CN103801316A - Preparation method of hydrodesulfurization catalyst - Google Patents

Abstract

The invention discloses a preparation method of a hydrodesulfurization catalyst. The preparation method of the hydrodesulfurization catalyst is as follows: using a coprecipitation method for preparation of a W, Ni, Al and Mg composite oxide precursor, introducing high molecular polyethylene glycol in the precipitation process, forming, washing, drying and roasting to obtain a catalyst intermediate, using a specific Co and Mo-containing impregnation liquid for impregnation, drying and roasting to obtain the hydrodesulfurization catalyst. The prepared catalyst is smaller in particle and larger in surface area, and enables an active metal to form a hybrid active center with excellently-matched hydrogenation performance and hydrogenolysis performance in the premise of uniform dispersion of the active metal, so that the hydrogenation and hydrogenolysis desulfurization effects of the catalyst active component can be better cooperatively played, ultra-deep desulfurization can be achieved, meanwhile no excess hydrogen consumption is produced, and the processing cost is reduced.

Description

The preparation method of Hydrobon catalyst

Technical field

The present invention relates to a kind of Hydrobon catalyst preparation method, particularly diesel oil ultra-deep hydrodesulfuration method for preparing catalyst.

Background technology

The heaviness of crude oil, the high sulfuration trend of the crude oil that in poor quality causes, in further expansion, it is reported, sweet crude only accounts for 17wt% in the world at present, and the sour crude of sulfur-bearing > 2wt% is up to 58wt%.

SOx, NOx, CH and the soots etc. that sulphur, nitrogen and aromatic hydrocarbons etc. in diesel oil give off in combustion process can cause forming acid rain, photochemical fog, carcinogenic substance etc., environment is caused to severe contamination, residents ' health is caused to serious harm, more and more pay close attention to atmosphere is clean based on these national governments, more and more stricter to the requirement of derv fuel specification.Following clean diesel specification is just towards the future development without sulfuration, low aromatic hydrocarbons, low-density, high cetane number.

Diesel oil hydrofining raw material is straight bavin, burnt bavin mostly, urge one or both or two or more miscellas in bavin etc.In recent years refinery processes the high-sulphur crude in the areas such as the Middle East in a large number, sulfur content in perfectly straight diesel oil is increased substantially, the rising of Fcc Unit With Mixing Feed Including Residue, wax oil ratio makes the gatherings such as the large molecular sulfur compound of some higher boilings in catalytic diesel oil, nitride and polycyclic aromatic hydrocarbon, the reactivity worth of actual diesel oil hydrofining raw material further reduces, and difficulty of processing increases greatly.

Main three class sulfide in diesel oil distillate are alkylthrophene, alkylbenzene bithiophene and methyldibenzothiophene.The complexity of its desulfurization is thiophene < benzothiophene < dibenzothiophenes, and the 4-MDBT of β substd and 4,6-DMDBT hydrodesulfurization reaction activity are minimum.Much research shows, 4-MDBT and 4, the 6-DMDBT hydrodesulfurization in different catalysts mainly realizes by hydrogenation path.The hydrogenolysis desulfurization of DBT on the different activities such as Co-Mo, Ni-W metal component catalyst and the ratio of hydrodesulfurization have bigger difference.

While producing the diesel oil of sulfur-bearing 350 μ g/g, the sulfide that all reactivities are high and the dibenzothiophenes of unsubstituted can be removed.But produce sulfur-bearing 50 μ g/g or 10 μ g/g and following clean diesel, reactivity is poor, molecule is large, substituting group must remove at the dibenzothiophenes class sulfide of 4 or 4,6.

Large molecule basic nitrogen compound, polycyclic aromatic hydrocarbon etc. in feedstock oil are with 4, and 6-DMDBT class sulfide structure has similitude, and reaction mechanism has similitude, are all that the first hydrogenation of aromatic ring is saturated, then carry out next step reaction.The compound of these types can interact with catalyst surface in a similar fashion, and competitive Adsorption, blocks its hydrogenation reaction mutually.Especially the large molecule basic nitrogen compound in feedstock oil, more much easier in the absorption of catalyst surface than sulfur-containing compound and aromatic hydrocarbons, and its existence suppresses hydrodesulfurization reaction, particularly impact be difficult to remove 4, the hydrodesulfurization of 6-DMDBT.

