CN1006230B - Single-stage hydrotreating process - Google Patents
Single-stage hydrotreating process Download PDFInfo
- Publication number
- CN1006230B CN1006230B CN85106942.8A CN85106942A CN1006230B CN 1006230 B CN1006230 B CN 1006230B CN 85106942 A CN85106942 A CN 85106942A CN 1006230 B CN1006230 B CN 1006230B
- Authority
- CN
- China
- Prior art keywords
- weight
- catalyzer
- catalyst
- hydrogen
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Images
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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
Abstract
A process for catalytically hydrotreating hydrocarbon oils having a tendency to deactivate hydrotreating catalysts by coke formation, in the presence of hydrogen at elevated temp. and pressure comprises passing: (a) oils having a final b.pt. greater than 538 deg.C and contg. less than 2 % w of heptane asphaltenes, (b) oils having a final b.pt. 343 to 538 deg.C, or (c) mixtures thereof, downwardly with the hydrogen-contg. gas into a hydrotreating zone over a stacked-bed of hydrotreating catalysts under conditions suitable to convert more than 25% of H2S of a hydrotreating catalyst comprising a component from Group VIB, a Group VIII metal, metal oxide or metal sulphide and a lower zone comprising a component from Group VIB, a Group VIII metal, metal oxide or metal sulphide, and less than 0.5 % P and sepg. the reaction product from the hydrotreating zone into a hydrogen-rish gas and a liq. hydrocarbon oil having reduced sulphur and/or heavy metal content.
Description
The invention relates to particular form and arrange, the catalyzer that just is referred to as " stacking bed (Stacked bed) " is here handled the single-stage hydrotreating process of heavy oils.The present invention especially handles because of forming coke about the stackeding bed catalyst that adopts a kind of specific arrangement and makes hydrotreating catalyst that a kind of single-stage hydrotreating process of the oil plant of inactivation tendency be arranged.Handled oil plant be some have heavy cut oil plant and (or) have the low asphaltene content and an oil plant of heavy cut very.Have found that, adopt stacking bed increase catalyst life or the traditional catalyst comparison used, transformation efficiency is improved with these oil plants of processing.The present invention is useful especially for the needs that satisfy the hydrotreatment severity that improves constantly, the for example desulfurization of following these oil plants, promptly hot cracked from crude oil or crude oil fraction straight run distillation or the inferior heavy oil fraction that extracts and the mixture that comprises the arbitrary fraction these materials, the oil plant fraction of steam cracking or catalytic pyrolysis gained.
The continuous variation of petroleum refining industry, for example trend towards handling crude oil with poor quality, and the strict demand of oil product specification constantly increased (for example lower allow sulphur content), require positive part the refiner improve traditional oil plant fraction and (or) severity of the hydrotreatment of non-traditional treatment process fraction.The severity that is increased and (or) raw material extraordinary generally always can accelerate the hydrotreating catalyst deactivation rate.Adopt method of the present invention, can prolong the runtime of carrying out hydroprocessing technique with these fractions, and (perhaps) can allow to carry out than the operation of high severity and (or) the processing inferior oil material.
Use lower price or the local crude oil that can get usually can cause in the oil plant fraction sulphur and (or) nitrogen content increases.Method for transformation, thermo-cracking for example, coking and catalytic pyrolysis are just putting into production or at the processing inferior oil material.Contain the more as if such heteroatoms of sulphur with these method products obtained therefroms, and with from the product that carries out the straight run distillation gained than good quality crude oil products obtained therefrom or from crude oil or crude oil fraction by comparison, the hydrogen content deficiency.Therefore, by these method for transformation and (or) the crude oil with poor quality products obtained therefrom also must carry out hydrotreatment in addition to satisfy plurality of specifications and require or to prepare raw material as further processing/conversion.Yet, needed in order to remove unnecessary heteroatoms than High Operating Temperature, and insufficient like also will adding additional hydrogen the coke property except the hydrogen of these raw materials, and and this will cause making the quickening of hydrotreating catalyst deactivation rate because of coking.Hydrotreating catalyst active and (or) any increase of stability can make the refiner improve lesser value inferior oil material and (or) quality of cracking oil plant, thereby obtain remarkable economic efficiency.
As everyone knows, the insufficient inferior oil material of hydrogen can be under higher hydro-refining unit operational condition, promptly under the higher hydrogen partial pressure and (or) under bigger hydrogen/oil ratio example, (or) in duration of contact, carry out hydrotreatment/hydrofining at long oil plant-catalyzer with the low catalyst deactivation rate.In order to remain in the restriction condition certain some apparatus structure or design, perhaps, can only do quite little change to above these parameters in order to continue to process required former oil mass.Therefore, just must add the variation targets that very expensive hydrotreatment equipment can reach each parameter, unless use catalyzer with longer life.In other words, the refiner must approve very short catalyst life and stoppage time of increasing because of frequent more catalyst changeout or must use continuously or the semi continuous reclaim equiment.With these schemes need big and (or) more container and the utility appliance raw material of processing given quality.Wherein particularly importantly to the refiner, in existing hydrogenation unit the hydrogeneous insufficient oil of processing and (or) ability of inferior oil material, these existing hydrogenation units adopt existing catalyzer to operate in non-stackeding bed catalyst structure, wherein do not have enough hydrogen partial pressures to prevent that catalyzer from losing activity rapidly wastefully.Therefore, just be starved of and improve one's methods and the high stability catalyzer.
Some two-step approach hydroprocessing processs have been proposed, with some difficulties that occur in the process that overcomes hydrotreatment heavy oil in the present technique field.5 parts of patent specifications of following investigation have earlier wherein adopted two kinds of catalyticreactor equipment.
In US Patent specification 3,766, in 058, the decompression residue that has disclosed high sulfur content carries out the two-step approach that hydrogenating desulfurization is handled.The first step wherein is preferably at ZnO and Al
2O
3The cobalt-molybdenum catalyzer top that mixture is made carrier removes sulphur, and makes raw material partly carry out hydrogenation.In second step, the effluent that the first step is handled is further handled, its operational condition is to make asphaltene contained in the raw material and macromolecular resin carry out hydrocracking and desulfurization, preferred operational condition is to make to be reflected at aluminum oxide or silicon oxide and to do to take place on the molybdenum catalyst of carrier, and second kind of catalyzer wherein has bigger mean pore size than first kind of catalyzer.
