CN103374402A - Hydro-upgrading method of catalytic cracking raw oil - Google Patents
Hydro-upgrading method of catalytic cracking raw oil Download PDFInfo
- Publication number
- CN103374402A CN103374402A CN2012101075580A CN201210107558A CN103374402A CN 103374402 A CN103374402 A CN 103374402A CN 2012101075580 A CN2012101075580 A CN 2012101075580A CN 201210107558 A CN201210107558 A CN 201210107558A CN 103374402 A CN103374402 A CN 103374402A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- content
- carrier
- nickel
- weight
- 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.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention provides a hydro-upgrading method of catalytic cracking raw oil. The method comprises the step of contacting the raw oil with a catalyst composition under the hydrotreating reaction condition, wherein the catalyst composition comprises a hydrodemetallization catalyst I, a hydrodemetallization catalyst II and a hydrodemetallization catalyst III; the catalysts in the catalyst composition are arranged in such a manner that the raw oil is sequentially in contact with the catalyst I, the catalyst II and the catalyst III; with the total quantity of the catalyst composition as the benchmark, the content of the catalyst I is 5-60% by volume, the content of the catalyst II is 10-70% by volume, and the content of the catalyst III is 5-60% by volume; the catalyst II contains a carrier, metal components including molybdenum, cobalt and nickel and auxiliary components selected from phosphorus and boron; with the catalyst II as the benchmark, the content of molybdenum is 5-20wt%, the total content of cobalt and nickel is 1-6wt% and the contents of the auxiliary components selected from phosphorus and boron are 0.5-5wt% by oxides; and the atomic ratio of cobalt to nickel is 2-4.
Description
Technical field
The present invention relates to the hydroprocessing process of hydrocarbon ils, particularly relate to a kind of method of catalytically cracked stock being carried out upgrading by hydrotreatment.
Background technology
Be subjected to catalytic cracking process and catalysts influence, in order to improve light oil yield, reduce catalyst consumption, require that metal Ni+V content should be lower than 20ppm in the heavy oil catalytic cracking raw material oil, sulphur content is lower than 0.5%, and carbon residue content is less than 6.0%.But along with the continuous aggravation of present crude oil heaviness, in poor quality trend, residual hydrocracking just requires to have higher impurity removal ability and reaction stability as the fcc raw material preprocessing process.Improving impurity removal percentage can realize by the severity of deepening the hydrotreatment reaction, but also can cause the shortening in catalyst runs life-span like this.Therefore adopt new catalyzer and processing and treating method to be only the optimal selection of producing high-quality catalytically cracked material.
Summary of the invention
The technical problem to be solved in the present invention is for the prior art demand, and a kind of new, method of by hydrotreatment catalytically cracked stock being carried out upgrading is provided.
The present invention relates to following content:
1. the hydrogenation modification method of a catalytically cracked stock, be included under the hydrotreatment reaction conditions, described stock oil is contacted with a kind of catalyst combination, described catalyst combination comprises Hydrodemetalation catalyst I, Hydrodemetalation catalyst II and Hydrobon catalyst III, the layout of each catalyzer in the described catalyst combination so that described stock oil successively with comprise catalyst I, catalyst I I contacts with catalyst I II, by volume and take the total amount of described catalyst combination as benchmark, the content of described catalyst I is 5-60%, the content of catalyst I I is 10-70%, the content of catalyst I II is 5-60%, wherein, described catalyst I I contains carrier, the metal component molybdenum, cobalt and nickel, and the adjuvant component that is selected from phosphorus and boron, in oxide compound and take catalyst I I as benchmark, the content of described molybdenum is 5～20 % by weight, the content sum of cobalt and nickel is 1～6 % by weight, the content that is selected from the adjuvant component of phosphorus and boron is the 0.5-5 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2～4.
According to 1 described method, it is characterized in that 2, the content of molybdenum is 8～15 % by weight among the described catalyst I I, the content sum of cobalt and nickel is 1.5～4 % by weight, the content that is selected from the adjuvant component of phosphorus and boron is 1～4 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2.2～3.2.
According to 1 or 2 described methods, it is characterized in that 3, the content of nickel is less than 1.2% among the described catalyst I I.
According to 3 described methods, it is characterized in that 4, the content of nickel is 0.5～1.1% among the described catalyst I I.
According to 1 described method, it is characterized in that 5, by volume and take the total amount of described catalyst combination as benchmark, the content of the catalyst I in the described catalyst combination is 10-50%, the content of catalyst I I is 20-60%, and the content of catalyst I II is 10-50%
6, according to 1 described method, it is characterized in that, described catalyst I comprises catalyst I a, described catalyst I a contains carrier, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, contain or do not contain and be selected from boron, phosphorus, one or more adjuvant components in the fluorine, take catalyst I a as benchmark, take the content of the nickel of oxide compound and/or cobalt as the 0.3-8 % by weight, the content of molybdenum and/or tungsten is the 0.5-15 % by weight, the boron that is selected from element, phosphorus, the content of one or more adjuvant components in the fluorine is 0～5 % by weight, and wherein the pore volume of carrier is 0.6-1.4 ml/g, and specific surface area is to less than or equal to 350m greater than 90
2/ g.
According to 6 described methods, it is characterized in that 7, the pore volume of the carrier among the described catalyst I a is 0.7-1.2 ml/g, specific surface area is 100-200m
2/ g.
According to 6 or 7 described methods, it is characterized in that 8, the carrier among the described catalyst I a is selected from aluminum oxide.
According to 8 described methods, it is characterized in that 9, described aluminum oxide is the alumina supporter with double-hole.
According to 9 described methods, it is characterized in that 10, described double-hole alumina supporter accounts for total pore volume 40-90% at the pore volume of aperture 10-30 nanometer, the aperture accounts for total pore volume 10-60% at the pore volume of 100-2000 nanometer.
11, according to 1 described method, it is characterized in that, described catalyst I II contains the carrier that is selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, contain or do not contain and be selected from one or more adjuvant components in fluorine, boron and the phosphorus, take catalyst I II as benchmark, take the content of the nickel of oxide compound and/or cobalt as 1～5 % by weight, the content of molybdenum and/or tungsten is 10～35 % by weight, take the content that is selected from one or more adjuvant components in fluorine, boron and the phosphorus of element as 0～9 % by weight.
According to 11 described methods, it is characterized in that 12, the carrier among the described catalyst I II is selected from aluminum oxide.
According to 12 described methods, it is characterized in that 13, the pore volume of described aluminum oxide is not less than 0.35 ml/g, bore dia is that the pore volume in 40～100 dust holes accounts for more than 80% of total pore volume.
According to 6 described methods, it is characterized in that 14, described catalyst I comprises and catalyst I
aThe catalyst I of layered arrangement
b, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be below 40%, described layering so that described stock oil successively with catalyst I
bAnd catalyst I
aContact, described catalyst I
bContain carrier and randomly contain the hydrogenation active metals component that is selected from group vib and group VIII, in oxide compound and with catalyst I
bBe benchmark, the content of the metal component of described group vib is 0 to less than or equal to 10 % by weight, and the content of the metal component of described group VIII is 0 to less than or equal to 4 % by weight.