The Hydrogenation of catalyst excellence, more hydrogenation sites can be provided, in ultra-deep desulfurization process, sooner, more transform nitride, polycyclic aromatic hydrocarbon etc., reduce it to 4-MDBT and 4, the impact of 6-DMDBT class sulfide hydrodesulfurization, can easierly realize the production object of low-sulfur, low aromatic hydrocarbons, low-density, high cetane number clean diesel.

It is generally acknowledged, the contiguous substd of S atom of 4-MDBT and 4,6-DMDBT, connects absorption to S atom at the end of catalyst surface and has obstruction, causes its reactivity low, and desulfurization major part is by the absorption that lies low of aromatic ring, and realize in hydrogenation path.And if catalyst can provide activated centre, more seamed edge position, just can increase the ratio that 4-MDBT and 4,6-DMDBT end connect absorption, make its ratio of passing through hydrogenolysis desulfurization increase, improve its reactivity, in process, exceed again consumption hydrogen.

CN101172261A discloses the standby W-Mo-Ni hydrogenation catalyst of a kind of body phase legal system, this catalyst adopts the saline mixed solution of active metal Ni, W component and auxiliary agent and sodium aluminate solution co-precipitation to generate NixWyOz composite oxides precursor, then with MoO ₃making beating mixing, filtration, moulding, activation are final catalyst, and supporting of active metal is unrestricted, and more active metal total amounts can be provided.Though the W-Mo-Ni series hydrocatalyst of high metal has good Hydrogenation, can reach the object of ultra-deep desulfurization, but in diesel hydrogenation for removal sulphur process, part in the dibenzothiophenes class sulfide of the sulfide that reactivity is high and unsubstituted also can realize desulfurization by hydrogenation path, too much consumption hydrogen, increase processing cost, too high total metal content has also increased the cost of investment of catalyst simultaneously.

In the coprecipitation process of current disclosed most of bulk phase catalyst at the beginning of activity forms mutually, particle size is not all done to any restriction, if just formed large crystal grain in this step, in each step so afterwards, be difficult to make final catalyst to obtain high specific area, even if metal has obtained being uniformly distributed, also having the metal being partly wrapped in bulky grain can not play one's part to the full, become invalid component, reduce the utilization rate of metal.

CN101089132A discloses the Hydrobon catalyst of tetra-kinds of active metal components of a kind of W-Mo-Ni-Co, though adopted the W-Mo-Ni-Co-P active component of special ratios, make hydrogenolysis desulfurization performance and the good hydrodesulfurization performance of W-Ni type that Co-Mo type is good obtain comprehensive utilization, but supporting of its active component is all to realize by saturated total immersion technology, the loading of active metal is restricted, and more active metal total amount cannot be provided; The condition that simultaneously active component W-Mo-Ni-Co-P uncontrollable hydrogenation activity phase and the active phase front of hydrogenolysis body in primary drying roasting process forms, thus make the hydrogenation of catalyst and hydrogenolysis is desulphurizing activated can not well act synergistically.Though add the surface nature of phosphorus energy modulation carrier in maceration extract, improve the interaction between carrier and active metal, but in dipping process, the effect of phosphorus and carrier surface group can weaken the absorption of active component on carrier, active component is easily reunited, reduce the decentralization of active component in catalyst, thereby reduce catalyst activity.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of preparation method of Hydrobon catalyst.The method can be under the homodisperse prerequisite of active metal, form the mixed type activated centre of Hydrogenation and hydrogenolysis Performance Match excellence, there is more granule, tuftlet group more simultaneously, larger surface area is provided, more seamed edge position, to realize the better collaborative performance of catalyst activity component hydrogenation and hydrogenolysis desulfidation, when reaching ultra-deep desulfurization, exceed consumption hydrogen, the object cutting down finished cost.

The preparation method of Hydrobon catalyst of the present invention, comprise: (1) prepares W, Ni, Al, Mg composite oxides precursor by coprecipitation, (2) by W, Ni, Al, the moulding of Mg composite oxides precursor, washing, dry and roasting, obtains catalyst intermediate, (3) preparation is containing the maceration extract of Co, Mo, (4) catalyst intermediate that the maceration extract impregnation steps (2) obtaining by step (3) obtains, drying and roasting, obtain Hydrobon catalyst; Wherein step (1) process is as follows: the salting liquid of tungstenic, nickel, aluminium, magnesium is carried out with alkaline precipitating agent and flow plastic and react, the pH value of controlling reaction system is 8.0 ~ 10.5, preferably 8.0 ~ 9.5, then aging, filter, dry, obtain W, Ni, Al, Mg composite oxides precursor, wherein before plastic and/or in plastic process, adding molecular weight is that 200 ~ 10000(is preferably 1000 ~ 10000) polyethylene glycol, making the weight content of polyethylene glycol in W, Ni, Al, Mg composite oxides precursor is 1% ~ 10%, is preferably 1% ~ 5%; Step (3) process is as follows: molybdenum source, cobalt source, organic carboxyl acid, ammonia and water are mixed with in the maceration extract containing Co, Mo, and wherein the mol ratio of organic carboxyl acid used and Co is 0.5 ~ 1.2, and in maceration extract, the concentration of ammonia is 10wt% ~ 25wt%.