In US Patent specification 4,016, in 049, disclosed in the middle of one and steamed step and allow part material oil do the bypass circulation to come the asphaltene heavy oils that contains metal and sulphur is carried out the two-step approach that hydrogenating desulfurization is handled around the first step operating process.
In US Patent specification 4,048, in 060, disclosed the method for two-step approach hydrogenating desulfurization and hydrogenation and removing metal, wherein adopt different catalysts, and the catalyzer that the catalyzer that uses of second step uses than the first step has bigger aperture, and have specific pore size distribution in each step.
In US Patent specification 4,166, in 026, reported two-step approach, wherein the heavy hydrocarbon oil plant that contains a large amount of asphaltenes and heavy metal is carried out the hydrogenation and removing metal treatment, and be on the catalyzer that contains one or more catalytic metals on a kind of carrier of mainly forming, to select cracking by silicic acid * in the first step.Through separating or without the effluent of the first step of separating hydrogen-rich gas, contact with hydrogen having in the presence of the catalyzer, this * catalyzer is on a kind of carrier, preferably on aluminum oxide or silica-alumina carrier, contain one or more catalytic metals, and have specific pore volume and pore size distribution.This patent declares that this two-step approach is more effective than method commonly used, wherein in a step treating processes residual oil is directly carried out hydrogenating desulfurization and handles.
In US Patent specification 4,392, in 945, disclosed the two step hydrofining methods of handling the heavy oil that contains some kind organosulfur compound, wherein utilize the catalyzer of specific arrangement order, and carry out the intersegmental H that removes
2S and NH
3Processing.In the first step, have nickeliferous Hydrobon catalyst commonly used.In second step, adopted the Hydrobon catalyst commonly used that contains cobalt.The optimum condition that carries out the first step operation is the sulphur that removes 50 weight % at least, and the optimum condition that carries out the second step preferred operations is to reach the sulphur that removes about 90 weight % at least (these two all be that benchmark calculate with the sulphur that exists in the initial oily raw material that enters the first step operating process).This method mainly be applicable to handle contain seldom or do not contain heavy metal, boiling point is lower than the gas oil feed of 343 ℃ distillation procedure gained.
Patent specification above-mentioned all be about utilize some effective catalyzer and (or) carrier to various hydrocarbon oil crude materials carry out two the step hydrotreatments method.Also require to remove H in some method therein
2S and NH
3Yet, in the several patents specification sheets of mentioning in front any one all do not mentioned a kind of like this method, promptly with this method can the hydrotreatment full boiling point be 343 ℃ to 538 ℃ oil plant and (or) have low asphaltene content and have the oil plant of boiling point in the component more than 538 ℃, simultaneously, get up with the single catalyst systematic comparison, can improve life of catalyst significantly again.Have found that now, the stackeding bed catalyst that contains the specific arrangement of different catalysts active composition, can in single-stage hydrotreating process, be used for handling contain high boiling component (about 343 ℃～538 ℃) and (or) contain the oil plant of the very high component (boiling point is higher than 538 ℃) of low asphaltene content and boiling point, the life-span that can improve catalyst system simultaneously with (or) can improve the transformation efficiency of hydrotreatment for a kind of given raw material.According to method of the present invention, can change existing catalytic hydroprocessing reactor apparatus into stacking bed reactor apparatus that special catalyst is housed at an easy rate.Present method can turn round under (7500 kPas) hydrogen partial pressures well being lower than 75 crust.Therefore do not need to build other high-pressure reactor.According to the present invention, for a certain given oil plant, the time that the catalyst composite of this special stacking bed form is experienced in the time of can making the operating time ratio between catalyzer replacing or the regeneration use any catalyzer separately is more longer.In other words, according to the present invention, during the catalyzer of this stacking bed form of use single stage method, in identical catalyzer replacing or recovery time interval, under the transformation efficiency that is equal to, can process inferior oil material or, can obtain higher transformation efficiency for given oil plant.The present invention is the most useful under the occasion of meeting generation rapid catalyst deactivation.
Therefore, the invention relates to is having in the presence of the hydrogen, and a kind of method of catalytic hydroprocessing hydrocarbon ils material under the high temperature and high pressure condition is wherein incited somebody to action:
A) full boiling point is higher than 538 ℃ and be less than the oil plant of 2 weight % with the asphaltene content that heptane records,
B) full boiling point is 343 ℃ to 538 ℃ a oil plant, perhaps
C) their mixture,
Change under the operational condition of hydrogen sulfide the hydrotreatment district with hydrogen or a kind of downward feeding hydrotreating catalyst of hydrogen-containing gas on stacking bed at the sulphur compound that is suitable for wherein existing greater than 25%; The wherein said stacking bed upper area that comprises, the hydrotreating catalyst (is that benchmark calculates with the total catalyst) that wherein contains 15～85 volume %, the catalyzer here comprises the elementary composition of group VIB in the periodic table of elements, the metal of VIII family, the oxide compound of metal oxide or metallic sulfide and phosphorus and (or) sulfide, this stacking bed lower region in addition, 15～85 volume % hydrotreating catalysts (is that benchmark calculates with the total catalyst) wherein are housed, the catalyzer here comprises the elementary composition of group VIB, the metal of VIII family, metal oxide or metallic sulfide and the phosphorus that is lower than 0.5 weight %, and the reaction product that will obtain from said hydrotreatment zone is separated into the liquid hydrocarbon oil plant that hydrogen-rich gas and content of heteroatoms have reduced.
According to method of the present invention is to be particularly suitable for becoming those systems of a restriction condition because of coking makes catalyst deactivation.When removing of nitrogen was the problem of major concern, the catalyzer of bed lower curtate preferably helped catalysis by nickel, and when removing of sulphur was the problem of major concern, the catalyzer of bed bottom preferably helped catalysis by cobalt.
According to the present invention, with following oil plant, be that a) full boiling point is higher than 538 ℃, and be less than the oil plant of 2 weight % with the asphaltene content that heptane records, b) oil plant of full boiling point between 343 ℃ to 538 ℃, c) their mixture contacts with hydrogen or hydrogen-containing gas, and passes through downwards on stackeding bed catalyst under hydrodesulfurizationconditions conditions.Mentioned in this manual boiling point is by ASTM (American society for testing materials) (ASTM) method D2887-83(" with the boiling Range Distribution Analysis of gas chromatography determination petroleum fractions ") determine, generally be called the true boiling point that the TBP-GLC(gas liquid chromatography records).By the asphaltene (asphaltene) that obtains with the normal heptane analysis discussed herein is (" the asphaltene precipitation thing of measuring with normal heptane ") that method IP143/78 by London oil institute measures.
