CN102076611A - Catalyst composition with nanometer crystallites for slurry hydrocracking - Google Patents

Catalyst composition with nanometer crystallites for slurry hydrocracking Download PDF

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CN102076611A
CN102076611A CN2009801253141A CN200980125314A CN102076611A CN 102076611 A CN102076611 A CN 102076611A CN 2009801253141 A CN2009801253141 A CN 2009801253141A CN 200980125314 A CN200980125314 A CN 200980125314A CN 102076611 A CN102076611 A CN 102076611A
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iron
catalyzer
intermediate phase
crystallite
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CN102076611B (en
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A·巴塔查里亚
B·J·梅扎
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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Priority claimed from US12/165,192 external-priority patent/US8128810B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J35/393—
    • B01J35/40—
    • B01J35/615—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/06—Sulfides
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

A process and apparatus is disclosed for converting heavy hydrocarbon feed into lighter hydrocarbon products. The heavy hydrocarbon feed is slurried with a catalyst comprising iron oxide and alumina to form a heavy hydrocarbon slurry and hydrocracked to produce lighter hydrocarbons. The iron sulfide crystallites have diameters in the nanometer range.

Description

Be used for the catalyst composition that slurry hydrogenized cracked has nano microcrystalline
Background of invention
The present invention relates to handle the method and apparatus of crude oil, more specifically, relate to the hydrocracking that heavy hydrocarbon carries out in the presence of additive and catalyzer, be used for other purified raw material so that useable products is provided and further prepares.
Along with the decline of conventional crude reserves, heavy oil must be upgraded so that meet world's requirement.In heavy oil upgrading processing, heavier material is converted to lighter fraction, and must remove most sulphur, nitrogen and metal.Heavy oil comprises the heavy bituminous oil that material such as petroleum crude oil, atmospheric tower bottom product, vacuum column bottom product, heavy recycle stock, shale oil, coal are derived liquid, former oil residue, topped oil and refined from oil-sand.Interesting especially is the oil that oil-sand extracts, and it includes wide boiling range material, from petroleum naphtha to kerosene, gasoline, pitch, or the like, and the boiling point that contains vast scale is higher than about 524 ℃ material.The feature of these heavy hydrocarbon feeds can be, the low reactivity in viscosity breaking, and high coking trend is to the Wheat Protein of hydrocracking and be difficult to distillation.The most of residue oil raw material that is upgraded processing contains the bituminous matter of a tittle, and it generally is considered to the heptane insoluble compound, according to the mensuration of ASTM D3279 or ASTM D6560.Bituminous matter is can import the heteroatomic macromolecular compound of polar a kind of containing.
Before it was further processed into to enabled production, heavy oil must be upgraded in one-level is upgraded machining cell.One-level upgrading machining cell is known in this area, and it includes but not limited to, coking process is such as postponing or fluidisation coking and hydrogenation technique such as ebullated bed (ebullated bed) or slurry hydrogenized cracking (SHC).For example, at room temperature, from the bitum coking of Canada, the productive rate of product liquid is typically, 55 to 60 weight %, and the coke of a great deal of is as by product simultaneously.For similar raw material, the ebullated bed hydrocracking is generally produced the liquid product yield of 50 to 55 weight %.US5,755,955 have described a kind of SHC technology, and it has been found the liquid product yield that 75 to 80 weight % can be provided, and the use by additive, greatly reduces the formation of coke.
In SHC, the three-phase mixture of heavy liquid oil raw material at high temperature and add and depress, carries out cracking on solid catalyst in the presence of gaseous hydrogen, produce gently product.As the SHC catalyzer, for example, at US5, in 755,955, ferric sulfate is disclosed.The ferric sulfate monohydrate generally is ground into reduced size, so that better disperseed, and promotes mass transfer.Ferric sulfate (FeSO 4) need aerial careful thermal treatment usually, the water in the ferric sulfate that provides with hydrated form is provided generally.Water can suppress FeSO 4Be converted into the transformation efficiency of iron sulphide, generally must be removed.It is believed that the ferric sulfate monohydrate forms iron sulphide slow decomposition the in SHC.With ferric sulfate monohydrate dried in place, dehydration forms FeSO at first 4, as the formula (1).Yet, FeSO 4In its decomposition course also once more hydration become monohydrate, form iron sulphide, suc as formula (2).Finally, FeSO 4Be converted into iron sulphide, as the formula (3):
2Fe(SO 4)·H 2O+8H 2→2Fe(SO 4)+2H 2O+8H 2 (1)
2Fe(SO 4)+2H 2O+8H 2→FeS+Fe(SO 4)·H 2O+4H 2O+4H 2 (2)
FeS+Fe(SO 4)·H 2O+4H 2O+4H 2→2FeS+10H 2O (3)
Therefore, the water yield in system will limit the iron sulphide rate of formation.Thermal treatment also can be removed volatile matter, such as carbonic acid gas, makes catalyzer finer and close, and the hole of open catalyzer makes it have more activity.
Ferric sulfate has contained sulphur.Thermal treatment will transform the iron sulphide that iron in the ferric sulfate becomes catalytic activity.Sulphur in the ferric sulfate has increased the sulphur in the product, and it must be removed.Other ferruginous catalyzer is limonite for example, and it contains FeO (OH) nH 2O needs the prevulcanized thing to handle and is better disperseed and the better transformation efficiency from ferric oxide to active iron sulphide, according to CA2, and 426,374.The prevulcanized thing is handled the sulphur that has increased catalyzer, has therefore also increased the sulphur in the heavy hydrocarbon that will process.Like this, unnecessary sulphur generally all must be removed from product.In the iron sulphide catalyzer, need be at the active iron of+2 oxidation state obtaining enough transformation efficiencys and to the selectivity of useful liquid, and avoid higher coke to form.US4,591,426 have mentioned bauxite, but do not investigate it and limonite and laterite are enumerated as catalyzer.The SHC catalyzer generally is ground into very fine particle diameter and promotes to disperse and promote mass transfer.
Between the reaction period, it is important making coking reduce to minimum at SHC.Pfeiffer and Saal, PHYS.CHEM.44, the model in 139 (1940) shown, bituminous matter by resin layer or polar aromatics (it makes its stabilization in colloidal suspension) institute around.Under the situation that lacks the polarity aromatic hydrocarbon, if perhaps the polarity aromatic hydrocarbon is diluted by paraffin molecules or is converted to lighter paraffinic hydrocarbons and aromatic materials, these bituminous matters meeting self-associations, perhaps flocculation forms bigger molecule, produce intermediate phase and from solution, precipitate and separate out, form coke.
Toluene can be used as that solvent dissolves so that separating carbonaceous from the lighter hydrocarbons of SHC product (carbonaceous) solid.The solid that is insoluble to toluene comprises the organic residue of catalyzer and toluene insoluble (TIOR, toluene insoluble organic residue).TIOR comprises coke and intermediate phase, and heavier and more soluble than the bituminous matter that dissolves in heptane.Intermediate phase formation reaction is the key reaction restriction in the slurry hydrogenized cracking reaction.Intermediate phase is the hypocrystalline carbonaceous material, and it is defined as being present in the circular anisotropic particles in the pitch, and boiling point is more than 524 ℃.The existence of intermediate phase can be as the too violent early warning of the operational condition of SHC, and coking is formed under this condition and will takes place possibly.
Summary of the invention
The iron sulphide crystallite that we have found that nano-scale can provide dominant transformation efficiency in the SHC reaction.The iron sulphide crystallite usually has and the identical size of iron sulphide precursor crystallite, and this iron sulphide crystallite is obtained by iron sulphide precursor crystallite.In bauxite, iron sulphide precursor crystallite is a ferric oxide.Before SHC, the iron sulphide precursor is not heat-treated, iron sulphide precursor crystallite can sintering together and become bigger, allow catalytic activity iron sulphide crystallite to remain in the nanometer range thus.
