CN104449815A

CN104449815A - Hydrocarbon-oil hydrotreatment method

Info

Publication number: CN104449815A
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: 2015-03-25
Anticipated expiration: 2033-09-22
Also published as: CN104449815B

Abstract

A hydrocarbon-oil hydrotreatment method comprises contacting raw oil with a catalyst combination under hydrotreatment reaction conditions. The catalyst combination comprises a hdyrotreatment catalyst I and a hydrotreatment catalyst II, and the arrangement of the catalyst I and the catalyst II enables raw oil to be successively contacted with the catalyst I and the catalyst II. Based on the total amount of the catalyst combination in terms of volume, the content of the catalyst I is 5-40% and the content of the catalyst II is 60-95%. The catalyst I contains an aluminium oxide carrier with a double-peak pore structure, and mercury intrusion porosimetry, the carrier has the pore volume of 0.8-1.2 mL/g and the specific surface area of 120-400 m<2>/g, the pore volume of pores with the diameter of 6-30 nm accounts for 58-80% of the total pore volume, the pore volume of pores with the diameter of 10-30 nm is less than 55% of the total pore volume, and the pore volume of pores with the diameter of 300-500 nm accounts for 10-35% of the 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

Along with the continuous aggravation of crude oil heaviness trend and social development are to the continuous increase of light-end products demand, the COMBINED PROCESS of heavy-oil hydrogenation and catalytic cracking is subject to the generally favor of oil refining enterprise.Combination process not only can improve the yield of light-end products, and is conducive to the discharge reducing the pollutent such as sulphur, nitrogen, has obvious social and economic benefits.By catalytic cracking process and catalysts influence, in order to improve light oil yield, reduce Sulfur Content in Catalytic Cracking Gasoline, usually require that in catalyzed cracking processing stock oil, W metal+V content should lower than 1ppm, sulphur content is lower than 3000ppm.But because feedstock property is constantly deteriorated, heavy oil (typically referring to the stock oil of boiling point more than 350 DEG C) hydrotreatment just requires to have higher impurity removal ability and reaction stability as fcc raw material preprocessing process.Improve impurity removal percentage to be realized by the severity improving hydrotreatment reaction, but also can cause the shortening in catalyst runs life-span like this.Therefore adopt new catalyzer and processing and treating method to be production high-quality catalytically cracked material, improve the optimal selection of heavy-oil hydrogenation treating processes.

Summary of the invention

The technical problem to be solved in the present invention is for prior art demand, provides a kind of new method for hydrotreating hydrocarbon oil.

The content that the present invention relates to comprises:

1. a method for hydrotreating hydrocarbon oil, comprise at hydrotreating reaction conditions, stock oil is contacted with a kind of catalyst combination, described catalyst combination comprises hydrotreating catalyst I and hydrotreating catalyst II, in described catalyst combination catalyzer I and the layout of catalyst II make described stock oil successively with comprise catalyzer I and contact with catalyst II, by volume and with the total amount of described catalyst combination for benchmark, the content of described catalyzer I is 5-40%, the content of catalyst II is 60-95%, wherein, described catalyzer I is containing the alumina supporter with structure of double peak holes, characterize with mercury penetration method, the pore volume of described carrier is 0.8-1.2 ml/g, specific surface area is 120-400 rice ²/ gram, diameter is the 58-80% that the pore volume in 6-30nm hole accounts for total pore volume, diameter be wherein the pore volume in 10-30nm hole lower than 55% of total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume.

2, the method according to 1, is characterized in that, in described catalyzer I, the pore volume of carrier is 0.9-1.15 ml/g, and specific surface area is 150-300 rice ²/ gram, diameter is the 60-75% that the pore volume in 6-30nm hole accounts for total pore volume, diameter be wherein the pore volume in 10-30nm hole lower than 54% of total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.

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

4, the method according to 3, 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, with oxide basis and with catalyzer I for benchmark, the content of described metal component of group VIII is 0.8-8 % by weight, and the content of metal component of group VIB is 1-12 % by weight.

5, the method according to 4, is characterized in that, is benchmark with oxide basis and with catalyzer, and the content of described metal component of group VIII is 1-6 % by weight, and the content of metal component of group VIB is 2-10 % by weight.

6, the method according to 1, is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of the catalyzer I in described catalyst combination is 10-35%, the content of catalyst II is 65-90%.

7, the method according to 1, it is characterized in that, described catalyst II contains the carrier being selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, take catalyst II as benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 10 ~ 35 % by weight, is 0 ~ 9 % by weight in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element.

