CN100569920C - A kind of hydroprocessing process - Google Patents

Abstract

The present invention relates to a kind of hydroprocessing process.With the heavy ends is stock oil, and under hydroprocessing condition, stock oil mixes by the hydrotreatment reaction zone with hydrogen.Wherein having a kind of catalyzer in the catalyzer of hydrotreatment reaction zone at least is bulk phase catalyst, and bulk phase catalyst is composite oxides Ni _xW _yO _zWith oxide M oO ₃Weight ratio 1: 10～10: 1 constitute composite oxides Ni _xW _yO _zWith oxide M oO ₃Account for 40%～100% of catalyst composition gross weight.Compared with prior art, the inventive method can effectively reduce the operating severity of hydrotreatment reaction zone, improves the treatment capacity of device, prolongs the work-ing life of catalyzer or further improves the hydrotreatment degree of depth of stock oil.

Description

A kind of hydroprocessing process

Technical field

The present invention relates to a kind of hydroprocessing process, the particularly a kind of strong catalyzer of hydrogenation performance, method of heavy distillate inferior being carried out hydrotreatment selected for use.

Background technology

At present worldwide, the trend of crude oil heaviness and poor qualityization is accelerated, the increasingly stringent of the sustainable development of world economy and environmental regulation in addition, need to produce a large amount of light clean fuels, these all require existing oil Refining Technologies is improved, and produce satisfactory product with minimum cost.

Produce with heavy feed stock in the working method of light-end products, catalytic cracking (FCC) still accounts for critical role.Along with the requirement of crude quality variation and environmental regulation, the light-end products of catalytic cracking technology direct production are second-rate, and especially the sulphur content of catalytic gasoline is than higher, and catalytic diesel oil sulphur content and aromaticity content height, cetane value are low.The approach that improves the catalytic cracking quality product generally has two kinds, i.e. catalytic cracking generates oil subsidy and fills hydrofining and catalytically cracked material pre-treatment.Because FCC raw material hydrogenation preconditioning technique can be avoided the problem of loss of octane number in the catalytic gasoline hydrogenation treating process, and has following advantage: the replacing speed that can reduce the FCC catalyzer; Reduce the FCC coke yield; Improving the FCC product distributes, improves the purpose product yield, reduces non-purpose product yield; Directly improve the FCC quality product, reduce the product sulphur content; Reduce the quantity discharged of FCC revivifier SOx, NOx etc., so FCC raw material hydrogenation pretreatment technology is widely used.

The catalytically cracked material preconditioning technique is that the stock oil with catalytic cracking carries out hydrotreatment earlier, remove impurity such as wherein most of sulphur, nitrogen, aromatic hydrocarbons has obtained fractional saturation, thereby improved the stock oil quality of catalytic cracking, so just reduced the operating severity of catalytic cracking, and improved the catalytic cracking quality product, and can directly obtain the purpose product, perhaps reduced back purified difficulty.Common hydrotreating catalyst or special-purpose hydrotreating catalyst are all adopted in general hydrogenation hydrotreatment, be essentially the catalyzer of ordinary method preparation, along with raw material becomes heavy variation, existing catalyzer can not meet the demands, device is handled by the forced landing amount, to newly-built device, the loadings of catalyzer will increase.

