance carries out transforming is included under at least one copper activity source exists and this solid carbonaceous substance is heated the time being enough to be formed by this solid carbonaceous substance product liquid.In multiple embodiment, the copper activity source being supplied to carbonaceous material is catalyst precursor form, and this catalyst precursor is by the chemical reaction with one or more reagent (reagent) and/or change into catalyzer by other suitable process any.Catalyst precursor can be oil soluble, oil-dispersing property, water-soluble and/or water dispersible.In multiple embodiment, under the method is included in pretreatment temperature and under at least one copper activity source exists, this solid carbonaceous substance is carried out pre-treatment; In presence of hydrogen this pretreated material is heated to above the invert point of described pretreatment temperature; And make the substance reaction of this heating be enough to be formed by this solid carbonaceous substance the time of product liquid.
Suitable catalyst precursor comprises:
A) copper metal;
B) mineral compound of cupric, the vitriol of such as copper, nitrate, carbonate, sulfide, oxysulfide, oxide compound and hydrous oxide, ammonium salt and heteropolyacid;
C) following organic acid salt: the acyclic and alicyclic aliphatic carboxylic acid (limiting examples comprises acetate, oxalate (oxylate), Citrate trianion) such as containing two or more carbon atoms;
D) organometallics of cupric, it comprises inner complex such as 1,3-diketone, quadrol, ethylenediamine tetraacetic acid (EDTA), phthalocyanine, thiocarbamate class, thiophosphoric acid salt (phosporothioate) and their composition or mixture (limiting examples comprises alkyl dithiocarbamic acid copper, alkyl dithiophosphoric acid copper); And/or,
E) mantoquita of following organic amine: such as aliphatic amine, aromatic amine, quaternary ammonium compound, or their composition or mixture, and
F) copper-bearing mineral, comprises copper sulfide mineral.
In multiple embodiment, method solid carbonaceous substance being carried out transforming also is included at least one second metal active source and there is lower this solid carbonaceous substance of heating.In multiple embodiment, the second metal chosen from Fe, molybdenum, tungsten, nickel, cobalt, titanium and tin.In the embodiment that some are such, the activated source being supplied to the metal of carbonaceous material is catalyst precursor form, and this catalyst precursor is by the chemical reaction with one or more reagent and/or change into catalyzer by other suitable process any.Catalyst precursor can be oil soluble, oil-dispersing property, water-soluble and/or water dispersible.
In multiple embodiment, the catalyst composition for solid carbonaceous substance being carried out transforming also comprises at least one iron activated source.The Suitable catalyst precursor of iron activated source is provided to comprise:
A) ferrous metal;
B) mineral compound of iron content, the vitriol of such as iron, nitrate, carbonate, sulfide, oxysulfide, oxide compound and hydrous oxide, ammonium salt and heteropolyacid;
C) following organic acid salt: the acyclic and alicyclic aliphatic carboxylic acid (limiting examples comprises acetate, oxalate, Citrate trianion) such as containing two or more carbon atoms;
D) organometallics of iron content, it comprises ferrocene, inner complex such as 1,3-diketone, quadrol, ethylenediamine tetraacetic acid (EDTA), phthalocyanine, thiocarbamate class, thiophosphoric acid salt and their composition or mixture (limiting examples comprises alkyl dithiocarbamic acid iron, alkyl dithiophosphoric acid iron); And/or,
E) molysite of following organic amine: such as aliphatic amine, aromatic amine, quaternary ammonium compound or their composition or mixture, and
F) iron-bearing mineral.
Catalyst precursor can be formed in any suitable manner before hydroconversion process.In one embodiment, such as, one or more catalyst precursors are by following formation:
A) by the activated source of hydrocarbonaceous liquid (such as liquefaction solvent) and at least one metal (such as metal oxide as ferriferous oxide, or containing, for example other compound of any suitable metal discussed in this article) mixing to form catalyst precursor,
B) this catalyst precursor and carbonaceous material are merged;
C) optionally with one or more catalyst precursors are formed among carbonaceous material or on mode make this mixture stand pretreatment condition (such as under hydrogen pressure); And
D) heating of this mixture is enough to the time forming product liquid.
In multiple embodiment, catalyst precursor is by following formation:
A) hydrocarbonaceous liquid (such as liquefaction solvent) is mixed to form catalyst precursor with at least one copper activity source and at least one second metal active source;
B) this catalyst precursor and carbonaceous material are merged;
C) optionally with one or more catalyst precursors are formed among carbonaceous material or on mode make this mixture stand pretreatment condition; And
D) heating of this mixture is enough to the time forming product liquid.
In multiple embodiment, catalyst precursor is by following formation:
A) hydrocarbonaceous liquid is mixed with at least one metal active source,
B) to make the metal-containing compound of sulfuration be that this mixture and vulcanizing agent merge (such as by making hydrogen sulfide pass this mixture or being joined in this mixture by elemental sulfur) by the mode of dispersibility,
C) mixture of described sulfuration and carbonaceous material are merged,
D) optionally with one or more catalyst precursors are formed among carbonaceous material or on mode make this mixture stand pretreatment condition; And
E) heating of this mixture is enough to the time forming product liquid.
In multiple embodiment, catalyst precursor is by following formation:
A) hydrocarbonaceous liquid is mixed with at least one metal active source;
B) this catalyst precursor and carbonaceous material are merged;
C) this mixture and vulcanizing agent are merged;
D) optionally with one or more catalyst precursors are formed among carbonaceous material or on mode make this mixture stand pretreatment condition; And
E) heating of this mixture is enough to the time forming product liquid.
In another embodiment, one or more catalyst precursors are by following formation:
A) one or more metal-containing compounds, vulcanizing agent and water are mixed to form soliquid,
B) this soliquid and hydrocarbonaceous liquid (such as liquefaction solvent) are merged to be displaced from suspension by water,
C) this suspension and carbonaceous material are merged,
D) optionally with one or more catalyst precursors are formed among carbonaceous material or on mode make this suspension stand pretreatment condition (such as under hydrogen pressure); And
E) heating of this mixture is enough to the time forming product liquid.
In another embodiment, one or more catalyst precursors are by following formation:
A) substantially do not exist in hydrocarbon oil condition, lower than at the temperature of about 177 DEG C, in aqueous phase, used by the group vib metallic compound containing ammonium hydrogen sulfide sulfuration to form prevulcanized product; And
B) with one or more catalyst precursors are formed among carbonaceous material or on mode, ammonia is isolated to form sulfur product from described prevulcanized product.
In another embodiment, one or more catalyst precursors are formed by comprising following method:
A) by copper activity source and the second metal active source and water mixing to form soliquid or solution;
B) be enough under the condition in the depositing to a bimetallic part at least partially of copper [comprise on being wherein deposited on deposit to any crack goed deep in solid carbonaceous substance internal volume, hole or other perforate surface on] solid carbonaceous substance, this soliquid or solution and solid carbonaceous substance are being merged;
C) solid carbonaceous substance and hydrocarbonaceous liquid (such as liquefaction solvent) above with the metal active source of deposition are merged; And
D) optionally with one or more catalyst precursors are formed among carbonaceous material or on mode make described suspension stand pretreatment condition (such as under hydrogen pressure); And
E) heating of this mixture is enough to the time forming product liquid.
