CN103801319B - A kind of hydrotreating catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of hydrotreating catalyst and preparation method thereof.This catalyst contains W, Ni composite oxides and Mo, Co composite oxides of suitable proportion, its preparation method is as follows: prepare W, Ni composite oxides precursor by coprecipitation, through molding, washing, it is dried and roasting, obtains catalyst intermediate, with the specific dipping of the impregnation liquid containing Co, Mo, drying and roasting, obtain hydrotreating catalyst.The method can realize catalyst activity component hydrogenation and hydrogenesis preferably collaborative performance, improves the combination property of catalyst.This catalyst is particularly well-suited to diesel oil ultra-deep hydrodesulfuration process.

Description

A kind of hydrotreating catalyst and preparation method thereof

Technical field

The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly diesel oil ultra-deep hydrodesulfuration catalysis The preparation method of agent.

Background technology

The heaviness of crude oil, in poor quality cause the high-sulfurized trend of crude oil constantly expanding.It is reported, the lowest Sulfur crude oil only accounts for 17wt%, and the sour crude of sulfur-bearing ＞ 2wt% is up to 58wt%.

The SO that sulfur, nitrogen and aromatic hydrocarbons etc. in diesel oil give off in combustion_x、NO_x, CH and soot etc. can result in Acid rain, photochemical fog, carcinogen etc., cause severe contamination, residents ' health cause serious harm, based on these various countries environment Air cleaning is increasingly paid close attention to by government, and the requirement to derv fuel specification is more and more stricter.Following cleaning diesel oil regulation forward And develop without sulfuration, low aromatic hydrocarbons, low-density, the direction of high cetane number.

Diesel oil hydrofining raw material is straight bavin, burnt bavin mostly, urges one or more in bavin etc..In recent years, refinery is a large amount of The high-sulphur crude in the areas such as the processing Middle East, makes the sulfur content in straight-run diesel oil increase substantially, Fcc Unit With Mixing Feed Including Residue, wax The rising of oil ratio makes some high boiling point macromole sulfide, nitride and polycyclic aromatic hydrocarbon etc. in catalytic diesel oil assemble, actual The reactivity worth of diesel oil hydrofining raw material reduces further, and difficulty of processing is greatly increased.

Main three class sulfide in diesel oil distillate are alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene.Its The complexity of desulfurization is thiophene ＜ benzothiophene ＜ dibenzothiophenes, and the 4-MDBT and 4 of β substd, 6-DMDBT are hydrogenated with Desulphurization reaction activity is minimum.Many studies have shown that, 4-MDBT and 4, the 6-DMDBT hydrodesulfurization in different catalysts is mainly led to Cross hydrogenation path to realize.DBT hydrogenolysis desulfurization on the different activities metal component catalyst such as Co-Mo, Ni-W and hydrogenation are de- The ratio of sulfur has bigger difference.

When producing the diesel oil of sulfur-bearing 350 μ g/g, sulfide that all reactivities are high and the dibenzothiophenes of unsubstituted Can be removed.But sulfur-bearing 50 μ g/g to be produced or 10 μ g/g and following cleaning diesel oil, reactivity is poor, molecule is relatively big, take Dai Ji must remove at the dibenzothiophenes class sulfide of 4 or 4,6.

Macromole basic nitrogen compound in raw oil, polycyclic aromatic hydrocarbon etc. have similar to 4,6-DMDBT class sulfide structure Property, reaction mechanism has similarity, and it is saturated to be all that aromatic ring is first hydrogenated with, then carries out next step reaction.The compound meeting of these types Interact with catalyst surface in a similar fashion, competitive Adsorption, mutually blocks its hydrogenation reaction.Especially in raw oil Macromole basic nitrogen compound, more much easier in the absorption of catalyst surface than sulfur-containing compound and aromatic hydrocarbons, its existence suppression adds Hydrogen desulphurization reaction, particularly impact are difficult to 4 removed, the hydrodesulfurization of 6-DMDBT.

The Hydrogenation that catalyst is excellent, it is possible to provide more hydrogenation sites, during ultra-deep desulfurization faster, More convert nitride, polycyclic aromatic hydrocarbon etc., reduce its impact to 4-MDBT and 4,6-DMDBT class sulfide hydrodesulfurization, Easier can realize low-sulfur, low aromatic hydrocarbons, low-density, the production purpose of high cetane number cleaning diesel oil.

