CN104293383B

CN104293383B - A kind of hydroprocessing process optimizing catalytically cracked material character

Info

Publication number: CN104293383B
Application number: CN201310303931.4A
Authority: CN
Inventors: 胡大为; 孙淑玲; 杨清河; 刘佳; 聂红; 王奎; 李大东; 刘学芬; 戴立顺; 刘涛
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-07-18
Filing date: 2013-07-18
Publication date: 2016-03-23
Anticipated expiration: 2033-07-18
Also published as: CN104293383A

Abstract

A kind of hydroprocessing process optimizing catalytically cracked material character, comprise at hydrotreating reaction conditions, by heavy raw oil successively with comprise hydrotreating catalyst I, hydrotreating catalyst II contacts with the catalyst combination of hydrotreating catalyst III, wherein, described hydrotreating catalyst I contains shaped alumina alumina supporter, described pore volume is 0.8 ml/g ~ 1.2 mls/g, specific surface area is 90 meters squared per gram ~ 230 meters squared per gram, most probable bore dia is 20 nanometer ~ 30 nanometers, average pore diameter is 25 nanometer-35 nanometers, it is 95% ~ 99.8% that diameter 10 nanometer ~ 60 nanoporous volume accounts for total pore volume ratio, described hydrotreating catalyst II is containing the hydrogenation active metals component being selected from least one group vib and at least one VB race, be benchmark with oxide basis and with catalyst II, the content of described group vib metal component is 0.2-15 % by weight, and the content of VB race metal component is 0.2-12 % by weight.Compared with prior art, the present invention has better heavy hydrocarbon oil hydrotreatment performance.

Description

A kind of hydroprocessing process optimizing catalytically cracked material character

Technical field

The present invention relates to 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 catalyst consumption, require that in heavy oil catalytic cracking raw material oil, W metal+V content should lower than 20ppm, sulphur content is lower than 0.5%, and carbon residue content is less than 6.0%.But because feedstock property is constantly deteriorated, heavy-oil hydrogenation process 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 new catalyzer and processing and treating method is adopted to be the optimal selections of production high-quality catalytically cracked material.

Summary of the invention

The technical problem to be solved in the present invention is for prior art demand, provide a kind of newly, heavy feed stock oil hydrotreating method that catalytically cracked material character can be optimized.

The present invention relates to following content:

1, a kind of hydroprocessing process optimizing catalytically cracked material character, comprise at hydrotreating reaction conditions, by heavy raw oil successively with comprise hydrotreating catalyst I, hydrotreating catalyst II contacts with the catalyst combination of hydrotreating catalyst III, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreating catalyst I is 5-60%, the content of hydrotreating catalyst II is 5-50%, and the content of hydrotreating catalyst III is 10-60%; Wherein, described hydrotreating catalyst I contains shaped alumina alumina supporter, described pore volume is 0.8 ml/g ~ 1.2 mls/g, specific surface area is 90 meters squared per gram ~ 230 meters squared per gram, most probable bore dia is 20 nanometer ~ 30 nanometers, average pore diameter is 25 nanometer-35 nanometers, and it is 95% ~ 99.8% that diameter 10 nanometer ~ 60 nanoporous volume accounts for total pore volume ratio; Described hydrotreating catalyst II is containing the hydrogenation active metals component being selected from least one group vib and at least one VB race, be benchmark with oxide basis and with catalyst II, the content of described group vib metal component is 0.2-15 % by weight, and the content of VB race metal component is 0.2-12 % by weight.

2, the method according to 1, it is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreating catalyst I is 10-50%, the content of hydrotreating catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; The pore volume of the described carrier in described hydrotreating catalyst I is 0.8 ml/g ~ 1.2 mls/g, and specific surface area is 90 meters squared per gram ~ 230 meters squared per gram; The metal component of the group vib in described hydrotreating catalyst II is selected from molybdenum and/or tungsten, the metal component of VB race is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst II, the content of described group vib metal component is 0.5-12 % by weight, and the content of VB race metal component is 0.5-9 % by weight.

3, the method according to 1 or 2, it is characterized in that, the metal component of the described group vib in described hydrotreating catalyst II is molybdenum or tungsten, VB race metal component is vanadium, be benchmark with oxide basis and with catalyst II, the content of described group vib metal component is 5-12 % by weight, and the content of VB race metal component is 1-9 % by weight.

4, the method according to 1, it is characterized in that, described hydrotreating catalyst I contains hydrogenation active metals component, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, with oxide basis and with described catalyst I for benchmark, the content of group VIII metal component is for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 15 % by weight.

5, the method according to 4, it is characterized in that, described group VIII metal component is selected from nickel and/or cobalt, vib metal component is selected from molybdenum and/or tungsten, with oxide basis and with described catalyst I for benchmark, the content of group VIII metal component is 0.1-3 % by weight, and the content of group vib metal component is 0.5-10 % by weight.

6, the method according to 1, is characterized in that, described hydrotreating catalyst II is containing carrier, and characterize with mercury penetration method, the pore volume of described carrier is 0.95-1.2 ml/g, and specific surface is 50-300 rice ²/ gram, described carrier be 10-30nm and diameter is 300-500nm at diameter is bimodal pore distribution, and the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, and the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.