US 4880526 discloses a kind of Ni of containing, Mo, W, the Co high reactivity is used for bulk phase catalyst of hydrotreatment and preparation method thereof, and this preparation method adopts metal to mix kneading to be equipped with technology, and the different metal component distributes under the microcosmic in mutually also inhomogeneous at body.US6299760, US6156695, US6537442, US6440888, the disclosed VIII of containing of US6652738 family/group vib active metal component are used for bulk phase catalyst of hydrotreatment and preparation method thereof, adopt and prepare the metal-powder that contains Ni-Mo or Ni-Mo-W earlier, use aluminum oxide bonding again, or the metal-powder of Ni-Mo or Ni-Mo-W is mixed back dehydration, extrusion, drying with alumina gel.Because the catalyst metal content height of this method preparation, often lack enough interactions between metal and aluminum oxide and cause catalyst strength poor.Active ingredient is made up of a large amount of metals, has some interior metal components and can not be fully utilized and cause the active ingredient loss in forming Ni-Mo or Ni-Mo-W powder process, and this problem can not be by simple bonding the solution.CN1342102A discloses a kind of mixed metal catalyst, and concrete grammar is for to obtain three kinds of reactive metal co-precipitation, and its main weak point is not find the cooperation effect between the different activities metal.US6162350, CN1339985A disclose a kind of mixed metal catalyst composition, and it is solid-state keeping at least a metal in preparation process, forms another kind of soild oxide in this solid metal compound surface reaction, finally forms the core-shell type composition.This method can not make different metal obtain good cooperation.

US3983029 and US6793804 disclose hydroprocessing technique and catalyzer, and CN1313379 discloses a kind of hydroprocessing process of poor-quality raw material for catalytic cracking, and CN1646665 discloses the hydrotreatment of hydrocarbon raw material.The hydrotreating catalyst that these patents are used is the hydrotreating catalyst or the special-purpose catalyst of routine, and they are all prepared by ordinary method.Owing to be subjected to the influence that stock oil becomes heavy variation day by day, use existing hydrotreater, operating severity increases, and makes the catalyzer life cycle shorten, and is forced to reduce treatment capacity, and perhaps new device need increase catalyst consumption.

Summary of the invention

At the deficiencies in the prior art, the invention provides a kind of hydroprocessing process, can effectively reduce the operating severity of hydrogenation pretreatment unit, promptly can realize reducing working pressure, reduce temperature of reaction, increase the device processing power and prolong in the effect such as catalyzer work-ing life one or more.

Hydroprocessing process of the present invention comprises following content: be stock oil with the heavy ends, under the hydrotreatment operational condition, stock oil and hydrogen are by the hydrotreatment reaction zone, and the hydrotreatment that obtains generates oil and enters separation system; At least comprise a kind of bulk phase catalyst in the described hydrotreatment reaction zone, bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, and catalyzer W, Ni before sulfuration exist with the composite oxides form: Ni _xW _yO _z, z=x+3y, Mo exists with oxide form: MoO ₃Composite oxides Ni _xW _yO _zThe ratio of middle x and y (atomic molar ratio) is 1: 8～8: 1, is preferably 1: 4～4: 1.Composite oxides Ni _xW _yO _zWith oxide M oO ₃Weight ratio be 1: 10～10: 1, be preferably 1: 5～5: 1.Composite oxides Ni in the bulk phase catalyst _xW _yO _zWith oxide M oO ₃Gross weight content be 40%～100%, be preferably 50%～80%.

The stock oil that the inventive method is used can be the various VGO, the DAO that obtain in the petroleum refining process, among CGO, the HCO one or more, also can be coal tar, gelatin liquefaction wet goods.

The hydrotreatment operational condition is generally reaction pressure 3.0～20.0MPa, and hydrogen to oil volume ratio is 200: 1～2500: 1, and volume space velocity is 0.1～8.0h ^-1, 260 ℃～455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 4.0～18.0MPa, hydrogen to oil volume ratio 300: 1～2000: 1, volume space velocity 0.2～6.0h ^-1, 280～444 ℃ of temperature of reaction.

The catalyzer of hydrotreatment reaction zone of the present invention can all be a bulk phase catalyst, also can be the combination of conventional hydrotreating catalyst and bulk phase catalyst.During combination loading, bulk phase catalyst can be seated in the top of reaction zone, also can be seated in the bottom of reaction zone, and perhaps two types catalyzer loads at interval, the volume ratio of bulk phase catalyst and conventional catalyst is 90: 10～10: 90, preferred 20: 80～80: 20.During combination loading, preferred feed by common hydrotreating catalyst bed, by bulk phase catalyst bed of the present invention, helps bringing into play the catalyzer overall activity most earlier then.Wherein conventional hydrotreating catalyst can be various commercial catalysts, as Fushun Petrochemical Research Institute (FRIPP) develop 3926,3936, hydrotreating catalysts such as CH-20, FF-14, catalyzer such as the HR-416 of Inst Francais Du Petrole, HR-448, the TK-525 of Topsor company, TK-557 catalyzer, the KF-752 of AKZO company, KF-840, KF-901, KF-907 or the like.

