CN104449815B

CN104449815B - A kind of method for hydrotreating hydrocarbon oil

Info

Publication number: CN104449815B
Application number: CN201310432536.6A
Authority: CN
Inventors: 胡大为; 杨清河; 孙淑玲; 刘佳; 任亮; 蒋东红
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: 2013-09-22
Filing date: 2013-09-22
Publication date: 2016-07-20
Anticipated expiration: 2033-09-22
Also published as: CN104449815A

Abstract

A kind of method for hydrotreating hydrocarbon oil, 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, described catalyst combination in catalyst I make with the layout of catalyst II described raw oil successively with include that catalyst I and catalyst II contact, by volume and on the basis of the total amount that described catalyst combines, the content of described catalyst I is 5 40%, the content of catalyst II is 60 95%, wherein, described catalyst I is containing the alumina support with structure of double peak holes, characterize with mercury injection method, the pore volume of described carrier is 0.8 1.2 mls/g, specific surface area is 120 400 meters²/ gram, the pore volume in a diameter of 6 30nm holes accounts for the 58 80% of total pore volume, and the pore volume in a diameter of 10 30nm holes therein is less than the 55% of total pore volume, and the pore volume in a diameter of 300 500nm holes accounts for the 10 35% of total pore volume.

Description

A kind of method for hydrotreating hydrocarbon oil

Technical field

The present invention relates to a kind of method for hydrotreating hydrocarbon oil.

Background technology

Constantly aggravation and the social development continuous increasing to light-end products demand along with crude oil heaviness trend Adding, the COMBINED PROCESS of heavy-oil hydrogenation and catalytic cracking is by the generally favor of oil refining enterprise.Group technology Not only can improve the yield of light-end products, and advantageously reduce the discharge of the pollutant such as sulfur, nitrogen, have Significantly Social and economic benef@.Affected by catalytic cracking process and catalyst, received to improve light-end products Rate, reduces Sulfur Content in Catalytic Cracking Gasoline, usually requires that W metal+V in catalyzed cracking processing raw oil Content should be less than 1ppm, and sulfur content is less than 3000ppm.But owing to feedstock property is constantly deteriorated, heavy oil The raw oil of more than 350 DEG C (typically refer to boiling point) hydrotreating will as fcc raw material preprocessing process Ask and there is higher impurity removal ability and reaction stability.Improve impurity removal percentage to be hydrogenated with by raising The severity processing reaction realizes, but so also results in the shortening in catalyst runs life-span.Therefore use New catalyst and processing and treating method are to produce high-quality catalytically cracked material, improve heavy-oil hydrogenation and process The optimum selection of journey.

Summary of the invention

The technical problem to be solved in the present invention is for prior art requirement, it is provided that at a kind of new hydrocarbon oil hydrogenation Reason method.

The content that the present invention relates to includes:

1. a method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, by raw oil and one Planting catalyst combination contact, the combination of described catalyst includes hydrotreating catalyst I and hydrotreating catalyst II, in the combination of described catalyst the layout of catalyst I and catalyst II make described raw oil successively with include Catalyst I contacts with catalyst II, by volume and on the basis of the total amount that described catalyst combines, described The content of catalyst I is 5-40%, and the content of catalyst II is 60-95%, and wherein, described catalyst I contains Having the alumina support 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, the pore volume in a diameter of 6-30nm hole accounts for total pore volume 58-80%, the pore volume in a diameter of 10-30nm hole therein is less than the 55% of total pore volume, a diameter of 300- The pore volume in 500nm hole accounts for the 10-35% of 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 mls/g, specific surface area is 150-300 rice²/ gram, the pore volume in a diameter of 6-30nm hole accounts for total hole The 60-75% held, the pore volume in a diameter of 10-30nm hole therein is less than the 54% of total pore volume, a diameter of The pore volume in 300-500nm hole accounts for the 15-30% of total pore volume.

3, according to the method described in 1, it is characterised in that the hydrogenation active metals group in described catalyst I It is selected from least one metal component of group VIII and at least one metal component of group VIB, in terms of oxide also On the basis of catalyst I, the content of described metal component of group VIII is 0.5-10 weight %, group VIB gold The content belonging to component is 0.5-15 weight %.