15, according to 14 described methods, it is characterized in that described catalyst I
bCarrier contain the 0-aluminum oxide, characterize with mercury penetration method, the pore volume of described carrier is 0.5-0.75ml/g, specific surface area is 2-20m
2/ g.
16, according to 15 described methods, it is characterized in that described catalyst I
bThe pore volume of carrier be 0.52-0.73ml/g, specific surface area is 5-16m
2/ g, pore distribution curve two peaks occur at 45-1000 μ m and 0.2-1mm.
17, according to 16 described methods, it is characterized in that described catalyst I
bThe pore size distribution of carrier curve two peaks appear at 45-100 μ m and 0.2-1mm.
18, according to 14 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 5-30%.
According to 1 described method, it is characterized in that 19, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 ℃, volume space velocity is 0.1-1h during liquid
-1, hydrogen to oil volume ratio is 600-1500.
According to 19 described methods, it is characterized in that 20, the reaction conditions of described hydrotreatment reaction is: the hydrogen dividing potential drop is 10-18MPa, and temperature is 350-420 ℃, and volume space velocity is 0.2-0.6h during liquid
-1, hydrogen to oil volume ratio is 800-1100.
According to method provided by the invention, wherein, the carrier of described catalyst I I can be that any one is suitable for preparing the carrier that heavy oil hydrogenating treatment catalyst is used in the prior art, and they can be that commercially available commodity also can adopt arbitrarily prior art preparation.This class carrier has following physico-chemical property usually, comprising: pore volume is 0.5-1.0 ml/g, is preferably 0.6-0.9 ml/g, and specific surface is 160-400 rice
2/ gram is preferably 180-350 rice
2/ gram.Preferred alumina supporter wherein.
The preparation method of described catalyst I I is included in and introduces metal component molybdenum, cobalt and nickel on the carrier, and the adjuvant component that is selected from phosphorus and boron, in oxide compound and take the total amount of catalyzer as benchmark, the introducing amount of each component so that in the final catalyzer content of molybdenum be 5～20 % by weight, be preferably 8～15 % by weight, the content sum of cobalt and nickel is 1～6 % by weight, be preferably 1.5～4 % by weight, the content that is selected from the adjuvant component of phosphorus and boron is the 0.5-5 % by weight, be preferably 1～4%, the atomic ratio of described cobalt and nickel is 2～4, is preferably 2.2～3.2.In further preferred embodiment, in oxide compound and take the total amount of catalyzer as benchmark, the introducing amount of described nickel is more preferably 0.5～1.1% less than 1.2%.
Described method at carrier introducing metal component can be to prepare the usual method of hydrogenation catalyst, for example adopts the method for dipping.Steeping process can adopt the total immersion also can step impregnation.Namely adopt contain molybdenum, nickel and cobalt metal component and phosphorus or boron the method for solution impregnating carrier of compound introduce.This dipping can be with the solution impregnation that contains component composition preparation, also can be with the mixing solutions dipping that contains two or more component composition.By adjusting the contained concentration of each component composition and the consumption of steeping fluid of containing in the dipping, art technology realizes the content of each component of introducing catalyzer is controlled easily, does not give unnecessary details here.
The step that behind described dipping, also comprises drying, roasting or not roasting.The method of described drying and roasting and condition are conventional method and the condition that the catalyzer preparation is adopted.For example, the condition of described drying comprises: drying temperature is 60～150 ℃, and be 1～5 hour time of drying, and preferred drying temperature is 80～120 ℃, and be 2～4 hours time of drying; Described roasting condition comprises: maturing temperature is 350-550 ℃, and roasting time is 1-6 hour, and preferred maturing temperature is 400～500 ℃, and roasting time is 2～4 hours.
The described compound that contains the molybdenum component is selected from one or more in its soluble compound, such as in molybdenum oxide, molybdate, the paramolybdate one or more, and preferred molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein.
Described compound nickeliferous and that contain the cobalt metal component is selected from one or more in their soluble compound, such as in the soluble complexes of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and cobalt one or more, be preferably Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous dihydroxycarbonate; In the soluble complexes of nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickel one or more are preferably nickelous nitrate, basic nickel carbonate.
Described P contained compound is selected from one or more in their soluble compound, such as in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, the phosphoric acid salt one or more, is preferably phosphoric acid and ammonium phosphate salt.
Described boron-containing compound is selected from one or more in their soluble compound, such as in boric acid, ammonium borate, ammonium biborate, the borate one or more, is preferably boric acid and ammonium borate salt.
According to catalyst I I of the present invention, can also contain any impact and the invention provides the material that catalyst performance maybe can improve the catalytic performance of catalyzer provided by the invention.For example, can contain the components such as alkaline-earth metal, in oxide compound and take catalyzer as benchmark, the content of said components is no more than 10 % by weight, is preferably the 0.5-5 % by weight.
When also containing the components such as alkaline-earth metal in the described catalyzer, the introducing method of the components such as described alkaline-earth metal can be method arbitrarily, take the alumina supporter of preparation alkaline including earth metal as example, the introducing method of the components such as described alkaline-earth metal can be that the compound that will contain the component such as described alkaline-earth metal directly mixes with described pseudo-boehmite, moulding and roasting; Can be that the compound that will contain the component such as described alkaline-earth metal is mixed with mixing solutions with the compound that contains other components, use afterwards the described carrier of this solution impregnation; Can also be to contain the independent obtain solution of compound of the components such as alkaline-earth metal, to use respectively afterwards the described carrier of these solution impregnation.When the component such as alkaline-earth metal and other groups are introduced described carrier respectively, preferred at first with the described carrier of solution impregnation and the roasting that contain the component composition such as described alkaline-earth metal, use again afterwards the solution impregnation of the compound that contains other components, described maturing temperature is 250-600 ℃, be preferably 350-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to method provided by the invention, wherein, described catalyst I comprises that the effect of catalyst I a is to remove the macromole species such as metal, bituminous matter and colloid in the raw material by the hydrotreatment reaction at this catalyzer.Therefore, wherein said catalyst I can be selected from one or more in the catalyzer that can realize arbitrarily this function in the prior art.For example, be usually used in the hydrogenation protecting catalyst of mink cell focus processing usefulness, one or more in the Hydrodemetalation catalyst.They can be commercially available commodity or adopt arbitrarily existing method preparation.
This type of catalyzer contains heat-resistant inorganic oxide carrier and the hydrogenation active metals component that loads on this carrier usually.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silica-alumina-titanium oxide, the silica-alumina-magnesium oxide one or more are preferably aluminum oxide.Described hydrogenation activity component is selected from molybdenum and or tungsten, nickel and or cobalt.
