CN102666791A - Hydrogenation of solid carbonaceous materials using mixed catalysts - Google Patents

Hydrogenation of solid carbonaceous materials using mixed catalysts Download PDF

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CN102666791A
CN102666791A CN2010800530811A CN201080053081A CN102666791A CN 102666791 A CN102666791 A CN 102666791A CN 2010800530811 A CN2010800530811 A CN 2010800530811A CN 201080053081 A CN201080053081 A CN 201080053081A CN 102666791 A CN102666791 A CN 102666791A
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carbonaceousmaterial
metal
coal
titanium
catalyzer
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CN102666791B (en
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A·E·库珀曼
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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  • 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 titanium and at least one active source of a second metal at a reaction temperature of greater than 350 DEG C 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 with the solid carbonaceous substance hydrogenation
Technical field
The present invention relates to be used for carbonaceousmaterial carry out pre-treatment, with carbonaceousmaterial liquefaction and the system and method that improves the carbonaceousmaterial liquefaction efficiency.
Background technology
For many years about by solid carbonaceous substance for example the coal method that obtains the liquids and gases product made a lot of work.Known method comprises two kinds of catalyzed reaction and uncatalyzed reactions.In catalysis process, hydrocarbonaceous material typically is to carry out pulp with solvent and catalyzer, and makes its reaction under the temperature and pressure that raises in the presence of molecular hydrogen.
For example, USP 5,246,570 have described a kind of coal liquefaction method, wherein in preheater, the mixture of coal, catalyzer and solvent are heated rapidly to the temperature of 600-750 Fahrenheit degree, make then under its gelatin liquefaction condition in liquefaction reaction and react.USP 5; 573; 556 have described and a kind of carbonaceousmaterial have been converted into the normally method of the product of liquid; This method comprises the slurry that comprises carbonaceousmaterial, contains hydrocarbon solvent and catalyst precursor is heated to and is enough to make said catalyst precursor to be converted into the temperature of corresponding catalyst and this slurry is incorporated in the fluidized zone.USP 5,783,065 has described a kind of coal liquefaction method, and this method comprises with having the active catalyst soakage coal particle of hydrogenation or hydrogenolysis; Coal particle with dipping under at least about 400 ℃ temperature was incorporated in the turbulent flow of hydrogen-containing gas in the very short time; Be quenched to significantly temperature with the temperature that makes product less than 400 ℃.
Such ordinary method is that liquid and/or gas recovery ratio and the liquid that is obtained by such method and/or the quality of gaseous product of improving the carbonaceousmaterial of hydrocracking stay a lot of leeway.Therefore, still need be used for the system and method for the improvement of carbonaceousmaterial hydrocracking, and the feed material that is used for the improvement of such system and method.
Summary of the invention
The present invention relates to a kind of solid carbonaceous substance is converted into the method for product liquid, this method is included at least a titanium activated source and at least a second metal active source and exists and make solid carbonaceous substance under greater than 350 ℃ temperature of reaction and under the pressure at 300-5000psig, keep the time that is enough to form product liquid down.
On the one hand, this method comprises the compsn in preparation solid carbonaceous substance, at least a hydrocarbonaceous liquid, at least a titanium activated source and at least a second metal active source; With said composition deliver to the hydroconversion reactions district and with said solid carbonaceous substance under greater than 350 ℃ temperature of reaction and keep at least a portion that is enough to said solid carbonaceous substance under the pressure at 300-5000psig and be converted into boiling point at C 5The time of the product liquid to 650 ℃ the TR.
In others, the step for preparing said compsn comprises that preparation comprises the mixture at least a nickel activated source and at least a second metal active source; This mixture and coal are merged the coal particle that contains catalyzer with formation; Hydrocarbonaceous liquid is provided to this coal particle that contains catalyzer to prepare said compsn.
On the other hand, prepare said method for compositions and also be included in the before dry said coal that contains catalyzer of step of said compsn being delivered to the hydroconversion reactions district.
In others, this method also is included in to be delivered to said compsn before the hydroconversion reactions district, under 100-350 ℃ pretreatment temperature, said compsn is carried out pre-treatment and continues 5-600 minute time.
In others, before the pre-treatment step, during or afterwards, in said preparation of compositions, at least a active sulphur source is joined in the said solid carbonaceous substance, wherein the atomic ratio of sulphur and metal component is 1/1-10/1.
On the one hand, second metal is an iron.
As follows the of the present invention some embodiments that comprise the above-mentioned aspect of the present invention will be described in further detail.Usually, only if this paper indicates in addition, each in these aspects can be used with specific combined by various with others and embodiment.
Accompanying drawing is briefly described
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 have described the embodiment of the method that solid carbonaceous substance is transformed.
Detail
In whole specification sheets, will use following term, only and if other explanations are arranged, following term will have following meanings.
Term " catalyst precursor " be used for this paper be meant can through with one or more reagent (for example vulcanizing agent and/or reductive agent such as hydrogen; For example in the hydrocarbon medium) chemical reaction takes place and/or change the compound of catalyzer into through any other suitable processing (for example thermal treatment, the shock heating processing of multistep, pressure treatment or their any combination), wherein catalyst precursor at least partly is decomposed into catalyzer.
Term " activated source " is used for this paper and is meant to catalyzer or catalyst precursor or can be converted into atoms of elements, molecule, complex compound or any other form of catalyzer or catalyst precursor.Activated source can be solution, slurry or particle form.When through plating for example, dipping, coating or brush when being deposited on activated source on the solid carbonaceous substance, can the mixture of single-activity source or activated source be deposited on the individual particles of solid carbonaceous substance.
Term " catalytic material " is used to be meant one or more active catalysts or catalyst precursor.The component of catalytic material can be slurry or particle form.During with particle form, can there be single or multiple catalyzer on the individual particles.Equally; When through plating for example, dipping, coating or brush when being deposited on catalytic material on the solid carbonaceous substance, can the single catalyst that constitute catalytic material or catalyst mixture or precursor mixture be deposited on 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 moisture determination and ASTM3174 and is used for ash content and quantizes.
" d " block elements is meant the element that the d subgrade of cycle atom is filled.Instance comprises iron, molybdenum, nickel, manganese, vanadium, tungsten, cobalt, copper, titanium, chromium, platinum, palladium, cerium, zirconium, zinc and tin.
Group of the lanthanides (or lanthanum family, perhaps be called rare earth metal sometimes) element is meant that cycle atom ordinal number is 15 kinds of elements of 57-71.
" oil-dispersing property " compound is represented that compound scatters or is dispersed in and is formed dispersion-s in the oil.In one embodiment, the oil-dispersing property compound is oil soluble, and it dissolves when mixing with oil.
With regard to the disclosure, unless otherwise prescribed, catalyst composition is defined as the compsn that joins the activated source in the technology, and with hydrocracking during the form of catalytic elements irrelevant.
The present invention relates to be used for comprising coal, shale oil, vacuum residuum and biofuel the raw material for example composition and the preparation manipulation of the sulfurized nickel-containing catalyst of the carbonaceousmaterial hydrocracking of xylogen.The invention still further relates in the presence of the nickeliferous catalyst composition of bag solid carbonaceous substance is converted into the hydrogenating conversion process of product liquid.In a plurality of embodiments, the invention still further relates to the method that carbonaceousmaterial is transformed, this method is included under the pretreatment temperature and in the presence of at least a nickel activated source and at least a second metal active source, solid carbonaceous substance is carried out pre-treatment; In the presence of hydrogen, said pretreated material is heated to above the invert point of said pretreatment temperature; And the substance reaction that makes this heating is enough to formed by said solid carbonaceous substance the time of converted product.
Catalyst-type (Catalyst Formula)
In one embodiment, catalyzer is formed and is represented 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) hBe meant catalyst solid in this this formula, thereby in oil, constitute catalyst pulp.In this formula, M and L be at least a " d " block elements of indication cycle's table separately, for example iron, molybdenum, nickel, manganese, vanadium, tungsten, cobalt, copper, titanium, chromium, platinum, palladium, cerium, zirconium, zinc and tin.M is different with L.R chooses wantonly, at least a lanthanon of its indication cycle's table, for example La, Ce, Nd etc.In another embodiment, R is a for example magnesium of at least a earth alkali metal.
In this external this formula, p, t, u, v, w, x, y, z represent the total charge of various components (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; M and L have subscript a and b, and the value of a and b is respectively 0-5, and (0 ≤b/a ≤5); S representes that the value of subscript d is the sulphur of 0.5 (a+b) to 5 (a+b); C representes that subscript e has the carbon of the value of 0 to 11 (a+b); H is that the value of f is the hydrogen of 0 to 7 (a+b); O representes that the value of g is the oxygen of 0 to 5 (a+b); Represent that with N h has the nitrogen of the value of 0 to 2 (a+b).
In a plurality of embodiments, M is an iron, and L is titanium (or vice versa).In some such embodiments, catalyzer has formula (Fe zTi 1-z) a(S) d(C) e(H) f(O) g(N) h, wherein titanium is 9:1-1:9 (in wt.%) with the ratio of iron.In some such embodiments, titanium is 1:5-5:1 with the ratio of iron; Or 1:10-1:5.
Pretreatment process
In a plurality of embodiments; The present invention relates to carbonaceousmaterial is carried out pretreated system and method; This system and method is used for making one or more catalyzer or catalyst precursor to be distributed to carbonaceousmaterial; In order to improve the transformation efficiency of carbonaceousmaterial (for example natural solid carbonaceousmaterial such as coal), has reactive carbonaceousmaterial of raising in order to preparation, in order to improve the efficient of carbonaceousmaterial (for example coal) liquefaction to liquid and/or gaseous product; This efficient is for example measured through transformation efficiency and liquid yield, and/or in order to reduce the hydrogen consumption during carbonaceousmaterial liquefies.
In one embodiment, this pre-treatment of carbonaceousmaterial use during pre-treatment step, do not take place basically the carbonaceousmaterial hydrocracking (promptly wherein less than about 20%, less than about 10% or even transform less than about 1% carbonaceousmaterial) reaction conditions (perhaps a plurality of conditions such as temperature, pressure and/or the combination of pre-treatment time length) implement or accomplish.Any suitable method capable of using or operational condition are come the pre-treatment carbonaceousmaterial.In one embodiment; Pretreatment compositions is heated to enough temperature so that one or more catalyzer or catalyst precursor are distributed in the carbonaceousmaterial, and makes it under this pretreatment temperature, keep, control and/or keep time enough or sustained periods of time so that one or more catalyzer or catalyst precursor are distributed to the dispersion that reaches required degree in the carbonaceousmaterial, integrated (integration) and/or homogeneity.In one embodiment, pretreatment compositions is heated to about 100-350 ℃ temperature (for example about 150-300 ℃ or even about 180-220 ℃).In some such embodiments, said pre-treatment step under about 100-350 ℃ temperature about 10-360 minute.