Description of drawings
For better understanding the present invention, referring to described accompanying drawing.
Fig. 1 is the schematic flow sheet of SHC equipment.
Fig. 2 is the XRD figure of TIOR sample, and its peak shows with shade in the hydrocarbon zone.
Fig. 3 is the XRD figure of TIOR sample, and its non--intermediate phase peak shows with shade in the hydrocarbon zone.
Fig. 4 is the XRD figure of the TIOR that makes of a series of Ferric Sulfate Hydrafe agent.
Fig. 5 is the XRD figure of the TIOR that makes of a series of catalyzer of the present invention.
Fig. 6 is the XRD figure of the TIOR that makes of iron sulphide monohydrate catalyzer.
Fig. 7 is the SEM Photomicrograph of iron sulphide monohydrate catalyzer.
Fig. 8 is the XRD figure of the TIOR that makes of limonite catalyzer.
Fig. 9 is the SEM Photomicrograph of limonite catalyzer.
Figure 10 is the XRD figure of the TIOR that makes of bauxite catalyzer.
Figure 11 is the STEM Photomicrograph of bauxite catalyzer.
Figure 12 is the PLM Photomicrograph of the TIOR that makes of iron sulphide monohydrate catalyzer.
Figure 13 is the PLM Photomicrograph of the TIOR that makes of limonite catalyzer.
Figure 14 is the PLM Photomicrograph of the TIOR that makes of bauxite catalyzer.
The narration of preferred embodiment
Method and apparatus of the present invention can be used in the various heavy hydrocarbon feeds of processing.It can process aromatic raw material, and the raw material that is very difficult to hydrogenation processing traditionally, vacuum residuum for example, and viscosity breaking vacuum residuum, the diasphaltene base material, defective pitch, the sediment at the bottom of the fuel reserve tank, or the like.Proper raw material comprises the long residuum of boiling point at 650 ℉ (343 ℃), and heavy vacuum gas oil (VGO) and vacuum residuum, its boiling point surpass the vacuum residuum of 950 ℉ (510 ℃) at 800 ℉ (426 ℃) and boiling point.In this specification, boiling point should be understood that be, calculate atmosphere boiling point (AEBP, atmospheric equivalent boiling point) of equal value by observing boiling point and distillation pressure, the formula that provides among the ASTM D1160 for example is provided.In addition, term " pitch " refers to vacuum residuum, perhaps has the material greater than the AEBP of 975 ℉ (524 ℃).Wherein to be greater than or equal to the raw material of 572 ℉ (300 ℃) will be suitable to the boiling point of 90 weight % materials.Proper raw material comprises that api gravity is no more than 20 degree, generally is no more than 10 degree, and can comprises the raw material that is lower than 5 degree.
In exemplary SHC processing method, as shown in Figure 1, a kind of, two kinds or all heavy hydrocarbon oil are input to pipeline 8, and the recirculation pitch materials flow that contains granules of catalyst in pipeline 39 can merge at pipeline 10 at pipeline 37 together with recycle of heavy VGO.Merging materials flow in the pipeline 10 is heated in well heater 32, and is pumped through the bottom inlet that introduction pipe line 12 enters tubular type SHC reactor 13.The solid particulate matter catalystic material can be directly be added to the heavy hydrocarbon oil that adds SHC reactor 13 from pipeline 6, perhaps can be before entering reactor 13 from pipeline 6 ' with pipeline 12 heavy hydrocarbon oil mix the slurry that forms in the reactor 13.This is optional, and catalyzer is added in the upstream of well heater 32 may be disadvantageous.In this well heater, iron particle possibility sintering or gathering produce bigger iron particle, and it will be avoided.It can be suitable that various mixing and pump line system are arranged.What consider simultaneously is that the feeding materials flow can be to add to independently in the SHC reactor 13.Recycle hydrogen in the pipeline 30 and hydrogen make-up, join in the SHC reactor 13 through after the heating of well heater 31 by pipeline 14.Hydrogen in pipeline 14, it is not carry out pre-mixing with raw material, adds by pipeline 12 on the position on the material inlet.Hydrogen in raw material in the pipeline 12 and the pipeline 14 all distributes by suitable divider in SHC reactor 13.In addition, hydrogen can be added in the raw material in the pipeline 10 (before it heats in well heater 32), and is sent in the SHC reactor by pipeline 12.Preferably, the raw material of the adding SHC reactor 13 of 5 to 15 weight % has been formed in the recirculation pitch materials flow in pipeline 39, and the heavy VGO in the pipeline 37 has formed the raw material of 5 to 50 weight % simultaneously, depends on raw materials quality and single-pass conversion level.The raw material that enters this SHC reactor 13 comprises three-phase, solid catalyst particle, liquid and hydrocarbon solid raw material and gaseous hydrogen and vaporized hydrocarbon.
Processing method of the present invention can be operated under quite medium pressure, and its scope is 500 to 3500psi (3.5 to 24MPa), preferably arrives between the 2500psi (10.3 to 17.2MPa) 1500, and does not have coke to form in SHC reactor 13.Temperature of reactor is generally 400 ℃ to 500 ℃, and 440 ℃ to 465 ℃ is comparatively suitable, and preferred 445 ℃ to 460 ℃.LHSV generally is lower than 4hr -1, based on fresh feed, preferred 0.1 to 3hr -1, preferred especially 0.3 to 1h -1Though SHC can carry out in various known upper reaches or downflow reactor, it is particularly suitable for tubular reactor, and wherein raw material, catalyzer and gas move up by it.Therefore, the outlet of SHC reactor 13 is higher than import.Although only shown one among Fig. 1, can the in parallel or one or more SHC reactors 13 of series connection use.Because liquid starting material is converted to gaseous product, in SHC reactor 13, tend to occur foam.Also can add defoamer in the SHC reactor 13, preferably join reactor head, reduce foam and produce tendency.Suitable defoamer comprises siloxanes, and as US4,969,988 is disclosed.
Gas-liquid mixture is discharged by pipeline 15 from SHC reactor 13, and preferably logical superheated high-pressure separator 20 separates, and its separation temperature is (392 and 878 ℉) between 200 ℃ and 470 ℃, preferably under the pressure of SHC reactor.In heat separator 20, the relief liquor of SHC reactor 13 is separated into gas streams 18 and liquid stream 16.Liquid stream 16 contains heavy VGO.Gas streams 18 is included in the hydrocarbon product of the SHC reactor 13 of 35 to 80 volume %, and the step of going forward side by side processes and reclaims hydrocarbon and hydrogen, so that recirculation.
The after separating that can occur in liquid vacuum separation column 24, the liquid portion product of heat separator 20 can be used for being formed into the recycle stream in the SHC reactor 13.Pipeline 16 has been introduced the liquid distillate of hot high-pressure separator 20, preferably join vacuum tower 24, its pressure remain on 0.25 and 1.5psi (1.7 and 10.0kPa) between, and be in the vacuum distilling temperature, make atmosphere cut point of equal value be between lightweight VGO and the heavy VGO, between 250 ℃ and 500 ℃ (482 ° and 932 ℉).Can in the liquid separation column, separate three cuts: the lightweight VGO overhead fraction in the overhead line 38, it can further be processed, obtain the pitch materials flow from the heavy VGO materials flow of side stream in the pipeline 29 (sidecut) with by tower bottom tube line 40, its general boiling point is higher than 450 ℃.Since can looping back by pipeline 39, the materials flow of at least a portion pitch formed the part of the feed slurry of SHC reactor 13.The residual catalyst particle of SHC reactor 13 will appear in the pitch materials flow, and can be circulated back to easily in the SHC reactor 13.Any remainder of pitch materials flow reclaims by pipeline 41.Between the reaction period, it is important making coking reduce to minimum at SHC.Add rudimentary polarity aromatic oil and in raw material, will lower the coking generation.The polarity aromatic materials can be from various sources.The part of heavy VGO in the pipeline 29 can be passed through pipeline 37 recirculation, forms the part material slurry of SHC reactor 13.The remainder of heavy VGO can reclaim by pipeline 35.
