CN102076611B - Catalyst composition with nanometer crystallites for slurry hydrocracking - Google Patents

Catalyst composition with nanometer crystallites for slurry hydrocracking Download PDF

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CN102076611B
CN102076611B CN200980125314.1A CN200980125314A CN102076611B CN 102076611 B CN102076611 B CN 102076611B CN 200980125314 A CN200980125314 A CN 200980125314A CN 102076611 B CN102076611 B CN 102076611B
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iron
crystallite
iron sulphide
catalyzer
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CN102076611A (en
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A·巴塔查里亚
B·J·梅扎
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Honeywell UOP LLC
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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

The catalyst composition with nano microcrystalline for slurry hydrocracking
background of invention
The present invention relates to process the method and apparatus of crude oil, more specifically, relate to the hydrocracking that heavy hydrocarbon carries out under additive and catalyzer exist, to provide useable products and further for the preparation of the raw material of refining in addition.
Along with the decline of conventional crude reserves, heavy oil must be upgraded to 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 material such as petroleum crude oil, atmospheric tower bottom product, vacuum column bottom product, heavy recycle stock, shale oil, the derivative liquid of coal, former oil residue, topped oil and the heavy bituminous oil refining from oil-sand.Interesting is especially the oil that sand oil extracting is produced, and it includes wide boiling range material, from petroleum naphtha to kerosene, gasoline, pitch, etc., and the boiling point that contains vast scale is higher than the material of approximately 524 ℃.The feature of these heavy hydrocarbon feeds can be, the low reactivity in viscosity breaking, high coking trend, to the Wheat Protein of hydrocracking and be difficult to distillation.Be upgraded the bituminous matter that the most of residue oil raw material of processing contains a tittle, it is generally considered to be heptane insoluble compound, according to the mensuration of ASTM D3279 or ASTM D6560.Bituminous matter is a kind of heteroatomic macromolecular compound containing importing polarity.
Before it is further processed into as 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, and such as postponing or fluidisation coking, and hydrogenation technique such as ebullated bed (ebullated bed) or slurry hydrocracking (SHC).For example, at room temperature, from the bitum coking of Canada, the productive rate of product liquid, is typically, 55 to 60 % by weight, and the coke of a great deal of is as by product simultaneously.For similar raw material, the liquid product yield of 50 to 55 % by weight is generally produced in boiling bed hydrogenation cracking.US5,755,955 have described a kind of SHC technique, and it has been found to provide the liquid product yield of 75 to 80 % by weight, and by the use of additive, greatly reduces the formation of coke.
In SHC, the three-phase mixture of heavy liquid oil raw material, under gaseous hydrogen exists, at high temperature and add and depress, carries out cracking on solid catalyst, produces lighter product.As SHC catalyzer, for example, at US5, in 755,955, ferric sulfate is disclosed.Ferric sulfate monohydrate is generally ground into reduced size, to better disperseed, and promotes mass transfer.Ferric sulfate (FeSO 4) conventionally need aerial careful thermal treatment, the water in the ferric sulfate generally providing with hydrated form is provided.Water can suppress FeSO 4be converted into the transformation efficiency of iron sulphide, generally must be removed.It is believed that ferric sulfate monohydrate slowly decomposes and forms iron sulphide in SHC.By ferric sulfate monohydrate dried in place, dehydration forms FeSO at first 4, shown in (1).Yet, FeSO 4in its decomposition course, also hydration becomes monohydrate again, forms iron sulphide, suc as formula (2).Finally, FeSO 4be converted into iron sulphide, shown in (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 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 becomes the iron in conversion ferric sulfate in the iron sulphide of catalytic activity.Sulphur in ferric sulfate has increased the sulphur in product, and it must be removed.The catalyzer of other iron content is limonite for example, and it contains FeO (OH) nH 2o, needs prevulcanized thing to process better to be disperseed and the better transformation efficiency from ferric oxide to active iron sulphide, according to CA2, and 426,374.Prevulcanized thing is processed 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 iron sulphide catalyzer, need to be at the active iron of+2 oxidation state to obtain enough transformation efficiencys and the selectivity to 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 to catalyzer.SHC catalyzer is generally ground into very fine particle diameter and promotes to disperse and promote mass transfer.
At SHC, between the reaction period, it is important making coking reduce to minimum.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.In the situation that lacking polarity aromatic hydrocarbon, if or polarity aromatic hydrocarbon is diluted by paraffin molecules or is converted to lighter paraffinic hydrocarbons and aromatic materials, these bituminous matters meeting self-associations, or flocculation forms larger molecule, in the middle of producing mutually and from solution Precipitation, 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 middle phase, and heavier and more soluble than the bituminous matter that dissolves in heptane.The middle reaction of formation is mutually the key reaction restriction in slurry hydrocracking reaction.Centre is hypocrystalline carbonaceous material mutually, and it is defined as being present in the circular anisotropic particles in pitch, and boiling point is more than 524 ℃.The existence of middle phase can be as the too violent early warning of the operational condition of SHC, and coking is formed under this condition and will occurs possibly.
summary of the invention
The iron sulphide crystallite that we have found that nano-scale can provide dominant transformation efficiency in SHC reaction.Iron sulphide crystallite usually has the size identical with iron sulphide precursor crystallite, and this iron sulphide crystallite is obtained by iron sulphide precursor crystallite.In bauxite, iron sulphide precursor crystallite is ferric oxide.Before SHC, iron sulphide precursor is not heat-treated, iron sulphide precursor crystallite can not be sintered together and become larger, allows thus catalytic activity iron sulphide crystallite to remain in nanometer range.
Accompanying drawing explanation
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 Ting region, its peak shows with shade.
Fig. 3 is the XRD figure of TIOR sample, and its Ting region, non--middle phase peak shows with shade.
Fig. 4 is the XRD figure of the TIOR that makes of a series of ferric sulfate catalysts.