Used raw material will be under hydroprocessing condition in according to the method described in the present invention, and particularly those have because of coke formation makes hydrotreating catalyst the oil plant of inactivation tendency is arranged under hydrodesulfurizationconditions conditions.
" downwards " speech meaning of using in the present invention is in order to point out flow direction, is not orientation, therefore, should not think the orientation restriction to the present invention's operation.In order continuously by reactor, this is common operating method under handled oil plant and the gas flow; Yet people can reverse reactor from conceptive.Oil plant and gas feed from the bottom, at the catalyzer of first catalysis region of the bottom catalyzer of phosphorus (nickeliferous and) should be and the oil plant gentle contacted first main catalyzer, thereby should be the bottoms that is in first reactor.As industrial known, the staged reactor that is connected in series is to arrange separately one by one.Wherein the gentle body and function pipe-line transportation of oil plant of coming out from a certain reactor is to the top of next reactor; Yet, also can reverse this process.Above-mentioned reactor structure and concerning those skilled in the art known other reactor structure be considered within the scope of the invention.
Can take from the hydrocarbon-bearing material of virgin stock (uncracked oil plant) or thermo-cracking, steam cracking or catalytic pyrolysis according to the used raw material of method of the present invention.Suitable raw material comprises from crude oil or the crude oil fractions gas oil with the petroleum derivation of normal pressure or underpressure distillation gained; Solvent extraction oil for example generally is referred to as the extract oil of deasphalting oil plant; The oil plant of thermo-cracking or steam cracking gained or their cut, for example coker gas oil; Mixture from the gas oil of catalytic pyrolysis gained or turning oil and two kinds or multiple above-mentioned oil plant.
According to method of the present invention, these raw materials after preliminary treatment also can be made multiple use.According to the difference of processed concrete raw material, suitable purposes can comprise the additive that can make the raw material that goes in significantly reduced those devices of molecular weight as delivering to, and these devices for example have catalytic cracking unit or hydrocracking device; Directly use or by behind other oil plant of fusion or the additive as if the such transport fuel sale of diesel oil, or as the refinery fuel sales.
According at first comprising a kind of common nickeliferous and phosphorated hydrotreating catalyst commonly used in the used stackeding bed catalyst system of method of the present invention.The second kind of catalyzer that contacts with oil plant generally includes a kind of low phosphorus content or phosphorated custom catalysts not, and second kind of catalyzer is preferably not phosphorous.This second kind of catalyzer also is custom catalysts, in it is formed, contain nickel and (or) cobalt.When desulfurization was the main purpose of hydrotreatment, this second kind of catalyzer contained cobalt and is better than containing nickel; And when denitrogenation was main purpose, this second kind of catalyzer preferably contained nickel, nickeliferously was better than containing cobalt.Wherein catalyzer can prepare by the technology of knowing in the art.Advantage of the present invention mainly derives from the specific combination form of the hydrotreating catalyst of stacking bed middle practicality, rather than derives from any particular form or the method for making catalyzer.
According to the catalyzer in first kind of used main hydrogenation zone of the inventive method suitable be to comprise a kind of nickeliferous and phosphorated hydrogenation catalyst commonly used.The hydrogenation catalyst commonly used that is suitable for first catalyst area generally comprise the phosphorus that gets up with a kind of carrier combinations oxide compound and (or) sulfide composition, with component that is selected from group VIB in the periodic table of elements and group VIII metal, metal oxide, or metallic sulfide and (or) their mixture.These catalyzer will contain and be up to 10 weight %, normally, 1 group VIII metal compound (is that benchmark calculates by this metal content) to about 5 weight %, the phosphorus compound (is that benchmark calculates by phosphorus content) of 3 group VIB metallic compounds (is that benchmark calculates by this metal content) and 0.1 to 10 weight % to about 15 weight %.Catalyzer preferably includes the nickel component, molybdenum and (or) the tungsten component, make carrier with aluminum oxide, this carrier can contain silicon oxide in addition.Preferred catalyzer contains the nickel component, molybdenum component and phosphorus component, make carrier with aluminum oxide, this carrier also can contain small amounts silicon, the preferable amount of these components is nickel components (is that benchmark calculates with this metal content) of 2 to 4 weight %, the molybdenum component of 8 to 15 weight % (is that benchmark calculates with this metal content) and 1 to 4 weight %, the more preferably phosphorus component of 2 to 4 weight % (is that benchmark calculates with the phosphorus content).Catalyzer can be taked different shape, for example spherical and extrudate form.Preferred shape is three foliated extrudates, and as known in the art, the most handy before use sulfide of catalyzer is handled.
Owing to coking makes the catalyst reduction inactivation, use low-phosphorous catalyzer to be considered to favourable in second zone.
Has high-specific surface area (greater than about 200m
2/ g) (0.6 to 0.85g/cm with the high compact tap density
2) the catalyzer of low phosphorus content preferably be used in second zone have high activity because they be it seems.Because the diffusion of active ingredient generally can be strengthened, and can increase speed of reaction so have high specific surface area.The catalyzer of higher density can make active metal component and the promotor that more amount is housed in the unit reactor volume, this industrial be a significant factor.The metal content of afore mentioned rules can make the per unit reactor volume have high activity.Usually can make activity of such catalysts too low than low-metal content, and make it be not suitable for being used in the working method of the present invention.Be equipped with than the more metal of the amount of afore mentioned rules and bring significant interests can for this operation scheme, and therefore can not make full use of these metals, this will increase the expense of catalyzer and can not get what benefit.Because the deposition of coke is considered to cause most catalyst deactivations, so the pore volume of live catalyst should be in proper level or be higher than proper level (0.4 to 0.8cm
3/ g, narrower range is 0.5 to 0.7cm
2/ g).The catalyzer of second area also can resemble and adopt different shape the catalyzer of first area.As known, preferably catalyzer is handled with sulfide earlier before use in the present technique field.
The custom catalysts that the nickel-containing catalyst that is used for the first area is preferably highly active, be suitable for high hydrotreatment degree.This catalyzer has high specific surface area (to be higher than 140cm
2/ g) (0.65 to 0.95g/cm with high dense packing density
3, narrower range is 0.7 to 0.95g/cm
2).Because the diffusion of active ingredient can be strengthened usually, so high specific surface area can improve speed of reaction.The catalyzer of higher density can make the reactive metal and the promotor of per unit reactor volume filling more amount, and this is industrial significant.The metal of afore mentioned rules and the content of phosphorus make the per unit reactor volume have high activity.Lower metal content can make activity of such catalysts too low, and makes it be not suitable for being used in the working method of the present invention.Higher metal content brings significant interests can for this operation scheme, and therefore can not make full use of these metals, will improve the expense of catalyzer like this.Because the deposition of coke is considered to cause most catalyst deactivations, so the pore volume of live catalyst should be that (0.4 to 0.8cm at optimal level
2/ g, narrower range is 0.4 to 0.6cm
2/ g).
