CN104774656B - Method and apparatus for producing hydrocarbon fuel and compositionss - Google Patents
Method and apparatus for producing hydrocarbon fuel and compositionss Download PDFInfo
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- CN104774656B CN104774656B CN201510114165.6A CN201510114165A CN104774656B CN 104774656 B CN104774656 B CN 104774656B CN 201510114165 A CN201510114165 A CN 201510114165A CN 104774656 B CN104774656 B CN 104774656B
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Classifications
-
- 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
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
-
- 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
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Heavy hydrocarbon charge is carried out into slurry hydrocracking production HVGO streams and Colophonium stream.At least a portion asphalt material is made to flow through by SDA to prepare the DAO streams of depleted metal.DAO is mixed to provide turbine or marine fuel with the acceptable performance of burning or marine fuel grade in gas turbine with least a portion HVGO stream.
Description
The application is the divisional application of the application for a patent for invention of Application No. 201080056121.8, the applying date of original application
It is on November 29th, 2010, entitled：Method and apparatus for producing hydrocarbon fuel and compositionss.
The priority request of early stage national applications
This application claims being the U. S. application Nos.12/636,135 of the submission of on December 11st, 2009；12/636,137 He
12/636,142 priority.
Invention field
The present invention relates to be used for the method for preparing hydrocarbon fuel by slurry hydrocracking (SHC) and solvent deasphalting (SDA)
And equipment.
Description of Related Art
As the reserves of conventional crude decline, it is necessary to which heavy oil is upgraded (upgrade) to meet demand.During upgrading, general
Heavier material changes into lighter fraction and must be driven off most of sulfur, nitrogen and metal.It is generally first that crude oil is former in normal pressure
Process to provide the fuel product for including Petroleum, kerosene and diesel oil in oily distillation column.Normal pressure crude distillation bottom of towe is obtained generally
Into vacuum tower to obtain vacuum gas oil (VGO) (VGO), the vacuum gas oil (VGO) can be the raw material of FCC apparatus to portion's product stream
Or other purposes.VGO generally seethes with excitement in the range of -524 DEG C of 300 DEG C (572 ℉) (975 ℉).
SHC for the heavy hydrocarbon feedstocks that obtained by crude distillation, including the hydrocarbon residue from atmospheric tower or decompression column distillation
Or the primary upgrading of gas oil.In SHC, by these liquid charging stocks and hydrogen and solid catalyst particle such as granular metal
Compound such as metal sulfide mixes to provide slurry phase.Typical SHC methods are for example described in US 5,755,955 and US 5,474,
In 977.SHC methods produce Petroleum, diesel oil, gas oil such as VGO, and low value refractory Colophonium stream.Generally VGO streams are existed
Further refine in catalytic hydrocracking or fluid catalystic cracking (FCC) and product can be sold to provide.To prevent from reacting in SHC
Transition coking in device, can be such that weight VGO (HVGO) is recycled in SHC reactors.
SDA usually refers to using extracting in the presence of the solvent and the method for refining of for example above-mentioned hydrocarbon-fraction of upgrading.SDA holds
Perhaps and crack heavier hydrocarbons or degraded are not made compared with actual recovered under low temperature compared with heavy oil.With the volatility in distillation conversely, SDA will
Dissolubility of the hydrocarbon according to them in liquid flux is separated.Lower molecular weight and more paraffinic components are preferentially extracted.It is minimum
Solvable material is high molecular and most polarity (most polar) aromatic component.
Gas turbine has many purposes, including aero propulsion, generating and Ship Propeling.Due to gas turbine material technology
Development, burning zone temperature have improved hundreds of degree, allow the efficiency vast improvement in the circulation of Brighton.The gas turbine of peak efficiency
With the hot arc operated more than 1093 DEG C (2000 ℉), therefore can imitate with the much higher circulation of older generation's turbine is compared
Rate.The gas turbine of greater efficiency has produced the needs to tighter fuel specification.
According to article Svensson, DNV Approves Siemens Gas Turbine for HFO, 61 Royal
Belgian Institute of Marine Engineers 55 (2007), 17MW types SGT-500 gas turbine successfully Jing
By compbined test, using the fuel oil for meeting IF180 specifications and DNV (Det of the Norway's government with regard to marine applications is obtained
Norske Veritas) accreditation.When this article, during IFO180 heavy fuel oils are than generally burning in marine gas turbine
Between the cheap $ US200-250 of distillate.180 specifications of IFO are also referred to as 180 specifications of RME, and which is applied to non-turbine machine as generally existed
Remaining marine fuel used in the low RPM diesel engines found in marine system.
There are the needs to this fuel, because turbine ratio is used for generating electricity in little to middle sizable application, for example, be used for
The peak power of electrical network, for many other power sources of the fast boat such as Ship Propeling of ferryboat, military transport ship and other application
More effectively.The used heat for reclaiming turbine is to realize that height is always followed to prepare steam or provide the cogeneration plant of other low level heats
Ring efficiency, but other examples of the system of the fuel for needing to be suitable to turbine.
