CN103801317A - Hydrodesulfurization catalyst and preparation method thereof - Google Patents
Hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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- CN103801317A CN103801317A CN201210442656.XA CN201210442656A CN103801317A CN 103801317 A CN103801317 A CN 103801317A CN 201210442656 A CN201210442656 A CN 201210442656A CN 103801317 A CN103801317 A CN 103801317A
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Abstract
The invention discloses a a hydrodesulfurization catalyst and a preparation method thereof. The catalyst contains a W and Ni composite oxide and a Mo and Co composite oxide with a proper ratio. 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, forming, washing, drying and roasting to obtain a catalyst intermediate, using a Co and Mo-containing impregnation liquid for impregnation, drying and roasting to obtain the hydrodesulfurization catalyst. According to the method, 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
Technical field
The present invention relates to a kind of Hydrobon catalyst and preparation method thereof, particularly diesel oil ultra-deep hydrodesulfuration Catalysts and its preparation method.
Background technology
The heaviness of crude oil, the height that in poor quality causes crude oil sulfuration trend are in continuous 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%.
The SO that sulphur, nitrogen and aromatic hydrocarbons etc. in diesel oil give off in combustion process
x, NO
x, CH and soot etc. can cause forming acid rain, photochemical fog, carcinogenic substance etc., and environment is caused to severe contamination, and 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 more 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 straight-run 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.
CN101172261A discloses the standby W-Mo-Ni hydrogenation catalyst of a kind of body phase legal system, and this catalyst adopts the saline mixed solution of active metal Ni, W component and auxiliary agent and sodium aluminate solution co-precipitation to generate Ni
xw
yo
zcomposite 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 W-Mo-Ni series hydrocatalyst 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, increases processing cost.
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 Hydrobon catalyst and preparation method thereof.The catalyst of the method gained can be realized catalyst activity component hydrogenation and the better collaborative performance of hydrogenolysis desulfidation, exceeds consumption hydrogen, the object cutting down finished cost when reaching ultra-deep desulfurization.
Hydrobon catalyst of the present invention, contain W, Ni, Al, Mg composite oxides are that composite oxides I and Mo, Co composite oxides are composite oxides II, wherein, in composite oxides I, the mol ratio of W and Ni is 0.29 ~ 2.58, be preferably 0.44 ~ 1.84, Al in composite oxides I
2o
3content be 2.0% ~ 60.0%, the content that is preferably 15.0% ~ 60.0%, MgO is 0.7% ~ 8.0%, is preferably 1.0% ~ 7.0%; In composite oxides II, the mol ratio of Mo and Co is 0.26 ~ 6.51, is preferably 0.83 ~ 4.69; In composite oxides I, in the molal quantity of W and composite oxides II, the ratio of the molal quantity of Mo is 0.45 ~ 4.97, is preferably 0.7 ~ 3.1; Composite oxides I and composite oxides II account for 50% ~ 100% of total catalyst weight, are preferably 60% ~ 95%.
In Hydrobon catalyst of the present invention, composite oxides I introduces by coprecipitation, and composite oxides II introduces by total immersion method.
In Hydrobon catalyst of the present invention, in composite oxides I, also contain auxiliary agent P, with P
2o
5the weight content of meter in catalyst is 0.1% ~ 8.0%, is preferably 0.3% ~ 5.0%.Auxiliary agent P introduces by coprecipitation.
In Hydrobon catalyst of the present invention, in composite oxides I, also contain auxiliary agent Si, with SiO
2the weight content of meter in catalyst is 0.7 ~ 8.0%, is preferably 0.7% ~ 6.0%.Auxiliary agent Si introduces by coprecipitation.
In Hydrobon catalyst of the present invention, can also contain as required one or more in the components such as amorphous aluminum silicide, titanium oxide, Zirconium oxide, molecular sieve, the weight content of these components in catalyst is below 50%, is preferably below 40%.
The character of Hydrobon catalyst of the present invention is as follows: pore volume is 0.1 ~ 0.5 ml/g, and specific area is 110 ~ 350m
2/ g.
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, be dried and roasting, obtain catalyst intermediate, (3) preparation, containing the maceration extract of Co, Mo, wherein adds organic carboxyl acid and ammonia in maceration extract; (4) catalyst intermediate that the maceration extract impregnation steps (2) obtaining by step (3) obtains, drying and roasting, obtain Hydrobon catalyst.