Can contain in the components such as aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve one or more in the bulk phase catalyst of the present invention as required, the weight content of these components in catalyzer is 0～60%, is preferably 20%～50%.The specific surface area of bulk phase catalyst is 120～400m ²/ g, pore volume are 0.10～0.50ml/g.

The preparation process of bulk phase catalyst of the present invention comprises following content: (1) coprecipitation method generates Ni _xW _yO _zThe composite oxides precursor; (2) Ni _xW _yO _zComposite oxides precursor and MoO ₃Making beating mixes, filters; (3) moulding, activation are final catalyzer.

Wherein (1) described coprecipitation method generates Ni _xW _yO _zThe process of composite oxides precursor can adopt following method: with the salts solution of tungstenic, nickel, form required ratio in catalyzer and add in the glue jar, add precipitation agent and make gelatinous mixture.Precipitation agent can be inorganic or organic alkaline ammoniac compounds, is preferably ammonia, can working concentration ammoniacal liquor arbitrarily.

Add required catalyst adjuvant and add component in a step that can be in above-mentioned steps or a few step.Auxiliary agent generally comprise P, F, Ti, Si, B, Zr etc. one or more.Add component and be generally refractory porous mass and precursor thereof, as aluminum oxide and precursor (aluminium hydroxide, aluminum salt solution etc.), clay, sial, titanium oxide-magnesium oxide, molecular sieve etc.The method that adds auxiliary agent and interpolation component adopts this area ordinary method.

Though W, Mo, Ni are activity of hydrocatalyst component commonly used, find that through a large amount of The effects the performance of different fit system catalyzer has very big-difference.Particularly in the bigger bulk phase catalyst of total metal content, the different fit systems of these metals are bigger to the performance impact of catalyzer.The present invention finds by a large amount of experiments, is used for the body phase hydrogenation catalyst that the hydrocarbon material degree of depth is taken off impurity, earlier with W and Ni co-precipitation, makes Ni _xW _yO _zThe precursor of composite oxides, this composite oxides precursor again with MoO ₃Making beating mixes, and adopts conventional means to prepare preformed catalyst then, and this preparation process organically cooperates element W and Ni, forms a kind of composite oxides, then with MoO ₃Combination finally forms Ni _xW _yO _zThe composition of composite oxides and Mo oxide compound.The result shows when the catalyzer of this microtexture of the present invention is used for hydrocarbons hydrogenation, to have the outstanding impurity activity of taking off, and during especially for deep impurity removal process, significantly improves than the activity of such catalysts of similar chemical constitution.The mechanism that the composition of Ni-W composite oxides of the present invention and Mo oxide compound can improve catalyst activity is very not clear and definite as yet, and, in bulk phase catalyst, the content of reactive metal is higher, reactive metal exist form different fully with traditional loaded catalyst, therefore, can not be suitable for the metal cooperation theory of conventional negative supported catalyst.For example, it is generally acknowledged that Ni can promote the activity of Mo to improve, wishing has a stronger interaction between Ni and the Mo, and the present invention finds in experiment, for bulk phase catalyst, Mo and Ni is fully combined then take off impurity in the degree of depth and do not show perfect performance.The composition catalyzer of Ni-W composite oxides of the present invention and Mo oxide compound, the possible cause that takes off the unexpected raising of performance in the impurity in the degree of depth is, in the very high bulk phase catalyst of metal content, reactive metal exist form different with loaded catalyst, take off in the impurity process in the hydrocarbon raw material degree of depth, the Ni-W composite oxides have stronger hydrogenation activity after sulfuration, make to have the effective hydrogenation of complex construction hydrocarbon molecule, eliminate and take off the sterically hindered of impurity reaction.Has the stronger impurity activity of taking off after the Mo sulfuration in the bulk phase catalyst, simple in structure, the sterically hindered little heteroatoms hydrocarbon that contains is easy to react, reduced of the interference of this part heteroatoms hydro carbons, helped the hydrogenation that Ni-W high reactivity center is used for the complex construction molecule the Ni-W hydrogenation activity.After containing the effective hydrogenation in heteroatomic complex construction hydrocarbon molecule process Ni-W high reactivity center, take off the sterically hindered of impurity and reduce greatly, can in taking off impurity activity, remove easily in the heart.Therefore, the active centre of Ni-W composite oxides of the present invention and Mo oxide compound obtains cooperation, and combination catalyst takes off in the impurity reaction in the degree of depth and has outstanding activity.Bulk phase catalyst preparation method of the present invention does not use the salts solution of Mo, because the reaction product of Mo salts solution and precipitation agent generally has certain solubleness, has therefore avoided the loss of Mo.