For example, the disclosed a kind of catalyzer of ZL200310117322.6, this catalyzer contains a kind of macropore alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel that load on this carrier, in oxide compound and take catalyzer as benchmark, described catalyzer contains the carrier of the cobalt of the molybdenum of 0.5-15 % by weight and/or tungsten, 0.3-8 % by weight and/or nickel, equal amount, it is characterized in that described carrier contains a kind of halogen, take the carrier total amount as benchmark, this carrier contains the aluminum oxide of 95-99 % by weight.
ZL200410037670.7 discloses a kind of alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel that load on this carrier with double-hole, in oxide compound and take catalyzer as benchmark, described catalyzer contains the carrier of the cobalt of the molybdenum of 0.5-15 % by weight and/or tungsten, 0.3-8 % by weight and/or nickel, equal amount.
ZL200410096309.1 discloses a kind of residuum hydrogenating and metal-eliminating catalyst, this catalyzer contains a kind of bimodal porous aluminum oxide carrier and the molybdenum and/or tungsten and nickel and/or the cobalt metal component that load on this carrier, the pore volume of wherein said bimodal porous aluminum oxide carrier is 0.8-1.6 ml/g, and specific surface area is 150-350m
2/ g, the aperture accounts for total pore volume 40～90% at the pore volume of 10～30 nanometers, and the aperture accounts for total pore volume 10～60% at the pore volume of 100～2000 nanometers.
ZL200510115349.0 discloses a kind of hydrogenation activity protective material and preparation method thereof; this protective material contains alumina supporter, loads on hydrogenation active metals component and the halogen of significant quantity on this carrier; in element and take catalyzer as benchmark; the content of described halogen is the 0.5-10 % by weight, and the specific surface area of described carrier is 2-50m
2/ g, pore volume 0.4-1.2 ml/g, described carrier is by comprising the precursor of one or more aluminum oxide and/or aluminum oxide and the method preparation of at least a halogen-containing compound, moulding and roasting.
These catalyzer all can be selected to be used for the present invention as described catalyst I.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump they are quoted as the part of content of the present invention here.
According to method provided by the invention, wherein, the predictive role of catalyst I II is the macromolecular cpds such as saturated polycyclic aromatic hydrocarbons, makes wherein that the impurity such as the more difficult sulphur that removes, nitrogen further remove, and removes simultaneously the carbon residue in the stock oil.Therefore, described catalyst I II can be selected from one or more in any catalyzer that can realize this function of the prior art.For example, be selected from the Hydrobon catalyst that prior art arbitrarily provides one or more.They can be commercially available commodity or adopt arbitrarily existing method preparation.
This type of catalyzer contains heat-resistant inorganic oxide carrier, hydrogenation active metals component usually.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, the silicon oxide-titanium oxide are preferably aluminum oxide.Described hydrogenation active metals component is nickel and or cobalt, tungsten and or molybdenum.The example of this class catalyzer as:
The disclosed a kind of Hydrobon catalyst of ZL97112397.7, it consists of nickel oxide 1～5 heavy %, Tungsten oxide 99.999 12～35 heavy %, fluorine 1～9 heavy %, all the other are aluminum oxide, this aluminum oxide is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50, to be bore dia account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in bore dia 60～600 dust holes accounts for the aluminum oxide of total pore volume more than 70%.
ZL00802168.6 discloses a kind of Hydrobon catalyst, and this catalyzer contains a kind of alumina supporter and at least a VI B family's metal and/or at least a group VIII metal that load on this alumina supporter.The pore volume of described alumina supporter is not less than 0.35 ml/g, and bore dia is that the pore volume in 40～100 dust holes accounts for more than 80% of total pore volume, and it adopts special method preparation.
ZL200310117323.0 discloses a kind of Hydrobon catalyst, this catalyzer contains a kind of alumina supporter and the molybdenum that loads on this carrier, nickel and tungsten metal component, in oxide compound and take catalyzer as benchmark, described catalyzer contains the molybdenum of 0.5-10 % by weight, the nickel of 1-10 % by weight, the tungsten of 12-35 % by weight and the carrier of equal amount, the preparation method of described catalyzer comprises the solution of using successively molybdate compound and nickeliferous, the solution impregnation of alumina carrier of tungsten compound, wherein said alumina supporter carries out drying after with the solution impregnation of molybdate compound, with nickeliferous, carry out drying and roasting after the solution impregnation of tungsten compound, drying temperature is 100-300 ℃, be 1-12 hour time of drying, maturing temperature is 320-500 ℃, and roasting time is 1-10 hour.
These catalyzer all can be used as described catalyst I II and are used for the present invention.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump they are quoted as the part of content of the present invention here.
The contriver further finds; when described catalyst I is when comprising the combination of Ib and Ia, can further improve the described catalyst combination of hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III that comprises and be used for the performance that described stock oil adds man-hour.
Particularly, described catalyst I
bBe a kind of forming composition that contains or do not contain the low specific surface area of having of hydrogenation active metals and large pore volume, the pore distribution curve of further preferred this forming composition is that micron order (or grade) is bimodal distribution at bore dia.In a preferred embodiment, the preparation method of described carrier comprises:
(1) with hydrated aluminum oxide, but the organic additive of burn off, and acid or alkali and water mix, and carry out afterwards drying, fragmentation and screening, obtain 20-60 purpose particle;
(2) particle that step (1) is obtained mixes with aluminium colloidal sol and/or hydrated aluminum oxide slurries and moulding, carries out afterwards drying and roasting;
Wherein, hydrated aluminum oxide described in the step (1), but the organic additive of burn off, the ratio of mixture of acid or alkali and water is 100: 0.5-6: 0.5-10: 30-80; The particle that is obtained by step (1) in the described step (2) with take the weight ratio of mixture of the aluminium colloidal sol of aluminum oxide and/or hydrated aluminum oxide slurries as 100: 5-45; Described drying conditions comprises: temperature is 100-140 ℃, and the time is 1-10 hour; Described roasting condition comprises: temperature is 1100-1540 ℃, and the time is 1-10 hour.
Preferably wherein, step (1) but described in organic additive, acid or the alkali of hydrated aluminum oxide burn off and the ratio of mixture of water be 100: 0.6-3: 0.6-5: 35-75; The particle that is obtained by step (1) in the described step (2) with take the weight ratio of mixture of the aluminium colloidal sol of aluminum oxide and/or hydrated aluminum oxide slurries as 100: 5-40; Described drying conditions comprises: temperature is 110-130 ℃, and the time is 2-8 hour; Described roasting condition comprises: temperature is 1200-1500 ℃, and the time is 2-8 hour.But the organic additive of described burn off is selected from starch, Mierocrystalline cellulose, the polynary alcohol and carboxylic acid one or more, one or more in preferred starch, Mierocrystalline cellulose and the polyvalent alcohol.
