CN105727980A - Preparation method of catalyst for propane oxidative dehydrogenation to propylene - Google Patents
Preparation method of catalyst for propane oxidative dehydrogenation to propylene Download PDFInfo
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Abstract
The invention relates to a preparation method of a catalyst for propane oxidative dehydrogenation to propylene. The catalyst comprises an active ingredient, a first additive, a second additive and a carrier. The preparation method is as below: dissolving an active ingredient precursor and a first additive precursor in water to obtain a solution A; then adding the carrier, aging, drying, and calcining to obtain a catalyst precursor B; reducing the catalyst precursor B in a reducing atmosphere; adding the reduced catalyst precursor B and a polyol solution into a reaction kettle, carrying out a hydrogenation reaction, placing a reaction effluent, filtering and dying to obtain a catalyst precursor C; and dissolving an active ingredient precursor and a second additive precursor in water to obtain a solution D, then adding the catalyst precursor C, drying and calcining to obtain the catalyst. The method of the present invention promotes dispersion of more active ingredients on the surface of the carrier, improves the utilization of the active metal, as well as improves the conversion of propane and the selectivity of propylene.
Description
Technical field
The preparation method that the present invention relates to a kind of catalyst for preparing propene by oxidative dehydrogenation of propane, the preparation method especially relating to a kind of preparing propene by oxidative dehydrogenation of propane loading type nickel-based catalyst.
Background technology
Propylene is a kind of particularly important Organic Chemicals, is widely used to generate the serial important chemical products such as polypropylene, polyacrylonitrile, phenol, oxo alcohol, expoxy propane, acrylic aldehyde and acrylic acid.
At present, propylene is mainly produced by petroleum catalytic cracking, propane catalytic dehydrogenation.The production process of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane is by the control of thermodynamical equilibrium, severe reaction conditions, and exists and cause the problems such as rapid catalyst deactivation because of carbon distribution.And oxidative dehydrogenation of propane is a kind of new way preparing propylene, compared with catalytic dehydrogenation processes, it is possible to overcome the restriction of thermodynamical equilibrium, carrying out at a lower temperature, without carbon distribution, catalyst does not need frequent regeneration.
The research of catalyst for preparing propene by oxidative dehydrogenation of propane system is quite deep.The vanadium-based catalyst systems barium oxide etc. of load (V-Mg-O) and catalyst with base of molybdenum system (Mo-Mg-O, Ni-Mo-O etc.) is mainly included for the high performance catalyst system reported of target response.CN1396146 discloses a kind of with mesoporous molecular sieve SBA-15 for carrier, and with the V loaded catalyst being active component, the conversion of propane when 600 DEG C is 50%, and now the selectivity of propylene is 72%, and yield is 36%.CN1073893A discloses the composite catalyst of a kind of fluoride containing Rare-Earth Ce and oxide, and when reaction temperature is 500 DEG C, conversion of propane is 53.4%, and now the selectivity of propylene is 67.5%, and the yield of propylene is 36%.
And preparing propene by oxidative dehydrogenation of propane reaction or fast reaction (this fast reaction be typically at carry out under mass transfer limited condition), 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 preparation method that the invention provides a kind of catalyst for preparing propene by oxidative dehydrogenation of propane, catalyst prepared by the method has feature with low cost, that metal component utilization rate high, selectivity is good.
The preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, described catalyst includes active component, the first auxiliary agent, the second auxiliary agent and carrier, and active component is Ni and V；First auxiliary agent is W, and the second auxiliary agent is one or more in Mo, Co, Mg, Fe, Ce or La, it is preferred to Mo and Co, and carrier is any one in aluminium oxide, silicon oxide, SBA-15；In catalyst, each element quality accounts for the percentage ratio of carrier quality is benchmark, the content of active component Ni is 1wt%～5wt%, the content of active component V is 1wt%～15wt%, preferred 5wt%～10wt%, the content of the first auxiliary agent is 1wt%～5wt%, it is preferable that 1wt%～3wt%, and the content of the second auxiliary agent is 1wt%～5wt%, preferred 1wt%～3wt%, surplus is carrier；The preparation method of described catalyst comprises the steps:
(1) by soluble in water to active component Ni presoma and the first auxiliary agent presoma, solution A is obtained；
(2) carrier is joined in the solution A that step (1) obtains, after aging, dry, calcination process, obtain catalyst precarsor B；
(3) the catalyst precarsor B that step (2) is obtained by reducing atmosphere is adopted to carry out reduction treatment；
(4) the catalyst precarsor B after reduction step (3) 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；
(5) reaction effluent step (4) 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 C；
(6) by soluble in water to active component V presoma and the second auxiliary agent presoma, obtain solution D, be subsequently adding the catalyst precarsor C that step (5) obtains, after drying, calcination process, obtain catalyst.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, active component Ni presoma described in step (1) is one or more in nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride., it is preferable that nickel nitrate；Described first auxiliary agent presoma is the soluble-salt containing W, is specifically as follows ammonium tungstate and/or ammonium metatungstate；In described solution A, the concentration of active component Ni is 0.1～1.1mol/L, and the concentration of the first auxiliary agent W is 0.05～0.5mol/L.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, aging temperature described in step (2) is 10～90 DEG C, it is preferred to 20～60 DEG C, and ageing time is 1～24h, it is preferred to 4～12h；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 500～900 DEG C, it is preferred to 600～800 DEG C, and roasting time is 2～12h, it is preferred to 4～8h.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, the carrier described in step (2) is the one in aluminium oxide, silicon oxide, SBA-15；Described carrier can adopt commercially available product, it is also possible to prepares by method well known in the art.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, the mixing gas that reducing atmosphere is hydrogen or hydrogen and nitrogen described in step (3), in described mixing gas, hydrogen volume percentage composition 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.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, the polyhydric alcohol described in step (4) 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 B that polyhydric alcohol solutions and step (3) obtain is 5～10.
In the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention, in step (6), described active component V presoma is ammonium metavanadate and/or vanadium oxysulfate, it is preferable that ammonium metavanadate；Described second auxiliary agent presoma is one or more in ammonium molybdate, ammonium tetramolybdate, cobalt nitrate, cobaltous sulfate, cobaltous chloride, magnesium nitrate, magnesium chloride, ferric nitrate, iron sulfate, cerous nitrate, Lanthanum (III) nitrate, it is preferable that ammonium molybdate and cobalt nitrate；In described solution D, the concentration of active component V is 0.05～1.2mol/L, and the concentration range of the second promoter metal is 0.01～0.8mol/L.The concrete dipping process of auxiliary agent and active component is for adopting method well known to those skilled in the art.
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 preparing propene by oxidative dehydrogenation of propane reaction, and good process conditions are: the composition C of unstripped gas3H8/O2Mol ratio is 1～3, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, unstripped gas air speed 3000～9000mL 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, adopt aluminium oxide, silicon oxide or SBA-15 carrier, active metal component Ni that first load is a small amount of and the first auxiliary agent, the catalyst precarsor obtained is after reduction treatment, 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 V again of catalyst precarsor after treatment and the second 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 propane and the selectivity of propylene.
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 propane reaction carries out on atmospheric fixed bed micro-reaction equipment, catalyst loading amount 0.2g, reaction temperature 500 DEG C, reaction gas composition C3H8/O2/N2=1/1/4(mol ratio), flow velocity: 15mL/min, air speed 6000mL gcat -1·h-1, product is condensed dewater after use gas chromatograph on-line analysis.Starting sample analysis after reacting 1 hour, evaluation result is in Table 1.
Adopt active component V 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
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 1.06ml/g, and specific surface area is 387m to adopt equi-volume impregnating to be carried on 20g silicon oxide2/ g, spherical, equivalent diameter 0.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-2.
Embodiment 3
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；Adopting equi-volume impregnating to be carried on 20gSBA-15(pore volume is 1.23ml/g, and specific surface area is 701m2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-3.
Embodiment 4
Weigh 0.99g nickel nitrate and 0.28g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 1% in element, and W accounts for vehicle weight 1% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 2.29g ammonium metavanadate and 0.37g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 1%Ni, 1%W, the catalyst of 5%V, 1%Mo, is designated as C-4.
Embodiment 5
Weigh 4.95g nickel nitrate and 0.83g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 5% in element, and W accounts for vehicle weight 3% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 4.59g ammonium metavanadate and 1.11g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 5%Ni, 3%W, the catalyst of 10%V, 3%Mo, is designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 1.98g cobalt nitrate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Co, is designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-7.
Embodiment 8
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-8.
Embodiment 9
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the arabitol 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-9.
Embodiment 10
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-10.
Embodiment 11
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B activates in the mixed atmosphere of hydrogen, and in mixing gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), recovery time 4h；Catalyst precarsor B after reduction activation is joined in autoclave with the sorbitol solution that 300mL mass concentration is 8%, 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 C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as C-11.
Comparative example 1
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B is joined 50mLC6In alkane solvent, impregnate 20min, then filter, at room temperature dry, until catalyst precursor surface is without liquid phase, prepare catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as D-1.
Comparative example 2
Weigh 2.97g nickel nitrate and 0.55g ammonium tungstate is dissolved in appropriate amount of deionized water, obtain solution A；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt equi-volume impregnating to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, prepare catalyst precarsor B, wherein Ni accounts for vehicle weight 3% in element, and W accounts for vehicle weight 2% in element；Catalyst precarsor B is joined in the sorbitol solution that 300mL mass concentration is 10%, impregnate 20min, then filter, at room temperature dry, until catalyst precursor surface is without liquid phase, prepare catalyst precarsor C；Catalyst precarsor C is joined in the aqueous solution containing 3.67g ammonium metavanadate and 0.74g ammonium molybdate, it is evaporated in 80 DEG C of stirring to solution, put into and baking oven dries 12h at 110 DEG C, roasting 6h at 700 DEG C, molding, namely prepare and count quality with element and account for carrier percentage composition for 3%Ni, 2%W, the catalyst of 8%V, 2%Mo, is designated as D-2.
Comparative example 3
Weigh 2.97g nickel nitrate, 0.55g ammonium tungstate, 3.67g ammonium metavanadate, 0.74g ammonium molybdate are dissolved in deionized water, prepare aqueous solution；(pore volume is 0.72ml/g, and specific surface area is 242m to adopt infusion process to be carried on 20g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, aged at room temperature 6h, 100 DEG C of dry 12h, 700 DEG C of roasting 6h, namely prepare and count quality with element and account for the catalyst that carrier percentage composition is 3%Ni, 2%W, 8%V, 2%Mo, be designated as D-3.
The reactivity worth of table 1 catalyst
Table 2 catalyst activity component V content distribution (wt%)
Claims (14)
1. a preparation method for catalyst for preparing propene by oxidative dehydrogenation of propane, described catalyst includes active component, the first auxiliary agent, the second auxiliary agent and carrier, and active component is Ni and V；First auxiliary agent is W, and the second auxiliary agent is one or more in Mo, Co, Mg, Fe, Ce or La, it is preferred to Mo and Co, and carrier is any one in aluminium oxide, silicon oxide, SBA-15；In catalyst, each element quality accounts for the percentage ratio of carrier quality is benchmark, the content of active component Ni is 1wt%～5wt%, the content of active component V is 1wt%～15wt%, preferred 5wt%～10wt%, the content of the first auxiliary agent is 1wt%～5wt%, it is preferable that 1wt%～3wt%, and the content of the second auxiliary agent is 1wt%～5wt%, preferred 1wt%～3wt%, surplus is carrier；The preparation method of described catalyst comprises the steps:
(1) by soluble in water to active component Ni presoma and the first auxiliary agent presoma, solution A is obtained；
(2) carrier is joined in the solution A that step (1) obtains, after aging, dry, calcination process, obtain catalyst precarsor B；
(3) the catalyst precarsor B that step (2) is obtained by reducing atmosphere is adopted to carry out reduction treatment；
(4) the catalyst precarsor B after reduction step (3) 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；
(5) reaction effluent step (4) 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 C；
(6) by soluble in water to active component V presoma and the second auxiliary agent presoma, obtain solution D, be subsequently adding the catalyst precarsor C that step (5) obtains, after drying, calcination process, obtain catalyst.
2. the preparation method described in claim 1, it is characterised in that: active component Ni presoma described in step (1) is one or more in nickel nitrate, nickel acetate, nickel sulfate or Nickel dichloride., it is preferable that nickel nitrate.
3. the preparation method described in claim 1, it is characterised in that: described in step (1), the first auxiliary agent presoma is the soluble-salt containing W.
4. the preparation method described in claim 1, it is characterised in that: described in step (1), the first auxiliary agent presoma is ammonium tungstate and/or ammonium metatungstate.
5. the preparation method described in claim 1, it is characterised in that: in solution A described in step (1), the concentration of active component Ni is 0.1～1.1mol/L, and the concentration of the first auxiliary agent W is 0.05～0.5mol/L.
6. the preparation method described in claim 1, it is characterised in that: aging temperature described in step (2) is 10～90 DEG C, and ageing time is 1～24h, described baking temperature is 70～150 DEG C, drying time is 2～12h, and described sintering temperature is 500～900 DEG C, and roasting time is 2～12h.
7. the preparation method described in claim 6, it is characterised in that: aging temperature described in step (2) is 20～60 DEG C, and ageing time is 4～12h, described baking temperature is 80～120 DEG C, drying time is 4～8h, and described sintering temperature is 600～800 DEG C, and roasting time is 4～8h.
8. the preparation method described in claim 1, it is characterised in that: the mixing gas that reducing atmosphere is hydrogen or hydrogen and nitrogen described in step (3), in described mixing gas, hydrogen volume percentage composition is 10%～95%.
9. the preparation method described in claim 1, it is characterized in that: reduction treatment process described in step (3) 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.
10. the preparation method described in claim 1, it is characterised in that: the polyhydric alcohol described in step (4) is one or more in xylitol, sorbitol, mannitol, arabitol.
11. the preparation method described in claim 1 or 8, it is characterised in that: described in step (4), the mass concentration of polyhydric alcohol solutions is 5%～10%, and the volume ratio of the reduction rear catalyst precursor B that polyhydric alcohol solutions and step (3) obtain is 5～10.
12. the preparation method described in claim 1, it is characterised in that: active component V presoma described in step (6) is ammonium metavanadate and/or vanadium oxysulfate, it is preferable that ammonium metavanadate.
13. the preparation method described in claim 1, it is characterized in that: the second auxiliary agent presoma described in step (6) is one or more in ammonium molybdate, ammonium tetramolybdate, cobalt nitrate, cobaltous sulfate, cobaltous chloride, magnesium nitrate, magnesium chloride, ferric nitrate, iron sulfate, cerous nitrate, Lanthanum (III) nitrate, it is preferable that ammonium molybdate and cobalt nitrate.
14. the preparation method described in claim 1, it is characterised in that: in solution D described in step (6), the concentration of active component V is 0.05～1.2mol/L, and the concentration range of the second promoter metal is 0.01～0.8mol/L.
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| CN109939688A (en) * | 2019-04-03 | 2019-06-28 | 华东理工大学 | Iron gallium base propane dehydrogenation catalyst and preparation method thereof |
| CN114700084A (en) * | 2022-04-29 | 2022-07-05 | 北京海望氢能科技有限公司 | Catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, preparation method thereof and hydrogenation and dehydrogenation method of organic hydrogen storage liquid |
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