Compared with prior art, characteristics of the present invention are: because the present invention has used some or all of highly active bulk phase catalyst, strengthened the hydrogenation performance of hydrotreatment reaction zone catalyzer, can effectively reduce the content of impurity such as sulphur nitrogen in the stock oil, it is saturated to carry out the aromatic hydrocarbons degree of depth simultaneously, thereby can improve the hydrotreatment degree of depth of stock oil.When promptly reaching identical hydrotreatment and requiring, can reduce reaction pressure, reduce service temperature etc., perhaps under same reaction pressure, service temperature, increase the treatment capacity of device, perhaps reduce the usage quantity of catalyzer, reduced the construction investment and the running cost of device.

Embodiment

Method of the present invention is specific as follows: with in the heavy ends inferior one or more is stock oil, under the hydrotreatment operational condition, stock oil and hydrogen are by the hydrotreatment reaction zone, the hydrotreatment that obtains generates oil and uses in the gas circulation that gas-liquid separator separates obtains, also can go out system, the liquid fractionation that obtains obtains following products: one or more in gas, petroleum naphtha, diesel oil, the tail oil.

Bulk phase catalyst of the present invention can make as follows.

1, Ni _xW _yO _zComposite oxides precursor and MoO ₃The preparation of mixture

In retort, add the saline solution that contains reactive metal Ni, W component by catalyst component content proportioning.Contain nickel salt and can be single nickel salt, nickelous nitrate, nickelous chloride etc.Tungstenic salt can be sodium wolframate, ammonium metawolframate etc.Mix the back, precipitation agent is added under stirring state in the said mixture, until forming collosol intermixture.Becoming the glue temperature is 30-100 ℃, and becoming the glue pH value is 7.0-10.0.Can become under the glue temperature to wear out 1-5 hour after becoming glue.Becoming in the glue thing promptly is Ni _xW _yO _zThe precursor of composite oxides.Can filter or not filter before and after becoming glue, add the solid molybdic oxide, making beating mixes, and filters then and obtains filter cake, and filter cake can wash or not wash, and filter cake dehydrates under 50-150 ℃ of condition, 0.5～24 hour time of drying, obtains Ni _xW _yO _zComposite oxides precursor and MoO ₃Mixture.

Preferably 30～80 ℃ of described one-tenth glue temperature, gelation time was generally 0.5～5 hour, was preferably 0.5～3 hour, slurries pH value 7.0-9.0 preferably during cemented into bundles.Preferably 50～100 ℃ of described drying temperatures are preferably 1～8 hour time of drying.

Can add aluminum salt solution in the saline solution of Ni, W component, make the precursor that contains aluminum oxide in the throw out, aluminum salt solution can be aluminum nitrate, Tai-Ace S 150, aluminum chloride or aluminum acetate etc.Directly add aluminium hydroxide after also can becoming glue.The purpose of introducing aluminium in the catalyzer mainly is the intensity that increases catalyzer, and improves pore structure etc.In the preparation process of this mixture, can add auxiliary agent and additive etc. as required.

