CN104449832B - A kind of catalytically cracked stock weighted BMO spaces method - Google Patents

Abstract

A kind of catalytically cracked stock weighted BMO spaces method, including at hydrotreating reaction conditions, raw oil is contacted with a kind of catalyst combination, the combination of described catalyst includes hydrotreating catalyst I and hydrotreating catalyst II, in the combination of described catalyst catalyst I make with the layout of catalyst II described raw oil successively with include catalyst I and catalyst II contacts, the total amount combined by volume and with described catalyst is for benchmark, the content of described catalyst I is 5-40%, the content of catalyst II is 60-95%, wherein, described catalyst I is containing the boron-containing alumina carrier with structure of double peak holes, characterize with mercury injection method, the pore volume of described carrier is 0.8-1.2 ml/g, specific surface area is 120-400 rice²/ gram, diameter is the 58-80% that the pore volume in 6-30nm hole accounts for total pore volume, diameter therein be the pore volume in 10-30nm hole lower than the 55% of total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume。

Description

A kind of catalytically cracked stock weighted BMO spaces method

Technical field

The present invention relates to a kind of 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, reducing Sulfur Content in Catalytic Cracking Gasoline, usually require that in catalyzed cracking processing raw oil, W metal+V content should lower than 1ppm, sulfur content is lower than 3000ppm。But owing to feedstock property is constantly deteriorated, heavy oil (typically refers to the raw oil of boiling point more than 350 DEG C), and hydrotreatment 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 produce high-quality catalytically cracked material, improves the optimum selection of heavy-oil hydrogenation processing procedure。

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 charge oil hydrotreating method new, that be suitable for catalytically cracked material pretreatment。

The content that the present invention relates to includes:

1. a catalytically cracked stock weighted BMO spaces method, including at hydrotreating reaction conditions, raw oil is contacted with a kind of catalyst combination, the combination of described catalyst includes hydrotreating catalyst I and hydrotreating catalyst II, in the combination of described catalyst catalyst I make with the layout of catalyst II described raw oil successively with include catalyst I and catalyst II contacts, the total amount combined by volume and with described catalyst is for benchmark, the content of described catalyst I is 5-40%, the content of catalyst II is 60-95%, wherein, described catalyst I is containing the boron-containing alumina carrier with structure of double peak holes, characterize with mercury injection method, the pore volume of described carrier is 0.8-1.2 ml/g, specific surface area is 120-400 rice²/ gram, diameter is the 58-80% that the pore volume in 6-30nm hole accounts for total pore volume, diameter therein be the pore volume in 10-30nm hole lower than the 55% of total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume。

2, according to the method described in 1, it is characterised in that in described catalyst I, the pore volume of carrier is 0.9-1.15 ml/g, specific surface area is 150-300 rice²/ gram, diameter is the 60-75% that the pore volume in 6-30nm hole accounts for total pore volume, diameter therein be the pore volume in 10-30nm hole lower than the 54% of total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume。

3, according to the method described in 1, it is characterised in that with described carrier for benchmark and in oxide, in described carrier, the content of boron is 0.5-8 weight %。

4, according to the catalyst described in 3, it is characterised in that with the carrier of described catalyst I for benchmark and in oxide, in the carrier of described catalyst I, the content of boron is 1-6 weight %。

5, according to the catalyst described in 4, it is characterised in that with the carrier of described catalyst I for benchmark and in oxide, in the carrier of described catalyst I, the content of boron is 1.5-4 weight %。

6, according to the method described in 1, it is characterized in that, hydrogenation active metals component in described catalyst I is selected from least one metal component of group VIII and at least one metal component of group VIB, count with oxide and with catalyst I for benchmark, the content of described metal component of group VIII is 0.5-10 weight %, and the content of metal component of group VIB is 0.5-15 weight %。

7, according to the method described in 6, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, metal component of group VIB is selected from molybdenum and/or tungsten, count with oxide and with catalyst I for benchmark, the content of described metal component of group VIII is 0.8-8 weight %, and the content of metal component of group VIB is 1-12 weight %。

8, according to the method described in 7, it is characterised in that count with oxide and with catalyst I for benchmark, the content of described metal component of group VIII is 1-6 weight %, and the content of metal component of group VIB is 2-10 weight %。

9, according to the method described in 1, it is characterised in that the total amount combined by volume and with described catalyst is for benchmark, and the content of the catalyst I in the combination of described catalyst is 10-35%, and the content of catalyst II is 65-90%。

10, according to the method described in 1, it is characterized in that, described catalyst II contains 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, with catalyst II for benchmark, the nickel counted with oxide and/or the content of cobalt are 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 II。

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 angstroms of holes 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 0.2-3h^-1, hydrogen to oil volume ratio is 300-1500。

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 is 8-18MPa, and temperature is 320-420 DEG C, and during liquid, volume space velocity is 0.3-2h^-1, hydrogen to oil volume ratio is 400-1000。

In the present invention, the carrier of described catalyst I can be made into various easily operated article shaped depending on different requirement, for instance spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.)。

The preparation method of this carrier includes being mixed by the modifier P2 of hydrated alumina P1 and the P1 containing boehmite and introducing boron-containing compound in the mixture, aftershaping, dry also roasting, wherein, count with oxide and with described carrier total amount for benchmark, the introduction volume of described boron-containing compound makes the content of boron in described carrier be 0.5-8 weight %, described dry condition includes: temperature is 40-350 DEG C, time is 1-24 hour, the condition of described roasting includes: temperature is to less than 850 DEG C more than 500, time is 1-8 hour, the Mixing ratio by weight of described P1 and P2 is 20-95:5-80, the κ value of P2 is 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For the sour peptization index of the hydrated alumina P1 containing boehmite, DI2 is the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite。

Wherein, count with oxide and with described carrier total amount for benchmark, it is preferable that the introduction volume of described boron-containing compound makes the content of boron in described carrier be 1-6 weight %；The Mixing ratio by weight of described P1 and P2 is 70-95:5-30；The k value of described P2 is 0 to less than or equal to 0.6；The pore volume of described P1 is 0.9-1.4 ml/g, and specific surface is 100-350 rice²/ gram, most probable bore dia 8-30nm。

It is preferred that, the introduction volume of described boron-containing compound makes the content of boron in described carrier be 1-4 weight %；The pore volume of described P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, most probable bore dia 10-25nm。

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。

Preferred described dry condition includes: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting includes: temperature is 600-800 DEG C, and roasting time is 2-6 hour。

In the present invention, 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。

Dry condition in preferred 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。

Preferred described P2 is the particulate matter of 80-300 order in P1 modifier；The more preferably particulate matter of 100-200 order。

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。The method introducing boron-containing compound in described P1 and P2 mixture is conventional method, such as, can be directly the desired amount of boron-containing compound is mixed in aforesaid P1 and P2 mixed process, or boron-containing compound 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。Described boron-containing compound can one or more in the water soluble compound of preferred boracic。Such as, one or more in the water-soluble inorganic salt of boracic。

Described molding carries out according to a conventional method, for instance, a kind of method in spin, tabletting and extruded moulding or the combination of several 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。

In the preparation of the described carrier of catalyst I, after described acid peptization index D I refers to that the hydrated alumina containing boehmite and the hydrated alumina modifier containing boehmite add 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 contain before the hydrated alumina of boehmite and acid reaction and with acid reaction after with Al₂O₃The weight of meter。

The mensuration of DI includes: (1) (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours calcination base (also referred to as the butt) content of the mensuration hydrated alumina containing boehmite, weight weight ratio front with burning after its burning, it is expressed as a percentage), it 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。

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。

In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and most probable pore size, 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, the boehmite content in the described hydrated alumina P1 containing boehmite is not less than 50%, is more preferably not less than 60%。

Inventors of the present invention have surprisingly found that, hydrated alumina P1 containing boehmite is carried out heat treatment modified, the peptization index of its modifier changes, by this modifier with without heat treated P1 mixed-forming, dry and roasting after, obtained carrier has obvious bimodal pore distribution。Particularly at the granule by 80-300 order therein, it is preferable that the granule of 100-200 order with without after heat treated part mixed-forming, dry and roasting, obtained carrier bimodal in each unimodal pore size distribution concentrate especially。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%。

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。Wherein, the preferred span of parts by weight of P1 is 20-95, more preferably 70-95；The preferred span of parts by weight of P2 is 5-80, more preferably 5-30。

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 aforementioned several method is respectively obtained does not limit。

In the present invention, the preparation of described catalyst I includes adopting the method for dipping to introduce hydrogenation active metals component on carrier, it is dried afterwards, the step of roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one VIIIth race and the metal component of at least one group VIB, count with oxide and with catalyst for benchmark, the consumption of the described compound containing hydrogenation active metals concentration in described dipping solution and described solution makes the content of the metal component of the VIIIth race in final catalyst be 0.5-10 weight %, the content of the metal component of described group VIB is 0.5-15 weight %；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。

Preferably the metal component of described VIIIth race is selected from nickel and/or cobalt, the metal component of group VIB is selected from molybdenum and/or tungsten, count with oxide and with catalyst for benchmark, the consumption of the described compound containing hydrogenation active metals concentration in described dipping solution and described solution makes the content of the metal component of group VIII in final catalyst be 0.8-8 weight %, and the content of the metal component of group VIB is 1-12 weight %；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。

Further, count with oxide and with catalyst for benchmark, preferably the consumption of the described compound containing hydrogenation active metals concentration in described dipping solution and described solution makes the content of the metal component of group VIII in final catalyst be 1-6 weight %, and the content of the metal component of group VIB is 2-10 weight %。

Described dipping method is conventional method, for instance, it is possible to it is excessive immersion stain, hole saturation infusion process。Described is selected from one or more in the soluble compound in them, one or more in molybdenum oxide, molybdate, paramolybdate, it is preferable that molybdenum oxide therein, ammonium molybdate, ammonium paramolybdate containing the metal component compound selected from VI B race；One or more in tungstates, metatungstate, ethyl metatungstate, it is preferable that ammonium metatungstate therein, ethyl ammonium metatungstate。One or more in the described soluble compound being selected from them containing the compound selected from VIII race's metal component, one or more in the soluble complexes of cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt, it is preferred to cobalt nitrate, basic cobaltous carbonate；One or more in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, Nickel dichloride. and nickel, it is preferred to nickel nitrate, basic nickel carbonate。

According to catalyst I provided by the invention, it is also possible to containing any addO-on therapy not affecting the catalytic performance that the present invention provides catalyst performance maybe can improve catalyst provided by the invention。As contained the addO-on therapy such as phosphorus, counting with oxide and with catalyst for benchmark, the content of described addO-on therapy is less than 10 weight %, it is preferred to 0.1-4 weight %。

When in described catalyst I possibly together with addO-on therapy such as phosphorus, the introducing method of described addO-on therapy 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 impregnate described carrier after the compound containing components such as described phosphorus is configured to mixed solution with the compound containing hydrogenation active metals component；Can also is that and after the compound containing components such as phosphorus is individually prepared solution, impregnate described carrier roasting。When the addO-on therapy such as phosphorus introduce described carrier respectively with hydrogenation active metals, it is preferable that first with carrier roasting described in the solution impregnation containing described addO-on therapy compound, afterwards again by the solution impregnation containing hydrogenation active metals component composition。Wherein, described sintering temperature is 400-600 DEG C, it is preferred to 420-500 DEG C, and roasting time is 2-6 hour, it is preferred to 3-6 hour。

According to method provided by the invention, wherein, the effect of described catalyst II is in that to be reacted by the hydrotreatment at this catalyst, the macromolecular compound such as polycyclic aromatic hydrocarbon in saturated raw material, make wherein to be more difficult to the impurity such as the sulfur of elimination, nitrogen to remove further, improve product property。Described catalyst II is not had other to limit by the present invention, and namely catalyst II can be selected from the Hydrobon catalyst that arbitrary prior art provides。They can be commercially available commodity or adopt any existing method to prepare。

This type of catalyst usually contains heat-resistant inorganic oxide carrier, hydrogenation active metals component。Wherein, one or more in the various heat-resistant inorganic oxides being commonly used for catalyst carrier and/or substrate of described heat-resistant inorganic oxide carrier。Such as, one or more in aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica-titania it are selected from, it is preferred to aluminium oxide。Described hydrogenation active metals component be nickel and or cobalt, tungsten and or molybdenum, introduce active metal composition be calculated as 10～40% with oxide。

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。

According to method provided by the invention, described include hydrotreating catalyst I and hydrotreating catalyst II can be layered successively and fill in same reactor, can also be fill in successively in two or more reactors of series connection to use, this present invention is not particularly limited。

According to method provided by the invention, wherein, include hydrotreating catalyst I and hydrotreating catalyst II combination 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 hydrotreating 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。

The device of described hydrogenation reaction can make described raw oil carry out with the catalytic reactor of described catalyst at hydrotreating reaction conditions any being enough to, for instance, at described fixed bed reactors, moving-burden bed reactor or carry out in fluidized bed reactor。

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 component。

Catalyst provided by the invention can be used alone, can also use with the combination of other catalyst, this catalyst is particularly suitable for heavy oil particularly inferior heavy oil (such as, one or more in crude oil, deep drawing wax oil, frivolous coal tar, wax tailings etc.) carry out hydrotreatment, after the hydrotreatment thus obtained, the W metal+V content of oil is 1 below μ g/g, sulfur content 3000 below μ g/g。Can use directly as subsequent technique (such as catalytic cracking process) raw oil。

Detailed description of the invention

The present invention will be further described for the following examples, but should therefore understands that be not limitation of the invention。

Agents useful for same in example, except as expressly described, is chemically pure reagent。

Following example illustrate the inventive method catalyst I and preparation method thereof。

The boehmite used below in an example includes:

P1-1: (pore volume is 1.2 mls/g to the dry glue powder that Chang Ling catalyst branch company produces, and specific surface is 280 meters²/ gram, most probable 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: (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 boehmite content is 67%, and gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 17.2)。

Embodiment 1-5 explanation modifier P2 of described P1 preparing the carrier of catalyst I and preparation method thereof。

Embodiment 1

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 1。

Embodiment 2

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 1。

Embodiment 3

The each 200 grams of Homogeneous phase mixing of P2B that the P2A obtain embodiment 1 and embodiment 2 obtain, obtain the modifier P2C of P1-1。The k value of P2C is in Table 1。

Embodiment 4

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 1。

Embodiment 5

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 1。

Table 1

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

The preparation method that catalyst I carrier is prepared in embodiment 6-13 explanation。The preparation method that comparative example 1-2 illustrates conventional catalyst carrier。

Embodiment 6

Weigh 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing prepared with embodiment 1, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), aqueous solution 1440 milliliters containing diboron trioxide 2.4g, 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 800 DEG C of roastings of this article shaped 3 hours, obtains carrier Z1。The character of carrier Z1 is listed in table 2。

Embodiment 7

Weigh 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing prepared with embodiment 2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing diboron trioxide 2.4g, 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 840 DEG C of roastings of this article shaped 3 hours, obtains carrier Z2。The character of carrier Z2 is listed in table 2。

Embodiment 8

Weigh 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 3, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing diboron trioxide 2.4g, 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 750 DEG C of roastings of this article shaped 3 hours, obtains carrier Z3。The character of carrier Z3 is listed in table 2。

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 diboron trioxide 2.4g, 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 800 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ1。The character of carrier DZ1 is listed in table 2。

Embodiment 9

Weigh 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 4, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), containing diboron trioxide 14g aqueous solution 1440 milliliters, 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 800 DEG C of roastings of this article shaped 3 hours, obtains carrier Z4。The character of carrier Z4 is listed in table 2。

Embodiment 10

Weigh 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 5, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing diboron trioxide 14g, 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 750 DEG C of roastings of this article shaped 3 hours, obtains carrier Z5。The character of carrier Z5 is listed in table 2。

Embodiment 11

Weigh 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 3, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing diboron trioxide 14g, 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 800 DEG C of roastings of this article shaped 3 hours, obtains carrier Z6。The character of carrier Z6 is listed in table 2。

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 diboron trioxide 14g, 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 800 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ2。The character of carrier DZ2 is listed in table 2。

Embodiment 12

Weigh 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 4, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing diboron trioxide 28g, 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 750 DEG C of roastings of this article shaped 3 hours, obtains carrier Z7。The character of carrier Z7 is listed in table 2。

Embodiment 13

Weigh 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 5, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing diboron trioxide 28g, 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 830 DEG C of roastings of this article shaped 3 hours, obtains carrier Z8。The character of carrier Z8 is listed in table 2。

Table 2

Embodiment 14-19 illustrates that catalyst I and preparation method thereof, comparative example 3-5 illustrate reference catalyst and preparation method thereof。

Embodiment 14

Take 200 grams of carrier Z1, with 220 milliliters containing MoO₃20 g/l, the ammonium molybdate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst CI1。The composition of CI1 is listed in table 3。

Embodiment 15

Take 200 grams of carrier Z2, with 220 milliliters containing MoO₃20 g/l, the ammonium molybdate of CoO5 g/l and cobalt nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst CI2。The composition of CI2 is listed in table 3。

Embodiment 16

Take 200 carrier Z3, with 220 milliliters containing WO₃22 g/l, the ammonium metatungstate of NiO6 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst CI3。The composition of CI3 is listed in table 3。

Embodiment 17

Take 200 grams of carrier Z4, with 220 milliliters containing WO₃22 g/l, the ammonium metatungstate of CoO6 g/l and cobalt nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst CI4。The composition of CI4 is listed in table 3。

Embodiment 18

Take 200 grams of carrier Z5, with 220 milliliters containing MoO₃16 g/l, the ammonium molybdate of NiO4 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst CI5。The composition of CI5 is listed in table 3。

Embodiment 19

Take 200 grams of carrier Z8, with 220 milliliters containing MoO₃16 g/l, the ammonium molybdate of NiO4 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst CI6。The composition of CI6 is listed in table 3。

Contrast row 3

Take 200 grams of carrier DZ1, with 220 milliliters containing MoO₃20 g/l, the ammonium molybdate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst DCI1。The composition of DCI1 is listed in table 3。

Contrast row 4

Take 200 grams of carrier DZ2, with 220 milliliters containing MoO₃20 g/l, the ammonium molybdate of CoO5 g/l and cobalt nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst DCI2。The composition of DCI2 is listed in table 3。

Comparative example 5

Take 200 grams of carrier DZ1, with 220 milliliters containing WO₃22 g/l, the ammonium metatungstate of NiO6 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst DCI3。The composition of DCI3 is listed in table 3。

Table 3

In catalyst, the content of each metal component is value of calculation。

Embodiment 20-22 illustrates catalyst II provided by the invention and preparation method thereof。

Embodiment 20

Preparing catalyst II according to the embodiment 6 in patent ZL97112397.7 is C II 1, and it consists of nickel oxide 2.3 weight %, tungsten oxide 22.0 weight %, and fluorine 4 weight %, all the other are aluminium oxide。

Embodiment 21

Preparing catalyst II according to the embodiment 37 in patent ZL00802168.6 is C II 2, 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。

Embodiment 22

Preparing catalyst II according to the embodiment 3 in patent ZL200310117323.0 is C II 3, 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。

Embodiment 23-28 illustrates that the present invention provides method and effect thereof。

With Ni+V content be 12.8ppm, sulfur content be the mixing inferior heavy oil of 3.5% for raw material, on 500 milliliters of fixed bed reactors evaluate catalyst。

In oil sample, the content of 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)

In oil sample, sulfur content uses coulometry to measure (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP62-90)。

Catalyst usage ratio and process conditions are listed in table 4, and after operating 1000 hours, product property is listed in table 5。

Comparative example 6

Catalyst adopts the combination of DCI1, CII1, and the volume of each catalyst amount when process conditions are listed in table 4, and sample analysis after operating 1000 hours, result is listed in table 5。

Comparative example 7

Catalyst adopts the combination of DCI2, CII2, and the volume of each catalyst amount when process conditions are listed in table 4, and sample analysis after operating 1000 hours, result is listed in table 5。

Comparative example 8

Catalyst adopts the combination of DCI3, CII3, and the volume of each catalyst amount when process conditions are listed in table 4, and sample analysis after operating 1000 hours, result is listed in table 5。

Table 4

Table 5

It can be seen that after adopting raw catelyst and correlation technique, the 1000 hours back end hydrogenations that operates process the metal of product, sulfur content significantly lower than prior art, as FCC charging, product property be improved significantly, while art run stability better。

Claims (14)

1. a catalytically cracked stock weighted BMO spaces method, including at hydrotreating reaction conditions, raw oil is contacted with a kind of catalyst combination, the combination of described catalyst includes hydrotreating catalyst I and hydrotreating catalyst II, in the combination of described catalyst catalyst I make with the layout of catalyst II described raw oil successively with include catalyst I and catalyst II contacts, the total amount combined by volume and with described catalyst is for benchmark, the content of described catalyst I is 5-40%, the content of catalyst II is 60-95%, wherein, described catalyst I is containing the boron-containing alumina carrier with structure of double peak holes, characterize with mercury injection method, the pore volume of described carrier is 0.8-1.2 ml/g, specific surface area is 120-400 rice²/ gram, diameter is the 58-80% that the pore volume in 6-30nm hole accounts for total pore volume, diameter therein be the pore volume in 10-30nm hole lower than the 55% of total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume。

2. method according to claim 1, it is characterised in that in described catalyst I, the pore volume of carrier is 0.9-1.15 ml/g, specific surface area is 150-300 rice²/ gram, diameter is the 60-75% that the pore volume in 6-30nm hole accounts for total pore volume, diameter therein be the pore volume in 10-30nm hole lower than the 54% of total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume。

3. method according to claim 1, it is characterised in that with described carrier for benchmark and in oxide, in described carrier, the content of boron is 0.5-8 weight %。

4. method according to claim 3, it is characterised in that with the carrier of described catalyst I for benchmark and in oxide, in the carrier of described catalyst I, the content of boron is 1-6 weight %。

5. method according to claim 4, it is characterised in that with the carrier of described catalyst I for benchmark and in oxide, in the carrier of described catalyst I, the content of boron is 1.5-4 weight %。

6. method according to claim 1, it is characterized in that, hydrogenation active metals component in described catalyst I is selected from least one metal component of group VIII and at least one metal component of group VIB, count with oxide and with catalyst I for benchmark, the content of described metal component of group VIII is 0.5-10 weight %, and the content of metal component of group VIB is 0.5-15 weight %。

7. method according to claim 6, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, metal component of group VIB is selected from molybdenum and/or tungsten, count with oxide and with catalyst I for benchmark, the content of described metal component of group VIII is 0.8-8 weight %, and the content of metal component of group VIB is 1-12 weight %。

8. method according to claim 7, it is characterised in that count with oxide and with catalyst I for benchmark, the content of described metal component of group VIII is 1-6 weight %, and the content of metal component of group VIB is 2-10 weight %。

9. method according to claim 1, it is characterised in that the total amount combined by volume and with described catalyst is for benchmark, and the content of the catalyst I in the combination of described catalyst is 10-35%, and the content of catalyst II is 65-90%。

10. method according to claim 1, it is characterized in that, described catalyst II contains 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, with catalyst II for benchmark, the nickel counted with oxide and/or the content of cobalt are 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. method according to claim 10, it is characterised in that the support selected from alumina in described catalyst II。

12. method according to claim 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 angstroms of holes accounts for more than the 80% of total pore volume。

13. method according to claim 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 0.2-3h^-1, hydrogen to oil volume ratio is 300-1500。

14. method according to claim 13, it is characterised in that the reaction condition of described hydrotreatment reaction is: hydrogen dividing potential drop is 8-18MPa, and temperature is 320-420 DEG C, and during liquid, volume space velocity is 0.3-2h^-1, hydrogen to oil volume ratio is 400-1000。