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

9, the method according to 8, is characterized in that, the pore volume of described aluminum oxide is not less than 0.35 ml/g, and bore dia is that the pore volume in 40 ~ 100 dust holes accounts for more than 80% of total pore volume.

10, the method according to 1, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.2-3h ^-1, hydrogen to oil volume ratio is 300-1500.

11, the method according to 10, is characterized in that, the reaction conditions 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 catalyzer I requires depending on different the forming composition that carrier wherein can be made into various easy handling, such as spherical, cellular, nest like, tablet or bar shaped (trifolium, butterfly, cylindrical etc.).

The preparation method of this carrier comprises and being mixed by the modifier P2 of hydrated aluminum oxide P1 and P1 containing pseudo-boehmite, aftershaping, dry and roasting, wherein, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for being greater than 500 to being less than 850 DEG C, time is 1-8 hour, to be the κ value of 20-95:5-80, P2 be for the Mixing ratio by weight of described P1 and P2 0 to being less than or equal to 0.9, described κ=DI ₂/ DI ₁, DI ₁for the sour peptization index of the hydrated aluminum oxide P1 containing pseudo-boehmite, DI ₂for the sour peptization index of the modifier P2 of the hydrated aluminum oxide P1 containing pseudo-boehmite.

Wherein, the Mixing ratio by weight of preferred described P1 and P2 is 70-95:5-30; The k value of described P2 is 0 to being 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 rice ²/ gram, most probable bore dia 8-30nm.

The pore volume of preferred described P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice ²/ gram, most probable bore dia 10-25nm.

Preferred described P2 is 80-300 object particulate matter.Further preferred described P2 is 100-200 object particulate matter.

The condition of preferred described drying comprises: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is 600-800 DEG C, and roasting time is 2-6 hour.

In the present invention, that afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2 by shaping, dry for the described hydrated aluminum oxide P1 containing pseudo-boehmite by one of P1 method being modified as P2, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is forming composition roastings method one obtained, and maturing temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated aluminum oxide P1 containing pseudo-boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.

The condition of the drying in preferred described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in maturing temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.

Preferred described P2 is 80-300 object particulate matter in P1 modifier; More preferably 100-200 object particulate matter.

Wherein, the method mixed by the modifier P2 of described hydrated aluminum oxide P1 and P1 containing pseudo-boehmite is ordinary method, such as, is dropped in stirring-type mixer by P1 and P2 of powder mix according to ingredient proportion.Describedly shapingly to carry out according to a conventional method, such as, a kind of method in spin, compressing tablet and extruded moulding or the combination of several method.When shaping, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can add in described mixture water, extrusion aid and/or tackiness agent, containing or not containing expanding agent, then extrusion moulding, carry out drying also roasting afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, PVOH, described peptizing agent can be mineral acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and tensio-active agent.Synthetic cellulose is wherein preferably one or more in Walocel MT 20.000PV, methylcellulose gum, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyoxyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, one or more in the vinylcarbinol multipolymer that tensio-active agent is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is 200-10000 and maleic acid copolymer.

In the preparation of the described carrier of catalyst I, after described sour peptization index D I refers to that hydrated aluminum oxide containing pseudo-boehmite and the hydrated aluminum oxide modifier containing pseudo-boehmite add nitric acid by certain sour aluminum ratio, within certain reaction times by the hydrated aluminum oxide containing pseudo-boehmite of peptization with Al ₂o ₃the percentage ratio of meter, DI=(1-W ₂/ W ₁) × 100%, W ₁and W ₂before being respectively hydrated aluminum oxide containing pseudo-boehmite and acid-respons and with acid-respons after with Al ₂o ₃the weight of meter.

The mensuration of DI comprises: (calcination base content refers to quantitative pseudo-boehmite in 600 DEG C of roastings 4 hours calcination base (also referred to as the butt) content of hydrated aluminum oxide (1) measuring containing pseudo-boehmite, its ratio burning rear weight and burn front weight, be expressed as a percentage), count a; (2) take the hydrated aluminum oxide W containing pseudo-boehmite with analytical balance ₀gram, W ₀amount meet with Al ₂o ₃the W of meter ₁be 6 grams of (W ₁/ a=W ₀), take deionized water W gram, W=40.0-W ₀, under stirring, the hydrated aluminum oxide containing pseudo-boehmite taken and deionized water are added in beaker and mix; With 20mL transfer pipet pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, is joined by this acid solution in the beaker of step (2), stirs lower reaction 8 minutes; (4) step (3) reacted slurries are carried out centrifugation in centrifuges, inserted by throw out in the crucible of having weighed, afterwards, by it in 125 DEG C of dryings 4 hours, in retort furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W ₂gram; (5) according to formula DI=(1-W ₂/ W ₁) × 100% calculates.

