CN103374389B - The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents - Google Patents
The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents Download PDFInfo
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Abstract
The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents, comprise at hydrotreating reaction conditions, heavy raw oil high to iron and calcium contents is contacted with a kind of catalyst combination, described catalyst combination comprises hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III, in described catalyst combination the layout of each catalyzer make described stock oil successively with comprise hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrogenation activity guard catalyst I is 3-40%, the content of Hydrodemetalation catalyst II is 10-50%, the content of hydrotreating catalyst III is 20-70%, wherein, described hydrogenation activity guard catalyst I comprises catalyst I a, described catalyst I a contains titanium dioxide-aluminum oxide shaping carrier and hydrogenation active metals component.
Description
Technical field
The present invention relates to a kind of hydroprocessing process of heavy raw oil.
Background technology
Due to the feature of Lu Sheng crude oil, iron, the calcium contents all higher (iron and calcium sum are greater than 30 μ g/g) of China's major part crude oil, research shows, the impurity such as iron, calcium deposits between granules of catalyst, cause catalyst deactivation in this type of stock oil course of processing, beds fouling, pressure drop rise, affects important factor running period of hydroprocessing processes.In addition, in the secondary processing of this type of oil, such as, in catalytic cracking conversion reaction, the impurity such as iron, calcium also can cause the poisoning and deactivation of cracking catalyst, causes light oil yield to decline.Therefore most of high ferro, calcium contents heavy raw oil due to difficulty of processing comparatively large, the raw material mostly as coking is processed.But constantly soaring along with crude oil price, the drawback that coking yield of light oil is low is exaggerated, and therefore carries out the demand of hydrotreatment production added value more high product in continuous increase to high ferro, calcium contents inferior feedstock oil.Develop the impurity such as iron, calcium adaptability high, the hydrogenation catalyst and the processing and treating method supporting therewith that are conducive to reduction bed pressure drop have the huge market requirement for this reason.
Summary of the invention
The technical problem to be solved in the present invention is for prior art demand, provide a kind of newly, the hydroprocessing process that is suitable for iron, heavy raw oil that calcium contents is higher.
The present invention relates to following content:
1. the hydroprocessing process of an iron and the high mink cell focus of calcium contents, comprise at hydrotreating reaction conditions, heavy raw oil high to iron and calcium contents is contacted with a kind of catalyst combination, described catalyst combination comprises hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III, in described catalyst combination the layout of each catalyzer make described stock oil successively with comprise hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrogenation activity guard catalyst I is 3-40%, the content of Hydrodemetalation catalyst II is 10-50%, the content of hydrotreating catalyst III is 20-70%, wherein, described hydrogenation activity guard catalyst I comprises catalyst I a, described catalyst I a contains titanium dioxide-aluminum oxide shaping carrier and hydrogenation active metals component, wherein, described titanium dioxide-aluminum oxide shaping carrier contains the aluminum oxide of 70-99 % by weight and the titanium oxide of 1-30 % by weight, the crushing strength of described shaping carrier is 20-300N/ grain, pore volume is 0.3-0.9 ml/g, specific surface area is greater than 30 to being less than or equal to 150 meters
2/ gram.
2, the method according to 1, it is characterized in that, titanium dioxide-aluminum oxide shaping carrier in described catalyst I a contains the aluminum oxide of 75-96 % by weight and the titanium oxide of 4-25 % by weight, the crushing strength of described forming composition is 50-200N/ grain, pore volume is 0.4-0.8 ml/g, and specific surface area is greater than 50 to being less than or equal to 140 meters
2/ gram.
3, the method according to 2, it is characterized in that, titanium dioxide-aluminum oxide shaping carrier in described catalyst I a contains the aluminum oxide of 85-96 % by weight and the titanium oxide of 4-15 % by weight, the crushing strength of described forming composition is 70-200N/ grain, pore volume is 0.4-0.8 ml/g, and specific surface area is greater than 80 to being less than or equal to 120 meters
2/ gram.
4, the method according to 1,2 or 3 any one, is characterized in that, the filling voidage of the titanium dioxide-aluminum oxide shaping carrier in described catalyst I a is 26-60%.
5, the method according to 4, is characterized in that, the filling voidage of the titanium dioxide-aluminum oxide shaping carrier in described catalyst I a is 30-50%.
6, the method according to 1, it is characterized in that, hydrogenation active metals component in described catalyst I a is selected from least one group VIII metal component and at least one vib metal component, with oxide basis and with described catalyzer for benchmark, the content of group VIII metal component is for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 10 % by weight.
7, the method according to 6, it is characterized in that, group VIII metal component in described catalyst I a is selected from cobalt and/or nickel, vib metal component is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyzer, the content of group VIII metal component is 0.1-3 % by weight, and the content of group vib metal component is 0.5-8 % by weight.
8, the method according to 7, is characterized in that, is benchmark with oxide basis and with catalyzer, and the content of the group VIII metal component in described catalyst I a is 0.5-2.5 % by weight, and the content of group vib metal component is 3.5-8 % by weight.
9, the method according to 1; it is characterized in that; by volume and with the total amount of described catalyst combination for benchmark; the content of the described hydrogenation activity guard catalyst I in described catalyst combination is 5-30%; the content of Hydrodemetalation catalyst II is 20-40%, and the content of hydrotreating catalyst III is 30-60%
10, method according to 1, it is characterized in that, described Hydrodemetalation catalyst II contains carrier, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, containing or not containing being selected from boron, phosphorus, one or more adjuvant components in fluorine, with catalyst I I for benchmark, with the content of the nickel of oxide basis and/or cobalt for 0.3-8 % by weight, the content of molybdenum and/or tungsten is 0.5-15 % by weight, boron is selected from element, phosphorus, the content of one or more adjuvant components in fluorine is 0 ~ 5 % by weight, wherein the pore volume of carrier is 0.6-1.4 ml/g, specific surface area is for being greater than 90 to being less than or equal to 350m
2/ g.
11, the method according to 10, is characterized in that, the pore volume of the carrier in described Hydrodemetalation catalyst II is 0.7-1.2 ml/g, and specific surface area is 100-200m
2/ g.
12, the method according to 10 or 11, is characterized in that, the support selected from alumina in described Hydrodemetalation catalyst II.
13, the method according to 12, is characterized in that, described aluminum oxide is the alumina supporter with double-hole.