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 traditionally hydrogenation processing, vacuum residuum for example, and viscosity breaking vacuum residuum, diasphaltene base material, defective pitch, the sediment at the bottom of fuel reserve tank, etc.Suitable raw material comprises that boiling point is at the long residuum of 650 °F (343 ℃), heavy vacuum gas oil (VGO) and vacuum residuum, and its boiling point surpasses the vacuum residuum of 950 °F (510 ℃) at 800 °F (426 ℃) and boiling point.In this specification, boiling point should be understood to be, and by observing boiling point and distillation pressure, calculates atmosphere boiling point (AEBP, atmospheric equivalent boiling point) of equal value, for example, the formula providing in ASTM D1160 is provided.In addition, term " pitch " refers to vacuum residuum, or has the material of the AEBP that is greater than 975 °F (524 ℃).Wherein the boiling point of 90 % by weight materials will be suitable greater than or equal to the raw material of 572 °F (300 ℃).Suitable raw material comprises that api gravity is no more than 20 degree, is generally no more than 10 degree, and can comprises the raw material 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 asphalt material that the contains granules of catalyst stream in pipeline 39 can merge at pipeline 10 with recycle of heavy VGO together with pipeline 37.Merging material stream heating in well heater 32 in pipeline 10, and be pumped through the bottom inlet that introduction pipe line 12 enters tubular type SHC reactor 13.Solid particulate matter catalystic material can directly be added to the heavy hydrocarbon oil that adds SHC reactor 13 from pipeline 6, or can before entering reactor 13, from pipeline 6 ', mix to form the slurry in reactor 13 with the heavy hydrocarbon oil with pipeline 12.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 larger iron particle, and it will be avoided.It can be suitable that various mixing and pump line system are arranged.Consider, feeding material stream can be to add to independently in SHC reactor 13 simultaneously.Recycle hydrogen in pipeline 30 and hydrogen make-up, by pipeline 14, after the heating through well heater 31, join in SHC reactor 13.Hydrogen in pipeline 14, it is not carry out pre-mixing with raw material, on the position on material inlet, by pipeline 12, adds.Hydrogen in raw material in pipeline 12 and pipeline 14 all distributes by suitable divider in SHC reactor 13.In addition, hydrogen can be added to (before it heats in well heater 32) in the raw material in pipeline 10, and is sent in SHC reactor by pipeline 12.Preferably, the recirculation asphalt material stream in pipeline 39 has formed the raw material that adds SHC reactor 13 of 5 to 15 % by weight, and the heavy VGO in pipeline 37 has formed the raw material of 5 to 50 % by weight simultaneously, depends on raw materials quality and single-pass conversion level.Enter the raw material packet of this SHC reactor 13 containing three-phase, solid catalyst particle, liquid and hydrocarbon solid raw material and gaseous hydrogen and vaporized hydrocarbon.
Processing method of the present invention can operate under quite medium pressure, its scope is 500 to 3500psi (3.5 to 24MPa), preferably 1500, arrive between 2500psi (10.3 to 17.2MPa), and in SHC reactor 13, do not have coke to form.Temperature of reactor is generally 400 ℃ to 500 ℃, and 440 ℃ to 465 ℃ is comparatively suitable, and preferably 445 ℃ to 460 ℃.LHSV is generally lower than 4hr -1, based on fresh feed, preferably 0.1 arrive 3hr -1, particularly preferably 0.3 arrive 1hr -1.Although SHC can carry out in various known upper reaches or downflow reactor, it is particularly suitable for tubular reactor, and its Raw, catalyzer and gas move up by it.Therefore, the outlet of SHC reactor 13 is higher than import.Although only shown one in 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.In SHC reactor 13, also can add defoamer, 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 by hot high-pressure separator 20, carries out separation, and its separation temperature is (392 and 878 °F) 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 further processes to reclaim 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 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 in vacuum distilling temperature, make atmosphere cut point of equal value between lightweight VGO and heavy VGO, between 250 ℃ and 500 ℃ (482 ° and 932 °F).Can be in liquid separation column separated three cuts: the lightweight VGO overhead fraction in overhead line 38, it can further be processed, heavy VGO material from side stream in pipeline 29 (sidecut) flows and is flowed by tower bottom tube line 40 acquisition asphalt materials, and its general boiling point is higher than 450 ℃.At least a portion asphalt material stream has formed a part for the feed slurry of SHC reactor 13 since can looping back by pipeline 39.The residual catalyst particle of SHC reactor 13 will appear in asphalt material stream, and can be circulated back to easily in SHC reactor 13.Any remainder of asphalt material stream reclaims by pipeline 41.At SHC, between the reaction period, it is important making coking reduce to minimum.Add rudimentary polarity aromatic oil and will lower coking generation in raw material.Polarity aromatic materials can be from various sources.A part of heavy VGO in 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 pipeline 18 generally contains than the lower aromatic component of liquid distillate concentration in pipeline 16, and may need to carry out further refining.Gas streams in 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 material stream in pipeline 18 by pipeline 18.Suitable hydrotreating catalyst of the present invention is any known conventional hydrotreating catalyst, and comprises that comprising at least one loads on high surface area support material such as the VIII family metal on refractory oxide and at least one VI family metal, those.Air-flow and hydrotreating catalyst contact between 200 ℃ and 600 ℃ (430 ° and 1112 °F), under hydrogen exists, 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 pipeline 46.
The relief liquor deriving from the pipeline 46 of hydrotreating reactor 44 is admitted in cold high pressure separator 19.In cold separator 19, product is separated into hydrogen rich stream, and it is deviate from from tower top by pipeline 22, and liquid hydrocarbon product, and it is deviate from from bottom by pipeline 28.Fu Qing material stream 22 can, by filling washing tower 23, wherein wash to remove hydrogen sulfide and ammonia by the washings in pipeline 25.The washings with crossing in pipeline 27 can be reproduced and recirculation, is generally amine.Washed rich hydrogen material stream is discharged from washer by pipeline 34, and merges with the hydrogen make-up in fresh pipeline 33, and gets back in 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 pipeline, although only shown one in Fig. 1.Product fractionator is produced the C reclaiming in overhead line 52 4 -, the naphtha products material stream in pipeline 54, the lightweight VGO material stream in the diesel stream in pipeline 56 and tower bottom tube line 58.