In the embodiment that some are such, described method also comprises and being merged in soliquid or solution and active sulphur source and solid carbonaceous substance.
The catalystic material of any appropriate amount can be used in the context of the present invention by carbonaceous material hydrocracking.In one embodiment, the total weight that the mixture of catalyst precursor, carbonaceous material and hydrocarbonaceous liquid comprises based on this mixture is about 25-10000ppm(such as about 50-9000ppm, about 100-8000ppm, about 250-5000, about 500-3000ppm or even about 1000-2000ppm) one or more catalyzer of weight or catalyst precursor.The metal content of catalyzer or catalyst precursor refers to added metal, does not comprise the metal originally belonging to carbonaceous material or the metal eaten away from treatment facility.
Catalytic material can use by any suitable form in the context of the present invention, such as but not limited to particle form, is immersed in carbonaceous material, is dispersed in hydrogen donor solvent and/or dissolves in hydrogen donor solvent.In addition, catalytic material may be used for adopting in the method for fixed bed, moving-bed and ebullated bed and slurry reactor.
Can such as when liquefaction before or period when not adding other reactant, make this catalyst precursor change catalyzer into by thermolysis.In other embodiments, after pre-processing, one or more other reactants can be joined in pretreated carbonaceous material mixture (such as before liquefaction step or period), to change the catalyst precursor of dispersion into catalyzer.Any suitable reactant can be used thus, such as any suitable vulcanizing agent or reductive agent.
Vulcanizing agent component
In multiple embodiment, catalyst composition also comprises at least one active sulphur source.Use in those embodiments of catalyst precursor wherein, after pre-treatment step, then can add one or more sulphur compounds with the active catalyst by the activation of this catalyst precursor being its corresponding sulfuration.After the pre-treatment one or more sulphur compounds can be introduced in the optional position of system.In one embodiment, after carrying out preprocessing process and before pretreatment compositions is transported to fluidized zone, one or more sulphur compounds are incorporated in pretreating zone.In another embodiment, one or more sulphur compounds are incorporated in fluidized zone.
In one embodiment, catalyzer uses the vulcanizing agent of solution form to be prepared, and this vulcanizing agent is decomposed into hydrogen sulfide under current condition.Such vulcanizing agent with any suitable amount in Kaolinite Preparation of Catalyst, such as, can use to exceed the stoichiometric amount formed needed for catalyzer.In one embodiment, vulcanizing agent is that at least 3:1 exists with the mol ratio of sulphur and copper.In addition, any suitable vulcanizing agent (such as discussed about catalyst precursor) can be used above.
In one embodiment, vulcanizing agent is moisture ammonium sulfide.Such vulcanizing agent can be such as prepared by hydrogen sulfide and ammonia in any suitable way.The ammonium sulfide of this synthesis is soluble in water and can easily be stored in before the use in the aqueous solution in storage tank.
Suitable vulcanizing agent comprises any sulphur compound that such as can be easy to releasing pattern, such as the hydrocarbon of hydrogen sulfide, ammonium sulfide, dimethyl disulfide, ammonium sulfate, dithiocarbonic anhydride, elemental sulfur and sulfur-bearing.Preferred elemental sulfur in some embodiments, this is because its hypotoxicity, low cost and be easy to treatability.Other vulcanizing agent comprises such as ammonium sulfide, ammonium polysulfide, ammonium thiosulfate, Sulfothiorine, thiocarbamide, dimethyl thioether, tert-butyl polysulfide, tertiary nonylpolysulfide and their mixture.In another embodiment, vulcanizing agent is selected from alkali metalsulphide and/or alkaline earth sulfide, alkali metal hydrosulfide and/or alkaline-earth metal sulfhydrate, and their mixture.
Vulcanizing agent can add by any suitable form.In one embodiment, by elemental sulfur to distil powder type or join in the mixture of carbonaceous material as masterbatched dispersion (being such as purchased sulphur fine powder).The allotropic substance such as rhombic sulfur and monoclinic sulphur of elemental sulfur are also suitable for herein.In one embodiment, one or more sulphur compounds are the form of distillation powder (flowers of sulfur), molten sulfur, sulfur vapor or their combination or mixture.
Vulcanizing agent can use by any suitable concentration.In one embodiment, the sulphur concentration introduced makes the atomic ratio of sulphur and metal in catalyst precursor be about 10:1 for about 1:1-, such as, be that about 2:1-is about 8:1, about 2:1-and is about 7:1, about 2:1-and is about 6:1, about 2:1-and is about 9:1, about 2:1-and is about 8:1, about 2:1-7:1, about 3:1-and is about 9:1, about 3:1-and is about 8:1, about 3:1-and is about 7:1 or even about 3:1-is about 6:1.
Catalyzer
Catalyzer contains the active catalytic components of simple substance or compound form.Example comprises transition element, particularly the periodic table of elements is (as Handbook of Chemistry and Physics, 45th edition, Chemical Rubber Company, shown in 1964) IV-B, V-B, VI-B race or the fine particle of VIII, salt or compound.In multiple embodiment, alkaline earth element can be comprised, such as magnesium.In multiple embodiment, can comprise group of the lanthanides (or lanthanum race, or be sometimes called rare earth metal) element, it refers to that periodictable Atom ordinal number is 15 kinds of elements of 57-71.
Catalyzer can comprise when carrying out carbonaceous material (such as coal) and/or being suitable for any copper-containing substance of carbonaceous material (such as coal) hydroconversion process when carbonaceous material (such as coal) experiences suitable catalytic reaction condition.Catalyzer also comprises any suitable metal, such as, be selected from following metal: IIB race metal, IIIB race metal, IVA race metal, IVB race metal, VB race metal, group vib metal, VIIB race metal, group VIII metal, such as, or their composition or mixture, combine with one or more in oxygen, sulphur, nitrogen and phosphorus.In multiple embodiment, the second metal is selected from Fe, Mo, W, Co, Ni, Cu, Ti and Sn.
In multiple embodiment, the copper containing catalyst of sulfuration can be CuS-FeS, CuS-MoS 2, CuS-WS 2, CuS-CoS, CuS-NiS, ZnS-CuS, CuS-TiS2, CuS-SnS and their arbitrary composition and mixture such as CuS-MoS 2-TiS 2.In catalyst system, Cu can be rich phase (rich phase) or serve as doping agent.
As the catalyst component of catalyzer and the amount of the copper provided is enough to catalytic solid carbonaceous material is converted into liquid hydrocarbon; Equally, the bimetallic amount provided as catalyst component is enough to the conversion of catalytic solid carbonaceous material.In multiple embodiment, copper is to be present in catalyzer based on the amount of dry ashless coal 10ppm-10wt%.In the embodiment that some are such, copper is present in catalyzer with the amount of 0.1wt%-5wt%.Copper is the amount of 0.5wt%-2.5wt% as the exemplary amount that metal is present in catalyzer.