Optionally, can also comprise that in described step (1) or (2) introducing is selected from siliceous, phosphorus, the step of the compound of one or more adjuvant components in alkali or the alkaline-earth metal, in oxide compound and take carrier as benchmark, the described introducing amount that contains the compound of adjuvant component, make the content of adjuvant component described in the final carrier be no more than 25 % by weight, be preferably the 1-20 % by weight.Described silicon-containing compound is selected from silicon sol, and P contained compound is selected from aluminium dihydrogen phosphate, and alkali metal-containing compound is selected from alkali-metal oxyhydroxide, and the alkaline including earth metal compound is selected from oxide compound or the oxyhydroxide of alkaline-earth metal.
Here, described pore distribution curve refers to that pore volume (pore volume) is with the velocity of variation (ordinate zou is dV/dlogD, and X-coordinate is bore dia D (logD)) of bore dia.
Wherein, the described hydrated aluminum oxide in the preparation method of described carrier is selected from one or more the mixture among hibbsite, monohydrate alumina (comprising pseudo-boehmite) and the amorphous hydroted alumina.Described acid can be any compound that reacts acid in water medium, and for example, they can be formic acid, acetic acid, propionic acid, sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, silicofluoric acid, hydrofluoric acid, preferred nitric acid, hydrochloric acid, sulfuric acid wherein; Described alkali can be the compound of any react acid in water medium, for example, they can be ammonia, ammoniacal liquor, alkali-metal oxyhydroxide (such as sodium hydroxide, potassium hydroxide, magnesium hydroxide), alkali-metal carbonate (such as salt of wormwood, Quilonum Retard, yellow soda ash, saleratus, calcium carbonate, magnesiumcarbonate, barium carbonate), preferred salt of wormwood, Quilonum Retard wherein.
Be enough to make described hydrated aluminum oxide, but the organic additive of burn off, acid or alkali and water fully mix, obtain under the prerequisite of 20-60 purpose particulate matter after this mixture drying, the fragmentation, the present invention to realize that this mixes in the step (1), broken mode without limits.For example, but can be in banded extruder, at first hydrated aluminum oxide to be mixed with the organic additive of burn off, acid or alkali are mixed with water, afterwards, with mixing solutions and the mixing of materials in the banded extruder of acid or alkali and water and extrude extrudate drying, fragmentation and screening.Mixing in the step (2) is take the requirement of satisfying moulding as prerequisite, and the method for described moulding can be carried out according to a conventional method, such as can be compressing tablet, spin, extrusion moulding etc.For satisfying the needs of different forming methods, comprise that in moulding process introducing helps forming agent, for example, introduce an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the Mierocrystalline cellulose one or more), describedly help the consumption of forming agent and adjustment thereof to be well known to those skilled in the art, be not repeated herein.
When described catalyst I b contains the hydrogenation active metals component, in the preparation method of this catalyzer, be included in the step of introducing the hydrogenation active metals component in the described forming composition, the method of introducing the hydrogenation activity component is preferably pickling process, comprise the solution of preparing the compound that contains hydrogenation active metals and use this solution impregnating carrier, carry out afterwards drying, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of group vib and the metal component of group VIII, in oxide compound and take catalyzer as benchmark, the content of metal component that the described compound that contains hydrogenation active metals makes the group vib in the final catalyzer at the consumption of the concentration of described solution and described solution is greater than 0 to less than or equal to 10 % by weight, the content of the metal component of described group VIII greater than 0 to less than or equal to 4 % by weight; Described drying conditions comprises: temperature is 100-250 ℃, and the time is 1-10 hour; Described roasting condition comprises: temperature is 360-500 ℃, and the time is 1-10 hour.Preferably, the metal component of described group vib is selected from molybdenum and/or tungsten, the metal component of group VIII is selected from cobalt and/or nickel, in oxide compound and take catalyzer as benchmark, it is the 3-6 % by weight that the described compound that contains hydrogenation active metals makes the content of the metal component of the group vib in the final catalyzer at the consumption of the concentration of described solution and described solution, and the content of the metal component of group VIII is the 1-3 % by weight; Described drying conditions comprises: temperature is 100-140 ℃, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 ℃, and the time is 2-6 hour.
Wherein, the described compound that contains the group vib metal is selected from one or more in the soluble compound of these metals, for example, can be in silicotungstic acid, silicotungstate, phospho-molybdic acid, phosphomolybdate, molybdate, paramolybdate, tungstate, metatungstate, the ethyl metatungstate one or more.
The described compound that contains the group VIII metal is selected from one or more in the soluble compound of these metals, for example, is selected from one or more in their nitrate, carbonate, subcarbonate, hypophosphite, phosphoric acid salt, vitriol, muriate.
According to method provided by the invention; the described catalyst combination that comprises hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III successively layering fills in the same reactor, also can be to fill in successively in the reactor of several series connection to use.Be enough to so that described stock oil successively with comprise hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and prerequisite that hydrotreating catalyst III contacts under, this present invention is not particularly limited.
The present invention is owing to adopt a kind of catalyst combination that has fine better demetalization, desulfurization and take off the over-all propertieies such as carbon residue, be particularly suitable for being selected from the hydrotreatment of one or more stock oils in vacuum residuum, deep drawing wax oil, frivolous asphalt oil, heavy deasphalted oil, the wax tailings etc., can be catalytic cracking unit stock oil through hydro-upgrading is provided.
The metal content of oil is below the 20 μ g/g after the hydrotreatment that obtains according to described method, and sulphur content is below 0.5%, and carbon residue content is below 6.0%.
Embodiment
The following examples will the present invention is described further.
Agents useful for same in the example except specifying, is chemically pure reagent.
Embodiment 1-4 explanation the invention provides method catalyst I I and preparation thereof.
The carrier that Kaolinite Preparation of Catalyst II uses and preparation thereof:
Carrier Z1 and preparation thereof:
The pseudo-boehmite dry glue powder RPB110 of 300 gram Chang Ling catalyst plant productions and the sesbania powder of 10 grams are mixed, it at room temperature is 1% aqueous nitric acid with the concentration of this mixture and 360 milliliters, mix, after double screw banded extruder continuation kneading is plastic, be extruded into the trilobal bar of 1.5 millimeters of ф, wet bar after 3 hours, 3 hour obtains carrier Z1 in 700 ℃ of roastings through 120 ℃ of dryings.Measure specific surface, pore volume and the pore size distribution of Z1, the results are shown in Table 1.
Carrier Z2 and preparation thereof:
The pseudo-boehmite dry glue powder of the pseudo-boehmite dry glue powder RPB90 that 300 gram Chang Ling catalyst plants are produced) and 10 restrain the sesbania powder and mix, add 330 ml concns and be 1% aqueous nitric acid, mix, after double screw banded extruder continuation kneading is plastic, be extruded into the butterfly bar of 1.1 millimeters of ф, wet bar after 2 hours, 4 hour obtains carrier Z2 in 600 ℃ of roastings through 110 ℃ of dryings.Measure specific surface, pore volume and the pore size distribution of Z2, the result is as shown in table 1.
Table 1
Carrier specific surface, pore volume and pore size distribution adopt B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.