Under being enough to make final carrier meet the prerequisite of application claims, the present invention does not specially require the described hydrated aluminum oxide P1 containing pseudo-boehmite, it can be pseudo-boehmite prepared by any prior art, also can be the mixture of pseudo-boehmite and other hydrated aluminum oxide, other hydrated aluminum oxide described be selected from one or more in a Water oxidize aluminium, alumina trihydrate and amorphous hydrated aluminum oxide.

In the present invention, the pore volume of the hydrated aluminum oxide containing pseudo-boehmite, specific surface area and most probable pore size are that the described hydrated aluminum oxide containing pseudo-boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtained.

In further preferred embodiment, characterize with X diffraction, the pseudo-boehmite content in the described hydrated aluminum oxide P1 containing pseudo-boehmite is not less than 50%, is more preferably not less than 60%.

The present inventor is surprised to find, hydrated aluminum oxide P1 containing pseudo-boehmite is heat-treated modified, the peptization index of its modifier changes, by this modifier with without heat treated P1 mixing moulding, dry and after roasting, the carrier obtained has obvious bimodal pore distribution.Particularly by 80-300 object particle wherein, preferred 100-200 object particle with without heat treated part mixing moulding, dry and after roasting, the carrier obtained bimodal in each unimodal pore distribution concentrated especially.Here, described 80-300 object particle, preferred 100-200 object particle refers to that described modifier is through sieve (step comprising fragmentation or grinding if desired), its screening thing (screen underflow) meets 80-300 object particle, the percentage ratio (by weight) that preferred 100-200 object particulate matter accounts for total amount is not less than 60%, is preferably not less than 70% further.

The Mixing ratio by weight of described P1 and P2 refers to the ratio of the shared parts by weight of P1 and P2 difference in the mixture of every hundred parts of described P1 and P2.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 concrete enforcement, described P2 conveniently can be obtained by following method:

(1) obtain P2 based on drying, comprise and prepare in regular oxidation alumina supporter process by the hydrated aluminum oxide P1 containing pseudo-boehmite is shaping according to a conventional method, the tailing of drying by-product, such as: in extruded moulding, bar shaped forming composition is at tailing (being called dry waste material traditionally) that is dry, integer process by-product, this tailing is milled, sieves and obtain P2.

(2) obtain based on roasting, comprise and prepare in regular oxidation alumina supporter process by the hydrated aluminum oxide P1 containing pseudo-boehmite is shaping according to a conventional method, through the tailing (being called roasting waste material traditionally) of roasting by-product, such as, in roller forming, the tailing of spheroidal particle by-product in roasting process, mills this tailing, sieves and obtain P2; Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.

(3) two or more be mixed to get in the modifier P2 obtained based on preceding method.When adopting blending means to obtain P2, the blending ratio of the modifier P2 that aforementioned several method obtains respectively is not limited.

In the present invention, the preparation of described catalyst I comprises and adopts the method for dipping on carrier, introduce hydrogenation active metals component, carry out drying afterwards, the step of roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one the VIIIth race and the metal component of at least one group VIB, be benchmark with oxide basis and with catalyzer, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of the VIIIth race in final catalyzer be 0.5-10 % by weight, the content of the metal component of described group VIB is 0.5-15 % by weight, described drying conditions comprises: temperature is 100-250 DEG C, and the time is 1-10 hour, described roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.

Preferably the metal component of described VIIIth race is selected from nickel and/or cobalt, the metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyzer, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of group VIII in final catalyzer be 0.8-8 % by weight, and the content of the metal component of group VIB is 1-12 % by weight; Described drying conditions comprises: temperature is 100-140 DEG C, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 DEG C, and the time is 2-6 hour.

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

Described dipping method is ordinary method, such as, can be excessive immersion stain, hole saturation method pickling process.One or more in the described soluble compound be selected from containing the metal component compound being selected from VI B race in them, as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstate, metatungstate, ethyl metatungstate, preferably ammonium metawolframate, ethyl ammonium metawolframate wherein.Described containing the compound being selected from VIII race's metal component be selected from their soluble compound one or more, as one or more in the soluble complexes of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and cobalt, be preferably Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous dihydroxycarbonate; One or more in the soluble complexes of nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickel, are preferably nickelous nitrate, basic nickel carbonate.