14, the method according to 13, 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, and aperture accounts for total pore volume 10-60% at the pore volume of 100-2000 nanometer.
15, the method according to 1, it is characterized in that, described hydrotreating catalyst III contains the carrier being 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, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, with catalyst I II for benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 10 ~ 35 % by weight, is 0 ~ 9 % by weight in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element.
16, the method according to 15, is characterized in that, the support selected from alumina in described hydrotreating catalyst III.
17, the method according to 16, is characterized in that, the pore volume of described aluminum oxide 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.
18, the method according to 1, is characterized in that, described hydrogenation activity guard catalyst I comprises and catalyst I
athe catalyst I of layered arrangement
b, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be less than 40%, described layering make described stock oil successively with catalyst I
band catalyst I
acontact, described catalyst I
bhydrogenation active metals component containing carrier and the metal component optionally containing the metal component and group VIII that are selected from group vib, with oxide basis and with catalyst I
bfor benchmark, the content of the metal component of described group vib is 0 to being less than or equal to 10 % by weight, and the content of the metal component of described group VIII is 0 to being less than or equal to 4 % by weight.
19, the method according to 18, is characterized in that, described catalyst I
bcarrier contain Alpha-alumina, with mercury penetration method characterize, the pore volume of described carrier is 0.5-0.75ml/g, and specific surface area is 2-20m
2/ g.
20, the method according to 19, 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, there are two peaks at 45-1000 μm and 0.2-1mm in pore distribution curve.
21, the method according to 20, is characterized in that, described catalyst I
bthe pore distribution curve of carrier there are two peaks at 45-100 μm and 0.2-1mm.
22, the method according to 18, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%.
23, the method according to 1, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1.0h
-1, hydrogen to oil volume ratio is 600-1500.
24, the method according to 23, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop is 10-18MPa, and temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h
-1, hydrogen to oil volume ratio is 800-1100.
According to method provided by the invention, wherein, in described catalyst combination, effective elimination, deposition the impurity such as the iron held in described stock oil and calcium are, to avoid or to delay the therefore rising of the bed pressure drop caused to the predictive role of catalyst I.
Contriver finds, under hydrotreatment reaction conditions, the organic compound such as Fe, Ca contained in heavy raw oil are easy to reaction and transform.Therefore, how making the organic compound such as Fe, Ca diffuse to protective material granule interior and react, deposit, is improve the key of catalyst I in described catalyst combination effect.Catalyst I a of the present invention contains titanium dioxide-aluminum oxide shaping carrier and hydrogenation active metals component, wherein, described titanium dioxide-aluminum oxide shaping carrier contains the aluminum oxide of 70-99 % by weight and the titanium oxide of 1-30 % by weight, the crushing strength of described shaping carrier is 20-300N/ grain, pore volume is 0.3-0.9 ml/g, and specific surface area is greater than 30 to being less than or equal to 150 meters
2/ gram.This catalyzer maintenance comparatively moderate pore volume and specific surface area while, there is good crushing strength, by it and Hydrodemetalation catalyst II and hydrotreating catalyst III combinationally uses time, the performance of described catalyst combination is obviously improved.
The catalyst I a that arbitrary prior art processability meets the demands can be adopted, in a preferred embodiment, the preparation method of catalyst I a comprises and prepares carrier and the component of load hydrogenation active metals on this carrier, and wherein, described carrier is prepared by following step:
(1) hydrated aluminum oxide to be mixed with titanium-containing compound and shaping;
(2) the dry also roasting of forming composition step (1) obtained, described drying temperature is 60-300 DEG C, and time of drying is 1-10 hour, and maturing temperature is 600-1000 DEG C, and roasting time is 1 ~ 10 hour;
Wherein, the hydrated aluminum oxide described in step (1) and the consumption of titanium-containing compound make consisting of of final molding thing: the aluminum oxide of 70-99 % by weight and the titanium oxide of 1-30 % by weight.
Hydrated aluminum oxide described in preferred steps (1) and the consumption of titanium-containing compound make consisting of of final molding carrier: the aluminum oxide of 75-96 % by weight and the titanium oxide of 4-25 % by weight; Described drying temperature is 100-250 DEG C, and time of drying is 2-8 hour, and maturing temperature is 700-1000 DEG C, and roasting time is 2-5 hour.Further preferred wherein said maturing temperature is 850-1000 DEG C.The method of described drying and roasting is field of catalyst preparation customary way.
Described hydrated aluminum oxide is selected from one or more in pseudo-boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides, and preferred described hydrated aluminum oxide is pseudo-boehmite; Described titanium-containing compound is selected from titanium oxide, titanate, molecular sieve containing titanium, titaniferous hydrated aluminum oxide, and preferred described titanium-containing compound is selected from titanium oxide, titanate.
The geometrical shape of described shaping carrier directly determines the filling voidage of described titanium dioxide-aluminum oxide shaping carrier, and in embodiment, the filling voidage of the preferred described shaping carrier of the present invention is 26-60%, is more preferably 25-50%.The example that can meet the shaping carrier of this requirement is as the spheroid carrier etc. of honeycomb post, Raschig ring or multi-pore channel.
Here, described filling voidage is the physical parameter of the described forming composition measured by the following method.Described measuring method comprises: forming composition to be measured is placed in container (inside diameter of vessel is greater than 20 times of forming composition median size to be measured) to 1 liter, then slowly pure water is injected, continue the volume adding water to 1 liter afterwards catalyzer water suction is saturated, then taken out by catalyst filtration, the volume (liter) of remaining liquid is multiplied by divided by 1 (liter) bed voidage that 100% is catalyzer.
The preparation method of described shaping carrier can be arbitrary prior art, and to this, the present invention is not particularly limited.Such as, described forming method can be by template extrusion moulding, spin or by compressing tablet and be the forming method of several existing forming method combination.For ensureing shapingly to carry out smoothly, water, extrusion aid and/or tackiness agent can be added, then extrusion moulding in material (mixture as hydrated aluminum oxide and titanium oxide), carrying out drying afterwards and roasting.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art.Such as, common extrusion aid can be selected from one or more in sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, PVOH, and described peptizing agent can be mineral acid and/or organic acid.Synthetic cellulose is wherein preferably one or more in Walocel MT 20.000PV, methylcellulose gum, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, and polymeric alcohol is preferably one or more in polyoxyethylene glycol, poly-propyl alcohol, polyvinyl alcohol.
