CN103801344A - Preparation method of hydrogenation catalyst composition - Google Patents
Preparation method of hydrogenation catalyst composition Download PDFInfo
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- CN103801344A CN103801344A CN201210442652.1A CN201210442652A CN103801344A CN 103801344 A CN103801344 A CN 103801344A CN 201210442652 A CN201210442652 A CN 201210442652A CN 103801344 A CN103801344 A CN 103801344A
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Abstract
The invention discloses a preparation method of a hydrogenation catalyst composition. The preparation method is as follows: using a coprecipitation method for preparation of a W and Ni composite oxide precursor, adding high molecular polyethylene glycol before coprecipitation and /or in the precipitation process, then beating and mixing with MoO3, filtering, forming, washing, drying and roasting to obtain the hydrogenation catalyst composition. According to the method, at the beginning of the formation of a particulate matter, the aggregation growth of the W and Ni composite oxide precursor can be controlled, a catalyst precursor with smaller particle and larger superficial area can be obtained, the catalyst hydrogenation performance can be improved, the catalyst strength is increased, abrasion is reduced, and the catalyst use performance is improved.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenating catalyst composition, particularly the preparation method of diesel oil ultra-deep hydrodesulfuration carbon monoxide-olefin polymeric.
Background technology
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 the high sulfuration trend of crude oil that the heaviness of crude oil, in poor quality cause is in further expansion, 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 finds that the sulfur content in diesel oil takes off to 50 μ g/g or 10 μ g/g and when following, and substituting group still exists at the dibenzothiophenes class sulfide of 4 or 4,6.4-MDBT and 4, the contiguous substd of S atom of 6-DMDBT, S atom is connected to absorption at the end of catalyst surface and have obstruction, cause its reactivity low, desulfurization major part is by the absorption that lies low of aromatic ring, and realize in hydrogenation path, and especially 4, the hydrodesulfurization reaction of 6-DMDBT, more than 80% by hydrogenation path implement.
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.
CN1289828A discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof, and take silicon-containing alumina as carrier, P is auxiliary agent, and W-Mo-Ni is active component, by segmentation total immersion technology supported active metal.Infusion process active metal load capacity is limited, cannot obtain higher total metal content, the catalyst of higher Hydrogenation.Though introduce the surface nature of auxiliary agent P energy modulation carrier simultaneously in dipping process, 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.
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.But in the coprecipitation process of this catalyst at the beginning of activity forms mutually, particle size is not 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 and has also had the metal that is wrapped in bulky grain of part and can not play one's part to the full, become invalid component, reduce the utilization rate of metal.Simultaneously because tenor is high, the bad adhesion of material, can affect outward appearance, the intensity etc. of extrudate, increases the abrasion in catalyst use procedure.The bulk phase catalyst of high tenor, in extrusion process, needs larger power consumption in addition, very large to mechanical wearing and tearing.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of hydrogenating catalyst composition.The method makes under the homodisperse prerequisite of active metal, has more granule, tuftlet group more, and larger surface area is provided, and more seamed edge position, makes reactant have more sufficient chemisorbed and transform place, improves by a relatively large margin the Hydrogenation of catalyst.
The preparation method of hydrogenating catalyst composition of the present invention, comprising: (1) prepares W, Ni composite oxides precursor by coprecipitation, and (2) are by W, Ni composite oxides precursor and MoO
3making beating mixes, filters, moulding, and washing, dry and roasting, obtains carbon monoxide-olefin polymeric of the present invention; Wherein, before step (1) co-precipitation and/or in precipitation process, adding molecular weight is that 200 ~ 10000(is preferably 1000 ~ 10000) polyethylene glycol, make to contain polyethylene glycol 1% ~ 10% in W, Ni composite oxides precursor, be preferably 1% ~ 5%.
In the preparation method of hydrogenating catalyst composition of the present invention, the described coprecipitation of step (1) is prepared the process of W, Ni composite oxides precursor, can adopt with the following method: the salting liquid of tungstenic, nickel is carried out with alkaline precipitating agent and flow plastic and react, the pH of reaction system is 7.0 ~ 9.5, preferably 7.3 ~ 9.0, then aging, filter, dry, obtain W, Ni composite oxides precursor.The temperature of plastic reaction is 30 ~ 80 ℃, and reaction is controlled in 0.5 ~ 2.0h and completes.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 being cooled to after slurries are aging below large molecule polyethylene glycol freezing point is filtered, and the large molecule polyethylene glycol adding is retained in filter cake, and to increase the adhesive property of material, greasy property and plasticity, make it easier moulding, extrude.