CN101172261A discloses W-Mo-Ni hydrogenation catalyst prepared by a kind of body phase method, and this catalyst uses activity The saline mixed solution of W metal, W component and auxiliary agent generates Ni with sodium aluminate solution co-precipitation_xW_yO_zComposite oxides Precursor, then with MoO₃Making beating mixing, filtration, molding, activation are final catalyst, and supporting of active metal is unrestricted, More active metal total amount can be provided.Though W-Mo-Ni series hydrocatalyst has good Hydrogenation, can reach ultra-deep The purpose of desulfurization, but during diesel hydrogenation for removal sulphur, sulfide that reactivity is high and the dibenzothiophenes class of unsubstituted Part in sulfide also can realize desulfurization, too much consumption hydrogen by hydrogenation path, increases processing cost.

CN101089132A discloses the Hydrobon catalyst of a kind of tetra-kinds of active metal components of W-Mo-Ni-Co, though adopting By the W-Mo-Ni-Co-P active component of special ratios, make hydrogenolysis desulfurization performance that Co-Mo type is good and the good hydrogenation of W-Ni type Desulfurization performance is comprehensively utilized, but supporting of its active component is all to be realized by saturated total immersion technology, active metal Loading is restricted, and cannot provide more active metal total amount；Active component W-Mo-Ni-Co-P is at primary drying simultaneously The condition that in roasting process, uncontrollable hydrogenation activity phase and hydrogenolysis activity phase front body are formed, so that the hydrogenation of catalyst and hydrogen Solve desulphurizing activated can not good synergism.Though adding the surface nature of phosphorus energy modulation carrier in impregnation liquid, improve carrier And the interaction between active metal, but in dipping process, phosphorus can weaken active component with the effect of carrier surface group Absorption on carrier, makes active component easily reunite, and reduces the dispersion of active component in catalyst, thus reduces catalysis Agent activity.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of hydrotreating catalyst and preparation method thereof.The method Catalyst activity component hydrogenation can be realized and hydrogenesis is preferably collaborative plays, only reach while ultra-deep removing impurities matter Consume hydrogen more, reduce the purpose of processing cost.

The hydrotreating catalyst of the present invention, containing W, Ni composite oxides i.e. composite oxides I and Mo, Co combined oxidation Thing i.e. composite oxides II, wherein in composite oxides I, the mol ratio of W Yu Ni is 0.29 ~ 2.58, preferably 0.44 ~ 1.84； In composite oxides II, the mol ratio of Mo Yu Co is 0.26 ~ 6.51, preferably 0.83 ~ 4.69；In composite oxides I W mole Number is 0.45 ~ 4.97 with the ratio of the molal quantity of Mo in composite oxides II, preferably 0.7 ~ 3.1；Composite oxides I and composite oxygen Compound II accounts for the 50% ~ 100% of total catalyst weight, and preferably 60% ~ 95%.

In the hydrotreating catalyst of the present invention, W, Ni composite oxides are introduced by coprecipitation, and Mo, Co are compound Oxide is introduced by total immersion method.

In the hydrotreating catalyst of the present invention, possibly together with auxiliary agent P in composite oxides I, with P₂O₅Count in the catalyst Weight content is 0.1% ~ 8.0%, preferably 0.3% ~ 5.0%.Auxiliary agent P is introduced by coprecipitation.

In the hydrotreating catalyst of the present invention, possibly together with auxiliary agent Si in composite oxides I, with SiO₂Meter is in the catalyst Weight content be 0.7 ~ 8.0%, preferably 0.7% ~ 6.0%.Auxiliary agent Si is introduced by coprecipitation.

Hydrotreating catalyst of the present invention can also contain aluminium oxide, amorphous silica-alumina, titanium oxide, zirconium as required One or more in the component such as oxide, molecular sieve, these components weight content in the catalyst is less than 50%, preferably It is less than 40%.