In multiple embodiment, the second metal in catalyzer exists in the amount based on dry ashless coal 10ppm-10wt%.In the embodiment that some are such, the second metal is present in catalyzer with the amount of 0.1wt%-5wt%.In the amount that the bimetallic exemplary amount of metal is 0.5wt%-2.5wt%.In the embodiment that some are such, the second metal in catalyzer is iron.So, iron is to be present in catalyzer based on the amount of dry ashless coal 10ppm-10wt%.In the embodiment that some are such, iron is present in catalyzer with the amount of 0.1wt%-5wt%.Iron is the amount of 0.5wt%-2.5wt% as the exemplary amount that metal is present in catalyzer.In multiple embodiment, the Cu in composition and the molecular ratio of other metal can be 0.1:1-10:1.
In multiple embodiment, catalytic material adds as following material: granular metal solid in small, broken bits, their the such as FeSx such as oxide compound, sulfide; From discarded fines such as iron, molybdenum and the nickel of metal refining process; The coal ash of the spent catalyst such as waste stream fluidized catalytic cracking fines, hydrotreatment fines, the recovery that crush and gelatin liquefaction solid residue.In multiple embodiment, copper and the second metal add by the granular solids of difference (separate).In other embodiments, catalyst composition comprises and is comparatively rich in copper and the comparatively poor particle containing the second amount of metal, or comprises the particle being comparatively rich in the second metal and comparatively poor copper content.In another embodiment, copper and other metal can be formed as catalyst precursor bimetal compound instead of be added in charging.As an example, Cu xfe (1-x)oOH is by using NH 3h 2o titration FeSO 4and CuSO 4mixture solution, then carries out oxidation to be prepared in fluidizing air at the temperature raised.Cu xfe (1-x)oOH can prevulcanized be Cu before mixing with charging xfe (1-x)s.
In multiple embodiment, between carbonaceous material transition phase, will granules of catalyst attachment, absorption at least partially, absorb, load in solid carbonaceous substance at least partially or with this at least partially solid carbonaceous substance be closely combined.In multiple embodiment, before pre-processing or period catalyzer or catalyst precursor be deposited in solid carbonaceous substance at least partially, it makes use or organic liquid so that described catalyzer or catalyst precursor are carried to carbonaceous material.In multiple embodiment, during step solid carbonaceous substance being heated to invert point or during conversion process, by being deposited at least partially on described material of catalyzer or catalyst precursor.
In one embodiment, catalyzer uses the metallic catalyst precursor of bag to be prepared, and described catalyst precursor comprises water-soluble copper component, such as cupric nitrate, copper sulfate, neutralized verdigris, cupric chloride or their mixture.In another embodiment, catalyzer uses the metallic catalyst precursor of bag to be prepared, described catalyst precursor comprises copper compound, it is solid state at least partly, such as water-insoluble copper compound is as copper carbonate, copper hydroxide, cupric phosphate, phosphorous acid copper, Tubercuprose, cupric sulfide, copper molybdate, cupric wolframate, cupric oxide, copper alloy is as copper-molybdenum alloy or copper-iron alloy, or their mixture.In another embodiment, catalyzer uses the metallic catalyst precursor of bag to be prepared, described catalyst precursor comprises water-soluble copper-bath, this solution optionally also comprises the second promoter metal compounds, the acetate of such as chosen from Fe, muriate, formate, nitrate, vitriol or their mixture with the iron component of solute state.In one embodiment, catalyzer uses the metallic catalyst precursor of bag to be prepared, and described catalyst precursor comprises copper sulfate solution.
In multiple embodiment, during pre-treatment step, during step carbonaceous material being heated to invert point, or during conversion process, at least part of granules of catalyst is disperseed as the particle be separated with described carbonaceous material.
In multiple embodiment, using catalyst dissolution in or be otherwise such as suspended in liquid phase as fine particle, emulsion droplet etc.Dispersion catalyzer can with hydrocarbonaceous liquid comes into contact before join in coal, it can join in hydrocarbonaceous liquid before contacting with coal, or it can join in coal-liquid slurry.In the embodiment that some are such, the catalyzer of dispersion adds with the form of the oil/water solution milk sap of the water-soluble cpds of catalyst hydrogenation component.The water-soluble salt of catalytic metal can be any water-soluble salt of metal catalyst substantially.Nitrate or acetate can be the most suitable forms of some metals.The non-limiting activated source of copper comprises cupric nitrate and venus crystals.The non-limiting source of iron is iron nitrate or ironic acetate.In multiple embodiment, also use metallo-organic complex such as ferrocene as source of iron.For molybdenum, tungsten or vanadium, can the preferably molybdate of complex salts such as basic metal or ammonium, tungstate or vanadate.The mixture of two or more metal-salts can also be used.Special salt is four hydration Ammonium Heptamolybdate [(NH 4) 6mo 7o 244H 2o], Nickelous nitrate hexahydrate [Ni (NO 3) 26H 2o] and Disodium tungstate (Na2WO4) dihydrate [NaWO 42H 2o].Can use any suitable method that salts solution is carried out emulsification in hydrocarbon medium.Dispersing and dissolving (dispersed dissolution) catalyzer can also be the oil-soluble compounds containing catalytic metal, such as ferrocene, phospho-molybdic acid, the naphthenate of molybdenum, chromium and vanadium, etc.Can be catalyst-solvent by suitable oil-soluble compounds converted in-situ.
In multiple embodiment, beaded catalyst comprises copper and the second metal as unsupported catalyst, this means that the component of this catalyzer does not combine with inorganic carrier such as silicon-dioxide, aluminum oxide, magnesium oxide, carbon etc. or do not have load thereon.In other embodiments, at least part of metal component of catalyst composition be combined with at least one inorganic carrier or tackiness agent or load thereon.Adhesive material can comprise any material of the tackiness agent be conventionally used as in hydrotreating catalyst.Suitable adhesive material comprises such as silicon-dioxide, and aluminum oxide is if (plan) boehmite, silica-alumina compound, gibbsite, titanium dioxide, zirconium white, cationic clay or anionic clay are as saponite, bentonite, kaolin, sepiolite or hydrotalcite or their combination or mixture.In one embodiment, one or more adhesive materials are selected from silicon-dioxide, the colloid silica of adulterated al, silica-alumina, aluminum oxide, titanium, zirconium white or their mixture.In another embodiment, adhesive material comprises the refractory oxide material of the titanium dioxide by oxide basis with at least 50 % by weight.Any suitable alumina adhesive can be used in catalyst preparation process.In one embodiment, the surface-area of alumina adhesive is 100-400m 2/ g, the volume of voids recorded by nitrogen adsorption method is 0.5-1.5m/g.Similarly, any suitable titanium dioxide tie agent can be used in catalyst preparation process.In one embodiment, the titanium dioxide of tackiness agent has the median size being less than 50 microns (being such as less than about 5 microns) and/or being greater than 0.005 micron.In another embodiment, the titanium dioxide of tackiness agent has 10-700m 2the BET surface-area of/g.