In the inventive method, the temperature of step (1) plastic reaction is 30 ~ 80 ℃, plastic reaction time 0.5 ~ 2.0h.Alkaline precipitating agent can be inorganic or organic alkaline water soluble compound, as in NaOH, sodium carbonate, sodium acid carbonate, ammoniacal liquor, urea etc. one or more, be preferably ammoniacal liquor, the concentration of ammoniacal liquor can be any feasible ratio.The temperature that filtration temperature after aging is preferably in below polyethylene glycol freezing point is filtered, and the polyethylene glycol adding is retained in filter cake, to increase adhesive property, greasy property and the plasticity of material, makes it easier moulding, extrudes.

In the inventive method, step (3) organic carboxyl acid can be one or more in carboxylic acid (citric acid, tartaric acid), amino acid (nitrilotriacetic acid, ethylenediamine tetra-acetic acid), optimization citric acid.In every 100 milliliters of maceration extracts, contain MoO ₃17 ~ 33g, containing CoO3 ~ 7g.

The present invention is containing also adding as required the polyalcohol that one or more contain two or more hydroxyls in the maceration extract of Co, Mo, and such as one or more in sweet mellow wine, ethylene glycol, glycerine, the mol ratio of polyalcohol and Co is 0.1 ~ 0.5.

In a step in step (1) or a few step, add required catalyst promoter and/or add component.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 clay, amorphous aluminum silicide, titanium oxide, zirconia, molecular sieve etc.Add the method for auxiliary agent and interpolation component to adopt this area conventional method.Above-mentioned auxiliary agent and/or the weight content of interpolation component in catalyst are, below 50%, to be preferably below 40%.In a step in step (1) or a few step, preferably add auxiliary agent P and/or Si, make in Hydrobon catalyst, P is with P ₂o ₅the weight content of meter is that 0.1% ~ 8.0%, Si is with SiO ₂the weight content of meter is 0.7% ~ 8.0%.

The preparation method of Hydrobon catalyst of the present invention, step (2) can adopt conventional forming method, such as extrinsion pressing etc.In forming process, can add appropriate shaping assistant, such as adhesive, extrusion aid etc.Described washing can adopt water purification washing and/or ethanolic solution washing, and wash temperature is generally 50 ℃ ~ 70 ℃, preferably can make most of polyethylene glycol be dissolved in cleaning solution, also removes polyethylene glycol in washing away impurity.Described drying condition is as follows: at 50 ~ 120 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.

The preparation method of Hydrobon catalyst of the present invention, step (4) dipping used can adopt saturated infusion process.After dipping, drying condition is as follows: at 60 ~ 150 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.

In the preparation method of Hydrobon catalyst of the present invention, the consumption of each raw material is definite as required, and in W, Ni, Al, Mg composite oxides, the mol ratio of W and Ni is 0.29 ~ 2.58, is preferably 0.44 ~ 1.84, Al ₂o ₃account for W, Ni, Al, Mg composite oxides weight is 2.0% ~ 60.0%, is preferably 20.0% ~ 60.0%, MgO and accounts for 0.7% ~ 8.0% of W, Ni, Al, Mg composite oxides weight, is preferably 1.0% ~ 7.0%; In gained catalyst, the mol ratio of Mo and Co is 0.26 ~ 6.51, and the mol ratio that is preferably 0.83 ~ 4.69, W and Mo is 0.45 ~ 4.97, is preferably 0.7 ~ 3.1.

The character of Hydrobon catalyst of the present invention is as follows: pore volume is 0.15 ~ 0.65 ml/g, and specific area is 130 ~ 380m ²/ g.