4, according to the method described in 3, it is characterised in that described metal component of group VIII selected from nickel and/or Cobalt, metal component of group VIB is selected from molybdenum and/or tungsten, counts and on the basis of catalyst I by oxide, described The content of metal component of group VIII is 0.8-8 weight %, and the content of metal component of group VIB is 1-12 weight %.

5, according to the method described in 4, it is characterised in that count and on the basis of catalyst by oxide, institute The content stating metal component of group VIII is 1-6 weight %, and the content of metal component of group VIB is 2-10 weight %.

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

7, according to the method described in 1, it is characterised in that described catalyst II contain selected from aluminium oxide and/or The carrier of silica-alumina, selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, contains Or without one or more adjuvant components in fluorine, boron and phosphorus, on the basis of catalyst II, with oxide The nickel of meter and/or the content of cobalt are 1～5 weight %, and the content of molybdenum and/or tungsten is 10～35 weight %, with The content of one or more adjuvant components in fluorine, boron and phosphorus of element meter is 0～9 weight %.

8, according to the method described in 7, it is characterised in that the support selected from alumina in described catalyst II.

9, according to the method described in 8, it is characterised in that the pore volume of described aluminium oxide is not less than 0.35 milliliter / gram, bore dia is that the pore volume in 40～100 angstroms of holes accounts for more than the 80% of total pore volume.

10, according to the method described in 1, it is characterised in that the reaction condition of described hydrotreating 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。

11, according to the method described in 10, it is characterised in that the reaction condition of described hydrotreating reaction For: 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 oil body Long-pending ratio is 400-1000.

In the present invention, depending on difference, the carrier of described catalyst I requires that carrier therein can be made into various being prone to and grasps The article shaped made, the most spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder Shape etc.).

The preparation method of this carrier includes the modifier of hydrated alumina P1 and P1 containing boehmite P2 mix, aftershaping, be dried and roasting, wherein, described dry condition includes: temperature is 40- 350 DEG C, the time is 1-24 hour, and the condition of described roasting includes: temperature is to less than 850 more than 500 DEG C, the time is 1-8 hour, and the Mixing ratio by weight of described P1 and P2 is the κ value of 20-95:5-80, P2 It is 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For the hydrated alumina P1 containing boehmite Sour peptization index, DI₂Sour peptization for the modifier P2 of the hydrated alumina P1 containing boehmite refers to Number.

Wherein, the Mixing ratio by weight of the most 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.

The pore volume of the most described P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, Can a few bore dia 10-25nm.

The most described P2 is the particulate matter of 80-300 mesh.Further preferred described P2 is 100-200 purpose Particulate matter.

The most described dry condition includes: temperature is 100-200 DEG C, and the time is 2-12 hour, described roasting The condition burnt includes: temperature is 600-800 DEG C, and roasting time is 2-6 hour.

In the present invention, it is by the described hydration oxygen containing boehmite by one of P1 method being modified as P2 Changing aluminum P1 molding, be dried, it be completely or partially 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 roasting method one obtained, sintering temperature is to less than or equal to 1400 DEG C more than 350, during roasting Between be 1-8 hour, afterwards it is completely or partially ground, sieves, obtaining powder body thing is P2；Method Three be that the hydrated alumina P1 containing boehmite is dodged dry, dodge dry temperature for more than 150 to being less than Equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder body thing is P2；The four of method are by method One of, the two of method and the modifier that obtains with the three of method in one or more be mixed to get.

The condition being dried 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；Method it Sudden strain of a muscle in three is done temperature and 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 mesh in P1 modifier；More preferably 100-200 Purpose particulate matter.

