CN104449833B

CN104449833B - A kind of method for hydrotreating hydrocarbon oil

Info

Publication number: CN104449833B
Application number: CN201310439475.6A
Authority: CN
Inventors: 杨清河; 胡大为; 孙淑玲; 刘佳; 聂红; 王奎; 赵新强; 戴立顺; 邵志才; 李大东
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-09-24
Filing date: 2013-09-24
Publication date: 2016-06-15
Anticipated expiration: 2033-09-24
Also published as: CN104449833A

Abstract

A kind of method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, raw oil is contacted with a kind of catalyst combination, the combination of described catalyst includes hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III, in the combination of described catalyst the layout of each catalyst make described raw oil successively with hydrotreating catalyst I, hydrotreating catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyst for benchmark, the content of described hydrotreating catalyst I is 5-60%, the content of hydrotreating catalyst II is 5-50%, the content of hydrotreating catalyst III is 10-60%, wherein, described hydrotreating catalyst I contains halogen-containing shaped alumina alumina supporter, described carrier is 10-30nm and diameter be 300-500nm is bimodal pore distribution at diameter, the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.

Description

A kind of method for hydrotreating hydrocarbon oil

Technical field

The present invention is about a kind of method for hydrotreating hydrocarbon oil.

Background technology

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

Summary of the invention

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

The content that the present invention relates to includes:

1. a method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, raw oil is contacted with a kind of catalyst combination, the combination of described catalyst includes hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III, in the combination of described catalyst the layout of each catalyst make described raw oil successively with hydrotreating catalyst I, hydrotreating catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyst for benchmark, the content of described hydrotreating catalyst I is 5-60%, the content of hydrotreating catalyst II is 5-50%, the content of hydrotreating catalyst III is 10-60%, wherein, described hydrotreating catalyst I contains halogen-containing shaped alumina alumina supporter, characterize with mercury injection method, the pore volume of described carrier is 0.95-1.2 ml/g, specific surface is 50-300 rice²/ gram, described carrier is 10-30nm and diameter be 300-500nm is bimodal pore distribution, the hole of diameter 10-30nm at diameter

Accounting for the 55-80% of total pore volume, the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.

2. according to the method described in 1, it is characterized in that, the total amount combined by volume and with described catalyst is for benchmark, and the content of described hydrotreating catalyst I is 10-50%, the content of hydrotreating catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; Characterizing with mercury injection method, the pore volume of described halogen-containing shaped alumina alumina supporter is 0.95-1.15 ml/g, and specific surface area is 80-200 rice²/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.

3. according to the method described in 1, it is characterised in that one or more in fluorine, chlorine, bromine and iodine of described halogen component, with described carrier for benchmark and in element, in described carrier, the content of halogen is 0.1-6 weight %.

4. according to the method described in 3, it is characterised in that described halogen is fluorine, counting with element and with described carrier for benchmark, in described carrier, the content of halogen is 0.3-4 weight %.

5. according to the method described in 4, it is characterised in that with described carrier for benchmark and in element, in described carrier, the content of halogen is 0.5-2.5 weight %.

6. according to the method described in 1, it is characterized in that, described hydrotreating catalyst I contains hydrogenation active metals component, described hydrogenation active metals component is selected from least one metal component of group VIII and at least one Group VB metal component, count with oxide and with hydrotreating catalyst I for benchmark, the content of described metal component of group VIII is that the content of Group VB metal component is to less than or equal to 5 weight % more than 0 more than 0 to less than or equal to 0.8 weight %.

7. according to the method described in 6, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, Group VB metal component is selected from vanadium and/or niobium, count with oxide and with catalyst for benchmark, the content of described metal component of group VIII is 0.1-0.7 weight %, and the content of Group VB metal component is 1-4 weight %.

8. according to the method described in 7, it is characterised in that count with oxide and with catalyst for benchmark, the content of described metal component of group VIII is 0.2-0.6 weight %, and the content of Group VB metal component is 1.5-3.5 weight %.