In bulk phase catalyst, the fit system of active metal is very large to the performance impact of catalyst.The inventive method is by first adopting coprecipitation to prepare W, Ni, Al, Mg composite oxides precursor, then catalyst intermediate is made in moulding, then utilize specific dipping method supported active metal Co and Mo, be conducive to like this form the active phase of W-Ni and the active phase of Co-Mo.Adopt coprecipitation to prepare W, Ni, Al, in Mg composite oxides precursor process, add large molecule polyethylene glycol, make W, Ni, Al, agglomeration at the beginning of Mg composite oxides precursor particle forms is controlled, formation has more granule, more tuftlet group, more seamed edges position, the more W of high surface area, Ni composite oxides, in addition the hydrophily of polyethylene glycol also can impel the hydroxide colloid in plastic process to adsorb more water or hydroxyl, make it to form in drying and roasting process afterwards anion and the cation vacancy of porous or unsaturated (CUB), improve suction dehydrogenation capacity and the speed of catalyst, introduce auxiliary agent Mg simultaneously, be conducive to and Ni, W metal synergy forms the higher compound of hydrogen storage capability, further improve suction dehydrogenation capacity and the speed of catalyst, improve the Hydrogenation of catalyst.Preparation is containing organic acid Co, Mo ammoniacal liquor maceration extract, wherein maceration extract is not only stable, and active metal wherein and organic acid form chelate, being conducive to Co, Mo better coordinates and weakens the interaction between active metal Co, Mo and catalyst intermediate, more be dispersed in catalyst intermediate, promote the formation of the active phase of Co-Mo, especially form more, the active phase of II type Co-Mo that granularity is less, that activity is higher, improved the hydrogenolysis performance of catalyst.The matched well of the active phase of prepared catalyst W-Ni and the active phase of Co-Mo, make Hydrogenation and the hydrogenolysis performance of catalyst reach cooperation well, and catalyst has more granule, more seamed edges position, more high surface area and porous, increase substantially the combination property of catalyst.

The specific embodiment

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

(1) prepare W, Ni, Al, Mg composite oxides precursor by coprecipitation

according to catalytic component content proportioning, preparation contains W, Ni, Al, the salting liquid of Mg, can be nickelous sulfate containing nickel salt, nickel nitrate, nickel chloride, basic nickel carbonate, one or more in nickel oxalate etc., tungsten salt can be ammonium metatungstate, one or more in sodium tungstate etc., can be aluminium chloride containing aluminium salt, aluminum nitrate, one or more in aluminum sulfate etc., can be magnesium chloride containing magnesium salts, one or more in the solubility magnesium salts such as magnesium nitrate, auxiliary agent Si, P, Ti, B, Zr etc. can need to introduce by proportioning according to catalyst in mixed liquor, preferably Si and/or P, silicon source can be waterglass, one or more in Ludox etc., phosphorus source can be phosphoric acid, phosphorous acid, ammonium phosphate, ammonium hydrogen phosphate, one or more in ammonium dihydrogen phosphate (ADP) etc.

In retort, add appropriate water purification, add appropriate large molecule polyethylene glycol to be under agitation heated to plastic temperature, molecular weight polyethylene glycol is 200 ~ 10000, is preferably 1000 ~ 10000.

By adding in retort and carry out plastic containing salting liquid and alkaline precipitating agent the stream of W, Ni, Al, Mg, then aging, cooling, filter, dry, obtain W, Ni composite oxides precursor.Wherein, plastic temperature is 30 ~ 80 ℃, and controlling the pH of slurries in retort is 8.0 ~ 10.5, preferably 8.0 ~ 9.5, and the reaction time is controlled at 0.5 ~ 2.0h; Alkaline precipitating agent can be inorganic or organic alkaline water soluble compound, as NaOH, sodium carbonate, sodium acid carbonate, ammoniacal liquor, urea etc., is preferably ammoniacal liquor, and the concentration of ammoniacal liquor can be any feasible ratio.Wherein slurries aging after, be cooled to temperature below large molecule polyethylene glycol freezing point and filter, the cooling any mode that can make the cooling of plastic slurries that adopts.

(2) preparation of catalyst intermediate

Add shaping assistant to carry out moulding W, Ni composite oxides precursor, washing, be dried and roasting, obtain catalyst intermediate, wherein washing is that the ethanolic solution of formation wet bar 3wt% ~ 5wt% is embathed, the temperature of embathing will make the large molecule polyethylene glycol adding be dissolved in cleaning solution, to remove polyethylene glycol and impurity.Wherein drying condition is that roasting condition is at 450 ~ 600 ℃ of roasting 3 ~ 6h at 50 ~ 120 ℃ of dry 2 ~ 8h.The shape of catalyst can be made sheet, spherical, cylindrical bars and irregular bar (as clover, bunge bedstraw herb), preferably cylindrical bars and irregular bar as required.