Previously make a lot of effort, suitable gas turbine fuel is prepared by low value hydrocarbon residue.A kind of method is related to
Hydroprocess petroleum residue, wherein regularization condition are removing the sulfur and nitrogen of only fraction, but most metals at " finishing method "
Middle Jing catalyst for demetalation is removed.The example of the method as Japan Gasoline Corporation GEFINERY
Know.The cost for thinking the method is unreasonably high based on limited upgrading limit.
Other method suggestions will be dissolved from coal by hydrotreating or the residue of " solvent refining " coal product lifts value
(valorize) producing decompression distillation.The example of the method is SRC (solvent refined coal) methods and Japan New
The Hypercoal methods of Energy Development Organization.In other method, undergo Residual petroleum
The yield of SDA, wherein deasphalted oil (DAO) remains relatively low to avoid any organo-metallic compound being drawn in DAO.
A kind of last method combines the downstream purification of SDA and DAO or hydrotreating to remove metal.These three method examples are considered as
Be it is unfavorable because they produce meet can application specification suitable fuel it is limited in one's ability.
Specific fuel (being present subject matter) can be more less expensive than typical marine diesel oil or kerosene production.Even if due to needing
Downstream contamination controls SO is removed from aerofluxussxAnd NOx, but it is favourable for this fuel combustion in turbine.
Need at present to prepare cheaply and for the hydrocarbon fuel composition in gas turbine and marine engine.
Summary of the invention
In typical embodiments, the present invention relates to the method for preparing hydrocarbon fuel, methods described includes entering heavy feedstocks
Row is slurry hydrocracking with the slurry hydrocracking product of offer.Separate slurry hydrocracking product to provide Colophonium stream and HVGO
Stream.At least a portion Colophonium stream is mixed a part of Colophonium is dissolved in solvent with solvent.By the Colophonium of dissolving part
It is blended to obtain blended product with least a portion HVGO stream.In this respect, blended product includes not more than 5wppm sodium, no
More than 50wppm vanadium and at least the blended product of 80 volumes % is seethed with excitement at a temperature of 426 DEG C (800 ℉) or more.
In another typical embodiments, the present invention relates to the method for preparing hydrocarbon fuel, methods described includes entering heavy
Material carries out slurry hydrocracking to provide slurry hydrocracking product.Separate slurry hydrocracking product with provide Colophonium stream and
HVGO streams.By at least a portion Colophonium stream solvent deasphalting providing DAO.By DAO with least a portion HVGO stream altogether
Mix to provide blended product.
In another typical embodiments, the present invention relates to prepare the equipment of hydrocarbon fuel, the equipment is comprising for heavy
Charging and hydrogen react to produce the slurry hydrocracking reactor of slurry hydrocracking product under catalyst action.With slurry
The distillation stage of hydrocracking reactor connection incites somebody to action the slurry hydrocracking product fractionation of at least a portion.Distillation stage has for discharging
The side outlet of HVGO streams or HVGO are exported and for discharging the outlet at bottom or asphalt outlet of Colophonium stream.Connect with asphalt outlet
Logical SDA towers produce DAO streams.Which is from DAO outlet drains.Will at least one with the container or pipeline of side outlet and DAO outlets
Part HVGO streams and the blending of DAO streams.
In another typical embodiments, the equipment comprising connect with SHC reactors for by hydrogen from slurry hyd
Detached separator in crackate.
In even another typical embodiments, the distillation stage of equipment also comprising for discharge diesel stream side outlet and
For discharging the side outlet of light VGO (LVGO) stream.
In even another typical embodiments, the present invention relates to include no less than 73 weight % aromatic hydrocarbons, be not more than 5 weights
Amount % heptane insolubles and the not more than compositions of hydrocarbons of 50wppm vanadium.At least the compositionss of 80 volumes % 426 DEG C (800 ℉) with
On temperature under seethe with excitement.In other side, compositionss can include not more than 5 weight % comprising no less than 75 weight % aromatic hydrocarbons
Hexane undissolved substance or not more than 5 weight % pentane insolubes.On the other hand, at least the compositionss of 90 volumes % 426 DEG C with
On temperature under seethe with excitement.On the other hand, compositionss have not more than 30wppm or not more than 10wppm vanadium.On the other hand,
Compositionss are with the viscosity for being not more than 180cSt at 50 DEG C.It yet still another aspect, compositionss have not more than 5wppm sodium.
It is according to the present invention to be learned by detailed description with embodiment in terms of these and other.
Definition
Term " aromatic hydrocarbons " is meant as determined comprising the material containing toroidal molecule by ASTM D 2549.
Term " connection " means operationally to allow that material flows between listed component.
Term " communicating downstream " means that the material that at least a portion is flowed in communicating downstream main body operationally can be flowed from it
The main body of connection.
Term " upstream connection " means that at least a portion can operationally flow into it from the material that upstream connects main body and connect
In logical main body.
As used herein, term " boiling temperature " means to be calculated by the boiling temperature and distillation pressure observed, such as uses
Entitled " Practice for Converting Observed Vapor Temperatures to Atmospheric
The equivalent boiling point of the normal pressure (AEBP) calculated by the ASTM D1160 appendix As 7 of Equivalent Temperatures ".