Gas streams in the pipeline 18 generally contains than the lower aromatic component of liquid distillate concentration in the pipeline 16, and may need to carry out further refining.Gas streams in the pipeline 18 can be passed through catalytic hydroprocessing reactor 44, and it has the bed that is filled with hydrotreating catalyst.If necessary, hydrogen make-up can be added in the materials flow in the pipeline 18 by pipeline 18.Suitable hydrotreating catalyst of the present invention is any known conventional hydrotreating catalyst, and comprises and comprise at least a high surface area support material such as VIII family metal on the refractory oxide and at least a VI family metal of loading on, those.Air-flow and hydrotreating catalyst contact between 200 ℃ and 600 ℃ (430 ° and 1112 ℉), in the presence of hydrogen, 5.4 and 34.5MPa (800 and 5000psia) between.The product that derives from the hydrotreatment of hydrotreating reactor 44 can be by discharging in the pipeline 46.
The relief liquor that derives from the pipeline 46 of hydrotreating reactor 44 is admitted in the cold high pressure separator 19.In cold separator 19, product is separated into hydrogen rich stream, and it is deviate from from cat head by pipeline 22, and liquid hydrocarbon product, and it is deviate from from the bottom by pipeline 28.Rich hydrogen materials flow 22 can wherein be washed so that remove hydrogen sulfide and ammonia by the washings in the pipeline 25 by filling washing tower 23.Exhausted washings in the pipeline 27 can be reproduced and recirculation, is generally amine.Washed rich hydrogen materials flow is discharged from washer by pipeline 34, and merges with hydrogen make-up in the fresh pipeline 33, and gets back in the reactor 13 by recycle gas compressor 36 and pipeline 30 recirculation.Tower bottom tube line 28 can carry the product of liquid hydrotreatment to product fractionator 26.
Product fractionator 26 can comprise one or several pipelines, although only shown one in Fig. 1.The product fractionator is produced the C that reclaims in the overhead line 52 4 -, the naphtha products materials flow in the pipeline 54, the lightweight VGO materials flow in diesel stream in the pipeline 56 and the tower bottom tube line 58.
The granules of catalyst that we have found that the ferric oxide that comprises between the 2 and 45 weight % and the aluminum oxide between the 20 and 90 weight % obtains excellent SHC catalyzer.Ferruginous bauxite is the mineral that can obtain in a large number that preferably have these character.Bauxite typically has 10 to 40 weight % ferric oxide, Fe 2O 3And 54 to 84 weight % aluminum oxide, and can have 10 to 35 weight % ferric oxide and 55 to 80 weight % aluminum oxide.Bauxite also can comprise silica, SiO 2, and titanium dioxide, TiO 2, its common total amount is no more than 10 weight %, and general total amount is no more than 6 weight %.Iron is present in the bauxite with form of iron oxide, and aluminium is present in the bauxite with form of iron oxide.Volatile matter such as water and carbonic acid gas, also can be present in the mineral that can obtain in a large number, but aforementioned proportion has been got rid of volatile matter.Ferric oxide is also with hydrated form, Fe 2O 3NH 2O is present in the bauxite.Again, aforementioned ratio has been got rid of the water in the hydrate.
Bauxite can be exploited, and grinds to form the particle of 0.1 to 5 micron of average particulate diameter.Particle diameter is the length of the orthogonal axle of particulate maximum.We have found that average particulate diameter is not less than 200 microns aluminum oxide and ferric oxide catalyst, it uses drying means to measure particle diameter, shown can with the suitable performance of same catalyzer that is ground to 0.1 to 5 micron.Therefore, average particulate diameter is lower than 200 microns, is lower than 249 microns suitably, preferably be lower than 250 microns aluminum oxide and ferric oxide catalyst, can be used to promote SHC reaction.In one embodiment, catalyzer should not surpass 600 microns, preferably be no more than 554 microns, measures with regard to the average particulate diameter that particle diameter obtains with regard to using desiccating method.Average particulate diameter is all average particulate diameters that are fed to the granules of catalyst in the reactor, and it can be measured by the representative sampling method.Therefore, can spend less energy and granules of catalyst is worn into than minor diameter be promoted SHC, substantially lower time and cost.The mensuration of granularity uses desiccating method to carry out, and it can more relevantly simulate a large amount of catalyzer is how to run into hydrocarbon feed at first.As if the wet method of measuring particle diameter can be divided into bauxite ore particles than small-particle, and it may show when catalyzer being joined in the SHC reactor, and what can take place.
Aluminum oxide in catalyzer can be an a few types, comprises alpha, gamma, θ, and boehmite is intended boehmite, gibbsite, diaspore, bayerite, nordstrandite (nordstrandite) and silicon carbide.Aluminum oxide can derivative, is provided in the catalyzer such as spinel and uhligite.Suitable bauxite can be from Stow, and the Saint-Gobain Norpro company of Ohio obtains, and it provides product air dried and that grind, but these processing are optional to the performance of SHC catalyzer.
We have found that these are salic and granules of catalyst ferric oxide is more effective, if they are not at first heat-treated or sulfide is handled.We find that also water does not form active iron sulphide in the ferric oxide of obstruction from bauxite, therefore, do not need to come except that anhydrating by heat or any other drying treatment.Water on the catalyzer can be to be chemically bonded on ferric oxide, aluminum oxide or other catalyst component, or with the catalyzer physical bond.Catalyzer can have the water that surpasses 23 weight %, and can not influence catalyst performance.We have found that 39 weight % water can not influence the performance of catalyzer, and the water that expection reaches at least 40 weight % can not influence performance yet in catalyzer.Water on catalyzer can pass through loss on ignition, and (loss on ignition LOI) measures, and it comprises that heatable catalyst arrives the temperature of rising, such as 900 ℃.All volatile matters all leave, and comprise water, but are that non-water volatile matter is unimportant.
Iron in the ferric oxide is at aluminum oxide, under the existence such as bauxite, in the presence of heavy hydrocarbon feeds and hydrogen, under the needed high temperature of other SHC catalyzer, before joining conversion zone, promptly be converted into active iron sulphide, and it is excessive not need sulphur to exist in catalyzer.Iron sulphide has several molecular form, therefore usually by molecular formula Fe xS represents that wherein X is between 0.7 and 1.3.We have found that basically all ferric oxide by heat hydrocarbon and catalyzer to 410 ℃, in the presence of hydrogen and sulphur, are transformed into iron sulphide.In this respect, " owning basically " refers on the XRD figure of intensity to 2 θ angles (two theta degree), do not produce the peak of ferric oxide at 33.1 place, 2 θ angles, or is not less than 99 weight % iron sulphide transformation efficiencys.Sulphur may reside in the hydrocarbon feed, as organic sulfide.Therefore, the iron in catalyzer can be added in the heavy hydrocarbon, with the form adding of+3 oxidation state, preferably as Fe 2O 3In reaction zone or before entering reaction zone and without pre-treatment, catalyzer can be added in the raw material.Ferric oxide and aluminium oxide catalyst are being mixed with the heavy hydrocarbon feeds that includes machine sulfide, and heated mixt is after temperature of reaction, the organic sulfide in the raw material is converted into the hydrogen sulfide and the hydrocarbon of sulfur-bearing not.In the catalyzer+the hydrogen sulfide in conversion zone that the iron of 3 oxidation state is promptly produced with the reaction of organosulfur and hydrogen under temperature of reaction reacts.Iron sulphide has been produced in the reaction of ferric oxide and hydrogen sulfide, and it is the activity of such catalysts form.Then, iron is present in the reactor with+2 oxidation state.Ferric oxide has allowed not adding the operation of sulphur in the raw material, if exist the sulphur of enough available quantities to guarantee the conversion fully of iron sulphide in raw material to the transformation efficiency of iron sulphide.Otherwise, can add sulphur in the low-sulfur raw material, if necessary, so that whole ferric oxide are converted into iron sulphide.Because ferric oxide and aluminium oxide catalyst are so effective in the conversion ferric oxide reacts with promotion SHC to iron sulphide, can add less iron to the SHC reactor.Therefore, need less sulphur that ferric oxide is converted to iron sulphide, thereby minimized the needs that sulphur is added.Ferric oxide and aluminium oxide catalyst needn't carry out processing at elevated temperatures in the presence of hydrogen, carry out the conversion of iron sulphide.Conversion is carried out being lower than under the SHC temperature of reaction.By avoiding heating and sulfide pre-treatment, realized that processing method is simplified and the reduction of material cost.In addition, the hydrogen demand also is minimized, and hydrogen sulfide still less and other sulphur must be removed from the SHC product.