9. according to the method described in 1, it is characterized in that, described catalyst II contains carrier, metal component molybdenum, cobalt and nickel, count with oxide and with catalyst II for benchmark, the content of described molybdenum is 5～20 weight %, the content sum of cobalt and nickel is 1～6 weight %, and wherein, the atomic ratio of cobalt and nickel is 2～4.

10., according to the method described in 9, it is characterised in that count with oxide and with catalyst II for benchmark, in described catalyst II, the content of molybdenum is the content sum of 8～15 weight %, cobalt and nickel is 1.5～4 weight %, and wherein, the atomic ratio of cobalt and nickel is 2.2～3.2.

11. according to the method described in 10, it is characterised in that counting with oxide and with catalyst II for benchmark, the content of described nickel is less than 1.2%.

12. according to the method described in 11, it is characterised in that count with oxide and with catalyst II for benchmark, the content of described nickel is 0.5～1.1%.

13. according to the method described in 1 or 9, it is characterised in that described catalyst II contains the adjuvant component selected from phosphorus and boron, count with oxide and with described catalyst II for benchmark, the described content selected from phosphorus and the adjuvant component of boron is 0.5-5 weight %.

14. according to the method described in 13, it is characterised in that count with oxide and with described catalyst II for benchmark, the described content selected from phosphorus and the adjuvant component of boron is 1-4 weight %.

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

16. according to the method described in 15, it is characterised in that the support selected from alumina in described catalyst III.

17. according to the method described in 16, it is characterised in that the pore volume of described aluminium oxide is not less than 0.35 ml/g, the pore volume that bore dia is 40～100 angstroms of holes accounts for more than the 80% of total pore volume.

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

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

In the present invention, the preparation method of described hydrotreating catalyst I includes preparing carrier the component of load hydrogenation active metals on this carrier, wherein, the preparation of described carrier includes being mixed by the modifier P2 of hydrated alumina P1 and the P1 containing boehmite and introducing halogen-containing compound in the mixture, aftershaping, dry and roasting, wherein, the Mixing ratio by weight of described P1 and P2 is 20-95:5-80, it is preferred to 70-95:5-30; The κ value of P2 is 0 to less than or equal to 0.9, it is preferred to 0 to less than or equal to 0.6; Described κ=DI₂/DI₁, DI₁For the sour peptization index of the hydrated alumina P1 containing boehmite, DI₂Sour peptization index for the modifier P2 of the hydrated alumina P1 containing boehmite.

Preferred described halogen is selected from the one in fluorine, chlorine, bromine and iodine and mixture thereof, more preferably fluorine, count with element and with carrier for benchmark, the introduction volume of described halogen contained compound makes the content of halogen in final carrier be 0.1-6 weight %, it is preferably 0.3-4 weight %, more preferably 0.5-2.5 weight %.

Preferred described P1 is 0.9-1.4 ml/g selected from pore volume, and specific surface is 100-350 rice²/ gram, can and the hydrated alumina containing boehmite of bore dia 8-30nm. It is preferred that P1 be 0.95-1.3 ml/g selected from pore volume, specific surface is 120-300 rice²/ gram, can and the hydrated alumina containing boehmite of bore dia 10-20nm.

Preferred described P2 is the particulate matter of 80-300 order in described modifier, the more preferably particulate matter of 100-200 order.

Preferred described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour, and the condition of described roasting includes: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500. It is preferred that described dry condition include: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting includes: temperature for more than 800 to less than or equal to 1000 DEG C, roasting time is 2-6 hour.

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

Require that carrier therein can be made into various easily operated article shaped depending on difference, for instance spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.). Wherein, it is conventional method by the modifier P2 of described hydrated alumina P1 and the P1 containing the boehmite method mixed, for instance, P1 and the P2 of powder body is put into mixing in stirring-type batch mixer according to ingredient proportion. The method introducing halogen-containing compound in described P1 and P2 mixture is conventional method, such as, in a concrete embodiment preparing carrier, the method introducing halogen-containing compound in the mixture of the modifier P2 of described hydrated alumina P1 and the P1 containing boehmite is that halogen-containing compound is configured to aqueous solution, this aqueous solution is mixed into while described P1 and P1 mixes or again this aqueous solution is mixed into after described P1 and P1 mixes, aftershaping, dry and roasting. Described halogen-containing compound can be arbitrary halogen water soluble compound in one or more. Such as fluorochemical can be selected from Fluohydric acid., one in ammonium fluoride and mixture thereof.