We have found that the ferric oxide that comprises between 2 and 45 % by weight and the granules of catalyst of the aluminum oxide between 20 and 90 % by weight obtain excellent SHC catalyzer.The bauxite of iron content is the mineral that can obtain in a large number preferably with these character.Bauxite typically has 10 to 40 % by weight ferric oxide, Fe 2o 3, and 54 to 84 % by weight aluminum oxide, and can there are 10 to 35 % by weight ferric oxide and 55 to 80 % by weight aluminum oxide.Bauxite also can comprise silica, SiO 2, and titanium dioxide, TiO 2, its common total amount is no more than 10 % by weight, and general total amount is no more than 6 % by weight.Iron is present in bauxite with form of iron oxide, and aluminium is present in 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 bauxite.Again, aforementioned ratio has been got rid of the water in 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 axle of the maximum quadrature of particle.We have found that average particulate diameter is not less than aluminum oxide and the ferric oxide catalyst of 200 microns, it measures particle diameter with drying means, has shown performance that can be suitable with the same catalyzer that is ground to 0.1 to 5 micron.Therefore, average particulate diameter is lower than 200 microns, suitably lower than 249 microns, preferably 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, with regard to measure the average particulate diameter that particle diameter obtains by desiccating method with regard to.Average particulate diameter is all average particulate diameters that are fed to the granules of catalyst in reactor, and it can be measured by representative sampling method.Therefore, can spend less energy and granules of catalyst is worn into small diameter promote SHC, substantially lower time and cost.The mensuration of granularity is undertaken by desiccating method, and it can more relevantly simulate a large amount of catalyzer is how to run into hydrocarbon feed at first.The wet method of measuring particle diameter seems bauxite ore particles to be divided into compared with small-particle, and it in the time of may having shown in catalyzer is joined to SHC reactor, what can occur.
Aluminum oxide in catalyzer can be a few types, comprises alpha, gamma, θ, and boehmite, intends boehmite, gibbsite, diaspore, bayerite, nordstrandite (nordstrandite) and silicon carbide.Aluminum oxide can derivative, such as spinel and uhligite, provides in catalyzer.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 first they do not heat-treat or sulfide removal.We also find that water does not hinder in the ferric oxide from bauxite and forms active iron sulphide, therefore, do not need to come except anhydrating by heat or any other drying treatment.Water on catalyzer can be to be chemically bonded on ferric oxide, aluminum oxide or other catalyst component, or with catalyzer physical bond.Catalyzer can have the water that surpasses 23 % by weight, and can not affect catalyst performance.We have found that 39 % by weight water can not affect the performance of catalyzer, and the water that expection reaches at least 40 % by weight is in catalyzer, also can not affect performance.Water on catalyzer can pass through loss on ignition (1oss on ignition, LOI) to be measured, 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 ferric oxide, at aluminum oxide, under the existence such as bauxite, under heavy hydrocarbon feeds and hydrogen existence, 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 conventionally by molecular formula Fe xs represents, wherein X is between 0.7 and 1.3.We have found that all ferric oxide, by heat hydrocarbon and catalyzer to 410 ℃, under hydrogen and sulphur existence, are transformed into iron sulphide substantially.In this respect, " substantially all " refer to intensity to the XRD figure of 2 θ angles (two theta degree) on, at 33.1 2 places, θ angles, do not produce the peak of ferric oxide, or be not less than 99 % by weight iron sulphide transformation efficiencys.Sulphur may reside in hydrocarbon feed, as organic sulfide.Therefore, the iron in catalyzer can be added in heavy hydrocarbon, adds, preferably as Fe with the form of+3 oxidation state 2o 3.In reaction zone or before entering reaction zone and without pre-treatment, catalyzer can be added in 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 raw material is converted into hydrogen sulfide and the hydrocarbon of sulfur-bearing not.In catalyzer+iron of 3 oxidation state promptly reacts with the hydrogen sulfide in conversion zone of producing that reacts of organosulfur and hydrogen under temperature of reaction.Iron sulphide has been produced in the reaction of ferric oxide and hydrogen sulfide, and it is the activity form of catalyzer.Then, iron is present in reactor with+2 oxidation state.Ferric oxide has allowed do not adding sulphur to the operation in raw material, if exist the sulphur of enough available quantities to guarantee the conversion completely of iron sulphide in raw material to the transformation efficiency of iron sulphide.Otherwise, can add sulphur in low-sulfur raw material, if necessary, to whole ferric oxide are converted into iron sulphide.Because ferric oxide and aluminium oxide catalyst, transforming ferric oxide to iron sulphide and promoting SHC effectively like this in reacting, can add less iron to 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 under hydrogen exists, and carry out the conversion of iron sulphide.Conversion is carried out under lower than SHC temperature of reaction.By avoiding heating and sulfide pre-treatment, realized the reduction of processing method simplification and material cost.In addition, hydrogen demand is also minimized, and hydrogen sulfide still less and other sulphur must be removed from SHC product.
In SHC, for the performance characterization of ferric oxide and aluminium oxide catalyst, should be noted that several terms." iron level " refers to respect to non-gaseous material in SHC reactor, the weight ratio of the iron in catalyzer.Non-pneumatic material in reactor is generally hydrocarbon liquids and solid, and catalyzer, does not comprise reactor and supplementary unit." aluminium content " refers to respect to non-gaseous material in SHC reactor, the weight ratio of aluminium." pitch transformation efficiency " is to be 524 ℃ or lower than the material weight ratio of 524 ℃, with respect to the material higher than 524 ℃ at raw material mid-boiling point at product mid-boiling point." C 5-524 ℃ of productive rates " refer at product mid-boiling point at C 5the weight ratio of the material of boiling range to 524 ℃, with respect to total hydrocarbon raw material." TIOR " refers to the organic residue of toluene insoluble, and it is illustrated in product part mid-boiling point higher than the non-catalytic solid of 524 ℃." middle 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 mobility that represents material.It is identical with this average grain or crystallite diameter that average grain or crystallite diameter should be understood to, and comprise respectively whole particles or the crystallite in sample.