As used herein, " Colophonium " mean as by any standard gas chromatograph simulate distillating method such as ASTM D2887,
D6352 or D7169 (which is all by petroleum industry use) determines hydrocarbon material of the boiling point in 538 DEG C of (975 ℉) more than AEBP.
As used herein, " pitch conversion ratio " means that the material that boiling point is 524 DEG C (975 ℉) more than is changed into boiling point exists
The conversion ratio of 524 DEG C (975 ℉) or following material.
As used herein, " weight vacuum gas oil (VGO) " means as simulated distillating method such as ASTM by any standard gas chromatograph
D2887, D6352 or D7169 (which is all by petroleum industry use) determine boiling point at -538 DEG C of 427 DEG C (800 ℉) (975 ℉)
The hydrocarbon material of AEBP.
As used herein, solvent " insoluble matter " means insoluble in the material in the solvent.
Term " liquid hourly space velocity (LHSV) " means the volume flow rate of the liquid feedstock of every reactor volume, and wherein solvent is related to 16 DEG C
Standard temperature.
Brief description
Accompanying drawing is the schematic diagram of the inventive method and equipment.
Detailed description of the invention
Many low value VACUUM TOWER BOTTOM product streams are changed into 524 DEG C (975 ℉) and lighter by slurry hydrocracking energy imparting
The conversion ratio of at most 80-95 weight % of distillation and a small amount of Colophonium.The SHC seethed with excitement under 524 DEG C (975 ℉) or higher temperature
The Toluene Soluble part of product has relatively low molecular weight, for example, surveyed by vapour pressure osmometry according to ASTM D 2503
Amount 700-900, and by some nickel and pollution of vanadium.Act in ferrum-based catalyst under 20.7MPa (3000psig) pressure below
Under it is slurry hydrocracking with open metalloporphyrin ring limited capability., it is surprising that learn from 80 weight % with
On conversion ratio slurry hydrocracking asphaltic residue seethed with excitement more than 524 DEG C under ferrum-based catalyst effect pentane it is solvable
Contain low-down nickel and vanadium concentration in property part.This with containing an adequate amount of solubility organic metal nickel and vanadium and can not possibly be most
The solvent deasphalting virgin oil run in turbine of new generation is contrary.These fuel for being loaded with metal only can use some technologies such as
Metal passivation additives and off line water (offline water) washing are transported in cooling turbine with removing blade deposit sediment
OK.
Also learn by 524+ DEG C of residue being entered blood stasis expelling under ferrum-based catalyst effect with conversion ratios more than 80 weight %
The pressure reduction gas oily distillate seethed with excitement under 426-524 DEG C of (800-975 ℉) equivalent boiling point of normal pressure that slurry is hydrocracked and prepares
Most important part (referred to as HVGO) not comprising measurable nickel and vanadium.The material is also containing the alkane in the range of some C30-C45
Hydrocarbon and polycyclic aromatic hydrocarbon and hetero atom material.The material has excellent fuel performance and dumpable at room temperature.From slurry
Be hydrocracked in the 343-426 DEG C of equivalent boiling spread of (650-800 ℉) normal pressure the pressure reduction gas oily distillate of boiling compared with
Light part (referred to as LVGO) is adapted as turbine fuel and directly burns, but generally needs the oil is upgraded in being processed further
Preferably it is worth into Petroleum and diesel oil with giving the stream.
Therefore, the HVGO for being obtained by SHC and the Colophonium of solvent deasphalting can be blended together and meet 180 Hes of RME to provide
The hydrocarbon fuel of 180 fuel specifications of IFO.Therefore, hydrocarbon fuel can burn without entering one in gas turbine and marine engine
Step upgrading.The concrete composition of the hydrocarbon fuel prepared by the inventive method and equipment can be used directly or with other fuel into
The blend for criticizing mixing or the blend for mixing when in use are used.
Embodiment of the present invention is related to carry out slurry hydrocracking escalating into fuel with primary by heavy hydrocarbon feedstocks.According to
One embodiment, such as heavy hydrocarbon feedstocks include vacuum tower residue.The representativeness of heavy hydrocarbon feedstocks other components are included in 566
Residual oil, tar, asphalt, kerosene and the shale oil seethed with excitement more than DEG C (1050 ℉).Asphalt is also referred to as bitumen, Tar sands
Or oil-sand.Asphalt is defined as the rock containing the hydrocarbon more more tacky than 10,000cSt, or can from exploit or rock of quarrying is extracted this
Class hydrocarbon.Some natural bitumens for solid, such as Uintahite, grahamite and ceresine, which passes through striped, fusibleness and dissolubility area
Not.Other asphaltenes-containibinders materials also are used as the component processed by SHC.In addition to asphaltene, heavy hydrocarbon feedstocks these other
Possible component, in other attributes, also contains significant metal pollutant in general manner, and such as nickel, ferrum and vanadium, high-load have
Machine sulfur and nitrogen compound, and high Conradson carbon residue value.The tenor of this kind of component may be, for example, 100-1,000 weight ppm, always
Sulfur content can be 1-7 weight %, and api gravity can be -5 to 35 °.The Conradson carbon residue value of this kind of component is in general manner
At least 5 weight %, usually 10-30 weight %.