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

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

The mensuration of DI includes: the (1) calcination base content (calcination base (also referred to as butt) content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, weight weight ratio front with burning after its burning) of the mensuration hydrated alumina containing boehmite, is calculated as a; (2) weigh the hydrated alumina W containing boehmite with analytical balance₀Gram, W₀Amount meet with Al₂O₃The W of meter₁It is 6 grams of (W₁/a=W₀), weigh deionized water W gram, W=40.0-W₀, under stirring, the hydrated alumina containing boehmite weighed and deionized water are added mixing in beaker; With 20mL pipet pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, is joined by this acid solution in the beaker of step (2), the lower reaction of stirring 8 minutes; (4) being centrifuged step (3) reacted serosity in centrifuges separating, inserted by precipitate in the crucible weighed, afterwards, it is dry 4 hours in 125 DEG C, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W₂Gram; (5) according to formula DI=(1-W₂/W₁) × 100% calculates and obtains.

Described P1 in the present invention can be boehmite prepared by any prior art, can also be boehmite and the mixture of other hydrated alumina, one or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide of other hydrated alumina described. In a preferred embodiment, characterizing with X diffraction, in the described hydrated alumina containing boehmite, boehmite content is not less than 50%, is more preferably not less than 60%.

In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and can and aperture, be by the described hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, BET N2 adsorption characterize and obtain.

Inventors of the present invention have surprisingly found that, hydrated alumina P1 containing boehmite is carried out heat treatment modified, the peptization index of its modifier changes, by this modifier with without heat treated P1 mixed-forming, dry and roasting after, obtained carrier has obvious bimodal pore distribution. Particularly at the granule by 80-300 order therein, it is preferable that the granule of 100-200 order with without after heat treated part mixed-forming, dry and roasting, obtained carrier bimodal in each unimodal pore size distribution concentrate especially. Here, the granule of described 80-300 order, the granule of preferred 100-200 order refers to that described modifier is through sieve (including step that is broken or that grind if desired), its screening thing (siftage) meets the granule of 80-300 order, the particulate matter of preferred 100-200 order accounts for the percent (by weight) of total amount and is not less than 60%, it is preferred that be not less than 70%.

The Mixing ratio by weight of described P1 and P2 refers to the ratio of P1 and P2 shared parts by weight respectively in the mixture of every hundred parts of described P1 and P2. Wherein, the preferred span of parts by weight of P1 is 20-95, more preferably 70-95; The preferred span of parts by weight of P2 is 5-80, more preferably 5-30.

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

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

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

(3) two or more be mixed to get in the modifier P2 obtained based on preceding method. When adopting mixed method to obtain P2, the mixed proportion of the modifier P2 that aforementioned several method is respectively obtained does not limit.

The described method in supported on carriers hydrogenation active metals component is infusion process, including the solution of the preparation compound containing hydrogenation active metals and use this solution impregnating carrier, it is dried afterwards, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one VIIIth race and the metal component of at least one Group VB, preferably the metal component of described VIIIth race is selected from nickel and/or cobalt, the metal component of Group VB is selected from vanadium and/or niobium, count with oxide and with catalyst for benchmark, the described compound containing hydrogenation active metals make in the concentration of described solution and the consumption of described solution the content of the metal component of the VIIIth race in final catalyst for more than 0 to less than or equal to 0.8 weight %, it is preferably 0.2-0.6 weight %, the content of the metal component of described Group VB is to less than or equal to 5 weight % more than 0, it is preferably 1.5-3.5 weight %, described drying condition includes: temperature is 100-250 DEG C, it is preferred to 100-140 DEG C, and the time is 1-10 hour, it is preferred to 1-6 hour, described roasting condition includes: temperature is 360-500 DEG C, it is preferred to 360-450 DEG C, and the time is 1-10 hour, it is preferred to 2-6 hour.