Preferably make pretreatment compositions under pretreatment temperature, keep, keep and/or control time enough or sustained periods of time so that carbonaceousmaterial swelling and allow catalyzer or catalyst precursor to be distributed in the carbonaceousmaterial (for example to disperse fully and/or homodisperse).In one embodiment; For example, with pretreatment compositions in suitable temperature maintenance, control and/or keep the suitable time length and improve about 5% or about more than 25% so that this carbonaceousmaterial (or each carbonaceousmaterial particle) before carbonaceousmaterial and the pre-treatment is compared total void volume.In one embodiment, thus, pretreatment compositions is kept the time of 5-600 minute or 10-360 minute at pretreatment temperature.
The pre-treatment of carbonaceousmaterial can be carried out under any suitable atmosphere.In one embodiment, the pre-treatment of carbonaceousmaterial is carried out under inert atmosphere.In another embodiment, pre-treatment is for example carried out under hydrogen and/or synthetic gas (" syn-gas ") pressure in reducing atmosphere.In some embodiments, for example, to about 500psig, carry out pre-treatment under the pressure of for example about 100-450psig or about 200-350psig at normal atmosphere.In other embodiments, pre-treatment under the pressure that hydroconversion process limits, for example about 300-5000psig such as 500-3500psig, about 1000-3000psig or even the pressure of about 1500-2600psig under, under reducing atmosphere, carry out.Can use any suitable synthetic gas thus, for example comprise the 1:1-2:1 mixture of hydrogen and carbon monoxide, and the optional synthetic gas that also contains carbonic acid gas, methane and/or other component.
In one embodiment, such pre-treatment is being enough in part catalyzer or catalyst precursor deposit to and carry out under the condition on the solid carbonaceous substance or accomplish at least between pre-treatment period.In some such embodiments, one or more catalyzer or catalyst precursor and liquid contact with solid carbonaceous substance.
The pretreatment compositions that comprises carbonaceousmaterial, one or more catalyzer or catalyst precursor and hydrocarbonaceous liquid can prepare in any suitable way.In one embodiment, carbonaceousmaterial, catalyzer or catalyst precursor and hydrocarbonaceous liquid are simply mixed with the formation pretreatment compositions, and make this pretreatment compositions stand pretreatment condition.In another embodiment, carbonaceousmaterial is contacted with catalyzer or catalyst precursor, and make this pretreatment compositions stand pretreatment condition.In another embodiment, in the presence of one or more catalyzer or catalyst precursor and hydrocarbonaceous liquid, grind carbonaceousmaterial to produce the pretreatment compositions of slurry form; And make this pretreatment compositions stand pretreatment condition.In another embodiment, in the presence of hydrocarbonaceous liquid, grind carbonaceousmaterial to produce slurry; One or more catalyst precursors are joined in this slurry to form pretreatment compositions; With make this pretreatment compositions stand pretreatment condition.In other embodiments, begin to add catalyzer or catalyst precursor at preprocessing process.In another embodiment, in whole preprocessing process, add catalyzer or catalyst precursor at set intervals.In other embodiments, part catalyzer or catalyst precursor are deposited on the carbonaceousmaterial at least during pre-processing.
After the pre-treatment of carbonaceousmaterial, carbonaceousmaterial and dispersed catalyst or catalyst precursor, optional with hydrocarbonaceous liquid, be formed for the improved charging of hydroconversion process.This improved charging can be used for any suitable hydroconversion process with preparation liquid and/or gaseous product.
Carbonaceousmaterial
Carbonaceousmaterial can be any suitable solid carbonaceous substance, for example any natural solid or be generally the solid carbonaceousmaterial.Particularly, for example carbonaceousmaterial can be coal such as hard coal, bituminous coals, inferior bituminous coals, brown coal or their any compsn or mixture.Carbonaceousmaterial can also be any contain heteroatomic solid carbonaceous substance or charging; And any heavy hydrocarbonaceous feed, for example coal, coke, mud coal, shale oil and/or similar substance are like any solid carbonaceous substance of containing high relatively ratio of carbon-hydrogen or their compsn or mixture.In some embodiments, at least a portion of carbonaceousmaterial is particle or the particulate form in small, broken bits with any suitable dimension.For example, the carbonaceousmaterial at least about 50 weight % is that median size is less than about 0.5 inch particulate form.In a plurality of embodiments, the carbonaceousmaterial greater than 70 weight % is that median size is the particulate form of about 0.1-0.4 inch at least.In one embodiment, the carbonaceousmaterial greater than about 80 weight % is that mean diameter is less than about 0.25 inch particulate form.In another embodiment, the carbonaceousmaterial greater than 80wt% is that mean diameter is 50 microns-500 microns for example 100 microns particulate forms.Such particle can for example form through at least a portion of grinding carbonaceousmaterial in any suitable way.In one embodiment, in the presence of one or more catalyzer or catalyst precursor and hydrocarbonaceous liquid, grind at least a portion of carbonaceousmaterial.In another embodiment, at least a portion of in the presence of hydrocarbonaceous liquid, grinding carbonaceousmaterial forms slurry, and (for example subsequently) mixes this slurry with one or more catalyzer or catalyst precursor.In other embodiments, for example grind carbonaceousmaterial under hydrogen, nitrogen, helium, argon gas, synthetic gas or their any compsn or the mixture in inertia or reducing atmosphere.Can use any method or equipment to grind carbonaceousmaterial, beater grinder for example, ball mill (for example wet-type ball mill, conical bell mill, rubber roll milling train), rod mill, perhaps their combination.
Hydrocarbonaceous liquid
Hydrocarbonaceous liquid can be any suitable liquid (for example solvent or thinner) that is used for carbonaceousmaterial (for example solid carbonaceous substance such as coal) liquefaction known in the art.In one embodiment, hydrocarbonaceous liquid is that hydrogen is given the body solvent, for example in the hydrocracking condition, plays any compound of hydrogen to the body effect.Hydrocarbonaceous liquid can have any suitable hydrogen supply capacity (hydrogen donatability), for example measures the hydrogen supply capacity of about 1.0wt% through NMR.
In one embodiment, hydrocarbonaceous liquid comprises coal deutero-solvent, or its cut.In another embodiment, hydrocarbonaceous liquid comprises hydrogenant aromatic substance, naphthenic hydrocarbon, aldehydes matter or similar compound, perhaps their compsn or mixture.In another embodiment, hydrocarbonaceous liquid comprises one or more aromatic substance, and for example one or more alkyl replace aromatic substance.Known during liquefying the solvent of hydrogen supply comprise for example dihydronaphthalene, C 10-C 12Naphthane, six hydrogen fluorenes, dihydro-, tetrahydrochysene-, six hydrogen-and octahydro is luxuriant and rich with fragrance, C 12-C 13Acenaphthene, tetrahydrochysene-, six hydrogen-and decahydro pyrene (decahydropyrene), two-, four-and octahydro anthracene, and other verivate of the aromatic substance of fractional saturation.They can stand conventional hydrogenator through the overhead product materials flow of arrogant steam distillation method in the future and prepare.Especially effectively mixed solvent comprises that initial boiling point is that about 343 ℃ (650 ° of F) and full boiling point are the heavy gas oil fraction (so-called vacuum gas oil, or VGO) of about 538 ℃ (1000 ° of F).This materials flow comprises aromatic substance, hydrogenant aromatic substance, naphthene, aldehydes matter and similar compound.If use the solvent that does not have the hydrogen that can supply, then hydrogen can be added by the another kind source.
The boiling point of solvent is generally the temperature greater than 300 ℃, for example the temperature of 450-900 or 650-850 ° F.In one embodiment, hydrocarbonaceous liquid is that boiling point is FCC (FCC) the type process oil fraction (FCC type technical oil (cuts of 500 ° of F+)) of about 500 ° of F or higher temperature.In another embodiment, hydrocarbonaceous liquid is boiling point at about 500 ° of F or the FCC type technical oil of low temperature (" FCC type technical oil (cuts of 500 ° of F-) ") more.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 of one or more atmospheric boiling points for about 350-850 ° F.
Can in context of the present invention, use any suitable hydrocarbonaceous liquid and the ratio of carbonaceousmaterial (for example carbonaceous particles or even coal particle), for example, be expressed as the about 10:1 of about 1:10-with the weight of this mixture, like the about 6:1 of 1:6-, or the about 2:1 of about 1:2-.In one embodiment, the hydrocarbonaceous liquid that uses in the preprocessing process is the about 1:1 of about 0.75:1-with the ratio of carbonaceousmaterial.
Catalyst precursor
The method that solid carbonaceous substance is transformed is included in catalyst composition existence this carbonaceousmaterial of heating down.In a plurality of embodiments, the method that solid carbonaceous substance is transformed is included in the time that at least a titanium activated source exists is enough to this solid carbonaceous substance heating to be formed by this solid carbonaceous substance product liquid down.In a plurality of embodiments, the titanium activated source that offers carbonaceousmaterial is the catalyst precursor form, and this catalyst precursor can be through changing into catalyzer with the chemical reaction of one or more reagent (reagent) and/or through any other suitable processing.Catalyst precursor can be oil soluble, oil-dispersing property, water-soluble and/or water dispersible.In a plurality of embodiments, this method is included under the pretreatment temperature and in the presence of at least a titanium activated source carries out pre-treatment with this solid carbonaceous substance; The invert point that will this pretreated material in the presence of hydrogen be heated to above said pretreatment temperature; And the substance reaction that makes this heating is enough to formed by this solid carbonaceous substance the time of product liquid.
The appropriate catalyst precursor comprises:
A) titanium metal;
B) titaniferous mineral compound, the vitriol of titanium for example, nitrate salt, 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) that for example contains two or more carbon atoms;
D) titaniferous organometallics; It comprises inner complex for example 1; 3-diketone, quadrol, YD 30, phthalocyanine, thiocarbamate class, thiophosphoric acid salt (phosporothioate) and their compsn or mixture (limiting examples comprises alkyl dithiocarbamic acid titanium, alkyl dithiophosphoric acid titanium); And/or,
E) titanium salt of following organic amine: for example aliphatic amine, aromatic amine, quaternary ammonium compound, perhaps their compsn or mixture, and
F) titaniferous ore.
In a plurality of embodiments, the method that solid carbonaceous substance is transformed also is included at least a second metal active source existence this solid carbonaceous substance of heating down.In a plurality of embodiments, the second metal chosen from Fe, molybdenum, tungsten, nickel, cobalt, titanium and tin.In some such embodiments, the activated source that offers the metal of carbonaceousmaterial is the catalyst precursor form, and this catalyst precursor can be through changing into catalyzer with the chemical reaction of one or more reagent and/or through any other suitable processing.Catalyst precursor can be oil soluble, oil-dispersing property, water-soluble and/or water dispersible.