In SHC,, should be noted that several terms for the performance characterization of ferric oxide and aluminium oxide catalyst." iron level " refers to respect to non-gaseous material in the SHC reactor, the weight ratio of the iron in the catalyzer.Non-pneumatic material in reactor generally is hydrocarbon liquids and solid, and catalyzer, does not comprise reactor and supplementary unit." aluminium content " refers to respect to non-gaseous material in the SHC reactor, the weight ratio of aluminium." pitch transformation efficiency " is to be 524 ℃ or to be lower than 524 ℃ material weight ratio at the product mid-boiling point, with respect to the material that is higher than 524 ℃ at the raw material mid-boiling point." C 5-524 ℃ of productive rates " refer at the product mid-boiling point at C 5The weight ratio of the material of boiling range to 524 ℃ is with respect to total hydrocarbon raw material." TIOR " refers to the organic residue of toluene insoluble, and it is illustrated in the non-catalytic solid that product part mid-boiling point is higher than 524 ℃." intermediate phase " refers to the component of TIOR, and it has shown the existence of coking, another TIOR component." api gravity index " refers to the parameter of the flowability of expression material.It is identical with this average grain or crystallite diameter that average grain or crystallite diameter should be understood that, and comprise whole particles or crystallite in the sample respectively.
In the SHC reactor, the catalyzer iron level is generally 0.1 to 4.0 weight %, is not more than 2.0 weight % of catalyzer and liquid among the SHC usually.Because iron is at aluminum oxide, under the existence such as bauxite, it is very efficient generating the iron sulphide crystallite at rapid sulphur from hydrocarbon feed, need still less promote the conversion of heavy hydrocarbon feeds enough in the SHC reactor at iron on ferric oxide and the aluminium oxide catalyst.Iron level at catalyst reactor is that effectively no more than suitably 1 weight %, and preferred 0.7 weight % are with respect to the non-pneumatic material in the reactor being lower than or equaling 1.57 weight % concentration.In one embodiment, the iron level of catalyst reactor is answered 0.4 weight % at least.With regard to pitch transformation efficiency, C 5-524 ℃ of productive rates, TIOR productive rate and intermediate phase productive rate, other mineralogical property that can obtain in a large number that contains iron is not as ferric oxide and aluminium oxide catalyst with the bauxite form.Under the situation of 2 weight % iron, only after carrying out a large amount of pre-treatment with sulfide, limonite can be suitable with bauxite, and after the sulfide pre-treatment, limonite can produce too much intermediate phase productive rate.On the catalyzer in reactor, under the lower concentration of 0.7 weight % iron, the catalyzer of test can not be as playing a role as ferric oxide and aluminium oxide catalyst, and suppress TIOR and intermediate phase productive rate.Under the about 1 and 1.5 weight % iron levels, bauxite is better than ferric sulfate monohydrate and limonite performance in reactor.We further find can be realized being four times at least by the product that ferric oxide and aluminium oxide catalyst catalysis obtain the api gravity of raw material, and nearly at least six times to raw material with surpass 24 times to raw material, has shown excellent heavy hydrocarbon transformation efficiency.Ferric oxide and aluminium oxide catalyst have allowed the outstanding transformation efficiency of heavy hydrocarbon feeds to desired product such as the use of bauxite, simultaneously catalyzer still less and a small amount of or do not produce the intermediate phase that produces sign as coking.
The existence of aluminum oxide in iron-containing catalyst has favorable influence to performance.Improved characteristic in the SHC reaction with other iron-containing catalyst bonded aluminum oxide, particularly in the generation that suppresses intermediate phase.Natural bauxite has better properties than the catalyzer of other iron content and aluminium.On catalyzer, suitable aluminium content is 0.1 to 20 weight %, with respect to the non--gaseous state solid in the reactor.Preferably be no more than the aluminium content of 10 weight %.
The iron sulphide crystallite that is generated by bauxite in reactor and under reaction conditions has the diameter that passes through crystallite in the nanometer range.The iron sulphide crystal is a kind of solid, and wherein component iron sulphide molecule is piled up according to orderly order, and repeat pattern is expanded on all three-dimensional space.The iron sulphide crystallization forms the zone of the solid matter with same structure, as independent iron sulphide crystal.The iron sulphide crystallite of nano-scale good dispersion in catalyzer and reaction liquid.Iron sulphide crystallite granularity general and iron sulphide precursor crystallite is similar, and the iron sulphide crystallite is produced by described precursor crystallite.In bauxite, iron sulphide precursor crystallite is a ferric oxide.Because without thermal treatment bauxite, the ferric oxide crystal can also not become big by sintering together.Therefore, the catalytic activity iron sulphide crystallite that is generated by ferric oxide remains in the nanometer range.The iron sulphide crystallite can have average largest diameter be 1 and 150nm between, generally be no more than 100nm, be no more than 75nm suitably, preferably be no more than 50nm, more preferably no more than 40nm, it is measured by electron microscope technique.The iron sulphide crystallite has average crystallite diameter suitably for being not less than 5nm, preferably is not less than 10nm and most preferably is not less than 15nm, and it is measured by electron microscope technique.Electron microscope technique shown, the iron sulphide crystallite is at the suitable homogeneous of diametrically, good dispersion, and mainly exist with monocrystalline.Use XRD to measure the iron sulphide crystallite size, obtain less crystallite size, perhaps this be because the different iron that is present in the iron sulphide provides peak near 2 identical θ angles to the atomic ratio of sulphur.XRD shown iron sulphide crystallite mean diameter be 1 and 25nm between, preferably 5 and 15nm between and most preferably 9 and 12nm between.To the transformation efficiency of iron sulphide, for example, in reactor, generated the composition that comprises 2 to 45 weight % iron sulphide and 20 to 98 weight % aluminum oxide for ferric oxide, and be dispersed in the heavy hydrocarbon medium slurry is provided.Composition comprises the iron sulphide crystallite of above-mentioned nanometer range.We have found that iron oxide precursor crystallite in the bauxite have with by the identical particle diameter of iron sulphide crystallite that forms with reaction of Salmon-Saxl.We find that further aluminum oxide and ferric oxide catalyst can be recycled in the SHC reactor at least twice, and can not make the iron sulphide crystallite become big.
Cross polarization light microtechnique (PLM) can be used to use ASTM D4616-95 to measure from intermediate phase structure among the TIOR of SHC reaction and quantitative intermediate phase concentration.The hypocrystalline attribute of intermediate phase makes it have optical activity under cross polarization light.Collect the TIOR sample, embed in the epoxy it and polishing.Use PLM and generate sample image and identification and to the counting of the intermediate phase in the PLM image, the relative quantity of intermediate phase can be by quantitatively.
