CN103923693B - A kind of method reducing heavy raw oil studies on asphaltene and carbon residue content - Google Patents
A kind of method reducing heavy raw oil studies on asphaltene and carbon residue content Download PDFInfo
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- CN103923693B CN103923693B CN201310012712.0A CN201310012712A CN103923693B CN 103923693 B CN103923693 B CN 103923693B CN 201310012712 A CN201310012712 A CN 201310012712A CN 103923693 B CN103923693 B CN 103923693B
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Abstract
A kind of method reducing heavy raw oil studies on asphaltene and carbon residue content, comprise at hydrotreating reaction conditions, heavy raw oil is contacted with a kind of catalyst combination, described catalyst combination comprises hydrogenation protecting catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III, in described catalyst combination the layout of each catalyzer make described stock oil successively with hydrogenation protecting catalyst I, Hydrodemetalation catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyzer for benchmark, the content of described hydrogenation protecting catalyst I is 5-60%, the content of Hydrodemetalation catalyst II is 5-50%, the content of hydrotreating catalyst III is 10-60%, wherein, the filling voidage of described hydrogenation protecting catalyst I is 25-60%, described Hydrodemetalation catalyst II is containing salic shaping carrier, characterize with mercury penetration method, the pore volume of described carrier is 0.95-1.2 ml/g, specific surface is 50-300 rice
2/ gram, the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, and the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.
Description
Technical field
The present invention relates to the hydroprocessing process of heavy raw oil.
Background technology
Hydrotreatment and catalytic cracking combined technique processing heavy oil, such as residual oil, can make it be able to lighting and clean.Therefore, along with the continuous aggravation of crude oil heaviness, in poor quality trend, this technology is by wide popularization and application.
Containing a large amount of metallic impurity such as iron, calcium, nickel, vanadium and the macromole species such as bituminous matter, colloid being difficult to conversion in residual oil, easily to cause in the course of processing catalyst surface due to metal deposition and carbon deposit coking inactivation, affect quality product and shorten the operational cycle.Thus, bitum hydrocracking and metallic impurity to remove and hold be key in residual hydrogenation process.In prior art, adopt the catalyst series of grating to realize this purpose, but overall performance still awaits further raising.
Summary of the invention
The technical problem to be solved in the present invention is for prior art demand, provides a kind of heavy raw oil working method with good bituminous matter hydrocracking performance newly.
The present invention relates to following invention:
1, a kind of method reducing heavy raw oil studies on asphaltene and carbon residue content, comprise at hydrotreating reaction conditions, heavy raw oil is contacted with a kind of catalyst combination, described catalyst combination comprises hydrogenation protecting catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III, in described catalyst combination the layout of each catalyzer make described stock oil successively with hydrogenation protecting catalyst I, Hydrodemetalation catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyzer for benchmark, the content of described hydrogenation protecting catalyst I is 5-60%, the content of Hydrodemetalation catalyst II is 5-50%, the content of hydrotreating catalyst III is 10-60%, wherein, the filling voidage of described hydrogenation protecting catalyst I is 25-60%, described Hydrodemetalation catalyst II is containing salic shaping carrier, characterize with mercury penetration method, the pore volume of described carrier is 0.95-1.2 ml/g, specific surface is 50-300 rice
2/ gram, the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, and the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.
2, 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 described hydrogenation protecting catalyst I is 10-50%, the content of Hydrodemetalation catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; The filling voidage of described hydrogenation protecting catalyst I is 30-50%; The pore volume of the carrier of described Hydrodemetalation catalyst II is 0.95-1.15 ml/g, and specific surface area is 80-200 rice
2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
3, the method according to 1 or 2; it is characterized in that, described hydrogenation protecting catalyst I contains shaping carrier and hydrogenation active metals component, and the crushing strength of described 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, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, with oxide basis and with described catalyst I 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.
4, the method according to 3, is characterized in that, the crushing strength of described carrier 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, described group VIII metal component is selected from nickel and/or cobalt, and vib metal component is selected from molybdenum and/or tungsten, and with oxide basis and with described catalyst I for benchmark, 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.
5, the method according to 4, is characterized in that, the crushing strength of described carrier is 70-200N/ grain, and pore volume is 0.4-0.7 ml/g, and specific surface area is greater than 80 to being less than or equal to 120 meters
2/ gram, with oxide basis and with described catalyst I for benchmark, the content of group VIII metal component is 0.5-2.5 % by weight, and the content of group vib metal component is 3.5-8 % by weight.
6, the method according to 3; it is characterized in that, the shaping carrier in described hydrogenation protecting catalyst I is the forming composition of titanium dioxide-aluminum oxide, with described carrier for benchmark; in described carrier, the content of aluminum oxide is 70-99 % by weight, and the content of titanium oxide is 1-30 % by weight.
7, the method according to 6, is characterized in that, with described carrier for benchmark, in described carrier, the content of aluminum oxide is 75-96 % by weight, and the content of titanium oxide is 4-25 % by weight.
8, the method according to 7, is characterized in that, with described carrier for benchmark, in described carrier, the content of aluminum oxide is 85-96 % by weight, and the content of titanium oxide is 4-15 % by weight.