Described dipping method is conventional method, for instance, it is possible to it is excessive immersion stain, hole saturation infusion process. It is selected from one or more in the soluble compound in them containing the described metal component compound selected from V B race, one or more in vanadic anhydride, ammonium vanadate, ammonium metavanadate, Sulfovanadic acid, vanada polyacid can be selected from, it is preferable that ammonium metavanadate therein, ammonium vanadate. One or more in their soluble compound it are selected from containing the described compound selected from VIII race's metal component, one or more in the soluble complexes of cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt, it is preferred to cobalt nitrate, basic cobaltous carbonate; One or more in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, Nickel dichloride. and nickel, it is preferred to nickel nitrate, basic nickel carbonate.

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

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

In the present invention, the effect of described catalyst II is in that organic metal impurity Ni and the V removing in raw material further, the macromole species such as asphalitine and colloid and partial vulcanization thing.

According to method provided by the invention, wherein, under meeting the premise that described hydrotreating catalyst II is required by the present invention, described hydrotreating catalyst II can be commercially available commodity, it would however also be possible to employ prepared by arbitrary prior art. Such as, Catalysts and its preparation method disclosed in 20110276687.3 and 201110039566.1 is entirely appropriate for the present invention. About the more detailed preparation method of above-mentioned catalyst, all on the books in above-mentioned patent documentation, in the lump they are quoted as a part for present invention here.

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

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

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

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

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

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

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

According to method provided by the invention, wherein, include hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III catalyst combine before, afterwards or they between any two, it is possible to include any other catalyst or filler contributing to improving described catalyst composite behaviour. Such as, added such as fillers such as porcelain ball, active supporters before described Hydrodemetalation catalyst I, to improve raw oil distribution etc. in the reactor. Use etc. about this filler is conventionally known to one of skill in the art, does not repeat here.

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

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

According to method provided by the invention, being particularly suitable for for the higher raw oil of formed asphalt content, they can be selected from one or more in crude oil, decompression residuum, deep drawing wax oil, frivolous coal tar, wax tailings etc.

Can reach according to the weight of oil after the hydrotreatment that described method obtains: asphalt content is less than 1.2%, and W metal+V content is 20 below μ g/g, sulfur content less than 0.5%, and carbon residue content is less than 6.0%.

Detailed description of the invention

The present invention is described further for the following examples.

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

Embodiment 1-5 illustrates to prepare P1 and the P2 of catalyst I carrier of the present invention and source thereof or preparation method.

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

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

Embodiment 1

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

Embodiment 2

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

Embodiment 3

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

Embodiment 4

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

Embodiment 5

Weigh 1000 grams of P1-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier P2E of P1-2. The k value of P2E is in Table 1.

Table 1

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

Embodiment 6-13 illustrates carrier preparing catalyst I of the present invention and preparation method thereof. Comparative example 1-2 illustrates carrier of reference catalyst and preparation method thereof.

Embodiment 6

Weigh 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing prepared with embodiment 1, add the aqueous solution 1440 milliliters containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), fluorinated ammonium 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 1. The character of carrier Z I 1 is listed in table 2.

Embodiment 7

Weigh 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing prepared with embodiment 2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 2. The character of carrier Z I 2 is listed in table 2.

Embodiment 8

Weigh 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 3, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 950 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 3. The character of carrier Z I 3 is listed in table 2.

Comparative example 1

Weigh 1000 grams of P1-1, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 9.8g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ I 1.The character of carrier DZ I 1 is listed in table 2.

Embodiment 9

Weigh 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 4, add the aqueous solution 1440 milliliters containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), fluorinated ammonium 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 4. The character of carrier Z I 4 is listed in table 2.

Embodiment 10

Weigh 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 5, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 5. The character of carrier Z I 5 is listed in table 2.

Embodiment 11

Weigh 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 3, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 6. The character of carrier Z I 6 is listed in table 2.

Comparative example 2

Weigh 1000 grams of P1-2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 19.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ I 2. The character of carrier DZ I 2 is listed in table 2.

Embodiment 12

Weigh 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 4, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 39.2g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 7. The character of carrier Z I 7 is listed in table 2.