We find that also the semi-crystalline character of intermediate phase also allows it to occur on the XRD figure picture.The existence that we have found that intermediate phase shows that by the peak of locating at 26 2 θ angles it is within ± 0.3 °, preferably within ± 0.2 ° on the XRD figure picture.This intermediate phase peak in the XRD figure picture is corresponding with the intermediate phase that PLM finds.We find that the wide shape of the scope between 20 and 29.5 2 θ angles can be relevant with intermediate phase.
For the intermediate phase of analytic sample, use solvent, such as toluene, mix centrifugal and decant liquid phase with the sample of hydrocarbon material.Can repeat these steps.Then can be in vacuum drying oven drying solid, such as 90 ℃ dry 2 hours down.At this moment, the oven dry sample just is ready to by PLM or XRD and carries out intermediate phase mensuration.For XRD, with a standard, add solid sample such as silicon, form slurry with solvent such as acetone, so that allow sample to mix with standard.Solvent should promptly be evaporated, and stays the sample of the standard with predetermined concentration.The sample and the standard of about 1 gram are spread on the XRD sample holder, and put into the XRD instrument,, and use the pre-determined range parameter to scan such as Scintag XDS-2000 XRD instrument.The sweep limit parameter is suitable such as 2.0/70.0/0.02/0.6 (sec) and 2.0/70.0/0.04/10 (sec).Other parameter also can be suitable.For example use Livermore, the JADE software of the Materials Data Inc. company of California comes the drawing result data, and it can be loaded on the XRD instrument.JADE software has used International Center for Diffraction Data (ICDD) to carry out the evaluation of phase and search for matching feature automatically as standard database.
In order to calculate intermediate phase concentration, should calculate the peak in the total carbon zone total area of (rightmost edges at the silicon peak at 2 θ angles from 20 ° the 2 θ angle right sides to 28.5 °).The rightmost edges at silicon peak is 29.5 2 θ angles.If used the standard that is different from silicon, the calculating in total carbon zone should comprise nearly 29.5 2 θ angles.The wide shape part at intermediate phase peak may be arranged in the total carbon zone.In JADE software, can use Peak Paint function to obtain the peak area in total carbon zone from the XRD figure picture.The total carbon zone is included in the intermediate phase peak at 26 ° 2 θ angles, if there is intermediate phase, and the silicon peak that derives from 28.5 ° 2 θ angles of the silicon standard that joins in the sample.In case measured the peak total area in total carbon zone, can be determined at the non-intermediate phase peak in total carbon zone, and calculate the total area of they and silicon peak area, and from the peak total area at peak, total carbon zone, deduct, obtain the area at intermediate phase peak.Non--intermediate phase peak in the total carbon zone can use JADE software to measure, and it can mate peak image in the collection of illustrative plates and the base peak image in the ICDD database.Bauxite for example, generally comprises titanium dioxide, and it provides the peak at 26.2 2 θ angles.Other non--intermediate phase can be determined, to deduct the respective peaks area from the intermediate phase peak area.The baseline at non-intermediate phase peak can be such the draws, the baseline of the bottom of each side that connects the peak of promptly drawing, and it is made a distinction from the intermediate phase peak.These non-intermediate phase peaks and silicon peak in the total carbon zone use the Peak Paint function of JADE software to come highlighted demonstration, and calculate its area.Non-intermediate phase peak with respect to the intermediate phase peak area, is not tangible especially.Subsequently, can use two areas at intermediate phase peak and silicon peak to calculate intermediate phase weight fraction in sample, use formula (1):
X m＝X st(A m/A st) (1)
X wherein mBe the intermediate phase weight fraction in sample, X StBe the weight fraction that adds standard such as the silicon of sample, A mBe the intermediate phase peak area, A StIt is the peak area of standard.Use term " intermediate phase weight fraction " to be because the correction factor of description standard and the peak-to-peak relation of intermediate phase can be useful in formula (1), but we do not expect that this correction factor will significantly change the result of formula (1).Calculate intermediate phase productive rate umber, it is the intermediate phase umber of the hydrocarbon production that offers the SHC reactor of every weight part, and the intermediate phase of producing in determining whether reacting is too much, shows the risk that too much coking produces thus.The TIOR productive rate umber that every weight part hydrocarbon feed is produced in reaction is calculated by formula (2):
Y TIOR＝M TIOR/M HCBN (2)
Y wherein TIORIt is the productive rate umber of TIOR in product; M TIORBe the quality of the product of TIOR in the product, M HCBNIt is the quality of the hydrocarbon in raw material.In successive reaction, can the mass velocity form be used as quality and be used in the calculating, and in batch reaction, use rest mass to be used as quality.Calculate intermediate phase productive rate umber by formula (3):
Y Intermediate phase=X m* Y TIOR(3)
Y wherein Intermediate phaseIt is the productive rate umber of intermediate phase.These formula can calculate the productive rate umber of TIOR, Y TIOR, it is the TIOR quality that every mass parts offers the hydrocarbon production of SHC reactor, it can multiply by the intermediate phase umber in the TIOR sample, X n, measure intermediate phase productive rate umber, Y Intermediate phase, it is the intermediate phase quality that every mass parts offers the hydrocarbon production of SHC reactor.If intermediate phase productive rate umber surpasses 0.5 weight %, should reduce SHC reactor harshness, to avoid the excessive coking in reactor, because intermediate phase production is sizable.In other embodiments, should control severity, be low to moderate 0.3 and high to 0.8 weight % if intermediate phase productive rate umber should surpass.
By the amount of the intermediate phase measured according to the optics PLM method of ASTM D 4616-95, ASTM D 4616-95 is to use the method for making sample as the two-dimensional areas of partial volume.XRD method is used the three-D volumes sample, and should provide more accurate intermediate phase indication, with regard to regard to raw materials in part by weight.Refractory phase hopes that two kinds of methods can provide identical result, but they should be corresponding mutually.
Embodiment 1
Table I has characterized the raw material that is suitable for SHC.Except as otherwise noted, all use this raw material in all embodiments.
Test Vacuum substrate (975 ℉+)
Proportion, g/cc 1.03750
Api gravity -0.7
The ICP metal
Ni, ppm by weight 143
V, weight Ppm 383
Fe, ppm by weight 68.8
Little carbon residue, weight % 25.5
C, weight % 80.3
H, weight % 9.0
N, weight % 0.4
Total N, ppm by weight 5744
Oxygen, the weight % in the organism 0.78
Sulphur, weight % 7
Ash, weight % 0.105
Heptane insolubles, weight % 16.1
Pentane insolubles, weight % 24.9
Total chlorine, quality ppm 124
Saybolt viscosity, 150 ℃ of Cst 1400
Saybolt viscosity, 177 ℃ of Cst 410
" ICP " expression inductively coupled plasma atomic emission spectrum, it is a method of measuring metal content.
Embodiment 2
The intermediate phase of the TIOR sample that the analysis of use XRD method obtains in this wise, promptly react by SHC, use heavy oil feedstock among the embodiment 1 and the iron level in the 0.7 weight % ferric sulfate monohydrate catalyzer, its as in the SHC reactor non--the gaseous material percentage recently.The sample of SHC product material is mixed with toluene, centrifugal then, and pour out liquid phase.Remaining solid is repeated these steps repeatedly.Dry remaining solid in vacuum drying oven is following dry 2 hours at 90 ℃ then.By adding silicon solid and acetone solvent in the TIOR sample and smash into slurry with mortar and pestle the silicon standard is joined in the sample, obtain 5.3 weight % concentration.Acetone is evaporated from slurry, stay the solid of the mixture that comprises TIOR and silicon standard.With being deployed on the XRD sample fixer of about 1g, and put into the XRD instrument, and use the parameter of 2.0/70.0/0.04/10 (sec) to scan with standard blended solid sample.The XRD instrument is a Scintag X1 instrument, and it is the fixed slit system that θ-θ protractor, Peltier cooled detector and copper pipe are housed.The XRD instrument moves under the condition of 45kV and 35mA.The JADE software that use is carried on the XRD instrument comes the drawing result data.
