CN105727976A - Preparation method of catalyst for partial oxidation of methane to synthetic gas - Google Patents
Preparation method of catalyst for partial oxidation of methane to synthetic gas Download PDFInfo
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Abstract
The invention relates to a preparation method of a catalyst for partial oxidation of methane to synthetic gas. The catalyst comprises an active ingredient, an additive and a carrier. The preparation method is as below: treating a waste residue oil hydrogenation catalyst to prepare a catalyst precursor A; reducing the catalyst precursor A in a reducing atmosphere; adding the reduced catalyst precursor A and a polyol solution into a high pressure reactor, carrying out a hydrogenation reaction, placing a reaction effluent, filtering and dying to obtain a catalyst precursor B; and dissolving an active ingredient precursor in water to obtain a solution C, then adding the catalyst precursor B, drying and calcining to obtain the catalyst. The method of the present invention not only makes full use of waste residue oil hydrogenation catalyst, saves cost, but also promotes dispersion of more active ingredients on the surface of the carrier. The method improves the utilization of the active metal, and the conversion of methane and selectivity of products.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst for methane portion oxidation synthesis gas, especially relate to a kind of loading type nickel-based catalyst preparation method for methane portion oxidation synthesis gas.
Background technology
The 90% of gas component is above methane, by methane through synthesis gas resynthesis fuels and chemicals, is one of the effective way of gas utilization.With traditional vapour reforming ratio, methane portion oxidation synthesis gas has that required reaction vessel volume is little, reaction rate is fast, energy consumption is low and the synthesis gas that generates is suitable as the advantage such as unstripped gas of methanol and Fiscber-Tropscb synthesis.It addition, exploitation methane portion oxidation technology likely replaces highly endothermic methane steam reformation technique for producing synthesis gas, especially for remote or offshore natural gas resource utilization is significant.
The main catalyst system of methane portion oxidation synthesis gas is by active component noble metal (Pt, Pd, Rh, Ru, Ir), nickel or cobalt load on the carriers such as aluminium oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, alkali metal, alkaline-earth metal or rare-earth oxide can be adopted to be modified improving the reactivity worth of catalyst simultaneously.
It is catalyst based and preparation method thereof that CN101049566A discloses a kind of Ni for methane portion oxidation synthesis gas.The carrier of catalyst is complex carrier Mg-Al-Ce-Zr-O, and active component is NiO.This patent adopts coprecipitation method to prepare complex carrier, and prepared carrier is dipped in Ni (NO3)2In solution, on obtained catalyst, methane conversion reaches more than 84%, and CO selectivity reaches more than 99%.
CN101219393A discloses a kind of cobalt-based loaded catalyst for methane portion oxidation synthesis gas and preparation method thereof.Catalyst takes step impregnation method to prepare, and with Co for active component, with a kind of alkaline-earth metal or rare earth metal for auxiliary agent, with HZSM-5 for carrier, prepared catalyst activity is high, coking resistivity is strong, good stability.
CN101284241A discloses the Catalysts and its preparation method of a kind of methane portion oxidation synthesis gas.With transition metal Co and noble metal for active component, with a kind of element selected from alkaline-earth metal for auxiliary agent, with γ-Al2O3For carrier, employing infusion process prepares the catalyst of methane portion oxidation synthesis gas.The advantage that catalyst has high activity, excellent coking resistivity, high stability.
Although the catalyst that above-mentioned patented method prepares all obtains good methane portion oxidation synthesis gas reactivity worth, but owing to this reaction is a fast reaction (this fast reaction be typically under mass transfer limited condition carry out), namely reactant completes at the simultaneous reactions arriving catalyst external surface, thus the inner surface of catalyst is little to target response contribution, this has resulted in using rate of metal relatively low in carrier duct, also can accelerate the deep oxidation of product simultaneously.
Summary of the invention
For overcoming weak point of the prior art, the invention provides a kind of method for preparing catalyst for methane portion oxidation synthesis gas, catalyst prepared by the method has that with low cost, metal component utilization rate is high, selectivity is good, anti-carbon deposition ability is strong and the feature of good stability.