In a plurality of embodiments, the catalyst composition that is used for that solid carbonaceous substance is transformed also comprises at least a iron activated source.Provide the suitable catalyst precursor of iron activated source to comprise:
A) ferrous metal;
B) ferruginous mineral compound, the vitriol of iron for example, nitrate salt, 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) that for example contains two or more carbon atoms;
D) ferruginous organometallics; It comprises ferrocene; Inner complex for example 1; 3-diketone, quadrol, YD 30, phthalocyanine, thiocarbamate class, thiophosphoric acid salt and their compsn or mixture (limiting examples comprises alkyl dithiocarbamic acid iron, alkyl dithiophosphoric acid iron); And/or,
E) molysite of following organic amine: for example aliphatic amine, aromatic amine, quaternary ammonium compound or their compsn or mixture and
F) iron content inorganics.
Catalyst precursor can form before hydroconversion process in any suitable manner.In one embodiment, for example, one or more catalyst precursors are through following formation:
A) activated source of hydrocarbonaceous liquid (for example liquefaction solvent) and at least a metal (for example MOX such as ferriferous oxide, or contain other compound of any suitable metal of discussing just like this paper) is mixed forming catalyst precursor,
B) this catalyst precursor and carbonaceousmaterial are merged;
C) randomly so that one or more catalyst precursors are formed among the carbonaceousmaterial or on mode make this mixture stand pretreatment condition (for example under hydrogen pressure); And
D) this mixture heating up is enough to form time of product liquid.
In a plurality of embodiments, catalyst precursor is through following formation:
A) hydrocarbonaceous liquid (for example liquefaction solvent) is mixed with at least a titanium activated source and at least a second metal active source to form catalyst precursor;
B) this catalyst precursor and carbonaceousmaterial are merged;
C) randomly so that one or more catalyst precursors are formed among the carbonaceousmaterial or on mode make this mixture stand pretreatment condition; And
D) this mixture heating up is enough to form time of product liquid.
In a plurality of embodiments, catalyst precursor is through following formation:
A) hydrocarbonaceous liquid is mixed with at least a metal active source,
B) so that being the mode of dispersibility, sulfurized containing metal compound this mixture and vulcanizing agent are merged (for example perhaps elemental sulfur being joined in this mixture) through making hydrogen sulfide pass this mixture,
C) said sulfurized mixture and carbonaceousmaterial are merged,
D) randomly so that one or more catalyst precursors are formed among the carbonaceousmaterial or on mode make this mixture stand pretreatment condition; And
E) this mixture heating up is enough to form time of product liquid.
In a plurality of embodiments, catalyst precursor is through following formation:
A) hydrocarbonaceous liquid is mixed with at least a metal active source;
B) this catalyst precursor and carbonaceousmaterial are merged;
C) this mixture and vulcanizing agent are merged;
D) randomly so that one or more catalyst precursors are formed among the carbonaceousmaterial or on mode make this mixture stand pretreatment condition; And
E) this mixture heating up is enough to form time of product liquid.
In another embodiment, one or more catalyst precursors are through following formation:
A) one or more containing metal compounds, vulcanizing agent and water are mixed with the formation soliquid,
B) this soliquid and hydrocarbonaceous liquid (for example liquefaction solvent) are merged so that water is displaced from suspension-s,
C) this suspension-s and carbonaceousmaterial are merged,
D) randomly so that one or more catalyst precursors are formed among the carbonaceousmaterial or on mode make this suspension-s stand pretreatment condition (for example under hydrogen pressure); And
E) this mixture heating up is enough to form time of product liquid.
In another embodiment, one or more catalyst precursors are through following formation:
A) do not exist basically in the situation of hydrocarbon ils, be lower than under about 177 ℃ temperature, the group vib metallic compound that will contain ammonium vulcanizes to form the prevulcanized product with hydrogen sulfide at aqueous phase; And
B) so that one or more catalyst precursors are formed among the carbonaceousmaterial or on mode, ammonia is isolated from said prevulcanized product to form sulfur product.
In another embodiment, one or more catalyst precursors form through comprising following method:
A) titanium activated source and the second metal active source and water are mixed to form soliquid or solution;
B) at least a portion of titanium and the part of second metal are deposited under the condition on [comprise on wherein being deposited on and depositing on the surface of going deep into any crack, hole or other perforate in the solid carbonaceous substance internal volume] solid carbonaceous substance being enough to, this soliquid or solution and solid carbonaceous substance are merged;
C) will above have a sedimentary metal active source solid carbonaceous substance and hydrocarbonaceous liquid (for example liquefaction solvent) merging; And
D) randomly so that one or more catalyst precursors are formed among the carbonaceousmaterial or on mode make said suspension-s stand pretreatment condition (for example under hydrogen pressure); And
E) this mixture heating up is enough to form time of product liquid.
In some such embodiments, said method also comprises soliquid or solution and active sulphur source and solid carbonaceous substance merging.
The catalystic material that in context of the present invention, can use any appropriate amount is with the carbonaceousmaterial hydrocracking.In one embodiment, catalyst precursor, carbonaceousmaterial and hydrocarbonaceous mixtures of liquids comprise one or more catalyzer or the catalyst precursor of the about 25-10000ppm of gross weight meter (for example about 50-9000ppm, about 100-8000ppm, about 250-5000, about 500-3000ppm or even the about 1000-2000ppm) weight based on this mixture.In a plurality of embodiments, the metal content of catalyzer or catalyst precursor is meant the metal that is added, and does not comprise belonging to the metal of carbonaceousmaterial or the metal that eats away from treatment facility originally.
Catalystic material can use by any suitable form in context of the present invention, such as but not limited to particle form, be immersed in the carbonaceousmaterial, be dispersed in hydrogen and give in the body solvent and/or dissolve in hydrogen and give in the body solvent.In addition, catalystic material can be used for adopting the method for fixed bed, moving-bed and liquid bed and slurry reactor.
Can be for example before the liquefaction or during under the situation that does not add other reactant, make this catalyst precursor change catalyzer into through thermolysis.In other embodiments, after pre-treatment, can the reactant that one or more are other join in the pretreated carbonaceousmaterial mixture (for example before liquefaction step or during), to change the dispersed catalyst precursor into catalyzer.Can use any suitable reactant thus, for example any suitable vulcanizing agent or reductive agent.
The vulcanizing agent component
In a plurality of embodiments, catalyst composition also comprises at least a active sulphur source.Use therein in those embodiments of catalyst precursor, can after pre-treatment step, then add one or more sulphur compounds so that this catalyst precursor activation is its corresponding sulfurized active catalyst.Can after pre-treatment, one or more sulphur compounds 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 the pretreating zone.In another embodiment, one or more sulphur compounds are incorporated in the fluidized zone.
In one embodiment, catalyzer uses the vulcanizing agent of solution form to prepare, and this vulcanizing agent can resolve into hydrogen sulfide under underlying condition.Such vulcanizing agent can for example form the required stoichiometric amount use of catalyzer to surpass with any appropriate vol in the preparation catalyzer.In one embodiment, vulcanizing agent exists for 3:1 at least with the mol ratio of sulphur and nickel.In addition, can use any suitable vulcanizing agent (for example preceding text are discussed about catalyst precursor).
In one embodiment, vulcanizing agent is moisture ammonium sulfide.Such vulcanizing agent can for example be prepared by hydrogen sulfide and ammonia in any suitable way.This synthetic ammonium sulfide is soluble in water and before using, can easily be stored in the aqueous solution in the storage tank.
Suitable vulcanizing agent comprises any sulphur compound that for example can be easy to releasing pattern, the for example hydrocarbon of hydrogen sulfide, ammonium sulfide, NSC 9370, ammonium sulfate, dithiocarbonic anhydride, elemental sulfur and sulfur-bearing.Preferred in some embodiments elemental sulfur, this is because of its hypotoxicity, low cost and is easy to the property handled.Other vulcanizing agent comprises for example ammonium sulfide, ammonium polysulfide, ammonium thiosulfate, Sulfothiorine, thiocarbamide, dimethyl thioether, tertiary butyl polysulfide, uncle's nonyl polysulfide and their mixture.In another embodiment, vulcanizing agent is selected from alkali metalsulphide and/or alkaline earth sulfide, alkali metal hydrosulfide and/or earth alkali metal sulfhydrate and their mixture.
Vulcanizing agent can add by any suitable form.In one embodiment, elemental sulfur is joined in the mixture of carbonaceousmaterial with the distillation powder type or as concentrated dispersion-s (for example being purchased the sulphur fine powder).The allotropic substance of elemental sulfur for example rhombic sulfur and monoclinic sulphur also is suitable for this paper.In one embodiment, one or more sulphur compounds are distillation powder (flowers of sulfur), molten sulfur, sulphur steam or their combination or the form of mixture.
Vulcanizing agent can use by any suitable concentration.In one embodiment; The sulphur concentration of introducing makes that the atomic ratio of sulphur and metal is the about 10:1 of about 1:1-in the catalyst precursor, for example is the about 8:1 of about 2:1-, the about 7:1 of about 2:1-, the about 6:1 of about 2:1-, the about 9:1 of about 2:1-, the about 8:1 of about 2:1-, about 2:1-7:1, the about 9:1 of about 3:1-, the about 8:1 of about 3:1-, the about 7:1 of about 3:1-or even the about 6:1 of about 3:1-.
Catalyzer
Catalyzer contains the active catalytic components of simple substance or compound form.Instance comprises transition element; Particularly the periodic table of elements is (like Handbook of Chemistry and Physics; The 45th edition, Chemical Rubber Company is shown in 1964) particle in small, broken bits, salt or the compound of IV-B, V-B, VI-B family or VIII family.In a plurality of embodiments, can comprise alkaline earth element, for example magnesium.In a plurality of embodiments, can comprise group of the lanthanides (or lanthanum family, perhaps be called rare earth metal sometimes) element, it is meant that cycle atom ordinal number is 15 kinds of elements of 57-71.
Catalyzer can comprise when any titanium-containing materials that carbonaceousmaterial (for example coal) is carried out and/or when carbonaceousmaterial (for example coal) experiences suitable catalytic reaction condition, be suitable for carbonaceousmaterial (for example coal) hydroconversion process.Catalyzer also comprises any suitable metal; For example; Be selected from following metal: IIB family metal, IIIB family metal, IVA family metal, IVB family metal, VB family metal, group vib metal, VIIB family metal, VIII family metal; Perhaps their compsn or mixture, for example with oxygen, sulphur, nitrogen and phosphorus in one or more combinations.In a plurality of embodiments, second metal is selected from Fe, Mo, W, Co, Ni, Cu, Ti and Sn.