Fig. 2 and 3 has shown the XRD figure picture of gained TIOR sample.The centre of form (centroid) has shown the existence of intermediate phase at the peak at 26.0 2 θ angles.At the peak total area in the total carbon zone of the silicon peak rightmost edges at 2 θ angles from 20 ° 2 θ angles to 28.5 °, as shown in Figure 2, being calculated is 253,010 square measures, uses the Peak Paint function of JADE software.The rightmost edges at the peak in the total carbon zone is 29.5 2 θ angles.In Fig. 3, use Peak Paint function to discern and tint, and the centre of form is at the silicon peak at 28.5 2 θ angles at the non-intermediate phase peak in total carbon zone.Bauxite for example, generally comprises titanium dioxide, and it provides the peak at 26.2 2 θ angles.In Fig. 3, so identify other non-intermediate phase peak and highlighted demonstration.The baseline that has shown non-intermediate phase peak in Fig. 3, this baseline has connected the substrate of each side at each peak, and its remainder from the intermediate phase peak is separated.These non-intermediate phase peaks and silicon peak in the total carbon zone use the Peak Paint function of JADE software to come highlighted demonstration, and calculate its area.The area at silicon peak is 43,190 square measures, and is 1,374 square measure at other non-intermediate phase peak area in total carbon zone, and it is inessential comparatively speaking.In the hydrocarbon scope and the total area irrelevant peak of intermediate phase use Peak Paint function to calculate, and are 44,564 square measures.Deduct non-intermediate phase area from the total area at peak, total carbon zone, obtain the area at intermediate phase peak, it is 208,446 square measures.Subsequently, two areas at use intermediate phase peak and silicon peak calculate the percentage ratio of the intermediate phase in sample, use formula (1):
X m＝0.053*(208446/43190)＝0.2558 (1)
In order to measure the productive rate umber of TIOR, use formula (2):
Y TIOR＝M TIOR/M HCBN＝18.85gTIOR/342gHCBN＝0.0551 (2)
Thus, use formula (3) to calculate the productive rate umber of intermediate phase:
Y Intermediate phase=X m* Y TIOR=0.249*0.0551=0.0141 (3)
Y Intermediate phaseBe expressed as 1.41 weight % percentage ratios, its intermediate phase concentration with 1.22% is associated, and uses ASTM D 4616-95 to measure by PLM.Because intermediate phase productive rate umber is big (it is higher than 0.5 weight %) quite, reaction has the danger of excessive coking, should control its severity rapidly.
Embodiment 3
In this embodiment, we have checked that the iron in the ferric sulfate monohydrate is converted into the ability of active iron sulphide.The vacuum residuum of ferric sulfate monohydrate and embodiment 1 is mixed under 450 ℃ and 2000psi (137.9 crust), and its consumption makes that iron level is 2 weight % iron, based on the non--gaseous material in the reactor.Selecting this temperature, is because it is the optimal temperature of sulphur monohydrate catalyzer in pitch transforms.Set up semicontinuous reaction, make in reactor, to keep liquid hydrocarbon and catalyzer; Yet, the hydrogen of 6.5 standard liter/min (sl/m) is passed through slurry, and from reactor, emits.In the differential responses stage, characterize carrying out X-ray diffraction (XRD) with the isolating solid material of vacuum residuum feed, show Fe (SO 4) H 2O is more slowly to the conversion of FeS.Fig. 4 has shown the XRD figure picture of the sample that obtains from semicontinuous reaction under the various timed intervals.Fig. 4 has shown the relation of intensity with respect to 2 θ angles, corresponding to four XRD figure pictures that obtained in 0,15,30,60 and 80 minute, its in Fig. 4 from being up to minimum image.Time opening measures after the reactor heating reached reaction conditions in 30 minutes.In resembling, XRD figure shown Fe (SO 4) H 2The existence of O, its peak are 18.3 and 25.9 2 θ angles.Following Table II has provided the Fe (SO of each time 4) H 2The O ratio.Be reflected at after the heating in 0 minute, only have the Fe of 30 weight % to show as iron sulphide, its peak is 44 2 θ angles.Only after 80 minutes, most of Fe (SO 4) H 2O is converted into FeS.
Table II
Reaction times (minute) Fe(SO 4)·H 2O (weight %)
0 70
15 16
30 14
60 5
80 4
Embodiment 4
To form iron sulphide in order understanding, to have carried out following experiment, the vacuum residuum among the embodiment 1 is added in the semi batch reacor from bauxite, 460 ℃ of temperature, 2000psi (137.9 crust) passes through residue with hydrogen with the speed of 6.5sl/m.The bauxite catalyzer after 30 minutes, allows reaction carry out with preliminary heating 80 minutes.After the preliminary heating, in the time of 0,15 and 80 minute, the solid of collecting in the reactor is measured its X-ray diffraction image.Carry out the second cover experiment under the same conditions, except temperature of reactor being set in 410 ℃, and after preliminary heating, in the time of 0 and 80 minute, collect solid.In Fig. 5, shown the XRD figure picture.The experiment of carrying out under 460 ℃ is three minimum among Fig. 5 XRD figure pictures, and the experiment of carrying out under 410 ℃ is three the highest among Fig. 5 XRD figure pictures.In all cases, just formed iron sulphide when reactor reaches temperature of reaction, its peak is 44 2 θ angles.Equal no evidence shows the existence of ferric oxide in any XRD figure picture, shows that all basically ferric oxide have been converted into iron sulphide.
Embodiment 5
Contain with Fe 2O 3Bauxite and other iron-bearing minerals that can obtain in a large number of 17.7 weight %Fe that form exists and the 32.9 weight %Al that exist with boehmite alumina, such as ferric sulfate monohydrate and Yandi limonite ore, it derives from various sources, compares.Use the wet method of ASTM UOP856-07 to characterize granularity.The characterization data that in Table III, has shown all material.
Table III
Sample description Bauxite The ferric sulfate monohydrate Rhombohedral iron ore The limonite chip
Al, weight % 32.9 ＜0.006 0.7
Fe, weight % 17.7 29.1 67.8 52.4
Ti, weight % 1.88 ＜0.003 0.029
LOI under 900 ℃, quality % 7.6 54.6 0.8 17.1
Iron cpd Fe 2O 3 Fe(SO 4) Fe 2O 3 FeOOH
Iron cpd, weight % 25.3 79.1 97.0 83.4
SiO 2 4.5
Al 2O 3 62.2 1.3
S 0.0 18.7 0.0
The BET surface-area, m 2/g 159.0 5.0 94.0
The LANG surface-area, m 2/g 276.0 162.0
Volume of voids, cc/g 0.2 0.0 0.1
Pore diameter, A 53.0 104.0 41.0
Granularity
Median diameter, μ 1.2 2.9 3.8 2.8
Mean diameter, μ 1.0 2.3 2.7 26.7
＜10μ 0.5 1.1 1.3 0.3
＜25μ 0.7 1.8 2.4 0.9
＜50μ 1.2 2.9 3.8 2.8
＜75μ 1.9 4.1 5.3 26.9
＜90μ 2.8 5.5 6.9 91.1
In model experiment, in 1 liter of autoclave, add the vacuum residuum of the embodiment 1 of 334 grams, mix with one of source of iron, add the iron amount between 0.4 and 2 weight %.Among the embodiment that lists in Table IV, autoclave is heated to 445 ℃ and reaches 80 minutes, and pressure is 2000psi (137.9 crust).Hydrogen is added reactor by sparger continuously, pass reactor, its speed is 6.5 standard Liter Per Minutes, and by vacuum breaker to keep pressure.Hydrogen is separated from lighter products, and it is in cold gas-liquid separation capture tank (knock-out trap pot) condensation.At heated mixt before the temperature of reaction, some limonite catalyzer are carried out pre-treatment in this wise, promptly by adding 1 or 2 weight % sulphur, based on raw material and catalyzer, and heated mixt to 320 ℃ or 350 ℃, pressure is 2000psi (137.9 crust), in hydrogen one hour, comes deactivated catalyst.