In SHC reactor, catalyzer iron level is generally 0.1 to 4.0 % by weight, is conventionally not more than 2.0 % by weight of catalyzer and liquid in SHC.Because iron is at aluminum oxide, under existence such as bauxite, it is very efficient at rapid sulphur from hydrocarbon feed, generating iron sulphide crystallite, and needs iron on ferric oxide and aluminium oxide catalyst still less promotes the conversion of heavy hydrocarbon feeds enough in SHC reactor.The iron level of catalyst reactor lower than or to equal 1.57 % by weight concentration be effectively, no more than 1 % by weight suitably, and preferred 0.7 % by weight, with respect to the non-pneumatic material in reactor.In one embodiment, the iron level of catalyst reactor is at least answered 0.4 % by weight.With regard to pitch transformation efficiency, C 5-524 ℃ of productive rates, TIOR productive rate and middle 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 bauxite form.The in the situation that of 2 % by weight iron, only, after carrying out a large amount of pre-treatment with sulfide, limonite can be suitable with bauxite, and after sulfide pre-treatment, limonite can produce too much middle phase productive rate.On catalyzer in reactor, under the lower concentration of 0.7 % by weight iron, the catalyzer of test can not be as playing a role as ferric oxide and aluminium oxide catalyst, and suppress TIOR and middle phase productive rate.In reactor, under approximately 1 and 1.5 % by weight iron levels, bauxite is better than ferric sulfate monohydrate and limonite performance.The product that our further discovery is obtained by ferric oxide and aluminium oxide catalyst catalysis can be realized the api gravity that is at least four times in raw material, reaches at least six times to raw material, and surpasses 24 times to raw material, has shown excellent heavy hydrocarbon transformation efficiency.Ferric oxide and aluminium oxide catalyst, 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 middle phase that produces sign as coking.
The existence of aluminum oxide in iron-containing catalyst has favorable influence to performance.Improved the characteristic in SHC reaction with the aluminum oxide that other iron-containing catalysts are combined, particularly in suppressing the generation of middle 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 % by weight, with respect in reactor non--gaseous state solid.Preferably be no more than the aluminium content of 10 % by weight.
In reactor and the iron sulphide crystallite being generated by bauxite under reaction conditions there is the diameter that passes through crystallite in nanometer range.Iron sulphide crystal is a kind of solid, and wherein component FeS molecule is piled up according to orderly order, and repeat pattern is expanded on all three-dimensional space.Iron sulphide crystallization forms the region 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 iron sulphide crystallite is produced by described precursor crystallite.In bauxite, iron sulphide precursor crystallite is ferric oxide.Due to without thermal treatment alum clay ore deposit, it is large that ferric oxide crystal can not be sintered together and become.Therefore the catalytic activity iron sulphide crystallite, being generated by ferric oxide remains in nanometer range.Iron sulphide crystallite can have average largest diameter be 1 and 150nm between, be generally no more than 100nm, be no more than suitably 75nm, be preferably no more than 50nm, more preferably no more than 40nm, it is measured by electron microscope technique.Iron sulphide crystallite has average crystallite diameter suitably for being not less than 5nm, is preferably not less than 10nm and is most preferably not less than 15nm, and it is measured by electron microscope technique.Electron microscope technique shown, iron sulphide crystallite is at the suitable homogeneous of diametrically, good dispersion, and mainly with monocrystalline, exist.With XRD, measure iron sulphide crystallite size, obtain less crystallite size, perhaps this be because the different iron being present in iron sulphide provides the peak that approaches 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.For ferric oxide, to the transformation efficiency of iron sulphide, for example, in reactor, generated the composition that comprises 2 to 45 % by weight iron sulphide and 20 to 98 % by weight aluminum oxide, and be dispersed in heavy hydrocarbon medium slurry is provided.The iron sulphide crystallite that composition comprises above-mentioned nanometer range.We have found that iron oxide precursor crystallite in bauxite has the particle diameter identical with iron sulphide crystallite by forming with reaction of Salmon-Saxl.We further find that aluminum oxide and ferric oxide catalyst can be recycled in SHC reactor at least twice, and can not make iron sulphide crystallite become large.
Cross polarization light display microtechnology (PLM) can be used to use ASTM D4616-95 to measure from the middle phase structure in the TIOR of SHC reaction and quantitatively phase concentration.The hypocrystalline attribute of middle phase makes it under cross polarization light, have optical activity.Collect TIOR sample, embedded in epoxy and polishing.Use PLM also generate sample image identification and the centre in PLM image is counted mutually, the relative quantity of middle phase can be by quantitatively.
We also find that the semi-crystalline character of middle phase also allows it on XRD figure picture, to occur.In the middle of we have found that, the existence of phase shows by the peak of locating at 26 2 θ angles on XRD figure picture, and it is within ± 0.3 °, preferably within ± 0.2 °.This phase peak, centre in XRD figure picture is mutually corresponding with the centre that PLM finds.We find, and the wide shape of the scope between 20 and 29.5 2 θ angles can be mutually relevant with centre.
For the middle phase of analytic sample, with 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 at 90 ℃ dry 2 hours.Now, drying sample is just ready to carry out centre by PLM or XRD and measures mutually.For XRD, by a standard, such as silicon, add solid sample, such as acetone, form slurry with solvent, to allow sample to mix with standard.Solvent should promptly be evaporated, and leaves the sample of the standard with predetermined concentration.The sample of about 1 gram and standard are spread in XRD sample holder, and put into XRD instrument, such as Scintag XDS-2000XRD instrument, and use pre-determined range parameter to scan.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 can be also suitable.For example use Livermore, the JADE software of the Materials Data Inc. company of California carrys out drawing result data, and it can be loaded on XRD instrument.JADE software application International Center for Diffraction Data (ICDD) as standard database, carry out evaluation and the automatic search matching feature of phase.