The preparation method of Hydrobon catalyst of the present invention, the described coprecipitation of step (1) is prepared the process of W, Ni, Al, Mg composite oxides precursor, can adopt with the following method: by the salting liquid of tungstenic, nickel, aluminium, magnesium, forming required ratio in catalyst adds in plastic cans, carrying out plastic with alkaline precipitating agent reacts, then aging, filter, dry.Coprecipitation can adopt conventional coprecipitation method of the prior art, preferably adopts and flows coprecipitation method.The temperature of plastic reaction is 30 ~ 80 ℃, and the pH value of controlling reaction system is 8.0 ~ 10.5, preferably 8.0 ~ 9.5, and react to be controlled in 0.5 ~ 2.0h and complete.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 preparation method of Hydrobon catalyst of the present invention, adds organic carboxyl acid and ammonia containing in the maceration extract of Co, Mo in step (3), and wherein the mol ratio of organic carboxyl acid used and Co is 0.5 ~ 1.2.In maceration extract, the concentration of ammonia is 10wt% ~ 25wt%.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, be preferably P and/or Si.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.
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 generally adopts water purification washing.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 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 to make catalyst intermediate be W, Ni, Al, Mg composite oxides 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 in W, Ni, Al, Mg composite oxides precursor process and add auxiliary agent Mg, be conducive to form with Ni, W metal synergy the compound that hydrogen storage capability is higher, increase the suction dehydrogenation capacity 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 the active phase of more active higher II type Co-Mo, 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, makes the Hydrogenation of catalyst and hydrogenolysis performance reach cooperation well, is conducive to the raising of catalyst combination property.
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.
By adding in the retort that water purification is housed and carry out plastic containing salting liquid and alkaline precipitating agent the stream of W, Ni, Al, Mg, then aging, filter, dry, obtain W, Ni, Al, Mg composite oxides precursor.Wherein, plastic temperature is 30 ~ 80 ℃, and controlling the pH value of reaction system 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.
(2) preparation of catalyst intermediate
Add shaping assistant to carry out moulding W, Ni, Al, Mg composite oxides precursor, washing, be dried and roasting, obtain catalyst intermediate, wherein washing is to wash to catalyst intermediate free from admixture with water purification, 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 is 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 in every 100 milliliters of maceration extracts, contain MoO
317 ~ 33g, containing CoO3 ~ 7g, the mol ratio of organic 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 preferably 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, 32g nickel chloride, 9.8g magnesium chloride, 2.5g ammonium dihydrogen phosphate (ADP), add wherein and stir.
In a container B, add 300ml water purification, 38g 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 2.2%.
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.
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, after aging end, filter slurries, 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, after moulding, through washing, then in baking oven, under 110 ℃ of conditions, be dried 8 hours, then obtain the catalyst precarsor bar containing active metal W, Ni at 500 ℃ of calcination activation 3h.
By 23g citric acid, 18g basic cobaltous carbonate and 91g ammonium molybdate, be mixed with the maceration extract that 300ml ammonia concn is 20wt%, 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 salting liquid preparation in catalyst precarsor bar preparation process, add ammonium metatungstate 40g, nickel chloride 30g, aluminium chloride 73g, magnesium chloride 5g, do not add ammonium dihydrogen phosphate (ADP) and rare water glass solution, maceration extract preparation adds basic cobaltous carbonate 18g, ammonium molybdate 84g, citric acid 23g, obtains catalyst B of the present invention.
Embodiment 3
the whole preparation process of catalyst is with embodiment 1, and wherein salting liquid preparation in catalyst precarsor bar preparation process, adds ammonium metatungstate 37g, nickel chloride 32g, and aluminium chloride 64g, magnesium chloride 7.2g, containing SiO
2rare water glass solution 100ml of (weight) 3.0%, does not add ammonium dihydrogen phosphate (ADP), and maceration extract preparation adds basic cobaltous carbonate 20g, ammonium molybdate 86g, and sweet mellow wine 10g, citric acid 26.0g, 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, plastic temperature is 60 ℃, and salting liquid preparation adds ammonium metatungstate 42g, nickel chloride 28g, aluminium chloride 67g, magnesium chloride 6.0g, ammonium dihydrogen phosphate (ADP) 3.3g, does not add rare water glass solution, basic cobaltous carbonate 18g in maceration extract, ammonium molybdate 80g, citric acid 22g, obtains 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, plastic temperature is 60 ℃, and salting liquid preparation adds ammonium metatungstate 33g, nickel chloride 24g, and aluminium chloride 78g, magnesium chloride 7.2g, ammonium dihydrogen phosphate (ADP) 2.5g, containing SiO
2rare water glass solution 100ml of 2.0wt%.Basic cobaltous carbonate 20g in maceration extract, ammonium molybdate 107g, citric acid 26.0g, obtains 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, plastic temperature is 60 ℃, and salting liquid preparation adds ammonium metatungstate 41g, nickel chloride 21g, and aluminium chloride 75g, magnesium chloride 8.4g, adds ammonium dihydrogen phosphate (ADP) 3.3g, containing SiO
2rare water glass solution 100ml of 2.2wt%.Basic cobaltous carbonate 21g in maceration extract, ammonium molybdate 80g, citric acid 26g, obtains catalyst F of the present invention.