That adopts in second catalyst system zone is low-phosphorous or does not have the hydrotreating catalyst commonly used of phosphorus.Can adopt aptly contain cobalt and (or) nickeliferous custom catalysts.It mainly is aspect its low phosphorus content (being lower than 0.5 weight %) that the catalyzer of second area is different from the first area catalyzer, the phosphorus content of preferred catalyzer is lower than about 0.5 weight %, and comprise the group VIB component and the group VIII metal that get up with a kind of carrier combinations, metal oxide, or metallic sulfide and (or) their mixture, this catalyzer preferably comprise nickel and (or) cobalt component and molybdenum and (or) the tungsten component, and make carrier with aluminum oxide, this carrier can also contain silicon oxide in addition.Preferred metal content is up to 10 weight %, normally contains the metal component of group VIII (is that benchmark calculates with this metal content) of 1 to 5 weight % and the metal component of group VIB (is that benchmark calculates with this metal content) of 3 to 30 weight %.More preferably catalyzer comprises cobalt or nickel component and molybdenum component, and makes carrier with aluminum oxide.
Preferred method involved in the present invention is about making hydrotreating catalyst that the method for the hydrotreatment oil plant of inactivation tendency be arranged because of forming coke, wherein a) full boiling point is higher than 538 ℃ and be lower than the oil plant of 2 weight % with the asphaltene content that heptane records, b) full boiling point is 343 ℃ to 538 ℃ a oil plant, or c) their mixture, with hydrogen or hydrogen-containing gas (mixture), the sulphur compound greater than 25% that wherein contains is changed under the condition of hydrogen sulfide being suitable for, feed the hydrotreatment district on two kinds of hydrotreating catalysts stacking bed downwards being equipped with, the wherein said stacking bed upper area that comprises, the high-activity hydrogenation catalyst (is that benchmark calculates with the total catalyst) that wherein contains 15 to 85 volume %, the catalyzer here comprises the nickel of 2 to 4 weight %, the phosphorus of the molybdenum of 8 to 15 weight % and 1 to 4 weight %, and make carrier with the material that mainly constitutes by aluminum oxide, also has a lower region in stacking bed, the high activity hydrogenation and desulphurization catalyst (is that benchmark calculates with the total catalyst) that wherein contains 15 to 85 volume %, the catalyzer here comprise 2 to 4 weight % cobalt and (or) molybdenum of nickel 8 to 15 weight % and the phosphorus that content is lower than 0.5 weight %, and make carrier with the main material that constitutes by aluminum oxide; And the reaction product that will obtain from said hydrotreatment district be separated into hydrogen-rich gas and sulphur wherein and (or) the liquid oil plant that reduced of the content of heavy metal.
The physical property of the catalyzer of here mentioning is very familiar to the those of ordinary skill in the catalyst development technical field involved in the present invention." surface-area " speech meaning is meant the adsorption surface area of nitrogen, preferably determines by 3.Pore size distribution is measured by mixing silver-colored method, and calculates with the contact angle of 130 degree.Said pore volume is the pore volume of water, the required volume of water of per unit weight catalyzer when its expression water is filled to this catalyzer initial humidity with catalyst pores.
In the present invention, first kind of catalyst volume accounts for 15 to 85 volume % of main catalyst loading capacity.The rest part of main catalyst loading capacity is made up of second kind of catalyzer.The distribution of the catalyst volume in bed on each zone depend on to the requirement of nitrogen transformation with to stability with as if remove the relation of the requirement of other such hydrotreatment reaction of sulphur and metal.Stacking bedly can be used to satisfy denitride amount, desulfurization amount and demetalization and system stability.Increasing by first catalyst consumption will increase the amount of removing of nitrogen, but this hydrogenating desulfurization (HDS) that will influence this catalyst system is active and stable.Catalyst ratio below 15: 85 on (top: under the situation bottom), do not have much practical significances more than 85: 15 with the benefit that stacking bed system obtained.Use stacking bed or other less per-cent aspect unactual restriction.
Here the catalyzer of mentioning can be in same or the different reactor.For the existing apparatus that has a reactor, can repeatedly be contained in a reactor top of another reactor, many hydrotreatment reaction units are to be formed by two or more reactors in series.Catalyst area has more than the specific volume that is limited to a reactor, also can expand and enters another (formerly) reactor.Zone discussed herein refers to main catalyst bed.In common knowledge as the those of ordinary skill in the present technique field, when reactor charge, usually adopt the catalyzer of the small-sized lamination form of variable grain size.In by operating process of the present invention, also can make carry out between reactor heat exchange and (or) hydrogen make-up.
The aperture of catalyzer does not play a crucial role in by method of the present invention.Catalyzer in two zones can be based on same vehicle.Usually, its mean pore size of finished product catalyzer has the difference of microwave, and this is because the loadings of various metals and phosphorus has difference.
List in the table I according to the operational condition that catalyst system of the present invention is suitable.
The table I
The close limit of the wide region wide region close limit of condition
The hydrogen dividing potential drop, crust 6.5-75 20-75 20-55 34-55
Stagnation pressure, crust 13.6-95 27-95 27-75 47-75
Hydrogen/raw material ratio, 17-1780 17-890 51-255 85-255
Standard liter/public affairs
The jin raw material
Temperature, ℃ 150-455 285-455 285-425 345-425
Liquid hourly space velocity, 0.1-10.0-0.5-5.0-
Kg/kg
Hour
Be lower than 285 ℃ (to the raw material of heavy very) and be lower than under the temperature of 150 ℃ (to heavy feed stocks), catalyzer does not present enough activity to reach the transformation efficiency with practical significance.Be higher than under 455 ℃ of temperature, it is excessive that coking and rate of cleavage all become, to such an extent as to the working order of practical significance occurs not having.More than 455 ℃, under elevated pressures, the reactor metallurgical performance also may become the restricted condition of this working method.