In a step in step (1) or a few step, add required catalyst promoter and/or add component.Auxiliary agent generally comprises one or more in P, F, Ti, Si, B, Zr, Mg etc., is preferably P and/or Si.Add component and be generally refractory porous mass and precursor thereof, as one or more in aluminium oxide, 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.Described auxiliary agent and/or the weight content of interpolation component in catalyst are, below 60%, to be preferably below 50%.In a step in step (1) or a few step, preferably add auxiliary agent P and/or Si, make in hydrogenating catalyst composition, 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 hydrogenating catalyst composition of the present invention, step (2) making beating can adopt conventional methods of beating, W, Ni composite oxides precursor and solid molybdenum trioxide (MoO that plastic is obtained
3) pull an oar together 0.5 ~ 1.0 hour, it is uniformly dispersed after filter.Moulding 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 drying condition is as follows: at 60 ~ 150 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.Described washing can adopt water purification and/or ethanolic solution to wash, and wash temperature is generally 50 ℃ ~ 70 ℃, is dissolved in cleaning solution so that polyethylene glycol is as much as possible, removes polyethylene glycol in removing impurity.
in the preparation method of hydrogenating catalyst composition of the present invention, the consumption of each raw material is determined as required, in W, Ni composite oxides, the mol ratio of W and Ni is 0.2 ~ 3.0, is preferably 0.3 ~ 1.3, in gained catalyst, the mol ratio of W and Mo is 0.4 ~ 2.8, is preferably 0.6 ~ 2.5.
The character of hydrogenating catalyst composition 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 the inventive method, first adopt coprecipitation to prepare W, Ni composite oxides precursor, then with MoO
3making beating, filter, the W containing high total metal content is made in moulding, Mo, Ni hydrogenating catalyst composition, wherein at W, before Ni composite oxides precursor plastic or in plastic process, add large molecule polyethylene glycol, make W, agglomeration at the beginning of Ni composite oxides precursor particle forms is controlled, formation has more granule, more tuftlet group, more seamed edges position, the more catalyst precarsor of high surface area, 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, can improve the Hydrogenation of catalyst.The characteristics such as the viscosity of large molecule polyethylene glycol, plasticity, lubricity, also can improve adhesive property, plasticity and the greasy property of high metalliferous material, high metalliferous material is more easily extruded, alleviate power consumption and mechanical wear in its extrusion process, make article shaped smooth surface, adhesion, increase catalyst strength, reduce attrition of catalyst, promote the serviceability of catalyst.
The specific embodiment
the invention provides the preparation method of carbon monoxide-olefin polymeric, a kind of concrete preparation process is as follows:
(1) prepare W, Ni composite oxides precursor by coprecipitation
salting liquid according to the preparation of catalytic component content proportioning containing W, Ni, can be one or more in nickelous sulfate, nickel nitrate, nickel chloride, basic nickel carbonate, nickel oxalate etc. containing nickel salt, tungsten salt can be one or more in ammonium metatungstate, sodium tungstate etc., auxiliary agent Si, P, Ti, B, Zr, Mg etc. can need to introduce by proportioning according to catalyst in mixed liquor, preferably Si and/or P, silicon can be one or more in waterglass, Ludox etc., and phosphorus can be one or more in phosphoric acid, phosphorous acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) etc.
In retort, add appropriate water purification, add large molecule polyethylene glycol to be under agitation heated to plastic temperature, the molecular weight of polyethylene glycol is 200 ~ 10000, preferably 1000-10000.Polyethylene glycol consumption is 1% ~ 10% of W, Ni composite oxides weight, is preferably 1% ~ 5%.
Salting liquid containing W, Ni is added in retort and carries out plastic with alkaline precipitating agent stream, then aging, cooling, filter, obtain W, Ni composite oxides precursor.Wherein, plastic temperature is 30 ~ 80 ℃, and the pH that controls slurries in retort is 7.0-9.5, preferably 7.3-9.0, 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.The temperature that wherein slurries are cooled to after aging below large molecule polyethylene glycol freezing point is filtered, the cooling any mode that can make the cooling of plastic slurries that adopts.