Embodiment 1
Get 200 gram Z1, contain MoO with 500 milliliters
3120 grams per liters, NiO 8 grams per liters, CoO 20 grams per liters, B
2O
3The ammonium molybdate of 15 grams per liters, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and boric acid mixing solutions dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 4 hours obtained catalyst I I1 after filtering.Take the gross weight of catalyzer as benchmark, adopt Xray fluorescence spectrometer to measure molybdenum oxide, cobalt oxide, nickel oxide and B among the catalyst I I1
2O
3Content, measurement result is as shown in table 2.(all appts is Rigaku electric machine industry Co., Ltd. 3271 type Xray fluorescence spectrometers, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP133-90)
Embodiment 2
Get 200 gram Z2, contain MoO with 220 milliliters
3172 grams per liters, NiO 9 grams per liters, CoO 32 grams per liters, P
2O
5The molybdenum oxide of 43 grams per liters, basic nickel carbonate, cobaltous dihydroxycarbonate and phosphoric acid mixing solutions dipping 2 hours, in 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 2 hours obtained catalyst I I2.Measure molybdenum oxide, cobalt oxide, nickel oxide and P among the catalyst I I2 according to the mode identical with embodiment 1
2O
5Content, the result is as shown in table 2.
Embodiment 3
Get 200 gram Z2, contain MoO with 200 milliliters
3122 grams per liters, NiO 9 grams per liters, CoO 18 grams per liters, P
2O
5The molybdenum oxide of 35 grams per liters, basic nickel carbonate, cobaltous dihydroxycarbonate and phosphoric acid mixing solutions dipping 1 hour, in 120 ℃ of oven dry 2 hours, 480 ℃ of roastings 4 hours obtained catalyst I I3.Measure molybdenum oxide, nickel oxide and cobalt oxide, P among the catalyst I I3 according to the mode identical with embodiment 1
2O
5Content, the result is as shown in table 2.
Embodiment 4
Get 200 gram Z1, contain CoO 12 grams per liters, B with 500 milliliters
2O
3The Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 9 grams per liters, boric acid mixing solutions dipping 1 hour, in 110 ℃ of oven dry 3 hours, 350 ℃ of roastings 2 hours contained MoO with 200 milliliters after filtering
392 grams per liters, the molybdenum oxide of NiO 7 grams per liters, basic nickel carbonate mixing solutions dipping 1 hour, in 120 ℃ of oven dry 2 hours, 480 ℃ of roastings 4 hours obtained catalyst I I4.Measure molybdenum oxide, nickel oxide and cobalt oxide, B among the catalyst I I4 according to the mode identical with embodiment 1
2O
3Content, the result is as shown in table 2.
Comparative Examples 1
Get 200 gram Z1, contain MoO with 500 milliliters
3120 grams per liters, the ammonium molybdate of NiO 28 grams per liters and nickelous nitrate mixing solutions dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 4 hours obtained catalyzer DII1 after filtering.Measure molybdenum oxide among the catalyzer DII1 and the content of nickel oxide according to the mode identical with embodiment 1, the result is as shown in table 2.
Comparative Examples 2
Get 200 gram Z2, contain MoO with 500 milliliters
3135 grams per liters, NiO 12 grams per liters, the ammonium molybdate of CoO 20 grams per liters, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES mixing solutions dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 4 hours obtained catalyzer DII2 after filtering.Take the gross weight of catalyzer as benchmark, adopt Xray fluorescence spectrometer to measure the content of molybdenum oxide among the catalyzer DII2, cobalt oxide, nickel oxide, measurement result is as shown in table 2.(all appts is Rigaku electric machine industry Co., Ltd. 3271 type Xray fluorescence spectrometers, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP133-90)
Table 2
Embodiment 5-8
Embodiment 5-8 illustrates application and the performance thereof of catalyst I I provided by the invention.
Take nickel content as 29ppm, content of vanadium as 83ppm, sulphur content as 4.7%, carbon residue is raw material, evaluate catalysts on 100 milliliters of small fixed reactors as the long residuum of 15% nitrogen content 0.3%.
Respectively catalyst I I 1, II 2, II 3, II 4 are broken into the particle of diameter 2-3 millimeter, the catalyzer loading amount is 100 milliliters.Reaction conditions is: volume space velocity is 0.6 hour when 380 ℃ of temperature of reaction, hydrogen dividing potential drop 14 MPas, feeding liquid
-1, hydrogen to oil volume ratio is 1000, reacts sampling after 200 hours, the content of nickel and vanadium in the oil after employing inductive coupling plasma emission spectrograph (ICP-AES) mensuration is processed.(instrument is the U.S. PE-5300 of PE company type plasma quantometer, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP124-90)
Use coulometry to measure the content (concrete grammar is seen Petrochemical Engineering Analysis method RIPP62-90) of sulphur.
Use coulometry to measure the content (concrete grammar is seen Petrochemical Engineering Analysis method RIPP63-90) of nitrogen.
Use microdetermination carbon residue content (concrete grammar is seen Petrochemical Engineering Analysis method RIPP148-90).
Calculate respectively the decreasing ratio of sulphur, carbon residue, nitrogen and metal according to following formula:
The results are shown in Table 3.
Comparative Examples 3-4
Every impurity removal performance according to method evaluation catalyzer DII1, the DII2 of embodiment 5-8 the results are shown in Table 3.
Table 3
Can be seen by the whole impurity removal specific activity prior art that the invention provides catalyzer obvious lifting being arranged by table 3 result, especially in desulfurization and take off promote aspect the carbon residue more remarkable.
Embodiment 9-13 explanation the invention provides method hydrogenation protecting catalyst Ib and preparation thereof.
Embodiment 9
The aqueous solution that 100 gram pseudo-boehmites (the Chang Ling catalyst plant is produced, and butt is 65 % by weight), 3 gram sesbania powder and 155 grams is contained 1.5% nitric acid.Kneading and extruding with the cylindrical orifice plate of φ 2.0mm in double screw banded extruder, wet bar be in 120 ℃ of dryings 4 hours, with dried bar pulverizing and sieve.
Get the aforementioned screening of 40 grams and obtain 40-60 purpose particulate matter, it is mixed with 10 gram pseudo-boehmites and 1.2 gram magnesium oxide, (brightness silica gel company limited is built in Qingdao to add entry 5 grams and 15 gram silicon sol in mixture, dioxide-containing silica 29%) and according to the moulding of roller forming method, obtaining particle diameter is the 5.5-6.5mm spheroidal particle.Afterwards, in 120 ℃ of dryings 4 hours, 1200 ℃ of roastings 3 hours got hydrogenation protecting catalyst Ib-1 (Z9) with this particle.
Adopt the X-ray diffraction to characterize, catalyst I b-1 has the Alpha-alumina structure, adopt and press the mercury method to characterize, catalyst I b-1 pore distribution curve two peaks occur at 45-1000 μ m and 0.2-1mm, and its pore volume, specific surface area and pore distribution value and catalyst I b-1 composition are listed in table 4.
