CN105363443A - Catalyst used for preparing low-carbon olefin through low-carbon alkane dehydrogenation and using method thereof - Google Patents
Catalyst used for preparing low-carbon olefin through low-carbon alkane dehydrogenation and using method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst used for preparing low-carbon olefin through low-carbon alkane dehydrogenation and application thereof. The catalyst mainly solves the problems that an existing catalyst for preparing low-carbon olefin through low-carbon alkane dehydrogenation is low in olefin selectivity, severe in carbon deposit and poor in one-way stability on the high-temperature condition. According to the catalyst for preparing low-carbon olefin through low-carbon alkane dehydrogenation and the application thereof, metal composite oxide is used as a carrier of the catalyst, a platinum element is used as an active component, an IB family element, Sn, a rare earth element and IIIA family element oxide are used as auxiliaries, an impregnating method is adopted for loading, catalyst charking regeneration is carried out, the problems are solved well, and the catalyst can be applied to industrial production of preparing low-carbon olefin through low-carbon alkane dehydrogenation.
Description
Technical field
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins and uses thereof.
Background technology
Low-carbon alkene is important Organic Chemicals, has industrial use widely, and low-carbon alkene is widely used in the production of plastics, synthetic rubber, medicine, gasoline additive, ion exchange resin, washing agent, spices and various chemical intermediate.Along with the development of chemical industry, very fast to the demand growth of low-carbon alkene, to develop by the low carbon alkane preparing low-carbon olefins process of added value for making full use of low-carbon alkanes resource, open up new alkene and originate significant.Propylene/isobutene mainly from naphtha and the steam cracking of liquefied petroleum gas and the coproduction of refinery factory fluid catalytic cracking process or by-product, has only been difficult to by said method the demand meeting China's chemical industry fast development at present.Propane/dehydrogenation of isobutane technology has become propylene/isobutene source important after the coproduction or by-product of steam cracking and fluid catalytic cracking process.Propane/dehydrogenation of isobutane is industrialization now, mainly comprises the technique such as Linde of the Oleflex technique of Uop Inc., the Star technique of Phillips company, the Catofin technique of AirProduct & Chemical company, FDB-4 and the Linde company of SnamprogettiSPA company.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, and the catalyst of exploitation high activity, high selectivity and high stability becomes the key of this technology.Industrialized catalyst mainly contains two classes at present, one class take metal oxide as active component, as Chinese patent (CN200910012450.1, CN200610126812.6) disclose with the catalyst of chromium element for main active component, there is the advantages such as activity is high, cost is lower, but inactivation is fast, and poisonous, be difficult to meet environmental requirement.Another kind of is loaded noble metal catalyst, and the catalyst reported as United States Patent (USP) (US4438288) is active component with Pt, take Sn as auxiliary agent, uses infusion process that platinum, tin are carried on γ-Al
2o
3, SiO
2or on the carrier such as MgO, and dipping adds alkali metal or alkaline-earth metal, the shortcoming of this catalyst is that activity and selectivity is lower, and iso-butane conversion ratio is 39% ~ 44%.The disclosed catalyst of Chinese patent (CN96117222.3), infusion process is adopted Pt to be loaded to MgAl (O) composite oxide carrier, the initial iso-butane conversion ratio of this catalyst is 59%, selective isobutene is 97% ~ 98%, but catalysqt deactivation is very fast, reacts iso-butane conversion ratio after 5 hours and is down to 45.6%.Chinese patent (CN200710020064.8) and (CN200710133324.2) disclose platinum-Xi-rare earth catalyst prepared by infusion process and react for dehydrogenating propane, carrier is containing the X-type of Na, Y type or ZSM-5 molecular sieve, there is higher Propylene Selectivity, but conversion of propane is maintained at about 30%, this patent does not provide the stability data of repeatedly coke-burning regeneration process.
Catalyst for dehydrogenation of low-carbon paraffin obtains greater advance at present, but still it is lower to there is olefine selective in higher alkane conversion situation, and the easy coking deactivation of catalyst, the problem such as activity decrease after frequent regeneration.The present invention take composite oxide of metal as carrier, take platinum group as active component, with IB race element, Sn, rare earth and IIIA race element oxide for auxiliary agent, significantly improve dehydrogenation and the coking resistivity of catalyst, improve the stability of catalyst, reduce catalytic dehydrogenation processes cost.