The character of the hydrotreating catalyst of the present invention is as follows: pore volume is 0.1 ~ 0.5 mL/g, and specific surface area is 110 ~ 350m²/g。

The preparation method of hydrotreating catalyst of the present invention, including: (1) prepares W, Ni composite oxides by coprecipitation Precursor, (2), by W, Ni composite oxides precursor molding, washing, are dried and roasting, obtain catalyst intermediate, and (3) prepare Impregnation liquid containing Co, Mo, wherein adds organic carboxyl acid and ammonia in impregnation liquid；(4) the impregnation liquid impregnation steps obtained by step (3) (2) catalyst intermediate obtained, drying and roasting, obtain hydrotreating catalyst.

The preparation method of hydrotreating catalyst of the present invention, the coprecipitation described in step (1) prepares W, Ni combined oxidation The process of thing precursor, can adopt with the following method: by tungstenic, the saline solution of nickel, add in the required ratio of catalyst composition In glue tank, carry out plastic reaction with alkaline precipitating agent, the most aging, filter, be dried.Coprecipitation can use in prior art Conventional coprecipitation method, preferably use and flow coprecipitation method.The temperature of plastic reaction is 30 ~ 80 DEG C, controls the pH of reaction system It is 8.0 ~ 10.5, preferably 8.0 ~ 9.5, reaction controlling completes in 0.5 ~ 2.0h.Alkaline precipitating agent can be inorganic or organic Alkali water-soluble compound, as in sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, carbamide etc. one or more, be preferably Ammonia, the concentration of ammonia can be the most feasible ratio.

The preparation method of hydrotreating catalyst of the present invention, contains in step (3) and adds organic carboxyl acid in the impregnation liquid of Co, Mo And ammonia, wherein organic carboxyl acid used is 0.5 ~ 1.2 with the mol ratio of Co.In impregnation liquid, the concentration of ammonia is 10wt% ~ 25wt%.Organic Carboxylic acid can be one or more in hydroxy acid (citric acid, tartaric acid), aminoacid (nitrilotriacetic acid, ethylenediaminetetraacetic acid), Optimization citric acid.Containing MoO in every 100 milliliters of impregnation liquid₃17 ~ 33g, containing CoO3 ~ 7g.

The present invention also can be added as needed on one or more in the impregnation liquid containing Co, Mo and contain two or more hydroxyls One or more in the polyhydric alcohol of base, such as mannitol, ethylene glycol, glycerol, the mol ratio of polyhydric alcohol and Co is 0.1 ~ 0.5。

A step in step (1) or a few step add required catalyst promoter and/or addO-on therapy.Auxiliary agent generally comprises One or more in P, F, Ti, Si, B, Zr, Mg etc., preferably P and/or Si.AddO-on therapy be generally refractory porous mass and Its precursor, such as one or more in aluminium oxide, clay, amorphous silica-alumina, titanium oxide, zirconium oxide, molecular sieve etc..Addition helps The method of agent and addO-on therapy uses this area conventional method.

The preparation method of hydrotreating catalyst of the present invention, step (2) can use the forming method of routine, such as be squeezed into Type method etc..In forming process, appropriate shaping assistant, such as binding agent, extrusion aid etc. can be added.Described washing is general Employing water purification washs.Described drying condition is as follows: be dried 2 ~ 8h at 50 ~ 120 DEG C；Roasting condition is as follows: 450 ~ 600 DEG C of roastings Burn 3 ~ 6h.

The preparation method of hydrotreating catalyst of the present invention, the dipping used by step (4) can use saturated infusion process.Dipping After, drying condition is as follows: be dried 2 ~ 8h at 60 ~ 150 DEG C；Roasting condition is as follows: at 450 ~ 600 DEG C of roasting 3 ~ 6h.