9, the method according to 1 or 2, it is characterized in that, hydrogenation active metals component in described Hydrodemetalation catalyst II is selected from least one VIII race's metal component and at least one VI B metal component, be benchmark with oxide basis and with catalyst II, the content of described VIII race's metal component is for being greater than 0.5 to being less than or equal to 6 % by weight, and the content of VI B race metal component is for being greater than 1 to being less than or equal to 15 % by weight.
10, the method according to 9, it is characterized in that, VIII race's metal component in described catalyst II is selected from cobalt and/or nickel, VI B metal component is selected from molybdenum and/or tungsten, with oxide basis and with described catalyst II for benchmark, the content of described VIII race's metal component is 0.8-4 % by weight, and the content of VI B race metal component is 2-10 % by weight.
11, the method according to 1 or 2, it is characterized in that, described catalyzer III is containing 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 oxide basis and with catalyzer III for benchmark, the content of described nickel and/or cobalt is 1-5 % by weight, the content of molybdenum and/or tungsten is 10-35 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element for 0-9 % by weight.
12, the method according to 11, is characterized in that, consisting of of described Hydrobon catalyst: the heavy % of nickel oxide 1-5 heavy %, Tungsten oxide 99.999 12-35 heavy %, fluorine 1-9, all the other are aluminum oxide.
13, the method according to 11, is characterized in that, described support selected from alumina, and the pore volume of alumina supporter is not less than 0.35 ml/g, and bore dia is that the pore volume in 40-100 dust hole accounts for more than 80% of total pore volume.
14, the method according to 11, is characterized in that, described hydrogenation active metals component is selected from nickel, molybdenum and tungsten, 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.
15, 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.
16, the method according to 15, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 10-18MPa, 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, the effect of described hydrogenation protecting catalyst I is the iron, the calcium that remove in raw material and removes colloid and carbon residue at least partly, and effectively deposits accommodation to impurity such as removed iron, calcium and carbon deposits.
Contriver finds, the filling hole of hydrogenation protecting catalyst I is blunt connects the above-mentioned functions affecting hydrogenation protecting catalyst I.The filling porosity of the preferred hydrogenation protecting catalyst I of the present invention is 25-60%, more preferably 30-50%.Putting before this, the present invention is not particularly limited hydrogenation protecting catalyst I.Such as, the hydrogenation active metals component in described hydrogenation protecting catalyst and content can be the component often selected of conventional hydro guard catalyst and content.Such as, hydrogenation active metals component can be selected from least one group VIII metal component and at least one vib metal component, and preferred group VIII metal component is nickel and/or cobalt, and preferred vib metal component is molybdenum and/or tungsten.With oxide basis and with described catalyst I for benchmark, the content of group VIII metal component, for being greater than 0 to being less than or equal to 5 % by weight, is preferably 0.1-3 % by weight, more preferably 0.5-2.5 % by weight; The content of group vib metal component, for being greater than 0 to being less than or equal to 10 % by weight, is preferably 0.5-8 % by weight, more preferably 3.5-8 % by weight.Be 25-60% being enough to make the filling porosity of final catalyzer, under the prerequisite of more preferably 30-50%, the present invention is not particularly limited described shaping carrier pattern, and such as, the pattern of described shaping carrier can be the spheroid etc. of honeycomb post, Raschig ring or multi-pore channel.
The crushing strength of the preferred described carrier of the present invention is 20-300N/ grain, more preferably 50-200N/ grain, be more preferably 70-200N/ grain, preferred pore volume is 0.3-0.9 ml/g, more preferably 0.4-0.8 ml/g, be more preferably 0.4-0.7 ml/g, preferred specific surface area is greater than 30 to being less than or equal to 150 meters
2/ gram, be preferably greater than 50 further to being less than or equal to 140 meters
2/ gram, be further preferably greater than 80 to being less than or equal to 120 meters
2/ gram.They can be commercially available commodity, and arbitrary prior art also can be adopted to prepare.
In the present invention, described filling voidage is a kind of physical parameter characterizing forming composition bulk property.Its 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 according to the density of industrial landfill, 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 the bed voidage of catalyzer divided by 100%.
In a concrete preferred implementation; the carrier of described hydrogenation protecting catalyst I is selected from a kind of titanium dioxide-aluminum oxide forming composition; with described carrier for benchmark; in described carrier, the content of aluminum oxide is 70-99 % by weight; be preferably 75-96 % by weight, more preferably 85-96 % by weight, the content of titanium oxide is 1-30 % by weight; be preferably as 4-25 % by weight, more preferably 4-15 % by weight.
When hydrogenation activity guard catalyst I to select with the forming composition of titanium dioxide-aluminum oxide as carrier, the preparation method of this catalyzer, comprise and prepare carrier the component of load hydrogenation active metals on this carrier, 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, time of drying is 1-10 hour, maturing temperature is 600-1000 DEG C, and roasting time is 1 ~ 10 hour, and preferred described drying temperature is 100-250 DEG C, time of drying is 2-8 hour, maturing temperature is 700-1000 DEG C, and roasting time is 2-5 hour, and preferred maturing temperature is 850-1000 DEG C further;
Wherein, the hydrated aluminum oxide described in step (1) and the consumption of titanium-containing compound make the alumina content in final molding thing be that 70-99 % by weight is preferably 75-96 % by weight, and titanium oxide content is 1-30 % by weight, are preferably 4-25 % by weight.