In Table IV, " intermediate phase productive rate, XRD, weight % " shows by XRD and discerns intermediate phase, and express based on total hydrocarbon feed." intermediate phase optics " is the percentage ratio by the intermediate phase of discerning in sample of polarized light microtechnique mensuration.All productive rate numerical value calculate with the ratio to raw material.
Ferric oxide and the higher pitch transformation efficiency of aluminium oxide catalyst explanation, higher C 5-524 ℃ of productive rates and lower TIOR are than the comparative catalyst of similar iron level.Only after a large amount of pre-treatment and high 2 weight % iron heap(ed) capacities, limonite approaches the corresponding 2 weight % iron that obtaining in pretreated bauxite.Pretreated limonite is only better at the TIOR productive rate, but has unacceptable high intermediate phase productive rate.Under 0.7 weight %Fe, than contrast material, bauxite embodiment has shown higher pitch transformation efficiency, C 5-524 ℃ of productive rates, lower TIOR productive rate.Bauxite also is better than 97 weight %Fe 2O 3Rhombohedral iron ore (hematite), show that the aluminum oxide in bauxite provides performance advantage.The conversion data that derives from these experiments shows that the slow formation of the iron sulphide in ferric sulfate monohydrate and limonite may hinder transformation efficiency, and has improved the TIOR productive rate undesirably.
Under many situations of Table IV,, related good with the amount of the intermediate phase of XRD determining by the middle phasor of the optical method measuring of ASTM D 4616-95.
Embodiment 6
The catalyzer of a series of experiments experimental data that generates among the embodiment 5, wherein the weight based on liquid in the SHC reactor and catalyzer is that 0.7 weight % iron is recovered, and measures by XRD spectrum and scanning electronic microscope (SEM).
Fig. 6 has shown that the XRD figure of the ferric sulfate monohydrate catalyzer that uses in the numbering 523-4 experiment of listing resembles in embodiment 5.XRD figure among Fig. 6 resembles, and has shown the sharp peak at 43 2 θ angles, and it is identified as iron sulphide, shows big relatively micro crystal material.The broad peak at 2 θ angles 26 is identified as intermediate phase.Show the Photomicrograph of the iron sulphide crystallite that terrible ferric sulfate monohydrate precursor crystallite of numbering the 523-4 experiment certainly forms among Fig. 7, it forms by SEM, under 10,000 times, has shown various crystallite sizes, is typically 150 to 800nm.The iron sulphide crystallite is the black particle in Fig. 7.
Fig. 8 has shown that the XRD figure of the TIOR that the limonite catalyzer with numbering 522-73 experiment listed produces resembles in embodiment 5.XRD figure among Fig. 8 resembles and has also shown sharp peak, and at 43 2 θ angles, it is identified as iron sulphide, shows big relatively micro crystal material.Again, the big broad peak at 26 2 θ angles is identified as intermediate phase.The Photomicrograph of the iron sulphide crystallite that the limonite precursor crystallite from numbering 522-73 experiment in Fig. 9 forms, it forms by SEM, and 50,000 times, show various crystallite sizes, its scope is generally 50 to 800nm.In Fig. 9, the iron sulphide crystallite is a black particle.
Figure 10 has shown that the XRD figure of the bauxite catalyzer of numbering 522-125 experiment resembles, and it is listed in embodiment 5.XRD figure has looked like to show wide Fang Feng, and it is identified as iron sulphide at 43 2 θ angles.This broad peak shape is the performance of nanocrystal material.2 θ angles 26 do not have the peak can be identified as intermediate phase.The peak at 2 θ angles 25.5 is likely the titanium dioxide that is present in bauxite and/or the silver, and it is guessed to be the pollutent on the equipment liner.The peak at 2 θ angles 26.5 also is likely the silver chloride pollutent.The peak at 2 θ angles 28 is the boehmites in the catalyzer.Because bauxite also contains the boehmite alumina of a great deal of outside the deironing, the crystallite size of uncertain iron sulphide from SEM.
The Photomicrograph of the bauxite catalyzer of the numbering 522-82 experiment in embodiment 5 is presented among Figure 11.Chart by the compound X ray of scanning transmission electron microscope art (STEM) and to make the Photomicrograph of Figure 11.Photomicrograph shows, the granularity of boehmite particles is from 70 to 300nm, and iron sulphide crystallite scope is equably at 25 μ m simultaneously, 15 and 40nm between.The iron sulphide crystallite is a material more black among Figure 11, and several are irised out as an example.In Figure 11, many iron sulphide crystallites are identified as single crystallite.In Figure 11, alumina particle is bigger light gray material.Aterrimus material in the central upper portion of Figure 11 is confirmed to be impurity.
When having 0.7 weight % iron level in the SHC reaction zone, show to have seldom or do not have intermediate phase in ferric oxide and the aluminium oxide catalyst by XRD, other catalyzer have formed the intermediate phase of significant quantity simultaneously.
Embodiment 7
The TIOR of a series of experiments experimental data that generates among the embodiment 5, wherein the weight based on liquid in the SHC reactor and catalyzer is that 0.7 weight % iron is recovered, and by polarized light microtechnique (PLM) spectrum, confirm intermediate phase in embodiment 5 and 6 according to ASTM D4616-95.
Figure 12 is the PLM image of the numbering 523-4 experiment TIOR of generation in the presence of ferric sulfate monohydrate catalyzer among the embodiment 5, and the XRD figure of its catalyzer resembles in Fig. 6 and provides, and has provided the SEM Photomicrograph of embodiment 6 in Fig. 7.Photo among Figure 12 has shown has the material of remarkable quantity to coalesce together, and it is the sign of intermediate phase.The PLM picture of Figure 12 has been supported the result of XRD analysis, phasor and confirmed the existence of intermediate phase by the 1.03 weight % that XRD calculates in the middle of its peak by 26 2 θ angles and 1.7% the optics that calculated by ASTM D4616-95.
Figure 13 is the PLM picture of the TIOR of the numbering 522-73 experiment among the embodiment 5, and it has used the limonite catalyzer, has provided its XRD figure picture in Fig. 8, has provided its SEM image in Fig. 9.Picture among Figure 13 shows that compare with Figure 12, less material coalesces together, but the structure of air bubble-shaped has shown intermediate phase.The PLM photo of Figure 13 has been supported the result of XRD analysis, and wherein phasor and the 1.35 weight % that calculate by XRD in the middle of the peak at 2 θ angles by 26 among Fig. 8 and 4.65% the optics that calculated by ASTM D4616-95 have confirmed the existence of intermediate phase.
Figure 14 is the PLM image of the TIOR of numbering 522-125 experiment among the embodiment 5, and it has used the bauxite catalyzer, has provided its XRD figure and resemble in Figure 11.The Photomicrograph of Figure 14 has shown that than Figure 12 and 13, material still less is coalescent.Only the intermediate phase of trace is present in the PLM Photomicrograph, this has supported the result of XRD analysis, phasor is 0.00 in the middle of calculating promptly by not shown the existence of no intermediate phase basically at the peak at 26 2 θ angles, and according to ASTMD4616-95, and by XRD calculating is 0.03 weight %.