In bulk phase catalyst, the fit system of active metal is the biggest to the performance impact of catalyst.The inventive method is led to Using coprecipitation to prepare W, Ni composite oxides precursor after first, then catalyst intermediate is made in molding, then utilizes spy Fixed dipping method supported active metals Co and Mo, so advantageously forms W-Ni activity phase and Co-Mo activity phase.Use coprecipitated Shallow lake method prepares W, Ni composite oxides precursor, beneficially Ni, W synergism, forms W-Ni activity phase, improves adding of catalyst Hydrogen performance.Preparation is containing Co, Mo ammonia impregnation liquid of organic acid, and wherein impregnation liquid is not only stable, and active metal therein with Organic acid forms chelate, beneficially Co, Mo and preferably coordinates and weaken between active metal Co, Mo and catalyst intermediate Interact, be evenly dispersed in catalyst intermediate, promote the formation of Co-Mo activity phase, especially form more activity Higher II type Co-Mo activity phase, improves the hydrogenolysis performance of catalyst.Prepared catalyst W-Ni activity phase and Co-Mo The matched well of activity phase, makes the Hydrogenation of catalyst and hydrogenolysis performance reach to be well matched with, and beneficially catalyst is comprehensive The raising of performance.

Detailed description of the invention

The present invention provides the preparation method of catalyst, and a kind of concrete preparation process is as follows:

(1) W, Ni composite oxides precursor is prepared by coprecipitation

According to the catalytic component content proportioning preparation saline solution containing W, Ni, can be nickel sulfate, nickel nitrate, chlorine containing nickel salt Changing one or more in nickel, basic nickel carbonate, nickel oxalate etc., tungsten salt can be the one in ammonium metatungstate, sodium tungstate etc. Or several, auxiliary agent Si, P, Ti, B, Zr, Mg etc. can need to introduce in mixed liquor by proportioning according to catalyst, preferably Si and/or P, silicon source can be one or more in waterglass, Ludox etc., and phosphorus source can be phosphoric acid, phosphorous acid, ammonium phosphate, phosphoric acid hydrogen One or more in ammonium, ammonium dihydrogen phosphate etc..

Plastic is carried out, the most always in saline solution containing W, Ni is equipped with the retort of water purification with alkaline precipitating agent stream Change, filter, be dried, obtain W, Ni composite oxides precursor.Wherein, gelling temperature is 30 ~ 80 DEG C, controls the pH of reaction system Value is 8.0 ~ 10.5, preferably 8.0 ~ 9.5, and the response time controls at 0.5 ~ 2.0h；Alkaline precipitating agent can be inorganic or organic Alkali water-soluble compound, such as sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, carbamide etc., preferably ammonia, ammonia dense Degree can be the most feasible ratio.

(2) preparation of catalyst intermediate

W, Ni composite oxides precursor addition shaping assistant is shaped, washing, is dried and roasting, obtains catalyst Intermediate, wherein washing is to wash to catalyst intermediate free from admixture with water purification, and wherein drying condition is to be dried 2 at 50 ~ 120 DEG C ~ 8h, roasting condition is at 450 ~ 600 DEG C of roasting 3 ~ 6h.The shape of catalyst can make lamellar, spherical, cylinder as required Bar and irregular bar (such as Herba Trifolii Pratentis, Herba Galii Bungei), preferably cylindrical bars and irregular bar.

(3) preparation impregnation liquid containing Co, Mo

First to measure, before impregnation liquid preparation, the catalyst intermediate water absorption rate (2) prepared, the concentration of impregnation liquid is according to catalysis The water absorption rate of agent composition requirement and catalyst intermediate determines.

Weigh a certain amount of organic carboxyl acid, it is also possible to add polyhydric alcohol, with water dissolution, add a certain amount of cobalt source and molybdenum source And ammonia.In impregnation liquid, the concentration of ammonia is 10wt% ~ 25wt%.Containing MoO in the most every 100 milliliters of impregnation liquid₃17 ~ 33g, containing CoO3 ~ 7g, organic acid is 0.5 ~ 1.2 with the mol ratio of Co, and polyhydric alcohol is 0.1 ~ 0.5 with the mol ratio of Co.The cobalt provided in impregnation liquid One or more in basic cobaltous carbonate, cobalt carbonate, the cobalt nitrate etc. of source, it is provided that molybdenum source selected from ammonium molybdate, molybdic acid, oxidation One or more in molybdenum etc..

(4) preparation of hydrotreating catalyst

The catalyst intermediate that the impregnation liquid impregnation steps (2) obtained by step (3) obtains, drying and roasting, obtain Hydrotreating catalyst；Wherein impregnate preferably with saturated infusion process.Drying condition is as follows: be dried 2 ~ 8h at 60 ~ 150 DEG C；Roasting Burning condition is as follows: at 450 ~ 600 DEG C of roasting 3 ~ 6h.