Wherein, the modifier P2 of described hydrated alumina P1 and P1 containing boehmite is mixed Method is conventional method, such as, is put in stirring-type batch mixer according to ingredient proportion by P1 and P2 of powder body Mixing.Described molding is carried out according to a conventional method, such as, and a kind of method in spin, tabletting and extruded moulding Or the combination of several method.When molding, such as extruded moulding, for ensureing that described molding is smoothed out, Water, extrusion aid and/or adhesive can be added, with or without expanding agent, then in described mixture Extrusion molding, is dried and roasting afterwards.Described extrusion aid, the kind of peptizer and consumption are ability Well known to field technique personnel, the most common extrusion aid can be selected from sesbania powder, methylcellulose, shallow lake One or more in powder, polyvinyl alcohol, PVOH, described peptizer can be mineral acid and/or organic Acid, described expanding agent can be the one in starch, synthetic cellulose, polymeric alcohol and surfactant or Several.Synthetic cellulose therein is preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl One or more in base fiber fat alcohol polyethylene ether, polymeric alcohol is preferably Polyethylene Glycol, poly-propanol, gathers One or more in vinyl alcohol, surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and Derivant, molecular weight are the one or several in the propenyl copolymer of 200-10000 and maleic acid copolymer Kind.

In the preparation of the described carrier of catalyst I, described acid peptization index D I refers to containing intending thin water aluminum The hydrated alumina of stone and the hydrated alumina modifier containing boehmite add nitre by certain acid aluminum ratio After acid, by the hydrated alumina containing boehmite of peptization with Al within certain response time₂O₃Meter Percent, DI=(1-W₂/W₁) × 100%, W₁And W₂Be respectively containing boehmite hydrated alumina with Before acid reaction and with acid reaction after with Al₂O₃The weight of meter.

The mensuration of DI includes: the calcination base (1) measuring the hydrated alumina containing boehmite is (the most dry Base) (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours content, after it burns Weight weight ratio front with burning, is expressed as a percentage), it is calculated as a；(2) weigh containing intending thin with analytical balance The hydrated alumina W of diaspore₀Gram, W₀Amount meet with Al₂O₃The W of meter₁It is 6 grams of (W₁/a=W₀), claim Remove ionized water W gram, W=40.0-W₀, under stirring by the hydrated alumina containing boehmite that weighs and Deionized water adds in beaker and mixes；With 20mL pipet pipette 20mL, concentration is dilute nitre of 0.74N Acid solution, joins in the beaker of step (2) by this acid solution, the lower reaction of stirring 8 minutes；(4) will step Suddenly (3) reacted serosity is centrifuged separating in centrifuge, and precipitate is inserted the crucible weighed In, afterwards, it is dried 4 hours in 125 DEG C, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh To calcination sample size W₂Gram；(5) according to formula DI=(1-W₂/W₁) × 100% is calculated.

On the premise of being enough to make final carrier meet application claims, the present invention to described containing intend thin water aluminum The hydrated alumina P1 of stone does not specially require, and can be the boehmite prepared of any prior art, Can also be boehmite and the mixture of other hydrated alumina, other hydrated alumina choosing described One or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.

In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and most probable hole Footpath, is by the described hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, by BET nitrogen Absorption representation obtains.

In further preferred embodiment, characterize with X diffraction, the described hydration containing boehmite Boehmite content in aluminium oxide P1 is not less than 50%, more preferably not less than 60%.

Inventors of the present invention have surprisingly found that, the hydrated alumina P1 containing boehmite is carried out heat Processing modified, the peptization index of its modifier changes, by this modifier with the most thermally treated After P1 mixed-forming, dry also roasting, obtained carrier has obvious bimodal pore distribution.Particularly exist By the granule of 80-300 mesh therein, the granule of preferably 100-200 mesh mixes with the most thermally treated part Molding, be dried and roasting after, obtained carrier bimodal in each unimodal pore size distribution concentrate especially. Here, the granule of described 80-300 mesh, the granule of preferably 100-200 mesh refers to that described modifier is through sieving (including step that is broken or that grind if desired), its screening thing (siftage) meets 80-300 purpose Grain, the particulate matter of preferably 100-200 mesh accounts for the percent (by weight) of total amount and is not less than 60%, enters one Step is preferably not less than 70%.

The Mixing ratio by weight of described P1 and P2 refers to P1 and P2 in the mixture of the most described P1 and P2 The ratio of the most shared parts by weight.Wherein, the preferred span of parts by weight of P1 is 20-95, enters one Step is 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) based on being dried to obtain P2, including by the hydrated alumina P1 containing boehmite according to a conventional method During regular oxidation alumina supporter is prepared in molding, the tailing of drying by-product, such as: in extruded moulding, Bar shaped article shaped is at dry, the tailing (being referred to as traditionally being dried waste material) of integer process by-product, by this tail Material is milled, and sieves and obtains P2.