The preparation method of methane portion oxidation synthesis gas catalyst of the present invention, described catalyst includes active component, auxiliary agent and carrier, and active component is Ni；Auxiliary agent is one or more in Co, Mo or V, and carrier is aluminium oxide；In catalyst, each element quality accounts for the percentage ratio of catalyst quality is benchmark, and the content of active component is 10wt%～30wt%, it is preferable that 15wt%～25wt%, and the content of auxiliary agent is 1wt%～15wt%, and surplus is carrier；The preparation method of described catalyst comprises the steps:
(1) oil on catalyst surface is removed in useless hydrotreating catalyst extracting, dried in 80～150 DEG C, carry out calcination process, obtain catalyst precarsor A, described sintering temperature is 300 ~ 600 DEG C, and roasting time is 2～6h；
(2) the catalyst precarsor A that step (1) is obtained by reducing atmosphere is adopted to carry out reduction treatment；
(3) the catalyst precarsor A after reduction step (2) obtained and polyhydric alcohol solutions join in autoclave, use hydrogen exchange 2～5 times after sealing, then regulate Hydrogen Vapor Pressure to 2～4MPa, react 2～5h at 200～300 DEG C；
(4) reaction effluent step (3) obtained places 1～3h, then filters, and gained solid sample is at room temperature dried, until sample surfaces is without liquid phase, obtains catalyst precarsor B；
(5) by soluble in water for active component presoma, obtain solution C, be subsequently adding the catalyst precarsor B that step (4) obtains, after drying, calcination process, obtain catalyst.
The present invention is in the method for preparing catalyst of methane portion oxidation synthesis gas, the described useless hydrotreating catalyst of step (1) refers to and does not reach former reaction requirement, or owing to grating reason is without the catalyst for hydrotreatment of residual oil used on the fixing bed of complete deactivation or ebullated bed, it is generally residuum hydrodesulfurization catalyst and/or residuum hydrogenating and metal-eliminating catalyst.Described useless hydrotreating catalyst is with aluminium oxide for carrier, active metal component is containing Mo and Co, described useless hydrotreating catalyst is owing to being hydrotreating catalyst used in hydrogenation process, so in hydrogenation process, generally having part metals Ni and V deposition.
The present invention is in the method for preparing catalyst of methane portion oxidation synthesis gas, and in the catalyst precarsor A described in step (1), the content that content is 5wt% ~ 15wt%, Co of Mo is the content that content is 1wt% ~ 3wt%, Ni of 1wt% ~ 3wt%, V is 1wt% ~ 5wt%.
The present invention is in the method for preparing catalyst of methane portion oxidation synthesis gas, and the mixing gas that reducing atmosphere is hydrogen or hydrogen and nitrogen described in step (2), in described mixing gas, hydrogen volume content is 10%～95%.Concrete reduction treatment process is as follows: under nitrogen atmosphere, catalyst precarsor is warming up to 300～600 DEG C, then passes to the mixing gas of hydrogen or hydrogen and nitrogen, in 0.1～0.5MPa(absolute pressure) process 4～8h after, be down to room temperature in a nitrogen atmosphere.
The present invention is in the method for preparing catalyst of methane portion oxidation synthesis gas, and the polyhydric alcohol described in step (3) can be one or more in xylitol, sorbitol, mannitol, arabitol；The mass concentration of polyhydric alcohol solutions is 5%～10%；The volume ratio of the reduction rear catalyst precursor A that described polyhydric alcohol solutions and step (2) obtain is 5～10.
The present invention is used in the method for preparing catalyst of methane portion oxidation synthesis gas, and the soluble-salt that active component presoma is Ni described in step (5) is specifically as follows nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride., it is preferable that nickel nitrate or nickel acetate；In described solution C, the concentration of active component nickel is 0.5～3.5mol/L.The concrete dipping process of active component is for adopting method well known to those skilled in the art.Described baking temperature is 70～150 DEG C, it is preferred to 80～120 DEG C, and drying time is 2～12h, it is preferred to 4～8h.Described sintering temperature is 350～650 DEG C, it is preferred to 400～600 DEG C, and roasting time is 2～12h, it is preferred to 4～8h.
Catalyst prepared by the inventive method can also make suitable particle shape according to the needs used, as made bar shaped, sheet-shaped, cylindricality etc..
Catalyst prepared by the inventive method can apply to methane portion oxidation synthesis gas reaction.Catalyst before use in a hydrogen atmosphere, 700～800 DEG C of prereduction 1～3h.Catalyst prepared by the inventive method is applied to methane portion oxidation synthesis gas reaction, and good process conditions are: the composition CH of unstripped gas4/O2Mol ratio is 1.75～2.2, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, unstripped gas air speed 20000～200000h-1, reaction pressure is 0.1～1Mpa, and reaction temperature is 600～900 DEG C.