7, the method according to 6, is characterized in that, the pore volume of described carrier is 0.95-1.15 ml/g, and specific surface area is 80-200 rice ²/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.

8, the method according to 6, is characterized in that, containing halogen in the shaping carrier of described hydrotreating catalyst II, in element and with the carrier of described catalyst II for benchmark, the content of described halogen is 0.1-6 % by weight.

9, the method according to 8, is characterized in that, described halogen component is selected from one or more in fluorine, chlorine, bromine, iodine and astatine, and with oxide basis and with the carrier of described catalyst II for benchmark, the content of described halogen is 0.3-4 % by weight.

10, the method according to 9, is characterized in that, described halogen is preferably fluorine, and with oxide basis and with the carrier of described catalyst II for benchmark, the content of described halogen is 0.5-2.5 % by weight.

11, the method according to 1, it is characterized in that, described catalyzer III is containing the carrier being selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, with catalyzer III for 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.

12, the method according to 11, is characterized in that, the support selected from alumina in described catalyzer III.

13, the method according to 12, 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.

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

15, the method according to 14, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 10-18MPa, temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h ^-1, hydrogen to oil volume ratio is 800-1100.

According to method provided by the invention, wherein, it is 0.8 ml/g ~ 1.2 mls/g meeting the described pore volume in described hydrotreating catalyst I, specific surface area is 90 meters squared per gram ~ 230 meters squared per gram, most probable bore dia is 20 nanometer ~ 30 nanometers, average pore diameter is 25 nanometer-35 nanometers, and it is under the prerequisite of 95% ~ 99.8% that diameter 10 nanometer ~ 60 nanoporous volume accounts for total pore volume ratio, and arbitrary prior art can be adopted to prepare this carrier.Such as, 201010188611.5 and 201010188605.X in this method is disclosed, here they are quoted as a reference.

Described hydrotreating catalyst I contains hydrogenation active metals component, and described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component.In the present invention, emphasize the effective elimination of catalyzer I, deposition the impurity performance such as the iron held in described stock oil and calcium, therefore, with oxide basis and with described catalyst I for benchmark, the content of preferred group VIII metal component is wherein for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 15 % by weight; Further preferred described group VIII metal component is selected from nickel and/or cobalt, vib metal component is selected from molybdenum and/or tungsten, with oxide basis and with described catalyst I for benchmark, the content of group VIII metal component is 0.1-3 % by weight, and the content of group vib metal component is 0.5-10 % by weight.

In a concrete embodiment, prepare carrier according to method disclosed in 201010188605.X, comprise the steps:

(1) aqueous solution of sodium metaaluminate and/or sodium aluminate and acidic solution are reacted, aging, to wash and dry, described reaction conditions comprises: pH value in reaction is 4.5 ~ 9, and temperature of reaction is 15 DEG C ~ 75 DEG C; Aging condition comprises: add aging dose, and aging temperature is 15 DEG C ~ 75 DEG C, and digestion time is 0.5 hour ~ 8 hours; Obtained wide aperture, high pore volume pseudo-boehmite after routine washing, drying.

(2) pseudo-boehmite that step (1) obtains is carried out shaping, dry also roasting, obtained wide aperture, high pore volume alumina supporter.Wherein, described shaping, drying means is usual, the conventional method in this area, and described maturing temperature is 850 DEG C ~ 1100 DEG C, and roasting time is 1.5 hours ~ 6 hours.

Wherein, acidic solution refers to the solution that the pH value that the aqueous solution of sodium metaaluminate and/or sodium aluminate carries out precipitating can be less than 7 in described step (1), it can be inorganic acid aqueous solution, it can be aqueous solutions of organic acids, can be the aqueous solution of various compound, also can be one or more in the above-mentioned aqueous solution.Described acidic solution is preferably one or more in aluminum sulfate aqueous solution, aluminum chloride aqueous solution, aluminum nitrate aqueous solution.In described step (1), reaction conditions is preferably: pH value in reaction 5.5 ~ 8.5, temperature of reaction 20 DEG C ~ 60 DEG C.Described aging condition is preferably: add aging dose, aging temperature 20 DEG C ~ 60 DEG C, digestion time is 2 hours ~ 6 hours.Described aging dose is volatile salt and/or bicarbonate of ammonia, or its aqueous solution, is preferably ammonium carbonate solution.Described washing is conventional method, its object is to the acid ion and the positively charged ion that remove other, meets the demands to make it.Described drying is conventional method, comprises the drying modes such as baking oven, flash distillation, spraying.

Forming method described in step (2) is usual, conventional forming method, such as, can be the methods such as compressing tablet, spin, extrusion.When adopting customary way shaping, for guaranteeing that shaping to carry out smoothly introducing auxiliary agent in described pseudo-boehmite be allow, such as, when extrusion, appropriate extrusion aid, peptizing agent and water can be introduced in described pseudo-boehmite, extrusion moulding afterwards.The kind of described extrusion aid and consumption can be all this area routines, such as, can be selected from one or more in sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, PVOH.The kind of described peptizing agent and consumption can be all this area routines, such as, can be selected from one or more in nitric acid, acetic acid, citric acid, oxalic acid.

