CN105727978A - Preparation method of catalyst for ethane oxidative dehydrogenation to ethylene - Google Patents
Preparation method of catalyst for ethane oxidative dehydrogenation to ethylene Download PDFInfo
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Abstract
The invention relates to a preparation method of a catalyst for ethane oxidative dehydrogenation to ethylene. 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 both improves the utilization of the active metal and the conversion of ethane and selectivity of ethylene.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst for making ethylene from ethane oxidative dehydrogenation, especially relate to a kind of loading type nickel-based catalyst preparation method for making ethylene from ethane oxidative dehydrogenation.
Background technology
Ethylene is important basic petrochemical raw material, obtains mainly through the cracking of alkane such as ethane.Compared with Pintsch process, making ethylene from ethane oxidative dehydrogenation (ODHE) is the approach of a low energy consumption, has huge application prospect, is one of the study hotspot of catalytic field in recent years.
The research of catalyst for making ethylene from ethane oxidative dehydrogenation, relates to the catalyst of a few individual system: alkaline earth oxide system, rare-earth oxide system, loaded noble metal catalyst system, transition metal oxide system.
CN1121844A discloses catalyst and the process of a kind of making ethylene from ethane oxidative dehydrogenation, described catalyst belongs to composite oxide type, formula is XaYbZcOd or XaYbZcOd/ carrier, wherein X is selected from Li, Na, K, Rb, at least one in Cs, Y is selected from La, Zr, Cr, Mo, W, Mn, Fe, Co, Ni, Pt, Pb, Cu, Zn, Cd, Tl, Pb, at least one in Sn, Z is selected from Be, Mg, at least one in Ca, the carrier silicon dioxide of supported catalyst, aluminium oxide, titanium dioxide or zirconium oxide, the total load amount of active component accounts for the 2% ~ 50% of gross weight.The catalyst reaction condition of this patent report comparatively relaxes, and has higher ethane conversion and ethylene selectivity.
CN1120470A discloses a kind of catalyst for making ethylene from ethane oxidative dehydrogenation, involved catalyst contains a kind of alkali earth metal fluoride, possibly together with the oxyfluoride that one is made up of more than one (containing one) rare earth metals, wherein oxyfluoride content in the catalyst is 5% ~ 95%.This catalyst has excellent oxidative dehydrogenation of ethane performance, and the selectivity particularly generating ethylene is high, can react, do not use carrier gas under high-speed, and reaction condition is gentle, and catalyst performance stabilised lasts a long time.
Although the catalyst that above-mentioned patented method prepares all obtains good making ethylene from ethane oxidative dehydrogenation 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, add catalyst cost, 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 making ethylene from ethane oxidative dehydrogenation, catalyst prepared by the method has feature with low cost, that metal component utilization rate high, selectivity is good.
Method for preparing catalyst for making ethylene from ethane oxidative dehydrogenation 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 Mo, Co, V；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 Ni is 10wt%～30wt%, and the content of auxiliary agent is 5wt%～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, wherein, 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 making ethylene from ethane oxidative dehydrogenation, 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 making ethylene from ethane oxidative dehydrogenation, 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 making ethylene from ethane oxidative dehydrogenation, 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 making ethylene from ethane oxidative dehydrogenation, 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 polyhydric alcohol solutions and step (2) obtain is 5～10.
The present invention is in the method for preparing catalyst of making ethylene from ethane oxidative dehydrogenation, and in step (5), described active component presoma is one or more in nickel nitrate, Nickel dichloride., nickel sulfate, nickel acetate, it is preferable that nickel nitrate；In described solution C, the concentration of active component Ni is 0.1～3mol/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 is applied to making ethylene from ethane oxidative dehydrogenation reaction, and good process conditions are: the composition C of unstripped gas2H6/O2Mol ratio is 1～3, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, unstripped gas air speed 10000～30000mL gcat -1·h-1, reaction pressure is normal pressure, and reaction temperature is 400～600 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 Ni 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 ethane and the selectivity of ethylene.