When liquid hourly space velocity was lower than 0.1Kg/Kg.h, oil plant can be looked in the residence time of reaction zone was enough to produce pyrolysis and coking.When liquid hourly space velocity was higher than 10Kg/Kg.h, the transformation efficiency of raw material in reactor was too low again, so that there is not the actual meaning of using.For air speed of mentioning here and air-fuel ratio calculated value, be volumetric under 15.5 ℃ and condition of normal pressure.
When the speed of the coking of measuring catalyzer and inactivation, the hydrogen dividing potential drop is very important.When pressure is lower than 6.8 crust, promptly use the oil plant that contains high boiling component than good quality, it is too fast that the coking speed of catalyst system also can become.When pressure was higher than 75 crust, it seems that the reason of the inactivation of catalyst system mainly be owing to there being metal deposition thereon, because if there is metal deposit to exist, will cause the aperture to stop up.As those skilled in the art are known, can determine the level of deactivation that causes because of precipitated metal with the catalyzer of different aperture degree.Because the reaction that takes place can consume hydrogen, causes the hydrogen deficiency at reactor bottom, therefore reach 17 standards liter/kilogram raw material by the used hydrogen of the inventive method and the proportion requirement of raw material during hydrotreatment.This hydrogen deficiency may cause the rapid coking of catalyzer, and causes having no the running situation of practical significance.When the ratio of hydrogen and raw material surpasses 890 standards liter/kilogram raw material, can not get tangible interests at all; Therefore exceed this ratio, the compression expense just can not get guaranteeing.
When the hydrotreatment heavy oils, denitrogenation is an important factor.Under these conditions, the phosphorated catalyzer may not be more stable in the process of handling heavy oils; Yet, compare with helped catalytic corresponding catalyst by phosphorus, the phosphorated catalyst dehydrogenation activity is not lower.In addition, with regard to denitrification activity, helped catalytic catalyzer than being helped catalytic catalyzer to come lowly by nickel by cobalt.Stackeding bed catalyst can satisfy desired denitrogenation, desulfurization and demetallated amount, and system stability.Have found that, compare that stacking bed system also can improve the activity (except denitrogenation) and the stability of whole catalyst system with arbitrary catalyzer of single use.When heavy oils mainly causes the condition of inactivation because of coking under, processing raw material, can adopt the stackeding bed catalyst system.
Should under being suitable for removing at least in the raw material 25% condition, operate by method of the present invention, generally will remove 30 to 80% of sulphur in the raw material, more preferably 45 to 75% with these conditions.As if during the such metal of nickel and vanadium, and when removing metal and being main purpose, this process can be operated under the situation of low desulfurization degree when existing in raw material.In raw material, exists and seldom measure metal, and demetalization is not when being not main purpose, people can be under than the situation of high desulfurization rate this process of operation.
The present invention is with Fig. 1 and Fig. 2, and wherein the result of some described in the embodiment explains with figure.
Fig. 1 is a line chart relatively, has wherein expressed and has adopted by of the present invention when stacking bed the advantage of reactor inlet temperature time to time change gained.
Fig. 2 also is a line chart relatively, has wherein expressed when adopting by the present invention when stacking bed, and the reactor outlet temperature changes the advantage of gained in time.
Following embodiment only is in order to further specify the present invention.
Example 1
Make carrier with gamma-alumina, the catalyst A that contains nickel, molybdenum and phosphorus is to prepare with the aluminum oxide powder that can get on the market.This carrier extrusion molding is become the small-particle of 1.6mm, and its cross section is three foliated lamellar.Press the dry hole volumetric method at this small-particle, promptly only add the method that q.s solution is full of the alumina pore volume, before flooding with suitable catalytically-active metals, be dried and calcine.Silicon oxide or magnesian carrier except containing aluminum oxide, also contain other component of low degree, as if also can be used.Can use nickelous nitrate, nickelous carbonate, phosphoric acid, the suitable aqueous solution of hydrogen peroxide and ammonium molybdate comes impregnated carrier.The metal sorption amount of drying, burnt catalyzer (A) and some other character are listed in the table II.
Make carrier with similar aluminum oxide, the catalyst B that contains cobalt and molybdenum prepares by the preparation method of catalyst A.Equally, also this carrier extrusion molding is become the small-particle of 1.6mm, its cross section is three foliated lamellar.Before flooding with suitable catalytically-active metals by the dry hole volume method with these small-particle dryings.Use cobaltous carbonate, the suitable aqueous solution of ammonium dimolybdate and ammonia comes impregnated carrier.The metal sorption amount of dry, burnt catalyzer (B) and other character are also listed in the table II.
The table II
Catalyst A B
Diameter 1.6mm 1.6mm
Cross section three foliated lamellar three foliated lamellar
Form weight %
Ni 3.0 -
Co - 3.2
Mo 13.0 9.6
P 3.2 -
Dense packing density, g/cm
20.82 0.71
Specific surface area, m
2/ g 164 226
Mercury-pore volume, cm
2/ g 0.47 0.61
With main filling nickel-molybdenum-phosphorus/aluminium oxide catalyst, cobalt-molybdenum/aluminium oxide catalyst with on cobalt-molybdenum/aluminium oxide catalyst, load nickel-molybdenum-phosphorus/aluminium oxide catalyst stacking bedly carry out three kinds of different type approval tests.Be the required reactor inlet temperature of the sulphur of keeping 0.3 weight % in the product (RIT(℃)) in time (my god) relation table that changes is shown among Fig. 1, this is a kind of measuring method that makes things convenient for of general catalyst activity, the Ni-Mo-P catalyst data is represented with circle (top that root line), the Co-Mo catalyst data is piled up catalyst data and is represented with rhombus (following that root line) with trilateral (middle that root line) expression.Stacking bed system has than higher activity and stable.Help desulfurization and denitrogenation.The average operation condition of the average properties of raw material and device is listed in the table III.Raw materials usedly be heavy decompression gas oil, its full boiling point is higher than 538 ℃, and the asphaltene content that records with heptane is lower than 2 weight %.Add raw material in the auto levelizer and the condition of device is suitable constant at duration of test, therefore can think that this device is a kind of industrial feasible device.The Ni-Mo-P catalyzer accounts for the about 33% of main loaded catalyst in the stackeding bed catalyst system, and the rest part in the main catalyzer is then used the Co-Mo catalyst loading.Oil plant is gentle to flow to into single stage method operation system, and in turn at first on the Ni-Mo-P catalyzer, flows through on the Co-Mo catalyzer then.