Embodiment 13

Weigh 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 5, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters of fluorinated ammonium 39.2g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm. Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z I 8. The character of carrier Z I 8 is listed in table 2.

Table 2

Embodiment 14～19 is used for catalyst I of the present invention and preparation method thereof is described. Comparative example 3-6 illustrates reference catalyst and preparation method thereof.

Embodiment 14

Taking 200 grams of carrier Z I 1, with 220 milliliters containing V2O528.6 g/l, the ammonium molybdate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C I 1. The composition of C I 1 is listed in table 3.

Embodiment 15

Taking 200 grams of carrier Z I 2, with 220 milliliters containing V2O528.6 g/l, the ammonium metatungstate of CoO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C I 2.The composition of C I 2 is listed in table 3.

Embodiment 16

Taking 200 carrier Z3, with 220 milliliters containing V2O525 g/l, the ammonium molybdate of NiO3 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C I 3. The composition of C I 3 is listed in table 3.

Embodiment 17

Taking 200 grams of carrier Z I 4, with 220 milliliters containing V2O525 g/l, the ammonium molybdate of CoO3 g/l and cobalt nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C I 4. The composition of C I 4 is listed in table 3.

Embodiment 18

Taking 200 grams of carrier Z I 5, with 220 milliliters containing V2O519.0 g/l, the ammonium molybdate of NiO2 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C I 5. The composition of C I 5 is listed in table 3.

Embodiment 19

Taking 200 grams of carrier Z I 8, with 220 milliliters containing V2O519.0 g/l, the ammonium metatungstate of NiO2 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C I 6. The composition of C I 6 is listed in table 3.

Contrast row 3

Taking 200 grams of carrier DZ I 1, with 220 milliliters containing V2O528.6 g/l, the ammonium molybdate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC I 1. The composition of DC I 1 is listed in table 3.

Contrast row 4

Taking 200 grams of carrier DZ1, with 220 milliliters containing WO328.6 g/l, the ammonium metatungstate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC I 2. The composition of DC I 2 is listed in table 3.

Comparative example 5

Taking 200 grams of carrier DZ I 2, with 220 milliliters containing V2O525 g/l, the ammonium molybdate of NiO3 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC I 3. The composition of DC I 3 is listed in table 3.

Comparative example 6

Taking 200 grams of carrier DZ I 2, with 220 milliliters containing MoO325 g/l, the ammonium molybdate of CoO3 g/l and cobalt nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC I 4. The composition of DC I 4 is listed in table 3.

Table 3

Embodiment 20-21 illustrates to be suitable for carrier preparing hydrotreating catalyst II and preparation method thereof.

Embodiment 20

The boehmite dry glue powder RPB110 that 300 grams of Chang Ling catalyst plants are produced and the sesbania powder mix homogeneously of 10 grams, at room temperature by the aqueous solution of nitric acid that concentration is 1% of this mixture and 360 milliliters, mix homogeneously, continuing kneading on double screw banded extruder is after plastic, it is extruded into the trilobal bar of ф 1.5 millimeters, wet bar, after 120 DEG C dry 3 hours, obtains carrier Z II 1 in 3 hours in 700 DEG C of roastings. Measuring the specific surface of Z II 1, pore volume and pore-size distribution, result is in Table 4.

Carrier specific surface, pore volume and pore-size distribution adopt B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.

Embodiment 21

By the boehmite dry glue powder of the boehmite dry glue powder RPB90 that 300 grams of Chang Ling catalyst plants produce) and 10 grams of sesbania powder mix homogeneously, add the aqueous solution of nitric acid that 330 ml concns are 1%, mix homogeneously, continuing kneading on double screw banded extruder is after plastic, it is extruded into the butterfly bar of ф 1.1 millimeters, wet bar, after 110 DEG C dry 2 hours, obtains carrier Z II 2 in 4 hours in 600 DEG C of roastings.Measuring the specific surface of Z II 2, pore volume and pore-size distribution, result is as shown in table 4.

Table 4

Embodiment 22-25 illustrates by catalyst II provided by the invention and preparation method thereof.