According to carrying alumina preparation provided by the invention, in described step (2), maturing temperature is preferably 900 DEG C ~ 1000 DEG C, and roasting time is preferably 2 hours ~ 4.5 hours.

Be enough under the prerequisite that described hydrogenation active metals component is loaded on carrier, the present invention in the preparation of described catalyst I the method for load hydrogenation active metals component be not particularly limited.The preferred method adopting dipping.The method of described dipping is for preparing hydrogenation class catalyzer customary way, can be such as containing being selected from VIII and being selected from the solution impregnating carrier of metal component compound of group vib with excessive, can be with containing being selected from VIII and being selected from the solution hole saturation method impregnated carrier of metal component compound of group vib, carry out drying, roasting or not roasting afterwards.The method of described drying and roasting is conventional method, and preferred drying conditions comprises: drying temperature is 60 ~ 150 DEG C, and time of drying is 1 ~ 10 hour, and preferably drying temperature is 80 ~ 120 DEG C further, and time of drying is 2 ~ 8 hours; Preferred roasting condition comprises: maturing temperature is 350-550 DEG C, and roasting time is 1-6 hour, and preferably maturing temperature is 400 ~ 500 DEG C further, and roasting time is 2 ~ 4 hours.

One or more in the described soluble compound be selected from containing the metal component compound being selected from group vib in them, as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstate, metatungstate, ethyl metatungstate, preferably ammonium metawolframate, ethyl ammonium metawolframate wherein.

Described containing the compound being selected from group VIII metal component be selected from their soluble compound one or more, as one or more in the soluble complexes of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and cobalt, be preferably Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous dihydroxycarbonate; One or more in the soluble complexes of nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickel, are preferably nickelous nitrate, basic nickel carbonate.

Contriver finds, by hydrogenation active metals component be the combination being selected from catalyzer and hydrotreating catalyst I of the present invention and hydrotreating catalyst III that the metal component of at least one group vib and at least one are selected from the metal component of VB race be used for mink cell focus hydrotreatment time, there is good mink cell focus hydrotreatment performance, be particularly suitable for the hydrotreatment of mink cell focus to produce FCC charging.

In a preferred embodiment, the carrier in described catalyst II is formed alumina, and characterize with mercury penetration method, the pore volume of described carrier is 0.95-1.2 ml/g, and specific surface is 50-300 rice ²/ gram, described carrier be 10-30nm and diameter is 300-500nm at diameter is bimodal pore distribution, and the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, and the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.Preferably, in described Hydrodemetalation catalyst II, the pore volume of carrier is 0.95-1.15 ml/g, and specific surface area is 80-200 rice ²/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.In further preferred embodiment, containing halogen in described shaped alumina alumina supporter, in element and with the carrier of described catalyst II for benchmark, the content of described halogen is 0.1-6 % by weight, and the content of preferred described halogen is 0.3-4 % by weight; The content of further preferred described halogen is 0.5-2.5 % by weight.

According to method provided by the invention, wherein, the preparation method of described catalyst II comprises and prepares carrier and the component of load hydrogenation active metals on this carrier, wherein, the preparation of described carrier comprises and being mixed by the modifier P2 of hydrated aluminum oxide P1 and P1 containing pseudo-boehmite, aftershaping, dry and roasting.

The Mixing ratio by weight of described P1 and P2 is 20-95:5-80, is preferably 70-95:5-25.The Mixing ratio by weight of described P1 and P2 refers to the ratio of the shared parts by weight of P1 and P2 difference in the mixture of every hundred parts of described P1 and P2.The κ value of P2 is 0 to being less than or equal to 0.9, is preferably 0 to being less than or equal to 0.6.Described κ=DI ₂/ DI ₁.DI ₁for the sour peptization index of the hydrated aluminum oxide P1 containing pseudo-boehmite, DI ₂for the sour peptization index of the modifier P2 of the hydrated aluminum oxide P1 containing pseudo-boehmite.

Wherein, after described sour peptization index D I refers to that the hydrated aluminum oxide containing pseudo-boehmite adds nitric acid by certain sour aluminum ratio, within certain reaction times by peptization containing the hydrated aluminum oxide of pseudo-boehmite with Al ₂o ₃the percentage ratio of meter, DI=(1-W ₂/ W ₁) × 100%, W ₁and W ₂be respectively intend thin water aluminium and acid-respons front and with acid-respons after with Al ₂o ₃the weight of meter.

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

The condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour, and being preferably temperature is 100-200 DEG C, and the time is 2-12 hour; The condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour, is preferably temperature for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour.

Wherein, that afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2 by shaping, dry for the described hydrated aluminum oxide P1 containing pseudo-boehmite by one of P1 method being modified as P2, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is forming composition roastings method one obtained, and maturing temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated aluminum oxide P1 containing pseudo-boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.Preferably, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in maturing temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.

In concrete enforcement, described P2 conveniently can be obtained by following method:

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

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

(3) two or more be mixed to get in the modifier P2 obtained based on preceding method.

When adopting blending means to obtain P2, can optionally at random adjust the blending ratio of the modifier P2 that aforementioned several method obtains respectively, the present invention is not limited in this respect.