Major advantage by the represented stacking bed system of this embodiment comprises a) as can be seen in Figure 1, the stability of catalyzer significantly increases, the reactor of stacking bed system and single catalyst system by comparison, the amount that its temperature in increases in time is quite little (3.1 ℃/month: 12.5 ℃/month); B) catalyst activity increases, and this is that the low about 8.1 ℃ mode of reactor inlet temperature initial with identical sulphur content in product is represented; C) stacking bed and single bed is compared, because its catalyst activity and stability is improved, so the catalyst life of estimating can significantly improve about 400%.The terminal point of test temperature is 416 ℃, and the successive linear gradient is used to estimate the catalyst life of stacking bed system.
The table III
Raw material/process characteristic
Hydrogen dividing potential drop 38 crust
Liquid hourly space velocity 3Kg/Kgh
Sulphur, weight % 1.1
Nickel, ppm 0.6
Vanadium, ppm 0.7
RCR, weight % 0.3
The gas liquid chromatography true boiling point, ℃
Initial boiling point/10% 365/347
90/95% 524/538
Example 2
Also carried out second group of two type approval test, employing be Ni-Mo-P/AlO catalyzer and Co-Mo/Al
2O
3Load Ni-Mo-P/Al on the catalyzer
2O
3Catalyzer stacking bed.When considering that hydrogenation, denitrogenation and desulfurization catalyst are active, Ni-Mo-P/Al
2O
3Catalyzer will be that the those of ordinary skill in the present technique field is generally a kind of custom catalysts of handling this raw material and selecting, and without the Co-MO catalyzer.The table IV has been summarized the approximate average operation condition and the property of raw material of device.This oil plant is the admixture of straight run decompression gas oil (from non-cracked oil distillation gained) and coking heavy gas oil.In the table V, summarized approximate average characteristics at twice catalyzer this second trial in the usage period, Fig. 2 explanation single catalyst system and stacking bed system be respectively make in the product sulphur content reach 0.75 weight % and the necessary reactor outlet temperature of 0.6 weight % in time (day) and the situation of variation.
In this example, with single bed system by comparison, even the major advantage that adopts stacking bed system to obtain comprises a) than higher sulphur transformation efficiency is also arranged under the low operating temperature, b) when processing same type raw material, after being arranged, higher catalyst stability-about 60 days investigates stability, c) after can processing raw material than heavy-stay about 60 days under the stability condition that roughly is equal to, investigate stability, and d) even than also adding more hydrogen in the reaction under the low operating temperature.As can be seen from Figure 2, single bed system initial operation temperature in one or two initial week is lower, but this temperature is equivalent to contain in the product sulphur of 0.75 weight %, and for stacking bed system, this temperature only is equivalent to contain in the product sulphur of 0.60 weight %.In order to begin also to obtain the sulphur content of 0.6 weight % in the product, just also need to increase by 7.5 ℃ temperature with single bed system.Make single bed system begin to have about 4.4 ℃ of low activity temperature thus.Can obviously find out from Fig. 2, though (operating for reaching different sulphur contents) these two kinds different catalyzer of arranging have the similar operations temperature when process running beginning, but stacking bed temperature accounts for 12.5 ℃ temperature advantage greatly after two months, show promptly that when processing contains the same type raw material of coking material of about 30 volume % stacking bed have an advantages of higher stability.After about 60 days, because the amount of the coking heavy gas oil of full range is reduced to 20 volume %(by shown in the arrow in that root line above Fig. 2 from about 30 volume %), the coking of sending into the raw material of single bed system is inclined to and has been reduced.Use the raw material that the coking tendency reduced and the single bed system stability beginning that is improved near the stability of stacking bed system, although the sulphur content in product is still higher.These data show that stacking bed system can be used for processing the raw material with higher coking tendency with the catalyzer that is equal to work-ing life, even also can get higher sulphur transformation efficiency.Some data that the table V provides show that the hydrogen consumption of stacking bed system is than single bed system low about 6%.Best relatively is on 1st month point, and wherein catalyzer is being handled same materials.Temperature in whole reactor raises more for a long time (the temperature of reactor variable quantity in the table V), reflects more hydrogen consumption; The additional of hydrogen is the principal element of heat release in the hydrotreatment process.
The table IV
Feedstock property and operating parameters
Raw material decompression gas oil/coking heavy gas oil
Ratio 40/60
Final boiling point, ℃＞538 ℃
Sulphur in the raw material, weight %～3
Liquid hourly space velocity, kg/kgh 2.76
H
2Press at (reactor inlet place) crust 49.3
H
2/ oil plant ratio (standard liter/kilogram raw material) 289
Various raw material decompression gas oil coking heavy gas oil
Molecular weight 369 312
C, weight % 85.4 85.2
H, weight % 11.8 11.0
S, weight % 2.5 3.2
Gas liquid chromatography records
When true boiling point is 538 ℃
Weight % 91.2 95.0
The table V
Catalyzer and behaviour in service
1 month 4 months duration of service of catalyzer
Catalyzer * 11 and 211 and 2
Temperature of reactor, outlet, ℃ 360 357.2 376.7 362.8
The temperature of reactor variable quantity, ℃ 37.5 40.6 34.4 40.6
H
2Consumption, standard liter/kilogram raw material 63.8 68 63.8 68
Sulphur in the product, weight % 0.75 0.6 0.75 0.6
* catalyzer 1 is Ni-Mo-P
Catalyzer 2 is Co-Mo
Example 3
The 3rd group of two type approval tests also are to use Ni-Mo-P/Al
2O
3Catalyzer and Ni-Mo-P/Al
2O
3Catalyzer and Co-Mo/Al
2O
3Catalyzer stacking bed carries out.Raw materials used full boiling point is between 343 ℃ to 538 ℃, comprises the straight run light gas oil, coking naphtha and light cycle oil.The approximate operational condition and the feedstock property of this device in VI, have been summarized.Analyze these two test for data and show, comparing by the used stacking bed and single catalyst of the present invention has following advantage:
A) lower temperature in,
B) make in the product sulphur content lower,
C) even when the temperature in of reactor is low, also can under the situation of same reactor temperature variation, operate.
The table VI
Raw material and operating parameters
Raw material proportion 0.92
Final boiling point, ℃ 455
Sulphur in the raw material, weight % 1.3
Liquid hourly space velocity, kg/kgh 2.6
H
2* (reactor inlet place, crust) 35.4
H
2The oil plant ratio, standard liter/kilogram raw material 168.3
Claims (19)
1, in the presence of hydrogen and at 13.6～95 crust stagnation pressures, the method for catalytic hydroprocessing hydrocarbonaceous oil plant wherein will comprise under 150～455 ℃ of temperature and the 0.1～10.0kg/kg.h liquid hourly space velocity degree:
A) full boiling point is higher than 538 ℃ and be lower than the oil plant of 2 weight % by the asphaltene content that heptane records.