2, Preparation of Catalyst

The filter cake that above-mentioned drying is good rolls extruded moulding.Can or contain with water purification after the moulding and can decompose salt (as ammonium acetate) solution and wash.The activation of catalyzer comprises processes such as dry and roasting.To wash back stripe shape thing drying, roasting obtains final catalyst prod.Dry and roasting can be adopted this area normal condition, as 50～200 ℃ of dryings 1～48 hour, 450～600 ℃ of roastings 0.5～24 hour, is preferably 1～8 hour.Also can introduce auxiliary agent and additive as required in the catalyst preparation process.

Catalyst shape can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei) as required.The diameter of carrier can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.

Catalyzer has higher hydrodenitrification, hydrogenating desulfurization, the saturated isoreactivity energy of aromatic hydrocarbons.

Further specify Preparation of catalysts method of the present invention and use properties below by embodiment.Unspecified percentage composition is a weight percentage.

Embodiment 1

In retort, add 1000mL water, add nickelous chloride 40g dissolving then, add ammonium metawolframate 52g dissolving again, add zirconium oxychloride 5g dissolving again, add 10% ammoniacal liquor then and become glue, until pH value is 8, becoming the glue temperature is 50 ℃, wears out 1 hour behind the one-tenth glue, filters then, filter cake adds 600ml water purification and 16g molybdic oxide and 32g aluminium hydroxide, making beating stirs, and filters, and filter cake was 80 ℃ of dryings 5 hours, extruded moulding then, with water purification washing 3 times, wet bar is 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyst A, composition and main character see Table 1.

Embodiment 2

Method according to embodiment 1, press the component concentration proportioning of catalyst B in the table 1, adding aluminum chloride, nickelous chloride, sodium wolframate in retort, add 16% ammoniacal liquor then and become glue, is 9 until pH value, becoming the glue temperature is 80 ℃, wore out 3 hours after becoming glue, filter then, filter cake washs 2 times with the 500mL water purification, add water purification and molybdic oxide, making beating stirs, and filters, and filter cake was 70 ℃ of dryings 7 hours, extruded moulding then, with water purification washing 2 times, wet bar is 100 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours, obtain final catalyst B, composition and main character see Table 1.

Embodiment 3

Method according to embodiment 1, press the component concentration proportioning of catalyzer C in the table 1, in retort, add nickelous nitrate, ammonium metawolframate, aluminium hydroxide, silicon sol, add 12% ammoniacal liquor then and become glue, until pH value is 10, and becoming the glue temperature is 60 ℃, wears out 2 hours behind the one-tenth glue, filter then, filter cake adds molybdic oxide, and making beating stirs, and filters, filter cake was 120 ℃ of dryings 1 hour, extruded moulding then, wet bar is 130 ℃ of dryings 3 hours, 600 ℃ of roastings 3 hours, obtain final catalyzer C, composition and main character see Table 1.

Embodiment 4

Method according to embodiment 1, press the component concentration proportioning of catalyzer D in the table 1, in retort, add 1000mL water, add nickelous chloride 48g dissolving then, add ammonium metawolframate 40g dissolving again, adding 10% ammoniacal liquor then and become glue, is 8 until pH value, and becoming the glue temperature is 40 ℃, wore out 3 hours after becoming glue, filter then, filter cake adds 600ml water purification and 28g molybdic oxide and 17g aluminium hydroxide, and making beating stirs, filter, filter cake is 80 ℃ of dryings 5 hours, and extruded moulding then is with water purification washing 3 times, wet bar was 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyzer D, composition and main character see Table 2.

Comparative example

Catalyzer according to embodiment 1 is formed, and presses the disclosed method for preparing catalyst of Chinese patent CN1342102A, preparation reference agent E.

In retort, add 1000mL water, add Ammonium Heptamolybdate 25g dissolving then, add ammonium metawolframate 52g dissolving again, add 25% ammoniacal liquor then and become glue, until pH value is 10.0, and being heated to temperature is 90 ℃, drips the solution that contains the 40g nickelous chloride simultaneously in retort.The suspension liquid that forms is continued to stir 90 ℃ of temperature 30 minutes.Filter then, the filter cake hot wash, 100 ℃ of dryings 5 hours add 32g aluminium hydroxide extruded moulding then, and wet bar 500 ℃ of roastings 4 hours, obtains final reference catalyst E 100 ℃ of dryings 8 hours, and composition and main character see Table 2.Prepare catalyzer by this kind method, the molybdic oxide yield can only reach 80%, and in order to guarantee metal content and proportioning in the catalyzer, Ammonium Heptamolybdate adds 20% when feeding intake.

The catalyzer and the character of the preparation of table 1 the inventive method

The catalyzer numbering	A	B	C	D	E
						NiO，wt％	18.1	17.1	12.5	22.1	17.9
WO 3，wt％	42.3	21.3	28.4	32.2	41.8
						MoO 3，wt％	16.5	57.6	18.6	28.1	17.0
Al 2O 3，wt％	Surplus	Surplus	Surplus	Surplus	Surplus
						Other, wt%	ZrO 2/2.0	Do not have	SiO 2/4.0	TiO 2/3.0	Do not have
Specific surface/m 2·g -1	143	258	202	135	105
						Pore volume/mlg -1	0.216	0.40	0.258	0.12	0.132
Intensity/Nmm -1	11.5	11.0	16.7	18.2	8.6

Embodiment 5

Stock oil character sees Table 2, catalyst property sees Table 3, and processing condition and test-results see Table 4.Oxidized catalyst is carried out conventional sulfidizing before use.As under the 8.0MPa condition, vulcanize with the diesel oil that contains dithiocarbonic anhydride 2.0wt%, 230 ℃ of constant temperature 8 hours, 330 ℃ of constant temperature 10 hours, volume space velocity was 1.0h during liquid ^-1, hydrogen to oil volume ratio is 1000: 1.

From table 4 test-results as can be seen, adopt technology of the present invention can effectively improve hydrotreatment reaction zone activity of such catalysts, can reduce working pressure, reduce service temperature, perhaps improve treatment capacity, also can reduce the usage quantity of catalyzer, saved facility investment and process cost.Simultaneously because the more intense hydrogenation performance of Hydrobon catalyst, thereby in deep hydrodesulfurizationof, denitrogenation, make the saturated quality of improving product of the aromatic hydrocarbons degree of depth.

Table 2 stock oil character

The stock oil title	Stock oil-1 *	Stock oil-2 **	Stock oil-3 ***
				Density (20 ℃)/gcm -3	0.931	0.902	0.924
The boiling range scope/℃	360～600	360～560	340～610
				Sulphur content, wt%	3.10	1.60	2.40
Aromaticity content, wt%	58	43	54

^*Stock oil-1 is mixing oil (VGO: CGO: DAO=50 wherein: 25: 25 weight ratios)

^*Stock oil-2 is mixing oil (VGO: CGO=60 wherein: 40 weight ratios)

^{* *}Stock oil-3 is mixing oil (CGO: DAO=70 wherein: 30 weight ratios)

The main composition and the character of table 3. Hydrobon catalyst

Catalyzer	3936	FF-14
			Catalyzer is formed
MoO 3，wt％	24.5	24.0
			NiO，wt％	3.8	2.0
CoO，wt％		1.6
			Carrier, wt%	Surplus	Surplus
The main character of catalyzer
			Specific surface, m 2/g	＞160	＞160
Pore volume ml/g	0.33	＞0.30