As shown in drawings, for converting heavy hydrocarbons are passed through SHC units 10 and solvent deasphalting into the present invention of hydrocarbon fuel
Unit 110 is illustrated.
Heavy feedstocks stream in pipeline 12 is shown as the charging of SHC units 10 as shown in drawings.Can be by the weight in pipeline 14
Matter product recycle stream is mixed with heavy feedstocks stream 12.By the granular material of coke suppressant additive or catalyst in pipeline 16
Material mixes to form homogenous slurry with the feed stream in pipeline 12.Many kinds of solids catalyst granules can be used as granular material
Material.Useful especially catalyst granules is those described in US 4,963,247.Therefore, granule usually has less than 45 μm
Granularity and one side, most of, i.e., at least 50 weight % have the ferrous sulfate of the granularity less than 10 μm.Ferrous sulfate one is hydrated
Thing is preferred catalyst.Can also preferred bauxite catalyst.On the one hand, will be 0.01-4.0 weight % based on new raw material
During coke suppresses catalyst granules to add incoming mixture.Oil-soluble coke suppressant additive is used alternatively or in addition can.
Oil soluble additive includes the metal naphthanates based on the new raw material with molybdenum, tungsten, ruthenium, nickel, cobalt or ferrum for 50-1000wppm
Or metal octoates.
The slurry of the catalyst in pipeline 18 and heavy hydrocarbon charge can be mixed and via pipeline with the hydrogen in pipeline 20
24 are transferred in fired heater 22.Combined feed is heated in heater 22, tubular type SHC is flowed into by suction line 26 anti-
In answering the entrance of 30 bottom of device.In heater 22, from pipeline 16, the new ferrum-based catalyst granule for adding generally converts to be formed
Iron sulfide with catalysis activity.There are some decomposition in SHC reactors 30.For example, iron sulfate monohydrate can be changed into
Iron sulfuret. and when heater 22 is left with less than 0.1 or or even 0.01 μm of granularity.SHC reactors 30 can be taken not to be had
There is the form of the three-phase such as solid-liquid-solid/liquid/gas reactions device of stationary solid bed, catalyst, hydrogen and oil charging are with pure motion movement upwards
By wherein, while the back-mixing with some degree.Many other mixing and pumping configuration may be adapted to will charging, hydrogen and catalysis
Agent is delivered in reactor 30.
In SHC reactors 30, heavy feedstocks and hydrogen react to produce slurry hyd in the presence of above-mentioned catalyst
Crackate.SHC reactors 30 can be operated under the pressure as mild as a dove in the range of 3.5-24MPa and not form coke.Reaction
Device temperature is usually 350-600 DEG C, preferred 400-500 DEG C of temperature.LHSV is usually 4hr based on fresh feed-1Hereinafter, preferably
0.1-3hr-1, particularly preferred 0.2-1hr-1.Pitch conversion ratio can be at least 80 weight %, and suitably at least 85 weight %, excellent
Choosing at least 90 weight %.Hydrogen gas feed rate is 674-3370Nm3/m3(4000-20,000SCF/bbl) oil.SHC is particularly suitable for
The tubular reactor that charging and gas are moved upwardly through.Therefore, the outlet of SHC reactors 30 is in entrance top.Although accompanying drawing
In only show one, but one or more SHC reactors 30 can be used in parallel or in series.Due to elevated gas velocity,
Foaming can occur in SHC reactors 30.Also defoamer can be added in SHC reactors 30 to reduce producing the tendency of foam.Close
Suitable defoamer includes the silicone as disclosed in US 4,969,988.In addition, can be by the hydrogen quenching material injection SHC from pipeline 32
The top of reactor 30 cooling down slurry hydrocracking product when reactor is left.
Slurry hydrocracking product stream comprising solution-airmixture is taken from the top of SHC reactors 30 by pipeline 34
Go out.Slurry hydrocracking stream is made up of several products, including VGO and Colophonium, can be isolated with a large amount of different modes.Will
On the one hand slurry hydrocracking effluent from the top of SHC reactors 30 is being maintained at 200-470 DEG C (392-878 ℉)
Under separation temperature, on the one hand separate in the high pressure hot separator 36 under the pressure of SHC reactions.High pressure hot separator is anti-with SHC
Answer 30 communicating downstream of device.Optional quenching material in pipeline 32 can help product is quenched to needed for high pressure hot separator 36
Temperature.In high pressure hot separator 36, by the effluent from SHC reactors 30 in pipeline 34 be separated into comprising hydrogen with
The air-flow of gasification product and the liquid stream comprising slurry hydrocracking product.Air-flow is under the temperature and pressure of high pressure hot separator
Flash vaporized product.Equally, liquid stream is the flashed liquid under the temperature and pressure of high pressure hot separator 36.By air-flow on top
Portion is taken out from high pressure hot separator 36 by pipeline 38, while by liquid distillate in the bottom of high pressure hot separator 36 by pipe
Line 40 takes out.