The solution of the present invention and effect is further illustrated below by specific embodiment.Wt% is mass fraction.

Embodiment 1

In a container A, add 500mL water purification, by 48g ammonium metatungstate, 33g Nickel dichloride., 2.5g ammonium dihydrogen phosphate, add Enter and wherein stir.

In a container B, add 300mL water purification, 48g aluminum chloride is added thereto stirring and dissolving.

In a container C, compound concentration is with SiO₂Dilute water glass solution 100mL of (weight) meter 2.2%.

After liquor alumini chloridi in container B is added in container A under stirring, then by the dilute waterglass in container C Solution instills in container A under stirring, and overall solution volume water purification is adjusted to 1000mL, obtain containing metal W, Ni and Al₂O₃、P₂O₅、SiO₂The saline solution of precursor.

By the saline solution prepared above and the ammonia spirit of 15wt% and flow plastic, controlling gelling temperature is 50 DEG C, serosity pH Being 8.2 ± 0.2, complete plastic in 1h, then by aging for serosity 3 hours, filter serosity after aging end, the filter cake obtained exists Baking oven is dried under the conditions of 70 DEG C, through rolling extruded moulding, by Φ 2.0 Herba Trifolii Pratentis orifice plate extrusion, through washing after molding, then exists In baking oven under the conditions of 110 DEG C be dried 8 hours, then 500 DEG C of calcination activation 3h obtain containing active metal W, Ni catalyst before Body bar.

By 24g citric acid, 19g basic cobaltous carbonate and 91g ammonium molybdate, it is configured to the leaching that 300mL ammonia concn is 20wt% Stain liquid, airtight preservation is stand-by.

Take the catalyst precarsor bar containing W, Ni to be placed in converter, spray with the impregnation liquid 75mL prepared above, sprayed Cheng Hou, is dried 8 hours under the conditions of material taking-up in an oven 110 DEG C, and in high temperature furnace, under the conditions of 500 DEG C, calcination activation 3 is little Time, obtain catalyst A of the present invention.

Embodiment 2

The whole preparation process of catalyst is with embodiment 1, and wherein in catalyst precarsor bar preparation process, saline solution is prepared, and adds Ammonium metatungstate 41g, Nickel dichloride. 30g, aluminum chloride 81g, be not added with ammonium dihydrogen phosphate and dilute water glass solution, and impregnation liquid preparation adds alkali Formula cobalt carbonate 18g, ammonium molybdate 86g, citric acid 22g, obtain catalyst B of the present invention.

Embodiment 3

The whole preparation process of catalyst is with embodiment 1, and wherein in catalyst precarsor bar preparation process, saline solution is prepared, and adds Ammonium metatungstate 38g, Nickel dichloride. 33g, aluminum chloride 74g, containing SiO₂Dilute water glass solution 100mL of (weight) 3.1%, is not added with di(2-ethylhexyl)phosphate Hydrogen ammonium, impregnation liquid preparation adds basic cobaltous carbonate 22g, ammonium molybdate 87g, mannitol 10g, citric acid 20g, obtains present invention catalysis Agent C.

Embodiment 4

The whole preparation process of catalyst is with embodiment 1, and wherein in catalyst precarsor bar preparation process, gelling temperature is 60 DEG C, Saline solution preparation adds ammonium metatungstate 43g, Nickel dichloride. 30g, aluminum chloride 75g, ammonium dihydrogen phosphate 3.5g, is not added with dilute waterglass molten Liquid, basic cobaltous carbonate 18g in impregnation liquid, ammonium molybdate 81g, citric acid 22g, obtain catalyst D of the present invention.

Embodiment 5

The whole preparation process of catalyst is with embodiment 1, and wherein in catalyst precarsor bar preparation process, gelling temperature is 60 DEG C, Saline solution preparation adds ammonium metatungstate 36g, Nickel dichloride. 27g, aluminum chloride 83g, and ammonium dihydrogen phosphate 2.5g, containing SiO₂2.0wt%'s is dilute Water glass solution 100mL.Basic cobaltous carbonate 22g in impregnation liquid, ammonium molybdate 93g, citric acid 26g, obtain catalyst E of the present invention.