Comparative example 1
in a container A, add 500ml water purification, add 29g nickel chloride, 2.5g ammonium dihydrogen phosphate (ADP) stirring and dissolving, then add 41g 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 84g stirring and dissolving to be mixed with acid working solution 2.
In a plastic cans, add 200ml water purification, temperature rises to 60 ℃, in the situation that stirring, solution 2 and 18wt% ammoniacal liquor stream is added to plastic in retort, and plastic temperature 60 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 the ammoniacal liquor of 18wt%, 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 16.3g 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% | 38.9 | 33.2 | 31.0 | 35.2 | 26.5 | 33.1 | 33.0 |
| MoO 3，wt% | 18.3 | 17.0 | 17.3 | 16.1 | 21.6 | 16.0 | 16.1 |
| NiO，wt% | 18.2 | 17.1 | 18.3 | 16.0 | 13.5 | 12.0 | 16.1 |
| CoO，wt% | 3.1 | 3.1 | 3.5 | 3.0 | 3.5 | 4.0 | 0 |
| MgO， wt% | 4.1 | 2.1 | 3.0 | 2.5 | 3.0 | 3.5 | 0 |
| SiO 2，wt% | 2.0 | 0 | 3.0 | 0 | 1.9 | 2.0 | 2.0 |
| P 2O 5，wt% | 1.5 | 0 | 0 | 2.0 | 1.5 | 1.5 | 1.5 |
| Al 2O 3，wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Catalyst property | ? | ? | ? | ? | ? | ? | ? |
| Specific area, m 2/g | 153 | 175 | 182 | 193 | 202 | 208 | 198 |
| Pore volume, mL/g | 0.210 | 0.198 | 0.203 | 0.242 | 0.248 | 0.240 | 0.235 |
| Intensity, N/mm | 19.3 | 16.8 | 19.0 | 18.0 | 17.9 | 18.3 | 15.6 |
the data of table 1 show, catalyst of the present invention has high total metal content, active metal ratio can be in a big way modulation, there is larger pore volume and specific area.
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, under the condition that hydrogen to oil volume ratio is 500, on 200ml small hydrogenation device, carry 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 | 0.8620 |
| Boiling range scope, ℃ | 178-371 |
| S，μg/g | 12197 |
| N，μg/g | 290 |
| Cetane number | 46.2 |
Table 3 catalyst hydrogenation desulfurization performance evaluation result
| Catalyst | E | F | G |
| Generate oil density (20 ℃), g/cm 3 | 0.8337 | 0.8333 | 0.8335 |
| Boiling range scope, ℃ | 165-367 | 166-369 | 163-368 |
| S，μg/g | 26 | 27 | 32 |
| N，μg/g | 1.5 | 1.5 | 2.5 |
| Cetane number | 52.5 | 52.3 | 52.0 |
the data of table 3 show, catalyst of the present invention has excellent hydrodesulfurization and hydrodenitrogeneration ability, 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 to oil volume 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.
The representative hydrogenation of table 4 the present invention and comparative example catalyst and hydroformylation product solution ratio
| Catalyst numbering | E | F | G |
| r(DBT ) | 0.31 | 0.30 | 0.96 |
| r (4-MDBT) | 1.58 | 1.55 | 2.6 |
| r(4,6-DMDBT) | 4.79 | 4.81 | 5.11 |
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 3 and table 4 shows, catalyst of the present invention can be in realizing diesel oil ultra-deep hydrodesulfuration reduction hydrogen consumption by a relatively large margin, reduce processing cost.
Claims (23)
1. a Hydrobon catalyst, contains W, Ni, Al, Mg composite oxides are that composite oxides I and Mo, Co composite oxides are composite oxides II, and wherein, in composite oxides I, the mol ratio of W and Ni is 0.29 ~ 2.58, Al
2o
3content be 2.0% ~ 60.0%, MgO content is 0.7% ~ 8.0%; In composite oxides II, the mol ratio of Mo and Co is 0.26 ~ 6.51; In composite oxides I, in the molal quantity of W and composite oxides II, the ratio of the molal quantity of Mo is 0.45 ~ 4.97; Composite oxides I and composite oxides II account for 50% ~ 100% of total catalyst weight.
2. according to catalyst claimed in claim 1, it is characterized in that, in described composite oxides I, the mol ratio of W and Ni is 0.44 ~ 1.84, Al
2o
3content be 15.0% ~ 60.0%, MgO content is 1.0% ~ 7.0%.