In a plurality of embodiments, the sulfurized cobalt-containing catalyst can be TiS-FeS, TiS-MoS 2, TiS-WS 2, TiS-CoS, TiS-NiS, TiS-CuS, ZnS-TiS2, TiS-SnS and their arbitrary composition and mixture TiS-MoS for example 2-TiS 2In catalyst system, Ti can be rich phase (rich phase) or serve as doping agent.
As the catalyst component of catalyzer and the amount of the titanium that provides is enough to the catalytic solid carbonaceousmaterial is converted into liquid hydrocarbon; The amount of second metal that provides as catalyst component equally, is enough to the conversion of catalytic solid carbonaceousmaterial.In a plurality of embodiments, titanium is present in the catalyzer in the amount based on dry ashless coal 10ppm-10wt%.In some such embodiments, titanium is present in the catalyzer with the amount of 0.1wt%-5wt%.The exemplary amount that titanium is present in the catalyzer is the amount of 0.5wt%-2.5wt%.
In a plurality of embodiments, second metal in the catalyzer exists in the amount based on dry ashless coal 10ppm-10wt%.In some such embodiments, second metal is present in the catalyzer with the amount of 0.1wt%-5wt%.Exemplary amount in second metal of metal is the amount of 0.5wt%-2.5wt%.In some such embodiments, second metal in the catalyzer is an iron.So, iron is present in the catalyzer in the amount based on dry ashless coal 10ppm-10wt%.In some such embodiments, iron is present in the 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 the catalyzer.In a plurality of embodiments, the Ti in the compsn and the molecular ratio of other metal can be 0.1:1-10:1.
In a plurality of embodiments, catalytic material adds as following material: granular metal solid in small, broken bits, their FeS for example such as oxide compound, sulfide xFrom the discarded fines of refining of metal technology for example iron, molybdenum and nickel; The coal ash and the gelatin liquefaction solid residue of the for example useless FCC fines of the spent catalyst of crushing, hydrotreatment fines, recovery.In a plurality of embodiments, the titanium and second metal are by the granular solids adding of (separate) respectively.In other embodiments, catalyst composition comprises and comparatively is rich in titanium and the comparatively poor particle that contains second amount of metal, perhaps comprises the particle that comparatively is rich in second metal and comparatively poor titaniferous amount.In another embodiment, titanium and other metal can form as the bimetal compound of catalyst precursor rather than joined in the charging respectively.As an example, Ti xFe (1-x)OOH is through using NH 3H 2O titration FeSO 4And TiSO 4Mixture solution then carries out oxidation and prepares under the temperature that raises in fluidizing air.Ti xFe (1-x)OOH can prevulcanized be Ti before mixing with charging xFe (1-x)S.
In a plurality of embodiments, between the carbonaceousmaterial transition phase, at least a portion granules of catalyst is adhered to, adsorbs, absorbs, loads at least a portion solid carbonaceous substance or combines closely with this at least a portion solid carbonaceous substance.In a plurality of embodiments, before the pre-treatment or during at least a portion of catalyzer or catalyst precursor is deposited on the solid carbonaceous substance, it is to use water-based or organic liquid so that said catalyzer or catalyst precursor are carried to carbonaceousmaterial.In a plurality of embodiments, during the step that solid carbonaceous substance is heated to invert point or during conversion process, at least a portion of catalyzer or catalyst precursor is deposited on the said material.
In one embodiment, catalyzer uses the catalyst precursor that comprises metal to prepare, and said catalyst precursor comprises the water-soluble titanium component, for example Titanium Nitrate, titanium sulfate, acetic acid titanium, titanium chloride or their mixture.In another embodiment; Catalyzer uses the catalyst precursor that comprises metal to prepare; Said catalyst precursor comprises titanium compound, and it is a solid state at least partly, for example water-insoluble titanium compound such as titanium carbonate, titanium hydroxide, titanium phosphate, phosphorous acid titanium, formic acid titanium, titanium sulfide, molybdic acid titanium, wolframic acid titanium, titanium oxide; Titanium alloy such as titanium-molybdenum alloy or titanium-iron alloy, perhaps their mixture.In another embodiment; Catalyzer uses the catalyst precursor that comprises metal to prepare; Said catalyst precursor comprises water-soluble titanium sulfate solution; This solution randomly also comprises second promoter metal compounds, for example the iron component with the solute state of the acetate of chosen from Fe, muriate, formate, nitrate salt, vitriol or their mixture.In one embodiment, catalyzer uses the catalyst precursor that comprises titanium sulfate aqueous solution to prepare.
In a plurality of embodiments, during pre-treatment step, during carbonaceousmaterial was heated to the step of invert point, perhaps during conversion process, the conduct of part granules of catalyst disperseed with the isolating particle of said carbonaceousmaterial at least.
In a plurality of embodiments, with catalyst dissolution in or otherwise for example be suspended in the liquid phase as fine particle, emulsion droplet etc.Dispersed catalyst can join in the coal before contacting with hydrocarbonaceous liquid, and it can join in the hydrocarbonaceous liquid before contacting with coal, and perhaps it can join in coal-liquid slurry.In some such embodiments, dispersed catalyst adds with the form of the oil/aqueous 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 basically.Nitrate salt or acetate can be the most suitable forms of some metals.The non-limiting activated source of titanium comprises Titanium Nitrate and acetate titanium.The non-limiting source of iron is iron nitrate or ironic acetate.In a plurality of embodiments, also use metallo-organic complex for example ferrocene as source of iron.For molybdenum, tungsten or vanadium, for example molybdate, tungstate or the vannadate of basic metal or ammonium of complex salts preferably.Can also use the mixture of two kinds or more kinds of metal-salts.Special salt is four hydration Ammonium Heptamolybdate [(NH 4) 6Mo7O 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 the hydrocarbon medium.Dispersing and dissolving (dispersed dissolution) catalyzer can also be the oil-soluble compounds that contains catalytic metal, ferrocene for example, and phospho-molybdic acid, the naphthenate of molybdenum, chromium and vanadium, or the like.Can with suitable oil-soluble compounds converted in-situ catalyst-solvent.
In a plurality of embodiments, beaded catalyst comprises the titanium and second metal as unsupported catalyst, and the component that this means this catalyzer is less than for example silicon-dioxide, aluminum oxide, Natural manganese dioxide, carbon etc. combine or do not have load on it with inorganic carrier.In other embodiments, the component of part metals at least of catalyst composition and at least a inorganic carrier or adhesive bond or load are on it.Adhesive material can comprise any material of the tackiness agent that is conventionally used as in the hydrotreating catalyst.The suitable binder material comprises for example silicon-dioxide, and aluminum oxide is like (plan) boehmite, silica-alumina compound, gibbsite, titanium oxide, zirconium white, cationic clay or anionic clay such as saponite, bentonite, kaolin, sepiolite or hydrotalcite or their combination or mixture.In one embodiment, one or more adhesive materials are selected from colloid silica, silica-alumina, aluminum oxide, titanium, zirconium white or their mixture of silicon-dioxide, adulterated al.In another embodiment, adhesive material comprises the refractory oxide material that has the titanium oxide of at least 50 weight % by oxide compound.In catalyst preparation process, can use any suitable alumina adhesive.In one embodiment, the surface-area of alumina adhesive is 100-400m 2/ g, the volume of voids that records through nitrogen adsorption method is 0.5-1.5m/g.Similarly, can in catalyst preparation process, use any suitable titanium oxide tackiness agent.In one embodiment, the titanium oxide of tackiness agent has less than 50 microns (for example less than about 5 microns) and/or greater than 0.005 micron median size.In another embodiment, the titanium oxide of tackiness agent has 10-700m 2The BET surface-area of/g.
In some embodiments, adhesive material is the tackiness agent that stands peptization.In another embodiment, the precursor of adhesive material uses in Preparation of catalysts, during catalyst preparation process, is effectively or functional adhesive with this precursor conversion wherein.Thus; The suitable binder material precursor comprises alkali metal aluminate (to obtain alumina adhesive); Water glass (to obtain silica binder); The mixture of alkali metal aluminate and water glass (to obtain the silica alumina tackiness agent), two-, three-and/or the mixture in the tetravalent metal source mixture of the water-soluble salt of magnesium, aluminium and/or silicon (to produce cationic clay and/or anionic clay) for example, chloro hydrol (chlorohydrol); Tai-Ace S 150, perhaps their combination or mixture.In the situation of loaded catalyst, metal component (being the titanium and second metal component) is 10:1-1:10 with the weight ratio of carrier component.
In a plurality of embodiments, at least a portion of granules of catalyst comprises other component, for example catalyst promoting agent.This type promotor is selected from non-your VIII family metal (for example Ni, Co, Fe), group vib metal (for example Cr), IVB family metal (for example Ti), IIB family metal (for example Zn), IB family metal (for example Cu) and their compsn or mixture.
During the conversion process (this section in the period solid carbonaceous substance contact with the activated source of catalyst composition; And randomly under 100-350 ℃ temperature, carry out pre-treatment; Be heated to the invert point that carbonaceousmaterial is converted into liquid substance then), the activity of such catalysts source is converted into their activity form.Through being joined, sulphur promotes this conversion process in the catalyzer.
Sulfurized titanium material TiS and alkyl dithiocarbamic acid titanium, alkyl dithiophosphoric acid titanium and sulfurized metallics MoS for example for example suitably 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 can directly be used as catalyst precursor under the situation of not carrying out prevulcanized.For unvulcanized metal precursor, comprise titanium metal, titanium oxide, acetate titanium, Titanium Nitrate, titanium sulfate and other titanium salt, Ti-inorganic thing and the titanium organic cpds of titanium base; The ferrous metal of iron-based, ferriferous oxide, ferrous sulfate, iron nitrate and other molysite, red mud and other iron inorganics, ferrocene and other ferric organic compounds; The molybdenum base, the tungsten base, Ni-based; Cobalt-based; The titanium base, the metal of copper base or tinbase, oxide compound, salt, inorganics and organic cpds etc. can use elemental sulfur or other vulcanizing agent for example DMDS, H 2S, CS 2(NH 4) 2S to form metallic sulfide, perhaps directly adds the catalyst precursor prevulcanized vulcanizing agent at the hydrocracking run duration and with the atomic ratio by (S/ (other metal of Ti+))=1/1-10/1 catalyzer is suitably vulcanized.Perhaps, can be during pre-treatment step or add one or more sulphur compounds afterwards so that catalyzer or catalyst precursor activation are its corresponding sulfurate activity catalyzer.Can introduce one or more sulphur compounds in the optional position of system.In context of the present invention, can use one or more sulphur compounds of any appropriate vol.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 the pretreating zone.In another embodiment, one or more sulphur compounds are incorporated in conversion (i.e. liquefaction) district.The concentration of the sulphur of being introduced in one embodiment, makes that the atomic ratio of sulphur and metal is the about 10:1 of about 2:1-in the catalyzer.