For phase concentration in the middle of calculating, should calculate peak in total carbon region the total area of (rightmost edges at the silicon peak at the 2 θ angles from the 2 θ angle right sides to 28.5 of 20 ° °).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 region should comprise nearly 29.5 2 θ angles.The wide shape part at middle phase peak may be arranged in total carbon region.In JADE software, can use Peak Paint function to obtain the peak area in total carbon region from XRD figure picture.Total carbon district inclusion is at the middle phase peak at the 2 θ angles of 26 °, if phase in the middle of existing, and the silicon peak that derives from the 2 θ angles of 28.5 ° of the silicon standard joining in sample.Once measure the peak total area in total carbon region, in the middle of total carbon region non-, phase peak can be determined, and calculates the total area of they and silicon peak area, and from the peak total area at peak, total carbon region, deducts the area at phase peak in the middle of obtaining.Non--middle phase peak in total carbon region can be measured with JADE software, and it can mate the peak image in collection of illustrative plates with the base peak image in ICDD database.Bauxite, for example, generally comprise titanium dioxide, and it provides the peak at 26.2 2 θ angles.Other non--centre mutually can be determined, to deduct respective peaks area from middle phase peak area.In the middle of non-, the baseline at phase peak can be such the draws, and draws the baseline of bottom of each side of connecting peak, and it is made a distinction from middle phase peak.These He Gui peaks, non-middle phase peak in total carbon region, carry out highlighted demonstration by the Peak Paint function of JADE software, and calculate its area.In the middle of non-, phase peak, with respect to middle phase peak area, is not obvious especially.Subsequently, can calculate with two areas at He Gui peak, middle phase peak the middle phase weight fraction in sample, use formula (1):
X m＝X st(A m/A st)(1)
X wherein mthe middle phase weight fraction in sample, X stthe weight fraction that adds the standard of sample such as silicon, A mphase peak area in the middle of being, A stit is the peak area of standard.Using term " middle phase weight fraction " is because description standard can be useful with the correction factor of middle mutually peak-to-peak relation in formula (1), but we do not expect that this correction factor will significantly change the result of formula (1).Phase productive rate umber in the middle of calculating, it is the middle phase umber of the hydrocarbon production that offers SHC reactor of every weight part, determines whether that the centre producing in reaction is mutually too much, shows thus the risk that too much coking produces.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 tIORthe quality of the product of TIOR in product, M hCBNit is the quality of the hydrocarbon in raw material.In successive reaction, can mass velocity form be used as quality and be used in calculating, and in batch reaction, use rest mass to be used as quality.Phase productive rate umber in the middle of calculating by formula (3):
Y middle phase=X m* Y tIOR(3)
Y wherein middle phasethe productive rate umber of phase in the middle of being.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 be multiplied by the middle phase umber in TIOR sample, X n, phase productive rate umber in the middle of measuring, Y middle phase, it is the middle phase quality that every mass parts offers the hydrocarbon production of SHC reactor.If middle phase productive rate umber surpasses 0.5 % by weight, should reduce SHC reactor harshness, to avoid the excessive coking in reactor, because centre produces mutually, be sizable.In other embodiments, should control severity, if middle phase productive rate umber should surpass, be low to moderate 0.3 and high to 0.8 % by weight.
By the amount of the middle phase measured according to the optics PLM method of ASTM D4616-95, ASTM D4616-95 is used as the two-dimensional areas of partial volume to make the method for sample.XRD method is used three-D volumes sample, and should provide more accurate middle indication mutually, with regard to the parts by weight with respect to raw material.Refractory phase hopes that two kinds of methods can provide identical result, but they should be mutually corresponding.
embodiment 1
Table I has characterized the raw material that is suitable for SHC.Except as otherwise noted, all use in all embodiments this raw material.
Test Vacuum substrate (975 °F+)
Proportion, g/cc 1.03750
Api gravity -0.7
ICP metal ?
Ni, ppm by weight 143
V, weight Ppm 383
Fe, ppm by weight 68.8
Micro-carbon residue, % by weight 25.5
C, % by weight 80.3
H, % by weight 9.0
N, % by weight 0.4
Total N, ppm by weight 5744
Oxygen, the % by weight in organism 0.78
Sulphur, % by weight 7
Ash, % by weight 0.105
Heptane insolubles, % by weight 16.1
Pentane insolubles, % by weight 24.9
Total chlorine, quality ppm 124
Saybolt viscosity, Cst150 ℃ 1400
Saybolt viscosity, Cst177 ℃ 410
" ICP " represents inductively coupled plasma atomic emission spectrum, and it is the method for measuring metal content.