The component of hydrogenation active metals described in catalyst I a is selected from one or more in group VIII metal component and vib metal component, the described method in supported on carriers hydrogenation active metals component is pickling process, be benchmark with oxide basis and with catalyzer, described dipping makes the content of the group VIII metal component in final catalyzer for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 10 % by weight.Preferred described group VIII metal component is selected from cobalt and/or nickel, vib metal component is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyzer, be benchmark with oxide basis and with catalyzer, described dipping makes the content of the group VIII metal component in final catalyzer be 0.1-3 % by weight, more preferably 0.5-2.5 % by weight, the content of group vib metal component is 0.5-8 % by weight, more preferably 3.5-8 % by weight.
Be enough under the prerequisite loading on described carrier by described hydrogenation active metals component, the method for the present invention to load hydrogenation active metals component is not particularly limited.Preferred dipping method wherein, the method of described dipping is for preparing hydrogenation class catalyzer customary way, can be such as containing being selected from VIII and being selected from the solution impregnating carrier of metal component compound of group vib with excessive, can be with containing being selected from VIII and being selected from the solution hole saturation method impregnated carrier of metal component compound of group vib, carry out drying, roasting or not roasting afterwards.The method of described drying and roasting is conventional method, and preferred drying conditions comprises: drying temperature is 60-150 DEG C, and time of drying is 1-10 hour, and preferably drying temperature is 80-120 DEG C further, and time of drying is 2-8 hour; Preferred roasting condition comprises: maturing temperature is 350-550 DEG C, and roasting time is 1-6 hour, and preferably maturing temperature is 400-500 DEG C further, and roasting time is 2-4 hour.
The described compound containing group vib metal component is selected from one or more in the soluble compound in them, as one or more in molybdenum oxide, molybdate, paramolybdate, and preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstate, metatungstate, ethyl metatungstate, preferably ammonium metawolframate, ethyl ammonium metawolframate wherein.
The described compound containing group VIII metal component is selected from one or more in their soluble compound, as one or more in the soluble complexes of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and cobalt, be preferably Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous dihydroxycarbonate; One or more in the soluble complexes of nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickel, are preferably nickelous nitrate, basic nickel carbonate.
According to method provided by the invention, wherein, the predictive role of described catalyst I I is by hydrotreatment reaction in the presence of the catalyst, removes organo-metallic impurity Ni and V in raw material, the macromole such as bituminous matter and colloid species and partial vulcanization thing.Therefore, described catalyst I I can be selected from one or more that can realize in the catalyzer of this function any of the prior art.They can be commercially available commodity or adopt any existing method preparation.
This type of catalyzer is usually containing heat-resistant inorganic oxide carrier and load hydrogenation active metals component on this carrier.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides being commonly used for support of the catalyst and/or matrix.Such as, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica-alumina-titania, silicaalumina-magnesia, are preferably aluminum oxide.Described hydrogenation active component is selected from molybdenum and or tungsten, nickel and or cobalt.The example of this kind of catalyzer as:
A kind of catalyzer disclosed in ZL200310117322.6, this catalyzer contains a kind of macropore alumina supporter and load molybdenum on this carrier and/or tungsten and cobalt and/or nickel, be benchmark with oxide basis and with catalyzer, described catalyzer contains the carrier of the molybdenum of 0.5-15 % by weight and/or tungsten, the cobalt of 0.3-8 % by weight and/or nickel, equal amount, it is characterized in that, described carrier contains a kind of halogen, and with carrier total amount for benchmark, this carrier contains the aluminum oxide of 95-99 % by weight.
ZL200410037670.7 disclose a kind of there is double-hole alumina supporter and load molybdenum on this carrier and/or tungsten and cobalt and/or nickel, be benchmark with oxide basis and with catalyzer, described catalyzer contains the carrier of the molybdenum of 0.5-15 % by weight and/or tungsten, the cobalt of 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-pore alumina support and load molybdenum on this carrier and/or tungsten and nickel and/or cobalt metal component, the pore volume of wherein said Bimodal-pore alumina support is 0.8-1.6 ml/g, and specific surface area is 150-350m
2/ g, aperture accounts for total pore volume 40 ~ 90% at the pore volume of 10 ~ 30 nanometers, and aperture accounts for total pore volume 10 ~ 60% at the pore volume of 100 ~ 2000 nanometers.
These catalyzer all can be used as described catalyst I I 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 their parts as content of the present invention are quoted 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, the wherein more difficult impurity such as sulphur, nitrogen removed is removed further, removes the carbon residue in stock oil simultaneously.Therefore, described catalyst I II can be selected from one or more that can realize in the catalyzer of this function any of the prior art.Such as, one or more in the Hydrobon catalyst that arbitrary prior art provides are selected from.They can be commercially available commodity or adopt any existing method preparation.
This type of catalyzer is usually containing heat-resistant inorganic oxide carrier, hydrogenation active metals component.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides being commonly used for support of the catalyst and/or matrix.Such as, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica-titania, are preferably aluminum oxide.Described hydrogenation active metals component is nickel and or cobalt, tungsten and or molybdenum.The example of this kind of catalyzer as:
A kind of Hydrobon catalyst disclosed in ZL97112397.7, it consists of the heavy % of nickel oxide 1 ~ 5, the heavy % of Tungsten oxide 99.999 12 ~ 35, the heavy % of fluorine 1 ~ 9, all the other are aluminum oxide, this aluminum oxide be by one or more little porous aluminum oxides and one or more macroporous aluminium oxides according to 75: 25 ~ 50: 50 weight ratio be composited, wherein little porous aluminum oxide is the aluminum oxide that pore volume that bore dia is less than 80 dust holes accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminum oxide that the pore volume in bore dia 60 ~ 600 dust hole accounts for total pore volume more than 70%.
ZL00802168.6 discloses a kind of Hydrobon catalyst, and this catalyzer contains at least one VI B race's metal on this alumina supporter of a kind of alumina supporter and load and/or at least one group VIII metal.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.
ZL200310117323.0 discloses a kind of Hydrobon catalyst, this catalyzer contains a kind of alumina supporter and load molybdenum on this carrier, nickel and tungsten metal component, be benchmark with oxide basis and with catalyzer, 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 and uses the solution of molybdate compound and nickeliferous successively, the solution impregnation of alumina carrier of tungsten compound, wherein said alumina supporter carries out drying after by the solution impregnation of molybdate compound, with nickeliferous, drying and roasting is carried out after the solution impregnation of tungsten compound, drying temperature is 100-300 DEG C, time of drying is 1-12 hour, maturing temperature is 320-500 DEG C, roasting time is 1-10 hour.