Can use any suitable sulphur compound thus.In one embodiment, vulcanizing agent is hydrogen sulfide (H 2S).In one embodiment, vulcanizing agent is the solution form that under current (prevailing) condition, can resolve into hydrogen sulfide, exists to surpass the required stoichiometric amount of formation 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), NSC 9370 (DMDS), dimethyl thioether (DMS), tertiary butyl polysulfide (PSTB), uncle's nonyl polysulfide (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 earth alkali metal sulfhydrate, and their mixture.Contain the use of the vulcanizing agent of basic metal and/or earth alkali metal, can need other separating technology step so that basic metal and/or earth alkali metal are removed from spent catalyst.
Can elemental sulfur be joined in the pretreatment compositions with the distillation powder type or as concentrated dispersion-s (for example being purchased the sulphur fine powder).The allotropic substance of elemental sulfur for example rhombic sulfur and monoclinic sulphur also is suitable for this paper.In one embodiment, one or more sulphur compounds are distillation powder (flowers of sulfur), molten sulfur, sulphur steam or their combination or the form of mixture.
Other additive
During pre-treatment step or any other additive capable of using subsequently, for example to strengthen or to promote pretreatment process (for example through strengthen, promote and/or strengthen catalyzer or catalyst precursor is distributed in the carbonaceousmaterial) and/or to strengthen or promote the hydrocracking of pretreated carbonaceousmaterial.
Any suitable tensio-active agent capable of using in context of the present invention is with dispersiveness, metal surface area, form and/or other characteristic of for example improving catalyzer or catalyst precursor.Suitable tensio-active agent comprises for example any AS, zwitterionic tensio-active agent, amphoterics, nonionogenic tenside, cats product, perhaps their combination or mixture.Suitable ionic surfactant pack is drawn together for example polyoxyethylene sorbitol mono-laurate, polyoxyethylene groups alkylphenol, polyoxyethylene groups alkylphenol b-oxide etc.Suitable cationic surfactants comprises the for example organic quaternary amine of long-chain, the organic quaternary amine of polyethoxylated long-chain etc., for example water-soluble cationic amine (for example hexadecyl trimethylammonium bromide, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium amine (amine), nonyl trimethyl ammonium chloride, dodecyl phenol quaternary amine soap or their compsn or mixture).Suitable AS for example sodium succinate compound comprises for example dioctyl sodium sulphosuccinate or two (2-ethylhexyl) sodium sulfosuccinate).Suitable tensio-active agent also can comprise the vehicle substance with high surface tension properties, for example ethylene carbonate; UVNUL MS-40; The benzyl prussiate; Oil of mirbane; The 2-phenylethyl alcohol; 1, ammediol; 1, the 4-butyleneglycol; 1, the 5-pentanediol; Diethylene Glycol; Triethylene glycol; Glycerine; DMSO 99.8MIN.; The N-NMF; N-Methyl pyrrolidone; With their compsn or mixture.Suitable tensio-active agent also comprises having high capillary those tensio-active agents, for example N-Methyl pyrrolidone.Other instance of tensio-active agent comprises acetonitrile, acetone, ETHYLE ACETATE, hexane, diethyl ether, methyl alcohol, ethanol, methyl ethyl diketone, diethyl carbonate, chloroform, methylene dichloride, diethyl ketone and their compsn or mixture.In another embodiment, tensio-active agent comprises the organic additive of the nitrogenous or phosphorus with the carbon thioether phase that improves catalytic activity.To be added contain the amount that N/ contains the P organic additive and depend on that usually the expectation of final catalyst composition is active.
In another embodiment, tensio-active agent is formula R 1R 2R 3R 4The ammonium of Q+ or phosphine, wherein Q is nitrogen or phosphorus, wherein R 1, R 2, R 3, R 4In at least one be aryl or alkyl with 8-36 carbon atom (C for example 10H 21, C 16H 33, C 18H 37Or their combination), remaining R and wherein 1, R 2, R 3, R 4Be selected from hydrogen, have the alkyl of 1-5 carbon atom or their combination.This of tensio-active agent type suitable instance comprises: cetyltrimethyl ammonium, cetyl trimethyl phosphorus, octadecyl trimethylammonium phosphorus, cetyl pyridinium, tetradecyl trimethyl ammonium, eight alkyl trimethyl ammoniums, dodecyl trimethyl ammonium, dimethyl-two (dodecyl) ammonium (dimethyldidbdecylammonium) or their combination or mixture.The compound that derives above-mentioned ammonium or phosphorus can be for example oxyhydroxide, halogenide, silicate or their combination or mixture.
In one embodiment, tensio-active agent comprises nitrogenous organic additive, for example aromatic amine, cyclic aliphatic amine, many cycloaliphatic amines or their combination or mixture.In another embodiment; Tensio-active agent comprises and is selected from following nitrogenous organic additive: the compound (for example hexamethylene-diamine, monoethanolamine, diethylolamine, trolamine, N, N-dimethyl--N'-ethyl ethylene diamine or their combination or mixture) that contains at least one primary amine, secondary amine and/or tertiary amine group; Amino alcohol (for example 2 (2-aminoethylamino) ethanol, 2 (2-amino ethoxy or its combination or mixture) ethanol, 2-amino-1-butanols, 4-amino-1-butanols, 2; 2-diethoxy ethamine, 4; 4-diethoxy butylamine, 6-amino-1-hexanol, 2-amino-1; Ammediol, 3-amino-1,2-Ucar 35,3-amino-1-propyl alcohol, perhaps their combination or mixture); And aminoalkoxy-silane (for example 3-glycidyl oxygen propyl group) 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, for example tensio-active agent is a Hydrocerol A.In another embodiment, tensio-active agent is pentadecylic acid, capric acid or other similar long chain acid.In another embodiment, tensio-active agent is an alginic acid.
Optional additives can be used in any suitable moment before or after preprocessing process and/or hydroconversion process.In one embodiment, before the pre-treatment with one or more merging in one or more additives and carbonaceousmaterial, hydrocarbonaceous liquid and one or more catalyzer or the catalyst precursor.In another embodiment, during preprocessing process, additive and carbonaceousmaterial, hydrocarbonaceous liquid and catalyzer or catalyst precursor are merged.In another embodiment, after pre-treatment with before the hydrocracking, additive and pretreated carbonaceousmaterial are merged.In another embodiment, after hydroconversion process, additive and pretreated carbonaceousmaterial are merged.
Additive can use by any suitable concentration.In one embodiment, for example, additive uses with the concentration of about 0.001-5 weight % of total pre-treatment mixture.In another embodiment, additive uses with the concentration of about 0.005-3 weight % of total pre-treatment mixture.In another embodiment, additive uses with the concentration of about 0.01-2 weight % of total pre-treatment mixture.If separately additive is joined in the hydrocracking charging, for example like Acta Petrolei Sinica, Vol.19; Issue 4, pp.36-44, ISSN 10018719 and in Khimiya I Tekhnologiya Topilv I Masel; Issue 3; Year 1997, described in the pp.20-21, ISSN 00231169 (incorporating their content into this paper in full with it by reference); Amount to be added is the 0.001-0.05 weight % (for example about 0.005-0.01 weight %) of charging, perhaps adds with any suitable concentration.
Mix
Can use any suitable method or system that carbonaceousmaterial and hydrocarbonaceous liquid and catalyzer or catalyst precursor are merged and/or mix.In some embodiments, use any suitable mixing tank with carbonaceousmaterial, hydrocarbonaceous liquid and catalyzer or catalyst precursor simultaneously, mix in succession and/or continuously with the mode that is suitable for forming as required homogeneous or heterogeneous mixture (or slurry).In other embodiments; With mixing tank and any suitable shredder coupling (for example beater grinder, ball mill, rod mill or their combination etc.); Make and choose at least a portion of in the presence of hydrocarbonaceous liquid and/or one or more catalyzer or catalyst precursor, grinding carbonaceousmaterial wantonly, and it is mixed homogeneous or the heterogeneous slurry that forms with as required.In some embodiments, mixing tank and/or shredder contained gas delivery system are in order to provide inertia or reducing atmosphere (for example hydrogen, nitrogen, helium, argon gas, synthetic gas or their any compsn or mixture) in the mixing of carbonaceousmaterial, hydrocarbonaceous liquid and/or catalyzer or catalyst precursor and/or during grinding.In some embodiments, mixing tank and/or shredder are positioned at the upper reaches of pretreatment system.In other embodiments, mixing tank and/or shredder form the part of pretreatment system.In a plurality of embodiments, the catalyst precursor that is used for this method can directly be mixed in the coal or other carbonaceousmaterial of grinding before entering reactor drum, perhaps during the coal solvent grinds, joined in the coal.Can through use methanol/ethanol or water as the beginning profit method of solvating agent/wetting agent with catalyst dissolution to be ejected on the coal or be impregnated on the coal.Also can catalyzer be dispersed or dissolved in the solvent, then it be mixed with coal.
Embodiment of the present invention have been described in Fig. 1.The coal charging 3 less than 0.5 inch of the average particulate diameter of 50wt% coal particle is at least merged with catalytic material 5; The mol ratio that said catalytic material comprises titanium and iron is titanium activated source and the iron activated source of 0.1/1-10/1, and compsn 1 is delivered to preheating oven 20 in order to be heated to 350 ℃-500 ℃ temperature of reaction.The heating combination 23 that will leave coal and the catalytic material of this preheating oven is then delivered to reaction zone 30 and is converted into product liquid 33 in order to part coal at least.
Consider the illustrative methods of the present invention described in Fig. 2 at present; The coal charging 103 less than 0.5 inch of the average particulate diameter of 50wt% coal particle is at least merged with catalytic material 105; The mol ratio that said catalytic material comprises titanium and iron is titanium activated source and the iron activated source of 0.1/1-10/1, and compsn 101 is delivered to pretreating zone 110 in order to said composition is kept time of 5-600 minute at 100-350 ℃ pretreatment temperature.After pre-treatment, compsn 113 is delivered in the preheating oven 120 temperature of reaction in order to be heated to 350 ℃-500 ℃.The heating combination 123 that will leave coal and the catalytic material of this preheating oven is then delivered to reaction zone 130 and is converted into product liquid 133 in order to part coal at least.