embodiment 2
The middle phase of the TIOR sample that the analysis of use XRD method obtains in this wise, by SHC, react, use the heavy oil feedstock in embodiment 1, and the iron level in 0.7 % by weight ferric sulfate monohydrate catalyzer, its as in SHC reactor non--gaseous material percentage recently.The sample of SHC product material is mixed with toluene, then centrifugal, and pour out liquid phase.Remaining solid is repeated to these steps repeatedly.Then dry remaining solid in vacuum drying oven is dried 2 hours at 90 ℃.By adding silicon solid and acetone solvent in TIOR sample and smashing into slurry with mortar and pestle, silicon standard is joined in sample, obtain 5.3 % by weight concentration.Acetone is evaporated from slurry, leave the solid of the mixture that comprises TIOR and silicon standard.The solid sample mixing with standard of about 1g is deployed on XRD sample fixer, and puts into XRD instrument, and use the parameter of 2.0/70.0/0.04/10 (sec) to scan.XRD instrument is Scintag X1 instrument, and it is the fixed slit system that θ-θ protractor, Peltier cooled detector and copper pipe are housed.XRD instrument moves under the condition of 45kV and 35mA.With the JADE software being carried on XRD instrument, carry out 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 middle phase at the peak at 26.0 2 θ angles.The peak total area in the total carbon region of the silicon peak rightmost edges at the 2 θ angles at the 2 θ angles to 28.5 from 20 ° °, 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 total carbon region is 29.5 2 θ angles.The phase peak in the middle of total carbon region non-of identifying by Peak Paint function in Fig. 3 and tint, and the centre of form is at the silicon peak at 28.5 2 θ angles.Bauxite, for example, generally comprise titanium dioxide, and it provides the peak at 26.2 2 θ angles.In Fig. 3, so identify other non-middle phase peak highlighted demonstration.The baseline that has shown non-middle phase peak in Fig. 3, this baseline has connected the substrate of each side at each peak, by its remainder from middle phase peak separately.These He Gui peaks, non-middle phase peak in total carbon region, carry out highlighted demonstration by the Peak Paint function of JADE software, and calculate its area.The area at silicon peak is 43,190 square measures, and is 1,374 square measure at other non-middle phase peak area in total carbon region, and it is inessential comparatively speaking.Within the scope of hydrocarbon and the total area mutually irrelevant peak, centre, calculate by Peak Paint function, is 44,564 square measures.From the total area at peak, total carbon region, deduct non-middle phase area, the area at phase peak in the middle of obtaining, it is 208,446 square measures.Subsequently, with two areas at He Gui peak, middle phase peak, calculate the percentage ratio of the middle 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 middle phase:
Y middle phase=X m* Y tIOR=0.249*0.0551=0.0141 (3)
Y middle phasebe expressed as 1.41 % by weight percentage ratios, it is associated with 1.22% middle phase concentration, with ASTM D4616-95, by PLM, measures.Because middle phase productive rate umber is large (it is higher than 0.5 % by weight) quite, reaction has the danger of excessive coking, should control rapidly its severity.
embodiment 3
In this embodiment, we have checked that the iron in 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 bar), and it is 2 % by weight iron that its consumption makes iron level, based in reactor non--gaseous material.Selecting this temperature, is because it is the optimal temperature of sulphur monohydrate catalyzer in pitch transforms.Set up semicontinuous reaction, make to retain liquid hydrocarbon and catalyzer in reactor; Yet, the hydrogen of 6.5 standard liter/min (sl/m) is passed through to slurry, and emits from reactor.In the differential responses stage, the solid material separated with vacuum residuum feed carried out to X-ray diffraction (XRD) and characterize, 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 obtaining 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 obtain for 0,15,30,60 and 80 minute, its in Fig. 4 from being up to minimum image.After reactor heating reaches reaction conditions in 30 minutes, the time opening measures.In resembling, XRD figure shown Fe (SO 4) H 2the existence of O, its peak is 18.3 and 25.9 2 θ angles.Lower Table II has provided the Fe (SO of each time 4) H 2o ratio.Reaction, after heating in 0 minute, only has the Fe of 30 % by weight to show as iron sulphide, the 2 θ angles that its peak is 44.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 (% by weight)
0 70
15 16
30 14
60 5
80 4
embodiment 4
In order understanding from bauxite, to form iron sulphide, to have carried out following experiment, the vacuum residuum in embodiment 1 is added in semi batch reacor, 460 ℃ of temperature, 2000psi (137.9 bar), passes through residue by hydrogen with the speed of 6.5sl/m.Bauxite catalyzer after 30 minutes, allows reaction carry out with preliminary heating 80 minutes.After preliminary heating, in the time of 0,15 and 80 minute, the solid of collecting in reactor is measured its X-ray diffraction image.Carry out under the same conditions the second cover experiment, except temperature of reactor being set in to 410 ℃, and after preliminary heating, in the time of 0 and 80 minute, collect solid.In Fig. 5, shown XRD figure picture.The experiment of carrying out at 460 ℃, is three XRD figure pictures minimum in Fig. 5, and the experiment of carrying out at 410 ℃, is three XRD figure pictures the highest in Fig. 5.In all cases, when reaching temperature of reaction, reactor just formed iron sulphide, the 2 θ angles that its peak is 44.In any XRD figure picture, equal no evidence shows the existence of ferric oxide, shows that substantially all ferric oxide have been converted into iron sulphide.
embodiment 5
Contain with Fe 2o 3the 17.7 % by weight Fe that form exists, and the bauxite of the 32.9 % by weight Al that exist with boehmite alumina and other iron-bearing minerals that can obtain in a large number, such as ferric sulfate monohydrate and Yandi limonite ore, it derives from various sources, compares.By the wet method of ASTMUOP856-07, characterize granularity.The characterization data that has shown all material in Table III.
Table III
Sample description Bauxite Ferric sulfate monohydrate Rhombohedral iron ore Limonite chip
Al, % by weight 32.9 ? ＜0.006 0.7
Fe, % by weight 17.7 29.1 67.8 52.4
Ti, % by weight 1.88 ? ＜0.003 0.029
LOI at 900 ℃, quality % 7.6 54.6 0.8 17.1
Iron cpd Fe 2O 3 Fe(SO 4) Fe 2O 3 FeOOH
Iron cpd, % by 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
BET surface-area, m 2/g 159.0 ? 5.0 94.0
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 iron amount between 0.4 and 2 % by weight.In the embodiment listing in Table IV, autoclave is heated to 445 ℃ and reaches 80 minutes, and pressure is 2000psi (137.9 bar).Hydrogen is added to reactor by sparger continuously, and through reactor, its speed is 6.5 standard Liter Per Minutes, and by vacuum breaker to maintain pressure.Hydrogen is separated from lighter products, and it is in cold gas-liquid separation capture tank (khock-out trap pot) condensation.At heated mixt to before temperature of reaction, some limonite catalyzer are carried out to pre-treatment in this wise, by adding 1 or 2 % by weight sulphur, based on raw material and catalyzer, and heated mixt to 320 ℃ or 350 ℃, pressure is 2000psi (137.9 bar), in hydrogen one hour, carrys out deactivated catalyst.