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.Such as, pore volume is 0.9-1.4 ml/g, and specific surface is 100-350 rice ²/ gram, can and bore dia 8-30nm; Preferred pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice ²/ gram, can and the hydrated aluminum oxide containing pseudo-boehmite of bore dia 10-25nm be just particularly suitable for the present invention.In the present invention, the pore volume of the hydrated aluminum oxide containing pseudo-boehmite, specific surface area and can and aperture, be 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 obtains.

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

Preferred described P2 is 80-300 object particulate matter, and further preferred described P2 is 100-200 object particulate matter.Here, described 80-300 object particle, preferred 100-200 object particle refers to that described modifier is through sieve (step comprising fragmentation or grinding if desired), its screening thing (screen underflow) meets 80-300 object particle, the percentage ratio (by weight) that preferred 100-200 object particulate matter accounts for total amount is not less than 60%, is preferably not less than 70% further.

The forming composition that carrier wherein can be made into various easy handling is required, such as spherical, cellular, nest like, tablet or bar shaped (trifolium, butterfly, cylindrical etc.) depending on different.Wherein, the method mixed by the modifier P2 of described hydrated aluminum oxide P1 and P1 containing pseudo-boehmite is ordinary method, such as, is dropped in stirring-type mixer by P1 and P2 of powder mix according to ingredient proportion.

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

Time in the shaping carrier of described Hydrodemetalation catalyst II containing halogen, comprise the step introducing halogen in the preparation of described carrier.The introducing method of described halogen is ordinary method.Such as, concrete prepare in the embodiment of carrier at one, the method introducing halogen contained compound in the mixture of the modifier P2 of described hydrated aluminum oxide P1 and P1 containing pseudo-boehmite is that halogen contained compound is mixed with the aqueous solution, this aqueous solution is mixed into while described P1 and P1 mixing or again this aqueous solution is mixed into after described P1 and P1 mixing, aftershaping, dry and roasting.Described halogen contained compound can be one or more in the water-soluble cpds of arbitrary halogen.For fluorine wherein, can be Neutral ammonium fluoride, hydrofluoric acid and composition thereof etc.In element and with described carrier for benchmark, the introduction volume of described halogen contained compound makes the content of halogen in final carrier be 0.1-6 % by weight, is preferably 0.3-4 % by weight, more preferably 0.5-2.5 % by weight.

Be enough under the prerequisite that described hydrogenation active metals component is carried on described carrier, the present invention is not particularly limited the carrying method of hydrogenation active metals component in described catalyst II preparation, preferred method is pickling process, comprise the dipping solution of preparation containing the compound of described metal, afterwards with the carrier described in this solution impregnation, carry out drying, roasting or not roasting afterwards.Described dipping method is ordinary method, such as, can be excessive immersion stain, hole saturation method pickling process.Described drying conditions comprises: temperature is 100-250 DEG C, and the time is 1-10 hour; Described roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.Preferred described drying conditions comprises: temperature is 100-140 DEG C, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 DEG C, and the time is 2-6 hour.

Wherein, one or more (are included in solubility promoter and there is lower water-soluble compound) in their water-soluble cpds are selected from containing the compound of described metal.For the molybdenum of group vib, can be selected from as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; For the tungsten of group vib, can be selected from as one or more in tungstate, metatungstate, ethyl metatungstate, preferably ammonium metawolframate, ethyl ammonium metawolframate wherein; For the vanadium of VB race, can be selected from as one or more in Vanadium Pentoxide in FLAKES, ammonium vanadate, ammonium meta-vanadate, Vanadosulfuric acid, vanadium heteropolyacid, preferably ammonium meta-vanadate, ammonium vanadate wherein.

According to method provided by the invention, wherein said hydrotreating catalyst II can also the invention provides containing any impact the material that catalyst performance maybe can improve the catalytic performance of catalyzer provided by the invention.As contained the components such as phosphorus, be benchmark with oxide basis and with catalyzer, the content of said components is no more than 10 % by weight, is preferably 0.5-5 % by weight.

When in described Hydrodemetalation catalyst II also containing the component such as phosphorus time, the introducing method of the components such as described phosphorus 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 by the compound containing components such as described phosphorus be mixed with containing the compound of hydrogenation active metals component after mixing solutions with described carrier contact; Can also be by after independent for the compound containing components such as phosphorus obtain solution with described carrier contact and roasting.When the components such as phosphorus and hydrogenation active metals introduce described carrier respectively, preferably first use containing auxiliary compound solution and described carrier contact and roasting, contact with the solution of the compound containing hydrogenation active metals component more afterwards, such as by the method for dipping, described maturing temperature is 400-600 DEG C, be preferably 420-500 DEG C, roasting time is 2-6 hour, is preferably 3-6 hour.

In the present invention, the effect of described catalyzer III is the macromolecular cpds such as saturated polycyclic aromatic hydrocarbons, the wherein more difficult impurity such as sulphur, nitrogen removed is removed further, removes the carbon residue in stock oil simultaneously, improves product property.Be enough under the prerequisite realizing above-mentioned functions, the present invention does not have other to limit to described catalyzer III, and namely catalyzer III can be selected from the catalyzer such as hydrofining, hydrotreatment that arbitrary prior art provides.They can be commercially available commodity or adopt any existing method preparation.