Consider the illustrative methods of the present invention described in Fig. 3, be that pretreating zone 210 is delivered in 50 microns-500 microns coal charging 203 with the average particulate diameter of 80wt% coal particle at least at present.In special illustrative methods, coal arrives pretreating zone as powder feeding.In another illustrative methods, coal is as the slurry in hydrocarbonaceous liquid, and for example coal deutero-cut is supplied with.
The mol ratio that will comprise cobalt and iron is that the titanium activated source of 3/1-1/3 and the catalytic material 205 of iron activated source merge in pretreating zone with coal particle.In one embodiment, for example the aqueous solution or the slurry of Titanium Nitrate, titanium chloride, titanium sulfate, acetate titanium, titanium sulfide, titanium oxide or titanium carbonate supply to pretreating zone to titanium as titanium salt.For example the aqueous solution or the slurry of iron nitrate, iron(ic)chloride, ferric sulfate, ironic acetate, iron sulfide, ferriferous oxide or iron carbonate supply to pretreating zone to iron as molysite.In another embodiment, titanium and iron as be included in liquid for example the organometallics in the coal deutero-cut add.Exemplary organometallics comprises alkyl dithiocarbamic acid titanium and ferrocene.Active sulphur source 207 is joined the sulphur and catalytic metal atom ratio so that 2/1-6/1 to be provided in the pretreating zone.Also hydrogen or hydrogen-containing gas 209 are supplied to pretreating zone and be in normal atmosphere to 500psig so that the pressure in this pretreating zone is kept.In another embodiment, hydrogen or hydrogen-containing gas are supplied to pretreating zone so that the pressure in the pretreating zone is kept is in the 500psig-3500psig.Material in the pretreating zone is maintained 180-220 ℃ pretreatment temperature and continues 5-600 minute time.After pre-treatment, compsn 213 is delivered in the preheating oven 220 temperature of reaction in order to be heated to 350 ℃-500 ℃.The heating combination 223 that will leave coal and the catalytic material of this preheating oven is then delivered to reaction zone 230 and is converted into product liquid 233 in order to part coal at least.
Consider the illustrative methods of the present invention described in Fig. 4 at present, the average particulate diameter of 50wt% coal particle is at least delivered to pretreating zone 310 less than 0.5 inch coal charging 303.The catalytic material 307 and the catalytic material 309 that comprises the iron activated source that will comprise the titanium activated source; Mol ratio with titanium and the iron of 0.1/1-10/1; Merge in pretreating zone with coal particle, and said composition is kept at 100-350 ℃ pretreatment temperature 5-600 minute time.After pre-treatment, compsn 313 is delivered in the preheating oven 320 temperature of reaction in order to be heated to 350 ℃-500 ℃.The heating combination 323 that will leave coal and the catalytic material of this preheating oven is then delivered to reaction zone 330 and is converted into product liquid 333 in order to part coal at least.
Hydrocracking
After the pre-treatment, make carbonaceousmaterial stand any suitable hydrocracking and/or liquefaction condition and be rich in the product of hydrocarbonaceous material with generation, said hydrocarbonaceous material comprises any required liquid and/or gaseous product.Carbonaceousmaterial (for example coal) is incorporated at least one hydroconversion zone; Run into suitable temperature, pressure and additive (for example sulfocompound) so that part or all activation basically at least of the catalyzer of this pretreated carbonaceousmaterial or catalyst precursor in this this pretreated carbonaceousmaterial, and produce liquid and/or gaseous product.In one embodiment; For example; The catalyzer of pretreated carbonaceousmaterial or catalyst precursor greater than about 50 weight %; For example about 55 weight %, about 60 weight %, about 65 weight %, about 70 weight %, about 75 weight %, about 80 weight %, about 85 weight %, about 90 weight %, about 95 weight %, about 96 weight %, about 97 weight %, about 98 weight % or even about 99 weight % become active catalyst, make it have and/or show the hydrocracking activity.
Suitable hydrocracking temperature includes but not limited to greater than about 350 ℃, for example greater than about 375 ℃, about 400 ℃, about 425 ℃, about 450 ℃, about 475 ℃, about 500 ℃ temperature.In some such embodiments, the material that heats is carried out the step of hydrocracking and under 350 ℃-500 ℃ temperature, implement.In some such embodiments, the material of heating is reacted time of at least 10 minutes in the hydrocracking step.
Suitable hydrocracking pressure includes but not limited to 300-5000psig (for example 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 for example contain gas (for example hydrogen/methane mixture or hydrogen/carbonic acid gas/water mixture) atmosphere and/or the synthetic gas atmosphere of hydrogen.In one embodiment, thus, pretreated carbonaceousmaterial is suitable for low or lower hydrocracking pressure (for example less than about 2000psig, as less than about 1800psig or even less than the hydrocracking pressure of about 1600psig).Particularly; For example; With compare without pretreated identical carbonaceousmaterial; Hydrocracking pressure less than about 2000psig (for example less than about 1800psig, or even less than about 1600psig) under, the hydrocracking of pretreated carbonaceousmaterial can produce the liquid product yield that exceeds at least about 10% (for example exceeding at least about 20%, about 40%, about 60%, about 80%, about 100%, about 150%, about 200%, about 300% or even at least about 400%).In another embodiment; Than without pretreated identical carbonaceousmaterial, the hydrocracking consumption of pretreated carbonaceousmaterial reduces the hydrogen of about 10% (for example reducing about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90% or even about 100%).
In a plurality of embodiments, the hydrocracking of solid carbonaceous substance was accomplished through the time that the heating of this solid carbonaceous substance is enough to form product liquid.In some such embodiments, heat solid carbonaceousmaterial in the presence of at least a titanium activated source and at least a second metal active source.In some such embodiments, heat solid carbonaceousmaterial under greater than 350 ℃ temperature of reaction and under the pressure at 300-5000psig.In some such embodiments, heat solid carbonaceousmaterial under 350 ℃-500 ℃ temperature of reaction.In some embodiments, with 5 minutes-600 minutes time of solid carbonaceous substance heating.
In one embodiment, the hydrocracking of carbonaceousmaterial and/or liquefaction are carried out in single reactor drum.In another embodiment; The hydrocracking of carbonaceousmaterial and/or liquefaction are carried out at zone or the reactor drum that two or more (for example a plurality of) are used for hydrocracking; Said zone or reactor drum can be provided with in any suitable way (for example by parallel connection or series system, make temperature in for example placed in-line each reactor drum improve gradually and/or each downstream reactor in the corresponding raising of hydrogen partial pressure).Preferably, the hydrocracking of pretreated carbonaceousmaterial and/or liquefaction separate with pretreatment reaction device or zone and/or different reactor drum or zone in carry out.
In one embodiment, the hydrocracking of carbonaceousmaterial and/or liquefaction produce 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 even greater than about 99% liquid yield.In one embodiment; Compare without the liquid product yield of pretreated similar carbonaceousmaterial before with hydrocracking, the pre-treatment of carbonaceousmaterial produces and exceeds the liquid yield at least about 10% (for example exceeding at least about 15%, about 20%, about 25%, about 30%, about 35% or even at least about 40%).In another embodiment, the hydrocracking of pretreated carbonaceousmaterial and/or liquefaction produce greater than about 80%, about 85%, about 90%, about 95% or even 99% total conversion rate (the for example total conversion rate of coal).
In some embodiments; Compare without the transformation efficiency of pretreated similar carbonaceousmaterial before with hydrocracking, the pre-treatment of carbonaceousmaterial produces and exceeds the total conversion rate (the for example total conversion rate of coal) at least about 5% (for example exceeding at least about 10%, about 12%, about 14%, about 16%, about 18% or even at least about 20%).In other embodiments, the hydrocracking of pretreated carbonaceousmaterial and/or liquefaction produce the C less than about 10% (for example less than about 8%, about 6%, about 4%, about 3%, about 2% or even less than about 1%) 1-C 3Gas.
The separation of hydroconverted products
Can the elute from hydroconversion zone be added in any suitable one or more disengaging zone.In one embodiment, elute is added in first disengaging zone, in this disengaging zone, removes light product for example gas, petroleum naphtha and distillment through overhead.First disengaging zone like this can moved under the normal atmosphere basically.Can be randomly with from first disengaging zone the bottoms or the high boiling fraction of elute be recycled to the hydroconversion reactions district.Can the whole of the residue elute of first disengaging zone or some be sent in second disengaging zone, in this disengaging zone, it be fractionated into gas oil fraction and bottoms cut.Can the bottoms cut of second disengaging zone be sent in the 3rd disengaging zone.Can the part of gas oil be recycled to hydroconversion zone.Thus, can in context of the present invention, use any suitable high pressure, middle pressure and light pressure separator.
The recovery of catalyzer or catalyst precursor
Can then one or more catalyzer and/or metal recovery system or zone behind one or more separation systems or the zone, wherein from one or more parts of hydrocracking carbonaceousmaterial or at least a portion (for example one or more metals) of cut recovery catalyzer and/or catalyst precursor.In one embodiment, in recovery system, from the solid fraction (for example residual solid fraction) of the hydrocracking carbonaceousmaterial (it can comprise ash) separation system, isolating and/or collect, retrieve from the catalyzer of containing metal and/or the metal of metallic catalyst precursor.
Can be under any suitable temperature, for example at about 1200-1900 ℃, for example about 1300-1800 ℃ or even 1400-1700 ℃ temperature under operate recovery system.In one embodiment; At metal is in the situation of molybdenum; The U.S. Patent application series No.60/015 that for example submits on December 19th, 2007; Described in 096 (incorporating its content into this paper in full with it by reference), recovery system provides to be suitable for making spent catalyst (for example moly-sulfide) to receive oxidation and to distil and has been MoO 3Air atmosphere.Can collect the metal of treated spent catalyst, catalyst precursor and/or recovery and they are sent to catalyzer or catalyst precursor preparation district from catalyst recovery zone.
The preparation of catalyzer or catalyst precursor
Can then be one or more catalyzer or catalyst precursor preparation system after one or more recovery systems, at least a portion (the for example metal of the catalyst precursor) reaction that wherein makes the catalyzer that in recovery system, reclaims or catalyst precursor be to form catalyzer or catalyst precursor (for example with initially be used for catalyzer that the carbonaceousmaterial pre-treatment is identical or catalyst precursor).
In one embodiment, for example, make the recovery metal (MoO for example of catalyzer or catalyst precursor 3) react to form the four thio ammonium molybdate catalyst precursor with sulphur compound (for example ammonium sulfide).The catalyzer or the catalyst precursor that then gained are formed, optional and new or fresh catalyst precursor combination is transported to pretreatment system and/or hydrocracking system.
The sign of catalyzer
In a plurality of embodiments, for will be at least the part solid carbonaceous substance be converted into product liquid and be active catalyzer, have 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 form and dispersing characteristic with improvement; Can use technology known in the art to characterize, said technology comprises ultimate analysis, surface-area analysis (BET), grain size analysis (PSA), powder x-ray diffraction (PXRD), scanning electron microscopy (SEM), can loose x-ray analysis (DES) and other method.In one approach, use electron microscope method and X-ray diffraction research match (complement).In another approach, use the BET method that the surface-area of catalyzer is measured.In another method, can use scanning tunnel microscope method (STM) and density functional theory (DFT) 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) hCatalyzer be characterised in that, in the coal upgrading, depend on process for upgrading configuration and catalyst system therefor concentration and excellent transformation efficiency is provided.In one embodiment, the transformation efficiency that slurry catalyst provides is at least 70% in the first embodiment, in second embodiment, is at least 75%, in the 3rd embodiment, is at least 80%, in the 4th embodiment, is at least 90%.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 the embodiment of the coal upgrading system of catalyzer, be than the light-weight product with the coal feedstock conversion of 98wt.% at least.In second embodiment, the coal feedstock conversion with at least 98.5% is than the light-weight product.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 is meant the conversion of coal raw material to the material that is lower than 1200 ° of F (650 ℃) boiling point.
In one embodiment, catalyzer has the pore volume according to the 0.05-5.0ml/g of nitrogen determining adsorption.In second embodiment, pore volume is 0.1-4.0ml/g, for example 0.1-3.0ml/g or 0.1-2.0ml/g.
In a plurality of embodiments, catalyzer has the 5m at least that measures through through the B.E.T. method 2/ g, or 10m at least 2/ g, or 50m at least 2/ g, or greater than 100m 2/ g, or greater than 200m 2The surface-area of/g.In a plurality of embodiments, for greater than 100m 2The total surface area of/g, catalyzer is characterised in that the aggregate into the crystal grain of 10-20 dust.
In a plurality of embodiments, catalyzer has the particle diameter of nanometer to micron (μ m) 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 a plurality of embodiments, the catalyzer of suspensoid form is characterised in that the median particle diameter of 30nm-6000nm.In a plurality of embodiments, catalyzer has the median size of 0.3-20 μ m.
In a plurality of embodiments, catalyzer comprises molecular scale and/or is the granules of catalyst of the nano sized particles of colloidal sized (promptly less than 1 micron or less than 0.1 micron or for the 0.1-0.001 micron).In some embodiments, through catalyst precursor is immersed in make on the coal catalyzer with the 1-100 nanoparticulate dispersed on the coal surface.In some embodiments, catalyzer forms slurry catalyst in hydrocarbon diluent, has colloidal solid " nanocluster (cluster) ", and this nanocluster has the median size of 1-100 micron.
As further describing among the following embodiment, system and method described herein can be used for obtaining optimization and validity aspect the preparation of liquid with any required ratio of various desired properties (or percentage yield) and/or gaseous product.Particularly, can realize FR hydroconverted products in (for example under the time length of low hydrogen pressure and/or weak point) under the various hydrocracking conditions through any various combinations of selecting hydrocarbonaceous liquid, catalyzer and/or catalyst precursor and pre-treatment and hydrocracking condition.By this way; This system and method provides great handiness for the user, and this handiness makes it possible to use any various various combinations of hydrocarbonaceous liquid, catalyzer and/or catalyst precursor and pre-treatment and hydrocracking condition to obtain required hydroconverted products by any solid carbonaceous substance.
Embodiment
Embodiment 1 (Fe/Zn)
Test 1--preparation is dissolved in the mixed catalyst precursor iron nitrate (Fe (NO in the methyl alcohol 3) 39H 2O) and zinc nitrate (Zn (NO 3) 26H 2O) solution.Reaching beginning with the solution of 1:1 and coal weight ratio impregnated granules size less than the coal feed sample of 100 purpose moisture-frees (promptly less than 1 weight % water) with this solution moistens; Acquisition for coal 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.Thereby under nitrogen, should remove methyl alcohol up to 24 hours through the coal of catalyst soakage then in 105 ℃ of dryings.Is that 1.6:1 mix with FCC type technical oil (cuts of 500 ° of F+) as solvent with the solvent and the ratio of coal through the coal of catalyst soakage with exsiccant.Ratio with the sulphur of the sulphur of 2:1 and iron mol ratio and 2:1 and zinc adds elemental sulfur so that iron and zinc are vulcanized.In container, this mixture is heated rapidly to 200 ℃ then, and kept 2 hours, and the interior hydrogen partial pressure of this container is brought up to about 1000psia from about 100psia simultaneously at 200 ℃.Under the hydrogen partial pressure of 2500psia, this mixture further is heated to 430 ℃ then, kept 3 hours at 430 ℃ afterwards.After 3 hours, the reaction vessel quenching that will contain sulfurized solvent and coal mixtures, hydrogen and any reaction product is to room temperature.With product gas (CO, CO 2, C 1, C 2And C 3) discharge to confirm gas recovery ratio through wet type tester (wet test meter).Through filtering solid (mainly being unconverted coal), ash and catalyst vulcanization thing are separated with product liquid (C4+).The coal transformation efficiency is performed as follows mensuration:
Coal transformation efficiency=(solid of recovery-(catalyzer of the ash+recovery in the coal))/coal charging
The solvent that is added when deducting on-test is pressed the coal instrumentation stand oil yield of dry ash-free basis.In Table I tabular product yield.
Test 2--uses zinc nitrate as catalyst precursor, in for coal based on the zinc carrying capacity of dry ash-free basis 2wt% zinc, revision test 1.Ratio with the sulphur of 2:1 and zinc adds elemental sulfur so that zinc is vulcanized.In Table I tabular product yield.
Test 3-uses iron nitrate as catalyst precursor, in for coal based on the iron carrying capacity of dry ash-free basis 2wt% iron, revision test 1.Ratio with the sulphur of 2:1 and iron adds elemental sulfur so that iron is vulcanized.The product yield of tabular shows in the Table I, and the catalyst composition that contains iron and zinc produces much higher liquid yield and coal transformation efficiency than the catalyzer that contains iron or zinc separately.
Figure BDA00001676556200301
Figure BDA00001676556200311
Embodiment 2 (Fe/Ti)
Test 4--uses iron nitrate (Fe (NO 3) 39H 2O) catalyst precursor, in for coal based on the iron carrying capacity of dry ash-free basis 1wt% iron, revision test 1.The diethyldithiocar bamic acid titanium is blended in the mixture of solvent and coal, in obtain with for coal based on the titanium carrying capacity of dry ash-free basis 1wt% titanium.Add elemental sulfur with the sulphur of 2:1 and sulphur and the iron mol ratio of titanium mol ratio and 2:1.Tabulation has shown product yield in Table II.
Test 5-with particle diameter is to mix under the condition of 1.6:1 at the solvent and the ratio of coal less than the coal material sample of 100 purposes anhydrous (promptly less than 1wt% water) and FCC type process oil (500 Fahrenheit degrees+cut) as solvent.The diethyldithiocar bamic acid titanium is blended in the mixture of solvent and coal, in obtain with for coal based on the titanium carrying capacity of dry ash-free basis 1wt% titanium.Sulphur and titanium mol ratio with 2:1 add elemental sulfur.In container, mixture is heated rapidly to 200 ℃ then, and kept 2 hours down at 200 ℃, the hydrogen partial pressure in the container is increased to about 1000psia from about 100psia simultaneously.Then mixture further is heated to 430 ℃, under the hydrogen partial pressure at 2500psia under 430 ℃, kept 3 hours then.Table II also shows the catalyst composition that contains iron and titanium and compares with the catalyzer that contains the sulfurized titanium and produced significantly higher liquid yield.
Figure BDA00001676556200312

Claims (15)

1. one kind is converted into the method for product liquid with solid carbonaceous substance, and this method is included at least a titanium activated source and at least a second metal active source and exists and make solid carbonaceous substance under greater than 350 ℃ temperature of reaction and under the pressure at 300-5000psig, keep the time that is enough to form product liquid down.
2. the method for claim 1, this method comprises:
A) compsn in preparation solid carbonaceous substance, at least a hydrocarbonaceous liquid, at least a titanium activated source and at least a second metal active source; And
B) said composition is delivered to the hydroconversion reactions district and with said solid carbonaceous substance under greater than 350 ℃ temperature of reaction and keep at least a portion that is enough to said solid carbonaceous substance under the pressure at 300-5000psig and be converted into boiling point at C 5The time of the product liquid to 650 ℃ the TR.
3. the method for claim 2, the step that wherein prepares said compsn comprises:
A) preparation comprises the mixture at least a titanium activated source and at least a second metal active source;
B) this mixture and coal are merged the coal particle that contains catalyzer with formation; And
C) hydrocarbonaceous liquid is provided to this coal particle that contains catalyzer to prepare said compsn.
4. the method for claim 3, this method also are included in delivers to the dry said coal particle that contains catalyzer before the step in hydroconversion reactions district with said compsn.
5. the method for claim 3, wherein said mixture also comprises tensio-active agent.
6. the method for claim 2 is also supplied with the active sulphur source to said compsn.
7. the method for claim 6, wherein with the atomic ratio of the sulphur of 0.1:1-10:1 and metal for supplying with the active sulphur source.
8. the method for claim 2, this method also comprise hydrogen or hydrogen-containing gas are supplied to the hydroconversion reactions district and in the presence of hydrogen or hydrogen-containing gas, keeps said solid carbonaceous substance.
9. the method for claim 2, this method also are included in to be delivered to said compsn before the hydroconversion reactions district, under 100-350 ℃ pretreatment temperature, said compsn is carried out pre-treatment and continues 5-600 minute time.
10. the method for claim 9, this method also are included in the active sulphur source and exist down said compsn is carried out pre-treatment.
11. the method for claim 9, this method also are included in hydrogen or the hydrogen-containing gas existence is carried out pre-treatment with said compsn down.
12. the process of claim 1 wherein the said second metal chosen from Fe, molybdenum, nickel, manganese, vanadium, tungsten, cobalt, copper, chromium, zinc and tin.
13. the process of claim 1 wherein that said second metal is an iron.
14. the process of claim 1 wherein that titanium exists in the amount based on dry ashless coal 10ppm-10wt%.
15. the process of claim 1 wherein that said second metal exists in the amount based on dry ashless coal 10ppm-10wt%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389230A (en) * 1993-06-11 1995-02-14 Exxon Research & Engineering Co. Catalytic hydroconversion process
CN101280207A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Method for direct liquefaction and comprehensive utilization of ravens

Family Cites Families (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3223698A (en) * 1961-01-09 1965-12-14 Inst Noguchi Method for liquefying lignin
US3645665A (en) * 1969-05-26 1972-02-29 Dan River Inc Dyeing cellulosic textiles with vat and sulfur dyes using sodium dithionite and an aldehyde-bisulfite addition product stabilizer
GB1481689A (en) * 1973-11-08 1977-08-03 Coal Ind Hydrogenation of coal
SE394191B (en) * 1975-10-07 1977-06-13 Anderson Ind Ab Paul STORAGE DEVICE FOR TRANSFER OF LARGE POWER INTENDED DEVICES AND DEVICE FOR THE IMPLEMENTATION OF THE KIT
AU506174B2 (en) * 1976-05-28 1979-12-13 Kobe Steel Limited Coal liquefaction
US4077867A (en) * 1976-07-02 1978-03-07 Exxon Research & Engineering Co. Hydroconversion of coal in a hydrogen donor solvent with an oil-soluble catalyst
US4080282A (en) * 1976-07-12 1978-03-21 Gulf Research & Development Company Catalytic reactor and process for hydrogenating solid-containing carbonaceous materials in said reactor
US4081361A (en) * 1976-07-26 1978-03-28 Gulf Research & Development Company Process for the conversion of carbonaceous materials
US4190518A (en) * 1977-12-29 1980-02-26 Gulf Research And Development Company Solvent refined coal process
US4323447A (en) * 1980-02-05 1982-04-06 Gulf Research & Development Company Coal Liquefaction process employing octahydrophenanthrene-enriched solvent
US4369106A (en) * 1980-04-10 1983-01-18 Exxon Research And Engineering Co. Coal liquefaction process
US4450066A (en) * 1980-09-02 1984-05-22 Exxon Research And Engineering Co. Hydrothermal pretreatment to prevent scale during liquefaction of certain solid carbonaceous materials
JPS5761082A (en) * 1980-09-30 1982-04-13 Kobe Steel Ltd Liquefaction of coal
US4485008A (en) * 1980-12-05 1984-11-27 Exxon Research And Engineering Co. Liquefaction process
US4417972A (en) * 1981-11-04 1983-11-29 Exxon Research And Engineering Co. Recovery of coal liquefaction catalysts
US4401549A (en) * 1981-11-17 1983-08-30 Uop Inc. Liquefaction of calcium-containing coals
US4401550A (en) * 1982-01-11 1983-08-30 Uop Inc. Liquefaction of calcium-containing coals
US4485006A (en) * 1982-03-04 1984-11-27 Exxon Research And Engineering Co. Start-up method for a hydrorefining process
US4434043A (en) * 1982-06-01 1984-02-28 Exxon Research And Engineering Co. Recovery of catalyst from coal liquefaction residues
US4578176A (en) * 1982-06-09 1986-03-25 Institute Of Gas Technology Fuel production by free fall countercurrent flow
JPS59109588A (en) * 1982-12-15 1984-06-25 Kobe Steel Ltd Liquefaction of brown coal
IT1163480B (en) * 1983-06-08 1987-04-08 Anic Spa STAGE PROCEDURE FOR DIRECT CHARCOAL LIQUEFATION
US5094991A (en) * 1983-08-29 1992-03-10 Chevron Research Company Slurry catalyst for hydroprocessing heavy and refractory oils
US5484755A (en) * 1983-08-29 1996-01-16 Lopez; Jaime Process for preparing a dispersed Group VIB metal sulfide catalyst
US4493761A (en) * 1983-12-05 1985-01-15 Standard Oil Company (Indiana) Catalytic hydroliquefaction using a Cr-Mo-Group VIII catalyst
US4917791A (en) * 1984-06-01 1990-04-17 Kang Chia Chen Chu Process and catalysts for hydroconversion of coal or petroleum asphaltene to distillate liquids
US4617105A (en) * 1985-09-26 1986-10-14 Air Products And Chemicals, Inc. Coal liquefaction process using pretreatment with a binary solvent mixture
US5236881A (en) * 1986-08-22 1993-08-17 Coal Industry (Patents) Limited Coal extract hydrocracking catalyst
USH669H (en) * 1986-12-08 1989-09-05 The United States Of America As Represented By The United States Department Of Energy Samarium-145 and its use as a radiation source
US4824558A (en) * 1987-09-04 1989-04-25 Exxon Research And Engineering Company Coal liquefaction process with metal/iodine cocatalyst
US4831003A (en) * 1987-09-14 1989-05-16 Exxon Research And Engineering Company Catalyst composition and process of making
US5051389A (en) * 1987-09-16 1991-09-24 Exxon Research And Engineering Company Catalyst composition prepared by vapor depositing onto a carbon support
US4948523A (en) * 1987-09-30 1990-08-14 Amoco Corporation Chlorine-free silver protective lubricant composition (I)
US4816141A (en) * 1987-10-16 1989-03-28 Hri, Inc. Catalytic two-stage liquefaction of coal utilizing cascading of used ebullated-bed catalyst
CA1317585C (en) * 1988-02-02 1993-05-11 Chandra Prakash Khulbe Hydrocracking of heavy oils in presence of iron-coal slurry
US5070064A (en) * 1989-08-07 1991-12-03 Exxon Research And Engineering Company Catalyst pretreatment method
US5151173A (en) * 1989-12-21 1992-09-29 Exxon Research And Engineering Company Conversion of coal with promoted carbon monoxide pretreatment
US5183561A (en) * 1990-01-25 1993-02-02 Mobil Oil Corp. Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material
US5015366A (en) * 1990-04-10 1991-05-14 The United States Of America As Represented By The United States Department Of Energy Process and apparatus for coal hydrogenation
US5039392A (en) * 1990-06-04 1991-08-13 Exxon Research And Engineering Company Hydroconversion process using a sulfided molybdenum catalyst concentrate
US5200063A (en) * 1990-06-21 1993-04-06 Exxon Research And Engineering Company Coal hydroconversion process comprising solvent enhanced pretreatment with carbon monoxide
JP2529031B2 (en) * 1991-01-30 1996-08-28 株式会社芝浦製作所 Sputtering equipment
US5246570A (en) * 1992-04-09 1993-09-21 Amoco Corporation Coal liquefaction process using soluble molybdenum-containing organophosphorodithioate catalyst
US5783065A (en) * 1992-09-03 1998-07-21 University Of Utah Research Foundation Method for coal liquefaction
US5338441A (en) * 1992-10-13 1994-08-16 Exxon Research And Engineering Company Liquefaction process
US5454934A (en) * 1992-12-23 1995-10-03 Exxon Research & Engineering Co. Coal liquefaction using atomically dispersed metals
US5344553A (en) * 1993-02-22 1994-09-06 Mobil Oil Corporation Upgrading of a hydrocarbon feedstock utilizing a graded, mesoporous catalyst system
US5332489A (en) * 1993-06-11 1994-07-26 Exxon Research & Engineering Co. Hydroconversion process for a carbonaceous material
US5489375A (en) * 1994-06-08 1996-02-06 Amoco Corporation Resid hydroprocessing method
US5573556A (en) * 1994-11-03 1996-11-12 Exxon Research And Engineering Company Conversion of solid carbonaceous material using polyoxoanions
US5620591A (en) * 1994-12-22 1997-04-15 Exxon Research & Engineering Company Hydroconversion process with plug-flow molybdenum catalyst concentrate preparation
US6054043A (en) * 1995-03-28 2000-04-25 Simpson; Theodore B. Process for the hydrogenation of hydro-carbonaceous materials (Carb-Mat) for the production of vaporizable products
US6190542B1 (en) * 1996-02-23 2001-02-20 Hydrocarbon Technologies, Inc. Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds
US6139723A (en) * 1996-02-23 2000-10-31 Hydrocarbon Technologies, Inc. Iron-based ionic liquid catalysts for hydroprocessing carbonaceous feeds
JP3715729B2 (en) * 1996-10-21 2005-11-16 株式会社神戸製鋼所 Coal liquefaction method
US5728656A (en) * 1997-03-20 1998-03-17 Chevron Chemical Company Lower-ash lubricating oil having ultra-neutral zinc dialkyldithiophosphates
US5744026A (en) * 1997-04-10 1998-04-28 Eastman Chemical Company Catalyst system and process for benzyl ether fragmentation and coal liquefaction
US6153155A (en) * 1997-12-31 2000-11-28 Exxon Research And Engineering Company Recovery of the transition metal component of catalyst used in heavy feed hydroconversion
JP3679643B2 (en) * 1999-02-26 2005-08-03 三洋電機株式会社 Disc recording device
US7095708B1 (en) * 1999-06-23 2006-08-22 Cingular Wireless Ii, Llc Methods and apparatus for use in communicating voice and high speed data in a wireless communication system
JP2001026785A (en) * 1999-07-15 2001-01-30 Agency Of Ind Science & Technol Method for coal liquefaction
US6153156A (en) * 1999-08-02 2000-11-28 Gnb Technologies, Inc. Method for purifying leady oxides
US6551965B2 (en) * 2000-02-14 2003-04-22 Chevron Oronite Company Llc Marine diesel engine lubricating oil composition having improved high temperature performance
GB0011115D0 (en) * 2000-05-09 2000-06-28 Infineum Int Ltd Lubricating oil compositions
US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
JP4018328B2 (en) * 2000-09-28 2007-12-05 新日本石油株式会社 Lubricating oil composition
ITMI20030992A1 (en) * 2003-05-20 2004-11-21 Solvay Solexis Spa PERFLUOROPOLITEREI ADDITIVES.
US7163911B2 (en) * 2003-05-22 2007-01-16 Chevron Oronite Company Llc Carboxylated detergent-dispersant additive for lubricating oils
US20050043191A1 (en) * 2003-08-22 2005-02-24 Farng L. Oscar High performance non-zinc, zero phosphorus engine oils for internal combustion engines
ITMI20032207A1 (en) * 2003-11-14 2005-05-15 Enitecnologie Spa INTEGRATED PROCEDURE FOR THE CONVERSION OF CHARGES CONTAINING CARBON IN LIQUID PRODUCTS.
US8030258B2 (en) * 2005-07-29 2011-10-04 Chevron Oronite Company Llc Overbased alkaline earth metal alkylhydroxybenzoates having low crude sediment
JP3920304B1 (en) * 2005-11-22 2007-05-30 株式会社神戸製鋼所 Method and apparatus for producing solid fuel using low-grade coal as raw material
US8298668B2 (en) * 2008-02-13 2012-10-30 David Walker Taylor Ambiphilic coal body surfaces
US8123934B2 (en) * 2008-06-18 2012-02-28 Chevron U.S.A., Inc. System and method for pretreatment of solid carbonaceous material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389230A (en) * 1993-06-11 1995-02-14 Exxon Research & Engineering Co. Catalytic hydroconversion process
CN101280207A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Method for direct liquefaction and comprehensive utilization of ravens

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