Embodiment 22

The carrier Z II 1200 grams of Example 20 preparation, with 500 milliliters containing MoO3120 g/l, NiO8 g/l, CoO20 g/l, the ammonium molybdate of B2O315 g/l, nickel nitrate, cobalt nitrate and boric acid mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C after filtration, 450 DEG C of roastings 4 hours, obtain catalyst C II 1. The content of molybdenum oxide in C II 1, cobalt oxide, nickel oxide and B2O3 is listed in table 5.

Embodiment 23

The carrier Z II 2200 grams of Example 20 preparation, with 220 milliliters containing MoO3172 g/l, NiO9 g/l, CoO32 g/l, the molybdenum oxide of P2O543 g/l, basic nickel carbonate, basic cobaltous carbonate and phosphoric acid mixed solution impregnate 2 hours, dry 2 hours in 120 DEG C, 550 DEG C of roastings 2 hours, obtain catalyst C II 2. The content of molybdenum oxide in catalyst C II 2, cobalt oxide, nickel oxide and P2O5 is listed in table 5.

Embodiment 24

The carrier Z II 2200 grams of Example 21 preparation, with 200 milliliters containing MoO3122 g/l, NiO9 g/l, CoO18 g/l, the molybdenum oxide of P2O535 g/l, basic nickel carbonate, basic cobaltous carbonate and phosphoric acid mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, 480 DEG C of roastings 4 hours, obtain catalyst C II 3. The content of molybdenum oxide in catalyst C II 3, nickel oxide and cobalt oxide, P2O5 is listed in table 5.

Embodiment 25

The carrier Z II 1200 grams of Example 20 preparation, with 500 milliliters containing CoO12 g/l, cobalt nitrate, the boric acid mixed solution of B2O39 g/l impregnate 1 hour, drying 3 hours in 110 DEG C after filtration, 350 DEG C of roastings 2 hours, with 200 milliliters containing MoO392 g/l, molybdenum oxide, the basic nickel carbonate mixed solution of NiO7 g/l impregnate 1 hour, dry 2 hours in 120 DEG C, 480 DEG C of roastings 4 hours, obtain catalyst C II 4. The content of molybdenum oxide in catalyst C II 4, nickel oxide and cobalt oxide, B2O3 is listed in table 5.

Table 5

Embodiment 26-31 illustrates that the present invention provides the effect of method hydrotreatment bituminous heavy charge. Comparative example 7-10 illustrates the effect of reference method hydrotreating heavy feedstocks.

With asphalt content for 6.8%, the mixed residue oil that Ni+V content is 102ppm, sulfur content is 3.6%, carbon residue is 14% is raw material, evaluates catalyst on 500 milliliters of fixed bed reactors.

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

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

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

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

Hydrotreating catalyst C III:

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

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

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

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

Comparative example 7

Catalyst adopts the combination of DCI1, CII1, C III 1, and the volume of each catalyst amount when process conditions are listed in table 6, and sample analysis after operating 1000 hours, result is listed in table 7.

Comparative example 8

Catalyst adopts the combination of DCI2, CII2, C III 2, and the volume of each catalyst amount when process conditions are listed in table 6, and sample analysis after after operating 1000 hours, result is listed in table 7.

Comparative example 9

Catalyst adopts the combination of DCI3, CII3, C III 3, and the volume of each catalyst amount when process conditions are listed in table 6, and sample analysis after after operating 1000 hours, result is listed in table 7.

Comparative example 10

Catalyst adopts the combination of DCI4, CII4, C III 3, and the volume of each catalyst amount when process conditions are listed in table 6, and sample analysis after after operating 1000 hours, result is listed in table 7.

Table 6

Table 7

It can be seen that after adopting raw catelyst and correlation technique, the 1000 hours back end hydrogenations that operate process the impurity contents such as the Colophonium of product, metal, sulfur, carbon residue substantially to be reduced, and product quality is improved significantly.