Embodiment 6

The whole preparation process of catalyst is with embodiment 1, and wherein in catalyst precarsor bar preparation process, gelling temperature is 60 DEG C, Saline solution preparation adds ammonium metatungstate 39g, Nickel dichloride. 23g, aluminum chloride 82g, adds ammonium dihydrogen phosphate 2.5g, containing SiO₂2.2wt% Dilute water glass solution 100mL.Basic cobaltous carbonate 24g in impregnation liquid, ammonium molybdate 91g, citric acid 29g, obtain present invention catalysis Agent F.

Comparative example 1

In a container A, add 500mL water purification, add 29g Nickel dichloride., 2.5g ammonium dihydrogen phosphate stirring and dissolving, then add Enter 41g ammonium metatungstate stirring and dissolving, under agitation instill containing SiO₂Dilute water glass solution 32mL of (weight) 7%, is configured to acid work Make solution 1.

Adding 300mL water purification in a container B, being subsequently adding aluminum chloride 88g stirring and dissolving, to be configured to acid work molten Liquid 2.

Adding 200mL water purification in a plastic cans, temperature rises to 60 DEG C, by solution 2 and 18wt% in the case of stirring Ammonia also flows plastic in addition retort, gelling temperature 60 DEG C, completes plastic in 0.5h, and plastic slurry pH controls 9.0±0.2.Then solution 1 is added in plastic cans, adds the ammonia of 18wt%, regulation slurry pH value 8.5, cemented into bundles The most aging 1 hour, then filtering, filter cake joins the container for stirring equipped with 600mL water purification, adds 16.3g molybdenum oxide and beats Slurry is rear to be filtered, and filter cake is dried 5 hours at 80 DEG C, then extruded moulding, washs 3 times with water purification, and wet bar is dried 5 at 120 DEG C Hour, 500 DEG C of calcination activations 4 hours, prepare catalyst G.

Catalyst of the present invention and the character such as table 1 of comparative example catalyst.

Table 1 present invention and comparative example catalyst property

Catalyst is numbered	A	B	C	D	E	F	G
								Catalyst forms
WO3, wt%	39.1	33.0	30.8	35.0	29.0	31.7	33.0
								MoO3, wt%	18.2	17.1	17.3	16.0	18.5	18.2	16.1
NiO, wt%	18.0	16.8	18.5	16.3	15.1	12.6	16.1
								CoO, wt%	3.1	3.0	3.4	2.9	3.5	3.9	0
SiO2, wt%	2.0	0	3.0	0	1.9	2.0	2.0
								P2O5, wt%	1.5	0	0	2.0	1.5	1.5	1.5
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
								Catalyst property
Specific surface area, m2/g	149	170	179	191	199	202	198
								Pore volume, mL/g	0.212	0.199	0.205	0.258	0.261	0.255	0.235
Intensity, N/mm	18.9	16.3	18.4	17.8	18.2	18.5	15.6

The data of table 1 show, catalyst of the present invention has high total metal content, and active metal ratio can be in a big way Modulation, has bigger pore volume and specific surface area.

Embodiment 7

Being 6.4MPa to catalyst E, F of the present invention and comparative example catalyst G in hydrogen dividing potential drop, reaction temperature is 360 DEG C, volume Air speed is 2.0h^-1, under conditions of hydrogen to oil volume ratio is 500, on 200mL small hydrogenation device, it is former with Maoming mixed diesel Material carries out hydrodesulfurization reaction performance evaluation.Raw oil main character such as table 2, evaluating catalyst result such as table 3.

Table 2 raw oil main character

Project	Analysis result
		Density (20 DEG C), g/cm3	0.8620
Boiling range scope, DEG C	178-371
		S, g/g	12197
N, g/g	290
		Cetane number	46.2

Table 3 catalyst HDS Evaluation results

Catalyst	E	F	G
				Generate oil density (20 DEG C), g/cm3	0.8340	0.8338	0.8335
Boiling range scope, DEG C	165-367	166-369	163-368
				S, g/g	30	31	32
N, g/g	2.2	2.4	2.5
				Cetane number	52.3	52.1	52.0

The data of table 3 show, catalyst of the present invention has hydrodesulfurization and the hydrodenitrogeneration ability of excellence, can realize low The production purpose of sulfur, low aromatic hydrocarbons, low-density, high cetane number cleaning diesel oil.