B) full boiling point is 343 ℃ to 538 ℃ a oil plant, perhaps
C) their mixture,
With hydrogen or hydrogen-containing gas, sulphur compound more than 25% is changed under the condition of hydrogen sulfide being suitable for, feed downwards the hydrotreatment district of being equipped with on hydrotreating catalyst stacking bed, wherein, the said stacking bed upper area that comprises, the hydrotreating catalyst (is that benchmark calculates with the total catalyst) that wherein contains 15 to 85 volume %, the catalyzer here comprises the component of group VIB in the periodic table of elements, group VIII metal, metal oxide or metallic sulfide, and the oxide compound of phosphorus and (or) sulfide; This is stacking bed to also have a lower region, wherein contains the hydrotreating catalyst (is that benchmark calculates with the total catalyst) of 15 to 85 volume %; It comprises the component of group VIB, group VIII metal, and metal oxide or metallic sulfide and content are lower than the phosphorus of 0.5 weight %; And the reaction product that will obtain from said hydrotreatment zone is separated into the liquid hydrocarbon-containing oil plant that hydrogen-rich gas and content of heteroatoms have reduced.
2, in accordance with the method for claim 1, wherein, employing stacking bed comprises a upper area, wherein contain the VIII family component that is up to 10 weight %, the phosphorus component of the group VIB component of 3 to 15 weight % and 0.1 to 10 weight %, this stacking bed lower region in addition.Wherein contain the VIII family component that is up to 10 weight % and the group VIB component of 3 to 30 weight %.
3, according to claim 1 or 2 described methods, wherein, that adopts stacking bedly comprises a upper area, comprising the nickel component that is present on the alumina supporter, molybdenum and (or) tungsten component and phosphorus, this carrier can also contain silicon oxide in addition, this is stacking bed to also have a lower region, comprising be present on the alumina supporter nickel and (or) cobalt component and molybdenum and (or) the tungsten component, this carrier can also contain silicon oxide in addition.
4, in accordance with the method for claim 3, wherein, employing stacking bed comprises a upper area, wherein contains the nickel that is present in mainly 2 to 4 weight % on the carrier that is made of aluminum oxide.The phosphorus of the molybdenum of 8 to 15 weight % and 1 to 4 weight %, this is stacking bed to also have a lower region, wherein contain the cobalt that is present in mainly 2 to 4 weight % on the carrier that constitutes by aluminum oxide and (or) nickel, the molybdenum of 8 to 15 weight % and be less than the phosphorus of 0.5 weight %.
5, in accordance with the method for claim 1, wherein, in employing stacking bed, the dense packing density of the catalyzer of its upper area is 0.65 to 0.95g/cm
2, particularly 0.76 to 0.88g/cm
2, and specific surface area is greater than 140m
2/ g.Particularly greater than 150m
2/ g; The dense packing density of lower region thereof catalyzer is 0.6 to 0.8g/cm
2, particularly 0.67 to 0.69g/cm
2, and specific surface area is greater than 180m
2/ g is particularly greater than 200m
2/ g.
6, in accordance with the method for claim 1, wherein, utilize a kind of stackeding bed catalyst, in stacking bed lower region, contain the cobalt of 2 to 4 weight %, and be substantially free of nickel and not phosphorous.
7, in accordance with the method for claim 1, wherein, utilize a kind of stackeding bed catalyst, in stacking bed lower region, contain the nickel of 2 to 4 weight %, and be substantially free of cobalt and not phosphorous.
8, in accordance with the method for claim 1, wherein, utilize a kind of stacking bed, at an upper portion thereof and (or) lower region contains three foliated lamellar catalyzer.
9, in accordance with the method for claim 8, wherein, adopt a kind of support of the catalyst, it is that to be extruded moulding before dipping be three foliated.
10, in accordance with the method for claim 1, wherein, in the single stage method reactor, comprise the hydrotreatment district, and used stacking bed upper area accounts for about 1/3rd of catalyzer cumulative volume.
11, in accordance with the method for claim 1, wherein, have and hydrotreating catalyst had lose activity the hydrocarbonaceous oil plant of tendency to carry out hydrotreatment by the following method because of forming coke, wherein will:
A) full boiling point is higher than 538 ℃ and be lower than the oil plant of 2 weight % by the asphaltene content that heptane records,
B) full boiling point is 343 ℃ to 538 ℃ a oil plant, perhaps
C) their mixture,
With hydrogen or hydrogen-containing gas, sulphur compound more than 25% is changed under the condition of hydrogen sulfide being suitable for, feed downwards the hydrotreatment zone of being equipped with on two kinds of hydrotreating catalysts stacking bed, the said stacking bed upper area that comprises, the high-activity hydrogenation catalyst (is that benchmark calculates with the total catalyst) that wherein contains 15 to 85 volume %, the catalyzer here comprises the nickel that is present in mainly 2 to 4 weight % on the carrier that is made of aluminum oxide, the molybdenum of 8 to 15 weight %, with the phosphorus of 1 to 4 weight %, the dense packing density of said catalyzer is 0.65 to 0.95g/cm
2, specific surface area is greater than 140m
2/ g; This stacking bed lower region in addition, the high activity hydrogenation and desulphurization catalyst (is that benchmark calculates with the total catalyst) that wherein contains 15 to 85 volume %, the catalyzer here comprise the cobalt that is present in mainly 2 to 4 weight % on the carrier of forming by aluminum oxide with (or) nickel, the molybdenum of 8 to 15 weight % and be less than the phosphorus of 0.5 weight %, the dense packing density of said catalyzer are 0.6 to 0.8g/cm
2Specific surface area is greater than 180m
2/ g; And the reaction product that will obtain from said hydrotreatment zone be separated into hydrogen-rich gas and sulphur and (or) the liquid hydrocarbon-containing oil plant that reduced of heavy metal content.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/735,620 US4776945A (en) | 1984-11-30 | 1985-05-21 | Single-stage hydrotreating process |