Usually, this type of catalyzer is usually containing heat-resistant inorganic oxide carrier, hydrogenation active metals component.Such as, described catalyzer III is containing the carrier being selected from aluminum oxide and/or silica-alumina, be selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, containing or not containing being selected from one or more adjuvant components in fluorine, boron and phosphorus, with oxide basis and with catalyzer III for benchmark, the content of described nickel and/or cobalt is 1-5 % by weight, and the content of molybdenum and/or tungsten is 10-35 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron and phosphorus of element for 0-9 % by weight.

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

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

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

These catalyzer all can be used as described catalyzer III for the present invention.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump their parts as content of the present invention are quoted here.

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

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

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

According to method provided by the invention, the reaction conditions of described hydrotreatment reaction is the normal condition of heavy oil hydrotreatment, and such as, described reaction conditions comprises: hydrogen dividing potential drop 6-20MPa, and temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1.0h ^-1, hydrogen to oil volume ratio is 600-1500, wherein preferred hydrogen dividing potential drop 10-18MPa, and temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h ^-1, hydrogen to oil volume ratio is 800-1100.

According to described method, raw material is selected from one or more in the poor crude oil of character, vacuum residuum, deep drawing wax oil, frivolous asphalt oil, wax tailings etc.

According to after the hydrotreatment that described method obtains oil asphalt content be less than 1.2%, iron, calcium contents are 15 below μ g/g, and W metal+V content is 20 below μ g/g, sulphur content less than 0.5%, and carbon residue content is less than 6.0%.

Embodiment

The present invention is described further for the following examples.

Hydrotreating catalyst I in the present invention and preparation method thereof:

Embodiment 1 ~ 3 illustrates pseudo-boehmite of the described catalyst I carrier of preparation and preparation method thereof.

Embodiment 1

Take 483 grams, aluminum chloride (Beijing Chemical Plant's product), add deionized water dissolving become volumetric molar concentration be 1 solution a1; Take sodium metaaluminate (Tianjin Jin Ke fine chemistry industry institute product) 210 grams, add deionized water dissolving become volumetric molar concentration be 3.0 solution b1; Take volatile salt (Beijing chemical reagents corporation product) 230 grams, add deionized water dissolving become volumetric molar concentration be 0.5 solution c1.Solution a1 and solution b1 is joined in the plastic cans of 10 liters in the mode also flowed simultaneously and reacts, control solution a1 and solution b1 inflow velocity, make the pH value of reaction process be 8.5, gelling temperature is 60 DEG C, after having reacted, add solution C 1, at 60 DEG C aging 2.5 hours, filter, the filter cake deionized water wash of 10 liters 60 DEG C, in loft drier, 150 DEG C of dryings 2 hours, obtain pseudo-boehmite A, after 600 DEG C of roastings, its pore volume, specific surface area, bore dia are listed in table 1.With pseudo-boehmite A for benchmark, by weight, in pseudo-boehmite A, Aluminum Carbonate Basic ammonium content is 7.3%.

Embodiment 2

Take 666 grams, Tai-Ace S 150 (Beijing Chemical Plant's product), add deionized water dissolving become volumetric molar concentration be 0.5 solution a2; Take sodium metaaluminate (Tianjin Jin Ke fine chemistry industry institute product) 210 grams, add deionized water dissolving become volumetric molar concentration be 2.0 solution b2; Take 370 grams, bicarbonate of ammonia (Beijing chemical reagents corporation product), add deionized water dissolving become volumetric molar concentration be 1.0 solution c2.Solution a2 and solution b2 is joined in the plastic cans of 10 liters in the mode also flowed simultaneously and reacts, control solution a2 and solution b2 inflow velocity, make the pH value of reaction process be 6.0, gelling temperature is 40 DEG C, after having reacted, add solution C 2, at 40 DEG C aging 6 hours, filter, the filter cake deionized water wash of 15 liters 40 DEG C, in loft drier, 100 DEG C of dryings 6 hours, obtain pseudo-boehmite B, after 600 DEG C of roastings, its pore volume, specific surface area, bore dia are listed in table 1.With pseudo-boehmite B for benchmark, by weight, in pseudo-boehmite B, Aluminum Carbonate Basic ammonium content is 5.5%.

Embodiment 3

Take aluminum nitrate (Beijing Chemical Plant's product) 750 grams, add deionized water dissolving become volumetric molar concentration be 1.5 solution a3; Take sodium metaaluminate (Tianjin Jin Ke fine chemistry industry institute product) 210 grams, add deionized water dissolving become volumetric molar concentration be 4.5 solution b3; Take volatile salt (Beijing chemical reagents corporation product) 300 grams, add deionized water dissolving become volumetric molar concentration be 1.5 solution c3.Solution a3 and solution b3 is joined in the plastic cans of 10 liters in the mode also flowed simultaneously and reacts, control solution a3 and solution b3 inflow velocity, make pH value in reaction process be 7.0, plastic cans temperature is 25 DEG C, after having reacted, add solution C 3, at 25 DEG C aging 4 hours, filter, the filter cake deionized water wash of 25 liters 25 DEG C, in loft drier, 120 DEG C of dryings 4 hours, obtain pseudo-boehmite C, after 600 DEG C of roastings, its pore volume, specific surface area, bore dia are listed in table 1.With pseudo-boehmite C for benchmark, by weight, in pseudo-boehmite C, Aluminum Carbonate Basic ammonium content is 9.6%.