(3) preparation is containing the maceration extract of Co, Mo

Before maceration extract preparation, will first measure the catalyst intermediate water absorption rate of (2) preparing, the concentration of maceration extract and consumption will be determined according to the water absorption rate of catalyst composition requirement and catalyst intermediate.

Take a certain amount of organic carboxyl acid, also can add polyalcohol, water dissolves, and adds He Mu source, a certain amount of cobalt source and ammoniacal liquor.In maceration extract, the concentration of ammonia is 10wt% ~ 25wt%.Wherein every 100 milliliters contain MoO ₃17 ~ 33g, containing CoO3 ~ 7g, the mol ratio of organic carboxyl acid and Co is 0.5 ~ 1.2, the mol ratio of polyalcohol and Co is 0.1 ~ 0.5.The cobalt source providing in maceration extract is selected from one or more in basic cobaltous carbonate, cobalt carbonate, cobalt nitrate etc., and the molybdenum source providing is selected from one or more in ammonium molybdate, molybdic acid, molybdenum oxide etc.

(4) preparation of Hydrobon catalyst

The catalyst intermediate that the maceration extract impregnation steps (2) obtaining by step (3) obtains, drying and roasting, obtain Hydrobon catalyst; Wherein dipping adopts saturated infusion process.Drying condition is as follows: at 60 ~ 150 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.　

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

Embodiment 1

in a container A, add 500ml water purification, by 47g ammonium metatungstate, 34g nickel chloride, 9.5g magnesium chloride, 2.5g ammonium dihydrogen phosphate (ADP), add wherein and stir.

In a container B, add 300ml water purification, 47g aluminium chloride is added to wherein stirring and dissolving.

In a container C, compound concentration is with SiO ₂rare water glass solution 100ml of (weight) meter 2.2wt%.

After during liquor alumini chloridi in container B is added to container A under stirring, the rarer water glass solution in container C is splashed in container A under stirring, overall solution volume is adjusted to 1000ml with water purification, obtain containing metal W, Ni and Al ₂o ₃, MgO, P ₂o ₅, SiO ₂the salting liquid of precursor.

in retort, add 500ml water purification, the polyethylene glycol that 2g molecular weight is 6000 stirs and is warming up to 50 ℃.

by the ammonia spirit of the salting liquid preparing above and 15wt% and flow plastic, controlling plastic temperature is 50 ℃, slurries pH is 8.2 ± 0.2, in 1h, complete plastic, then by aging slurries 3 hours, aging end is filtered after slurries are cooled to room temperature, the filter cake obtaining is dry under 70 ℃ of conditions in baking oven, through rolling extruded moulding, by Φ 2.0 clover orifice plate extrusions, moulding bar is in the water-bath of 60 ℃ of left and right, embathe with the ethanolic solution of 4wt%, wet bar is dried 8 hours under 110 ℃ of conditions in baking oven, then obtain containing active metal W at 500 ℃ of calcination activation 3h, the catalyst precarsor bar of Ni.

By 24g citric acid, 19g basic cobaltous carbonate and 78g ammonium molybdate, be mixed with the maceration extract that 300ml ammonia concn is 18wt%, airtight preservation is stand-by.

Get containing the catalyst precarsor bar of W, Ni and be placed in converter, spray with the maceration extract 75ml preparing above, after having sprayed, material is taken out in baking oven under 110 ℃ of conditions dry 8 hours, in high temperature furnace, calcination activation 3 hours under 500 ℃ of conditions, obtains catalyst A of the present invention.

Embodiment 2

the whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process, adds 2g molecular weight and be 4000 polyethylene glycol in retort water purification, salting liquid preparation, add ammonium metatungstate 40g, nickel chloride 28g, aluminium chloride 85g, magnesium chloride 7.3g, do not add ammonium dihydrogen phosphate (ADP) and rare water glass solution, maceration extract preparation adds basic cobaltous carbonate 19g, ammonium molybdate 77g, citric acid 22g, obtains catalyst B of the present invention.

Embodiment 3

The whole preparation process of catalyst is with embodiment 1, and wherein in retort water purification, to add 1g molecular weight be 6000 polyethylene glycol to catalyst precarsor bar preparation process, salting liquid preparation, add ammonium metatungstate 36g, nickel chloride 26g, aluminium chloride 97g, magnesium chloride 7.3g, ammonium dihydrogen phosphate (ADP) 2.5g, does not add rare water glass solution, and maceration extract preparation adds basic cobaltous carbonate 19g, ammonium molybdate 77g, sweet mellow wine 15 g, citric acid 22g, obtains catalyst C of the present invention.

Embodiment 4

The whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process, in retort water purification, adds 3g molecular weight and be 6000 polyethylene glycol, and salting liquid preparation adds ammonium metatungstate 32g, nickel chloride 23g, aluminium chloride 105g, magnesium chloride 7.2g, containing SiO ₂rare water glass solution 100ml of (weight) 2.2%, does not add ammonium dihydrogen phosphate (ADP).Maceration extract preparation adds basic cobaltous carbonate 19g, ammonium molybdate 75g, and citric acid 24g, obtains catalyst D of the present invention.

Embodiment 5

The whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process, in retort water purification, adds 2g molecular weight and be 6000 polyethylene glycol, and salting liquid preparation adds ammonium metatungstate 41g, nickel chloride 25g, aluminium chloride 76g, magnesium chloride 8.5g, add ammonium dihydrogen phosphate (ADP) 2.5g, containing SiO ₂rare water glass solution 100ml of (weight) 2.2%.Maceration extract preparation adds basic cobaltous carbonate 22g, ammonium molybdate 76g, and citric acid amount 26, obtains catalyst E of the present invention.

Embodiment 6

The whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process, in retort water purification, adds 2g molecular weight and be 6000 polyethylene glycol, and salting liquid preparation adds ammonium metatungstate 46g, nickel chloride 27g, aluminium chloride 64g, magnesium chloride 7.3g, add ammonium dihydrogen phosphate (ADP) 2.5g, containing SiO ₂rare water glass solution 100ml of (weight) 2.2%.Maceration extract preparation adds basic cobaltous carbonate 25g, ammonium molybdate 77g, and citric acid 30g, obtains catalyst F of the present invention.

Comparative example 1

In a container A, add 500ml water purification, 34g nickel chloride, 2.5g ammonium dihydrogen phosphate (ADP) stirring and dissolving, then add 46g ammonium metatungstate stirring and dissolving, under agitation splash into containing SiO ₂rare water glass solution 32ml of (weight) 7%, is mixed with acid working solution 1.

In a container B, add 300ml water purification, then add aluminium chloride 72g stirring and dissolving to be mixed with acid working solution 2.

In a plastic cans, add 200ml water purification, temperature rises to 50 ℃, in the situation that stirring, solution 2 and 18wt% ammoniacal liquor stream is added to plastic in retort, and plastic temperature 50 C completes plastic in 0.5h, and plastic slurry pH is controlled at 9.0 ± 0.2.Then solution 1 is added in plastic cans, then add 18% ammoniacal liquor, regulate slurry pH value 8.5, after cemented into bundles aging 1 hour, then filter, filter cake joins the container for stirring that 600ml water purification is housed, then filters after adding the making beating evenly of 16.5g molybdenum oxide, filter cake is dried 5 hours at 80 ℃, then extruded moulding, with water purification washing 3 times, wet bar is dried 5 hours at 120 ℃, 500 ℃ of calcination activations 4 hours, make catalyst G.

The character of catalyst of the present invention and comparative example catalyst is as table 1.

Table 1 the present invention and comparative example catalyst property

Catalyst numbering	A	B	C	D	E	F	G
								Catalyst composition	?	?	?	?	?	?	?
WO 3,wt%	38.3	31.8	29.0	25.2	33.0	37.0	36.9
								MoO 3,wt%	15.4	15.0	15.0	14.9	15.0	15.0	15.1
NiO,wt%	18.6	15.3	14.0	12.1	13.7	14.1	18.1
								CoO,wt%	3.1	3.0	3.0	3.1	3.5	4.0	0
MgO, wt%	3.9	3.0	3.O	3.0	3.5	3.0	0
								SiO 2,wt%	2.0	0	0	2.1	2.1	2.0	2.0
P 2O 5,wt%	1.5	0	1.5	0	1.5	1.5	1.5
								Al 2O 3,wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
Catalyst property	?	?	?	?	?	?	?
								Specific area, m 2/g	232	237	231	253	256	249	185
Pore volume, mL/g	0.278	0.268	0.292	0.279	0.301	0.288	0.212
								Intensity, N/mm	22.3	22.5	21.8	23.4	22.3	23.1	18.2

Embodiment 7

Be 6.4MPa to catalyst E of the present invention, F and comparative example catalyst G in hydrogen dividing potential drop, reaction temperature is 360 ℃, and volume space velocity is 2.0h ^-1, hydrogen to oil volume ratio is under 500 conditions, on 200ml small hydrogenation device, carries out hydrodesulfurization reaction performance evaluation take Maoming mixed diesel as raw material.Feedstock oil main character is as table 2, and evaluating catalyst result is as table 3.

Table 2 feedstock oil main character

Project	Analysis result
		Density (20 ℃), g/cm 3	0.8615
Boiling range scope, ℃	178-370
		S，μg/g	12213
N，μg/g	295
		Cetane number	45.8

Table 3 catalyst hydrogenation desulfurization performance evaluation result

Catalyst	E	F	G
				Generate oil density (20 ℃), g/cm 3	0.8328	0.8322	0.8340
Boiling range scope, ℃	165-369	164-368	163-368
				S，μg/g	21	12	28
N，μg/g	1.3	1.0	2.1
				Cetane number	52.3	53.0	52.3

The data of table 3 show, catalyst of the present invention has excellent hydrodesulfurization and hydrodenitrogeneration ability, suitably reducing after tenor, still there is higher desulfurization, denitrification activity than reference agent, can realize the production object of low-sulfur, low aromatic hydrocarbons, low-density, high cetane number clean diesel.

Embodiment 8

To contain DBT, 4-MDBT, 4, the toluene solution that tri-kinds of model compound concentration of 6-DMDBT are 2wt% is raw material, is 2.0MPa at hydrogen pressure respectively, and hydrogen-oil ratio is 200:1, air speed 3h ^-1, under 320 ℃ of conditions of reaction temperature, on micro-reaction equipment, catalyst of the present invention and comparative example catalyst are carried out to hydrogenation and the evaluation of hydrogenolysis desulfurization performance.

Reaction is carried out on micro-reaction equipment, and product quantitative analysis is used in conjunction to realize by Varian3800 type capillary gas chromatograph and Finnigan SSQ710X type level Four bar mass spectrograph with evaluation.

If with r representative model compound hydrogenation and hydrogenolysis speed ratio, during take DBT as model compound r with cyclohexyl benzene in DBT product the ratio value representation with biphenyl content; During take 4-MDBT as model compound, r represents with the ratio of cyclohexyl benzene class and biphenyl class content; R 1-methyl-3-(3-methylcyclohexyl benzene while being model compound with 4,6-DMDBT) with 3, the ratio of 3-dimethyl diphenyl content represents, the results are shown in Table 4.

Table 4 the present invention and comparative example catalyst hydrogenation and hydrogenolysis represent product ratio

Catalyst numbering	E	F	G
				r(DBT )	0.28	0.29	0.98
r (4-MDBT)	1.48	1.45	2.7
				r(4,6-DMDBT)	4.60	4.62	5.0

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

DBT class sulfide is as one of main component of diesel oil hydrofining raw material, major part can reduce hydrogen consumption by a relatively large margin by the desulfurization of hydrogenolysis path implement, reduce and 4 simultaneously, the competitive Adsorption of 6-DMDBT class sulfide to hydrogenation sites, thereby be 4,6-DMDBT class sulfide provides more hydrogenation reaction activated centre, increases its conversion ratio.

The aggregation of data of table 1, table 3 and table 4 shows, the high metals content catalysts of the present invention, in the situation that suitably reducing total metal content, still has higher activity, can, in diesel oil hydrogenation ultra-deep desulfurization, not consume hydrogen excessively, reduces processing cost.

Claims (18)

1. the preparation method of a Hydrobon catalyst, comprise: (1) prepares W, Ni, Al, Mg composite oxides precursor by coprecipitation, (2) by W, Ni, Al, the moulding of Mg composite oxides precursor, washing, dry and roasting, obtains catalyst intermediate, (3) preparation is containing the maceration extract of Co, Mo, (4) catalyst intermediate that the maceration extract impregnation steps (2) obtaining by step (3) obtains, drying and roasting, obtain Hydrobon catalyst; Wherein step (1) process is as follows: the salting liquid of tungstenic, nickel, aluminium, magnesium is carried out with alkaline precipitating agent and flow plastic and react, the pH value of controlling reaction system is 8.0 ~ 10.5, then aging, filter, dry, obtain W, Ni, Al, Mg composite oxides precursor, wherein before plastic and/or in plastic process, adding molecular weight is 200 ~ 10000 polyethylene glycol, and making the weight content of polyethylene glycol in W, Ni, Al, Mg composite oxides precursor is 1% ~ 10%; Step (3) process is as follows: molybdenum source, cobalt source, organic carboxyl acid, ammonia and water are mixed with to the maceration extract containing Co, Mo, and wherein the mol ratio of organic carboxyl acid used and Co is 0.5 ~ 1.2, and in maceration extract, the concentration of ammonia is 10wt% ~ 25wt%.