| US735,620 | 1985-05-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106942A CN85106942A (en) | 1987-02-04 |
| CN1006230B true CN1006230B (en) | 1989-12-27 |
Family
ID=24956534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106942.8A Expired CN1006230B (en) | 1985-05-21 | 1985-08-09 | Single-stage hydrotreating process |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0203228B2 (en) |
| JP (1) | JPH0633364B2 (en) |
| CN (1) | CN1006230B (en) |
| BR (1) | BR8503786A (en) |
| CA (1) | CA1272153A (en) |
| DE (1) | DE3570088D1 (en) |
| ES (1) | ES8604292A1 (en) |
| PT (1) | PT80934B (en) |
| ZA (1) | ZA855849B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5116484A (en) * | 1990-10-31 | 1992-05-26 | Shell Oil Company | Hydrodenitrification process |
| US5227353A (en) * | 1991-07-24 | 1993-07-13 | Mobil Oil Corporation | Hydroprocessing catalyst composition |
| TR199900205T2 (en) * | 1996-08-01 | 2000-09-21 | Shell Internationale Research Maatschappij B.V. | Hydrotreating process. |
| EP0870817A1 (en) | 1997-04-11 | 1998-10-14 | Akzo Nobel N.V. | Process for effecting deep HDS of hydrocarbon feedstocks |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
| US7288182B1 (en) * | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| US7229548B2 (en) | 1997-07-15 | 2007-06-12 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
| US7232515B1 (en) | 1997-07-15 | 2007-06-19 | Exxonmobil Research And Engineering Company | Hydrofining process using bulk group VIII/Group VIB catalysts |
| JP2007507590A (en) * | 2003-10-02 | 2007-03-29 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | How to improve naphtha quality |
| CA2455011C (en) | 2004-01-09 | 2011-04-05 | Suncor Energy Inc. | Bituminous froth inline steam injection processing |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2300038C2 (en) * | 1973-01-02 | 1987-05-07 | Basf Ag, 6700 Ludwigshafen | Use of a sulfurized catalyst for the production of technical white oils |
| US4016067A (en) * | 1975-02-21 | 1977-04-05 | Mobil Oil Corporation | Process for demetalation and desulfurization of petroleum oils |
| DE2837018A1 (en) * | 1978-08-24 | 1980-03-06 | Basf Ag | USE OF COBALT AND / OR NICKEL MOLYBDAEN OXIDE CATALYSTS FOR THE HYDRATING REFINING OF PETROLEUM HYDROCARBONS |
| AU530497B2 (en) * | 1978-09-28 | 1983-07-21 | Amoco Corporation | Catalyst comprising hydrogenation component on support containing alumina and phosphorus oxides |
| US4406779A (en) * | 1981-11-13 | 1983-09-27 | Standard Oil Company (Indiana) | Multiple catalyst system for hydrodenitrogenation of high nitrogen feeds |
| AU571189B2 (en) * | 1982-12-06 | 1988-04-14 | Amoco Corporation | Hydrotreating catalyst |
| US4500424A (en) * | 1983-04-07 | 1985-02-19 | Union Oil Company Of California | Desulfurization catalyst and process |
-
1985
- 1985-07-29 EP EP85201248A patent/EP0203228B2/en not_active Expired - Lifetime
- 1985-07-29 DE DE8585201248T patent/DE3570088D1/en not_active Expired
- 1985-08-02 ZA ZA855849A patent/ZA855849B/en unknown
- 1985-08-06 CA CA000488159A patent/CA1272153A/en not_active Expired - Fee Related
- 1985-08-09 CN CN85106942.8A patent/CN1006230B/en not_active Expired
- 1985-08-09 ES ES546041A patent/ES8604292A1/en not_active Expired
- 1985-08-09 JP JP60174439A patent/JPH0633364B2/en not_active Expired - Fee Related
- 1985-08-09 BR BR8503786A patent/BR8503786A/en not_active IP Right Cessation
- 1985-08-09 PT PT80934A patent/PT80934B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PT80934B (en) | 1987-09-30 |
| EP0203228B2 (en) | 1996-10-23 |
| PT80934A (en) | 1985-09-01 |
| DE3570088D1 (en) | 1989-06-15 |
| JPH0633364B2 (en) | 1994-05-02 |
| EP0203228B1 (en) | 1989-05-10 |
| BR8503786A (en) | 1986-12-09 |
| EP0203228A1 (en) | 1986-12-03 |
| CN85106942A (en) | 1987-02-04 |
| ZA855849B (en) | 1986-03-26 |
| JPS61266490A (en) | 1986-11-26 |
| ES546041A0 (en) | 1986-01-16 |
| ES8604292A1 (en) | 1986-01-16 |
| CA1272153A (en) | 1990-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1006229B (en) | Single-stage hydrotreating process | |
| EP0093552B1 (en) | Hydrocracking process | |
| US5593570A (en) | Catalyst system for combined hydrotreating and hydrocracking and a process for upgrading hydrocarbonaceous feedstocks | |
| AU2008237602B2 (en) | New hydrocracking process for the production of high quality distillates from heavy gas oils | |
| EP0247679B1 (en) | Hydrocarbon conversion catalysts | |
| US4137147A (en) | Process for manufacturing olefinic hydrocarbons with respectively two and three carbon atoms per molecule | |
| EP1238042B1 (en) | Two stage deep naphtha desulfurization with reduced mercaptan formation | |
| US6702935B2 (en) | Hydrocracking process to maximize diesel with improved aromatic saturation | |
| AU2003228827B2 (en) | Multi-stage hydrocracker with kerosene recycle | |
| US20010042699A1 (en) | Hydrocracking and hydrotreating separate refinery streams | |
| CN1006230B (en) | Single-stage hydrotreating process | |
| EP1042432A1 (en) | Middle distillate selective hydrocracking process | |
| EP0703003A1 (en) | Hydrocarbon conversion catalysts | |
| EP0755426B1 (en) | Process for cetane improvement of distillate fractions | |
| CN101724456B (en) | Hydrogenation method for producing aromatics extraction raw material | |
| KR100939698B1 (en) | Multiple hydroprocessing reactors with intermediate flash zones | |
| CA2065518C (en) | Hydrocracking process | |
| US4619757A (en) | Two stage hydrotreating pretreatment in production of olefins from heavy hydrocarbons | |
| US3598719A (en) | Hydrotreating catalyst and process | |
| US3505208A (en) | Hydrocracking process | |
| EP0214717A1 (en) | Hydrocracking process using zeolite beta | |
| CN109777483B (en) | Method for stabilizing quality of hydrocracking product | |
| CN100357402C (en) | Method for producing high cetane value and low sulfur content diesel oil | |
| CN101434864A (en) | Coking light distillate hydrogenation modification method | |
| US3575844A (en) | Hydrocracking process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |