CN104293382B

CN104293382B - A kind of catalytic cracking material pretreatment method

Info

Publication number: CN104293382B
Application number: CN201310303925.9A
Authority: CN
Inventors: 胡大为; 杨清河; 孙淑玲; 刘佳; 聂红; 王奎; 赵新强; 戴立顺; 邵志才; 李大东
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-07-18
Filing date: 2013-07-18
Publication date: 2016-06-22
Anticipated expiration: 2033-07-18
Also published as: CN104293382A

Abstract

A kind of catalytic cracking material pretreatment method, including at hydrotreating reaction conditions, raw oil is contacted with the catalyst combination including hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III successively, the total amount combined by volume and with described catalyst is for benchmark, the content of described hydrotreating catalyst I is 3-40%, the content of hydrotreating catalyst II is 10-50%, and the content of hydrotreating catalyst III is 20-70%；Wherein, described hydrotreating catalyst I contains the shaped alumina alumina supporter containing Group IVB metal component and hydrogenation active metals component, with the described shaped alumina alumina supporter containing Group IVB metal component for benchmark, in described carrier, the content of aluminium oxide is 70-99 weight %, and the content of titanium oxide is 1-30 weight %；Described hydrotreating catalyst II is containing the hydrogenation active metals component selected from least one vib and at least one Group VB, count with oxide and with catalyst II for benchmark, the content of described vib metals component is 0.2-15 weight %, and the content of Group VB metal component is 0.2-12 weight %。Compared with prior art, the present invention has better hydrocarbon oil hydrogenation process performance。

Description

A kind of catalytic cracking material pretreatment method

Technical field

The present invention relates to method for hydrotreating hydrocarbon oil。

Background technology

Along with the COMBINED PROCESS of constantly aggravation and social development being continuously increased light-end products demand, heavy-oil hydrogenation and the catalytic cracking of crude oil heaviness trend is subject to the generally favor of oil refining enterprise。Group technology not only can improve the yield of light-end products, and advantageously reduces the discharge of the pollutant such as sulfur, nitrogen, has obvious social and economic benefits。By catalytic cracking process and catalysts influence, in order to improve light oil yield, reduce catalyst consumption, it is desirable in heavy oil catalytic cracking raw material oil, W metal+V content should lower than 20ppm, and sulfur content is lower than 0.5%, and carbon residue content is less than 6.0%。But owing to feedstock property is constantly deteriorated, heavy-oil hydrogenation processes and just requires have higher impurity removal ability and reaction stability as fcc raw material preprocessing process。Improve impurity removal percentage to be realized by the severity of raising hydrotreatment reaction, but so also result in the shortening in catalyst runs life-span。Therefore adopting new catalyst and processing and treating method is the optimum selection producing high-quality catalytically cracked material。

Summary of the invention

The technical problem to be solved in the present invention is for prior art requirement, it is provided that a kind of heavy oil hydrogenation treatment method new, that be suitable for catalytically cracked material pretreatment。

The present invention relates to herein below:

1, a kind of catalytic cracking material pretreatment method, including at hydrotreating reaction conditions, raw oil is contacted with the catalyst combination including hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III successively, the total amount combined by volume and with described catalyst is for benchmark, the content of described hydrotreating catalyst I is 3-40%, the content of hydrotreating catalyst II is 10-50%, and the content of hydrotreating catalyst III is 20-70%；Wherein, described hydrotreating catalyst I contains the shaped alumina alumina supporter containing Group IVB metal component and hydrogenation active metals component, with the described shaped alumina alumina supporter containing Group IVB metal component for benchmark, in described carrier, the content of aluminium oxide is 70-99 weight %, the content of titanium oxide is 1-30 weight %, the crushing strength of described shaping carrier is 20-300N/ grain, and pore volume is 0.3-0.9 ml/g, specific surface area more than 30 to less than or equal to 150 meters²/ gram；Described hydrotreating catalyst II is containing the hydrogenation active metals component selected from least one vib and at least one Group VB, count with oxide and with catalyst II for benchmark, the content of described vib metals component is 0.2-15 weight %, and the content of Group VB metal component is 0.2-12 weight %。

2, according to the method described in 1, it is characterized in that, the total amount combined by volume and with described catalyst is for benchmark, and the content of described hydrotreating catalyst I is 5-30%, the content of hydrotreating catalyst II is 20-40%, and the content of hydrotreating catalyst III is 30-60%；Carrier in described hydrotreating catalyst I, with the described shaped alumina alumina supporter containing Group IVB metal component for benchmark, the content of aluminium oxide is 75-96 weight %, the content of titanium oxide is 4-25 weight %, the crushing strength of described carrier is 50-200N/ grain, pore volume is 0.4-0.8 ml/g, specific surface area more than 50 to less than or equal to 140 meters²/ gram；The metal component of the vib in described hydrotreating catalyst II is selected from molybdenum and/or tungsten, the metal component of Group VB is selected from vanadium and/or niobium, count with oxide and with catalyst II for benchmark, the content of described vib metals component is 0.5-12 weight %, and the content of Group VB metal component is 0.5-9 weight %。

3, the method according to 1 or 2, it is characterised in that the crushing strength of the described carrier in described hydrotreating catalyst I is 70-200N/ grain, and pore volume is 0.4-0.8 ml/g, specific surface area more than 80 to less than or equal to 120 meters²/ gram；The metal component of the described vib in described hydrotreating catalyst II is molybdenum or tungsten, Group VB metal component is vanadium, counting with oxide and with catalyst II for benchmark, the content of described vib metals component is 5-12 weight %, and the content of Group VB metal component is 1-9 weight %。

4, according to the method described in 1, it is characterized in that, described hydrotreating catalyst I contains hydrogenation active metals component, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, count with oxide and with described catalyst I for benchmark, the content of group VIII metal component is that the content of group vib metal component is to less than or equal to 10 weight % more than 0 more than 0 to less than or equal to 5 weight %。

5, according to the method described in 4, it is characterized in that, described group VIII metal component is selected from nickel and/or cobalt, vib metal component is selected from molybdenum and/or tungsten, count with oxide and with described catalyst I for benchmark, the content of group VIII metal component is 0.1-3 weight %, and the content of group vib metal component is 0.5-8 weight %。

6, according to the method described in 1, it is characterised in that described hydrotreating catalyst II, containing carrier, characterizes with mercury injection method, and the pore volume of described carrier is 0.95-1.2 ml/g, and specific surface is 50-300 rice²/ gram, described carrier is 10-30nm and diameter be 300-500nm is bimodal pore distribution at diameter, and 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。

7, according to the method described in 6, it is characterised in that the pore volume of described carrier is 0.95-1.15 ml/g, specific surface area is 80-200 rice²/ 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。

8, according to the method described in 6, it is characterised in that containing alkaline earth metal component in the shaping carrier of described hydrotreating catalyst II, counting with oxide and with the carrier of described catalyst II for benchmark, the content of described alkaline earth metal component is 0.1-6 weight %。

9, according to the method described in 8, it is characterised in that one or more in beryllium, magnesium, calcium, strontium and barium of described alkaline earth metal component, counting with oxide and with the carrier of described catalyst II for benchmark, the content of described alkaline earth metal component is 0.3-4 weight %。

10, according to the method described in 9, it is characterised in that described alkaline earth metal component is magnesium, counting with oxide and with the carrier of described catalyst II for benchmark, the content of described alkaline earth metal component is 0.5-2.5 weight %。

11, according to the method described in 1, it is characterized in that, described catalyst III is containing the carrier selected from aluminium oxide and/or silica-alumina, hydrogenation active metals component selected from nickel and/or cobalt, molybdenum and/or tungsten, containing or without one or more adjuvant components in fluorine, boron and phosphorus, count with oxide and with catalyst III for benchmark, the content of described nickel and/or cobalt is 1-5 weight %, the content of molybdenum and/or tungsten is 10-35 weight %, and the content of one or more adjuvant components in fluorine, boron and phosphorus counted with element is for 0-9 weight %。

12, according to the method described in 11, it is characterised in that the support selected from alumina in described catalyst III。

13, according to the method described in 12, it is characterised in that the pore volume of described aluminium oxide is not less than 0.35 ml/g, the pore volume that bore dia is 40～100 angstroms of holes accounts for more than the 80% of total pore volume。

14, according to the method described in 1, it is characterised in that the reaction condition of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1h^-1, hydrogen to oil volume ratio is 600-1500。

15, according to the method described in 14, it is characterised in that the reaction condition 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, meeting the present invention under the described hydrotreating catalyst I premise required, described hydrotreating catalyst I can be commercially available commodity, it would however also be possible to employ prepared by arbitrary prior art。Such as, Catalysts and its preparation method disclosed in 201110222117.0 is entirely appropriate for the present invention, it can be used as here with reference to quoting。

According to 201110222117.0, the preparation method of described catalyst, including preparing carrier the component of load hydrogenation active metals on this carrier, wherein, described carrier is prepared by following step:

(1) hydrated alumina is mixed also molding with titanium-containing compound；

(2) article shaped that step (1) obtains is dried also roasting, described baking temperature is 60-300 DEG C, it is preferably 100-250 DEG C, drying time is 1-10 hour, it is preferred to 2-8 hour, and sintering temperature is 600-1000 DEG C, it is preferably 700-1000 DEG C, more preferably 850-1000 DEG C, roasting time is 1～10 hour, it is preferred to 2-5 hour；

Wherein, the hydrated alumina described in step (1) makes the content of aluminium oxide in final molding thing be 70-99 weight % with the consumption of titanium-containing compound, it is preferred to 75-96 weight %, the content of titanium oxide is 1-30 weight %, it is preferred to 4-25 weight %。

One or more in boehmite, boehmite, aluminium hydroxide, trihydrate aluminium hydroxide of described hydrated alumina, it is preferred to for boehmite。

Described titanium-containing compound is selected from titanium oxide, titanate, molecular sieve containing titanium, titaniferous hydrated alumina, it is preferable that selected from titanium oxide, titanate。

Described molding makes the spheroid that pattern is honeycomb post, Raschig ring or multi-pore channel of shaping carrier。

The described method in supported on carriers hydrogenation active metals component is infusion process, count with oxide and with catalyst I for benchmark, described dipping makes the content of the group VIII metal component in final catalyst be to less than or equal to 5 weight % more than 0, it is preferably 0.1-3 weight % more preferably 0.5-2.5 weight %, the content of group vib metal component is to less than or equal to 10 weight % more than 0, it is preferably 0.5-8 weight %, more preferably 3.5-8 weight %。

Inventor have found that, when being be used for mink cell focus hydrotreatment selected from the combination of the metal component of at least one vib with the catalyst of at least one metal component selected from Group VB with hydrotreating catalyst I of the present invention and hydrotreating catalyst III by hydrogenation active metals component, there is good mink cell focus hydrotreatment performance, be particularly suitable for the hydrotreatment of mink cell focus to produce FCC charging。

In a preferred embodiment, the carrier in described catalyst II is formed alumina, characterizes with mercury injection method, and the pore volume of described carrier is 0.95-1.2 ml/g, and specific surface is 50-300 rice²/ gram, described carrier is 10-30nm and diameter be 300-500nm is bimodal pore distribution at diameter, and 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。Preferably, in described Hydrodemetalation catalyst II, the pore volume of carrier is 0.95-1.15 ml/g, and specific surface area is 80-200 rice²/ 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。

In further preferred embodiment, containing alkaline earth metal component in described shaped alumina alumina supporter, counting and with the carrier of described catalyst II for benchmark with unit's oxide, the content of described alkaline earth metal component is 0.1-6 weight %, it is preferred to 0.3-4 weight %；More preferably 0.5-2.5 weight %。Described alkaline earth metal component preferably is selected from one or more in beryllium, magnesium, calcium, strontium and barium, more preferably magnesium。

According to method provided by the invention, wherein, the preparation method of described catalyst II includes preparing carrier the component of load hydrogenation active metals on this carrier, wherein, the preparation of described carrier includes mixing the modifier P2 of hydrated alumina P1 and the P1 containing boehmite, aftershaping, dry and roasting。

The Mixing ratio by weight of described P1 and P2 is 20-95:5-80, it is preferred to 70-95:5-25。The Mixing ratio by weight of described P1 and P2 refers to the ratio of P1 and P2 shared parts by weight respectively in the mixture of every hundred parts of described P1 and P2。The κ value of P2 is 0 to less than or equal to 0.9, it is preferred to 0 to less than or equal to 0.6。Described κ=DI₂/DI₁。DI₁For the sour peptization index of the hydrated alumina P1 containing boehmite, DI₂Sour peptization index for the modifier P2 of the hydrated alumina P1 containing boehmite。

Wherein, after described acid peptization index D I refers to that the hydrated alumina containing boehmite adds nitric acid by certain acid aluminum ratio, by the hydrated alumina containing boehmite of peptization with Al within certain response time₂O₃The percent of meter, DI=(1-W₂/W₁) × 100%, W₁And W₂Respectively intend before thin water aluminum and acid reaction and with acid reaction after with Al₂O₃The weight of meter。

The mensuration of DI includes: the (1) calcination base (also referred to as butt, calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, weight weight ratio front with burning after its burning) of the mensuration hydrated alumina containing boehmite, is calculated as a；(2) weigh the hydrated alumina W containing boehmite with analytical balance₀Gram, W₀Amount meet with Al₂O₃The W of meter₁It is 6 grams of (W₁/a=W₀), weigh deionized water W gram, W=40.0-W₀, under stirring, the hydrated alumina containing boehmite weighed and deionized water are added mixing in beaker；With 20mL 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), the lower reaction of stirring 8 minutes；(4) being centrifuged step (3) reacted serosity in centrifuges separating, inserted by precipitate in the crucible weighed, afterwards, it is dry 4 hours in 125 DEG C, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W₂Gram；(5) according to formula DI=(1-W₂/W₁) × 100% calculates and obtains。

Described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour, it is preferred to temperature is 100-200 DEG C, and the time is 2-12 hour；The condition of described roasting includes: temperature is that the time is 1-8 hour, it is preferred to temperature is to less than or equal to 1000 DEG C more than 800, and roasting time is 2-6 hour to less than or equal to 1200 DEG C more than 500。

Wherein, being by described hydrated alumina P1 molding containing boehmite, dry by one of P1 method being modified as P2, it all or part of be ground afterwards, sieve, obtaining powder body thing is P2, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are article shaped roastings method one obtained, and sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C, it all or part of are ground afterwards, sieve, and obtaining powder body thing is P2；Hydrated alumina P1 containing boehmite is dodged to do by the three of method, and dodging dry temperature is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C, and obtaining powder body thing is P2；The four of method be by one of method, method two and the modifier that obtains with the three of method in one or more be mixed to get。Preferably, the dry condition in described method one includes: temperature is 100-200 DEG C, and the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is 0.1-6 hour；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour。

In being embodied as, described P2 conveniently can be obtained by following method:

(1) obtain P2 based on dry, including being prepared in regular oxidation alumina supporter process by the hydrated alumina P1 molding according to a conventional method containing boehmite, the tailing of drying by-product, such as: in extruded moulding, bar shaped article shaped is at tailing (being called dry waste material traditionally) dry, integer process by-product, this tailing is milled, sieves and obtain P2。

(2) obtain based on roasting, including being prepared in regular oxidation alumina supporter process by the hydrated alumina P1 molding according to a conventional method containing boehmite, the tailing (being called roasting waste material traditionally) of fired by-product, such as, in roller forming, spheroidal particle is the tailing of by-product in roasting process, is milled by 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 mixed method to obtain P2, the mixed proportion of the modifier P2 that can optionally at random aforementioned several method be respectively obtained is adjusted, and the present invention is not limited in this respect。

Make under the premise that final carrier meets application claims being enough to, the described hydrated alumina P1 containing boehmite is not specially required by the present invention, it can be the boehmite prepared of any prior art, can also be boehmite and the mixture of other hydrated alumina, one or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide of other hydrated alumina described。Such as, pore volume is 0.9-1.4 ml/g, and specific surface is 100-350 rice²/ gram, can and bore dia 8-30nm；Preferred pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, can and the hydrated alumina containing boehmite of bore dia 10-25nm be just particularly suitable for the present invention。In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and can and aperture, be by the described hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, BET N2 adsorption characterize and obtain。

In further preferred embodiment, characterizing with X diffraction, in the described hydrated alumina containing boehmite, boehmite content is not less than 50%, is more preferably not less than 60%。

Preferred described P2 is the particulate matter of 80-300 order, it is preferred that the particulate matter that described P2 is 100-200 order。Here, the granule of described 80-300 order, the granule of preferred 100-200 order refers to that described modifier is through sieve (including step that is broken or that grind if desired), its screening thing (siftage) meets the granule of 80-300 order, the particulate matter of preferred 100-200 order accounts for the percent (by weight) of total amount and is not less than 60%, it is preferred that be not less than 70%。

Require that carrier therein can be made into various easily operated article shaped depending on difference, for instance spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.)。Wherein, it is conventional method by the modifier P2 of described hydrated alumina P1 and the P1 containing the boehmite method mixed, for instance, P1 and the P2 of powder body is put into mixing in stirring-type batch mixer according to ingredient proportion。

Described molding carries out according to a conventional method。When molding, for instance extruded moulding, for ensureing that described molding is smoothed out, it is possible to add in described mixture water, extrusion aid and/or adhesive, containing or without expanding agent, then extrusion molding, be dried afterwards and roasting。Described extrusion aid, the kind of peptizer 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, starch, polyvinyl alcohol, PVOH, described peptizer can be mineral acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant。Synthetic cellulose therein is preferably one or more in hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in Polyethylene Glycol, poly-propanol, polyvinyl alcohol, and surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivant thereof, molecular weight are the propenyl copolymer of 200-10000 and one or more in maleic acid copolymer。

Time in the shaping carrier of described Hydrodemetalation catalyst II containing alkaline earth metal component, the preparation at described carrier includes the step introducing alkaline earth metal component。The introducing method of described alkaline earth metal component is conventional method。Such as, in a concrete embodiment preparing carrier, the method of the compound introducing alkaline including earth metal in the mixture of the modifier P2 of described hydrated alumina P1 and the P1 containing boehmite is that the compound of alkaline including earth metal is configured to aqueous solution, this aqueous solution is mixed into while described P1 and P1 mixes or again this aqueous solution is mixed into after described P1 and P1 mixes, aftershaping, dry and roasting。The compound of described alkaline including earth metal can be one or more in the water soluble compound of arbitrary alkaline-earth metal。Such as, the water soluble compound magnesium nitrate of magnesium。Counting with oxide and with described carrier for benchmark, the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier be 0.1-6 weight %, it is preferred to 0.3-4 weight %, more preferably 0.5-2.5 weight %。

Described hydrogenation active metals component is carried under the premise on described carrier being enough to, the carrying method of hydrogenation active metals component in the preparation of described catalyst II is not particularly limited by the present invention, preferred method is infusion process, dipping solution including the compound prepared containing described metal, afterwards with the carrier described in this solution impregnation, it is dried afterwards, roasting or not roasting。Described dipping method is conventional method, for instance, it is possible to it is excessive immersion stain, hole saturation infusion process。Described drying condition includes: temperature is 100-250 DEG C, and the time is 1-10 hour；Described roasting condition includes: temperature is 360-500 DEG C, and the time is 1-10 hour。Preferred described drying condition includes: temperature is 100-140 DEG C, and the time is 1-6 hour；Described roasting condition includes: temperature is 360-450 DEG C, and the time is 2-6 hour。

Wherein, one or more (the including water-soluble compound under cosolvent exists) in their water soluble compound it are selected from containing the compound of described metal。Molybdenum for vib, it is possible to selected from one or more in molybdenum oxide, molybdate, paramolybdate, it is preferable that molybdenum oxide therein, ammonium molybdate, ammonium paramolybdate；Tungsten for vib, it is possible to selected from one or more in tungstates, metatungstate, ethyl metatungstate, it is preferable that ammonium metatungstate therein, ethyl ammonium metatungstate；Vanadium for Group VB, it is possible to selected from one or more in vanadic anhydride, ammonium vanadate, ammonium metavanadate, Sulfovanadic acid, vanada polyacid, it is preferable that ammonium metavanadate therein, ammonium vanadate。

According to method provided by the invention, wherein said hydrotreating catalyst II can also contain any material not affecting the catalytic performance that the present invention provides catalyst performance maybe can improve catalyst provided by the invention。As contained the components such as phosphorus, counting with oxide and with catalyst for benchmark, the content of said components is less than 10 weight %, it is preferred to 0.5-5 weight %。

When in described Hydrodemetalation catalyst II possibly together with components such as phosphorus, the introducing method of the component such as described phosphorus can be arbitrary method, can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix, molding roasting；Can be that the compound containing components such as described phosphorus is configured to after mixed solution with the compound containing hydrogenation active metals component to contact with described carrier；Can also is that and contact with described carrier after the compound containing components such as phosphorus is individually prepared solution and roasting。When the components such as phosphorus introduce described carrier respectively with hydrogenation active metals, preferably first contact and roasting with described carrier with containing auxiliary compound solution, contact with the solution of the compound containing hydrogenation active metals component more afterwards, the such as method by impregnating, described sintering temperature is 400-600 DEG C, being preferably 420-500 DEG C, roasting time is 2-6 hour, it is preferred to 3-6 hour。

In the present invention, the effect of described catalyst III is in that the macromolecular compounds such as saturated polycyclic aromatic hydrocarbon so that it is in be more difficult to the sulfur of elimination, the impurity such as nitrogen removes further, the carbon residue in elimination raw oil, improves product property simultaneously。Under being enough to the premise realizing above-mentioned functions, described catalyst III is not had other to limit by the present invention, and namely catalyst III can be selected from the catalyst such as the hydrofinishing of arbitrary prior art offer, hydrotreatment。They can be commercially available commodity or adopt any existing method to prepare。

Usually, this type of catalyst usually contains heat-resistant inorganic oxide carrier, hydrogenation active metals component。Such as, described catalyst III is containing the carrier selected from aluminium oxide and/or silica-alumina, hydrogenation active metals component selected from nickel and/or cobalt, molybdenum and/or tungsten, containing or without one or more adjuvant components in fluorine, boron and phosphorus, count with oxide and with catalyst III for benchmark, the content of described nickel and/or cobalt is the content of 1-5 weight %, molybdenum and/or tungsten is 10-35 weight %, and the content of one or more adjuvant components in fluorine, boron and phosphorus counted with element is for 0-9 weight %。

Such as, the disclosed a kind of Hydrobon catalyst of ZL97112397, it consists of nickel oxide 1～5 weight %, tungsten oxide 12～35 weight %, fluorine 1～9 weight %, all the other are aluminium oxide, this aluminium oxide is to be composited according to the weight ratio of 75: 25～50: 50 by one or more little porous aluminum oxides and one or more macroporous aluminium oxides, wherein little porous aluminum oxide is that bore dia accounts for the aluminium oxide of total pore volume more than 95% less than the pore volume in 80 angstroms of holes, and macroporous aluminium oxide is the aluminium oxide that the pore volume in 60～600 angstroms of holes of bore dia accounts for total pore volume more than 70%。

ZL00802168 discloses a kind of Hydrobon catalyst, and this catalyst contains a kind of alumina support and the load at least one group VIB metal on this alumina support and/or at least one group VIII metal。The pore volume of described alumina support is not less than 0.35 ml/g, and the pore volume that bore dia is 40～100 angstroms of holes accounts for more than the 80% of total pore volume, and it adopts special method to prepare。

ZL200310117323 discloses a kind of Hydrobon catalyst, this catalyst contains a kind of alumina support and load molybdenum on this carrier, nickel and tungsten metal component, count with oxide and with catalyst for benchmark, described catalyst contains the molybdenum of 0.5-10 weight %, the nickel of 1-10 weight %, the tungsten of 12-35 weight % and the carrier of aequum, the preparation method of described catalyst includes using the solution of molybdate compound successively and nickeliferous, the solution impregnation of alumina carrier of tungsten compound, wherein said alumina support is dried after by the solution impregnation of molybdate compound, with nickeliferous, it is dried and roasting after the solution impregnation of tungsten compound, baking temperature is 100-300 DEG C, drying time is 1-12 hour, sintering temperature is 320-500 DEG C, roasting time is 1-10 hour。

These catalyst all can as described catalyst III for the present invention。About the more detailed preparation method of above-mentioned catalyst, all on the books in above-mentioned patent documentation, in the lump they are quoted as a part for present invention here。

According to method provided by the invention; described hydrogenation protecting catalyst I, Hydrodemetalation catalyst II and the hydrotreating catalyst III of including can be layered successively and fill in same reactor; can also be fill in successively in the reactor of several series connection to use, this present invention is not particularly limited。

According to method provided by the invention; wherein; include hydrogenation protecting catalyst I, Hydrodemetalation catalyst II and hydrotreating catalyst III catalyst combine before, afterwards or they between any two, it is possible to include any other catalyst or filler contributing to improving described catalyst composite behaviour。Such as, added such as fillers such as porcelain ball, active supporters before described Hydrodemetalation catalyst I, to improve raw 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 conventional method in this area, described hydrotreating catalyst is before the use, generally can be in presence of hydrogen, presulfurization is carried out with sulfur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can carry out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide。

According to method provided by the invention, the normal condition that reaction condition is heavy oil hydrotreatment of described hydrotreatment reaction, for instance, described reaction condition includes: hydrogen dividing potential drop 6-20MPa, and 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, wherein preferred hydrogen dividing potential drop 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。

Raw material according to described method is selected from one or more in the poor crude oil of character, decompression residuum, deep drawing wax oil, frivolous coal tar, wax tailings etc.。

Being less than 1.2% according to the asphalt content of oil after the hydrotreatment that described method obtains, ferrum, calcium content are 15 below μ g/g, and W metal+V content is 20 below μ g/g, sulfur content less than 0.5%, and carbon residue content is less than 6.0%。

Detailed description of the invention

The present invention is described further for the following examples。

Embodiment 1-4 illustrates to be suitable for carrier preparing hydrotreating catalyst I and preparation method thereof。

Embodiment 1

By the mixing of 1000 grams, 100 grams titanium dioxides of aluminium hydrate powder, in a mold compressing for high 10mm, diameter 40mm, wall thickness 2mm, include the honeycomb cylinder in 100 triangle ducts, after dry 4 hours, in 880 DEG C of roastings 4 hours, obtain carrier Z I 1 in 120 DEG C。Carrier Z I 1 physico-chemical property is in Table 1。

Embodiment 2

Aluminium hydrate powder 200 grams and aluminum titanate powder 80 grams is mixed, is pressed into external diameter 16mm in a mold and includes the seven apertures in the human head ball in diameter 3mm duct, dry 3 hours in 80 DEG C, in 950 DEG C of constant temperature 2 hours, obtain carrier Z I 2。Carrier Z I 2 physico-chemical property is in Table 1。

Embodiment 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 after dry 2 hours, in 900 DEG C of constant temperature 3 hours, obtain carrier Z I 3。Carrier Z I 3 physico-chemical property is in Table 1。

Embodiment 4

Aluminium hydrate powder 1000 grams is mixed with 40 grams of titanium dioxides, is pressed into high 10mm, diameter 8.0mm, wall thickness 1mm in a mold, includes the honeycomb cylinder in 15 irregular ducts, after dry 4 hours, in 980 DEG C of roastings 2 hours, obtain carrier Z I 4 in 100 DEG C。Carrier Z I 4 physico-chemical property is in Table 1。

Table 1

Example	1	2	3	4
					Bearer number	ZⅠ1	ZⅠ2	ZⅠ3	ZⅠ4
Al₂O₃, weight %	87	94	91	93
					TiO₂, weight %	13	6	9	7
Bed voidage, %	53	48	49	45
					Crushing strength, N/ grain	80	120	80	90
Pore volume, ml/g	0.62	0.48	0.60	0.68
					Specific surface, m²/g	105	80	90	110

Wherein, the measuring method of crushing strength carries out according to RIPP25-90 catalyst compressive resistance algoscopy。Vehicle group becomes value of calculation, and pore volume, specific surface area adopt BET to measure。

Example 5-8 illustrates catalyst I for the present invention and preparation method thereof。

Embodiment 5

Z2200 gram of the carrier for the treatment of excess syndrome example 1 preparation, with 500 milliliters containing WO370 g/l, the ammonium metatungstate of NiO15 g/l and nickel nitrate mixed solution impregnate 1 hour, in 100 DEG C of drying 4 hours after filtration, 450 DEG C of roastings 4 hours, obtain protective agent C I 1。The composition of protective agent C I 1 is listed in table 2。

Embodiment 6

Z2200 gram of the carrier for the treatment of excess syndrome example 2 preparation, with 500 milliliters containing MoO350 g/l, the ammonium molybdate of NiO8 g/l and nickel nitrate mixed solution impregnate 1 hour, in 120 DEG C of drying 2 hours after filtration, 480 DEG C of roastings 4 hours, obtain protective agent C I 2。The composition of protective agent C I 2 is listed in table 2。

Embodiment 7

Z3200 gram of the carrier for the treatment of excess syndrome example 3 preparation, with 500 milliliters containing MoO380 g/l, the ammonium molybdate of NiO20 g/l and nickel nitrate solution impregnate 1 hour, in 120 DEG C of drying 2 hours after filtration, 500 DEG C of roastings 4 hours, obtain protective agent C I 3。The composition of protective agent C I 3 is listed in table 2。

Embodiment 8

Z5200 gram of the carrier for the treatment of excess syndrome example 4 preparation, with 500 milliliters containing MoO340 g/l, the molybdic acid acid ammonium of CoO12 g/l and cobalt nitrate mixed solution impregnate 1 hour, in 90 DEG C of drying 4 hours after filtration, 480 DEG C of roastings 4 hours, obtain protective agent C I 4。The composition of protective agent C I 4 is listed in table 2。

Table 2

Embodiment 9-13 illustrates P1 and P2 preparing catalyst II carrier of the present invention and preparation method thereof。

The boehmite used below in an example includes:

P1-1: dry glue powder that Chang Ling catalyst branch company produces (pore volume is 1.2 mls/g, and specific surface is 280 meters 2/ gram, can and bore dia 15.8nm。Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 15.8)。

P1-2: dry glue powder that Yantai Heng Hui Chemical Co., Ltd. produces (pore volume is 1.1 mls/g, and specific surface is 260 meters 2/ gram, can and bore dia 12nm。Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 17.2)。

Embodiment 9

Weigh 1000 grams of P1-1, add the aqueous solution 1440 milliliters containing 10 milliliters of 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 in 120 DEG C dry 4 hours, obtain dried strip, by dried strip shaping, sieve, the length dried strip material (being commonly referred to as industrially drying bar waste material) less than 2mm is milled, sieves, take wherein 100～200 mesh sieves and divide, obtain the modifier P2A of P1-1。The k value of P2A is in Table 3。

Embodiment 10

Weigh 1000 grams of P1-1, dodge dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1。The k value of P2B is in Table 3。

Embodiment 11

The each 200 grams of Homogeneous phase mixing of P2B that the P2A obtain embodiment 1 and embodiment 10 obtain, obtain the modifier P2C of P1-1。The k value of P2C is in Table 3。

Embodiment 12

Weigh 1000 grams of P1-2, add the aqueous solution 1440 milliliters containing 10 milliliters of 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 in 120 DEG C dry 4 hours, 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the length carrier strip material less than 2mm (being commonly referred to as industry carrier waste material) is milled, sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier P2D of P1-2。The k value of P2D is in Table 3。

Embodiment 13

Weigh 1000 grams of P1-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier P2E of P1-2。The k value of P2E is in Table 3。

Table 3

Embodiment	Raw material	k
			1	P2A	0.5
2	P2B	0.4
			3	P2C	0.4
4	P2D	0
			5	P2E	0.3

Embodiment 14-21 illustrates carrier preparing catalyst II of the present invention and preparation method thereof。Comparative example 1-2 illustrates carrier of reference catalyst and preparation method thereof。

Embodiment 14

Weigh 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing prepared with embodiment 9, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), aqueous solution 1440 milliliters containing magnesium nitrate 14.7g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z II 1。The character of carrier Z II 1 is listed in table 4。

Embodiment 15

Weigh 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing prepared with embodiment 10, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 14.7g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z II 2。The character of carrier Z II 2 is listed in table 4。

Embodiment 16

Weigh 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 11, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 14.7g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 950 DEG C of roastings of this article shaped 3 hours, obtains carrier Z II 3。The character of carrier Z II 3 is listed in table 4。

Comparative example 1

Weigh 1000 grams of P1-1, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 14.7g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ II 1。The character of carrier DZ II 1 is listed in table 4。

Embodiment 17

Weigh 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 12, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), aqueous solution 1440 milliliters containing magnesium nitrate 14.7g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z II 4。The character of carrier Z II 4 is listed in table 4。

Embodiment 18

Weigh 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 13, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 51.5g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z II 5。The character of carrier Z II 5 is listed in table 4。

Embodiment 19

Weigh 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 11, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 51.5g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtains carrier Z II 6。The character of carrier Z II 6 is listed in table 4。

Comparative example 2

Weigh 1000 grams of P1-2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 51.5g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ II 2。The character of carrier DZ II 2 is listed in table 4。

Embodiment 20

Weigh 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 12, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 51.5g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z7。The character of carrier Z7 is listed in table 2。

Embodiment 21

Weigh 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 13, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing magnesium nitrate 51.5g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z II 8。The character of carrier Z II 8 is listed in table 4。

Table 4

Embodiment 22～29 is used for catalyst II of the present invention and preparation method thereof is described。Comparative example 3-5 illustrates reference catalyst and preparation method thereof。

Wherein, in catalyst, the content of active metal component adopts Xray fluorescence spectrometer to measure (all appts is Rigaku electric machine industry Co., Ltd. 3271 type Xray fluorescence spectrometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP133-90)。

Embodiment 22

Taking 200 grams of carrier Z II 1, with 220 milliliters containing MoO380 g/l, the ammonium heptamolybdate of V2O516 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst C II 1, C II 1 is listed in table 5。

Embodiment 23

Taking 200 grams of carrier Z II 2, with 220 milliliters containing MoO380 g/l, the ammonium heptamolybdate of V2O516 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst C II 2, C II 2 is listed in table 5。

Embodiment 24

Taking 200 grams of carrier Z II 3, with 220 milliliters containing MoO380 g/l, the ammonium heptamolybdate of V2O516 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst C II 3, C II 3 is listed in table 5。

Comparative example 3

Taking 200 grams of carrier Z II 1, with 220 milliliters containing MoO380 g/l, the ammonium heptamolybdate of NiO16 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, the composition obtaining Hydrodemetalation catalyst DC II 1, DC II 1 is listed in table 5。

Comparative example 4

Taking 200 grams of DZ II 1, with 220 milliliters containing MoO380 g/l, the ammonium heptamolybdate of NiO16 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, and 400 DEG C of roastings 2 hours, the composition obtaining Hydrodemetalation catalyst DC II 2, DC II 2 is listed in table 5。

Comparative example 5

Taking 200 grams of carrier DZ II 2, with 500 milliliters containing MoO380 g/l, the ammonium heptamolybdate of V2O516 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst DC II 3, DC II 3 is listed in table 5。

Embodiment 25

Taking 200 grams of carrier Z II 4, with 220 milliliters containing MoO390 g/l, the ammonium heptamolybdate of V2O520 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 4。The composition of Hydrodemetalation catalyst C II 4 is listed in table 5。

Embodiment 26

Taking 200 grams of Z II 5, with 220 milliliters containing WO390 g/l, the ammonium tungstate of V2O520 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 5。The composition of Hydrodemetalation catalyst C II 5 is listed in table 5。

Embodiment 27

Taking 200 grams of Z II 6, with 220 milliliters containing WO3100 g/l, the ammonium tungstate of V2O530 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 6。The composition of Hydrodemetalation catalyst C II 6 is listed in table 5。

Embodiment 28

Taking 200 grams of Z II 7, with 220 milliliters containing MoO360 g/l, the ammonium tungstate of V2O560 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 7。The composition of Hydrodemetalation catalyst C II 7 is listed in table 5。

Embodiment 29

Taking 200 grams of Z II 8, with 220 milliliters containing WO360 g/l, the ammonium tungstate of V2O560 g/l and ammonium metavanadate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 8。The composition of Hydrodemetalation catalyst C II 8 is listed in table 5。

Table 5

Embodiment 30-37 illustrates that the present invention provides the effect of method hydrotreating heavy feedstocks。Comparative example 6-8 illustrates the effect of reference method hydrotreating heavy feedstocks。

With Fe+Ca content for 36ppm, Ni+V content be 96ppm, sulfur content be 4.1%, carbon residue be the mixed residue oil of 12.8% for raw material, 500 milliliters of fixed bed reactors are evaluated catalyst。

In oil sample, the content of ferrum, calcium, nickel and vanadium adopts inductive coupling plasma emission spectrograph (ICP-AES) to measure (instrument is U.S.'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, sulfur 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)。

Hydrotreating catalyst III:

Hydrotreating catalyst III-1, prepares according to the embodiment 6 in patent ZL97112397.7, and it consists of nickel oxide 2.3 weight %, tungsten oxide 22.0 weight %, and fluorine 4 weight %, all the other are aluminium oxide。

Hydrotreating catalyst III-2, prepares according to the embodiment 37 in patent ZL00802168.6, and it consists of nickel oxide 2.6 weight %, molybdenum oxide 23.6 weight %, and fluorine 2.3 weight %, all the other are aluminium oxide。

Hydrotreating catalyst III-3, prepares according to the embodiment 3 in patent ZL200310117323.0, and it consists of nickel oxide 2.1 weight %, molybdenum oxide 2.5 weight %, and tungsten oxide 25.4 weight %, all the other are aluminium oxide。

Catalyst usage ratio and process conditions are listed in table 6, and after operating 1000 hours, product property is listed in table 7。

Comparative example 6

Catalyst adopts the combination of CI1, DCII1, C III 1, and the volume of each catalyst amount when process conditions are listed in table 6, and sample analysis after operating 1000 hours, result is listed in table 7。

Comparative example 7

Catalyst adopts the combination of CI2, DCII2, C III 2, and the volume of each catalyst amount when process conditions are listed in table 6, and sample analysis after after operating 1000 hours, result is listed in table 7。

Comparative example 8

Catalyst adopts the combination of CI3, DCII3, C III 3, and the volume of each catalyst amount when process conditions are listed in table 6, and sample analysis after after operating 1000 hours, result is listed in table 7。

Table 6

Table 7

It can be seen that adopt the present invention to provide 1000 hours back end hydrogenations of method operating to process the obvious low reference methods of impurity content such as the metal of product, sulfur, carbon residues。

Claims

1. a catalytic cracking material pretreatment method, including at hydrotreating reaction conditions, raw oil is contacted with the catalyst combination including hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III successively, the total amount combined by volume and with described catalyst is for benchmark, the content of described hydrotreating catalyst I is 3-40%, the content of hydrotreating catalyst II is 10-50%, and the content of hydrotreating catalyst III is 20-70%；Wherein, described hydrotreating catalyst I contains the shaped alumina alumina supporter containing Group IVB metal component and hydrogenation active metals component, with the described shaped alumina alumina supporter containing Group IVB metal component for benchmark, in described carrier, the content of aluminium oxide is 70-99 weight %, the content of titanium oxide is 1-30 weight %, the crushing strength of described shaping carrier is 20-300N/ grain, and pore volume is 0.3-0.9 ml/g, specific surface area more than 30 to less than or equal to 150 meters²/ gram；Described hydrotreating catalyst II, containing carrier, characterizes with mercury injection method, and the pore volume of the carrier of described catalyst II is 0.95-1.2 ml/g, and specific surface is 50-300 rice²/ gram, described carrier is 10-30nm and diameter be 300-500nm is bimodal pore distribution at diameter, and 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；Described hydrotreating catalyst II is containing the hydrogenation active metals component selected from least one vib and at least one Group VB, count with oxide and with catalyst II for benchmark, the content of described vib metals component is 0.2-15 weight %, and the content of Group VB metal component is 0.2-12 weight %。

2. according to the method described in 1, it is characterized in that, the total amount combined by volume and with described catalyst is for benchmark, and the content of described hydrotreating catalyst I is 5-30%, the content of hydrotreating catalyst II is 20-40%, and the content of hydrotreating catalyst III is 30-60%；Carrier in described hydrotreating catalyst I, with the described shaped alumina alumina supporter containing Group IVB metal component for benchmark, the content of aluminium oxide is 75-96 weight %, the content of titanium oxide is 4-25 weight %, the crushing strength of described carrier is 50-200N/ grain, pore volume is 0.4-0.8 ml/g, specific surface area more than 50 to less than or equal to 140 meters²/ gram；The metal component of the vib in described hydrotreating catalyst II is selected from molybdenum and/or tungsten, the metal component of Group VB is selected from vanadium and/or niobium, count with oxide and with catalyst II for benchmark, the content of described vib metals component is 0.5-12 weight %, and the content of Group VB metal component is 0.5-9 weight %。

3. the method according to 1 or 2, it is characterised in that the crushing strength of the described carrier in described hydrotreating catalyst I is 70-200N/ grain, and pore volume is 0.4-0.8 ml/g, specific surface area more than 80 to less than or equal to 120 meters²/ gram；The metal component of the described vib in described hydrotreating catalyst II is molybdenum or tungsten, Group VB metal component is vanadium, counting with oxide and with catalyst II for benchmark, the content of described vib metals component is 5-12 weight %, and the content of Group VB metal component is 1-9 weight %。

4. according to the method described in 1, it is characterized in that, described hydrotreating catalyst I contains hydrogenation active metals component, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, count with oxide and with described catalyst I for benchmark, the content of group VIII metal component is that the content of group vib metal component is to less than or equal to 10 weight % more than 0 more than 0 to less than or equal to 5 weight %。

5. according to the method described in 4, it is characterized in that, described group VIII metal component is selected from nickel and/or cobalt, vib metal component is selected from molybdenum and/or tungsten, count with oxide and with described catalyst I for benchmark, the content of group VIII metal component is 0.1-3 weight %, and the content of group vib metal component is 0.5-8 weight %。

6., according to the method described in 1, it is characterised in that the pore volume of described carrier is 0.95-1.15 ml/g, specific surface area is 80-200 rice²/ 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。

7. according to the method described in 6, it is characterised in that containing alkaline earth metal component in the shaping carrier of described hydrotreating catalyst II, counting with oxide and with the carrier of described catalyst II for benchmark, the content of described alkaline earth metal component is 0.1-6 weight %。

8. according to the method described in 7, it is characterised in that one or more in beryllium, magnesium, calcium, strontium and barium of described alkaline earth metal component, counting with oxide and with the carrier of described catalyst II for benchmark, the content of described alkaline earth metal component is 0.3-4 weight %。

9. according to the method described in 8, it is characterised in that described alkaline earth metal component is magnesium, counting with oxide and with the carrier of described catalyst II for benchmark, the content of described alkaline earth metal component is 0.5-2.5 weight %。

10. according to the method described in 1, it is characterized in that, described catalyst III is containing the carrier selected from aluminium oxide and/or silica-alumina, hydrogenation active metals component selected from nickel and/or cobalt, molybdenum and/or tungsten, containing or without one or more adjuvant components in fluorine, boron and phosphorus, count with oxide and with catalyst III for benchmark, the content of described nickel and/or cobalt is 1-5 weight %, the content of molybdenum and/or tungsten is 10-35 weight %, and the content of one or more adjuvant components in fluorine, boron and phosphorus counted with element is for 0-9 weight %。

11. according to the method described in 10, it is characterised in that the support selected from alumina in described catalyst III。

12. according to the method described in 11, it is characterised in that the pore volume of described aluminium oxide is not less than 0.35 ml/g, the pore volume that bore dia is 40-100 angstrom of hole accounts for more than the 80% of total pore volume。

13. according to the method described in 1, it is characterised in that the reaction condition of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1h^-1, hydrogen to oil volume ratio is 600-1500。

14. according to the method described in 13, it is characterised in that the reaction condition 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。