In some embodiments, adhesive material is the tackiness agent standing peptization.In another embodiment, the precursor of adhesive material uses in the preparation of catalyzer, is wherein effective by this precursor conversion during catalyst preparation process or functional adhesive.Thus, suitable adhesive material precursor comprises alkali metal aluminate (to obtain alumina adhesive), water glass (to obtain silica binder), the mixture (to obtain silica alumina tackiness agent) of alkali metal aluminate and water glass, two-, three-and/or the mixture (to produce cationic clay and/or anionic clay) of the mixture such as water-soluble salt of magnesium, aluminium and/or silicon in tetravalent metal source, chloro hydrol (chlorohydrol), Tai-Ace S 150, or their combination or mixture.In the situation of loaded catalyst, metal component (i.e. copper and the second metal component) is 10:1-1:10 with the weight ratio of carrier component.
In multiple embodiment, granules of catalyst comprise other component at least partially, such as catalyst promoting agent.This kind of promotor is selected from non-noble group VIII metal (such as Ni, Co, Fe), group vib metal (such as Cr), IVB race metal (such as Ti), IIB race metal (such as Zn), IB race metal (such as Cu) and their composition or mixture.
During conversion process, (within this period, solid carbonaceous substance contacts with the activated source of catalyst composition, and optionally at the temperature of 100-350 DEG C, carry out pre-treatment, then invert point carbonaceous material being converted into liquid substance is heated to), the activated source of catalyzer is converted into their activity form.This conversion process is promoted by being joined in catalyzer by sulphur.
The suitably metallics such as MoS of the copper material of sulfuration such as CuS and alkyl dithiocarbamic acid copper, alkyl dithiophosphoric acid copper and sulfuration 2, four thio ammonium molybdate, NiS, CoS, WS 2, SnS, TiS 2, CuS, FeS, Fe 2s 3, alkyl molybdenum dithiocarbamate, alkyl dithiocarbamic acid iron, alkyl dithiocarbamic acid titanium, alkyl dithiophosphoric acid iron directly can be used as catalyst precursor when not carrying out prevulcanized.For unvulcanized metal precursor, comprise the copper metal of copper base, copper oxide, venus crystals, cupric nitrate, copper sulfate and other mantoquita, copper mineral and copper organic compound; The ferrous metal of iron-based, ferriferous oxide, ferrous sulfate, iron nitrate and other molysite, red mud and other iron mineral, ferrocene and other ferric organic compounds, molybdenum base, tungsten base, Ni-based, copper base, titanium base, the metal of cobalt-based or tinbase, oxide compound, salt, mineral and organic compound etc., can use elemental sulfur or other vulcanizing agent such as DMDS, H 2s, CS 2(NH 4) 2catalyst precursor prevulcanized to form metallic sulfide, or is directly added vulcanizing agent with the atomic ratio by (S/ (other metal of Cu+))=1/1-10/1 by catalyzer suitably sulfuration at hydrocracking run duration by S.Or, one or more sulphur compounds can be added to activate catalyzer or catalyst precursor for its corresponding sulfurate activity catalyzer during pre-treatment step or afterwards.One or more sulphur compounds can be introduced in the optional position of system.One or more sulphur compounds of any suitable amount can be used in the context of the present invention.In one embodiment, after carrying out preprocessing process and before pretreatment compositions is transported to zone of transformation, one or more sulphur compounds are incorporated in pretreating zone.In another embodiment, one or more sulphur compounds are incorporated in conversion (namely liquefying) district.In one embodiment, the concentration of the sulphur introduced makes the atomic ratio of sulphur and metal in catalyzer be about 10:1 for about 2:1-.
Any suitable sulphur compound can be used thus.In one embodiment, vulcanizing agent is hydrogen sulfide (H 2s).In one embodiment, vulcanizing agent is the solution form being decomposed into hydrogen sulfide under current (prevailing) condition, exists to exceed the stoichiometric amount formed needed for catalyzer.In another embodiment, vulcanizing agent is selected from ammonium sulfide, ammonium polysulfide ((NH 4) 2s x), ammonium thiosulfate ((NH 4) 2s 2o 3), Sulfothiorine (Na 2s 2o 3), thiocarbamide (CSN 2h 4), dithiocarbonic anhydride (CS 2), dimethyl disulfide (DMDS), dimethyl thioether (DMS), tert-butyl polysulfide (PSTB), tertiary nonylpolysulfide (PSTN) and their mixture.In another embodiment, vulcanizing agent is selected from elemental sulfur and sulfur-bearing hydrocarbon.In another embodiment, vulcanizing agent is selected from alkali metalsulphide and/or alkaline earth sulfide, alkali metal hydrosulfide and/or alkaline-earth metal sulfhydrate, and their mixture.The use of the vulcanizing agent containing basic metal and/or alkaline-earth metal, can need other separate process steps basic metal and/or alkaline-earth metal to be removed from spent catalyst.
Can by elemental sulfur to distil powder type or join in pretreatment compositions as masterbatched dispersion (being such as purchased sulphur fine powder).The allotropic substance such as rhombic sulfur and monoclinic sulphur of elemental sulfur are also suitable for herein.In one embodiment, one or more sulphur compounds are the form of distillation powder (flowers of sulfur), molten sulfur, sulphur steam or their combination or mixture.
Other additive
During pre-treatment step or any other additive can be utilized subsequently, such as to strengthen or to promote pretreatment process (such as by strengthening, promote and/or strengthening catalyzer or catalyst precursor is distributed in carbonaceous material) and/or to strengthen or promote the hydrocracking of pretreated carbonaceous material.
Any suitable tensio-active agent can be utilized in the context of the present invention, such as to improve the dispersiveness of catalyzer or catalyst precursor, metal surface area, form and/or other characteristic.Suitable tensio-active agent comprises such as any anion surfactant, zwitterionic tensio-active agent, amphoterics, nonionogenic tenside, cats product, or their combination or mixture.Suitable nonionogenic tenside comprises such as polyoxyethylene sorbitol mono-laurate, polyoxyethylene groups alkylphenol, polyoxyethylene groups alkyl phenol ethoxylates etc.Suitable cats product comprises the organic quaternary amine of such as long-chain, the organic quaternary amine of polyethoxylated long-chain etc., such as water-soluble cationic amine (such as cetyltrimethylammonium bromide, CTAB, dodecyl trimethyl ammonium amine (amine), nonyl trimethyl ammonium chloride, dodecyl phenol quaternary amine soap or their composition or mixture).Suitable anion surfactant such as sodium succinate compound comprises such as dioctyl sodium sulphosuccinate or two (2-ethylhexyl) sodium sulfosuccinate).Suitable tensio-active agent also can comprise the vehicle substance with high surface tension properties, such as ethylene carbonate; Benzophenone; Benzyl cyanide; Oil of mirbane; 2-phenylethyl alcohol; 1,3-PD; BDO; 1,5-PD; Diethylene Glycol; Triethylene glycol; Glycerine; Dimethyl sulfoxide (DMSO); N-METHYLFORMAMIDE; N-Methyl pyrrolidone; With their composition or mixture.Suitable tensio-active agent also comprises and has high those tensio-active agents capillary, such as N-Methyl pyrrolidone.Other example of tensio-active agent comprises acetonitrile, acetone, ethyl acetate, hexane, diethyl ether, methyl alcohol, ethanol, methyl ethyl diketone, diethyl carbonate, chloroform, methylene dichloride, diethyl ketone and their composition or mixture.In another embodiment, tensio-active agent comprises the organic additive of the nitrogenous or phosphorus with the carbon thioether phase improving catalytic activity.To be added usually depend on that the expectation of final catalyst composition is active containing N/ containing the amount of P organic additive.