According to catalyst I provided by the invention, can also the invention provides containing any impact the addO-on therapy that catalyst performance maybe can improve the catalytic performance of catalyzer provided by the invention.As contained the addO-on therapy such as phosphorus, be benchmark with oxide basis and with catalyzer, the content of described addO-on therapy is no more than 10 % by weight, is preferably 0.1-4 % by weight.

When in described catalyst I also containing the addO-on therapy such as phosphorus time, the introducing method of described addO-on therapy can be arbitrary method, as can be by containing as described in the component such as phosphorus compound directly with as described in pseudo-boehmite mix, shaping and roasting; Can be flood described carrier after the compound containing components such as described phosphorus and the compound containing hydrogenation active metals component are mixed with mixing solutions; Can also be flood described carrier and roasting by after independent for the compound containing components such as phosphorus obtain solution.When the addO-on therapy such as phosphorus and hydrogenation active metals introduce described carrier respectively, preferably first use carrier described in the solution impregnation containing described addO-on therapy compound and roasting, afterwards again by the solution impregnation containing hydrogenation active metals component composition.Wherein, described maturing temperature is 400-600 DEG C, and be preferably 420-500 DEG C, roasting time is 2-6 hour, is preferably 3-6 hour.

According to method provided by the invention, wherein, the effect of described catalyst II is to be reacted by the hydrotreatment at this catalyzer, the macromolecular cpd such as polycyclic aromatic hydrocarbons in saturated raw material, the wherein more difficult impurity such as sulphur, nitrogen removed is removed further, improves product property.The present invention does not have other to limit to described catalyst II, 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 preparation.

This type of catalyzer is usually containing heat-resistant inorganic oxide carrier, hydrogenation active metals component.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides being commonly used for support of the catalyst and/or matrix.Such as, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica-titania, are preferably aluminum oxide.Described hydrogenation active metals component be nickel and or cobalt, tungsten and or molybdenum, introduce the composition of active metal with oxide basis for 10 ~ 40%.

Such as, a kind of Hydrobon catalyst disclosed in ZL97112397, it consists of the heavy % of nickel oxide 1 ~ 5, the heavy % of Tungsten oxide 99.999 12 ~ 35, the heavy % of fluorine 1 ~ 9, all the other are aluminum oxide, this aluminum oxide be by one or more little porous aluminum oxides and one or more macroporous aluminium oxides according to 75: 25 ~ 50: 50 weight ratio be composited, wherein little porous aluminum oxide is the aluminum oxide that pore volume that bore dia is less than 80 dust holes accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminum oxide that the pore volume in bore dia 60 ~ 600 dust hole accounts for total pore volume more than 70%.

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

ZL200310117323 discloses a kind of Hydrobon catalyst, this catalyzer contains a kind of alumina supporter and load molybdenum on this carrier, nickel and tungsten metal component, be benchmark with oxide basis and with catalyzer, described catalyzer contains the molybdenum of 0.5-10 % by weight, the nickel of 1-10 % by weight, the tungsten of 12-35 % by weight and the carrier of equal amount, the preparation method of described catalyzer comprises and uses the solution of molybdate compound and nickeliferous successively, the solution impregnation of alumina carrier of tungsten compound, wherein said alumina supporter carries out drying after by the solution impregnation of molybdate compound, with nickeliferous, drying and roasting is carried out after the solution impregnation of tungsten compound, drying temperature is 100-300 DEG C, time of drying is 1-12 hour, maturing temperature is 320-500 DEG C, roasting time is 1-10 hour.

According to method provided by the invention, describedly comprise hydrotreating catalyst I and hydrotreating catalyst II can layering fill in same reactor successively, also can be use in the two or more reactors filling in series connection successively, this present invention is not particularly limited.

According to method provided by the invention, wherein, comprise hydrotreating catalyst I and hydrotreating catalyst II combine before, afterwards or they between any two, any other catalyzer or the filler that contribute to improving described catalyst combination performance can be comprised.Such as, added as fillers such as porcelain ball, active upholders before described hydrotreating catalyst I, to improve stock oil distribution etc. in the reactor.Use etc. about this filler is conventionally known to one of skill in the art, does not repeat here.