(2) obtain based on roasting, become according to a conventional method including by the hydrated alumina P1 containing boehmite During regular oxidation alumina supporter prepared by type, the tailing (being referred to as 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 ground by this tailing Mill, sieves and obtains P2；Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, flash-off time 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.Mixed when using When conjunction method obtains P2, the mixed proportion of the modifier P2 respectively obtaining aforementioned several method does not limit System.

In the present invention, the preparation of described catalyst I includes that using the method for dipping to introduce on carrier adds Hydrogen activity metal component, is dried, roasting or the step of not roasting, described hydrogenation active metals group afterwards It is selected from the metal component of at least one the VIIIth race and the metal component of at least one group VIB, with oxide Count and on the basis of catalyst, the described compound containing hydrogenation active metals concentration in described dipping solution It is 0.5-10 weight with the content of the metal component that the consumption of described solution makes the VIIIth race in final catalyst %, the content of the metal component of described group VIB is 0.5-15 weight %；Described drying condition includes: temperature For 100-250 DEG C, the time is 1-10 hour；Described roasting condition includes: temperature is 360-500 DEG C, time Between be 1-10 hour.

The metal component of the most described VIIIth race is selected from nickel and/or cobalt, the metal component of group VIB selected from molybdenum and / or tungsten, to count and on the basis of catalyst by oxide, the described compound containing hydrogenation active metals is in described leaching Concentration in stain solution and the consumption of described solution make the content of the metal component of group VIII in final catalyst be 0.8-8 weight %, 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, the time is 2-6 hour.

Further, count and on the basis of catalyst by oxide, the preferably described change containing hydrogenation active metals The consumption of compound concentration in described dipping solution and described solution makes the group VIII metal in final catalyst The content of component is 1-6 weight %, and the content of the metal component of group VIB is 2-10 weight %.

Described dipping method is conventional method, for example, it may be excess immersion stain, hole saturation dipping Method.Described be selected from the soluble compound in them containing the metal component compound selected from VI B race one Plant or several, such as one or more in molybdenum oxide, molybdate, paramolybdate, oxidation preferably wherein Molybdenum, ammonium molybdate, ammonium paramolybdate；One or more in tungstates, metatungstate, ethyl metatungstate, Ammonium metatungstate preferably wherein, ethyl ammonium metatungstate.Described selects containing the compound selected from VIII race's metal component One or more in their soluble compound, such as cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, chlorine Change one or more in the soluble complexes of cobalt and cobalt, preferably cobalt nitrate, basic cobaltous carbonate；Nitric acid One or more in the soluble complexes of nickel, nickel acetate, basic nickel carbonate, Nickel dichloride. and nickel, preferably For nickel nitrate, basic nickel carbonate.

The catalyst I provided according to the present invention, it is also possible to provide catalyst performance containing any present invention that do not affects Maybe can improve the addO-on therapy of the catalytic performance of the catalyst that the present invention provides.As can be added containing phosphorus etc. Component, counts and on the basis of catalyst by oxide, and the content of described addO-on therapy is less than 10 weight %, preferably 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 is permissible Arbitrary method, can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix Conjunction, molding roasting；Can be by the compound containing components such as described phosphorus and containing hydrogenation active metals group The compound divided impregnates described carrier after being configured to mixed solution；Can also is that the chemical combination containing components such as phosphorus Thing impregnates described carrier roasting after individually preparing solution.When the addO-on therapy such as phosphorus and hydrogenation active metals difference When introducing described carrier, first with carrier described in the solution impregnation containing described addO-on therapy compound the most also Roasting, the most again by the solution impregnation containing hydrogenation active metals component composition.Wherein, described roasting temperature Degree is for 400-600 DEG C, and preferably 420-500 DEG C, roasting time is 2-6 hour, and preferably 3-6 is little Time.