These catalyzer all can be used as described catalyst I II 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 their parts as content of the present invention are quoted here.
Contriver finds further; when described catalyst I is the combination comprising Ib and Ia; because this combination has better deferrization and calcium performance, the catalyst combination comprising hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III described in can improving further adds the performance in man-hour for described stock oil.
Particularly, described catalyst I
bfor a kind of containing or containing hydrogenation active metals, there is lower specific surface area and the forming composition compared with large pore volume, further preferably the pore distribution curve of this forming composition is that micron order (or grade) is in bimodal distribution at bore dia.In a preferred embodiment, the preparation method of described carrier comprises:
(1) by hydrated aluminum oxide, can the organic additive of burn off, acid or alkali and water mixing, carry out drying, fragmentation afterwards and sieve, obtaining 20-60 object particle;
(2) particle step (1) obtained carries out mixing with Alumina gel and/or hydrated alumina slurry and shaping, carries out drying and roasting afterwards;
Wherein, hydrated aluminum oxide described in step (1), can the organic additive of burn off, and the ratio of mixture of acid or alkali and water is 100: 0.5-6: 0.5-10: 30-80; The particle obtained by step (1) in described step (2) with in the Mixing ratio by weight of the Alumina gel of aluminum oxide and/or hydrated alumina slurry for 100: 5-45; Described drying conditions comprises: temperature is 100-140 DEG C, and the time is 1-10 hour; Described roasting condition comprises: temperature is 1100-1540 DEG C, and the time is 1-10 hour.
Hydrated aluminum oxide described in preferred steps (1), can the organic additive of burn off, acid or alkali and water ratio of mixture be 100: 0.6-3: 0.6-5: 35-75; The particle obtained by step (1) in described step (2) with in the Mixing ratio by weight of the Alumina gel of aluminum oxide and/or hydrated alumina slurry for 100: 5-40; Described drying conditions comprises: temperature is 110-130 DEG C, and the time is 2-8 hour; Described roasting condition comprises: temperature is 1200-1500 DEG C, and the time is 2-8 hour.Described can the organic additive of burn off be selected from starch, Mierocrystalline cellulose, polynary alcohol and carboxylic acid one or more, one or more in preferred starch, Mierocrystalline cellulose and polyvalent alcohol.
Optionally, introducing can also be comprised in described step (1) or (2) and be selected from siliceous, phosphorus, the step of the compound of one or more adjuvant components in alkali or alkaline-earth metal, be benchmark with oxide basis and with carrier, the introduction volume of the described compound containing adjuvant component, make the content of adjuvant component described in final carrier be no more than 25 % by weight, be preferably 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 alkaline including earth metal compound is selected from oxide compound or the oxyhydroxide of alkaline-earth metal.
Here, described pore distribution curve refers to the velocity of variation (ordinate zou be dV/dlogD, X-coordinate be bore dia D (logD)) of pore volume (pore volume) with bore dia.
Wherein, the described hydrated aluminum oxide in the preparation method of described carrier is selected from the mixture of one or more among hibbsite, monohydrate alumina (comprising pseudo-boehmite) and amorphous hydroted alumina.Described acid can be any compound reacted acid in water medium, and such as, they can be formic acid, acetic acid, propionic acid, sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, silicofluoric acid, hydrofluoric acid, preferably nitric acid, hydrochloric acid, sulfuric acid wherein; Described alkali can be the compound of any react acid in water medium, such as, they can be ammonia, ammoniacal liquor, alkali-metal oxyhydroxide (as sodium hydroxide, potassium hydroxide, magnesium hydroxide), alkali-metal carbonate (as salt of wormwood, Quilonum Retard, sodium carbonate, saleratus, calcium carbonate, magnesiumcarbonate, barium carbonate), preferably salt of wormwood, Quilonum Retard wherein.
Be enough to make described hydrated aluminum oxide, can the organic additive of burn off, acid or alkali and water fully mix, under obtaining the prerequisite of 20-60 object particulate matter after this mixture drying, fragmentation, the present invention to realizing this mixing in step (1), broken mode does not limit.Such as, can be in banded extruder first by hydrated aluminum oxide with can the organic additive of burn off mix, acid or alkali are mixed with water, afterwards, the mixing of materials in the mixing solutions of acid or alkali and water and banded extruder are extruded, extrudate drying, fragmentation and sieve.Mixing in step (2) is to meet premised on shaping requirement, and described shaping method can be carried out according to a conventional method, such as, can be compressing tablet, spin, extrusion moulding etc.For the needs of satisfied different forming method, comprise introducing in moulding process and help forming agent, such as, introduce appropriate water, peptizing agent (as one or more being selected from nitric acid, acetic acid and citric acid), extrusion aid (as being one or more in sesbania powder, Mierocrystalline cellulose), described the help consumption of forming agent and adjustment thereof are well known to those skilled in the art, and are not repeated herein.
When described catalyst I b contains hydrogenation active metals component, the step introducing hydrogenation active metals component in described forming composition is included in the preparation method of this catalyzer, the method introducing hydrogenation active component is preferably pickling process, comprise preparation contain the solution of the compound of hydrogenation active metals and use this solution impregnating carrier, carry out drying afterwards, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one group VIII, be benchmark with oxide basis and with catalyzer, the described compound containing hydrogenation active metals makes the content of the metal component of the group vib in final catalyzer be greater than 0 to being less than or equal to 10 % by weight in the concentration of described solution and the consumption of described solution, the content of the metal component of described group VIII is greater than 0 to being less than or equal to 4 % by weight, described drying conditions comprises: temperature is 100-250 DEG C, and the time is 1-10 hour, described roasting condition comprises: temperature is 360-500 DEG C, 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, be benchmark with oxide basis and with catalyzer, the described compound containing hydrogenation active metals makes the content of the metal component of the group vib in final catalyzer be 3-6 % by weight in the concentration of described solution and the consumption of described solution, and the content of the metal component of group VIII is 1-3 % by weight; Described drying conditions comprises: temperature is 100-140 DEG C, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 DEG C, and the time is 2-6 hour.
Wherein, the described compound containing group vib metal is selected from one or more in the soluble compound of these metals, such as, can be one or more in silicotungstic acid, silicotungstate, phospho-molybdic acid, phosphomolybdate, molybdate, paramolybdate, tungstate, metatungstate, ethyl metatungstate.
The described compound containing group VIII metal is selected from one or more in the soluble compound of these metals, such as, 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 comprising hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III can layering fill in same reactor successively, also can be to use in the reactor filling in several series connection successively.Be enough to make described stock oil successively with comprise prerequisite that hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II contact with hydrotreating catalyst III under, this present invention is not particularly limited.
The present invention a kind ofly has the protective material that removes very well and hold iron and doped calcium thing or protective material combination owing to adopting, and is particularly suitable for one or more in iron and the higher crude oil, vacuum residuum, deep drawing wax oil, frivolous asphalt oil, wax tailings etc. of calcium contents.
Be 10 below μ g/g according to iron, the calcium contents of oil after the hydrotreatment that described method obtains, W metal+V content is 20 below μ g/g, sulphur content less than 0.5%, and carbon residue content is less than 6.0%, and the stock oil that can be used as the secondary processing such as catalytic cracking uses.
Embodiment
The present invention is described further for the following examples.
Embodiment 1-4 illustrates and the invention provides method hydrogenation protecting catalyst Ia and preparation thereof.
Example 1
By aluminium hydrate powder 1000 grams, the mixing of 100 grams of titanium dioxides, compression moulding is high 10mm, diameter 40mm, wall thickness 2mm, includes the honeycomb cylinder in 100 trilateral ducts in a mold, in 120 DEG C of dryings after 4 hours, in 880 DEG C of roastings 4 hours, obtains carrier Z1.Carrier Z1 physico-chemical property is in table 1.
Get carrier Z1 200 grams, with 500 milliliters containing WO3 70 grams per liter, ammonium metawolframate and the nickelous nitrate mixing solutions of NiO 15 grams per liter flood 1 hour, dry 4 hours after filtration in 100 DEG C, and 450 DEG C of roastings 4 hours, obtain catalyst I a-1.The composition of Ia-1 is listed in table 2.
Example 2
Aluminium hydrate powder 200 grams and aluminum titanate powder 80 grams is mixed, is pressed into the seven apertures in the human head ball that external diameter 16mm includes diameter 3mm duct in a mold, in 80 DEG C of dryings 3 hours, in 950 DEG C of constant temperature 2 hours, obtain carrier Z2.Carrier Z2 physico-chemical property is in table 1.
Get carrier Z2 200 grams, with 500 milliliters containing MoO3 50 grams per liter, ammonium molybdate and the nickelous nitrate mixing solutions of NiO 8 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain catalyst I a-2.The composition of Ia-2 is listed in table 2.
Example 3
One diaspore powder 200 grams is mixed containing titanium dioxide with 18 grams, double screw banded extruder is extruded into the ring of having loose bowels of external diameter 5.0mm wall thickness 1.5mm, in 120 DEG C of dryings after 2 hours, in 900 DEG C of constant temperature 3 hours, obtain carrier Z3.Carrier Z3 physico-chemical property is in table 1.
Get carrier Z3 200 grams, with 500 milliliters containing MoO3 80 grams per liter, ammonium molybdate and the nickel nitrate solution of NiO 20 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 500 DEG C of roastings 4 hours, obtain catalyst I a-3.The composition of Ia-3 is listed in table 2.
Example 4
Aluminium hydrate powder 1000 grams mixed with 40 grams of titanium dioxides, is pressed into high 10mm, diameter 8.0mm, wall thickness 1mm in a mold, include the honeycomb cylinder in 15 irregular ducts, in 100 DEG C of dryings after 4 hours, in 980 DEG C of roastings 2 hours, obtain carrier Z4.Carrier Z4 physico-chemical property is in table 1.
Get carrier Z4 200 grams, with 500 milliliters containing MoO3 40 grams per liter, the molybdic acid acid ammonium of CoO 12 grams per liter and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES mixing solutions flood 1 hour, dry 4 hours after filtration in 90 DEG C, and 480 DEG C of roastings 4 hours, obtain catalyst I a-4.The composition of I a-4 is listed in table 2.
Comparative example 1-2 illustrates reference hydrogenation protecting catalyst and preparation thereof.
Comparative example 1
The support porcelain ring DZ1 (aluminum oxide 62 % by weight, other are silicon, calcium, magnesium, potassium etc.) that a kind of commercially available Jiangsu produces.DZ1 physico-chemical property is in table 1.
Get carrier DZ1 200 grams, with 500 milliliters containing MoO
370 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO 10 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain protective material DC1.The composition of protective material DC1 is listed in table 2.
Comparative example 2
Mixed with 300 grams of aluminium hydrate powders by one diaspore powder 100 grams, double screw banded extruder is extruded into the ring of having loose bowels of external diameter 5.0mm wall thickness 1.5mm, in 120 DEG C of dryings after 2 hours, in 900 DEG C of constant temperature 3 hours, be supported agent DZ2.Propping agent DZ2 physico-chemical property is in table 1.
Get carrier DZ2 200 grams, with 500 milliliters containing MoO
350 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO 8 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain protective material DC2.The composition of protective material DC2 is listed in table 2.
Table 1
Wherein, the measuring method of crushing strength is carried out according to RIPP 25-90 catalyzer compressive strength assay method, and vehicle group becomes calculated value, and pore volume, specific surface area adopt BET to measure.
Table 2
Wherein, active metal component content adopts X-fluorescence part mensuration.
Example 5-8
Example 5-8 illustrates the performance that the invention provides the hydrogenation protecting catalyst Ia of method.
Take iron level as 20ppm, calcium contents is 125ppm vacuum residuum is raw material, evaluate catalysts in 500 milliliters of autoclave reactors.
Getting catalyst I a-1, Ia-2, Ia-3, Ia-4, is 1: 20 according to catalystoil ratio (volume), temperature of reaction 360 DEG C, hydrogen dividing potential drop 10 MPa, stirring velocity 180r/min.React sampling analysis after 8 hours, adopt plasma emission spectrum (AES/ICP) method to measure the content generating iron, calcium in oil, and calculate demetallization per, the method for calculation of total demetallization per are:
The results are shown in table 3.
Comparative example 3-4
According to the hydrodemetallation (HDM) performance of method evaluation catalyzer CD1, CD2 of example 5-8, the results are shown in Table 3.
Table 3
| Example number | Protective material is numbered | Demetallization per/% |
| 5 | Ia-1 | 80 |
| 6 | Ia-2 | 78 |
| 7 | Ia-3 | 85 |
| 8 | Ia-4 | 82 |
| Comparative example 3 | DC1 | 54 |
| Comparative example 4 | DC2 | 75 |
Embodiment 9-13 illustrates and the invention provides method hydrogenation protecting catalyst Ib and preparation thereof.
Embodiment 9
By 100 grams of pseudo-boehmites (Chang Ling catalyst plant produce, butt is 65 % by weight), 3 grams of sesbania powder and 155 grams containing 1.5% nitre aqueous acid.Kneading in double screw banded extruder is also extruded with the cylindrical orifice plate of φ 2.0mm, and dry bar, in 120 DEG C of dryings 4 hours, is pulverized and sieves by wet bar.
Get 40 grams of aforementioned screenings and obtain 40-60 object particulate matter, it is mixed with 10 grams of pseudo-boehmites and 1.2 grams of magnesium oxide, add 5 grams, water and 15 grams of silicon sol (Qingdao Jian Hui silica gel company limiteds in the mixture, dioxide-containing silica 29%) and shaping according to roller forming method, and obtaining particle diameter is 5.5-6.5mm spheroidal particle.Afterwards, by this particle in 120 DEG C of dryings 4 hours, 1200 DEG C of roastings 3 hours, obtain hydrogenation protecting catalyst Ib-1 (Z9).
X-ray diffraction is adopted to characterize, catalyst I b-1 has Alpha-alumina structure, adopting pressure mercury method to characterize, there are two peaks at 45-1000 μm and 0.2-1mm in catalyst I b-1 pore distribution curve, and its pore volume, specific surface area and pore distribution value and catalyst I b-1 composition list in table 4.
Embodiment 10
By 100 grams of pseudo-boehmites (Chang Ling catalyst plant produce, butt is 65 % by weight), 3 grams of sesbania powder and 155 grams containing the aqueous solution of 1.5% nitric acid and 0.5% salt of wormwood.Kneading in double screw banded extruder is also extruded with the cylindrical orifice plate of φ 2.0mm, and dry bar, in 120 DEG C of dryings 4 hours, is pulverized and sieves by wet bar.The rear sieve of pulverizing is got 40-60 mesh sieve and is divided.
Get aforementioned screening to obtain 40-60 object particulate matter 45g and mix with 5g pseudo-boehmite, add water 8g, (Yueyang is polymerized to Chemical Co., Ltd. to Alumina gel, solid content: after 25%) 20g and aluminium dihydrogen phosphate (Chinese and Western, Beijing tech science and technology limited Company) 2.1g mixes with aforementioned screening, extruded moulding.Shaping rear pelletizing, shaping, by bead after shaping 120 DEG C of dryings 4 hours, 1400 DEG C of roastings 3 hours, obtains carrier Z10.
Adopt X-ray diffraction to characterize, carrier Z10 has Alpha-alumina structure, and adopt pressure mercury method to characterize, carrier Z10 pore distribution curve occurs two peaks at 45-1000 μm and 0.2-1mm, its pore volume, specific surface area and pore distribution value and vehicle group in column in table 4.
Get carrier 20 grams of Z2, in saturated leaching mode with containing 1.42g ammonium molybdate (containing MoO
382%) and the solution 15.5 milliliters dipping of 1.3g nickelous nitrate (containing NiO 25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst Ib-2 of the present invention.The content adopting X-fluorescence method to measure hydrogenation active metals component in catalyzer lists in table 5.
Embodiment 11
By 100 grams of pseudo-boehmites (Chang Ling catalyst plant produce, butt is 65 % by weight), 3 grams of sesbania powder and 155 grams containing the aqueous solution of 1.5% nitric acid and 0.5% Quilonum Retard.Kneading in double screw banded extruder is also extruded with the cylindrical orifice plate of φ 5.0mm, and dry bar, in 120 DEG C of dryings 4 hours, is pulverized and sieves by wet bar.
Take 20-40 object screening 42g and 8g pseudo-boehmite to mix, take 25g Alumina gel (Yueyang is polymerized to Chemical Co., Ltd., solid content: 25%), after mixing, extruded moulding.Shaping rear pelletizing, shaping, by bead after shaping 120 DEG C of dryings 4 hours, 1100 DEG C of roastings 3 hours, obtains carrier Z11.
Adopt X-ray diffraction to characterize, carrier Z11 has Alpha-alumina structure, and adopt pressure mercury method to characterize, carrier Z11 pore distribution curve occurs two peaks at 45-1000 μm and 0.2-1mm, its pore volume, specific surface area and pore distribution value and vehicle group in column in table 4.
Get carrier 30 as one kind gram Z11, in saturated leaching mode with containing 2.2g ammonium molybdate (containing MoO
382%) and the solution 25 milliliters dipping of 2.0g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst Ib-3 of the present invention.The content adopting X-fluorescence method to measure hydrogenation active metals component in catalyzer lists in table 5.
Embodiment 12
By 100 grams of pseudo-boehmites (Chang Ling catalyst plant produce, butt is 65 % by weight), 3 grams of sesbania powder and 155 grams containing 1.8% nitre aqueous acid.Kneading in double screw banded extruder is also extruded with the cylindrical orifice plate of φ 5.0mm, and dry bar, in 120 DEG C of dryings 4 hours, is pulverized and sieves by wet bar.
Take 20-40 object screening 20g and 40-60 object screening 15g, mix with 15g pseudo-boehmite, take 25g silicon sol (Qingdao Jian Hui silica gel company limited, dioxide-containing silica 29%), mix with aforementioned screening, extruded moulding.Shaping rear pelletizing, shaping, by bead after shaping 120 DEG C of dryings 4 hours, 1400 DEG C of roastings 3 hours, obtains carrier Z12.
Adopt X-ray diffraction to characterize, carrier Z12 has Alpha-alumina structure, and adopt pressure mercury method to characterize, carrier Z12 pore distribution curve occurs two peaks at 45-1000 μm and 0.2-1mm, its pore volume, specific surface area and pore distribution value and vehicle group in column in table 4.
Get carrier 20 grams of Z12, in saturated leaching mode with containing 0.86g ammonium molybdate (containing MoO
382%) and the solution 13 milliliters dipping of 1.25g nickelous nitrate (containing NiO25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst Ib-4 of the present invention.The content adopting X-fluorescence method to measure hydrogenation active metals component in catalyzer lists in table 5.
Embodiment 13
By 100 grams of pseudo-boehmites (Chang Ling catalyst plant produce, butt is 65 % by weight), 3 grams of sesbania powder and 155 grams containing 1.5% nitre aqueous acid.Kneading in double screw banded extruder is also extruded with the cylindrical orifice plate of φ 2.0mm, and dry bar, in 120 DEG C of dryings 4 hours, is pulverized and sieves by wet bar.
Get 40-60 object and sieve to obtain 40 grams, it is mixed with 10 grams of pseudo-boehmites, (Yueyang is polymerized to Chemical Co., Ltd., solid content: 25%) shaping according to roller forming method, and obtaining particle diameter is 5.5-6.5mm spheroidal particle to add 5 grams, water and 15 grams of Alumina gel in the mixture.Afterwards, by this particle in 120 DEG C of dryings 4 hours, 1200 DEG C of roastings 3 hours, obtain carrier Z13.
Adopt X-ray diffraction to characterize, carrier Z13 has Alpha-alumina structure, and adopt pressure mercury method to characterize, carrier Z13 pore distribution curve occurs two peaks at 45-1000 μm and 0.2-1mm, its pore volume, specific surface area and pore distribution value and vehicle group in column in table 4.
Get carrier 20 grams of Z13, in saturated leaching mode with containing 1.45g ammonium molybdate (containing MoO
382%) and the solution 14 milliliters dipping of 1.30g nickelous nitrate (containing NiO 25%), 120 DEG C of dryings 4 hours after dipping, 420 DEG C of roastings 3 hours guard catalyst Ib-5 of the present invention.The content adopting X-fluorescence method to measure hydrogenation active metals component in catalyzer lists in table 5.
Table 4
Table 5
Embodiment 14-19 illustrates the effect adopting and the invention provides method processing high ferro calcium contents stock oil.
Stock oil is: the mixing heavy oil that iron level is 19ppm, calcium contents be 34ppm, Ni+V content is 60ppm, sulphur content is 3.9%, carbon residue is 13%.
Evaluating apparatus: 500 milliliters of fixed-bed reactor.
Catalyst combination layering is packed into reactor, and each catalyst levels volume ratio and reaction conditions list in table 6, and operate 1000 hours (h) sampling analysis afterwards, the results are shown in table 7.
Hydrodemetalation catalyst II:
Hydrodemetalation catalyst II-1, prepares according to the embodiment 7 in patent ZL200310117322.6, and it consists of the heavy % of heavy %, the NiO 1.8% of molybdenum oxide 7.9%, the carrier of equal amount.
Hydrodemetalation catalyst II-2, prepares according to the embodiment 5 in patent ZL200410037670.7, and it consists of the heavy % of heavy %, the NiO 1.5% of molybdenum oxide 7.8%, the carrier of equal amount.
Hydrodemetalation catalyst II-3, prepares according to the embodiment 13 in patent ZL200410096309.1, and it consists of the heavy % of heavy %, the NiO 1.6% of molybdenum oxide 8.2%, the carrier of equal amount.
Hydrodemetalation catalyst II-4, prepares according to the embodiment 14 in patent ZL200410096309.1, and it consists of the heavy % of heavy %, the NiO 2.2% of molybdenum oxide 12.0%, the carrier of equal amount.
Hydrotreating catalyst III:
Hydrotreating catalyst III-1, prepares according to the embodiment 6 in patent ZL97112397.7, and it consists of the heavy % of nickel oxide 2.3, the heavy % of Tungsten oxide 99.999 22.0, and the heavy % of fluorine 4, all the other are aluminum oxide.
Hydrotreating catalyst III-2, prepares according to the embodiment 37 in patent ZL00802168.6, and it consists of the heavy % of nickel oxide 2.6, the heavy % of molybdenum oxide 23.6, and the heavy % of fluorine 2.3, all the other are aluminum oxide.
Hydrotreating catalyst III-3, prepares according to the embodiment 3 in patent ZL200310117323.0, and it consists of the heavy % of nickel oxide 2.1, the heavy % of molybdenum oxide 2.5, and the heavy % of Tungsten oxide 99.999 25.4, all the other are aluminum oxide.
In oil sample, the content of iron, calcium, nickel and vanadium adopts inductive coupling plasma emission spectrograph (ICP-AES) to measure (instrument is U.S. PE company PE-5300 type plasma quantometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124-90).In oil sample, sulphur content uses coulometry to measure (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP62-90).In oil sample, carbon residue content uses microdetermination (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP149-90)
Comparative example 5
Catalyzer adopts the combination of DC-1, II-1, III-1, and the volume of each catalyst levels when processing condition is listed in table 6, and operate post-reactor pressure drop in 1000 hours and product property are listed in table 7 together.
Table 6
Table 7
Can find out, after adopting raw catalyst and catalyst combination scheme, the 1000 hours post-reactor Pressure Drops that operate keep lower always, and the metal content such as product iron, calcium is lower after hydrotreatment, do not adopt the reactor pressure decrease of proprietary catalysts and method sharply to increase in operation process at 1000 hours, in product, iron, calcium contents also increase to some extent simultaneously.
Claims (20)
1. the hydroprocessing process of an iron and the high mink cell focus of calcium contents, comprise at hydrotreating reaction conditions, heavy raw oil high to iron and calcium contents is contacted with a kind of catalyst combination, described catalyst combination comprises hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III, in described catalyst combination the layout of each catalyzer make described stock oil successively with comprise hydrogenation activity guard catalyst I, Hydrodemetalation catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrogenation activity guard catalyst I is 3-40%, the content of Hydrodemetalation catalyst II is 10-50%, the content of hydrotreating catalyst III is 20-70%, wherein, described hydrogenation activity guard catalyst I comprises catalyst I
awith catalyst I
athe catalyst I of layered arrangement
b, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be less than 40%, described layering make described stock oil successively with catalyst I
band catalyst I
acontact, described catalyst I
acontaining titanium dioxide-aluminum oxide shaping carrier and hydrogenation active metals component, described catalyst I
ain hydrogenation active metals component be selected from least one group VIII metal component and at least one vib metal component, with oxide basis and with described catalyzer for benchmark, the content of group VIII metal component is for being greater than 0 to being less than or equal to 5 % by weight, the content of group vib metal component is for being greater than 0 to being less than or equal to 10 % by weight, wherein, described titanium dioxide-aluminum oxide shaping carrier contains the aluminum oxide of 70-99 % by weight and the titanium oxide of 1-30 % by weight, the crushing strength of described shaping carrier is 20-300N/ grain, pore volume is 0.3-0.9 ml/g, specific surface area is greater than 30 to being less than or equal to 150 meters
2/ gram, described catalyst I
bcontaining carrier with optionally containing the hydrogenation active metals component being selected from group vib and group VIII, with oxide basis and with catalyst I
bfor benchmark, the content of the metal component of described group vib is 0 to being less than or equal to 10 % by weight, and the content of the metal component of described group VIII is 0 to being less than or equal to 4 % by weight, described catalyst I
bcarrier contain Alpha-alumina, with mercury penetration method characterize, the pore volume of described carrier is 0.52-0.73ml/g, and specific surface area is 5-16m
2/ g, there are two peaks at 45-1000 μm and 0.2-1mm in pore distribution curve.
2. method according to claim 1, is characterized in that, described catalyst I
ain titanium dioxide-aluminum oxide shaping carrier contain the aluminum oxide of 75-96 % by weight and the titanium oxide of 4-25 % by weight, the crushing strength of described forming composition is 50-200N/ grain, and pore volume is 0.4-0.8 ml/g, and specific surface area is greater than 50 to being less than or equal to 140 meters
2/ gram.
3. method according to claim 2, is characterized in that, described catalyst I
ain titanium dioxide-aluminum oxide shaping carrier contain the aluminum oxide of 85-96 % by weight and the titanium oxide of 4-15 % by weight, the crushing strength of described forming composition is 70-200N/ grain, and pore volume is 0.4-0.8 ml/g, and specific surface area is greater than 80 to being less than or equal to 120 meters
2/ gram.
4. the method according to any one of claim 1,2 or 3, is characterized in that, described catalyst I
ain the filling voidage of titanium dioxide-aluminum oxide shaping carrier be 26-60%.
5. method according to claim 4, is characterized in that, described catalyst I
ain the filling voidage of titanium dioxide-aluminum oxide shaping carrier be 30-50%.
6. method according to claim 1, is characterized in that, described catalyst I
ain group VIII metal component be selected from cobalt and/or nickel, vib metal component is selected from molybdenum and/or tungsten, is benchmark with oxide basis and with catalyzer, and the content of group VIII metal component is 0.1-3 % by weight, and the content of group vib metal component is 0.5-8 % by weight.
7. method according to claim 6, is characterized in that, is benchmark with oxide basis and with catalyzer, described catalyst I
ain the content of group VIII metal component be 0.5-2.5 % by weight, the content of group vib metal component is 3.5-8 % by weight.
8. method according to claim 1; it is characterized in that; by volume and with the total amount of described catalyst combination for benchmark; the content of the described hydrogenation activity guard catalyst I in described catalyst combination is 5-30%; the content of Hydrodemetalation catalyst II is 20-40%, and the content of hydrotreating catalyst III is 30-60%.
9. method according to claim 1, it is characterized in that, described Hydrodemetalation catalyst II contains carrier, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, containing or not containing being selected from boron, phosphorus, one or more adjuvant components in fluorine, with catalyst I I for benchmark, with the content of the nickel of oxide basis and/or cobalt for 0.3-8 % by weight, the content of molybdenum and/or tungsten is 0.5-15 % by weight, boron is selected from element, phosphorus, the content of one or more adjuvant components in fluorine is 0 ~ 5 % by weight, wherein the pore volume of carrier is 0.6-1.4 ml/g, specific surface area is for being greater than 90 to being less than or equal to 350m
2/ g.
10. method according to claim 9, is characterized in that, the pore volume of the carrier in described Hydrodemetalation catalyst II is 0.7-1.2 ml/g, and specific surface area is 100-200m
2/ g.
11. methods according to claim 9 or 10, is characterized in that, the support selected from alumina in described Hydrodemetalation catalyst II.
12. methods according to claim 11, is characterized in that, described aluminum oxide is the alumina supporter with double-hole.
13. methods according to claim 12, 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, and aperture accounts for total pore volume 10-60% at the pore volume of 100-2000 nanometer.
14. methods according to claim 1, it is characterized in that, described hydrotreating catalyst III contains the carrier being 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, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, with catalyst I II for benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 10 ~ 35 % by weight, is 0 ~ 9 % by weight in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element.
15. methods according to claim 14, is characterized in that, the support selected from alumina in described hydrotreating catalyst III.
16. methods according to claim 15, is characterized in that, the pore volume of described aluminum oxide 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.
17. methods according to claim 1, is characterized in that, described catalyst I
bthe pore distribution curve of carrier there are two peaks at 45-100 μm and 0.2-1mm.
18. methods according to claim 1, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%.
19. methods according to claim 1, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1.0h
-1, hydrogen to oil volume ratio is 600-1500.
20. methods according to claim 19, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop is 10-18MPa, and temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h
-1, hydrogen to oil volume ratio is 800-1100.
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Citations (4)
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|---|---|---|---|---|
| EP0204314A2 (en) * | 1985-06-05 | 1986-12-10 | Nippon Oil Co. Ltd. | Catalyst for hydrotreatment of heavy oils |
| CN1689702A (en) * | 2004-04-20 | 2005-11-02 | 中国石油化工股份有限公司 | Titanium oxide - aluminum oxide composite carrier, preparation method and application thereof |
| CN1990834A (en) * | 2005-12-30 | 2007-07-04 | 中国石油化工股份有限公司 | Residual oil hydroprocessing method |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0204314A2 (en) * | 1985-06-05 | 1986-12-10 | Nippon Oil Co. Ltd. | Catalyst for hydrotreatment of heavy oils |
| CN1689702A (en) * | 2004-04-20 | 2005-11-02 | 中国石油化工股份有限公司 | Titanium oxide - aluminum oxide composite carrier, preparation method and application thereof |
| CN1990834A (en) * | 2005-12-30 | 2007-07-04 | 中国石油化工股份有限公司 | Residual oil hydroprocessing method |
| 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 |
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