CN1033831A - Heavy oil cracking process - Google Patents
Heavy oil cracking process Download PDFInfo
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- CN1033831A CN1033831A CN88108102A CN88108102A CN1033831A CN 1033831 A CN1033831 A CN 1033831A CN 88108102 A CN88108102 A CN 88108102A CN 88108102 A CN88108102 A CN 88108102A CN 1033831 A CN1033831 A CN 1033831A
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- hydrogen
- heavy oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
Abstract
Heavy oil fraction is converted into the method for lighter fraction, and being included in temperature and being 400～550 ℃ and hydrogen dividing potential drop is that heavy oil fraction that asphalt content is low and hydrogen-containing gas streams are together by containing the reaction zone of non-acid, hydrogen activation catalyst under the conditions of 10～60 crust.
Description
The present invention relates to a kind ofly with heavy oil fraction, particularly contain the heavy oil of the bituminous matter component of limited quantity, cracking is the novel method than light constituent.
In the refining process of the crude oil of making the finished product, usually with last running, for example boiling point is 370 °～520 ℃ a cut, carries out such as the cracking of thermally splitting, fluid catalytic cracking and hydrocracking processing, so that these high boiling fractions are converted into the lighter fraction that has more value.
Now, to middle cut, for example the demand of kerosene and gas oil, particularly high-quality middle runnings is growing.The boiling point of kerosene is about 150～about 270 ℃, and it is mainly used in the fuel of jet plane.Kerosene, and with it a relevant main mass parameter of combustioncharacteristics be smoke point.The boiling point of gas oil is generally about 250 °～about 370 ℃, and it mainly is used as the fuel of self-igniton engine.Its important mass parameter comprises burning quality of representing with cetane value and the low-temperature fluidity of representing with cloud point.
As mentioned above, three kinds of main cracking methods in petroleum refining, have been used.
Fluid catalytic cracking is usually in lower pressure (1.5～3 crust), comparatively high temps (480～600 ℃) and have an acidic catalyst zeolite of catalyzer (as contain) to exist to carry out down.Being reflected at does not have to carry out under the hydrogen existence, and the residence time is lacked (0.1～10 second) very much.In reaction process, a large amount of carbon material (coke) is deposited on (3%～8%(weight of charging) on the catalyzer).Thereby by the burning-off coke cyclic regeneration is necessary.The product that obtains in this process contains alkene, isomery paraffinic hydrocarbon and the aromatic hydrocarbons of more boiling point in the gasoline boiling range.For example, a kind of primary product that obtains by the fluidized catalyst cracking is premium.In addition, can also obtain boiling point in the kerosene boiling range light cycle oil and some boiling points in the gas oil boiling range with interior or higher heavy cycle oil, the two is the kerosene and the gas oil of middle matter or low-quality.
Hydrocracking is carried out under higher hydrogen pressure (being generally 100～140 crust) and lesser temps (being generally 300～400 ℃) usually.The catalyzer that uses in this reaction has dual function: the acid catalysis cracking of hydrocarbon molecule and the activation of hydrogen and hydrogenation.(the liquids in general hourly space velocity is 0.3～2l/l/h) to have adopted the long reaction times.Because the pressure height of hydrogen, have only seldom sedimentation of coke on catalyzer, thereby both made and do not carry out regenerating, catalyzer also can use 0.5～2 year in fixed bed operation.In this process, the product that obtains depends on the mode of operation.In a kind of therein operating method, mainly obtain petroleum naphtha and light product.Naphtha fraction contains the alkane of Gao Yi/direct ratio, is a kind of valuable gasoline blending component.At heavy product is in the operating method of production direction, mainly obtains kerosene and gas oil.Even carry out deep hydrogenation, but because the existence of residue aromatic hydrocarbons and the Gao Yi/direct ratio of the alkane do not expected, the quality of these products only is medium.
Thermally splitting is usually at lower or middle pressure (common 5～30 crust), comparatively high temps (420～520 ℃), and do not have catalyzer and hydrogen to carry out under existing.Adopt the long reaction times (residence time is generally 20～60 minutes).Good from middle runnings quality for combustioncharacteristics that the thermally splitting of high boiling fraction obtains.But the content of high alkene and heteroatoms (particularly sulphur and nitrogen) need carry out the hydrogenation aftertreatment.The subject matter of thermally splitting is the condensation reaction that aromatic hydrocarbons takes place to form, so lower (the high carbon residue after high viscosity and evaporation and the pyrolysis of the quality of cracking resistates.(showing)) with Kang Laxun carbon residue (CCR) scale.
From USP4,017,380 can know, residual oil can be carried out hydrogenating desulfurization handles, and the Hydrobon catalyst of inactivation therefrom can be fixed as catalytically inactive and non-porous solid in hydrogenation viscosity breaking process or loaded (nonfluid) bed and use, this hydrogenation viscosity breaking process should be carried out in upstream.In this USP, under the viscosity breaking condition, in downdraft, use hydrotreating catalyst only can produce the back cracking of not expecting if spell out, and do not increase the productive rate of the middle runnings product of hope.
We have found that a kind of heavy oil fraction that is specially adapted to contain a spot of bituminous matter component is converted into the novel method that boiling point is the high quality middle runnings of 150～370 ℃ (kerosene and gas oil boiling ranges).This method, hydrogenation catalyst thermally splitting just (HCTC) be at elevated pressures (400～550 ℃), under the medium hydrogen pressure (10～60 crust), and and has non-sour hydrogen activation catalyst to carry out under existing.
Although the pressure of hydrogen is lower, it is very low that the coke of method of the present invention forms speed.This just reaches at least 1000 hours hitless operation at an easy rate in fixed-bed reactor.Depend on the actual conditions that is adopted, even can obtain the operating time of significant prolongation.If it should be noted that on the one hand in common hydropyrolysis process at this and to reduce hydrogen pressure, can be immediately because basic nitrogen and carbon laydown cause inactivation, thus limited the length of operating.
The present invention relates to a kind of method that heavy oil fraction is converted into lighter fraction, this method comprise make have low bituminous matter component concentration heavy oil fraction with hydrogen-containing gas streams at 400～550 ℃, better 410～530 ℃, be preferably under 440～510 ℃, and the hydrogen dividing potential drop is 10～60 crust, is preferably 20～40 crust down by containing the reaction zone of non-sour hydrogen activation catalyst.
The minimizing of molecular weight mainly is because the thermally splitting of material molecule causes.Therefore, opposite with catalytic cracking and hydrocracking, novel method does not depend on exist (it is active that this acid sites must keep) of acid sites on the catalyzer during cracking cycle or life of catalyst.Because the existence of hydrogen, even under relatively mild pressure, also have only very a spot of sedimentation of coke on catalyzer, therefore present method can be carried out with fixed bed mode (as the change type reactor) or moving-bed mode (as the bunker flow reactor).
Although contain the aromatic substance of some amount, because normal paraffin content height and the content of alkene is few, so the quality of the middle runnings that obtains therefrom is fine.Because aromatic substance is difficult to hydrogenation, thereby the consumption of the hydrogen of this method is lower.Another advantage of this method is to depend on described catalyzer, and the considerable part that is present in the sulphur in the charging can be converted into hydrogen sulfide, and therefore the product that obtains contains less sulphur.
The tower bottom material, the material of product of distillation had superior characteristic (viscosity, carbon residue amount and sulphur content), and can be used as valuable oil fuel blending component in the middle of promptly boiling point was higher than.In addition, this heavy material is a kind of good raw material of fluid catalytic cracking unexpectedly.When with the common raw material of fluid catalytic cracking reactor, compare as straight run flash distillation branch, the productive rate of gasoline and quality are all similar.When comparing as the charging of fluid catalytic cracking process, can obtain much higher gasoline yield with the tower bottom material that from the distillation thermal cracking reactor, obtains.
Compare with common thermal cracking process,, just can obtain similar middle runnings product if the thermally splitting product is carried out additional hydrogen aftertreatment.The quality of the unconverted cut of the product that obtains with novel method is more much higher than the quality of the unconverted cut of thermally splitting.Because activation the having of hydrogen in reaction process, so the last running that is obtained by present method has low viscosity, low poly-aromatic content and low sulphur content.
Compare with common catalyst cracking method, the HCTC method does not rely on the existence of acid sites on the catalyzer.The HCTC process can not have on catalyzer very suitably basically, or even does not have fully to carry out under the situation of acid sites.Therefore, containing the charging nitrogenous and/or sulphur compound of a considerable amount of alkalescence also can process without difficulty.Because the existence of activation hydrogen only has a spot of sedimentation of coke on catalyzer, but in fluid catalytic cracking, a large amount of sedimentation of coke is arranged on catalyzer, thereby must regenerate continuously.The product that is obtained by present method is prevailing high-quality middle runnings, and the heavy unconverted cut of better quality.The primary product that obtains by fluid catalytic cracking be a kind of gasoline blending component and lesser amt light cycle oil (this light cycle oil quality by in to low, this is because aromatic substance accounts for its major part).In process of the present invention, very difficult causing from the hydrogen transfer reactions of cycloalkanes and alkene formation (gathering) aromatic substance and alkane.
Compare with common hydrocracking process, method of the present invention does not rely on the existence in acid site on the catalyzer.Therefore, HCTC is to the impurity in the charging, and particularly (alkalescence) nitrogen and carbon residue (CCR) are not too responsive.Because method of the present invention is carried out depressing than low hydrogen basically, significantly reduces so compare cost with traditional hydrocracking process.The consumption of hydrogen is lower in the HCTC method.For the different/direct ratio of alkane, it should be noted that so its different/direct ratio is very low, this ignition quality to gas oil is very favorable owing to be the free radical cracking in the HCTC process.Traditional hydrocracking process is because the carbon ion reaction mechanism can cause high different direct ratio, and this ignition quality to the quality of middle cut, particularly gas oil has detrimentally affect.
The suitable charging of HCTC method of the present invention is the heavy oil fraction with low bituminous matter component concentration.The reduced pressure distillate of any crude oil and/or deasphalted oil (to sulphur and nitrogen content almost without limits) can be used.Bituminous matter components contents in the charging should be heavy less than 3%(), be preferably heavy less than 2%(), better for heavy less than 1.5%() and be preferably heavy less than 1.0%().In front in Xu Shu the bituminous matter component, " C
7-bituminous matter " refer to the asphaltenes fractions of from heavy oil fraction, removing by the heptane precipitator method.Charging can contain a considerable amount of carbon residues (CCR), and it is heavy that its value should be lower than 15%(), be preferably that to be lower than 10%(heavy), be preferably lower than 6%.It is heavy that the quantity of the sulphur in the charging should be lower than 10%(), it is heavy better to be lower than 6%(), it is heavy to be preferably lower than 4%().It is heavy that the quantity of nitrogen is lower than 6%(), be preferably that to be lower than 4%(heavy).
Very Shi Yi charging is that boiling point is 350～580 ℃ substantially, is preferably 370～520 ℃ reduced pressure distillate or flash distillation cut.Another kind of very suitable charging is diasphaltene residual oil (DAO), for example the long boiling range of propane, butane or pentane diasphaltene or short boiling range residual oil.
In addition, synthetic cut and/or the synthetic diasphaltene oil that obtains from integrated refinery is the suitable charging of method of the present invention.Produce and synthetic a kind of proper method of charging to comprise so-called residue oil fraction, for example the hydroconversion process of short boiling range residual oil.This hydroconversion process preferably includes and carries out a hydrodemetallation (HDM) step earlier, and then carries out hydrogenating desulfurization/hydrodenitrification step and/or hydrocracking step.It should be noted that synthesizing flash distillation cut or synthetic diasphaltene oil generally speaking processes in catalytic cracking process, but its primary product is a gasoline, and can not obtains satisfactory kerosene of quality or gas oil.It almost is impossible that traditional hydrocracking is carried out in this charging, and this is the extremely combustibility because of the nitrogen compound that exists, and needs low nitrogen charging in hydrocracking.Can be used for producing above-mentioned synthetic charging such as hydrogen oil process (H-oil), LC-processing method (LC-fining) and Esso company hydrodesulfurization of residual oil hydrogen conversion processes such as (Residfining).
The charging that another kind is very suitable for the HCTC method is the viscosity breaking product of for example lacking boiling range residual oil.If heavy oil residue is carried out thermally splitting, then its product is carried out flash distillation or distillation, can obtain boiling range and be substantially 350～520 ℃ cut, this is a kind of superior charging of process of the present invention.
For the formation that reduces coke, use the mixture of heavier and lighter charging, for example the mixture of DAO and flash distillation cut is very favorable.
This hydrogenation catalyst method for thermal cracking should be at 400～550 ℃, and better 410～530 ℃, better 440～510 ℃, preferably about 450 ℃ are carried out.Can obtain higher transformation efficiency under the higher temperature, this is because the thermally splitting of hydrocarbon speeds up under comparatively high temps.Obtain identical cracking speed, should adopt than being easier to the high temperature of cracked charging (a little) for the charging that is difficult to thermally splitting (for example being rich in the charging of ring compound).
In novel HCT method, the air speed of charging should be preferably 0.5～6l/l/h being 0.1～10l/l/h, is preferably 1.0～5/l/h.
Hydrogen dividing potential drop in the HCTC method is preferably 10～60 crust, is preferably 20～40 crust, is preferably about 25 crust.Stagnation pressure is generally 15～65 crust in the reactor, is preferably 25～45 crust, is preferably about 30 crust.In this regard, hydrogen dividing potential drop that it should be noted that the Reactor inlet place is clung to than the hydrogen dividing potential drop high 3～10 in exit usually.
The catalyzer that uses in the method for the present invention should have the hydrogen mobilizing function.Suitable catalyzer comprises one or more IV a, VI b or VIII family metal.
Suitable carriers is for example silicon oxide, aluminum oxide, aluminum phosphate, spinel compound, titanium oxide and zirconium white.Can adopt the combination of traditional VI b and VIII family metal.It should be noted that in this manual " nonacid " is meant the active acid sites that does not exist one or more energy to quicken the cracking reaction of hydrocarbon by the carbon ion chemical action basically.Under the initial reaction condition, may there be some acid sites.But since the formation of coke and the absorption of basic nitrogen, the rapid inactivation of these acid sitess meetings, and the hydrogen mobilizing function keeps constant substantially.
When catalyzer comprises the precious metal of VIII family, be preferably palladium and platinum.When catalyzer comprises IV a family metal, be preferably tin.When catalyzer comprises VI b family metal, be preferably molybdenum, chromium or tungsten.When using VIII family base metal, preferably iron, cobalt or nickel.
Having been found that when using Mo catalyst based, is 125～250m with silicon-dioxide as carrier and surface-area particularly
2Can obtain good result when the Mo of/g is catalyst based.Use this catalyzer can obtain good hydrodesulfurization activity and few coke formation.
Catalyzer should show significantly preferably, but limited hydrogenating desulfurization activity.This catalyzer becomes seldom the formation of coke, and makes the product performance of middle runnings become better.Under the HCTC condition, the second order reaction velocity constant of hydrodesulfurization reaction is preferably 0.1～1.0, is preferably 0.2～0.51/(h%s) (under stable condition, 450 ℃, and using Kuwait's flash distillation cut to measure).
Hydrogen/the charge ratio of method of the present invention can change in very wide scope.Suitable hydrogen/charge ratio is 50Nl/kg～5000Nl/kg, is in particular 100Nl/kg～2000Nl/kg.Situation is that hydrogen/charge ratio is 100～500Nl/kg preferably, is preferably 200～400Nl/kg.When the low hydrogen that uses these recommendations/charge ratio, the sedimentation of coke on the catalyzer is low surprisingly.In addition, can also obtain a high transformation efficiency.Compare with traditional method for hydrogen cracking, the remarkable step-down of the hydrogen/charge ratio of present method, this is very favorable economically.In the hydrocracking operation, common hydrogen/charge ratio is 700～1500Nl/kg.In hydrogenation, usually in fact, for the formation that suppresses coke with improve transformation efficiency, need high hydrogen/charge ratio.It is shocking that in the HCTC method, low gas velocity is not only possible, and STRENGTH ON COKE to form and transform two aspects all be favourable.
In above-mentioned recommended embodiment, adopted hydrogen/charge ratio of 200～400Nl/kg preferably and comprised VIII family precious metal, preferably the catalyzer of palladium and/or platinum.Adopt above-mentioned hydrogen/charge ratio and catalyzer can obtain a low-down coking speed simultaneously, the quantity of the sulphur on the catalyzer is also astonishing low simultaneously.
In another embodiment of the present invention, comprise the mixture of hydrogen and hydrogen sulfide in the hydrogen-containing gas streams.Carry out that the HCTC method can cause transformation efficiency and to the optionally growth of middle cut with the mixture of hydrogen and hydrogen sulfide.The quantity that appears at the hydrogen sulfide in this mixture in the reactor should be up to the 50%(V/V of hydrogen).The usage quantity of hydrogen is preferably 1～30%, is preferably 5～25%, is preferably about 10%.
HCTC reaction of the present invention should be carried out in the fixed bed mode, for example carries out in the trickle bed downflow reactor.In view of regular catalyst regeneration, preferably adopt two or more fixed-bed reactor, carry out the change type operation.The HCTC reaction can particularly when using gently charging, be carried out in last current flow fixed bed reactor easily.In this case, the application of last flow reactor can reduce the sedimentation velocity of coke, thereby has prolonged the time span between the regeneration.Compare with downward stream mode, last stream mode can reduce the deposition 50% of coke or more.Other of process of the present invention operating method preferably are moving-bed mode (for example bunker flow reactor) and ebullated bed mode.
The product of producing with the HCTC method can directly use or be further processed.Of course, for example part or all of product is sent to desulfurization and handles, particularly hydrogenating desulfurization is handled, and is adjusted to requested number with the sulphur content with product.Another kind may be as required, and part or all that will (hydrogenating desulfurization) product before or after (hydrogenating desulfurization) product distillation is sent to the hydrogenation reaction processing.Also at least a portion may be present in the unconverted materials circulation HCTC reactor in the product.
The regeneration of catalyzer is suitable for and will be deposited on carbon material on the catalyzer by the gas that uses oxygenous and/or water vapour and burns and carry out.Under the situation of fixed bed (as the conversion bed), regeneration can be carried out in cracking bed itself.Under the situation of for example bunker flow reactor, regeneration is carried out in independent revivifier usually.
The following example explanation the present invention, but in restriction the present invention.
Embodiment 1
The screening of catalyst experiment
Hydrogenation catalyst thermal cracking process of the present invention is sent in Kuwait's flash distillation.Feed properties is listed in the table 1.
This is reflected in the isothermal operation miniflow trickle bed downflow reactor and carries out.Except as otherwise noted, catalyzer is to prepare with traditional pore volume dipping technique.Adopted commodity carrier (silicon oxide or aluminum oxide) (catalyzer 1～12 and 19～21).In experiment 13～18, used commercial catalyst intact or that improve a little.The character of carrier is listed in the table II.Adopted inorganic matrix to prepare for example nitrate of metal of catalyzer 1～12 and 19～21(, ammonium molybdate).Saved the muriate parent.Tin is with the form deposition of organometallic compound (for example 2 ethyl hexanoic acid tin (II)).NiMo/SiO
2Be with BP2 for example, the deposition one precipitation technology preparation of describing in 189,163.Before use, earlier with catalyzer at 350～45 ℃ of following roasting (NiMo/SiO
2Except the catalyzer), crushing is small-particle (30～80 order) then.The characteristic of catalyst composition is listed in the table III.
With this catalyst exposure before reaction conditions, vulcanize.Particularly under the situation of catalysts containing molybdenum, this is a mode preferably, because as not, in experiment 1st hour usually too much sedimentation of coke can take place.
Carry out two vulcanisation step, first is earlier catalyzer and sulfur feed stock and hydrogen to be heated to 375 ℃ and keep this temperature overnight with the speed of 75 ℃/h together.Then, temperature is risen to 400 ℃, kept 6 hours, rise to 425 ℃ again and also keep spending the night.Be heated to 450 ℃ then.Another sulfuration and set up procedure H
2S carries out.With the H of catalyst exposure at 10 crust
2/ H
2S(7/1 V/V) speed with 75 ℃/h rises to 375 ℃ with temperature in the mixture.Import charging then and heat up with the speed of 75 ℃/h.Detection learns that two steps have all obtained same catalyst performance (for example coking property).For noble metal catalyst, prove before test also can obtain satisfied result with hydrogen reduction.
Being reflected at 450 ℃ is to carry out under 30 crust with stagnation pressure.Air speed (LHSV) is 1.0l/l/h.H
2/ charge ratio is 850～1100Nl/h.Reaction times is 170～220 hours.
Analyze and data processing
The boiling point of analyzing product liquid with TBP-GLC distributes.In addition, the GLC that also emits gas analyzes.With these analyses is foundation, calculates transformation efficiency and selectivity.Transformation efficiency is defined as the quantity that the boiling point of removing only is higher than 370 ℃ material.Product is split into gas (C
1-C
4), petroleum naphtha (C
5～150 ℃), middle runnings (150～370 ℃) and coke.Optionally calculating is the quantity of removing target product with the total quantity (material below 370 ℃ and coke) of product.The calculating of the consumption of hydrogen is the CME(Combustion Mass Spectrometric Element with charging and product liquid) analyze and gasometry is that benchmark carries out.Hydrodesulfurization activity (secondary velocity constant) is from the decision of the sulphur content of product liquid.Result of experiment is listed in the table IV.The product performance of the middle runnings that obtains is described among IV a and the IV b.The product performance of end cut is described among the table IV c.
Table 3
The characteristic of experiment catalyst that is used for the HCTC of Kuwait's flash distillation cut
*The tap density of crushing catalyst
The PV=pore volume of aquametry
The surface-area that SA=measures with nitrogen (BET method)
The embodiment II
The effect of pressure
Adopt the general reaction conditions of embodiment I, observe the effect of total pressure.The results are shown in the table V.
The embodiment III
Comparison with the active catalyzer of different HDS-
Adopt the general reaction conditions in the embodiment I, the hydrodesulfurization activity of some catalyzer and the relation between the coke selectivity are studied.The results are shown in the table VI.
The embodiment IV
The effect of temperature
Use the usual conditions of describing in the experimental example I, observe the effect of temperature.No. 16 catalyzer is used in the experiment 1,2 and 3, and No. 12 catalyzer is used in the experiment 4.The results are shown in the table VII.
The embodiment V
The effect of working length
Adopt the general condition in the embodiment I, observe working length at low H
2Effect under the/charge ratio.In all experiments, all use catalyzer 11, the results are shown in the table VIII.
The embodiment VI
The effect of catalyst composition when sulphur deposition is arranged
Adopt the common reaction conditions of embodiment I.The effect of the catalyst composition when observation has sulphur deposition.The results are shown in the table IX.
The embodiment VII
The effect of charging
Adopt the common reaction conditions in the embodiment I, three kinds of chargings are compared.The character of charging is listed in the table X.Kuwait's flash distillation cut is described in detail in the table I.Kuwait's diasphaltene oil is a kind of butane deasphalting short distance residual oil.The synthetic flash distillation cut of Maga is by carrying out the hydrodemetallation (HDM) and the hydrocracking of Maya residual oil earlier, carrying out flash distillation then and make.The data of experiment are listed in the table XI.
*At LHSV=0.5 1.1
-1h
-1The time
The n.d.=undetermined
The embodiment VIII
H in the hydrogen charging
2The effect of S
Adopt the common reaction conditions in the embodiment I, observe H in the hydrogen charging
2The effect of S.Adopt catalyzer No. 3.The results are shown in the table XII.
The embodiment IX
The use of HCTC-unconverted materials in fluid catalytic cracking
At 450 ℃, pressure is 30 crust, H
2/ charge ratio is that 900Nl/kg and LHSV are under the condition of 1.0l/l/h, uses No. 16 catalyzer and adopts Kuwait's flash distillation cut to carry out the HCTC experiment as charging.Unconverted materials, promptly boiling point is higher than the charging that 370 ℃ cut is used as fluid catalytic cracking (FCC) reaction.The FCC-device is operated under fixed coke growing amount and steam stripping efficiency.Second experiment carried out with Kuwait's flash distillation cut.Feed properties and FCC productive rate are listed in the table X III.
The embodiment X
Adopt of the charging of thermally splitting flash distillation cut as HCTC
The charging that the thermally splitting flash distillation cut that employing is obtained by Arabic heavy feedstocks is tested as HCTC.This HCTC experiment is 450 ℃ in temperature, and pressure is 30 crust, and LHSV is 1.01/l/h, H
2/ charge ratio is that 250Nl/kg and working length are under 161 hours the condition, to use No. 12 catalyzer to carry out.Feed properties: proportion (d 70/4): 0.9139, sulphur (%w): 2.22, nitrogen (%w): 0.31, RCT: 0.4(%w).Pure transformation efficiency is 42.7%.The results are shown in the table X I V.
The embodiment XI
Employing contains the bitum charging of strengthening quantity
As charging, is 450 ℃ in temperature with Kuwait head's boiling range residual oil, and pressure is 50 crust, and LHSV is 1.0l/l/h, H
2/ charge ratio is that 1000Nl/kg and working length are under 50 hours the condition, uses No. 12 catalyzer to carry out the HCTC experiment.Feed properties: proportion: (d 70/4): 0.9139, sulphur (%w): 3.69, nitrogen (%w): 0.15, metal (ppm): 42, RCT(%w): 5.1, C
7-bituminous matter (%w): 2.4.Pure transformation efficiency is 45%.Selectivity (%): C
1～C
4: 8.0, C
5-150 ℃: 11.1,150 ℃～370 ℃: 80.1, coke: 0.7.
Claims (16)
1, a kind of method that heavy oil fraction is converted into lighter fraction, it is 400～550 ℃ that this method is included in temperature, be preferably 410～530 ℃, be preferably 440～510 ℃, hydrogen partial pressure is 10～60 crust, being preferably heavy oil fraction under the condition of 20～40 crust that the bituminous matter component concentration is low flows by containing non-acid, the reaction zone of hydrogen activation catalyst with hydrogen-containing gas.
2, the process of claim 1 wherein that the asphalt component content of heavy oil fraction is heavy less than 3%(), better heavy less than 2%(), it is heavy to be preferably 1%().
3, claim 1 or 2 method, wherein the heavy oil fraction boiling range is (synthesizing) cut or (synthesizing) diasphaltene oil of 350～580 ℃ substantially.
4, claim 1 or 2 method, wherein heavy oil fraction is to be essentially 350～520 ℃ cut by the boiling range that the heavy oil residue thermally splitting obtains.
5, the method for any one in the claim 1～4, wherein catalyzer comprises one or more VIII family precious metals, is preferably palladium or platinum.
6, the method for any one in the claim 1～5, wherein catalyzer comprises one or more IV a family metal (particularly tin), one or more VI b metal (particularly molybdenum, chromium or tungsten) and/or one or more VIII family metals (particularly iron, cobalt or nickel), these metals are preferably sulphided form.
7, the method for claim 6, wherein catalyzer comprises the metal of one or more VI b family metal (particularly molybdenum, chromium or tungsten) and one or more chosen from Fe, cobalt or nickel, these metals are preferably sulphided form.
8, the method for any one in the claim 5～7, catalyzer wherein shows significantly, but limited hydrodesulfurization activity.
9, the method for any one in the claim 5～8, wherein catalyzer comprises the carrier that deposits metal on it, preferably the pore volume of this carrier is 0.2ml/g at least, particularly 0.5ml/g at least.
10, the method for any one in the claim 1～9, wherein the air speed of charging is 0.1～5l/l/h, is preferably 0.5～3l/l/h, and the ratio of hydrogen is 100～2000Nl/kg, is preferably 100～500Nl/kg
Be preferably 200～400Nl/kg.
11, the method for any one in the claim 1～10, hydrogen-containing gas streams wherein comprises the mixture of hydrogen and hydrogen sulfide, the quantity of hydrogen sulfide can be up to the 50%(V/V of hydrogen), be preferably 1～30%, be preferably 5～25%.
12, the method for any one in the claim 1～11 is wherein reacted in the fixed bed mode and is operated, better above stream mode operation.
13, the method for claim 1～12, wherein the unconverted materials at least a portion reaction product is recycled.
14, the method for any one in the claim 1～13, the wherein charging that the unconverted materials of reaction is reacted as fluid catalytic cracking.
15, the method that heavy oil fraction is converted into lighter fraction of any one during aforesaid right requires, these methods are described in the specification sheets, particularly among the embodiment.
16, or the oil distillate of multinomial described method preparation that requires according to aforesaid right.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8727777 | 1987-11-27 | ||
| GB878727777A GB8727777D0 (en) | 1987-11-27 | 1987-11-27 | Heavy oil cracking process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033831A true CN1033831A (en) | 1989-07-12 |
| CN1022043C CN1022043C (en) | 1993-09-08 |
Family
ID=10627619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88108102A Expired - Fee Related CN1022043C (en) | 1987-11-27 | 1988-11-23 | Heavy oil cracking process |
Country Status (25)
| Country | Link |
|---|---|
| EP (1) | EP0318125B1 (en) |
| JP (1) | JPH01170689A (en) |
| KR (1) | KR890008302A (en) |
| CN (1) | CN1022043C (en) |
| AR (1) | AR244309A1 (en) |
| AT (1) | ATE76893T1 (en) |
| AU (1) | AU608389B2 (en) |
| BR (1) | BR8806191A (en) |
| CA (1) | CA1326464C (en) |
| DD (1) | DD283643A5 (en) |
| DE (1) | DE3871732T2 (en) |
| DK (1) | DK655488A (en) |
| ES (1) | ES2032004T3 (en) |
| FI (1) | FI885467A (en) |
| GB (1) | GB8727777D0 (en) |
| GR (1) | GR3004811T3 (en) |
| IN (1) | IN173572B (en) |
| MX (1) | MX172342B (en) |
| MY (1) | MY104114A (en) |
| NO (1) | NO172898C (en) |
| NZ (1) | NZ227067A (en) |
| PH (1) | PH25825A (en) |
| RU (1) | RU1813095C (en) |
| SG (1) | SG45793G (en) |
| ZA (1) | ZA888798B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045100C (en) * | 1996-12-26 | 1999-09-15 | 南京兴达石油化工科技工贸公司 | Method for producing special kerosene type solvent naphtha |
| CN101429455B (en) * | 2007-09-07 | 2013-06-19 | 环球油品公司 | Hydrocracking process for fabricating distillate from fisher-tropsch waxes |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045462C (en) * | 1996-07-22 | 1999-10-06 | 中国石油化工总公司 | Middle-pressure hydrocracking process for heavy fractional oil |
| US7828958B2 (en) | 2003-12-19 | 2010-11-09 | Shell Oil Company | Systems and methods of producing a crude product |
| NL1027777C2 (en) * | 2003-12-19 | 2006-08-22 | Shell Int Research | Systems and methods for preparing a crude product. |
| JP5526408B2 (en) | 2010-01-19 | 2014-06-18 | 国立大学法人東北大学 | Fuel property determination method and fuel property determination device |
| JP5453221B2 (en) | 2010-11-18 | 2014-03-26 | 国立大学法人東北大学 | Combustion experiment equipment |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2801208A (en) * | 1954-02-04 | 1957-07-30 | Gulf Research Development Co | Process for hydrogen treatment of hydrocarbons |
| FR1568754A (en) * | 1967-06-30 | 1969-05-30 | ||
| DE2504248A1 (en) * | 1974-02-07 | 1975-08-21 | Exxon Research Engineering Co | CATALYST MIXTURE AND PROCESS FOR THE CONVERSION OF HEAVY PETROLEUM RAW MATERIALS |
| US4298458A (en) * | 1980-02-25 | 1981-11-03 | Mobil Oil Corporation | Low pressure hydrotreating of residual fractions |
-
1987
- 1987-11-27 GB GB878727777A patent/GB8727777D0/en active Pending
-
1988
- 1988-11-09 CA CA000582600A patent/CA1326464C/en not_active Expired - Fee Related
- 1988-11-23 CN CN88108102A patent/CN1022043C/en not_active Expired - Fee Related
- 1988-11-24 AU AU25892/88A patent/AU608389B2/en not_active Ceased
- 1988-11-24 AR AR88312548A patent/AR244309A1/en active
- 1988-11-24 NZ NZ227067A patent/NZ227067A/en unknown
- 1988-11-24 ZA ZA888798A patent/ZA888798B/en unknown
- 1988-11-24 FI FI885467A patent/FI885467A/en not_active Application Discontinuation
- 1988-11-24 MY MYPI88001349A patent/MY104114A/en unknown
- 1988-11-24 PH PH37854A patent/PH25825A/en unknown
- 1988-11-24 ES ES198888202685T patent/ES2032004T3/en not_active Expired - Lifetime
- 1988-11-24 KR KR1019880015525A patent/KR890008302A/en not_active Application Discontinuation
- 1988-11-24 NO NO885257A patent/NO172898C/en unknown
- 1988-11-24 MX MX013917A patent/MX172342B/en unknown
- 1988-11-24 DK DK655488A patent/DK655488A/en not_active Application Discontinuation
- 1988-11-24 DE DE8888202685T patent/DE3871732T2/en not_active Expired - Fee Related
- 1988-11-24 JP JP63294860A patent/JPH01170689A/en active Pending
- 1988-11-24 EP EP88202685A patent/EP0318125B1/en not_active Expired - Lifetime
- 1988-11-24 BR BR888806191A patent/BR8806191A/en not_active Application Discontinuation
- 1988-11-24 AT AT88202685T patent/ATE76893T1/en not_active IP Right Cessation
- 1988-11-24 IN IN829MA1988 patent/IN173572B/en unknown
- 1988-11-24 DD DD88322146A patent/DD283643A5/en not_active IP Right Cessation
- 1988-11-24 RU SU884356935A patent/RU1813095C/en active
-
1992
- 1992-06-04 GR GR920401155T patent/GR3004811T3/el unknown
-
1993
- 1993-04-14 SG SG457/93A patent/SG45793G/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045100C (en) * | 1996-12-26 | 1999-09-15 | 南京兴达石油化工科技工贸公司 | Method for producing special kerosene type solvent naphtha |
| CN101429455B (en) * | 2007-09-07 | 2013-06-19 | 环球油品公司 | Hydrocracking process for fabricating distillate from fisher-tropsch waxes |
Also Published As
| Publication number | Publication date |
|---|---|
| MX172342B (en) | 1993-12-14 |
| NO172898B (en) | 1993-06-14 |
| SG45793G (en) | 1993-06-25 |
| AR244309A1 (en) | 1993-10-29 |
| DD283643A5 (en) | 1990-10-17 |
| ATE76893T1 (en) | 1992-06-15 |
| AU2589288A (en) | 1989-06-01 |
| MY104114A (en) | 1993-12-31 |
| CN1022043C (en) | 1993-09-08 |
| FI885467A (en) | 1989-05-28 |
| JPH01170689A (en) | 1989-07-05 |
| EP0318125B1 (en) | 1992-06-03 |
| GB8727777D0 (en) | 1987-12-31 |
| NO172898C (en) | 1993-09-22 |
| BR8806191A (en) | 1989-08-15 |
| PH25825A (en) | 1991-11-05 |
| AU608389B2 (en) | 1991-03-28 |
| DE3871732T2 (en) | 1993-01-21 |
| IN173572B (en) | 1994-06-04 |
| ZA888798B (en) | 1989-07-26 |
| GR3004811T3 (en) | 1993-04-28 |
| RU1813095C (en) | 1993-04-30 |
| KR890008302A (en) | 1989-07-10 |
| NO885257D0 (en) | 1988-11-24 |
| EP0318125A2 (en) | 1989-05-31 |
| FI885467A0 (en) | 1988-11-24 |
| DK655488A (en) | 1989-05-28 |
| NO885257L (en) | 1989-05-29 |
| ES2032004T3 (en) | 1993-01-01 |
| EP0318125A3 (en) | 1990-03-14 |
| CA1326464C (en) | 1994-01-25 |
| DE3871732D1 (en) | 1992-07-09 |
| DK655488D0 (en) | 1988-11-24 |
| NZ227067A (en) | 1990-08-28 |
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