The catalyst that the present invention relates to, make use of Mo, Co, V, Ni metal in waste residue oil hydrotreating catalyst, also takes full advantage of the alumina catalyst support of dead catalyst, it is achieved that the comprehensive utilization of metal and carrier simultaneously, has saved cost；The dead catalyst processed is as catalyst precarsor, after reduction treatment, and catalytic polyol aqueous phase hydrogenation, the product C of generation in autoclave5And C6Catalyst precarsor can be processed further by liquid alkane as atent solvent；The load active component nickel again of catalyst precarsor after treatment, control the active metal amount of load in carrier duct preferably, promote that more multiple active components is in the dispersion of carrier surface, both improve the utilization rate of active metal, reduce catalyst cost, accelerating again reactant and the product adsorption desorption speed in catalyst surface and hole, thus avoiding the further oxidation of product, improve the conversion ratio of methane and the selectivity of product.
Detailed description of the invention
Further illustrate technology contents and the effect of the present invention below in conjunction with embodiment, but be not so limited the present invention.
Appreciation condition: use hydrogen reducing 2 hours at 700 DEG C before catalyst reaction of the present invention.Continuous sample introduction fixed-bed quartz reactor reacts, reaction temperature 750 DEG C, unstripped gas composition CH4/O2/ Ar=2/1/4(mol ratio), air speed 1 × 105h-1, product is condensed dewater after use gas chromatogram on-line analysis.Sample analysis after reacting 1 hour, evaluation result is in Table 1.
Adopt active component and auxiliary agent distribution situation on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.The scanning electron microscope analysis result of embodiment of the present invention gained catalyst activity component nickel is in Table 2.
Embodiment 1
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；Being activated in the mixed atmosphere of hydrogen by 20g catalyst precarsor A, in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor A after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 22.84g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V, is designated as C-1.
Embodiment 2
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；Being activated in the mixed atmosphere of hydrogen by 20g catalyst precarsor A, in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor A after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 31.16g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 30%Ni, 5.58%Mo, 1.22%Co, the catalyst of 1.35%V, is designated as C-2.
Embodiment 3
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；Being activated in the mixed atmosphere of hydrogen by 20g catalyst precarsor A, in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor A after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 14.94g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 15%Ni, 7.3%Mo, 1.6%Co, the catalyst of 1.76%V, is designated as C-3.
Embodiment 4
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；Being activated in the mixed atmosphere of hydrogen by 20g catalyst precarsor A, in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor A after reduction activation is joined in autoclave with the xylitol solution that 400mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 22.84g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V, is designated as C-4.
Embodiment 5
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；Being activated in the mixed atmosphere of hydrogen by 20g catalyst precarsor A, in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor A after reduction activation is joined in autoclave with the mannitol solution that 200mL mass concentration is 10%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 22.84g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V, is designated as C-5.
Embodiment 6
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；Being activated in the mixed atmosphere of hydrogen by 20g catalyst precarsor A, in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor A after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 5%, after sealing, uses hydrogen exchange 3 times, then regulate Hydrogen Vapor Pressure to 3MPa, at 220 DEG C, react 4h；Reacted mixture in above-mentioned autoclave being placed 2h, filters, gained solid sample is at room temperature dried to sample surfaces without liquid phase, obtains catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 22.84g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V, is designated as C-6.
Comparative example 1
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；20g catalyst precarsor A is joined 50mLC6In alkane solvent, impregnate 20min, then filter, at room temperature dry, until precursor surface is without liquid phase, prepare catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 22.84g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V, is designated as D-1.
Comparative example 2
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；20g catalyst precarsor A is joined in the sorbitol solution that 300mL mass concentration is 10%, impregnate 20min, then filter, at room temperature dry, until precursor surface is without liquid phase, prepare catalyst precarsor B；Catalyst precarsor B is joined in the aqueous solution containing 22.84g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V, is designated as D-2.
Comparative example 3
Select the useless hydrotreating catalyst (MoCo/Al of fixing bed residual hydrogenation commercial plant2O3), the oil on catalyst surface is removed through extracting, in 110 DEG C of dry 8h, gained catalyst is at 450 DEG C of roasting 4h, obtaining catalyst precarsor A, wherein Mo accounts for catalyst precarsor A weight 8.7wt%, Co in element and accounts for catalyst precarsor A weight 1.9wt% in element, Ni accounts for catalyst precarsor A weight 2.8wt%, V in element and accounts for catalyst precarsor A weight 2.1wt% in element；20g catalyst precarsor A is joined in the aqueous solution containing 22.84g nickel nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 4h at 400 DEG C, namely prepare and count quality with element and account for catalyst percentage composition for 20%Ni, 6.73%Mo, 1.47%Co, the catalyst of 1.62%V, is designated as D-3.
The reactivity worth of table 1 catalyst
Table 2 catalyst activity component nickel content distribution (wt%)
Claims (17)
1. a preparation method for methane portion oxidation synthesis gas catalyst, described catalyst includes active component, auxiliary agent and carrier, and active component is Ni；Auxiliary agent is one or more in Co, Mo or V, and carrier is aluminium oxide；In catalyst, each element quality accounts for the percentage ratio of catalyst quality is benchmark, and the content of active component is 10wt%～30wt%, it is preferable that 15wt%～25wt%, and the content of auxiliary agent is 1wt%～15wt%, and surplus is carrier；The preparation method of described catalyst comprises the steps:
(1) oil on catalyst surface is removed in useless hydrotreating catalyst extracting, dried in 80～150 DEG C, carry out calcination process, obtain catalyst precarsor A, described sintering temperature is 300 ~ 600 DEG C, and roasting time is 2～6h；
(2) the catalyst precarsor A that step (1) is obtained by reducing atmosphere is adopted to carry out reduction treatment；
(3) the catalyst precarsor A after reduction step (2) obtained and polyhydric alcohol solutions join in autoclave, use hydrogen exchange 2～5 times after sealing, then regulate Hydrogen Vapor Pressure to 2～4MPa, react 2～5h at 200～300 DEG C；
(4) reaction effluent step (3) obtained places 1～3h, then filters, and gained solid sample is at room temperature dried, until sample surfaces is without liquid phase, obtains catalyst precarsor B；
(5) by soluble in water for active component presoma, obtain solution C, be subsequently adding the catalyst precarsor B that step (4) obtains, after drying, calcination process, obtain catalyst.
2. in accordance with the method for claim 1, it is characterised in that: the waste residue oil hydrotreating catalyst described in step (1) is that active metal component is containing Mo and Co with aluminium oxide for carrier.
3. in accordance with the method for claim 1, it is characterised in that: the useless hydrotreating catalyst described in step (1) is catalyst for hydrotreatment of residual oil.
4. the method described in claim 1 or 2, it is characterised in that: the useless hydrotreating catalyst described in step (1) is residuum hydrodesulfurization catalyst and/or residuum hydrogenating and metal-eliminating catalyst.
5. the method according to any one of claims 1 to 3, it is characterised in that: the useless hydrotreating catalyst described in step (1) is with aluminium oxide for carrier, and active metal component is containing Mo and Co.
6. in accordance with the method for claim 1, it is characterised in that: in the catalyst precarsor A described in step (1), the content that content is 5wt% ~ 15wt%, Co of Mo is the content that content is 1wt% ~ 3wt%, Ni of 1wt% ~ 3wt%, V is 1wt% ~ 5wt%.
7. in accordance with the method for claim 1, it is characterised in that: the mixing gas that reducing atmosphere is hydrogen or hydrogen and nitrogen described in step (2), in described mixing gas, hydrogen volume content is 10%～95%.
8. in accordance with the method for claim 1, it is characterized in that: the reduction treatment process described in step (2) is as follows: under nitrogen atmosphere, catalyst precarsor is warming up to 300～600 DEG C, then pass to the mixing gas of hydrogen or hydrogen and nitrogen, in 0.1～0.5MPa(absolute pressure) process 4～8h after, be down to room temperature in a nitrogen atmosphere.
9. in accordance with the method for claim 1, it is characterised in that: the polyhydric alcohol described in step (3) is one or more in xylitol, sorbitol, mannitol, arabitol.
10. the method described in claim 1 or 8, it is characterised in that: the mass concentration of the polyhydric alcohol solutions described in step (3) is 5%～10%.
11. according to the method according to any one of claim 1,8 or 9, it is characterised in that: the volume ratio of the reduction rear catalyst precursor A that the polyhydric alcohol solutions described in step (3) and step (2) obtain is 5～10.
12. in accordance with the method for claim 1, it is characterised in that: the soluble-salt that active component presoma is Ni described in step (5).
13. in accordance with the method for claim 12, it is characterised in that: the active component presoma described in step (5) is nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride..
14. in accordance with the method for claim 13, it is characterised in that: the active component presoma described in step (5) is nickel nitrate or nickel acetate.
15. in accordance with the method for claim 1, it is characterised in that: in described solution C, the concentration of active component nickel is 0.5～3.5mol/L.
16. in accordance with the method for claim 1, it is characterised in that: described baking temperature is 70～150 DEG C, and drying time is 2～12h, and described sintering temperature is 350～650 DEG C, and roasting time is 2～12h.
17. in accordance with the method for claim 16, it is characterised in that: described baking temperature is 80～120 DEG C, and drying time is 4～8h, and described sintering temperature is 400～600 DEG C, and roasting time is 4～8h.
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