The described method preparing 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 extruded moulding, 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 described shaping pattern of shaping carrier that preferably makes is the spheroid of honeycomb post, Raschig ring or multi-pore channel.
The method of described drying and roasting and condition are field of catalyst preparation customary way and condition.
Described hydrated aluminum oxide is selected from mixtures in hibbsite, monohydrate alumina and amorphous hydroted alumina or several, is preferably pseudo-boehmite.They can be that commercially available commodity also can be prepared by any one method in prior art.
Described titanium-containing compound is selected from one in titanium oxide, titanate, molecular sieve containing titanium, titaniferous hydrated aluminum oxide and several, preferential oxidation titanium, titanate.
Be enough under the prerequisite loading on carrier by described hydrogenation active metals component, the method for the present invention to described load hydrogenation active metals component is not particularly limited.The method of preferred dipping, 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.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, be preferably 0.1-3 % by weight, more preferably 0.5-2.5 % 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, be preferably 0.5-8 % by weight, more preferably 3.5-8 % by weight.
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 hours; 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 hours.
One or more in the described soluble compound be selected from containing the metal component compound being selected from group vib in them, as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstate, metatungstate, ethyl metatungstate, preferably ammonium metawolframate, ethyl ammonium metawolframate wherein.
Described containing the compound being selected from group VIII metal component be selected from their soluble compound one or more, 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 effect of described catalyst II is to make the macromole species such as raw material studies on asphaltene and colloid to be transformed and metallic impurity Ni+V in effective elimination raw material, and partial vulcanization thing.
The preparation method of described catalyst II, comprise and prepare carrier and the component of load hydrogenation active metals on this carrier, wherein, the preparation of described carrier comprises and being mixed by the modifier P2 of hydrated aluminum oxide P1 and P1 containing pseudo-boehmite, aftershaping, dry and roasting.
Wherein, the Mixing ratio by weight of described P1 and P2 is 20-95:5-80, is preferably 70-95:5-25.The Mixing ratio by weight of described P1 and P2 refers to the ratio of the shared parts by weight of P1 and P2 difference in the mixture of every hundred parts of described P1 and P2.The κ value of P2 is 0 to being less than or equal to 0.9, is preferably 0 to being less than or equal to 0.6.Described κ=DI
2/ DI
1.DI
1for the sour peptization index of the hydrated aluminum oxide P1 containing pseudo-boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated aluminum oxide P1 containing pseudo-boehmite.
After sour peptization index D I in the preparation of described carrier refers to that the hydrated aluminum oxide containing pseudo-boehmite adds nitric acid by certain sour aluminum ratio, within certain reaction times by the hydrated aluminum oxide containing pseudo-boehmite of peptization with Al
2o
3the percentage ratio of meter, DI=(1-W
2/ W
1) × 100%, W
1and W
2be respectively intend thin water aluminium and acid-respons front and with acid-respons after with Al
2o
3the weight of meter.
The mensuration of DI comprises: the (1) calcination base (calcination base, also referred to as butt, refers to by quantitative pseudo-boehmite in 600 DEG C of roastings 4 hours, its ratio burning rear weight and burn front weight) of the hydrated aluminum oxide of mensuration containing pseudo-boehmite, counts a; (2) take the hydrated aluminum oxide W containing pseudo-boehmite with analytical balance
0gram, W
0amount meet with Al
2o
3the W of meter
1be 6 grams of (W
1/ a=W
0), take deionized water W gram, W=40.0-W
0, under stirring, the hydrated aluminum oxide containing pseudo-boehmite taken and deionized water are added in beaker and mix; With 20mL transfer pipet pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, is joined by this acid solution in the beaker of step (2), stirs lower reaction 8 minutes; (4) step (3) reacted slurries are carried out centrifugation in centrifuges, inserted by throw out in the crucible of having weighed, afterwards, by it in 125 DEG C of dryings 4 hours, in retort furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W
2gram; (5) according to formula DI=(1-W
2/ W
1) × 100% calculates.
The condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour, and being preferably temperature is 100-200 DEG C, and the time is 2-12 hour; The condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour, is preferably temperature for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour.
Wherein, that afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2 by shaping, dry for the described hydrated aluminum oxide P1 containing pseudo-boehmite by one of P1 method being modified as P2, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is forming composition roastings method one obtained, and maturing temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated aluminum oxide P1 containing pseudo-boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.Preferably, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in maturing temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
In concrete enforcement, described P2 conveniently can be obtained by following method:
(1) obtain P2 based on drying, comprise and prepare in regular oxidation alumina supporter process by the hydrated aluminum oxide P1 containing pseudo-boehmite is shaping according to a conventional method, the tailing of drying by-product, such as: in extruded moulding, bar shaped forming composition is at tailing (being called dry waste material traditionally) that is dry, integer process by-product, this tailing is milled, sieves and obtain P2.
(2) obtain based on roasting, comprise and prepare in regular oxidation alumina supporter process by the hydrated aluminum oxide P1 containing pseudo-boehmite is shaping according to a conventional method, through the tailing (being called roasting waste material traditionally) of roasting by-product, such as, in roller forming, the tailing of spheroidal particle by-product in roasting process, mills this tailing, sieves and obtain P2; Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.
(3) two or more be mixed to get in the modifier P2 obtained based on preceding method.
When adopting blending means to obtain P2, can optionally at random adjust the blending ratio of the modifier P2 that aforementioned several method obtains respectively, the present invention is not limited in this respect.
The described hydrated aluminum oxide P1 containing pseudo-boehmite can be pseudo-boehmite prepared by any prior art, also can be the mixture of pseudo-boehmite and other hydrated aluminum oxide, other hydrated aluminum oxide described be selected from one or more in a Water oxidize aluminium, alumina trihydrate and amorphous hydrated aluminum oxide.In a preferred embodiment, characterize with X diffraction, in the described hydrated aluminum oxide containing pseudo-boehmite, pseudo-boehmite content is not less than 50%, is more preferably not less than 60%.
The pore volume of the preferred described hydrated aluminum oxide P1 containing pseudo-boehmite is 0.9-1.4 ml/g further, and specific surface is 100-350 rice
2/ gram, most probable bore dia 8-30nm, the pore volume of the described hydrated aluminum oxide P1 containing pseudo-boehmite be more preferably is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, most probable bore dia 10-25nm.
In the present invention, the pore volume of the hydrated aluminum oxide containing pseudo-boehmite, specific surface area and most probable pore size are that the described hydrated aluminum oxide containing pseudo-boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtained.
Preferred described P2 is 80-300 object particulate matter, and further preferred described P2 is 100-200 object particulate matter.Here, described 80-300 object particle, preferred 100-200 object particle refers to that described modifier is through sieve (step comprising fragmentation or grinding if desired), its screening thing (screen underflow) meets 80-300 object particle, the percentage ratio (by weight) that preferred 100-200 object particulate matter accounts for total amount is not less than 60%, is preferably not less than 70% further.
The forming composition that carrier wherein can be made into various easy handling is required, such as spherical, cellular, nest like, tablet or bar shaped (trifolium, butterfly, cylindrical etc.) depending on different.Wherein, the method mixed by the modifier P2 of described hydrated aluminum oxide P1 and P1 containing pseudo-boehmite is ordinary method, such as, is dropped in stirring-type mixer by P1 and P2 of powder mix according to ingredient proportion.
Describedly shapingly to carry out according to a conventional method.When shaping, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can add in described mixture water, extrusion aid and/or tackiness agent, containing or not containing expanding agent, then extrusion moulding, carry out drying also roasting afterwards.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, described peptizing agent can be mineral acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and tensio-active agent.Synthetic cellulose is wherein preferably one or more in Walocel MT 20.000PV, methylcellulose gum, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyoxyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, one or more in the vinylcarbinol multipolymer that tensio-active agent is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is 200-10000 and maleic acid copolymer.
Be enough under the prerequisite that described hydrogenation active metals component is carried on described carrier, the present invention is not particularly limited described carrying method, preferred method is pickling process, comprise the dipping solution of preparation containing the compound of described metal, afterwards with the carrier described in this solution impregnation, carry out drying, roasting or not roasting afterwards.Described dipping method is ordinary method, such as, can be excessive immersion stain, hole saturation method pickling process.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.Preferred 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.
One or more in the described soluble compound be selected from containing the metal component compound being selected from VI B race in them, as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstate, metatungstate, ethyl metatungstate, preferably ammonium metawolframate, ethyl ammonium metawolframate wherein.Described containing the compound being selected from VIII race's metal component be selected from their soluble compound one or more, 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, in wherein said hydrogenation protecting catalyst I and Hydrodemetalation catalyst I I, can also not affect containing any the addO-on therapy that described catalyst performance maybe can improve the catalytic performance of described catalyzer.As contained the addO-on therapy such as phosphorus, halogen, alkaline-earth metal, be benchmark with oxide basis and with catalyzer, the content of described addO-on therapy is no more than 10 % by weight, is preferably 0.1-4 % by weight.
When also containing the addO-on therapy such as phosphorus, halogen, alkaline-earth metal in described catalyzer, the introducing method of described addO-on therapy can be arbitrary method, as can be by containing as described in the component such as phosphorus, halogen, alkaline-earth metal compound directly with as described in pseudo-boehmite mix, shaping and roasting; Can be flood described carrier after the compound containing components such as described phosphorus, halogen, alkaline-earth metal and the compound containing hydrogenation active metals component are mixed with mixing solutions; Can also be flood described carrier and roasting by after the independent obtain solution of compound containing components such as phosphorus, halogen, alkaline-earth metal.When the addO-on therapy such as phosphorus, halogen, alkaline-earth metal and hydrogenation active metals introduce described carrier respectively, preferably first use carrier described in the solution impregnation containing described addO-on therapy compound and roasting, afterwards again by the solution impregnation containing hydrogenation active metals component composition.Wherein, described maturing temperature is 400-600 DEG C, and be preferably 420-500 DEG C, roasting time is 2-6 hour, is preferably 3-6 hour.
According to method provided by the invention, wherein, the effect of described catalyzer III 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, improves product property.Be enough under the prerequisite realizing above-mentioned functions, the present invention does not have other to limit to described catalyzer III, and namely catalyzer III can be selected from the catalyzer such as hydrofining, hydrotreatment that arbitrary prior art provides.They can be commercially available commodity or adopt any existing method preparation.
Usually, this type of catalyzer is usually containing heat-resistant inorganic oxide carrier, hydrogenation active metals component.Such as, described catalyzer III is containing 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 oxide basis and with catalyzer III for benchmark, the content of described nickel and/or cobalt is 1-5 % by weight, and the content of molybdenum and/or tungsten is 10-35 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element for 0-9 % by weight.
Such as, a kind of Hydrobon catalyst disclosed in ZL97112397, 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 discloses a kind of Hydrobon catalyst, and this catalyzer contains at least one group VIB 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, and it adopts special method preparation.
ZL200310117323 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 catalyzer III 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, described Hydrodemetalation catalyst I, Hydrodemetalation catalyst II and the hydrotreating catalyst III of comprising can layering fill in same reactor successively, also can be use in the reactor filling in several series connection successively, this present invention is not particularly limited.
According to method provided by the invention; wherein; before the catalyst combination comprising hydrogenation protecting catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III, afterwards or they between any two, any other catalyzer or the filler that contribute to improving described catalyst combination performance can be comprised.Such as, added as fillers such as porcelain ball, active upholders before described hydrogenation protecting catalyst I, to improve stock oil distribution etc. in the reactor.Use etc. about this filler is conventionally known to one of skill in the art, does not repeat here.
According to the ordinary method in this area, described hydrotreating catalyst before the use, usually can be in presence of hydrogen, prevulcanized is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this prevulcanized can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.
One or more in raw material is selected from containing the metallic impurity such as nickel, vanadium according to described method crude oil, vacuum residuum, deep drawing wax oil, frivolous asphalt oil, wax tailings etc.
According to the asphalt content less than 0.5% of oil after the hydrotreatment that described method obtains, sulphur content less than 0.5%, carbon residue content is less than 6.0%.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.
The invention provides catalyst I used in method and preparation method thereof.
Be suitable for carrier preparing catalyst I of the present invention and preparation method thereof:
ZI-1: by aluminium hydrate powder 1000 grams, 100 grams of titanium dioxide mixing, 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, obtain carrier ZI-1.Carrier ZI-1 physico-chemical property is in table 1.
ZI-2: mixed by aluminium hydrate powder 200 grams and aluminum titanate powder 80 grams, 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, obtains carrier ZI-2.Carrier ZI-2 physico-chemical property is in table 1.
ZI-3: mixed containing titanium dioxide with 18 grams by a diaspore powder 200 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, obtains carrier ZI-3.Carrier ZI-3 physico-chemical property is in table 1.
ZI-4: aluminium hydrate powder 1000 grams is mixed with 40 grams of titanium dioxides, be 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 ZI-4.Carrier ZI-4 physico-chemical property is in table 1.
ZI-5: mixed with 500 grams of aluminium hydroxides by 40 grams of titanium dioxides, plunger type bar extruder is extruded into external diameter 4.5mm wall thickness 1.8mm hollow gear post, in 90 DEG C of dryings 4 hours, in 960 DEG C of roastings 2 hours, obtains carrier ZI-5.Carrier ZI-5 physico-chemical property is in table 1.
ZI-6: the support porcelain ring (aluminum oxide 62 % by weight, other are silicon, calcium, magnesium, potassium etc.) that a kind of commercially available Jiangsu produces.ZI-6 physico-chemical property is in table 1.
ZI-7: mixed with 300 grams of aluminium hydrate powders by a 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, and in 120 DEG C of dryings after 2 hours, in 900 DEG C of constant temperature 3 hours, obtain ZI-7, ZI-7 physico-chemical property was in table 1.
Table 1
| Carrier | ZI-1 | ZI-2 | ZI-3 | ZI-4 | ZI-5 | ZI-6 | ZI-7 |
| Al 2O 3, % by weight | 87 | 94 | 91 | 93 | 90 | 62 | 100 |
| TiO 2, % by weight | 13 | 6 | 9 | 7 | 10 | Other are silicon, calcium, magnesium, potassium etc. | - |
| Bed voidage, % | 53 | 48 | 49 | 45 | 48 | 50 | 49 |
| Crushing strength, N/ grain | 80 | 120 | 80 | 90 | 140 | 90 | 16 |
| Pore volume, ml/g | 0.62 | 0.48 | 0.60 | 0.68 | 0.72 | 0.05 | 0.58 |
| Specific surface, m 2/g | 105 | 80 | 90 | 110 | 130 | 5 | 95 |
The measuring method of crushing strength is carried out according to RIPP25-90 catalyzer compressive strength assay method.Vehicle group becomes calculated value, and pore volume, specific surface area adopt BET to measure.
Hydrogenation protecting catalyst I and preparation thereof:
CI-1: get 200 grams, ZI-2 carrier, with 500 milliliters containing WO
370 grams per liters, ammonium metawolframate and the nickelous nitrate mixing solutions of NiO15 grams per liter flood 1 hour, dry 4 hours after filtration in 100 DEG C, and 450 DEG C of roastings 4 hours, obtain catalyzer CI-1.The composition of catalyzer CI-1 is listed in table 2.
CI-2: get 200 grams, ZI-2 carrier, with 500 milliliters containing MoO
350 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO8 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain catalyzer CI-2.The composition of catalyzer CI-2 is listed in table 2.
CI-3: get 200 grams, ZI-3 carrier, with 500 milliliters containing MoO
380 grams per liters, the ammonium molybdate of NiO20 grams per liter and nickel nitrate solution flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 500 DEG C of roastings 4 hours, obtain catalyzer CI-3.The composition of catalyzer CI-3 is listed in table 2.
CI-4: get 200 grams, ZI-5 carrier, with 500 milliliters containing MoO
340 grams per liters, the molybdic acid acid ammonium of CoO12 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 catalyzer CI-4.The composition of catalyzer CI-4 is listed in table 2.
CI-5: get 200 grams, ZI-6 carrier, with 500 milliliters containing MoO
370 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO10 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain catalyzer CI-6.The composition of protective material CI-6 is listed in table 2.
CI-6: get 200 grams, ZI-7 carrier, with 500 milliliters containing MoO
350 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO8 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain catalyzer CI-7.The composition of catalyzer CI-7 is listed in table 2.
Table 2
In catalyzer, the content of active metal component adopts Xray fluorescence spectrometer to measure (RIPP133-90).
The invention provides catalyst II used in method and preparation method thereof.
The pseudo-boehmite (P1) used in embodiment comprising:
P1-1: (pore volume is 1.2 mls/g to the dry glue powder that Chang Ling catalyzer branch office produces, and specific surface is 280 meters
2/ gram, most probable bore dia 15.8nm.Butt is 73%, and wherein pseudo-boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 15.8).
P1-2: (pore volume is 1.1 mls/g to the dry glue powder that Yantai Heng Hui Chemical Co., Ltd. produces, and specific surface is 260 meters
2/ gram, most probable bore dia 12nm.Butt is 71%, and wherein pseudo-boehmite content is 67%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 17.2).
Modifier P2 of P1 and preparation method thereof:
P2A: take 1000 grams of P1-1, adds the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier P2A of P1-1.The k value of P2A is 0.5.
P2B: take 1000 grams of P1-1, dodges dry 6 minutes in 240 DEG C, obtains the modifier P2B of P1-1.The k value of P2B is 0.4.
P2C: the P2B that the P2A obtain embodiment 1 and embodiment 2 obtain each 200 grams of Homogeneous phase mixing, obtain the modifier P2C of P1-1.The k value of P2C is 0.4.
P2D: take 1000 grams of P1-2, adds the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 2mm is milled, sieve, get wherein 100 ~ 200 mesh sieves and divide, obtain the modifier P2D of P1-2.The k value of P2D is 0.
P2E: take 1000 grams of P1-2, dodges dry 10 minutes in 650 DEG C, obtains the modifier P2E of P1-2.The k value 0.3 of P2E.
Be suitable for carrier preparing catalyst I I of the present invention and preparation method thereof:
ZII-1: take 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 1 is obtained, adds the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier ZII-1.The character of carrier ZII-1 lists in table 4.
ZII-2: take 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing that embodiment 2 is obtained, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier ZII-2.The character of carrier ZII-2 lists in table 4.
ZII-3: take 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 950 DEG C of roastings 3 hours, obtains carrier ZII-3.The character of carrier ZII-3 lists in table 4.
ZII-4: take 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, adds the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier ZII-4.The character of carrier ZII-4 lists in table 4.
ZII-5: take 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier ZII-5.The character of carrier ZII-5 lists in table 4.
ZII-6: take 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 850 DEG C of roastings 3 hours, obtains carrier ZII-6.The character of carrier ZII-6 lists in table 4.
ZII-7: take 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier ZII-7.The character of carrier ZII-7 lists in table 4.
ZII-8: take 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier ZII-8.The character of carrier ZII-8 lists in table 4.
Carrier of the reference catalyst of Kaolinite Preparation of Catalyst II and preparation method thereof:
DZII-1: take 1000 grams of P1-1, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier DZII-1.The character of carrier DZII-1 lists in table 4.
DZII-2: take 1000 grams of P1-2, adds containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier DZII-2.The character of carrier DZII-2 lists in table 4.
DZII-3: the method provided according to patent CN1782031A embodiment 9, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier DZII-3.The character of carrier DZII-3 lists in table 4.
Table 4
Catalyst I I and preparation thereof:
CII-1: get 200 grams of carrier ZII-1, with 210 milliliters containing MoO
367.9 grams per liters, molybdenum oxide and the cobaltous dihydroxycarbonate mixing solutions of CoO11.3 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer CII-1.Molybdenum oxide in catalyzer CII-1 and the content of cobalt oxide list in table 5.
CII-2: get 200 carrier ZII-2, with 200 milliliters containing MoO
353.1 grams per liters, molybdenum oxide and the basic nickel carbonate mixing solutions of NiO10.6 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer CII-2.Molybdenum oxide in catalyzer CII-2 and the content of nickel oxide list in table 5.
CII-3: get 200 grams of carrier ZII-3, with 205 milliliters containing MoO
378.5 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO15.7 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer CII-3.Molybdenum oxide in catalyzer CII-3 and the content of nickel oxide list in table 5.
CII-4: get 200 grams of carrier ZII-4, with 210 milliliters containing MoO
367.9 grams per liters, molybdenum oxide and the basic nickel carbonate mixing solutions of NiO11.3 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer CII-4.Molybdenum oxide in catalyzer CII-4 and the content of nickel oxide list in table 5.
CII-5: get 200 grams of carrier ZII-8, with 200 milliliters containing MoO
382.8 grams per liters, molybdenum oxide and the cobaltous dihydroxycarbonate mixing solutions of CoO19.1 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer CII-5.Molybdenum oxide in catalyzer CII-5 and the content of cobalt oxide list in table 5.
The reference catalyst DCII of catalyst I I:
DCII-1: get 200 grams of carrier DZII-1, with 180 milliliters containing MoO
379.2 grams per liters, molybdenum oxide and the cobaltous dihydroxycarbonate mixing solutions of CoO13.2 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer DCII-1.Molybdenum oxide in catalyzer DCII-1 and the content of cobalt oxide list in table 5.
DCI I-2: get 200 carrier DZII-1, with 180 milliliters containing MoO
359.0 grams per liters, molybdenum oxide and the basic nickel carbonate mixing solutions of NiO11.8 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer DCII-2.Molybdenum oxide in catalyzer DCII-2 and the content of nickel oxide list in table 5.
DCII-3: get 200 grams of carrier DZII-2, with 180 milliliters containing MoO
387.2 grams per liters, molybdenum oxide and the basic nickel carbonate mixing solutions of NiO17.4 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer DCII-3.Molybdenum oxide in catalyzer DCII-3 and the content of nickel oxide list in table 5.
DCII-4: get 200 grams of carrier DZII-3, with 200 milliliters containing MoO
382.8 grams per liters, molybdenum oxide and the cobaltous dihydroxycarbonate mixing solutions of CoO19.1 grams per liter flood 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours, obtain catalyzer DCII-4.Molybdenum oxide in catalyzer DCII-4 and the content of cobalt oxide list in table 5.
Table 5
The invention provides catalyzer III used in method and preparation method thereof.
C III-1: adopt patent ZL97112397 method to prepare C III-1, it consists of the heavy % of nickel oxide 3, the heavy % of Tungsten oxide 99.999 25, and the heavy % of fluorine 2, all the other are aluminum oxide.
C III-2: adopt patent ZL97112397 method to prepare C III-2, it consists of the heavy % of nickel oxide 4, the heavy % of Tungsten oxide 99.999 30, and the heavy % of fluorine 2, all the other are aluminum oxide.
C III-3: adopt patent ZL00802168 method to prepare C III-3, it consists of the heavy % of nickel oxide 3.5, and the heavy % of molybdenum oxide 18, all the other are aluminum oxide.
Embodiment 1-3 illustrates method provided by the invention, and the method is used for the effect of hydrotreatment heavy oil residue raw material.
Be 7.8%, Fe+Ca content be 26ppm, Ni+V content with asphalt content be 90ppm, sulphur content be 3.9%, carbon residue be the mixed residue oil of 13% for raw material, evaluate catalysts on 500 milliliters of fixed-bed reactor.
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)
Oil sample studies on asphaltene content adopts normal heptane intermediate processing (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP10-90).
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)
Embodiment 1
CI-1, C II-1 and C III-1 catalyst combination is adopted to carry out hydrotreatment to aforementioned base materials oil.
Admission space ratio in catalyst combination in three kinds of hydrogen-catalyst reactors, operational condition list in table 6, and operate sampling analysis after 1000 hours, and product property is with listing in table 6.
Embodiment 2
CI-2, C II-2 and C III-2 catalyst combination is adopted to carry out hydrotreatment to aforementioned base materials oil.
Admission space ratio in catalyst combination in three kinds of hydrogen-catalyst reactors, operational condition list in table 6, and operate sampling analysis after 1000 hours, and product property is with listing in table 6.
Embodiment 3
CI-3, C II-3 and C III-3 catalyst combination is adopted to carry out hydrotreatment to aforementioned base materials oil.
Admission space ratio in catalyst combination in three kinds of hydrogen-catalyst reactors, operational condition list in table 6, and operate sampling analysis after 1000 hours, and product property is with listing in table 6.
Embodiment 4
CI-5, C II-4 and C III-3 catalyst combination is adopted to carry out hydrotreatment to aforementioned base materials oil.
Admission space ratio in catalyst combination in three kinds of hydrogen-catalyst reactors, operational condition list in table 6, and operate sampling analysis after 1000 hours, and product property is with listing in table 6.
Comparative example 1
CI-2, DC II-2 and C III-2 catalyst combination is adopted to carry out hydrotreatment to aforementioned base materials oil.
Admission space ratio in catalyst combination in three kinds of hydrogen-catalyst reactors, operational condition list in table 6, and operate sampling analysis after 1000 hours, and product property is with listing in table 6.
Comparative example 2
CI-3, DC II-3 and C III-3 catalyst combination is adopted to carry out hydrotreatment to aforementioned base materials oil.
Admission space ratio in catalyst combination in three kinds of hydrogen-catalyst reactors, operational condition list in table 6, and operate sampling analysis after 1000 hours, and product property is with listing in table 6.
Comparative example 3
CI-6, DC II-4 and C III-1 catalyst combination is adopted to carry out hydrotreatment to aforementioned base materials oil.
Admission space ratio in catalyst combination in three kinds of hydrogen-catalyst reactors, operational condition list in table 6, and operate sampling analysis after 1000 hours, and product property is with listing in table 6.
Table 6
Can find out, when adopting catalyst combination process residual oils heavy feed stock provided by the invention, the product asphalt content after back end hydrogenation process in 1000 hours that operates obviously reduces, metal and sulphur, carbon residue content also obviously reduce, and in reference method, after hydrotreatment, products obtained therefrom asphalt content is higher, and quality product obviously declines.
Claims (15)
1. one kind is reduced the method for heavy raw oil studies on asphaltene and carbon residue content, comprise at hydrotreating reaction conditions, heavy raw oil is contacted with a kind of catalyst combination, described catalyst combination comprises hydrogenation protecting catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III, in described catalyst combination the layout of each catalyzer make described stock oil successively with hydrogenation protecting catalyst I, Hydrodemetalation catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyzer for benchmark, the content of described hydrogenation protecting catalyst I is 5-60%, the content of Hydrodemetalation catalyst II is 5-50%, the content of hydrotreating catalyst III is 10-60%, wherein, the filling voidage of described hydrogenation protecting catalyst I is 25-60%, described Hydrodemetalation catalyst II is containing salic shaping carrier, characterize with mercury penetration method, the pore volume of described carrier is 0.95-1.2 ml/g, specific surface is 50-300 rice
2/ gram, the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, and the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.
2. 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 described hydrogenation protecting catalyst I is 10-50%, the content of Hydrodemetalation catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; The filling voidage of described hydrogenation protecting catalyst I is 30-50%; The pore volume of the carrier of described Hydrodemetalation catalyst II is 0.95-1.15 ml/g, and specific surface area is 80-200 rice
2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
3. method according to claim 1 and 2; it is characterized in that; described hydrogenation protecting catalyst I contains shaping carrier and hydrogenation active metals component; the crushing strength of the shaping carrier of described hydrogenation protecting catalyst I 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, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, with oxide basis and with described catalyst I 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.
4. method according to claim 3, is characterized in that, the crushing strength of the shaping carrier of described hydrogenation protecting catalyst I 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, described group VIII metal component is selected from nickel and/or cobalt, and vib metal component is selected from molybdenum and/or tungsten, with oxide basis and with described catalyst I for benchmark, 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.
5. method according to claim 4, is characterized in that, the crushing strength of the shaping carrier of described hydrogenation protecting catalyst I is 70-200N/ grain, and pore volume is 0.4-0.7 ml/g, and specific surface area is greater than 80 to being less than or equal to 120 meters
2/ gram, with oxide basis and with described catalyst I for benchmark, the content of group VIII metal component is 0.5-2.5 % by weight, and the content of group vib metal component is 3.5-8 % by weight.
6. method according to claim 3; it is characterized in that, the shaping carrier in described hydrogenation protecting catalyst I is the forming composition of titanium dioxide-aluminum oxide, with described carrier for benchmark; in described carrier, the content of aluminum oxide is 70-99 % by weight, and the content of titanium oxide is 1-30 % by weight.
7. method according to claim 6, is characterized in that, with described carrier for benchmark, in the shaping carrier of described hydrogenation protecting catalyst I, the content of aluminum oxide is 75-96 % by weight, and the content of titanium oxide is 4-25 % by weight.
8. method according to claim 7, is characterized in that, with described carrier for benchmark, in the shaping carrier of described hydrogenation protecting catalyst I, the content of aluminum oxide is 85-96 % by weight, and the content of titanium oxide is 4-15 % by weight.
9. method according to claim 1 and 2, it is characterized in that, hydrogenation active metals component in described Hydrodemetalation catalyst II is selected from least one VIII race's metal component and at least one VI B metal component, be benchmark with oxide basis and with catalyst II, the content of described VIII race's metal component is for being greater than 0.5 to being less than or equal to 6 % by weight, and the content of VI B race metal component is for being greater than 1 to being less than or equal to 15 % by weight.
10. method according to claim 9, it is characterized in that, VIII race's metal component in described catalyst II is selected from cobalt and/or nickel, VI B metal component is selected from molybdenum and/or tungsten, with oxide basis and with described catalyst II for benchmark, the content of described VIII race's metal component is 0.8-4 % by weight, and the content of VI B race metal component is 2-10 % by weight.
11. methods according to claim 1 and 2, it is characterized in that, described catalyzer III is containing 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 oxide basis and with catalyzer III for benchmark, the content of described nickel and/or cobalt is 1-5 % by weight, the content of molybdenum and/or tungsten is 10-35 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element for 0-9 % by weight.
12. methods according to claim 11, is characterized in that, consisting of of described catalyzer III: the heavy % of nickel oxide 1-5 heavy %, Tungsten oxide 99.999 12-35 heavy %, fluorine 1-9, all the other are aluminum oxide.
13. methods according to claim 11, is characterized in that, the support selected from alumina of described catalyzer III, and the pore volume of alumina supporter is not less than 0.35 ml/g, and bore dia is that the pore volume in 40-100 dust hole accounts for more than 80% of total pore volume.
14. 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.
15. methods according to claim 14, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 10-18MPa, 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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| US13/853,195 US9657236B2 (en) | 2012-03-31 | 2013-03-29 | Process for hydrotreating heavy raw oils |
| TW102111777A TWI537373B (en) | 2012-03-31 | 2013-04-01 | A hydrogenation method for heavy feedstock oil |
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| 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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| 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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