Embodiment 8

Respectively being former containing the tri-kinds of model compound concentration of DBT, 4-MDBT, 4,6-DMDBT toluene solution as 2wt% Material, is 2.0MPa at hydrogen pressure, and hydrogen to oil volume ratio is 200:1, air speed 3h^-1, under the conditions of reaction temperature 320 DEG C, fill at minisize reaction Put and catalyst of the present invention and comparative example catalyst are carried out hydrogenation and hydrogenolysis desulfurization performance evaluation.

Reaction is carried out on micro-reaction equipment, and product quantitative analysis and qualification are by Varian3800 type capillary tube Gas chromatograph and Finnigan SSQ710X type level Four bar mass spectrograph are used in conjunction and realize.

If with r representative model compound hydrogenation and hydrogenolysis rate ratio, with DBT for r DBT during model compound In product, cyclohexyl benzene represents with the ratio of diphenyl content；With 4-MDBT for r cyclohexyl benzene class and biphenyl during model compound The ratio of class content represents；With 4,6-DMDBT for r 1-methyl-3-(3-methylcyclohexyl benzene during model compound) with 3, The ratio of 3-dimethyl diphenyl content represents, the results are shown in Table 4.

Table 4 present invention and comparative example catalyst representativeness hydrogenation and hydroformylation product solution ratio

Catalyst is numbered	E	F	G
				r(DBT )	0.29	0.28	0.96
r (4-MDBT)	1.51	1.50	2.6
				r(4,6-DMDBT)	4.71	4.70	5.11

The data of table 4 show, the hydrogenolysis performance of catalyst of the present invention is better than comparative example catalyst, especially to reactivity Higher DBT class sulfide, can increase substantially its hydrogenolysis desulfurization performance.

DBT class sulfide is as one of the main component of diesel oil hydrofining raw material, and major part is by hydrogenolysis path implement Desulfurization can reduce hydrogen consumption by a relatively large margin, reduces and 4, the 6-DMDBT class sulfide competitive Adsorption to hydrogenation sites simultaneously, from And it being 4,6-DMDBT class sulfide provides more hydrogenation reaction active center, increases its conversion ratio.

Table 3 shows with the aggregation of data of table 4, and catalyst of the present invention can while realizing diesel oil ultra-deep hydrodesulfuration relatively Significantly reduce hydrogen consumption, reduce processing cost.

Claims (23)

1. a hydrotreating catalyst, the most multiple containing W, Ni composite oxides i.e. composite oxides I and Mo, Co composite oxides Closing oxide II, wherein in composite oxides I, the mol ratio of W Yu Ni is 0.29～2.58；In composite oxides II, Mo and Co Mol ratio be 0.26～6.51；In composite oxides I, the molal quantity of W with the ratio of the molal quantity of Mo in composite oxides II is 0.45～4.97；Composite oxides I and composite oxides II accounts for the 50%～100% of total catalyst weight.

2. according to the catalyst described in claim 1, it is characterised in that in described composite oxides I, the mol ratio of W with Ni is 0.44～1.84.

3. according to the catalyst described in claim 1, it is characterised in that in described composite oxides II, the mol ratio of Mo with Co is 0.83～4.69.

4. according to the catalyst described in claim 1,2 or 3, it is characterised in that the molal quantity of W and composite oxygen in composite oxides I In compound II, the ratio of the molal quantity of Mo is 0.7～3.1.

5., according to the catalyst described in claim 1,2 or 3, composite oxides I and composite oxides II accounts for total catalyst weight 60%～95%.

6., according to the catalyst described in claim 1, it is characterised in that in described catalyst, W, Ni composite oxides are by altogether The sedimentation method introduce, and Mo, Co composite oxides are introduced by total immersion method.

7., according to the catalyst described in claim 1, it is characterised in that in described catalyst, W, Ni composite oxides contain Auxiliary agent P, with P₂O₅Meter weight content in the catalyst is 0.1%～8.0%.