Claims

1. a method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, raw oil is contacted with a kind of catalyst combination, the combination of described catalyst includes hydrotreating catalyst I, hydrotreating catalyst II and hydrotreating catalyst III, in the combination of described catalyst the layout of each catalyst make described raw oil successively with hydrotreating catalyst I, hydrotreating catalyst II contacts with hydrotreating catalyst III, by volume and with the total amount of described catalyst for benchmark, the content of described hydrotreating catalyst I is 5-60%, the content of hydrotreating catalyst II is 5-50%, the content of hydrotreating catalyst III is 10-60%, wherein, described hydrotreating catalyst I contains halogen-containing shaped alumina alumina supporter, characterize with mercury injection method, the pore volume of described carrier is 0.95-1.2 ml/g, specific surface is 50-300 rice²/ gram, described carrier is 10-30nm and diameter be 300-500nm is bimodal pore distribution at diameter, and the hole of diameter 10-30nm accounts for the 55-80% of total pore volume, and the hole of diameter 300-500nm accounts for the 10-35% of total pore volume.

2. method according to claim 1, it is characterized in that, the total amount combined by volume and with described catalyst is for benchmark, and the content of described hydrotreating catalyst I is 10-50%, the content of hydrotreating catalyst II is 10-40%, and the content of hydrotreating catalyst III is 20-50%; Characterizing with mercury injection method, the pore volume of described halogen-containing shaped alumina alumina supporter is 0.95-1.15 ml/g, and specific surface area is 80-200 rice²/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.

3. method according to claim 1, it is characterised in that one or more in fluorine, chlorine, bromine and iodine of described halogen component, with described carrier for benchmark and in element, in described carrier, the content of halogen is 0.1-6 weight %.

4. method according to claim 3, it is characterised in that described halogen is fluorine, counts with element and with described carrier for benchmark, and in described carrier, the content of halogen is 0.3-4 weight %.

5. method according to claim 4, it is characterised in that with described carrier for benchmark and in element, in described carrier, the content of halogen is 0.5-2.5 weight %.

6. 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 metal component of group VIII and at least one Group VB metal component, count with oxide and with hydrotreating catalyst I for benchmark, the content of described metal component of group VIII is that the content of Group VB metal component is to less than or equal to 5 weight % more than 0 more than 0 to less than or equal to 0.8 weight %.

7. method according to claim 6, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, Group VB metal component is selected from vanadium and/or niobium, count with oxide and with catalyst for benchmark, the content of described metal component of group VIII is 0.1-0.7 weight %, and the content of Group VB metal component is 1-4 weight %.

8. method according to claim 7, it is characterised in that count with oxide and with catalyst for benchmark, the content of described metal component of group VIII is 0.2-0.6 weight %, and the content of Group VB metal component is 1.5-3.5 weight %.

9. method according to claim 1, it is characterized in that, described catalyst II contains carrier, metal component molybdenum, cobalt and nickel, count with oxide and with catalyst II for benchmark, the content of described molybdenum is 5～20 weight %, the content sum of cobalt and nickel is 1～6 weight %, and wherein, the atomic ratio of cobalt and nickel is 2～4.

10. method according to claim 9, it is characterised in that count with oxide and with catalyst II for benchmark, in described catalyst II, the content of molybdenum is 8～15 weight %, the content sum of cobalt and nickel is 1.5～4 weight %, and wherein, the atomic ratio of cobalt and nickel is 2.2～3.2.

11. method according to claim 10, it is characterised in that counting with oxide and with catalyst II for benchmark, the content of described nickel is less than 1.2%.

12. method according to claim 11, it is characterised in that count with oxide and with catalyst II for benchmark, the content of described nickel is 0.5～1.1%.

13. the method according to claim 1 or 9, it is characterised in that described catalyst II contains the adjuvant component selected from phosphorus and boron, counting with oxide and with described catalyst II for benchmark, the described content selected from phosphorus and the adjuvant component of boron is 0.5-5 weight %.

14. method according to claim 13, it is characterised in that count with oxide and with described catalyst II for benchmark, the described content selected from phosphorus and the adjuvant component of boron is 1-4 weight %.

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

16. method according to claim 15, it is characterised in that the support selected from alumina in described catalyst III.

17. method according to claim 16, it is characterised in that the pore volume of described aluminium oxide is not less than 0.35 ml/g, the pore volume that bore dia is 40～100 angstroms of holes accounts for more than the 80% of total pore volume.

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

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