2. it is characterized in that in accordance with the method for claim 1: the molecular weight of polyethylene glycol is 1000 ~ 10000.

3. according to the method described in claim 1 or 2, it is characterized in that: in W, Ni, Al, Mg composite oxides precursor, the weight content of polyethylene glycol is 1% ~ 5%.

4. the pH value that in accordance with the method for claim 1, it is characterized in that step (1) plastic reaction system is 8.0 ~ 9.5.

5. in accordance with the method for claim 1, it is characterized in that step (1) alkaline precipitating agent be in NaOH, sodium carbonate, sodium acid carbonate, ammoniacal liquor, urea one or more.

6. in accordance with the method for claim 1, it is characterized in that step (1) alkaline precipitating agent is ammoniacal liquor.

7. in accordance with the method for claim 1, it is characterized in that the temperature of the filtration temperature of step (1) after aging below polyethylene glycol freezing point filter.

8. in accordance with the method for claim 1, it is characterized in that the washing described in step (2) adopts water purification washing and/or ethanolic solution washing, wash temperature is 50 ℃ ~ 70 ℃, and polyethylene glycol is dissolved in cleaning solution.

9. in accordance with the method for claim 1, it is characterized in that containing in the maceration extract of Co, Mo in step (3), in every 100 milliliters of maceration extracts, contain MoO ₃17 ~ 33g, containing CoO 3 ~ 7g.

10. in accordance with the method for claim 1, it is characterized in that organic carboxyl acid used in step (3) is one or more in citric acid, tartaric acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid.

11. in accordance with the method for claim 1, it is characterized in that step (3) is containing adding polyalcohol in the maceration extract of Co, Mo, and polyalcohol is one or more in sweet mellow wine, ethylene glycol, glycerine, and the mol ratio of polyalcohol and Co is 0.1 ~ 0.5.

12. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (2) is as follows: at 50 ~ 120 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.

13. in accordance with the method for claim 1, it is characterized in that step (4) dipping used adopts saturated infusion process.

14. in accordance with the method for claim 1, it is characterized in that the drying condition of step (4) is as follows: at 60 ~ 150 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.

15. in accordance with the method for claim 1, it is characterized in that described W, Ni, Al, Mg composite oxides, and the mol ratio of W and Ni is 0.29 ~ 2.58, Al ₂o ₃account for W, Ni, Al, Mg composite oxides weight and be 2.0% ~ 60.0%, MgO and account for 0.7% ~ 8.0% of W, Ni, Al, Mg composite oxides weight; In gained catalyst, the mol ratio of Mo and Co is that the mol ratio of 0.26 ~ 6.51, W and Mo is 0.45 ~ 4.97.

16. in accordance with the method for claim 1, it is characterized in that described W, Ni, Al, Mg composite oxides, and the mol ratio of W and Ni is 0.44 ~ 1.84, Al ₂o ₃account for W, Ni, Al, Mg composite oxides weight and be 20.0% ~ 60.0%, MgO and account for 1.0% ~ 7.0% of W, Ni, Al, Mg composite oxides weight; In gained catalyst, the mol ratio of Mo and Co is that the mol ratio of 0.83 ~ 4.69, W and Mo is 0.7 ~ 3.1.

17. in accordance with the method for claim 1, it is characterized in that adding in step (1) required catalyst promoter and/or add component, auxiliary agent comprises one or more in P, F, Ti, Si, B, Zr, adding component is refractory porous mass and precursor thereof, as one or more in clay, amorphous aluminum silicide, titanium oxide, zirconia, molecular sieve.

18. in accordance with the method for claim 1, it is characterized in that adding auxiliary agent Si and/or P in step (1), makes in Hydrobon catalyst, and P is with P ₂o ₅the weight content of meter is that 0.1% ~ 8.0%, Si is with SiO ₂the weight content of meter is 0.7% ~ 8.0%.