In another embodiment, tensio-active agent is formula R 1r 2r 3r 4the ammonium of Q+ or phosphorus, wherein Q is nitrogen or phosphorus, wherein R 1, R 2, R 3, R 4in at least one be aryl or alkyl (the such as C with 8-36 carbon atom 10h 21, C 16h 33, C 18h 37or their combination), and wherein remaining R 1, R 2, R 3, R 4be selected from hydrogen, there is the alkyl of 1-5 carbon atom or their combination.This kind of suitable example of tensio-active agent comprises: cetyltrimethyl ammonium, cetyl trimethyl phosphorus, octadecyl trimethyl phosphorus, cetyl pyridinium, ammonium, decyl trimethyl ammonium, dodecyl trimethyl ammonium, dimethyl two (dodecyl) ammonium (dimethyldidbdecylammonium) or their combination or mixture.The compound deriving above-mentioned ammonium or phosphorus can be such as oxyhydroxide, halogenide, silicate or their combination or mixture.
In one embodiment, tensio-active agent comprises nitrogenous organic additive, such as aromatic amine, cyclic aliphatic amine, polycyclic aliphatic amine or their combination or mixture.In another embodiment, tensio-active agent comprises and is selected from following nitrogenous organic additive: the compound (such as hexamethylene-diamine, monoethanolamine, diethanolamine, trolamine, N, N-dimethyl-N '-ethylethylene residue diamines or their combination or mixture) containing at least one primary amine, secondary amine and/or tertiary amine group; Amino alcohol (such as 2 (2-aminoethylamino) ethanol, 2 (2-amino ethoxy or its combination or mixture) ethanol, 2-amino-n-butyl alcohol, 4-amino-n-butyl alcohol, 2,2-diethoxy ethamine, 4,4-diethoxy butylamine, 6-amino-1-hexanol, 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 3-amino-1-propyl alcohol, or their combination or mixture); With aminoalkoxy-silane (such as 3-glycidoxypropyl) Trimethoxy silane, 3-(2-aminoethylamino) propyl trimethoxy silicane, 3-aminopropyl) Trimethoxy silane or their combination or mixture).
In another embodiment, tensio-active agent is organic carboxylic acid surfactant or stablizer.In one embodiment, such as tensio-active agent is citric acid.In another embodiment, tensio-active agent is pentadecylic acid, capric acid or other similar long chain acid.In still another embodiment, tensio-active agent is alginic acid.
Optional additives can use in any suitable moment before or after preprocessing process and/or hydroconversion process.In one embodiment, before pre-processing one or more in one or more additives and carbonaceous material, hydrocarbonaceous liquid and one or more catalyzer or catalyst precursor is merged.In another embodiment, during preprocessing process, additive and carbonaceous material, hydrocarbonaceous liquid and catalyzer or catalyst precursor are merged.In another embodiment, after pre-processing with before hydrocracking additive and pretreated carbonaceous material are merged.In still another embodiment, after hydroconversion process, additive and pretreated carbonaceous material are merged.
Additive can use by any suitable concentration.In one embodiment, such as, additive uses with the concentration of the about 0.001-5 % by weight of total preconditioned mixture.In another embodiment, additive uses with the concentration of the about 0.005-3 % by weight of total preconditioned mixture.In another embodiment, additive uses with the concentration of the about 0.01-2 % by weight of total preconditioned mixture.If separately additive is joined in hydrocracking charging, such as at such as ActaPetrolei Sinica, Vol.19, Issue 4, pp.36-44, ISSN 10018719 and Khimiya I Tekhnologiya Topilv I Masel, Issue 3, Year 1997, pp.20-21, (their content be incorporated in full herein with it by reference) described in ISSN 00231169, amount to be added is the 0.001-0.05 % by weight (such as about 0.005-0.01 % by weight) of charging, or adds with any suitable concentration.
Mixing
Can use any suitable method or system that carbonaceous material and hydrocarbonaceous liquid and catalyzer or catalyst precursor are merged and/or mixed.In some embodiments, use any suitable mixing tank in the mode being suitable for being formed as required homogeneous or heterogeneous mixture (or slurry) by carbonaceous material, hydrocarbonaceous liquid and catalyzer or catalyst precursor simultaneously, in succession and/or continuously mix.In other embodiments, by mixing tank and any suitable shredder coupling (such as beater grinder, ball mill, rod mill or their combination etc.), make optionally under hydrocarbonaceous liquid and/or one or more catalyzer or catalyst precursor exist, to grind carbonaceous material at least partially, and mixed the homogeneous that formed as required or heterogeneous slurry.In some embodiments, mixing tank and/or shredder air inclusion delivery system in order to provide inertia or reducing atmosphere (such as hydrogen, nitrogen, helium, argon gas, synthetic gas or their any composition or mixture) during the mixing and/or grinding of carbonaceous material, hydrocarbonaceous liquid and/or catalyzer or catalyst precursor.In some embodiments, mixing tank and/or shredder are positioned at the upstream of pretreatment system.In other embodiments, mixing tank and/or shredder form a part for pretreatment system.In multiple embodiment, the catalyst precursor for the method in the coal being directly mixed into grinding before entering in reactor or other carbonaceous material, or can join in coal during the grinding of coal solvent.By use methanol/ethanol or water as solvating agent/wetting agent beginning profit method by catalyst dissolution to be ejected on coal or be impregnated on coal.Also can catalyzer be dispersed or dissolved in solvent, then it be mixed with coal.
Describe embodiment of the present invention in FIG.The coal charging 3 average particulate diameter of at least 50wt% coal particle being less than 0.5 inch merges with catalytic material 5, the mol ratio that described catalytic material comprises copper and iron is copper activity source and the iron activated source of 0.1/1-10/1, composition 1 is delivered to the temperature of reaction of preheating oven 20 in order to be heated to 350 DEG C-500 DEG C.Then the heating combination 23 of the coal and catalytic material that leave this preheating oven is delivered to reaction zone 30 in order at least part of coal is converted into product liquid 33.
Now consider the illustrative methods of the present invention described in Fig. 2, the coal charging 103 average particulate diameter of at least 50wt% coal particle being less than 0.5 inch merges with catalytic material 105, the mol ratio that described catalytic material comprises copper and iron is copper activity source and the iron activated source of 0.1/1-10/1, composition 101 is delivered to pretreating zone 110 in order to said composition is maintained time of 5-600 minute at the pretreatment temperature of 100-350 DEG C.After the pre-treatment, composition 113 is delivered to the temperature of reaction in order to be heated to 350 DEG C-500 DEG C in preheating oven 120.Then the heating combination 123 of the coal and catalytic material that leave this preheating oven is delivered to reaction zone 130 in order at least part of coal is converted into product liquid 133.