Table 4 embodiment 5 processing condition and test-results

Processing condition	Process program 1	Reference scheme 1	Reference scheme 2
				Catalyzer	A	FF-14	E
Stock oil	Stock oil-1	Stock oil-1	Stock oil-1
				Pressure/MPa	8.0	8.0	8.0
The inlet hydrogen to oil volume ratio	600∶1	600∶1	600∶1
				Air speed/h -1	1.5	1.5	1.5
Temperature/℃	360	380	365
				Diesel yield, wt%	14.3	15.4	14.6
Diesel oil sulphur content/μ gg -1	300	500	360
				Diesel cetane-number	52.1	46.0	49.2
The tail oil yield, wt%	84.1	83.4	83.9
				Tail oil sulphur content/μ gg -1	900	1000	990
The tail oil aromaticity content, wt%	38	45	40

Continuous table 4 embodiment 5 processing condition and test-results

Processing condition	Process program 2	Process program 3	Process program 4
				Stock oil	Stock oil-2	Stock oil-2	Stock oil-3
Catalyzer	B	3936/C	D
				The catalyst loading volume ratio	-	40∶60	-
Pressure/MPa	5.0	10.0	12.0
				Temperature/℃	355	360/370	390
Air speed/h -1	1.0	3.0/2.0	3.0
				The inlet hydrogen to oil volume ratio	1200∶1	600∶1	500∶1
Diesel yield, wt%	8.1	12.5	16.5
				Diesel oil sulphur content/μ gg -1	400	140	80
Diesel cetane-number	45.6	51.1	56.6
				The tail oil yield, wt%	90.4	86.4	82.1
Tail oil sulphur content/μ gg -1	1200	500	300
				The tail oil aromaticity content, wt%	29	26	31

Claims (7)

1, a kind of hydroprocessing process comprises following content: be stock oil with the heavy ends, under the hydrotreatment operational condition, stock oil and hydrogen are by the hydrotreatment reaction zone, and the hydrotreatment that obtains generates oil and enters separation system; It is characterized in that comprising a kind of bulk phase catalyst at least in the described hydrotreatment reaction zone, bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, catalyzer before sulfuration W, Ni with Ni _xW _yO _z, the composite oxides form of z=x+3y exists, and Mo is with MoO ₃Oxide form exists; Composite oxides Ni _xW _yO _zThe ratio of middle x and y is 1: 8～8: 1, composite oxides Ni _xW _yO _zWith oxide M oO ₃Weight ratio be 1: 10～10: 1, composite oxides Ni in the bulk phase catalyst _xW _yO _zWith oxide M oO ₃Gross weight content be 40%～100%.

2, in accordance with the method for claim 1, it is characterized in that composite oxides Ni in the described bulk phase catalyst _xW _yO _zThe ratio of middle x and y is 1: 4～4: 1, composite oxides Ni _xW _yO _zWith oxide M oO ₃Weight ratio be 1: 5～5: 1, composite oxides Ni in the bulk phase catalyst _xW _yO _zWith oxide M oO ₃Gross weight content be 50%～80%.

3, in accordance with the method for claim 1, it is characterized in that described hydrotreatment operational condition is reaction pressure 3.0～20.0MPa, hydrogen to oil volume ratio is 200: 1～2500: 1, and volume space velocity is 0.1～8.0h ^-1, 260 ℃～455 ℃ of temperature of reaction.

4, in accordance with the method for claim 1, it is characterized in that described hydrotreatment operational condition is reaction pressure 4.0～18.0MPa, hydrogen to oil volume ratio 300: 1～2000: 1, volume space velocity 0.2～6.0h ^-1, 280～444 ℃ of temperature of reaction.

5, in accordance with the method for claim 1, the catalyzer that it is characterized in that described hydrotreatment reaction zone all is a bulk phase catalyst, or the combination of conventional hydrotreating catalyst and bulk phase catalyst; When being used in combination, the volume ratio of bulk phase catalyst and conventional catalyst is 90: 10～10: 90.

6, in accordance with the method for claim 5, it is characterized in that described bulk phase catalyst is seated in the top of reaction zone, perhaps be seated in the bottom of reaction zone, perhaps two types catalyzer loads at interval.

7, in accordance with the method for claim 5, the volume ratio that it is characterized in that described bulk phase catalyst and conventional catalyst is 20: 80～80: 20.