(2) preparation of hydrogenating catalyst composition
W, Ni composite oxides precursor filter cake and solid molybdenum trioxide (MoO that filtration obtains
3) making beating, filter, moulding, washing, dry, roasting obtain carbon monoxide-olefin polymeric of the present invention.Wherein washing is that the ethanolic solution of formation wet bar 3wt% ~ 5wt% is embathed, and the temperature of embathing is 50 ℃ ~ 70 ℃.Drying condition is that roasting condition is at 450 ~ 600 ℃ of roasting 3 ~ 6h at 60 ~ 150 ℃ 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.
Further illustrate the solution of the present invention and effect below by specific embodiment, the percentage composition relating to is weight percentage.Wt% is mass fraction.
Embodiment 1
In a container A, add 500ml water purification, by 48g ammonium metatungstate, 32g nickel chloride, ammonium dihydrogen phosphate (ADP) 3.5g, adds wherein stirring and dissolving;
In a container B, add 300ml water purification, 57g 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%;
In retort, add 500ml water purification, adding 2g molecular weight is 6000 polyethylene glycol, stirs and is warming up to 50 ℃;
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, P
2o
5, SiO
2the salting liquid of precursor;
The ammonia spirit of the salting liquid preparing above and 15wt% stream are added to plastic in retort, and controlling plastic temperature is 50 ℃, and slurries pH is 8.2 ± 0.2, in 1h, complete plastic, then by aging slurries 3 hours, after aging end, slurries were cooled to room temperature filtration and obtain filter cake;
Together with filter cake obtained above is added to 500ml water purification with 18.5g molybdenum trioxide, pull an oar and extremely evenly refilter about 0.5 hour, the filter cake obtaining is dry under 70 ℃ of conditions in baking oven, rolls evenly, with the clover orifice plate extruded moulding of Φ 2.0;
Moulding bar, in the water-bath of 60 ℃ of left and right, embathes with the ethanolic solution of 4wt%;
The wet bar of catalyst is dried 8 hours under 110 ℃ of conditions in baking oven, then obtains the carbon monoxide-olefin polymeric containing active metal W-Mo-Ni at 500 ℃ of calcination activation 3h.
Embodiment 2
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst preparation process, in retort water purification, adds 2g molecular weight and be 6000 polyethylene glycol, and plastic temperature is 50 ℃.Salting liquid preparation, adds ammonium metatungstate 47g, nickel chloride 29g, and aluminium chloride 80g, does not add ammonium dihydrogen phosphate (ADP) and rare water glass solution, and making beating adds molybdenum trioxide 16.2g, obtains carbon monoxide-olefin polymeric B of the present invention.
Embodiment 3
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst preparation process, in retort water purification, add 3g molecular weight and be 4000 polyethylene glycol, plastic temperature is 50 ℃, salting liquid preparation adds ammonium metatungstate 47g, ammonium dihydrogen phosphate (ADP) 3.5g, aluminium chloride 89g, does not add rare water glass solution, making beating adds molybdenum trioxide 14.5g, obtains carbon monoxide-olefin polymeric C of the present invention.
Embodiment 4
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst preparation process, in retort water purification, adds 3g molecular weight and be 6000 polyethylene glycol, and plastic temperature is 50 ℃, and salting liquid preparation adds ammonium metatungstate 44g, nickel chloride 26g, and aluminium chloride 88g, containing SiO
2rare water glass solution 100ml of (weight) 2.2%, does not add ammonium dihydrogen phosphate (ADP), and the filtration cakes torrefaction obtaining after cemented into bundles, to moisture 50%, adds 1gPEG6000 to roll and mix rear extrusion together with 14.5g molybdenum trioxide, 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 plastic temperature is 50 ℃, salting liquid preparation adds ammonium metatungstate 42g, nickel chloride 24g, adds ammonium dihydrogen phosphate (ADP) 3.4g, containing SiO
2rare water glass solution 100ml of (weight) 2.2%, aluminium chloride 98g, making beating adds molybdenum trioxide 13.4g.Obtain catalyst E of the present invention.
Embodiment 6
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst preparation process, in retort water purification, adds 2g molecular weight and be 6000 polyethylene glycol, and plastic temperature is 50 ℃.Salting liquid preparation, adds ammonium metatungstate 48g, nickel chloride 29g, and ammonium dihydrogen phosphate (ADP) 3.5g, containing SiO
2rare water glass solution 100ml of (weight) 2.2%, aluminium chloride 60g, making beating adds molybdenum trioxide 16.2g, obtains catalyst F of the present invention.
Comparative example 1
In a container A, add 500ml water purification, 29g nickel chloride stirring and dissolving, then add 48g 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 75g 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 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 16.5g 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 carbon monoxide-olefin polymeric 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 | 38.0 | 36.8 | 34.9 | 34.1 | 38.1 | 38.2 |
| MoO 3,wt% | 18.2 | 15.9 | 13.8 | 16.2 | 12.9 | 16.0 | 15.8 |
| NiO,wt% | 18.1 | 16.0 | 14.1 | 14.2 | 13.1 | 15.9 | 16.2 |
| SiO 2,wt% | 2.0 | 0 | 0 | 2.0 | 2.0 | 2.0 | 1.9 |
| P 2O 5,wt% | 2.1 | 0 | 2.1 | 0 | 1.9 | 2.0 | 2.0 |
| Al 2O 3,wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Catalyst property | ? | ? | ? | ? | ? | ? | ? |
| Specific area, m 2/g | 224 | 242 | 218 | 256 | 242 | 248 | 178 |
| Pore volume, mL/g | 0.288 | 0.269 | 0.303 | 0.278 | 0.304 | 0.292 | 0.208 |
| Intensity, N/mm | 25.1 | 24.2 | 23.9 | 25.9 | 24.3 | 24.6 | 18.6 |
| Abrasion | 0.8 | 0.9 | 0.8 | 0.8 | 0.9 | 0.8 | 1.4 |
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, pore volume, specific surface are larger, wear away lowly, intensity is high, has improved serviceability and the adaptability to raw materials of catalyst.
Embodiment 7
To contain the positive flow silane solution of luxuriant and rich with fragrance model compound concentration as 1% as raw material, be 3.0MPa at hydrogen pressure, hydrogen-oil ratio is 200:1, air speed 2.0h
-1, under 260 ℃, 280 ℃ conditions of reaction temperature, on micro-reaction equipment, catalyst of the present invention and comparative example catalyst are carried out to Hydrogenation evaluation.
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 quadrupole mass spectrometer.
The conversion ratio of table 2 phenanthrene on the present invention and comparative example catalyst, wt%
| Catalyst numbering | A | C | D | F | G |
| 260 ℃ of reaction temperatures | 83 | 63 | 64 | 75 | 63 |
| 280 ℃ of reaction temperatures | 97 | 74 | 74 | 88 | 72 |
The data of table 2 show, the Hydrogenation of catalyst of the present invention is better than comparative example catalyst, and catalyst D total metal content prepared by the inventive method is during compared with comparative example catalyst G low 5%, still can reach close luxuriant and rich with fragrance hydrogenation conversion with comparative example catalyst.
Embodiment 8
Be 6.4MPa to catalyst D of the present invention, F and comparative example catalyst G in hydrogen dividing potential drop, reaction temperature is 360 ℃, and volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is under 500 conditions, on 200ml small hydrogenation device, carries out hydrodesulfurization reaction performance evaluation take huge port catalytic diesel oil as raw material.Feedstock oil main character is as table 3, and evaluating catalyst result is as table 4.
Table 3 feedstock oil main character
| Project | Analysis result |
| Density (20 ℃), g/cm 3 | 0.8935 |
| S，μg/g | 1702 |
| N，μg/g | 1576 |
| Polycyclic aromatic hydrocarbon, % | 33.0 |
| Cetane number | 28 |
Table 4 catalyst hydrogenation desulfurization performance evaluation result
| Catalyst | D | F | G |
| Generate oil density (20 ℃), g/cm 3 | 0.8632 | 0.8558 | 0.8666 |
| S，μg/g | 29 | 15 | 30 |
| N，μg/g | 76 | 55 | 73 |
| Polycyclic aromatic hydrocarbon, | 9.3 | 7.2 | 9.6 |
| Cetane number | 45.8 | 46.1 | 43.7 |
The data of table 4 show, catalyst of the present invention has excellent hydrodesulfurization, denitrogenation and aromatic saturation performance, can realize the production of low-sulfur, low aromatic hydrocarbons, low-density, high cetane number clean diesel.
Claims (15)
1. a preparation method for hydrogenating catalyst composition, comprising: (1) prepares W, Ni composite oxides precursor by coprecipitation, and (2) are by W, Ni composite oxides precursor and MoO
3making beating mixes, filters, moulding, and washing, dry and roasting, obtains hydrogenating catalyst composition; Wherein, before step (1) co-precipitation and/or in precipitation process, adding molecular weight is 200 ~ 10000 polyethylene glycol, makes to contain polyethylene glycol 1% ~ 10% in W, Ni composite oxides precursor.
2. it is characterized in that in accordance with the method for claim 1: the molecular weight of described polyethylene glycol is 1000 ~ 10000.
3. in accordance with the method for claim 1, it is characterized in that: step (1) is added polyethylene glycol, makes to contain polyethylene glycol 1% ~ 5% in W, Ni composite oxides precursor.
4. in accordance with the method for claim 1, it is characterized in that: the process that the described coprecipitation of step (1) is prepared W, Ni composite oxides precursor is as follows: the salting liquid of tungstenic, nickel is carried out with alkaline precipitating agent and flow plastic and react, the pH of reaction system is 7.0 ~ 9.5, then aging, filter, dry, obtain W, Ni composite oxides precursor.
5. in accordance with the method for claim 4, it is characterized in that: the salting liquid of tungstenic, nickel carries out with alkaline precipitating agent and flows plastic and react, and the pH of reaction system is 7.3 ~ 9.0.
6. in accordance with the method for claim 4, it is characterized in that: the temperature of plastic reaction is 30 ~ 80 ℃, and reaction is controlled at 0.5 ~ 2.0h and completes.
7. it is characterized in that in accordance with the method for claim 4: described alkaline precipitating agent be in NaOH, sodium carbonate, sodium acid carbonate, ammoniacal liquor, urea one or more.
8. it is characterized in that in accordance with the method for claim 4: described alkaline precipitating agent is ammoniacal liquor.
9. it is characterized in that in accordance with the method for claim 4: the temperature being cooled to after aging below polyethylene glycol freezing point is filtered.
10. it is characterized in that in accordance with the method for claim 1: the drying condition described in step (2) is as follows: at 60 ~ 150 ℃ of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.
11. in accordance with the method for claim 1, it is characterized in that: the described washing of step (2) adopts water purification and/or ethanolic solution to wash, and wash temperature is 50 ℃ ~ 70 ℃, and polyethylene glycol is dissolved in cleaning solution.
12. in accordance with the method for claim 1, it is characterized in that: in described W, Ni composite oxides, the mol ratio of W and Ni is 0.2 ~ 3.0, and in gained catalyst, the mol ratio of W and Mo is 0.4 ~ 2.8.
13. in accordance with the method for claim 1, it is characterized in that: in described W, Ni composite oxides, the mol ratio of W and Ni is 0.3 ~ 1.3, and in gained catalyst, the mol ratio of W and Mo is 0.6 ~ 2.5.
14. according to the method described in claim 1 or 13, it is characterized in that: in step (1), add required catalyst promoter and/or add component; Auxiliary agent comprises one or more in P, F, Ti, Si, B, Zr, Mg; Adding component is refractory porous mass and precursor thereof, as one or more in aluminium oxide, clay, amorphous aluminum silicide, titanium oxide, zirconia, molecular sieve; Above-mentioned auxiliary agent and/or the weight content of interpolation component in catalyst are below 60%.
15. according to the method described in claim 1 or 4, it is characterized in that: step adds auxiliary agent P and/or Si in (1), makes in hydrogenating catalyst composition, 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%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582694A (en) * | 2016-12-10 | 2017-04-26 | 辽宁石油化工大学 | Method for preparing ternary metal non-supported nickel-based catalyst by adding auxiliaries |
| CN106669714A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst |
| CN110038581A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A method of preparing Hydrobon catalyst |
| CN110038583A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
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| CN106669714A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst |
| CN106669714B (en) * | 2015-11-11 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN106582694A (en) * | 2016-12-10 | 2017-04-26 | 辽宁石油化工大学 | Method for preparing ternary metal non-supported nickel-based catalyst by adding auxiliaries |
| CN110038581A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A method of preparing Hydrobon catalyst |
| CN110038583A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN110038583B (en) * | 2018-01-16 | 2021-11-09 | 中国石油化工股份有限公司 | Preparation method of hydrofining catalyst |
| CN110038581B (en) * | 2018-01-16 | 2022-04-08 | 中国石油化工股份有限公司 | Method for preparing hydrofining catalyst |
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