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: oxidative dehydrogenation of ethane reaction carries out in normal pressure, continuously flowing fixed-bed quartz reactor, reaction temperature 500 DEG C, unstripped gas composition C2H6/O2/N2=1/1/4(mol ratio), air speed 20000mL gcat -1·h-1, product is condensed dewater after use gas chromatogram on-line analysis.Starting sample analysis after reacting 1 hour, evaluation result is in Table 1.
Adopt active component distribution situation on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.In the embodiment of the present invention, the scanning electron microscope analysis result of catalyst activity component V 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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 23.78g 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, 7.36%Mo, 1.69%Co, the catalyst of 1.84%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 8.97g 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 10%Ni, 8.61%Mo, 1.97%Co, the catalyst of 2.15%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 44.67g 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, 6.1%Mo, 1.4%Co, the catalyst of 1.53%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 23.78g 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, 7.36%Mo, 1.69%Co, the catalyst of 1.84%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 23.78g 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, 7.36%Mo, 1.69%Co, the catalyst of 1.84%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 23.78g 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, 7.36%Mo, 1.69%Co, the catalyst of 1.84%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 23.78g 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, 7.36%Mo, 1.69%Co, the catalyst of 1.84%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% 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 23.78g 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, 7.36%Mo, 1.69%Co, the catalyst of 1.84%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 9.6wt%, Co in element and accounts for catalyst precarsor A weight 2.2wt% in element, Ni accounts for catalyst precarsor A weight 2.1wt%, V in element and accounts for catalyst precarsor A weight 2.4wt% in element；20g catalyst precarsor A is joined in the aqueous solution containing 23.78g 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, 7.36%Mo, 1.69%Co, the catalyst of 1.84%V, is designated as D-3.
The reactivity worth of table 1 catalyst
Table 2 catalyst activity component Ni content distribution (wt%)
Claims (15)
1., for a method for preparing catalyst for making ethylene from ethane oxidative dehydrogenation, described catalyst includes active component, auxiliary agent and carrier, and active component is Ni；Auxiliary agent is one or more in Mo, Co, V；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 Ni is 10wt%～30wt%, and the content of auxiliary agent is 5wt%～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, wherein, 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 useless hydrotreating catalyst described in step (1) is catalyst for hydrotreatment of residual oil.
3. 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.
4. 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.
5. 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%.
6. 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%.
7. 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, after 0.1～0.5MPa processes 4～8h, it is down to room temperature in a nitrogen atmosphere.
8. 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.
9. 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%.
10. 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.
11. in accordance with the method for claim 1, it is characterised in that: active component presoma described in step (5) is one or more in nickel nitrate, Nickel dichloride., nickel sulfate, nickel acetate.
12. the method described in claim 1 or 11, it is characterised in that: active component presoma described in step (5) is nickel nitrate.
13. in accordance with the method for claim 1, it is characterised in that: in described solution C, the concentration of active component Ni is 0.1～3mol/L.
14. 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.
15. in accordance with the method for claim 14, 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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| CN106588539A (en) * | 2016-11-24 | 2017-04-26 | 中国石油大学(华东) | Method for preparing ethylene by using modification type platinum catalyst for catalyzing oxidative dehydrogenation of ethane |
| CN107597133A (en) * | 2017-10-15 | 2018-01-19 | 华东师范大学 | A kind of self-supporting nickel oxide-base catalyst and its preparation method and application |
| CN107866239A (en) * | 2016-09-26 | 2018-04-03 | 大连理工大学 | A kind of phosphorus series compound catalyst, its preparation method and application for manufacturing olefin by low-carbon alkane dehydrogenation |
| CN109843434A (en) * | 2016-10-18 | 2019-06-04 | 诺瓦化学品(国际)股份有限公司 | Use the method for hydro-thermal process and peroxide treatment production Oxydehydrogenation catalyst |
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