Table 1

Embodiment 4 ~ 6 illustrates carrier and the preparation thereof of catalyst I of the present invention.

Embodiment 4

Pseudo-boehmite A100 gram is mixed with 4 grams of polyvinyl alcohol, adding containing 2.5 grams of concentration is 65% nitre aqueous acid 130 milliliters, the trilobal bar that equivalent diameter is 1.2 millimeters is extruded on screw rod banded extruder, in 120 DEG C of dryings 2 hours, 900 DEG C of roastings 4.5 hours, obtain carrier Z I 1, its pore volume, specific surface area, bore dia are listed in table 2.

Embodiment 5

Pseudo-boehmite B100 gram is mixed with 4 grams of sesbania powder, add containing 3 grams of second aqueous acids 120 milliliters, the trilobal bar that equivalent diameter is 1.2 millimeters is extruded on screw rod banded extruder, in 120 DEG C of dryings 2 hours, 950 DEG C of roastings 3 hours, obtain carrier Z I 2, its pore volume, specific surface area, bore dia are listed in table 2.

Embodiment 6

Pseudo-boehmite C100 gram is mixed with 1.5 grams of methylcellulose gum, 2 grams of sesbania powder, add containing 4 grams of lemon aqueous acids 135 milliliters, the trilobal bar that equivalent diameter is 1.2 millimeters is extruded on screw rod banded extruder, in 120 DEG C of dryings 2 hours, 1000 DEG C of roastings 2 hours, obtain carrier Z I 3, its pore volume, specific surface area, bore dia are listed in table 2.

Table 2

Embodiment 7 ~ 9 illustrates described catalyst I and the preparation thereof of the present invention.

Embodiment 7

Carrier Z190 gram prepared by Example 4, with 120 milliliters containing molybdenum oxide 64 grams per liter, ammonium molybdate and the nickelous nitrate mixing solutions of nickel oxide 14 grams per liter flood 1 hour, and in 120 DEG C of oven dry 2 hours, 500 DEG C of roastings 4 hours, obtained catalyzer C I 1.The composition of catalyzer C I 1 is listed in table 3.

Example 8

Get carrier Z2200 gram prepared by example 2, with 500 milliliters containing MoO350 grams per liter, ammonium molybdate and the nickelous nitrate mixing solutions of NiO8 grams per liter flood 1 hour, and in 120 DEG C of oven dry 2 hours after filtration, 480 DEG C of roastings 4 hours, obtain catalyzer C I 2.The composition of catalyzer C I 2 is listed in table 3.

Example 9

Get carrier Z3200 gram prepared by example 3, with 500 milliliters containing MoO3100 grams per liter, the ammonium molybdate of NiO20 grams per liter and nickel nitrate solution flood 1 hour, and in 120 DEG C of oven dry 2 hours after filtration, 500 DEG C of roastings 4 hours, obtain catalyzer C I 3.The composition of catalyzer C I 3 is listed in table 3.

Table 3

Embodiment 10-14 illustrates P1 and P2 of preparation catalyst II carrier of the present invention and preparation method thereof.

The pseudo-boehmite used below in an example comprises:

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

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

Embodiment 10-14 illustrates modifier P2 of the described P1 of preparation carrier of the present invention and preparation method thereof.

Embodiment 10

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 4.

Embodiment 11

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 4.

Embodiment 12

The each 200 grams of Homogeneous phase mixing of the P2B that the P2A obtain embodiment 10 and embodiment 2 obtain, obtain the modifier P2C of P1-1.The k value of P2C is in table 4.

Embodiment 13

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 4.

Embodiment 14

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 4.

Table 4

Embodiment	Raw material	k
			10	P2A	0.5
11	P2B	0.4
			12	P2C	0.4
13	P2D	0
			14	P2E	0.3

Embodiment 15-22 illustrates carrier of preparation catalyst II of the present invention and preparation method thereof.Comparative example 1-2 illustrates reference catalyst carrier and preparation method thereof.

Embodiment 15

Take 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 10 is obtained, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), fluorinated ammonia 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier Z II 1.The character of carrier Z II 1 lists in table 5.

Embodiment 16

Take 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing that embodiment 11 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier Z II 2.The character of carrier Z II 2 lists in table 5.

Embodiment 17

Take 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing that embodiment 12 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 950 DEG C of roastings 3 hours, obtains carrier Z II 3.The character of carrier Z II 3 lists in table 5.

Comparative example 1

Take 1000 grams of P1-1, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier DZ II 1.The character of carrier DZ II 1 lists in table 5.

Embodiment 18

Take 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing that embodiment 13 is obtained, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), fluorinated ammonia 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier Z II 4.The character of carrier Z II 4 lists in table 5.

Embodiment 19

Take 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing that embodiment 14 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier Z II 5.The character of carrier Z II 5 lists in table 5.