In Table IV, " middle phase productive rate, XRD, % by weight " shows to identify middle phase by XRD, and expresses based on total hydrocarbon feed." in the middle of phase optics " is the percentage ratio of the middle phase of identifying in sample measured by polarizingmicroscopy.All productive rate numerical value calculate with the ratio to raw material.
Figure GSB00001046480900211
Ferric oxide and the higher pitch transformation efficiency of aluminium oxide catalyst explanation, higher C 5-524 ℃ of productive rates and lower TIOR, than the comparative catalyst of similar iron level.Only, after a large amount of pre-treatment and high 2 % by weight iron heap(ed) capacities, limonite is close to the 2 % by weight iron that obtaining in pretreated bauxite accordingly.Pretreated limonite is only better at TIOR productive rate, but has phase productive rate between unacceptable senior middle school.Under 0.7 % by weight Fe, than contrast material, bauxite embodiment has shown higher pitch transformation efficiency, C 5-524 ℃ of productive rates, lower TIOR productive rate.Bauxite is also better than 97 % by 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, the slow formation of iron sulphide in ferric sulfate monohydrate and limonite may hinder transformation efficiency, and has improved undesirably TIOR productive rate.
In many situations of Table IV, by the middle phasor of the optical method measuring of ASTM D4616-95, associated good with the amount of the middle phase of XRD determining.
embodiment 6
The catalyzer of series of experiments is used for generating the experimental data in embodiment 5, and wherein the weight of the liquid based in SHC reactor and catalyzer is that 0.7 % by 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 using in the numbering 523-4 experiment of listing in embodiment 5 resembles.XRD figure in Fig. 6 resembles, and has shown the sharp peak at 43 2 θ angles, and it is identified as iron sulphide, shows relatively large micro crystal material.Phase in the middle of the broad peak at the 2 θ angles 26 is identified as.The Photomicrograph that shows the iron sulphide crystallite that the terrible ferric sulfate monohydrate precursor crystallite from numbering 523-4 experiment forms in Fig. 7, it forms by SEM, under 10,000 times, has shown various crystallite sizes, is typically 150 to 800nm.Iron sulphide crystallite is the black particle in Fig. 7.
Fig. 8 has shown that the XRD figure of the TIOR of the limonite catalyzer generation with numbering 522-73 experiment of listing in embodiment 5 resembles.XRD figure in Fig. 8 resembles and has also shown sharp peak, and at 43 2 θ angles, it is identified as iron sulphide, shows relatively large micro crystal material.Again, phase in the middle of the large broad peak at 26 2 θ angles is identified as.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, iron sulphide crystallite is black particle.
Figure 10 has shown that the XRD figure of the bauxite catalyzer of numbering 522-125 experiment resembles, and it lists in embodiment 5.XRD figure has looked like to show wide Fang Feng, and it,, at 43 2 θ angles, is identified as iron sulphide.This broad peak shape is the performance of nanocrystal material.At 26 2 θ angles, do not have peak can be identified as middle phase.The peak at the 2 θ angles 25.5 is likely the titanium dioxide being present in bauxite and/or silver, and it is guessed for the pollutent on equipment liner.The peak at the 2 θ angles 26.5 is also likely silver chloride pollutent.The peak at the 2 θ angles 28 is the boehmites in catalyzer.Because bauxite also contains the boehmite alumina of a great deal of outside 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 in Figure 11.By the compound X ray of scanning transmission electron microscope art (STEM), chart 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.Iron sulphide crystallite is material more black in Figure 11, and severally irises out as an example.In Figure 11, many iron sulphide crystallites are identified as single crystallite.In Figure 11, alumina particle is larger light gray material.Aterrimus material in the central upper portion of Figure 11 is confirmed to be impurity.
While there is 0.7 % by weight iron level in SHC reaction zone, by XRD, show in ferric oxide and aluminium oxide catalyst, have few or there is no middle phase, other catalyzer have formed the middle phase of significant quantity simultaneously.
embodiment 7
The TIOR of series of experiments is used for generating the experimental data in embodiment 5, wherein the weight of the liquid based in SHC reactor and catalyzer is that 0.7 % by weight iron is recovered, and by polarizingmicroscopy (PLM) spectrum, according to ASTM D4616-95, confirm the middle phase in embodiment 5 and 6.
Figure 12 is the PLM image of the numbering 523-4 experiment TIOR of generation under ferric sulfate monohydrate catalyzer exists in 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 in Figure 12 has shown has the material of remarkable quantity to coalesce together, and it is the sign of middle phase.The PLM picture of Figure 12 has been supported the result of XRD analysis, and in the middle of its peak by 26 2 θ angles and 1.7% the optics that calculated by ASTM D4616-95, phasor and 1.03 % by weight calculated by XRD have confirmed the existence of middle phase.
Figure 13 is the PLM picture of the TIOR of the numbering 522-73 experiment in embodiment 5, and it has used limonite catalyzer, has provided its XRD figure picture in Fig. 8, has provided its SEM image in Fig. 9.Image Display in Figure 13, compares with Figure 12, and less material coalesces together, but the structure of air bubble-shaped has shown middle phase.The PLM photo of Figure 13 has been supported the result of XRD analysis, and wherein phasor in the middle of the peak at the 2 θ angles by 26 in Fig. 8 and 4.65% the optics that calculated by ASTM D4616-95, and 1.35 % by weight of calculating by XRD, has confirmed the existence of middle phase.
Figure 14 is the PLM image of numbering the TIOR of 522-125 experiment in embodiment 5, and it has used bauxite catalyzer, has provided its XRD figure and resemble in Figure 11.The Photomicrograph of Figure 14 shown, than Figure 12 and 13, material is still less coalescent.Only the centre of trace is present in PLM Photomicrograph mutually, this has supported the result of XRD analysis, by there is no at the peak at 26 2 θ angles, shown the existence without middle phase, and in the middle of calculating according to ASTMD4616-95, phasor is 0.00, what by XRD, calculated is 0.03 % by weight.
embodiment 8
The bauxite catalyzer of the numbering 522-124 experiment in embodiment 5, it contains aluminum oxide and ferric oxide, and has used the ferric oxide that there is no aluminum oxide, the ferric oxide that has boehmite alumina, the ferric sulfate of embodiment 1 raw material and has had the ferric sulfate of boehmite alumina to compare.Reaction conditions comprises, in semi batch reacor, and 445 ℃, pressure 2000psi (137.9 bar), 80 minutes residence time, and in the catalyzer of conversion zone, the iron of every hydrocarbon and catalyzer is 0.7 % by weight.The results are shown in Table V.