Embodiment 8
The bauxite catalyzer of the numbering 522-124 experiment in embodiment 5, it contains aluminum oxide and ferric oxide, with the ferric oxide that does not have aluminum oxide, the ferric oxide that boehmite alumina is arranged, ferric sulfate, the limonite that have used embodiment 1 raw material with there is the ferric sulfate of boehmite alumina to compare.Reaction conditions comprises, in semi batch reacor, and 445 ℃, pressure 2000psi (137.9 crust), 80 minutes residence time and in the catalyzer of conversion zone, the iron of every hydrocarbon and catalyzer is 0.7 weight %.The results are shown in the Table IV.
Table V
Figure BPA00001283934400251
Under each situation and under all parameters, the intermediate phase that the interpolation of aluminum oxide has all reduced iron-containing catalyst generates.The interpolation of boehmite alumina has improved the ferric sulfate performance of all kinds, but except reducing intermediate phase, not seeming helps ferric oxide.Bauxite has optimum performance in various types of.
Embodiment 9
Also ferric oxide of the present invention and aluminium oxide catalyst are tested, tested the ability that it improves the heavy hydrocarbon flowability of measuring by the API index.The heavy vacuum residuum feed of embodiment 1 has the API index for-0.7 degree, it is fed under simulated condition in the reactor of embodiment 4, and does not carry out the pre-treatment of any catalyzer.Catalyzer constitutes 3.7 weight % of non-gaseous material in the reactor.Iron constitutes 17.7 weight % of catalyzer, makes iron constitute hydrocarbon in the reactor and 0.7 weight % of catalyzer.The average particulate diameter of bauxite is between 1 and 5 micron, and its BET surface-area is 159m 2/ g.Different condition and results is provided in Table VI.
Table VI
Embodiment 1 2
Pressure 2000 1500
Temperature, ℃ 455 460
Reaction times, minute 80 80
Fitting of fluids, weight % 81.9 81.0
Coke yield, the weight % of raw material 1.7 0.6
Gas-selectively, weight % 16.4 18.9
The API of product liquid 24.0 23.8
The % of API increases 2470 2450
Table VI shows that the catalyzer of iron content and aluminum oxide provides the castering action aspect mobile, with regard to 24 times api gravity.
Embodiment 10
Test has the catalyzer that contains aluminum oxide and iron of different water-contents, is determined at the effect performance of the water on the identical bauxite catalyzer.For all experiments, 455 ℃ of conditions, 2000psi (137.9 crust), semi batch reacor, the hydrogen of 6.5sl/min and 80 minute residence time all are constant.The iron level of the catalyzer of the every non-pneumatic material in the SHC reactor is 0.7 weight %, also is constant.The bauxite catalyzer of test comprises 39.3 weight % aluminum oxide, and 15.4 weight % ferric oxide and loss on ignition (LOI) are 38.4 weight % in the time of 900 ℃, and it has mainly represented water, and having the BET surface-area is 235m 2/ g, average particulate diameter are 299 microns.Water-content on catalyzer, by 900 ℃ loss on ignitions (LOI) expression, it is listed in Table V by dried each numerical value.Run through full experiment, catalyzer comprises 63.8 weight % aluminum oxide and 25.0 weight % ferric oxide, based on non-volatile substance.
Table VII
Sample 523-87 523-93 523-94
LOI, weight % 38.4 23.3 10.6
The pitch transformation efficiency, weight % 84.42 84.31 84.25
The C1-C4 productive rate, the weight % of raw material 10.78 10.56 10.63
C5-525 ℃, the weight % of raw material 67.70 67.07 68.80
The TIOR productive rate, weight % 3.19 3.33 3.16
The intermediate phase productive rate, XRD, weight % 0.18 0.18 0.18
On all water-contents, the performance of aluminum oxide and ferric oxide catalyst all is comparable.This performance shows that water-content can not hinder the formation of the iron sulphide that starts from ferric oxide.
Embodiment 11
On different larger particles diameters, test contains the catalyzer of aluminum oxide and iron, estimates the performance of similar bauxite catalyzer.For all experiments, 455 ℃ of conditions, 2000psi (137.9 crust), semi batch reacor, the hydrogen of 6.5sl/min and 80 minute residence time all are constant.The iron level of the catalyzer in the SHC reactor is also constant to be 0.7 weight %.Use dry method and the wet method of ASTM UOP856-07,, on Microtrac S 3500 instruments, measure average particulate diameter by scattering of light.In wet method, the sample of weighing is the slurry in the water of known quantity, and through supersound process.Put an aliquot into sample chamber and carry out light scattering measurement.In dry method, use different sample fixers, directly measure particle, but also by scattering of light.We believe the diameter that dry method provides, and can reproduce the characteristic that the simulation catalyzer runs into hydrocarbon feed at first better.Average particulate diameter and performance in Table VIII, have been listed relatively.
Table VIII
Average particulate diameter surpass catalyst performance that 200 microns aluminum oxide and ferric oxide catalyst and average particulate diameter be lower than 5 microns show the same good.During up to 554 microns, also observe comparable performance at average particulate diameter.We do not believe that water-content has influenced performance relatively, does not influence performance basically because we have found that water-content.It is less significantly that the wet method particle is measured, and it can show that this method falls particle more in small, broken bits with granules of catalyst.This phenomenon may occur in the SHC reactor.
Embodiment 12
With the bauxite sample in embodiment 10 and 11, under the state identical, place SHC, except temperature of reactor is 455 ℃ with embodiment 5 with varying particle size.To ferric sulfate, temperature of reactor is 445 ℃.Use XRD to measure iron sulphide crystallite mean diameter, it is based on the iron sulphide peak width at 43 2 θ angles.Size for diffraction peak broadens, and uses the Debye-Scherrer formula to decide crystallite size.Crystallite size and intermediate phase productive rate umber in Table I X, have been listed.
Table I X
Figure BPA00001283934400291
The average crystallite diameter of the iron sulphide that XRD obtains for bauxite, is positioned at far below the narrow nanometer range for the average crystallite diameter of minimum iron sulphide of ferric sulfate.Catalyst sample is recycled to SHC once with twice after, the iron sulphide crystallite size does not change basically.

Claims (10)

1. composition of matter, it comprises the iron sulphide crystallite that mean diameter is 1 to 150 nanometer.
2. the composition of claim 1, wherein iron sulphide crystallite mean diameter is no more than 100 nanometers.
3. the composition of claim 1, wherein iron sulphide crystallite mean diameter is no more than 75 nanometers.
4. the composition of claim 1, wherein iron sulphide crystallite mean diameter is no more than 50 nanometers.
5. the composition of claim 1, wherein iron sulphide crystallite mean diameter is no more than 40 nanometers.
6. the composition of claim 1, wherein iron sulphide crystallite mean diameter is not less than 5 nanometers.
7. the composition of claim 1, wherein iron sulphide crystallite mean diameter is not less than 10 nanometers.
8. the composition of claim 1, wherein iron sulphide crystallite mean diameter is not less than 15 nanometers.
9. the composition of claim 1, it further comprises 20 to 98 weight % aluminum oxide.
10. one kind is converted into the processing method of light hydrocarbon product with heavy hydrocarbon feeds, and it comprises:
Described heavy hydrocarbon liquid raw material is mixed with granules of catalyst and hydrogen, form the heavy hydrocarbon slurry;
In hydrocracking reactor, in the presence of hydrogen and granules of catalyst, the hydrocracking hydrocarbon comes production hydrocracking slurry product in described heavy hydrocarbon slurry, and it comprises the light hydrocarbon product, and described granules of catalyst comprises the iron sulphide crystallite of mean diameter 1 to 150 nanometer; And,
From hydrocracking reactor, take out hydrocracking slurry product.
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