Embodiment 20

Take 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing that embodiment 12 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 850 DEG C of roastings 3 hours, obtains carrier Z II 6.The character of carrier Z II 6 lists in table 5.

Comparative example 2

Take 1000 grams of P1-2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier DZ II 2.The character of carrier DZ II 2 lists in table 5.

Embodiment 21

Take 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing that embodiment 13 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 39.2g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 1000 DEG C of roastings 3 hours, obtains carrier Z II 7.The character of carrier Z II 7 lists in table 5.

Embodiment 22

Take 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing that embodiment 14 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonia 39.2g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains forming composition, by this forming composition 900 DEG C of roastings 3 hours, obtains carrier Z II 8.The character of carrier Z II 8 lists in table 5.

Table 5

Embodiment 23 ~ 30 is for illustration of for described catalyst II of the present invention and preparation method thereof.Comparative example 3-5 illustrates reference catalyst and preparation method thereof.

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

Embodiment 23

Get 200 grams of carrier Z II 1, with 220 milliliters containing MoO380 grams per liter, Ammonium Heptamolybdate and the ammonium meta-vanadate mixing solutions of V2O516 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst C II 1, C II 1 is listed in table 6.

Embodiment 24

Get 200 grams of carrier Z II 2, with 220 milliliters containing MoO380 grams per liter, Ammonium Heptamolybdate and the ammonium meta-vanadate mixing solutions of V2O516 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst C II 2, C II 2 is listed in table 6.

Embodiment 25

Get 200 grams of carrier Z II 3, with 220 milliliters containing MoO380 grams per liter, Ammonium Heptamolybdate and the ammonium meta-vanadate mixing solutions of V2O516 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst C II 3, C II 3 is listed in table 6.

Comparative example 3

Get 200 grams of carrier Z II 1, with 220 milliliters containing MoO380 grams per liter, Ammonium Heptamolybdate and the nickelous nitrate mixing solutions of NiO16 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, the composition obtaining Hydrodemetalation catalyst DC II 1, DC II 1 is listed in table 6.

Comparative example 4

Get 200 grams of DZ II 1, with 220 milliliters containing MoO380 grams per liter, Ammonium Heptamolybdate and the nickelous nitrate mixing solutions of NiO16 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, the composition obtaining Hydrodemetalation catalyst DC II 2, DC II 2 is listed in table 6.

Comparative example 5

Get 200 grams of carrier DZ II 2, with 500 milliliters containing MoO380 grams per liter, Ammonium Heptamolybdate and the ammonium meta-vanadate mixing solutions of V2O516 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, the composition obtaining Hydrodemetalation catalyst DC II 3, DC II 3 is listed in table 6.

Embodiment 26

Get 200 grams of carrier Z II 4, with 220 milliliters containing MoO390 grams per liter, Ammonium Heptamolybdate and the ammonium meta-vanadate mixing solutions of V2O520 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 4.The composition of Hydrodemetalation catalyst C II 4 is listed in table 6.

Embodiment 27

Get 200 grams of Z II 5, with 220 milliliters containing WO390 grams per liter, ammonium tungstate and the ammonium meta-vanadate mixing solutions of V2O520 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 5.The composition of Hydrodemetalation catalyst C II 5 is listed in table 6.

Embodiment 28

Get 200 grams of Z II 6, with 220 milliliters containing WO3100 grams per liter, ammonium tungstate and the ammonium meta-vanadate mixing solutions of V2O530 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 6.The composition of Hydrodemetalation catalyst C II 6 is listed in table 6.

Embodiment 29

Get 200 grams of Z II 7, with 220 milliliters containing MoO360 grams per liter, ammonium tungstate and the ammonium meta-vanadate mixing solutions of V2O560 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 7.The composition of Hydrodemetalation catalyst C II 7 is listed in table 6.

Embodiment 30

Get 200 grams of Z II 8, with 220 milliliters containing WO360 grams per liter, ammonium tungstate and the ammonium meta-vanadate mixing solutions of V2O560 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C II 8.The composition of Hydrodemetalation catalyst C II 8 is listed in table 6.

Table 6

Embodiment 31-38 illustrates the hydrotreatment effect that the invention provides the mink cell focus of method.Comparative example 6-8 illustrates the hydrotreatment effect of the mink cell focus of reference method.

Be 7.2%, Fe+Ca content be 36ppm, Ni+V content with asphalt content be 102ppm, sulphur content be 4.09%, carbon residue be the mixed residue oil of 13.5% for raw material, evaluate catalysts on 500 milliliters of fixed-bed reactor.

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

Oil sample studies on asphaltene content adopts normal heptane intermediate processing (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP10-90).

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

In oil sample, carbon residue content uses microdetermination (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP149-90).

Hydrotreating catalyst III:

Hydrotreating catalyst III-1, prepares according to the embodiment 6 in patent ZL97112397.7, and 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.

Hydrotreating catalyst III-2, prepares according to the embodiment 37 in patent ZL00802168.6, and 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.

Hydrotreating catalyst III-3, prepares according to the embodiment 3 in patent ZL200310117323.0, and 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.