3. according to catalyst claimed in claim 1, it is characterized in that, in described composite oxides II, the mol ratio of Mo and Co is 0.83 ~ 4.69.
4. according to the catalyst described in claim 1,2 or 3, in the molal quantity that it is characterized in that W in composite oxides I and composite oxides 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 account for 60% ~ 95% of total catalyst weight.
6. according to catalyst claimed in claim 1, it is characterized in that in described catalyst, W, Ni, Al, Mg composite oxides are introduced by coprecipitation, and Mo, Co composite oxides are introduced by total immersion method.
7. according to catalyst claimed in claim 1, it is characterized in that containing auxiliary agent P in described composite oxides I, with P
2o
5the weight content of meter in catalyst is 0.1% ~ 8.0%.
8. according to the catalyst described in claim 1 or 7, it is characterized in that containing auxiliary agent Si in described composite oxides I, with SiO
2the weight content of meter in catalyst is 0. 7% ~ 8.0%.
9. according to catalyst claimed in claim 1, it is characterized in that containing one or more in amorphous aluminum silicide, titanium oxide, Zirconium oxide, molecular sieve in described catalyst, the weight content in catalyst is below 50%.
10. according to catalyst claimed in claim 1, it is characterized in that the character of described Hydrobon catalyst is as follows: pore volume is 0.1 ~ 0.5 ml/g, specific area is 110 ~ 350m
2/ g.
The preparation method of catalyst described in 11. claims 1, 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, be dried and roasting, obtain catalyst intermediate, (3) preparation, containing the maceration extract of Co, Mo, wherein adds organic carboxyl acid and ammonia in maceration extract; (4) catalyst intermediate that the maceration extract impregnation steps (2) obtaining by step (3) obtains, drying and roasting, obtain Hydrobon catalyst.
12. in accordance with the method for claim 11, it is characterized in that: step (1) process is as follows: the salting liquid of tungstenic, nickel, aluminium, magnesium and alkaline precipitating agent are carried out to plastic and react, and then aging, filter, dry.
13. in accordance with the method for claim 12, it is characterized in that: step (1) adopts and flows coprecipitation method, and the temperature of plastic reaction is 30 ~ 80 ℃, and the pH value of controlling reaction system is 8.0 ~ 10.5, and reaction is controlled at 0.5 ~ 2.0h.
14. in accordance with the method for claim 12, it is characterized in that: described alkaline precipitating agent be in NaOH, sodium carbonate, sodium acid carbonate, ammoniacal liquor, urea one or more.
15. in accordance with the method for claim 12, it is characterized in that: described alkaline precipitating agent is ammoniacal liquor.
16. in accordance with the method for claim 11, it is characterized in that: in step (3), add organic carboxyl acid and ammonia containing in the maceration extract of Co, Mo, 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%.
17. in accordance with the method for claim 11, it is characterized in that: in step (3), containing in the maceration extract of Co, Mo, contain MoO in every 100 milliliters of maceration extracts
317 ~ 33g, containing CoO 3 ~ 7g.
18. in accordance with the method for claim 16, it is characterized in that: organic carboxyl acid is one or more in citric acid, tartaric acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid.
19. according to the method described in claim 11 or 16, it is characterized in that: add polyalcohol containing in the maceration extract of Co, Mo, 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.
20. according to the method described in claim 11 or 15, it is characterized in that: in the step in step (1) or a few step, add 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 of clay, amorphous aluminum silicide, titanium oxide, zirconia, molecular sieve.
21. in accordance with the method for claim 11, it is characterized in that: the drying condition described in step (2) is as follows: at 50 ~ 120 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.
22. in accordance with the method for claim 11, it is characterized in that: step (4) dipping used adopts saturated infusion process.
23. in accordance with the method for claim 11, 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109894118A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of nickel-base hydrogenation catalyst and its application |
| CN110813333A (en) * | 2018-08-14 | 2020-02-21 | 南京大学 | Preparation method of fuel oil hydrofining catalyst |
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| CN1120972A (en) * | 1994-10-19 | 1996-04-24 | 中国石油化工总公司 | Hydrodesulfurizing catalyst |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
| CN101172261A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1120972A (en) * | 1994-10-19 | 1996-04-24 | 中国石油化工总公司 | Hydrodesulfurizing catalyst |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
| CN101172261A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109894118A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of nickel-base hydrogenation catalyst and its application |
| CN109894118B (en) * | 2017-12-07 | 2021-09-28 | 中国科学院大连化学物理研究所 | Nickel-based hydrogenation catalyst and application thereof |
| CN110813333A (en) * | 2018-08-14 | 2020-02-21 | 南京大学 | Preparation method of fuel oil hydrofining catalyst |
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