The method provided according to the present invention, wherein, the effect of described catalyst II is by this catalyst Hydrotreating reaction, the macromolecular compound such as polycyclic aromatic hydrocarbon in saturated raw material so that it is in be more difficult to removing The impurity such as sulfur, nitrogen removes further, improves product property.Described catalyst II is not had other to limit by the present invention The Hydrobon catalyst that system, i.e. catalyst II can provide selected from arbitrary prior art.They can be Commercially available commodity or use any existing method to prepare.

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

Such as, a kind of Hydrobon catalyst disclosed in ZL97112397, consisting of nickel oxide 1～5 weight %, tungsten oxide 12～35 weight %, fluorine 1～9 weight %, remaining be aluminium oxide, this aluminium oxide be by one or Multiple little porous aluminum oxide is combined according to the weight ratio of 75: 25～50: 50 with one or more macroporous aluminium oxides , the least porous aluminum oxide be bore dia be less than the pore volume in 80 angstroms of holes account for total pore volume 95% with On aluminium oxide, macroporous aluminium oxide is that the pore volume in bore dia 60～600 angstroms of holes accounts for total pore volume more than 70% Aluminium oxide.

ZL00802168 discloses a kind of Hydrobon catalyst, this catalyst contain a kind of alumina support and At least one the group VIB metal being supported 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 bore dia is the pore volume in 40～100 angstroms of holes Accounting for more than the 80% of total pore volume, it uses special method to prepare.

ZL200310117323 discloses a kind of Hydrobon catalyst, and this catalyst contains a kind of carrying alumina Body and load molybdenum, nickel and tungsten metal component on this carrier, count and on the basis of catalyst by oxide, Described catalyst contains the molybdenum of 0.5-10 weight %, the nickel of 1-10 weight %, the tungsten of 12-35 weight % With the carrier of aequum, the preparation method of described catalyst includes successively with the solution of molybdate compound with contain Nickel, the solution impregnation of alumina carrier of tungsten compound, wherein said alumina support is with molybdate compound Solution impregnation after be dried, be dried and roasting after the solution impregnation of nickeliferous, tungsten compound, Baking temperature is 100-300 DEG C, and drying time is 1-12 hour, and sintering temperature is 320-500 DEG C, Roasting time is 1-10 hour.

According to the present invention provide method, described in include hydrotreating catalyst I and hydrotreating catalyst II Can be layered successively and fill in same reactor, it is also possible to be fill in series connection successively two or more Reactor uses, this present invention is not particularly limited.

The method provided according to the present invention, wherein, is including hydrotreating catalyst I and hydrorefining catalyst Agent II combination before, afterwards or they between any two, can include that any contributing to improves described catalyst group Close other catalyst or the filler of performance.Such as, added such as porcelain before described hydrotreating catalyst I The fillers such as ball, activity supporter, to improve raw oil distribution etc. in the reactor.About this filler Uses etc. are known to those skilled in the art, do not repeat.

The device of described hydrogenation reaction can make described raw oil at hydrotreating reaction conditions any being enough to Reactor catalytic with described catalyst is carried out, such as, at described fixed bed reactors, moving bed Reactor or fluidized bed reactor are carried out.

According to the conventional method in this area, described hydrotreating catalyst before the use, generally can be at hydrogen In the presence of gas, at a temperature of 140-370 DEG C, carry out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this Presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component it loaded is converted into Metal sulfide component.

The catalyst that the present invention provides can be used alone, it is also possible to being applied in combination with other catalyst, this is urged Agent is particularly suitable for heavy oil particularly inferior heavy oil (such as, selected from crude oil, deep drawing wax oil, frivolous drip One or more in blue or green oil, wax tailings etc.) carry out hydrotreating, oil after thus obtained hydrotreating W metal+V content be 1 below μ g/g, sulfur content 3000 below μ g/g.Can be directly as rear Continuous technique (such as catalytic cracking process) raw oil uses.

Detailed description of the invention

The present invention will be further described for the following examples, but should be therefore understands that be not the limit to the present invention Fixed.

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:

(pore volume is 1.2 mls/g to the dry glue powder that P1-1: 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%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 15.8).

(pore volume is 1.1 mls/g to the dry glue powder that P1-2: Yantai Heng Hui Chemical Co., Ltd. produces, specific surface It it is 260 meters²/ gram, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 17.2).

Modifier P2 and the preparation side thereof of the described P1 of the carrier of catalyst I is prepared in the explanation of embodiment 1-5 Method.

Embodiment 1

Weigh 1000 grams of P1-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C it is dried 4 hours, obtains dried strip, by dried strip shaping, sieve, by length less than the dried strip of 2mm Material (commonly referred to as industrially drying bar waste material) is milled, and sieves, takes wherein 100～200 mesh sieve Point, obtain the modifier P2A of P1-1.The k value of P2A is shown 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.P2B K value be shown in Table 1.

Embodiment 3

The each 200 grams of uniform mixing of P2B that P2A embodiment 1 obtained and embodiment 2 obtain, obtain The modifier P2C of P1-1.The k value of P2C is shown in Table 1.

Embodiment 4

Weigh 1000 grams of P1-2, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C it is dried 4 hours, 1200 DEG C of roastings 4 hours, obtains carrier, by carrier strip shaping, sieve, by length Carrier strip material (commonly referred to as industry carrier waste material) less than 2mm is milled, and sieves, takes wherein 100～200 mesh sieves divide, and obtain the modifier P2D of P1-2.The k value of P2D is shown 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.P2E K value be shown 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 of catalyst I carrier is prepared in the explanation of embodiment 6-13.Comparative example 1-2 explanation routine is urged The preparation method of agent carrier.

Embodiment 6

Weighing 800 grams of P1-1, after the 200 grams of raw material P2A prepared with embodiment 1 uniformly mix, addition contains The aqueous solution 1440 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), at double screw banded extruder On be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should 800 DEG C of roastings of article shaped 3 hours, obtain carrier Z1.The character of carrier Z1 is listed in table 2.

Embodiment 7

Weighing 200 grams of P1-1, after the 800 grams of raw material P2B prepared with embodiment 2 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 840 DEG C of roastings of type thing 3 hours, obtain carrier Z2.The character of carrier Z2 is listed in table 2.

Embodiment 8

Weighing 500 grams of P1-1, after the 500 grams of raw material P2C prepared with embodiment 3 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 750 DEG C of roastings of type thing 3 hours, obtain carrier Z3.The character of carrier Z3 is listed in table 2.

Comparative example 1

Weigh 1000 grams of P1-1, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution of 10 milliliters 1440 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried in 120 DEG C 4 hours, obtain article shaped, by 800 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ1.Carrier DZ1 Character be listed in table 2.

Embodiment 9

Weighing 800 grams of P1-2, after the 200 grams of raw material P2D prepared with embodiment 4 uniformly mix, addition contains 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 is dried 4 hours in 120 DEG C, To article shaped, by 800 DEG C of roastings of this article shaped 3 hours, obtain carrier Z4.The character of carrier Z4 is listed in Table 2.

Embodiment 10

Weighing 900 grams of P1-1, after the 100 grams of raw material P2E prepared with embodiment 5 uniformly mix, addition contains The aqueous solution 1440 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), at double screw banded extruder On be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should 750 DEG C of roastings of article shaped 3 hours, obtain carrier Z5.The character of carrier Z5 is listed in table 2.

Embodiment 11

Weighing 850 grams of P1-2, after the 150 grams of raw material P2C prepared with embodiment 3 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 800 DEG C of roastings of type thing 3 hours, obtain carrier Z6.The character of carrier Z6 is listed in table 2.

Comparative example 2

Weigh 1000 grams of P1-2, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution of 10 milliliters 1440 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried in 120 DEG C 4 hours, obtain article shaped, by 800 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ2.Carrier DZ2 Character be listed in table 2.

Embodiment 12

Weighing 900 grams of P1-2, after the 100 grams of raw material P2D prepared with embodiment 4 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 750 DEG C of roastings of type thing 3 hours, obtain carrier Z7.The character of carrier Z7 is listed in table 2.

Embodiment 13

Weighing 850 grams of P1-2, after the 150 grams of raw material P2E prepared with embodiment 5 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 830 DEG C of roastings of type thing 3 hours, obtain carrier Z8.The character of carrier Z8 is listed in table 2.

Table 2

Embodiment 14-19 explanation catalyst I and preparation method thereof, comparative example 3-5 explanation reference catalyst and Preparation method.

Embodiment 14

Take 200 grams of carrier Z1, with 220 milliliters containing MoO₃20 grams per liters, the ammonium molybdate of NiO5 grams per liter and Nickel nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is hydrogenated with Process catalyst CI1.The composition of CI1 is shown in Table 3.

Embodiment 15

Take 200 grams of carrier Z2, with 220 milliliters containing MoO₃20 grams per liters, the ammonium molybdate of CoO5 grams per liter and Cobalt nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is hydrogenated with Process catalyst CI2.The composition of CI2 is shown in Table 3.

Embodiment 16

Take 200 carrier Z3, with 220 milliliters containing WO₃22 grams per liters, the ammonium metatungstate of NiO6 grams per liter and Nickel nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is hydrogenated with Process catalyst CI3.The composition of CI3 is shown in Table 3.

Embodiment 17

Take 200 grams of carrier Z4, with 220 milliliters containing WO₃22 grams per liters, the ammonium metatungstate of CoO6 grams per liter Impregnate 1 hour with cobalt nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Hydrogen processes catalyst CI4.The composition of CI4 is shown in Table 3.

Embodiment 18

Take 200 grams of carrier Z5, with 220 milliliters containing MoO₃16 grams per liters, the ammonium molybdate of NiO4 grams per liter and Nickel nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is hydrogenated with Process catalyst CI5.The composition of CI5 is shown in Table 3.

Embodiment 19

Take 200 grams of carrier Z8, with 220 milliliters containing MoO₃16 grams per liters, the ammonium molybdate of NiO4 grams per liter and Nickel nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is hydrogenated with Process catalyst CI6.The composition of CI6 is shown in Table 3.

Contrast row 3

Take 200 grams of carrier DZ1, with 220 milliliters containing MoO₃20 grams per liters, the ammonium molybdate of NiO5 grams per liter Impregnate 1 hour with nickel nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Process catalyst DCI1.The composition of DCI1 is shown in Table 3.

Contrast row 4

Take 200 grams of carrier DZ2, with 220 milliliters containing MoO₃20 grams per liters, the ammonium molybdate of CoO5 grams per liter Impregnate 1 hour with cobalt nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Process catalyst DCI2.The composition of DCI2 is shown in Table 3.

Comparative example 5

Take 200 grams of carrier DZ1, with 220 milliliters containing WO₃22 grams per liters, the ammonium metatungstate of NiO6 grams per liter Impregnate 1 hour with nickel nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrotreating catalyst DCI3.The composition of DCI3 is shown in Table 3.

Table 3

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

Catalyst II that the embodiment 20-22 explanation present invention provides and preparation method thereof.

Embodiment 20

Preparing catalyst II according to the embodiment 6 in patent ZL97112397.7 is C II 1, consisting of oxygen Changing nickel 2.3 weight %, tungsten oxide 22.0 weight %, fluorine 4 weight %, remaining is aluminium oxide.

Embodiment 21

Preparing catalyst II according to the embodiment 37 in patent ZL00802168.6 is C II 2, consisting of Nickel oxide 2.6 weight %, molybdenum oxide 23.6 weight %, fluorine 2.3 weight %, remaining is aluminium oxide.

Embodiment 22

Preparing catalyst II according to the embodiment 3 in patent ZL200310117323.0 is C II 3, its composition For nickel oxide 2.1 weight %, molybdenum oxide 2.5 weight %, tungsten oxide 25.4 weight %, remaining is aluminium oxide.

Embodiment 23-28 illustrates the hydrotreating heavy feedstocks of the present invention oil effect as catalytic cracking feeds.

With Ni+V content as 15.1ppm, sulfur content be the mixing inferior heavy oil of 3.3% as raw material, 500 Catalyst is evaluated on milliliter fixed bed reactors.

In oil sample, the content of nickel and vanadium uses 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 industry Analysis method RIPP124-90)

In oil sample, (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP62-to sulfur content use coulometry mensuration 90).

Catalyst uses ratio and process conditions to be shown in Table 4, and after operating 1000 hours, product property is listed in table In 5.

Comparative example 6

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

Comparative example 7

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

Comparative example 8

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

It is the most corresponding with table 3 that table 4(notes examining catalyst in this table, does not has 4-6 at least CII series Catalyst)

Table 5

It can be seen that after using raw catelyst and correlation technique, the 1000 hours back end hydrogenations that operate process product Metal, sulfur content be significantly lower than prior art, as FCC feed, product property be improved significantly, with Time new technique run stability more preferable.

Claims

1. a method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, by raw material Oil contacts with a kind of catalyst combination, and the combination of described catalyst includes hydrotreating catalyst I He Hydrotreating catalyst II, in the combination of described catalyst, the layout of catalyst I and catalyst II makes Described raw oil successively with include that catalyst I and catalyst II contact, by volume and with institute On the basis of stating the total amount of catalyst combination, the content of described catalyst I is 5-40%, catalyst The content of II is 60-95%, and the hydrogenation active metals component in described catalyst I is selected from least A kind of metal component of group VIII and at least one metal component of group VIB, in terms of oxide and with On the basis of catalyst I, the content of described metal component of group VIII is 0.5-10 weight %, the The content of VI B race metal component is 0.5-15 weight %, and wherein, described catalyst I contains Having the alumina support of 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, a diameter of 6-30nm hole Pore volume accounts for the 58-80% of total pore volume, and the pore volume in a diameter of 10-30nm hole therein is less than The 55% of total pore volume, the pore volume in a diameter of 300-500nm hole accounts for the 10-35% of total pore volume.

Method the most 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, and specific surface area is 150-300 rice²/ gram, diameter Pore volume for 6-30nm hole accounts for the 60-75% of total pore volume, a diameter of 10-30nm hole therein Pore volume less than total pore volume 54%, the pore volume in a diameter of 300-500nm hole accounts for total pore volume 15-30%.

Method the most according to claim 1, it is characterised in that described group VIII metal Component is selected from nickel and/or cobalt, and metal component of group VIB is selected from molybdenum and/or tungsten, in terms of oxide And on the basis of catalyst I, the content of described metal component of group VIII is 0.8-8 weight %, The content of metal component of group VIB is 1-12 weight %.

Method the most according to claim 3, it is characterised in that in terms of oxide and with On the basis of catalyst I, the content of described metal component of group VIII is 1-6 weight %, the VIth B The content of race's metal component is 2-10 weight %.

Method the most according to claim 1, it is characterised in that by volume and with institute On the basis of stating the total amount of catalyst combination, the content of the catalyst I in the combination of described catalyst is 10-35%, the content of catalyst II is 65-90%.

Method the most according to claim 1, it is characterised in that described catalyst II contains Have the carrier selected from aluminium oxide and/or silica-alumina, selected from nickel and/or cobalt, molybdenum and/ Or the hydrogenation active metals component of tungsten, with or without in fluorine, boron and phosphorus, one or more help Agent component, on the basis of catalyst II, nickel and/or the content of cobalt in terms of oxide are 1～5 The content of weight %, molybdenum and/or tungsten is 10～35 weight %, in terms of element selected from fluorine, boron It is 0～9 weight % with the content of one or more adjuvant components in phosphorus.

Method the most according to claim 6, it is characterised in that in described catalyst II Support selected from alumina.

Method the most according to claim 7, it is characterised in that the hole of described aluminium oxide Holding not less than 0.35 ml/g, bore dia is that the pore volume in 40～100 angstroms of holes accounts for total pore volume More than 80%.

Method the most according to claim 1, it is characterised in that described hydrotreating is anti- The reaction condition answered is: hydrogen dividing potential drop 6-20MPa, and temperature is 300-450 DEG C, and during liquid, volume is empty Speed is 0.2-3h^-1, hydrogen to oil volume ratio is 300-1500.

Method the most according to claim 9, it is characterised in that described hydrotreating is anti- The reaction condition answered is: hydrogen dividing potential drop is 8-18MPa, and temperature is 320-420 DEG C, volume during liquid Air speed is 0.3-2h^-1, hydrogen to oil volume ratio is 400-1000.