Embodiment 10
The aqueous solution that 100 gram pseudo-boehmites (the Chang Ling catalyst plant is produced, and butt is 65 % by weight), 3 gram sesbania powder and 155 grams is contained 1.5% nitric acid and 0.5% salt of wormwood.Kneading and extruding with the cylindrical orifice plate of φ 2.0mm in double screw banded extruder, wet bar be in 120 ℃ of dryings 4 hours, with dried bar pulverizing and sieve.The rear sieve of pulverizing is got the 40-60 mesh sieve and is divided.
Get that aforementioned screening obtains 40-60 purpose particulate matter 45g and the 5g pseudo-boehmite mixes, add entry 8g, (chemical industry company limited is gathered in Yueyang to aluminium colloidal sol, solid content: after 25%) 20g and aluminium dihydrogen phosphate (Chinese and Western, Beijing tech science and technology limited Company) 2.1g and aforementioned screening mix, extruded moulding.Pelletizing after the moulding, shaping 120 ℃ of dryings 4 hours, 1400 ℃ of roastings 3 hours, obtains carrier Z10 with bead after the shaping.
Adopt the X-ray diffraction to characterize, carrier Z10 has the Alpha-alumina structure, adopts and presses the mercury method to characterize, and carrier Z10 pore distribution curve two peaks occur at 45-1000 μ m and 0.2-1mm, and its pore volume, specific surface area and pore distribution value and carrier form lists in table 4.
Get carrier 20 gram Z10, (contain MoO in the saturated mode of soaking with containing the 1.42g ammonium molybdate
382%) and 15.5 milliliters of dippings of solution of 1.3g nickelous nitrate (containing NiO 25%), behind the dipping 120 ℃ of dryings 4 hours, 420 ℃ of roastings 3 hours guard catalyst Ib-2 of the present invention.The content that adopts the X-fluorescence method to measure hydrogenation active metals component in the catalyzer is listed in table 5.
Embodiment 11
The aqueous solution that 100 gram pseudo-boehmites (the Chang Ling catalyst plant is produced, and butt is 65 % by weight), 3 gram sesbania powder and 155 grams is contained 1.5% nitric acid and 0.5% Quilonum Retard.Kneading and extruding with the cylindrical orifice plate of φ 5.0mm in double screw banded extruder, wet bar be in 120 ℃ of dryings 4 hours, with dried bar pulverizing and sieve.
Take by weighing 20-40 purpose screening 42g and 8g pseudo-boehmite and mix, take by weighing 25g aluminium colloidal sol (chemical industry company limited is gathered in Yueyang, solid content: 25%), after mixing, extruded moulding.Pelletizing after the moulding, shaping 120 ℃ of dryings 4 hours, 1100 ℃ of roastings 3 hours, obtains carrier Z11 with bead after the shaping.
Adopt the X-ray diffraction to characterize, carrier Z11 has the Alpha-alumina structure, adopts and presses the mercury method to characterize, and carrier Z11 pore distribution curve two peaks occur at 45-1000 μ m and 0.2-1mm, and its pore volume, specific surface area and pore distribution value and carrier form lists in table 4.
Get carrier 30 as one kind gram Z11, (contain MoO in the saturated mode of soaking with containing the 2.2g ammonium molybdate
382%) and 25 milliliters of dippings of the solution of 2.0g nickelous nitrate (containing NiO25%), behind the dipping 120 ℃ of dryings 4 hours, 420 ℃ of roastings 3 hours guard catalyst Ib-3 of the present invention.The content that adopts the X-fluorescence method to measure hydrogenation active metals component in the catalyzer is listed in table 5.
Embodiment 12
The aqueous solution that 100 gram pseudo-boehmites (the Chang Ling catalyst plant is produced, and butt is 65 % by weight), 3 gram sesbania powder and 155 grams is contained 1.8% nitric acid.Kneading and extruding with the cylindrical orifice plate of φ 5.0mm in double screw banded extruder, wet bar be in 120 ℃ of dryings 4 hours, with dried bar pulverizing and sieve.
Take by weighing 20-40 purpose screening 20g and 40-60 purpose screening 15g, mix with the 15g pseudo-boehmite, take by weighing 25g silicon sol (brightness silica gel company limited, dioxide-containing silica 29% are built in Qingdao), mix extruded moulding with aforementioned screening.Pelletizing after the moulding, shaping 120 ℃ of dryings 4 hours, 1400 ℃ of roastings 3 hours, obtains carrier Z12 with bead after the shaping.
Adopt the X-ray diffraction to characterize, carrier Z12 has the Alpha-alumina structure, adopts and presses the mercury method to characterize, and carrier Z12 pore distribution curve two peaks occur at 45-1000 μ m and 0.2-1mm, and its pore volume, specific surface area and pore distribution value and carrier form lists in table 4.
Get carrier 20 gram Z12, (contain MoO in the saturated mode of soaking with containing the 0.86g ammonium molybdate
382%) and 13 milliliters of dippings of the solution of 1.25g nickelous nitrate (containing NiO25%), behind the dipping 120 ℃ of dryings 4 hours, 420 ℃ of roastings 3 hours guard catalyst Ib-4 of the present invention.The content that adopts the X-fluorescence method to measure hydrogenation active metals component in the catalyzer is listed in table 5.
Embodiment 13
The aqueous solution that 100 gram pseudo-boehmites (the Chang Ling catalyst plant is produced, and butt is 65 % by weight), 3 gram sesbania powder and 155 grams is contained 1.5% nitric acid.Kneading and extruding with the cylindrical orifice plate of φ 2.0mm in double screw banded extruder, wet bar be in 120 ℃ of dryings 4 hours, with dried bar pulverizing and sieve.
Get the 40-60 purpose and sieve to get 40 grams, it is mixed with 10 gram pseudo-boehmites, (chemical industry company limited is gathered in Yueyang, solid content: 25%) according to the moulding of roller forming method, obtaining particle diameter is the 5.5-6.5mm spheroidal particle with 15 gram aluminium colloidal sols to add entry 5 grams in mixture.Afterwards, in 120 ℃ of dryings 4 hours, 1200 ℃ of roastings 3 hours obtained carrier Z13 with this particle.
Adopt the X-ray diffraction to characterize, carrier Z13 has the Alpha-alumina structure, adopts and presses the mercury method to characterize, and carrier Z13 pore distribution curve two peaks occur at 45-1000 μ m and 0.2-1mm, and its pore volume, specific surface area and pore distribution value and carrier form lists in table 4.
Get carrier 20 gram Z13, (contain MoO in the saturated mode of soaking with containing the 1.45g ammonium molybdate
382%) and 14 milliliters of dippings of solution of 1.30g nickelous nitrate (containing NiO 25%), behind the dipping 120 ℃ of dryings 4 hours, 420 ℃ of roastings 3 hours guard catalyst Ib-5 of the present invention.The content that adopts the X-fluorescence method to measure hydrogenation active metals component in the catalyzer is listed in table 5.
Table 4
Table 5
The effect that embodiment 14-19 explanation the present invention produces fine quality catalytic cracking raw material.