Now consider illustrative methods of the present invention described in Fig. 3, pretreating zone 210 is delivered in the coal charging 203 being 50 microns-500 microns by the average particulate diameter of at least 80wt% coal particle.In special illustrative methods, coal as powder feeding to pretreating zone.In another illustrative methods, coal is as the slurry in hydrocarbonaceous liquid, and the cut that such as coal is derivative supplies.
Be that the copper activity source of 3/1-1/3 and the catalytic material 205 of iron activated source merge in pretreating zone with coal particle by the mol ratio comprising cobalt and iron.In one embodiment, copper is supplied to pretreating zone as the aqueous solution of mantoquita such as cupric nitrate, cupric chloride, copper sulfate, venus crystals, cupric sulfide, copper oxide or copper carbonate or slurry.Iron is supplied to pretreating zone as the aqueous solution of molysite such as iron nitrate, iron(ic) chloride, ferric sulfate, ironic acetate, iron sulfide, ferriferous oxide or iron carbonate or slurry.In another embodiment, copper and iron add as the organometallics be included in cut that liquid such as coal derives.Exemplary organometallics comprises alkyl dithiocarbamic acid copper and ferrocene.Active sulphur source 207 is joined in pretreating zone to provide the sulphur of 2/1-6/1 and catalytic metal atom ratio.Also hydrogen or hydrogen-containing gas 209 are supplied to pretreating zone and are in normal atmosphere in 500psig to make the pressure in this pretreating zone maintain.In another embodiment, hydrogen or hydrogen-containing gas are supplied to pretreating zone to be in 500psig-3500psig to make the pressure in pretreating zone maintain.Material in pretreating zone is maintained the pretreatment temperature of 180-220 DEG C and the time of lasting 5-600 minute.After the pre-treatment, composition 213 is delivered to the temperature of reaction in order to be heated to 350 DEG C-500 DEG C in preheating oven 220.Then the heating combination 223 of the coal and catalytic material that leave this preheating oven is delivered to reaction zone 230 in order at least part of coal is converted into product liquid 233.
Now consider illustrative methods of the present invention described in Fig. 4, pretreating zone 310 is delivered in the coal charging 303 that the average particulate diameter of at least 50wt% coal particle is less than 0.5 inch.To the catalytic material 307 in copper activity source be comprised and comprise the catalytic material 309 of iron activated source, think the copper of 0.1/1-10/1 and the mol ratio of iron, merge in pretreating zone with coal particle, and by the pretreatment temperature maintenance time of 5-600 minute of said composition at 100-350 DEG C.After the pre-treatment, composition 313 is delivered to the temperature of reaction in order to be heated to 350 DEG C-500 DEG C in preheating oven 320.Then the heating combination 323 of the coal and catalytic material that leave this preheating oven is delivered to reaction zone 330 in order at least part of coal is converted into product liquid 333.
Hydrocracking
After pre-treatment, make carbonaceous material stand any suitable hydrocracking and/or liquefaction condition to produce the product being rich in hydrocarbonaceous material, described hydrocarbonaceous material comprises any required liquid and/or gaseous product.Carbonaceous material (such as coal) is incorporated at least one hydroconversion zone, run into suitable temperature, pressure and additive (such as sulfocompound) in this this pretreated carbonaceous material all to activate at least partly or substantially with the catalyzer or catalyst precursor that make this pretreated carbonaceous material, and produce liquid and/or gaseous product.In one embodiment, such as, the catalyzer of pretreated carbonaceous material or catalyst precursor be greater than about 50 % by weight, such as about 55 % by weight, about 60 % by weight, about 65 % by weight, about 70 % by weight, about 75 % by weight, about 80 % by weight, about 85 % by weight, about 90 % by weight, about 95 % by weight, about 96 % by weight, about 97 % by weight, about 98 % by weight or even about 99 % by weight become active catalyst, it is had and/or shows hydrocracking activity.
Suitable hydrocracking temperature includes but not limited to be greater than about 350 DEG C, such as, be greater than the temperature of about 375 DEG C, about 400 DEG C, about 425 DEG C, about 450 DEG C, about 475 DEG C, about 500 DEG C.In the embodiment that some are such, the step of the material of heating being carried out hydrocracking is implemented at the temperature of 350 DEG C-500 DEG C.In the embodiment that some are such, the material of heating is reacted in hydroconversion steps the time of at least 10 minutes.
Suitable hydrocracking pressure includes but not limited to 300-5000psig(such as about 300-4800psig, about 300-4600psig, about 300-4400psig, about 300-4200psig, about 400-4000psig, about 500-3500psig, 1000-3000psig, 1200-2800psig, 1400-2600psig or even about 1500-2600psig) any suitable gas such as containing gas (such as hydrogen/methane mixture or the hydrogen/carbonic acid gas/water mixture) atmosphere of hydrogen and/or synthetic gas atmosphere.In one embodiment, thus, pretreated carbonaceous material is suitable for low or lower hydrocracking pressure (being such as less than about 2000psig, as being less than about 1800psig or being even less than the hydrocracking pressure of about 1600psig).Particularly, such as, compared with not pretreated identical carbonaceous material, be less than about 2000psig(at hydrocracking pressure and be such as less than about 1800psig, or be even less than about 1600psig) under, the hydrocracking of pretreated carbonaceous material can produce to exceed and such as exceed at least about 20%, about 40%, about 60%, about 80%, about 100%, about 150%, about 200%, about 300% or even at least about 400% at least about 10%() liquid product yield.In another embodiment, compared to not pretreated identical carbonaceous material, the hydrocracking consumption of pretreated carbonaceous material reduces that about 10%(such as reduces about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90% or even about 100%) hydrogen.
In multiple embodiment, the hydrocracking of solid carbonaceous substance was completed by the time being enough to the heating of this solid carbonaceous substance to be formed product liquid.In the embodiment that some are such, heat solid carbonaceous material under at least one copper activity source and at least one second metal active source exist.In the embodiment that some are such, to be greater than under the temperature of reaction of 350 DEG C and in the heating under pressure solid carbonaceous substance of 300-5000psig.In the embodiment that some are such, heat solid carbonaceous material under the temperature of reaction of 350 DEG C-500 DEG C.In some embodiments, solid carbonaceous substance is heated the time of 5 minutes-600 minutes.
In one embodiment, carbonaceous material hydrocracking and/or liquefaction carry out in single reactor.In another embodiment, the hydrocracking of carbonaceous material and/or liquefaction are carried out in two or more (such as multiple) are for the region of hydrocracking or reactor, described region or reactor can be arranged in any suitable way (such as by parallel or series system, such as, temperature in each reactor of connecting being improved gradually and/or the corresponding raising of hydrogen partial pressure in each downstream reactor).Preferably, the hydrocracking of pretreated carbonaceous material and/or liquefaction are separating from preatreating reactors or region and/or are carrying out in different reactors or region.
In one embodiment, the hydrocracking of carbonaceous material and/or liquefaction produce be greater than about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 87%, about 90%, about 95% or be even greater than about 99% liquid yield.In one embodiment, compared with the liquid product yield of similar carbonaceous material not pretreated before hydrocracking, the pre-treatment of carbonaceous material produces to exceed and such as exceeds at least about 15%, about 20%, about 25%, about 30%, about 35% or even at least about 40% at least about 10%() liquid yield.In another embodiment, the hydrocracking of pretreated carbonaceous material and/or liquefaction produce be greater than about 80%, about 85%, about 90%, about 95% or even 99% total conversion rate (total conversion rate of such as coal).
In some embodiments, compared with the transformation efficiency of similar carbonaceous material not pretreated before hydrocracking, the pre-treatment of carbonaceous material produces to exceed and such as exceeds at least about 10%, about 12%, about 14%, about 16%, about 18% or even at least about 20% at least about 5%() total conversion rate (total conversion rate of such as coal).In other embodiments, the hydrocracking of pretreated carbonaceous material and/or liquefaction generation be less than that about 10%(is such as less than about 8%, about 6%, about 4%, about 3%, about 2% or be even less than about 1%) C 1-C 3gas.
The separation of hydroconverted products
Effluent from hydroconversion zone can be added in any suitable one or more disengaging zone.In one embodiment, effluent is added in the first disengaging zone, in this disengaging zone, removes lighter product such as gas, petroleum naphtha and distillment by overhead line.The first disengaging zone like this can be run at substantially atmospheric pressure.Optionally by from the first disengaging zone the bottoms of effluent or high boiling fraction be recycled to hydroconversion reactions district.Can all or some of the residual stream effluent of the first disengaging zone be sent in the second disengaging zone, in this disengaging zone, be fractionated into gas oil fraction and bottoms cut.The bottoms cut of the second disengaging zone can be sent in the 3rd disengaging zone.A part for gas oil can be recycled to hydroconversion zone.Thus, any suitable high pressure, middle pressure and light pressure separator can be used in the context of the present invention.
The recovery of catalyzer or catalyst precursor
Can then be one or more catalyzer and/or metal recovery system or region behind one or more separation system or region, wherein reclaim from one or more part of hydrocracking carbonaceous material or cut catalyzer and/or catalyst precursor (such as one or more metals) at least partially.In one embodiment, in recovery system, from the solid fraction (such as residual solid fraction) of the hydrocracking carbonaceous material isolated separation system and/or collect (it can comprise ash), retrieve the metal from metallic catalyzer and/or metallic catalyst precursor.
Can at any suitable temperature, such as, at about 1200-1900 DEG C, such as about 1300-1800 DEG C or even operate recovery system at the temperature of 1400-1700 DEG C.In one embodiment, be in the situation of molybdenum at metal, such as at the U.S. Patent application No.60/015 that on December 19th, 2007 submits to, its content is incorporated to herein with it by 096(by reference in full) described in, recovery system provides and is suitable for spent catalyst (such as moly-sulfide) is oxidized and distils as MoO 3air atmosphere.Can collect treated spent catalyst, catalyst precursor and/or recovery metal and they are sent to catalyzer from catalyst recovery zone or catalyst precursor prepares district.
The preparation of catalyzer or catalyst precursor
Can then be one or more catalyzer or catalyst precursor preparation system after one or more recovery system, wherein make (metal of such as catalyst precursor) at least partially of catalyzer or the catalyst precursor reclaimed in recovery system to react to form catalyzer or catalyst precursor (such as with initial for by catalyzer identical for carbonaceous material pre-treatment or catalyst precursor).
In one embodiment, such as, Footwall drift (the such as MoO of catalyzer or catalyst precursor is made 3) react to form four thio ammonium molybdate catalyst precursor with sulphur compound (such as ammonium sulfide).Then the catalyzer formed by gained or catalyst precursor, optional and new or fresh catalyst precursor combines, and is transported to pretreatment system and/or hydrocracking system.
The sign of catalyzer
In multiple embodiment, at least part of solid carbonaceous substance being converted into product liquid in active catalyzer, there is formula (R p) i(M t) a(L u) b(S v) d(C w) e(H x) f(O y) g(N z) hand there is form and the dispersing characteristic of improvement, technology known in the art can be used to characterize, and described technology comprises ultimate analysis, Surface area analysis (BET), grain size analysis (PSA), powder x-ray diffraction (PXRD), scanning electron microscopy (SEM), can fall apart x-ray analysis (EDS) and other method.In one approach, electron microscope method is used to match (complement) with X-ray diffraction research.In another approach, the surface-area of BET method to catalyzer is used to measure.In another method, scanning tunnel microscope method (STM) and density functional theory (DFT) can be used to characterize catalyzer.
Formula (R p) i(M t) a(L u) b(S v) d(C w) e(H x) f(O y) g(N z) hthe feature of catalyzer be, in coal upgrading, depend on the configuration of process for upgrading and the concentration of used catalyst and excellent transformation efficiency be provided.In one embodiment, the transformation efficiency that slurry catalyst provides is at least 70% in the first embodiment, and be at least 75% in this second embodiment, be at least 80% in the 3rd embodiment, is at least 90% in the 4th embodiment.At use formula (R p) i(M t) a(L u) b(S v) d(C w) e(H x) f(O y) g(N z) hin an embodiment of the coal upgrading system of catalyzer, be the product compared with lightweight by the coal feedstock conversion of at least 98wt.%.In this second embodiment, by product that the coal feedstock conversion of at least 98.5% is compared with lightweight.In the 3rd embodiment, transformation efficiency is at least 99%.In the 4th embodiment, transformation efficiency is at least 95%.In the 5th embodiment, transformation efficiency is at least 80%.As used herein, transformation efficiency refers to the conversion of coal raw material to the material lower than 1200 °F of (650 DEG C) boiling points.
In one embodiment, catalyzer has the pore volume of the 0.05-5.0ml/g measured according to N2 adsorption.In this second embodiment, pore volume is 0.1-4.0ml/g, such as 0.1-3.0ml/g or 0.1-2.0ml/g.
In multiple embodiment, catalyzer has at least 5m by being measured by B.E.T. method 2/ g, or at least 10m 2/ g, or at least 50m 2/ g, or be greater than 100m 2/ g, or be greater than 200m 2the surface-area of/g.In multiple embodiment, for being greater than 100m 2the total surface area of/g, the feature of catalyzer is the aggregate of the crystal grain into 10-20 dust.
In multiple embodiment, catalyzer has the particle diameter of nanometer to micron (μm) size.The granules of catalyst of exemplary suspension has the median particle diameter of 0.0005-1000 micron, or the median particle diameter of 0.001-500 micron, or the median particle diameter of 0.005-100 micron, or the median particle diameter of 0.05-50 micron.In multiple embodiment, the feature of the catalyzer of suspension form is the median particle diameter of 30nm-6000nm.In multiple embodiment, catalyzer has the median size of 0.3-20 μm.
In multiple embodiment, catalyzer comprise molecular scale and/or for colloid size (be namely less than 1 micron or be less than 0.1 micron or for 0.1-0.001 micron) the granules of catalyst of nano sized particles.In some embodiments, make catalyzer with 1-100 nanoparticulate dispersed at coal on the surface by being immersed in by catalyst precursor on coal.In some embodiments, catalyzer forms slurry catalyst in hydrocarbon diluent, and have colloidal solid " nanocluster (cluster) ", this nanocluster has the median size of 1-100 micron.
As in embodiment below further describe, system and method described herein can be used for obtaining optimization and validity in any required liquid of ratio (or Percent yield) with various desired properties and/or the preparation of gaseous product.Particularly, under various hydrocracking condition (such as at low hydrogen pressure and/or under the short time length) by selecting hydrocarbonaceous liquid, any various combination of catalyzer and/or catalyst precursor and pre-treatment and hydrocracking condition can realize FR hydroconverted products.By this way, this system and method is great handiness for user provides, and this handiness makes it possible to use hydrocarbonaceous liquid, any various various combination of catalyzer and/or catalyst precursor and pre-treatment and hydrocracking condition obtains required hydroconverted products by any solid carbonaceous substance.
Embodiment
embodiment 1 (Fe/Zn)
Test 1--prepares the mixed catalyst precursor iron nitrate (Fe (NO be dissolved in methyl alcohol 3) 39H 2and zinc nitrate (Zn (NO O) 3) 26H 2o) solution.To reach with the coal feed sample that the solution of 1:1 and coal weight ratio impregnated granules size are less than 100 object moisture-frees (being namely less than 1 % by weight water) with this solution and begin to moisten, obtain based on the iron carrying capacity of drying ashless (daf) base meter 1% iron for coal, based on the zinc carrying capacity of dry ash-free basis meter 1wt% zinc for coal.Then under a nitrogen in this coal through catalyst soakage of 105 DEG C of dryings until 24 hours thus removing methyl alcohol.Using the coal through catalyst soakage of drying and the FCC type technical oil (500 °F+cut) as solvent with the ratio of solvent and coal for 1.6:1 mixes.Elemental sulfur is added with by iron and zinc sulfuration with the sulphur of 2:1 and iron mol ratio and the sulphur of 2:1 and the ratio of zinc.Then in a reservoir this mixture is heated rapidly to 200 DEG C, and keeps 2 hours at 200 DEG C, and the hydrogen partial pressure simultaneously in this container brings up to about 1000psia from about 100psia.Then under the hydrogen partial pressure of 2500psia, this mixture is heated to 430 DEG C further, keeps 3 hours at 430 DEG C afterwards.After 3 hours, by the reaction vessel quenching of the solvent containing sulfuration and coal mixtures, hydrogen and any reaction product to room temperature.By product gas (CO, CO 2, C 1, C 2and C 3) discharged by wet type tester (wet test meter) to determine gas recovery ratio.By filtering solid (mainly unconverted coal), ash and catalyst vulcanization thing and product liquid (C 4 +) be separated.Coal transformation efficiency is performed as follows mensuration:
Coal transformation efficiency=(solid-(catalyzer of the ash+recovery in coal) of recovery)/coal charging
The solvent added during by deducting on-test, by the coal measurement stand oil yield of dry ash-free basis.Tabular product yield in tablei.
Test 2--use zinc nitrate as catalyst precursor, in for coal based on the zinc carrying capacity of dry ash-free basis 2wt% zinc, revision test 1.Elemental sulfur is added with by zinc sulfuration with the sulphur of 2:1 and the ratio of zinc.Tabular product yield in tablei.
Test 3-use iron nitrate as catalyst precursor, in for coal based on the iron carrying capacity of dry ash-free basis 2wt% iron, revision test 1.Elemental sulfur is added with by iron sulfuration with the sulphur of 2:1 and the ratio of iron.The product yield display of tabular in Table I, the catalyst composition containing iron and zinc produces much higher liquid yield and coal transformation efficiency than the catalyzer separately containing iron or zinc.
embodiment 2 (Fe/Cu)
Test 4--uses iron nitrate (Fe (NO 3) 39H 2and cupric nitrate (CuNO O) 3) 22.5H 2o) catalyst precursor mixed, in for coal based on the iron carrying capacity of dry ash-free basis 1wt% iron, with based on the copper carrying capacity of dry ash-free basis meter 1wt% copper for coal, revision test 1.Elemental sulfur is added with by iron and copper sulfuration with the sulphur of 2:1 and iron mol ratio and the sulphur of 2:1 and the ratio of copper.List shows product yield in table ii.
Test 5--use cupric nitrate as catalyst precursor, in for coal based on the nickel carrying capacity of dry ash-free basis 2wt% copper, revision test 1.Elemental sulfur is added with by copper sulfuration with the sulphur of 2:1 and copper mol ratio.List shows product yield in table ii.
Embodiment 3(Zn/Cu)
Test 6--uses zinc nitrate (Zn (NO 3) 36H 2and cupric nitrate (CuNO O) 3) 22.5H 2o) catalyst precursor mixed, in for coal based on the zinc carrying capacity of dry ash-free basis 1wt% zinc, with based on the copper carrying capacity of dry ash-free basis meter 1wt% copper for coal, revision test 1.Elemental sulfur is added with the ratio of copper with the sulphur of 2:1 and zinc mol ratio and the sulphur of 2:1.List shows product yield in table iii.
Test 7--use cupric nitrate as catalyst precursor, in for coal based on the nickel carrying capacity of dry ash-free basis 2wt% copper, revision test 1.Elemental sulfur is added with by copper sulfuration with the sulphur of 2:1 and copper mol ratio.List shows product yield in table iii.

Claims (10)

1. solid carbonaceous substance is converted into a method for product liquid, the method comprises:
A) preparation comprises the mixture of at least one copper activity source and at least one iron activated source;
B) this mixture and coal are merged with the coal particle formed containing catalyzer;
C) hydrocarbonaceous liquid carrying is fed to this coal particle containing catalyzer to prepare composition;
D) the pre-treatment said composition time of at least 5-600 minute under the pretreatment temperature within the scope of 180-220 DEG C;
E) said composition is delivered to hydroconversion reactions district and described coal particle is enough to described coal particle to be converted into boiling point at least partially at C being greater than to maintain under the pressure under the temperature of reaction of 350 DEG C with at 300-5000psig 5to the time of the product liquid in the temperature ranges of 650 DEG C.
2. the method for claim 1, the dry described coal particle containing catalyzer before the method is also included in and described composition delivered to the step in hydroconversion reactions district.
3. the process of claim 1 wherein described mixture also comprises surfactant.
4. the method for claim 1, also comprises to described composition supply active sulphur source.
5. the method for claim 4, wherein supplies active sulphur source with the atomic ratio of the sulphur of 0.1:1-10:1 and metal.
6. the method for claim 1, the method also comprises and hydrogen or hydrogen-containing gas is supplied to hydroconversion reactions district and maintains described solid carbonaceous substance under hydrogen or hydrogen-containing gas exist.
7. the method for claim 1, described composition is carried out pre-treatment under being also included in the existence in active sulphur source by the method.
8. the method for claim 1, described composition is carried out pre-treatment under being also included in hydrogen or hydrogen-containing gas existence by the method.
9. the process of claim 1 wherein that copper exists in the amount based on dry ashless coal 10ppm-10wt%.
10. the process of claim 1 wherein that described iron exists in the amount based on dry ashless coal 10ppm-10wt%.
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