Table V
Figure GSB00001046480900251
In each situation and under all parameters, the centre that the interpolation of aluminum oxide has all reduced iron-containing catalyst generates mutually.The interpolation of boehmite alumina has improved the ferric sulfate performance of all kinds, but except in the middle of reducing mutually, do not seem and contribute to 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 mobility of measuring by API index.The heavy vacuum residuum feed of embodiment 1 has 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 forms 3.7 % by weight of non-gaseous material in reactor.Iron forms 17.7 % by weight of catalyzer, makes iron form hydrocarbon in reactor and 0.7 % by 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, % by weight 81.9 81.0
Coke yield, the % by weight of raw material 1.7 0.6
Gas-selectively, % by 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 mobility, with regard to the api gravity of 24 times.
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 identical bauxite catalyzer.For all experiments, 455 ℃ of conditions, 2000psi (137.9 bar), semi batch reacor, the hydrogen of 6.5sl/min and 80 minute residence time are all constant.The iron level of the catalyzer of the every non-pneumatic material in SHC reactor is 0.7 % by weight, is also constant.The bauxite catalyzer of test comprises 39.3 % by weight aluminum oxide, and 15.4 % by weight ferric oxide and loss on ignition (LOI) are 38.4 % by weight in the time of 900 ℃, and it has mainly represented water, and having BET surface-area is 235m 2/ g, average particulate diameter is 299 microns.Water-content on catalyzer, is represented by the loss on ignitions of 900 ℃ (LOI), it is listed in Table VII by dried each numerical value.Run through full experiment, catalyzer comprises 63.8 % by weight aluminum oxide and 25.0 % by weight ferric oxide, based on non-volatile substance.
Table VII
Sample 523-87 523-93 523-94
LOI, % by weight 38.4 23.3 10.6
Pitch transformation efficiency, % by weight 84.42 84.31 84.25
C1-C4 productive rate, the % by weight of raw material 10.78 10.56 10.63
C5-525 ℃, the % by weight of raw material 67.70 67.07 68.80
TIOR productive rate, % by weight 3.19 3.33 3.16
Middle phase productive rate, XRD, % by weight 0.18 0.18 0.18
On all water-contents, the performance of aluminum oxide and ferric oxide catalyst is all comparable.This performance shows, water-content can not hinder the formation of the iron sulphide that starts from ferric oxide.
embodiment 11
On different larger particles diameters, test the catalyzer that contains aluminum oxide and iron, evaluate the performance of similar bauxite catalyzer.For all experiments, 455 ℃ of conditions, 2000psi (137.9 bar), semi batch reacor, the hydrogen of 6.5sl/min and 80 minute residence time are all constant.The iron level of the catalyzer in SHC reactor is also constant is 0.7 % by weight.Use dry method and the wet method of ASTM UOP856-07, by scattering of light, on Microtrac S3500 instrument, measure average particulate diameter.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 better the characteristic that simulation catalyzer runs into hydrocarbon feed at first.Average particulate diameter and Performance Ratio in Table VIII, have been listed.
Table VIII
Figure GSB00001046480900281
The aluminum oxide of average particulate diameter over 200 microns is equally good lower than the catalyst performance performance of 5 microns with average particulate diameter with ferric oxide catalyst.At average particulate diameter, during up to 554 microns, also observe comparable performance.We do not believe that water-content has affected Performance Ratio, because we have found that water-content does not affect performance substantially.It is significantly less that wet process granule is measured, and it can show that the method falls into particle more in small, broken bits by granules of catalyst.This phenomenon may occur in SHC reactor.
embodiment 12
The bauxite sample with varying particle size by embodiment 10 and 11 is placed in SHC under the state identical with embodiment 5, except temperature of reactor is 455 ℃.To ferric sulfate, temperature of reactor is 445 ℃.With XRD, measure iron sulphide crystallite mean diameter, the iron sulphide peak width at its 2 θ angles based on 43.Size for diffraction peak broadens, and uses Debye-Scherrer formula to decide crystallite size.Crystallite size and middle phase productive rate umber in Table I X, have been listed.
Table I X
Figure GSB00001046480900291
The average crystallite diameter of iron sulphide that XRD obtains, for bauxite, is positioned at the narrow nanometer range far below the average crystallite diameter of minimum iron sulphide for ferric sulfate.After catalyst sample is recycled to SHC once with twice, iron sulphide crystallite size there is no change.

Claims (10)

1. a composition of matter, it comprises the iron sulphide crystallite that mean diameter is 1 to 150 nanometer, and described iron sulphide crystallite comprises the Fe that is not less than 99 % by weight xs, wherein x is between 0.7 and 1.3.
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 % by weight aluminum oxide.
10. heavy hydrocarbon feeds is converted into a processing method for light hydrocarbon product, it comprises:
Described heavy hydrocarbon liquid raw material is mixed with granules of catalyst and hydrogen, form heavy hydrocarbon slurry;
In hydrocracking reactor, under hydrogen and granules of catalyst existence, in described heavy hydrocarbon slurry, hydrocracking of hydrocarbon carrys out production hydrocracking slurry product, it comprises light hydrocarbon product, the iron sulphide crystallite that described granules of catalyst comprises mean diameter 1 to 150 nanometer, described iron sulphide crystallite comprises the Fe that is not less than 99 % by weight xs, wherein x is between 0.7 and 1.3; And,
From hydrocracking reactor, take out hydrocracking slurry product.
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第1栏第23至26行
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