By the liquid distillate in pipeline 40 with 36 identical temperature of high pressure hot separator but in 690-3,447kPa (100-
It is delivered under pressure 500psig) in heat-lightening steaming pot 42.Vapor overhead product in pipeline 44 is cooled down simultaneously in cooler 46
It is combined in pipeline 50 with the liquid bottoms product knot from cold high pressure separator in pipeline 48.Liquid distillate is in pipeline 52
In leave heat-lightening steaming pot.
Will be the overhead from high pressure hot separator 36 in pipeline 38 cold in one or more that cooler 54 is represented
But relatively low temperature is cooled in device.Water washing (not shown) on pipeline 38 be generally used for washing out salt such as curing ammonium or
Ammonium chloride.Water washing can remove nearly all ammonia and some hydrogen sulfide from the stream in pipeline 38.By the stream in pipeline 38
It is delivered in the cold high pressure separator 56 with 36 communicating downstream of SHC reactors 30 and high pressure hot separator.On the one hand, cold anticyclone point
From device 56 than 36 lower temperature of high pressure hot separator, but operate at the same pressure.Cold high pressure separator 56 is maintained at
Under the pressure of the temperature and SHC reactors 30 of 10-93 DEG C (50-200 ℉).In cold high pressure separator 56, thermal high is separated
The top product of device 36 be separated in the air-flow comprising hydrogen and pipeline 48 in pipeline 58 comprising slurry hydrocracking product
Liquid stream.Air-flow is the flash vaporized fraction under the temperature and pressure of cold high pressure separator 56.Equally, liquid stream is in cold anticyclone
Flashed liquid product under the temperature and pressure of separator 56.By using this kind of separator, gained exit flow is mainly contained
Hydrogen and some impurity such as hydrogen sulfide, ammonia and light hydrocarbon gas.
It there can be washed by the cleaning mixture in pipeline 62 by the hydrogen rich stream in pipeline 58 through filling scrubbing tower 60
Wash to remove hydrogen sulfide and ammonia.Useless cleaning mixture in pipeline 64 is renewable and recirculation, and usually amine.The hydrogen rich stream of washing
Discharge from scrubber via pipeline 66 and be recirculated back in SHC reactors 30 by circulating air compressor 68 and pipeline 20.
Recycled hydrogen can be combined with the fresh supplemented hydrogen added by pipeline 70.
Liquid fraction in pipeline 48 transports product liquid with the heat of the neighbouring cooling that cooler 46 is left in pipeline 44
, to produce pipeline 50, the pipeline 50 is with 56 identical temperature of cold high pressure separator and such as heat-lightening steaming pot for flash drum overhead product
Cold flash tank 72 is fed under the lower pressure of 690-3,447kPa (100-500psig) in 42.Top gas in pipeline 74
Can be the fuel gas comprising C4- materials, can be reclaimed and be utilized.The liquid bottom of the next self cooling flash tank 72 in pipeline 76
Portion's product and the bottom product pipeline 52 from heat-lightening steaming pot 42 are each flowed in distillation stage 80.
Distillation stage 80 is with 30 communicating downstream of SHC reactors with general's at least a portion slurry hydrocracking product fractionation.
Distillation stage 80 can include one or several containers, although a container is only shown in figure.Distillation stage 80 can be comprising atmospheric stripping point
Tower and reduced-pressure flash tank tower are evaporated, but is only single vacuum tower in one aspect.On the one hand, can be by noble gases such as middle pressure steam
Feed in pipeline 82 near 80 bottom of distillation stage so that lighter component is stripped from heavier component.Distillation stage 80 is produced in pipeline 84
In from top exit 83 discharge top gas product, in pipeline 86 from side outlet 85 discharge naphtha products stream, pipe
In line 90 from side outlet 88 discharge diesel product stream, in pipeline 92 from side outlet 91 discharge LVGO streams, in pipeline 94
In from side outlet 93 discharge HVGO streams and in bottom product pipeline 98 from outlet at bottom 96 discharge Colophonium stream.
The SHC Asphalt Production logistics from outlet at bottom 96 in bottom product pipeline 98 attach most importance to aromatic hydrocarbons and containing SHC be catalyzed
Agent.Colophonium generally seethes with excitement more than 524 DEG C (975 ℉).Separated from bitumen in pipeline 98 is into the pipeline 100 into SDA units 110
With for being recirculated back to the pipeline 102 of SHC reactors 30.The HVGO product streams from side outlet in pipeline 94 be separated into for
The pipeline 106 of blending and the pipeline 108 for being recirculated back in SHC reactors 3.Stream in pipeline 102 and 108 can be in pipeline
Combine in 14.HVGO product streams seethe with excitement and less than the boiling range of Colophonium more than 427 DEG C (800 ℉).At least HVGO of 80 weight %
Stream is seethed with excitement more than 427 DEG C.On the other hand, the HVGO streams of at least 80 weight % are boiled below at 524 DEG C (975 ℉).
Pipeline 106 transports HVGO stream of at least a portion from pipeline 94.
Colophonium stream in pipeline 100 is entered in SDA units 110.Charging in SDA methods, in as pipeline 112
Before in the first extraction tower 120, by pipeline 100 bitumen feed stream pumping and with pipeline 116 in recycle solvent
Mix with the supplementing solvent in pipeline 118.Other solvents, such as recycle solvent can be added extraction tower 120 via pipeline 122
Lower end.Light paraffinic hydrocarbon solvent, usually one in propane, butane, pentane, hexane, heptane or its mixture dissolution solvent
Divide Colophonium.The Colophonium being dissolved in solvent rises to the top of tower 120.The decisive quality of the solvability of light hydrocarbon solvent is it
Density, so the solvent equivalent to special solvent has equal density.For example, in one embodiment, heptane is for most
Dense solvent, which in DAO can not lift the vanadium of high concentration and use.Solvent with the density lower than heptane is also suitable for
The vanadium of (lift) low concentration is lifted in DAO.Specifically, solvent dissolves alkane and less polarity in bitumen feed
Aromatic compounds.Pentane is suitable solvent.The heavier part of feed stream 112 is insoluble and as in pipeline 124
From asphalt outlet 123 asphalitine or Colophonium stream settle, and by a DAO streams in pipeline 126 from DAO export
Extract in the extract of 127 discharges.DAO streams in pipeline 126 are the Colophonium of dissolving part.Extraction tower 120 is generally in 93-
Operate under 204 DEG C (200-400 ℉) and 3.8-5.6MPa (550-850psi).The temperature and pressure of extraction tower 120 is generally molten
Below the critical point of agent, but can be in critical point above and below, condition is to be advantageously controlled density.DAO streams in pipeline 126
With the metal concentration lower than the feed stream in pipeline 112.By a DAO streams in heat exchanger 128 and fired heater 129
Or in other heat exchangers by with solvent recirculation line 136 in hot solvent indirect heat exchange and be heated to the supercritical of solvent
Temperature.The solvent of supercritical heated is divided with DAO in the DAO knockout towers 130 of the top communicating downstream of the first extraction tower 120
From.Solvent recycle stream leaves DAO knockout towers 130 in solvent recirculation line 136.Solvent recycle stream is by changing
In hot device 128 with pipeline 126 in extract indirect heat exchange and condenser 154 and condense.DAO knockout towers 130 generally exist
Operate under 177-287 DEG C (350-550 ℉) and 3.8-5.2MPa (550-750psi).Extractor bottom product in pipeline 124
Flow containing the metal concentration bigger than the charging in pipeline 112.By the bottom product stream in pipeline 124 in fired heater 140
In or heat and strip in asphaltene stripper 150 lean in bottom product pipeline 152 to obtain by other heat exchange methods
The first solvent recovery stream in solvent Colophonium stream and pipeline 134.Steam from pipeline 133 can be in asphaltene stripper 150
In be used as strip liquid.123 communicating downstream of asphalt outlet of asphaltene stripper 150 and the solvent deasphalting tower 120 is with by solvent
With separated from bitumen.Colophonium stripper 150 is generally under 204-260 DEG C (400-500 ℉) and 344-1,034kPa (50-150psi)
Operation.Lean solvent DAO streams are left DAO knockout towers 130 in pipeline 132 and are entered and the bottom of DAO knockout towers 130 and described
DAO is exported in the DAO strippers 160 of 127 communicating downstreams.DAO strippers 160 are by under low pressure by DAO from the solvent carried secretly
It is middle stripping and further the second solvent recovery stream 162 is separated with DAO streams 132.Steam from pipeline 163 can be in DAO
It is used as to strip liquid in stripper 160.DAO strippers 160 are generally in 149-260 DEG C (300-500 ℉) and 344-1,034kPa
(50-150psi) operate under.Second solvent recovery stream is left in pipeline 162 and is being condensed and stored by cooler 164
In the first solvent recovery stream being attached in pipeline 134 before in the solvent tank 166.Recovered solvent is as needed from storage
Tank 166 is by 168 recirculation of pipeline with the solvent in 136 that makes up line to mix with the Colophonium stream in pipeline 100.In pipeline
The DAO for being substantially free of solvent is provided in 172, which is DAO of at least a portion from 127 discharge of DAO outlets.
Will in pipeline 172 for Colophonium dissolving part DAO in container as shown in the figure or pipeline 180 with pipeline 106
HVGO is blended to provide blended product, and which has comprising no less than 73 weight % aromatic hydrocarbons, preferably no less than 75 weight % aromatic hydrocarbons
Compositions of hydrocarbons.Pipeline 180 or not shown container export 127 communicating downstreams with HVGO side outlets 93, asphalt outlet 96 and DAO.
Said composition can have not more than 5 weight % heptane insolubles and not more than 50wppm vanadium.In another embodiment, hydrocarbon combination
Thing can have not more than 5 weight % hexane undissolved substances and not more than 30wppm vanadium.In yet another embodiment, compositions of hydrocarbons can have
There are not more than 5 weight % pentane insolubes and not more than 10wppm vanadium.At least 80 volumes %, the compositionss of preferably 90 volumes % exist
Seethe with excitement at a temperature of 426 DEG C (800 ℉) or more.In one embodiment, compositions of hydrocarbons includes not more than 3.5 weight %
Sulfur, suitably not more than 1.0 weight % sulfur, preferably no more than 0.5 weight % sulfur.In another embodiment, hydrocarbon combination is blended
Thing with 50 DEG C be not more than 180cSt viscosity and no more than 500 mean molecule quantity.In one embodiment, hydrocarbon group
Compound has the not more than sodium of 5wppm, preferably no more than 2wppm, so it can be suitable turbine fuel.
Embodiment
Carry out following examples to prove the serviceability of the present invention.
Embodiment 1
Converted from Alberta with the Colophonium level of conversion of 80 and 90 weight % using SHC reactors, it is Canadian
The asphaltic decompression residuum of Peace River rock stratum.Separate corresponding SHC products to provide bitumen product and HVGO products.
By ASTM D2549-02 (2007) standard test method, (which is used for typical case's virtue that high boiling point oil is separated by elution chromatography
Hydrocarbon and non-aromatic hydrocarbon-fraction) determine SHC product fracs density of aromatic hydrocarbon.The Colophonium of SHC reactors is left more than 80 weight %
100% aromatic molecules are rendered as under all transform levels cosily.For each HVGO fractions determine density of aromatic hydrocarbon in tablei
Be given.
Table I
| SHC products | Conversion ratio, weight % | Boiling range, DEG C | Aromatic hydrocarbons, weight % |
| HVGO | 80 | 425-524 | 71.3 |
| HVGO | 90 | 425-524 | 70.8 |
| Colophonium | All | 524+ | 100 |
Embodiment 2
Converted from Alberta with the Colophonium level of conversion of 87 weight % using SHC reactors, Canadian Peace
The asphaltic decompression residuum of River rock stratum.Separate corresponding SHC products to provide bitumen product and HVGO products.Then make
Bitumen product undergoes using pentane solvent and solvent is separated and extracts DAO.Carry out blending to calculate to determine compositions of hydrocarbons and institute
The performance of the blend of the DAO of the HVGO products and extraction into heptane of selection percentage.Compared with RME180/IFO180 specifications, blending
The performance of compositions of hydrocarbons is shown in Table II.RME180/IF180 specifications are from iso standard 8217:2005 (E) table 2：
Obtain in Requirements for Marine Residual Oils.In Table II, the density of aromatic hydrocarbon of blend is used as in Table I
The weight of the density of aromatic hydrocarbon in HVGO and pitch fractions is determined.
Table II
The all blends of expection are based on according to Procedure 2B8.1 of the API Petroleum Refining
Technical Handbook, its physical property of volume 1 (1987) are respectively provided with the pour point less than 30 DEG C.According to API
Petroleum Refining Handbook, program 2B2.1 and 2B2.3 in volume 1 (1987) are counted at a temperature of 30 DEG C
Calculate HVGO:The ratio of pentane soluble asphalt is equal to 79:21 blend has the viscosity of 1201Cst, calculates HVGO:Pentane is solvable
Property Colophonium ratio be equal to 88:12 blend has the viscosity of 349cSt.Therefore, it is contemplated that all compositionss in table are less than 30
It is dumpable at DEG C.
HVGO:The ratio of pentane soluble asphalt is equal to 79:Prepared compositionss of 21 blend for SHC products.HVGO:
The ratio of pentane soluble asphalt is equal to 85:15 blend has and meets viscosity specification at 50 DEG C, but it is somewhat too dense and
It is unsatisfactory for the composition of density specification.HVGO:The ratio of pentane soluble asphalt is equal to 88:12 blend has to meet and owns
The composition of RME180/IF180 specifications.
Measurement HVGO:The ratio of pentane soluble asphalt is equal to 88:12 blend has less than 2wppm sodium.It is expected all
Blend has the na concn less than 2wppm.
Embodiment 3
Converted from Peace River, Alberta with the Colophonium level of conversion of 87 weight % using SHC reactors, plus taken
Big asphaltic decompression residuum.Corresponding SHC products are separated to provide bitumen product.Bitumen product has what Table III was provided
Performance.
Table III
| Asphalt density, g/cc | 1.185 |
| Nickel, wppm | 120 |
| Vanadium, wppm | 109 |
Then bitumen product is made to undergo to extract DAO using the separation of several solvents solvent.Check and lifted by different solvents
Colophonium metal concentration and density be shown in Table IV.
Table IV
In this experiment, the nickel and vanadium concentration in discovery extraction oil is linear with solvent density or weight % yield.
Hexane is not actually tested, but therefore performance is pushed away based on solvent density is interior between pentane and heptane.It is surprisingly this
Seldom nickel and vanadium are present in the oil by bitumen extraction.
Do not further describe, it is believed that those skilled in the art can use previous description, and most integrated degree ground is using this
Invention.Therefore, aforementioned preferred embodiment is interpreted as being merely illustrative, and never in any form in limit publicity
The remainder of appearance.
Above, unless otherwise noted, DEG C to describe, all parts and percent are by weight for all temperature.
In being previously described, those skilled in the art are readily determined the principal character of the present invention, and can be without departing from which
The various changes and modifications of the present invention are made spirit and scope to make it suitable for various uses and condition.
Claims (5)
1. compositions of hydrocarbons, which includes：
No less than the aromatic hydrocarbons of 73 weight %；
The not more than heptane insolubles of 5 weight %；With
The not more than vanadium of 50wppm；
The compositionss of 80 volume % of wherein at least more than 426 DEG C at a temperature of seethe with excitement.
2. compositions of hydrocarbons according to claim 1, its further hexane undissolved substance comprising not more than 5 weight %.
3. compositions of hydrocarbons according to claim 1, its further pentane insolubes comprising not more than 5 weight %.
4. compositions of hydrocarbons according to claim 1, which is further comprising less than 10wppm vanadium.
5. compositions of hydrocarbons according to claim 1, the compositionss of 90 volume % of wherein at least more than 426 DEG C at a temperature of
Boiling.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/636,135 | 2009-12-11 | ||
| US12/636,135 US8193401B2 (en) | 2009-12-11 | 2009-12-11 | Composition of hydrocarbon fuel |
| US12/636,137 US9074143B2 (en) | 2009-12-11 | 2009-12-11 | Process for producing hydrocarbon fuel |
| US12/636,142 | 2009-12-11 | ||
| US12/636,137 | 2009-12-11 | ||
| US12/636,142 US8133446B2 (en) | 2009-12-11 | 2009-12-11 | Apparatus for producing hydrocarbon fuel |
| CN201080056121.8A CN102652169B (en) | 2009-12-11 | 2010-11-29 | Process and apparatus for producing hydrocarbon fuel and composition |
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| CN201080056121.8A Division CN102652169B (en) | 2009-12-11 | 2010-11-29 | Process and apparatus for producing hydrocarbon fuel and composition |
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| CN102888244B (en) * | 2012-10-22 | 2015-07-15 | 北京金海畅能源投资有限公司 | Production method of ship fuel oil |
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| US9695369B2 (en) | 2014-11-21 | 2017-07-04 | Lummus Technology Inc. | Process to upgrade partially converted vacuum residua |
| FR3046176A1 (en) * | 2015-12-23 | 2017-06-30 | Axens | HYDROPROCESSING OR HYDROCONVERSION PROCESS WITH STRIPER AND LOW PRESSURE SEPARATOR BALL ON THE FRACTION SECTION |
| US10836964B2 (en) | 2016-08-19 | 2020-11-17 | Siemens Aktiengesellschaft | Method and device for preparing a vanadium-containing combustible |
| JP6803465B2 (en) * | 2016-10-18 | 2020-12-23 | マウェタール エルエルシー | Fuel composition from light tight oil and high sulfur fuel oil |
| RU2681527C1 (en) | 2016-12-30 | 2019-03-07 | Бейджинг Хуаши Юнайтед Энерджи Технолоджи энд Девелопмент Ко., Лтд. | Light petroleum products from heavy oil production method and device by the hydrogenation in the fluidized bed method |
| US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
| US12025435B2 (en) | 2017-02-12 | 2024-07-02 | Magēmã Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US20190233741A1 (en) | 2017-02-12 | 2019-08-01 | Magēmā Technology, LLC | Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil |
| EP3638752A1 (en) | 2017-06-15 | 2020-04-22 | Saudi Arabian Oil Company | Converting carbon-rich hydrocarbons to carbon-poor hydrocarbons |
| WO2019046355A1 (en) | 2017-08-29 | 2019-03-07 | Saudi Arabian Oil Company | Integrated residuum hydrocracking and hydrofinishing |
| US10920624B2 (en) * | 2018-06-27 | 2021-02-16 | Uop Llc | Energy-recovery turbines for gas streams |
| JP2020122150A (en) * | 2020-04-01 | 2020-08-13 | マウェタール エルエルシー | Process for reducing sulfur-containing emissions from ship |
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| CN1487989A (en) * | 2000-11-30 | 2004-04-07 | ���ջ�����ʽ���� | Method of refining petroleum |
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| EP2510076A4 (en) | 2015-04-15 |
| EP2510076A2 (en) | 2012-10-17 |
| CA2862613A1 (en) | 2011-06-16 |
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| CN102652169A (en) | 2012-08-29 |
| WO2011071705A3 (en) | 2011-10-20 |
| BR112012013470A2 (en) | 2016-05-17 |
| SG178981A1 (en) | 2012-04-27 |
| RU2517186C2 (en) | 2014-05-27 |
| CA2773584C (en) | 2016-04-05 |
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| CA2773584A1 (en) | 2011-06-16 |
| JP2016138277A (en) | 2016-08-04 |
| SG188922A1 (en) | 2013-04-30 |
| JP2013513693A (en) | 2013-04-22 |
| RU2012129236A (en) | 2014-01-20 |
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| CN104774656A (en) | 2015-07-15 |
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