Stock oil is: nickel content is that 29ppm, content of vanadium are that 83ppm, sulphur content are 4.7%, carbon residue is the long residuum of 15% nitrogen content 0.3%.
Evaluating apparatus: 500 milliliters of fixed-bed reactor.
The catalyst combination layering is packed into reactor, and each catalyst levels volume ratio and reaction conditions are listed in table 6, and sampling analysis after turn round 300 hours (h) the results are shown in table 7.
Hydrodemetalation catalyst Ia:
Hydrodemetalation catalyst Ia-1, according to embodiment 6 preparations among the patent ZL200310117322.6, it consists of molybdenum oxide 5.5% heavy %, NiO 1.1% heavy %, equal amount carrier.
Hydrodemetalation catalyst Ia-2, according to embodiment 5 preparations among the patent ZL200410037670.7, it consists of molybdenum oxide 7.8% heavy %, NiO 1.5% heavy %, equal amount carrier.
Hydrodemetalation catalyst Ia-3, according to embodiment 13 preparations among the patent ZL200410096309.1, it consists of molybdenum oxide 8.2% heavy %, NiO 1.6% heavy %, equal amount carrier.
Hydrotreating catalyst III:
Hydrotreating catalyst III-1, according to embodiment 6 preparations among the patent ZL97112397.7, it consists of nickel oxide 2.3 heavy %, Tungsten oxide 99.999 22.0 heavy %, fluorine 4 heavy %, all the other are aluminum oxide.
Hydrotreating catalyst III-2, according to embodiment 37 preparations among the patent ZL00802168.6, it consists of nickel oxide 2.6 heavy %, molybdenum oxide 23.6 heavy %, fluorine 2.3 heavy %, all the other are aluminum oxide.
Hydrotreating catalyst III-3, according to embodiment 3 preparations among the patent ZL200310117323.0, it consists of nickel oxide 2.1 heavy %, molybdenum oxide 2.5 heavy %, Tungsten oxide 99.999 25.4 heavy %, all the other are aluminum oxide.
The content of nickel and vanadium adopts inductive coupling plasma emission spectrograph (ICP-AES) to measure (instrument is the U.S. PE-5300 of PE company type plasma quantometer, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP124-90) in the oil sample.Sulphur content uses coulometry to measure (concrete grammar is seen Petrochemical Engineering Analysis method RIPP62-90) in the oil sample.Carbon residue content uses microdetermination (concrete grammar is seen Petrochemical Engineering Analysis method RIPP149-90) in the oil sample.
Comparative Examples 5
Catalyzer adopts the combination of Ia-1, D II-1, III-1, and the volume of each catalyst levels when processing condition is listed in the table 6, and the sampling analysis after 300 hours that turns round the results are shown in table 7.
Comparative Examples 6
Catalyzer adopts the combination of Ia-2, D II-2, III-1, and the volume of each catalyst levels when processing condition is listed in the table 6, and the rear sampling analysis after 300 hours that turns round the results are shown in table 7.
Table 6
Table 7
Can find out, adopt raw catalyst and catalyst combination scheme, the foreign matter contents such as the metal of 300 hours back end hydrogenation treating product of running, sulphur, carbon residue obviously reduce, as the FCC charging, product property be improved significantly.
Claims (20)
1. the hydrogenation modification method of a catalytically cracked stock, be included under the hydrotreatment reaction conditions, described stock oil is contacted with a kind of catalyst combination, described catalyst combination comprises Hydrodemetalation catalyst I, Hydrodemetalation catalyst II and Hydrobon catalyst III, the layout of each catalyzer in the described catalyst combination so that described stock oil successively with comprise catalyst I, catalyst I I contacts with catalyst I II, by volume and take the total amount of described catalyst combination as benchmark, the content of described catalyst I is 5-60%, the content of catalyst I I is 10-70%, the content of catalyst I II is 5-60%, wherein, described catalyst I I contains carrier, the metal component molybdenum, cobalt and nickel, and the adjuvant component that is selected from phosphorus and boron, in oxide compound and take catalyst I I as benchmark, the content of described molybdenum is 5～20 % by weight, the content sum of cobalt and nickel is 1～6 % by weight, the content that is selected from the adjuvant component of phosphorus and boron is the 0.5-5 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2～4.
2. according to 1 described method, it is characterized in that the content of molybdenum is 8～15 % by weight among the described catalyst I I, the content sum of cobalt and nickel is 1.5～4 % by weight, the content that is selected from the adjuvant component of phosphorus and boron is 1～4 % by weight, and wherein, the atomic ratio of cobalt and nickel is 2.2～3.2.
3. according to 1 or 2 described methods, it is characterized in that the content of nickel is less than 1.2% among the described catalyst I I.
4. according to 3 described methods, it is characterized in that the content of nickel is 0.5～1.1% among the described catalyst I I.
5. according to 1 described method, it is characterized in that by volume and take the total amount of described catalyst combination as benchmark, the content of the catalyst I in the described catalyst combination is 10-50%, the content of catalyst I I is 20-60%, and the content of catalyst I II is 10-50%.
6. according to 1 described method, it is characterized in that, described catalyst I comprises catalyst I a, described catalyst I a contains carrier, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, contain or do not contain and be selected from boron, phosphorus, one or more adjuvant components in the fluorine, take catalyst I a as benchmark, take the content of the nickel of oxide compound and/or cobalt as the 0.3-8 % by weight, the content of molybdenum and/or tungsten is the 0.5-15 % by weight, the boron that is selected from element, phosphorus, the content of one or more adjuvant components in the fluorine is 0～5 % by weight, and wherein the pore volume of carrier is 0.6-1.4 ml/g, and specific surface area is to less than or equal to 350m greater than 90
2/ g.
7. according to 6 described methods, it is characterized in that the pore volume of the carrier among the described catalyst I a is 0.7-1.2 ml/g, specific surface area is 100-200m
2/ g.
8. according to 6 or 7 described methods, it is characterized in that the carrier among the described catalyst I a is selected from aluminum oxide.
9. according to 8 described methods, it is characterized in that described aluminum oxide is the alumina supporter with double-hole.
10. according to 9 described methods, it is characterized in that described double-hole alumina supporter accounts for total pore volume 40-90% at the pore volume of aperture 10-30 nanometer, the aperture accounts for total pore volume 10-60% at the pore volume of 100-2000 nanometer.
11. according to 1 described method, it is characterized in that, described catalyst I II contains the carrier that is selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, contain or do not contain and be selected from one or more adjuvant components in fluorine, boron and the phosphorus, take catalyst I II as benchmark, take the content of the nickel of oxide compound and/or cobalt as 1～5 % by weight, the content of molybdenum and/or tungsten is 10～35 % by weight, take the content that is selected from one or more adjuvant components in fluorine, boron and the phosphorus of element as 0～9 % by weight.
12., it is characterized in that the carrier among the described catalyst I II is selected from aluminum oxide according to 11 described methods.
13., it is characterized in that the pore volume of described aluminum oxide is not less than 0.35 ml/g according to 12 described methods, bore dia is that the pore volume in 40～100 dust holes accounts for more than 80% of total pore volume.
14., it is characterized in that described catalyst I comprises and catalyst I according to 6 described methods
aThe catalyst I of layered arrangement
b, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be below 40%, described layering so that described stock oil successively with catalyst I
bAnd catalyst I
aContact, described catalyst I
bContain carrier and randomly contain the hydrogenation active metals component that is selected from group vib and group VIII, in oxide compound and with catalyst I
bBe benchmark, the content of the metal component of described group vib is 0 to less than or equal to 10 % by weight, and the content of the metal component of described group VIII is 0 to less than or equal to 4 % by weight.
15., it is characterized in that described catalyst I according to 14 described methods
bCarrier contain Alpha-alumina, characterize with mercury penetration method, the pore volume of described carrier is 0.5-0.75ml/g, specific surface area is 2-20m
2/ g.
16., it is characterized in that described catalyst I according to 15 described methods
bThe pore volume of carrier be 0.52-0.73ml/g, specific surface area is 5-16m
2/ g, pore distribution curve two peaks occur at 45-1000 μ m and 0.2-1mm.
17., it is characterized in that described catalyst I according to 16 described methods
bThe pore size distribution of carrier curve two peaks appear at 45-100 μ m and 0.2-1mm.
18. according to 14 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 5-30%.
19., it is characterized in that the reaction conditions of described hydrotreatment reaction is according to 1 described method: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 ℃, volume space velocity is 0.1-1h during liquid
-1, hydrogen to oil volume ratio is 600-1500.
20., it is characterized in that the reaction conditions of described hydrotreatment reaction is: the hydrogen dividing potential drop is 10-18MPa, and temperature is 350-420 ℃, and volume space velocity is 0.2-0.6h during liquid according to 19 described methods
-1, hydrogen to oil volume ratio is 800-1100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210107558.0A CN103374402B (en) | 2012-04-13 | 2012-04-13 | Hydro-upgrading method of catalytic cracking raw oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210107558.0A CN103374402B (en) | 2012-04-13 | 2012-04-13 | Hydro-upgrading method of catalytic cracking raw oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103374402A true CN103374402A (en) | 2013-10-30 |
| CN103374402B CN103374402B (en) | 2015-05-20 |
Family
ID=49460249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210107558.0A Active CN103374402B (en) | 2012-04-13 | 2012-04-13 | Hydro-upgrading method of catalytic cracking raw oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103374402B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113559867A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
| CN113563922A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
| CN114425356A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002034865A1 (en) * | 2000-10-24 | 2002-05-02 | Jgc Corpopation | Refined oil and process for producing the same |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
| CN101007964A (en) * | 2006-01-27 | 2007-08-01 | 中国石油化工股份有限公司 | Hydrogenation method for producing good quality catalytic cracking material |
| CN101020843A (en) * | 2006-02-14 | 2007-08-22 | 中国石油化工股份有限公司 | Hydrogenation process for producing catalytically cracked material |
| CN101745400A (en) * | 2008-12-17 | 2010-06-23 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN101928601A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Processing method for catalytic cracking heavy oil |
| WO2011005476A2 (en) * | 2009-06-22 | 2011-01-13 | Saudi Arabian Oil Company | Alternative process for the treatment of heavy crudes in a coking refinery |
| CN102161910A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Method for producing high-quality diesel by using heavy crude oil |
-
2012
- 2012-04-13 CN CN201210107558.0A patent/CN103374402B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002034865A1 (en) * | 2000-10-24 | 2002-05-02 | Jgc Corpopation | Refined oil and process for producing the same |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
| CN101007964A (en) * | 2006-01-27 | 2007-08-01 | 中国石油化工股份有限公司 | Hydrogenation method for producing good quality catalytic cracking material |
| CN101020843A (en) * | 2006-02-14 | 2007-08-22 | 中国石油化工股份有限公司 | Hydrogenation process for producing catalytically cracked material |
| CN101745400A (en) * | 2008-12-17 | 2010-06-23 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| WO2011005476A2 (en) * | 2009-06-22 | 2011-01-13 | Saudi Arabian Oil Company | Alternative process for the treatment of heavy crudes in a coking refinery |
| CN101928601A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Processing method for catalytic cracking heavy oil |
| CN102161910A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Method for producing high-quality diesel by using heavy crude oil |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113559867A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
| CN113563922A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
| CN113559867B (en) * | 2020-04-28 | 2023-04-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
| CN113563922B (en) * | 2020-04-28 | 2023-04-11 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
| CN114425356A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
| CN114425356B (en) * | 2020-09-28 | 2024-01-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103374402B (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11642664B2 (en) | Silica containing alumina supports, catalysts made therefrom and processes using the same | |
| EP0449144B2 (en) | Catalyst composition for hydrotreating of hydrocarbons and hydrotreating process using the same | |
| EP1027156B1 (en) | Hydrocracking catalyst, producing method thereof, and hydrocracking method | |
| CN103374387B (en) | A kind of nickel and the high heavy oil hydrogenation treatment method of content of vanadium | |
| CN103374402B (en) | Hydro-upgrading method of catalytic cracking raw oil | |
| CN103374392B (en) | A kind of hydrogenation modification method of catalytically cracked stock | |
| CN102188990B (en) | Hydrotreating catalyst and application thereof | |
| CN103374388B (en) | The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents | |
| JPH10296091A (en) | Catalyst for hydrogenation treatment and method for hydrogenation treatment for hydrocarbon oil using the same | |
| JP2711871B2 (en) | Method for producing hydrotreating catalyst from hydrogel | |
| CN104293390B (en) | A kind of process for hydrogenating residual oil | |
| CN104293389B (en) | A kind of process for hydrogenating residual oil | |
| CN103923692B (en) | A kind of hydroprocessing process of heavy raw oil | |
| CN103374389B (en) | The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents | |
| JP3782893B2 (en) | Hydrotreating catalyst and hydrotreating method of hydrocarbon oil using the hydrotreating catalyst | |
| CN103923697B (en) | A kind of mink cell focus hydroprocessing process of high metal content | |
| CN104293381B (en) | A kind of method improving heavy-oil hydrogenation product property | |
| JP2986838B2 (en) | Hydrotreatment of residual oil | |
| JP3782887B2 (en) | Hydrotreating catalyst and hydrotreating method of hydrocarbon oil using the hydrotreating catalyst | |
| CN101173187B (en) | Method for producing hydrogenation catalyst with fluidized bed | |
| JPS63123446A (en) | Manufacture of hydrogenating treating catalyst from hydrogel | |
| JP2001314770A (en) | Catalyst for hydrogenating heavy hydrocarbon oil and hydrogenating method to use the same | |
| CN103923693B (en) | A kind of method reducing heavy raw oil studies on asphaltene and carbon residue content | |
| CN103923691B (en) | A kind of hydroprocessing process of heavy raw oil of high asphalt content | |
| CN104293382A (en) | Pretreatment method for catalytic cracking feedstock |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |