CN105642305A - Preparation method of catalyst for methane steam reforming to produce hydrogen - Google Patents
Preparation method of catalyst for methane steam reforming to produce hydrogen Download PDFInfo
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Abstract
The invention relates to a preparation method of a catalyst for methane steam reforming to produce hydrogen. The catalyst comprises an active component, an auxiliary agent, and a carrier. The preparation method comprises the following steps: processing the catalyst for waste residual oil hydrogenation to produce a catalyst precursor (A); then reducing the catalyst precursor (A) in a reducing atmosphere; adding the reduced catalyst precursor (A) and a polyol solution into a high pressure reactor to carry out hydrogenation reactions, collecting the effluents of the reactions, filtering, drying to obtain a catalyst precursor (B); dissolving an active component precursor and an auxiliary agent precursor into water to prepare a solution (C), adding the catalyst precursor (B), drying, and burning to obtain the catalyst. The catalyst for waste residual oil hydrogenation is fully utilized to produce the provided catalyst, the cost is reduced, moreover, more active components are dispersed on the surface of carriers, the utilization rate of active metal is improved, and the conversation rate of methane and product selectivity are both improved.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst for hydrogen production from methane vapor reforming, especially relate to a kind of loading type nickel-based catalyst preparation method for hydrogen production from methane vapor reforming.
Background technology
Methane resource enriches, and hydrogen-carbon ratio is high, is good hydrogen feedstock. And hydrogen as efficient, clean secondary energy sources by one of main energy sources becoming Future Society. In recent years, hydrogen, as the raw material of fuel cell, has unrivaled superiority compared with other fuel, and such as hydrogen calorific value height, without air pollution etc., the application of Hydrogen Energy solves energy shortage problem on the one hand, does not cause again environmental pollution on the other hand.
At present, with methane for raw material for preparing hydrogen mainly by two kinds of approach: one is by preparing synthesis gas (H2Gaseous mixture with CO) thus obtaining hydrogen; The Direct Resolution that another kind is by methane obtains hydrogen. The method of methane synthesis gas mainly has three kinds: steam reforming method (SRM), CO 2 reformation method (DMR), partial oxidation process (POM).
The steam reforming method of methane, H in theory2/ CO=3, for hydrogen-rich synthetic gas, CO content is less, and can make H by suitable catalyst2Ratio increases further, it is possible to as the desirable route of fuel cell hydrogen source. Methane-steam reforming is strong endothermic reaction, it is desirable at high temperature carry out, and general reaction temperature is at 700 ~ 900 DEG C. The carrier of at present conventional SMR catalyst be aluminium oxide, zirconium oxide, cerium oxide, magnesium oxide, lanthana, niobium oxide, zeolite, perovskite, silicon dioxide clay, yittrium oxide, cobalt oxide, ferrum oxide and mixture thereof or one of. Research shows, during by noble metal Ru, Rh, Pd even load on suitable carrier, all has higher reactivity and anti-carbon performance, but the shortcoming of noble metal is that expensive; In base metal, Raney nickel has higher reactivity, is generally adopted Ni/Al2O3Catalyst, reaction condition is 1.5 ~ 3MPa, 850 ~ 900 DEG C, the H of generation2The ratio of/CO is about 3.
Although in prior art, method for preparing methane vapor reforming nickel-base catalyst all can obtain the catalyst with better activity, 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 hydrogen production from methane vapor reforming, 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.
Method for preparing catalyst for hydrogen production from methane vapor reforming 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 Mg, Ca, Mo, Co, Zr, Ce or La, 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 20wt%��30wt%, and the content of auxiliary agent is 1wt%��15wt%, and surplus is carrier; The preparation method of described catalyst comprises the steps:
(1) useless hydrotreating catalyst extracting being removed the oil on catalyst surface, carry out calcination process after drying in 80��150 DEG C, 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 to active component presoma and auxiliary agent 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 hydrogen production from methane vapor reforming, 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 hydrogen production from methane vapor reforming, 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 hydrogen production from methane vapor reforming, 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 hydrogen production from methane vapor reforming, 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 in the method for preparing catalyst of hydrogen production from methane vapor reforming, the soluble-salt that active component presoma is Ni described in step (5), be specifically as follows in nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride. one or more, it is preferable that nickel nitrate or nickel acetate; Auxiliary agent presoma is one or more in magnesium nitrate, calcium nitrate, zirconium nitrate, cerous nitrate, Lanthanum (III) nitrate, it is preferable that magnesium nitrate; In described solution C, the concentration of active component nickel is 0.5��3.5mol/L, and the concentration of promoter metal is 0.1��1.0mol/L. The concrete dipping process of auxiliary agent and 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 hydrogen production from methane vapor reforming reaction. Catalyst before use in a hydrogen atmosphere, 700��800 DEG C of prereduction 2��5h. Catalyst prepared by the inventive method is applied to hydrogen production from methane vapor reforming reaction, and good process conditions are: the composition H of unstripped gas2O/CH4Mol ratio is 1��4, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, unstripped gas air speed 1000��3000h-1, reaction pressure is 0.2��3Mpa, and reaction temperature is 600��800 DEG C.
The catalyst that the present invention relates to, make use of Mo, Co, 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 again of catalyst precarsor after treatment and adjuvant component, 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 3 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 H2O/CH4/N2=6.75/2.25/1(mol ratio), air speed 2000h-1, product is condensed dewater after use gas chromatogram on-line analysis. Starting sample analysis after reacting 1 ~ 3 hour, evaluation result is in Table 1. Reaction result in table 1 is the average activity after catalyst works 100h at 750 DEG C.
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 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 34.98g nickel nitrate and 9.65g magnesium 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 25%Ni, 3%Mg, 6.1%Mo, the catalyst of 1.18%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 42.02g nickel nitrate and 17.95g magnesium 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%Mg, 5.54%Mo, the catalyst of 1.1%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 25.91g nickel nitrate and 15.49g magnesium 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, 5%Mg, 6.4%Mo, the catalyst of 1.2%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 34.98g nickel nitrate and 9.65g magnesium 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 25%Ni, 3%Mg, 6.1%Mo, the catalyst of 1.18%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 34.98g nickel nitrate and 9.65g magnesium 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 25%Ni, 3%Mg, 6.1%Mo, the catalyst of 1.18%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 34.98g nickel nitrate and 9.65g magnesium 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 25%Ni, 3%Mg, 6.1%Mo, the catalyst of 1.18%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 34.98g nickel nitrate and 9.65g magnesium 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 25%Ni, 3%Mg, 6.1%Mo, the catalyst of 1.18%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% 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 34.98g nickel nitrate and 9.65g magnesium 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 25%Ni, 3%Mg, 6.1%Mo, the catalyst of 1.18%Co, 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 9.3wt%, Co in element and accounts for catalyst precarsor A weight 1.8wt% in element, Ni accounts for catalyst precarsor A weight 2.9wt%, V in element and accounts for catalyst precarsor A weight 1.7wt% in element; 20g catalyst precarsor A is joined in the aqueous solution containing 34.98g nickel nitrate and 9.65g magnesium 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 25%Ni, 3%Mg, 6.1%Mo, the catalyst of 1.18%Co, is designated as D-3.
The reactivity worth of table 1 catalyst
| Catalyst | CH4Conversion ratio, % | CO selectivity, % |
| C-1 | 96.3 | 88.2 |
| C-2 | 98.4 | 90.3 |
| C-3 | 94.2 | 86.7 |
| C-4 | 93.7 | 86.1 |
| C-5 | 95.1 | 87.3 |
| C-6 | 92.6 | 85.5 |
| D-1 | 80.4 | 76.1 |
| D-2 | 77.3 | 72.7 |
| D-3 | 73.2 | 67.3 |
Table 2 catalyst activity component nickel content distribution (wt%)
| Catalyst | Center is to 1/4 radius | 1/4 radius is to 2/4 radius | 2/4 radius is to 3/4 radius | 3/4 radius is to appearance |
| C-1 | 6.35 | 3.62 | 4.17 | 42.98 |
| C-2 | 8.63 | 4.96 | 5.34 | 47.58 |
| C-3 | 5.79 | 2.96 | 3.27 | 35.98 |
| C-4 | 7.28 | 4.37 | 4.69 | 42.58 |
| C-5 | 6.73 | 3.94 | 4.32 | 42.71 |
| C-6 | 8.01 | 5.12 | 3.45 | 42.13 |
| D-1 | 22.02 | 22.02 | 18.43 | 32.62 |
| D-2 | 36.09 | 27.35 | 25.31 | 24.40 |
| D-3 | 6.25 | 18.75 | 31.25 | 43.75 |
Claims (18)
1., for a method for preparing catalyst for hydrogen production from methane vapor reforming, described catalyst includes active component, auxiliary agent and carrier, and active component is Ni; Auxiliary agent is one or more in Mg, Ca, Mo, Co, Zr, Ce or La, 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 20wt%��30wt%, and the content of auxiliary agent is 1wt%��15wt%, and surplus is carrier; The preparation method of described catalyst comprises the steps:
(1) useless hydrotreating catalyst extracting being removed the oil on catalyst surface, carry out calcination process after drying in 80��150 DEG C, 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 to active component presoma and auxiliary agent 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).
7. in accordance with the method for claim 6, it is characterised in that: in the mixing gas described in step (2), 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, after 0.1��0.5MPa processes 4��8h, it is 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 9, 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 described in claim 1,9 or 10, 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 one or more in 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: the auxiliary agent presoma described in step (5) is one or more in magnesium nitrate, calcium nitrate, zirconium nitrate, cerous nitrate, Lanthanum (III) nitrate, it is preferable that magnesium nitrate.
16. in accordance with the method for claim 1, it is characterised in that: in the solution C described in step (5), the concentration of active component nickel is 0.5��3.5mol/L, and the concentration of promoter metal is 0.1��1.0mol/L.
17. 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.
18. in accordance with the method for claim 17, 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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| CN201410732130.4A CN105642305B (en) | 2014-12-06 | 2014-12-06 | A kind of method for preparing catalyst for hydrogen production from methane vapor reforming |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134102A (en) * | 2018-01-04 | 2018-06-08 | 四川天科技股份有限公司 | A kind of catalyst for methane steam reforming in fuel cell |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011138A1 (en) * | 2002-07-26 | 2004-02-05 | Sud-Chemie, Inc. | Nickel-catalyst for syngas generation by mixed reforming using co2 and steam |
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
| CN102299345A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of methane reforming catalyst to molten carbonate fuel cell |
| US20130116118A1 (en) * | 2011-11-09 | 2013-05-09 | Basf Se | Catalyst composition for the steam reforming of methane in fuel cells |
| CN103611538A (en) * | 2013-11-29 | 2014-03-05 | 华东理工大学 | Multifunctional catalyst for methane steam reforming hydrogen production and preparation method thereof |
| CN103769173A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for utilizing waste hydro-treatment catalyst |
-
2014
- 2014-12-06 CN CN201410732130.4A patent/CN105642305B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011138A1 (en) * | 2002-07-26 | 2004-02-05 | Sud-Chemie, Inc. | Nickel-catalyst for syngas generation by mixed reforming using co2 and steam |
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
| CN102299345A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of methane reforming catalyst to molten carbonate fuel cell |
| US20130116118A1 (en) * | 2011-11-09 | 2013-05-09 | Basf Se | Catalyst composition for the steam reforming of methane in fuel cells |
| CN103769173A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for utilizing waste hydro-treatment catalyst |
| CN103611538A (en) * | 2013-11-29 | 2014-03-05 | 华东理工大学 | Multifunctional catalyst for methane steam reforming hydrogen production and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134102A (en) * | 2018-01-04 | 2018-06-08 | 四川天科技股份有限公司 | A kind of catalyst for methane steam reforming in fuel cell |
| CN108134102B (en) * | 2018-01-04 | 2020-10-09 | 西南化工研究设计院有限公司 | Catalyst for methane steam reforming in fuel cell |
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Inventor after: Ren Jinchen Inventor after: Sun Xiaodan Inventor after: Zhang Shudong Inventor after: Zhang Xinwei Inventor after: Liu Jihua Inventor before: Sun Xiaodan Inventor before: Zhang Shudong Inventor before: Zhang Xinwei Inventor before: Liu Jihua |