Catalyzer usage ratio and processing condition are listed in table 7, and the product property after 1000 hours that operates is listed in table 8.

Comparative example 6

Catalyzer adopts the combination of CI1, DCII1, C III 1, and the volume of each catalyst levels when processing condition is listed in table 7, and operate sampling analysis after 1000 hours, the results are shown in table 8.

Comparative example 7

Catalyzer adopts the combination of CI2, DCII2, C III 2, and the volume of each catalyst levels when processing condition is listed in table 7, and operate after 1000 hours sampling analysis afterwards, the results are shown in table 8.

Comparative example 8

Catalyzer adopts the combination of CI3, DCII3, C III 3, and the volume of each catalyst levels when processing condition is listed in table 7, and operate after 1000 hours sampling analysis afterwards, the results are shown in table 8.

Table 7

Table 8

Can find out, after adopting raw catalyst and correlation technique, the foreign matter content such as pitch, metal, sulphur, carbon residue of running 1000 hours back end hydrogenation treating product is starkly lower than prior art, and the FCC charging that can be used as high-quality uses.

Claims

1. optimize the hydroprocessing process of catalytically cracked material character for one kind, comprise at hydrotreating reaction conditions, by heavy raw oil successively with comprise hydrotreating catalyst I, hydrotreating catalyst II contacts with the catalyst combination of hydrotreating catalyst III, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreating catalyst I is 5-60%, the content of hydrotreating catalyst II is 5-50%, and the content of hydrotreating catalyst III is 10-60%; Wherein, described hydrotreating catalyst I contains shaped alumina alumina supporter, described pore volume is 0.8 ml/g ~ 1.2 mls/g, specific surface area is 90 meters squared per gram ~ 230 meters squared per gram, most probable bore dia is 20 nanometer ~ 30 nanometers, average pore diameter is 25 nanometer-35 nanometers, and it is 95% ~ 99.8% that diameter 10 nanometer ~ 60 nanoporous volume accounts for total pore volume ratio; Described hydrotreating catalyst II is containing the hydrogenation active metals component being selected from least one group vib and at least one VB race, be benchmark with oxide basis and with catalyst II, the content of described group vib metal component is 0.2-15 % by weight, the content of VB race metal component is 0.2-12 % by weight, described hydrotreating catalyst II is containing carrier, characterize with mercury penetration method, the pore volume of carrier is 0.95-1.2 ml/g, and specific surface is 50-300 rice ²/ gram, carrier be 10-30nm and diameter is 300-500nm at diameter is bimodal pore distribution, and the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, and the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.

2. method according to claim 1, it is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of described hydrotreating catalyst I is 10-50%, the content of hydrotreating catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; The pore volume of the described carrier in described hydrotreating catalyst I is 0.8 ml/g ~ 1.2 mls/g, and specific surface area is 90 meters squared per gram ~ 230 meters squared per gram; The metal component of the group vib in described hydrotreating catalyst II is selected from molybdenum and/or tungsten, the metal component of VB race is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst II, the content of described group vib metal component is 0.5-12 % by weight, and the content of VB race metal component is 0.5-9 % by weight.

3. method according to claim 1 and 2, it is characterized in that, the metal component of the described group vib in described hydrotreating catalyst II is molybdenum or tungsten, VB race metal component is vanadium, be benchmark with oxide basis and with catalyst II, the content of described group vib metal component is 5-12 % by weight, and the content of VB race metal component is 1-9 % by weight.

4. method according to claim 1, it is characterized in that, described hydrotreating catalyst I contains hydrogenation active metals component, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, with oxide basis and with described catalyst I for benchmark, the content of group VIII metal component is for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 15 % by weight.

5. method according to claim 4, it is characterized in that, described group VIII metal component is selected from nickel and/or cobalt, vib metal component is selected from molybdenum and/or tungsten, with oxide basis and with described catalyst I for benchmark, the content of group VIII metal component is 0.1-3 % by weight, and the content of group vib metal component is 0.5-10 % by weight.

6. method according to claim 1, is characterized in that, the pore volume of the carrier of described hydrotreating catalyst II is 0.95-1.15 ml/g, and specific surface area is 80-200 rice ²/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.

7. method according to claim 1, is characterized in that, containing halogen in the shaping carrier of described hydrotreating catalyst II, in element and with the carrier of described catalyst II for benchmark, the content of described halogen is 0.1-6 % by weight.

8. method according to claim 7, is characterized in that, described halogen component is selected from one or more in fluorine, chlorine, bromine, iodine and astatine, and with oxide basis and with the carrier of described catalyst II for benchmark, the content of described halogen is 0.3-4 % by weight.

9. method according to claim 8, is characterized in that, described halogen is preferably fluorine, and with oxide basis and with the carrier of described catalyst II for benchmark, the content of described halogen is 0.5-2.5 % by weight.

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

11. methods according to claim 10, is characterized in that, the support selected from alumina in described catalyst I II.

12. methods according to claim 11, 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 hole accounts for more than 80% of total pore volume.

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

14. methods according to claim 13, is characterized in that, the reaction conditions of described hydrotreatment reaction is: hydrogen dividing potential drop 10-18MPa, temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h ^-1, hydrogen to oil volume ratio is 800-1100.