8., according to the catalyst described in claim 1 or 7, it is characterised in that in described catalyst, W, Ni composite oxides contain There is auxiliary agent Si, with SiO₂Meter weight content in the catalyst is 0.7%～8.0%.

9. according to the catalyst described in claim 1, it is characterised in that in described catalyst containing aluminium oxide, amorphous silica-alumina, One or more in titanium oxide, Zirconium oxide, molecular sieve, weight content in the catalyst is less than 50%.

10. according to the catalyst described in claim 1, it is characterised in that containing aluminium oxide in described catalyst, in the catalyst Weight content be less than 50%.

11. according to the catalyst described in claim 1, it is characterised in that the character of described hydrotreating catalyst is as follows: pore volume Being 0.1～0.5 mL/g, specific surface area is 110～350m²/g。

The preparation method of catalyst described in 12. claim 1, including: before (1) prepares W, Ni composite oxides by coprecipitation Body thing, (2), by W, Ni composite oxides precursor molding, washing, are dried and roasting, obtain catalyst intermediate, and (3) preparation contains The impregnation liquid of Co, Mo, wherein adds organic carboxyl acid and ammonia in impregnation liquid；(4) the impregnation liquid impregnation steps obtained by step (3) (2) catalyst intermediate obtained, drying and roasting, obtain hydrotreating catalyst.

13. according to the preparation method of the catalyst described in claim 12, it is characterised in that: step (1) process is as follows: will contain Tungsten, the saline solution of nickel, carry out plastic reaction with alkaline precipitating agent, the most aging, filters, and is dried.

14. according to the preparation method of the catalyst described in claim 13, it is characterised in that: step (1) uses and flows coprecipitation method, The temperature of plastic reaction is 30～80 DEG C, and the pH controlling reaction system is 8.0～10.5, and reaction controlling is 0.5～2.0h.

15. according to the preparation method of the catalyst described in claim 13, it is characterised in that: alkaline precipitating agent be sodium hydroxide, In sodium carbonate, sodium bicarbonate, ammonia, carbamide one or more.

16. according to the preparation method of the catalyst described in claim 13, it is characterised in that: dipping containing Co, Mo in step (3) Adding organic carboxyl acid and ammonia in liquid, wherein organic carboxyl acid used is 0.5～1.2 with the mol ratio of Co, the concentration of ammonia in impregnation liquid For 10wt%～25wt%.

17. according to the preparation method of the catalyst described in claim 13, it is characterised in that: dipping containing Co, Mo in step (3) In liquid, containing MoO in every 100 milliliters of impregnation liquid₃17～33g, containing CoO 3～7g.

18. according to the preparation method of the catalyst described in claim 13, it is characterised in that: organic carboxyl acid is citric acid, winestone One or more in acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid.

19. according to the preparation method of the catalyst described in claim 12 or 16, it is characterised in that: in the impregnation liquid containing Co, Mo Adding polyhydric alcohol, polyhydric alcohol is one or more in mannitol, ethylene glycol, glycerol, and polyhydric alcohol is 0.1 with the mol ratio of Co ～0.5.

20. according to the preparation method of the catalyst described in claim 12 or 16, it is characterised in that: a step in step (1) or Adding required catalyst promoter and/or addO-on therapy in several steps, auxiliary agent includes the one in P, F, Ti, Si, B, Zr, Mg or several Kind, addO-on therapy is refractory porous mass and precursor thereof, addO-on therapy be aluminium oxide, clay, amorphous silica-alumina, titanium oxide, One or more in zirconium oxide, molecular sieve.

21. according to the preparation method of the catalyst described in claim 12, it is characterised in that: the drying condition described in step (2) As follows: to be dried 2～8h at 50～120 DEG C；Roasting condition is as follows: in 450～600 DEG C of roastings 3～6h.

22. according to the preparation method of the catalyst described in claim 12, it is characterised in that: the dipping used by step (4) uses Saturated infusion process.

23. according to the preparation method of the catalyst described in claim 12, it is characterised in that: the drying condition of step (4) is as follows: It is dried 2～8h at 60～150 DEG C；Roasting condition is as follows: in 450～600 DEG C of roastings 3～6h.