The device of described hydrogenation reaction can carry out in the reactor that described stock oil is reacted with described catalyst exposure at hydrotreating reaction conditions in any being enough to, and such as, at described fixed-bed reactor, carries out in moving-burden bed reactor or ebullated bed reactor.

According to the ordinary method in this area, described hydrotreating catalyst before the use, usually can be in presence of hydrogen, prevulcanized is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this prevulcanized can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.

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

Embodiment

The present invention will be further described for the following examples, but therefore should not be interpreted as limitation of the invention.

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

Following examples illustrate the inventive method catalyzer I and preparation method thereof.

The pseudo-boehmite used below in an example comprises:

P1-1: (pore volume is 1.2 mls/g to the dry glue powder that Chang Ling catalyzer branch office produces, and specific surface is 280 meters ²/ gram, most probable bore dia 15.8nm.Butt is 73%, and wherein pseudo-boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 15.8).

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

Embodiment 1-5 illustrates modifier P2 of the described P1 of the carrier of Kaolinite Preparation of Catalyst I and preparation method thereof.

Embodiment 1

Take 1000 grams of P1-1, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier P2A of P1-1.The k value of P2A is in table 1.

Embodiment 2

Take 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 the 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

Take 1000 grams of P1-2, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 2mm is milled, sieve, get wherein 100 ~ 200 mesh sieves and divide, obtain the modifier P2D of P1-2.The k value of P2D is in table 1.

Embodiment 5

Take 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

Embodiment 6-13 illustrates the preparation method of Kaolinite Preparation of Catalyst I carrier.Comparative example 1-2 illustrates the preparation method of conventional catalyst carrier.

Embodiment 6

Take 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 1 is obtained, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 800 DEG C of roastings 3 hours, obtains carrier Z1.The character of carrier Z1 lists in table 2.

Embodiment 7

Take 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing that embodiment 2 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 840 DEG C of roastings 3 hours, obtains carrier Z2.The character of carrier Z2 lists in table 2.

Embodiment 8

Take 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 750 DEG C of roastings 3 hours, obtains carrier Z3.The character of carrier Z3 lists in table 2.

Comparative example 1

Take 1000 grams of P1-1, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 800 DEG C of roastings 3 hours, obtains carrier DZ1.The character of carrier DZ1 lists in table 2.

Embodiment 9

Take 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), the 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, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 800 DEG C of roastings 3 hours, obtains carrier Z4.The character of carrier Z4 lists in table 2.

Embodiment 10

Take 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 750 DEG C of roastings 3 hours, obtains carrier Z5.The character of carrier Z5 lists in table 2.

Embodiment 11

Take 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 800 DEG C of roastings 3 hours, obtains carrier Z6.The character of carrier Z6 lists in table 2.

Comparative example 2

Take 1000 grams of P1-2, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 800 DEG C of roastings 3 hours, obtains carrier DZ2.The character of carrier DZ2 lists in table 2.

Embodiment 12

Take 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 750 DEG C of roastings 3 hours, obtains carrier Z7.The character of carrier Z7 lists in table 2.

Embodiment 13

Take 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 830 DEG C of roastings 3 hours, obtains carrier Z8.The character of carrier Z8 lists in table 2.

Table 2

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

Embodiment 14

Get 200 grams of carrier Z1, with 220 milliliters containing MoO ₃20 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO5 grams per liter flood 1 hour, and 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

Get 200 grams of carrier Z2, with 220 milliliters containing MoO ₃20 grams per liters, ammonium molybdate and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES mixing solutions of CoO5 grams per liter flood 1 hour, and 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

Get 200 carrier Z3, with 220 milliliters containing WO ₃22 grams per liters, ammonium metawolframate and the nickelous nitrate mixing solutions of NiO6 grams per liter flood 1 hour, and 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

Get 200 grams of carrier Z4, with 220 milliliters containing WO ₃22 grams per liters, ammonium metawolframate and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES mixing solutions of CoO6 grams per liter flood 1 hour, and 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

Get 200 grams of carrier Z5, with 220 milliliters containing MoO ₃16 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO4 grams per liter flood 1 hour, and 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

Get 200 grams of carrier Z8, with 220 milliliters containing MoO ₃16 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO4 grams per liter flood 1 hour, and 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

Get 200 grams of carrier DZ1, with 220 milliliters containing MoO ₃20 grams per liters, ammonium molybdate and the nickelous nitrate mixing solutions of NiO5 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain adding process catalyzer DCI1.The composition of DCI1 is listed in table 3.

Contrast row 4

Get 200 grams of carrier DZ2, with 220 milliliters containing MoO ₃20 grams per liters, ammonium molybdate and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES mixing solutions of CoO5 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain adding process catalyzer DCI2.The composition of DCI2 is listed in table 3.

Comparative example 5

Get 200 grams of carrier DZ1, with 220 milliliters containing WO ₃22 grams per liters, ammonium metawolframate and the nickelous nitrate mixing solutions of NiO6 grams per liter flood 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 catalyzer, the content of each metal component is calculated value.

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

Embodiment 20

Be C II 1 according to embodiment 6 Kaolinite Preparation of Catalyst II in patent ZL97112397.7, it consists of the heavy % of nickel oxide 2.3, the heavy % of Tungsten oxide 99.999 22.0, and the heavy % of fluorine 4, all the other are aluminum oxide.

Embodiment 21

Be C II 2 according to embodiment 37 Kaolinite Preparation of Catalyst II in patent ZL00802168.6, it consists of the heavy % of nickel oxide 2.6, the heavy % of molybdenum oxide 23.6, and the heavy % of fluorine 2.3, all the other are aluminum oxide.

Embodiment 22

Be C II 3 according to embodiment 3 Kaolinite Preparation of Catalyst II in patent ZL200310117323.0, it consists of the heavy % of nickel oxide 2.1, the heavy % of molybdenum oxide 2.5, and the heavy % of Tungsten oxide 99.999 25.4, all the other are aluminum oxide.

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

With Ni+V content be 15.1ppm, sulphur content be the mixing inferior heavy oil of 3.3% for raw material, evaluate catalysts on 500 milliliters of fixed-bed reactor.

In oil sample, the content of nickel and vanadium adopts inductive coupling plasma emission spectrograph (ICP-AES) to measure (instrument is U.S. PE company PE-5300 type plasma quantometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124-90)

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

Catalyzer usage ratio and processing condition are listed in table 4, and the product property after 1000 hours that operates is listed in table 5.

Comparative example 6

Catalyzer adopts the combination of DCI1, CII1, and the volume of each catalyst levels when processing condition is listed in table 4, and operate sampling analysis after 1000 hours, the results are shown in table 5.

Comparative example 7

Catalyzer adopts the combination of DCI2, CII2, and the volume of each catalyst levels when processing condition is listed in table 4, and operate after 1000 hours sampling analysis afterwards, the results are shown in table 5.

Comparative example 8

Catalyzer adopts the combination of DCI3, CII3, and the volume of each catalyst levels when processing condition is listed in table 4, and operate after 1000 hours sampling analysis afterwards, the results are shown in table 5.

Whether table 4(notes examining catalyzer in this table corresponding with table 3, does not at least have 4-6 catalyzer in CII series)

Table 5

Can find out, after adopting raw catalyst and correlation technique, metal, the sulphur content of running 1000 hours back end hydrogenation treating product are starkly lower than prior art, as FCC charging, product property be improved significantly, new technology run stability is better simultaneously.

Claims

2. the method according to 1, is characterized in that, in described catalyzer I, the pore volume of carrier is 0.9-1.15 ml/g, and specific surface area is 150-300 rice ²/ gram, diameter is the 60-75% that the pore volume in 6-30nm hole accounts for total pore volume, diameter be wherein the pore volume in 10-30nm hole lower than 54% of total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.

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

4. the method according to 3, 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, with oxide basis and with catalyzer I for benchmark, the content of described metal component of group VIII is 0.8-8 % by weight, and the content of metal component of group VIB is 1-12 % by weight.

5. the method according to 4, is characterized in that, with oxide basis and with catalyzer I for benchmark, the content of described metal component of group VIII is 1-6 % by weight, and the content of metal component of group VIB is 2-10 % by weight.

6. the method according to 1, is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of the catalyzer I in described catalyst combination is 10-35%, the content of catalyst II is 65-90%.

7. the method according to 1, it is characterized in that, described catalyst II contains the carrier being selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, take catalyst II as benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 10 ~ 35 % by weight, is 0 ~ 9 % by weight in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element.

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

9. the method according to 8, is characterized in that, the pore volume of described aluminum oxide is not less than 0.35 ml/g, and bore dia is that the pore volume in 40 ~ 100 dust holes accounts for more than 80% of total pore volume.

10. the method according to 1, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 6-20MPa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.2-3h ^-1, hydrogen to oil volume ratio is 300-1500.

11. methods according to 10, is characterized in that, the reaction conditions 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.