Summary of the invention
Technical problem to be solved by this invention is that olefine selective is low under the high temperature conditions, carbon deposit serious, the problem of one way poor stability for the existing catalyst for dehydrogenating low-carbon alkane producing light olefins, a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins is newly provided, this method for preparing catalyst is easy, units activity component effective rate of utilization is high, have when using under the high temperature conditions, the advantage that catalyst olefine selective is high, coking deactivation speed is slow, catalyst stability is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins, comprises following component by weight percentage:
A) with MO-Al
2o
3the composite oxides of structure are carrier, and wherein M has the+metal of divalent, and carrier is 83 ~ 99.83% of catalyst weight;
B) with one or both in platinum group for active component, described active component is 0.01 ~ 1.0% of catalyst weight;
C) with IB race element for auxiliary agent, described IB race element is 0 ~ 1.0% of catalyst weight;
D) with the oxide of rare earth element for auxiliary agent, described rare earth oxide is 0.01 ~ 10% of catalyst weight;
E) with IIIA race element oxide for auxiliary agent, described IIIA race element oxide is 0.1 ~ 1.0% of catalyst weight;
F) with the oxide of Sn for auxiliary agent, the oxide of described Sn is 0.05 ~ 4.0% of catalyst weight.
In technique scheme, described low-carbon alkanes is propane or iso-butane; Composite oxide carrier is selected from MgAl
2o
4, ZnAl
2o
4, FeAl
2o
4, CoAl
2o
4, CaAl
2o
4, BaAl
2o
4or SrAl
2o
4in one, be preferably MgAl
2o
4, ZnAl
2o
4or CaAl
2o
4in one; In active component, a kind of platinum group is Pt, another kind of platinum group is selected from the one in Ru, Rh, Pd, Os or Ir, preferable range is the one in Ru, Rh or Pd, and the percentage by weight that active component accounts for catalyst is 0.01 ~ 1.0%, and content preferable range is 0.1 ~ 0.8%; IB race element is selected from the one in Cu, Ag or Au, and preferable range is Cu or Au, and be wherein the best with Au, IB race element is 0 ~ 1.0% of catalyst weight, and content preferable range is 0.05 ~ 1.0%; Rare earth oxide auxiliary agent is selected from the one in La, Ce or Nd, and preferable range is the one in La or Ce, and rare earth oxide auxiliary agent is 0.01 ~ 10% of catalyst weight, and content preferable range is 0.1 ~ 5%; IIIA race element auxiliary agent is selected from the one in Ga, In or Tl, and preferable range is the one in Ga or In, and IIIA race element oxide is 0.1 ~ 1.0% of catalyst weight, and content preferable range is 0.1 ~ 0.8%; Sn oxide is 0.05 ~ 4.0% of catalyst weight, and content preferable range is 0.2 ~ 1.6%.
The preparation method of a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins involved in the present invention, can adopt following steps:
1) solution of described adjuvant component and described carrier incipient impregnation will be contained, dipping temperature is 10 DEG C ~ 80 DEG C, dip time is 1 ~ 24 hour, drying, roasting is carried out after dipping, baking temperature is 90 DEG C ~ 150 DEG C, drying time is 1 ~ 24 hour, and sintering temperature is 400 DEG C ~ 650 DEG C, and roasting time is 1 ~ 24 hour;
2) solution of active component platinum group and described carrier incipient impregnation will be contained, dipping temperature is 10 DEG C ~ 80 DEG C, dip time is 1 ~ 24 hour, drying, roasting is carried out after dipping, baking temperature is 90 DEG C ~ 150 DEG C, and drying time is 1 ~ 24 hour, and sintering temperature is 400 DEG C ~ 650 DEG C, roasting time is 1 ~ 24 hour, then through hydrogen 400 DEG C ~ 650 DEG C reduction treatments 1 ~ 10 hour.
In technique scheme, immersion solvent adopts the one in water or ethanol.For improving the activity of catalyst, catalyst is after hydrogen reducing, and also available water steam processes, treatment temperature 400 DEG C ~ 650 DEG C, 1 ~ 10 hour time.
Catalyst involved in the present invention application in manufacturing olefin by low-carbon alkane dehydrogenation, can adopt and comprise following processing step:
1) catalytic dehydrogenation: with low-carbon alkanes and H
2or the gaseous mixture of steam is raw material, reaction temperature is 400 DEG C ~ 600 DEG C, and reaction pressure is 0.08MPa ~ 0.12MPa, and alkane mass space velocity is 3.0 ~ 8.0h
-1, raw material and described catalyst carry out catalytic dehydrogenating reaction and obtain low-carbon alkene in the reactor;
2) catalyst regeneration: reacted decaying catalyst carries out coke-burning regeneration, in-situ regeneration or ex-situ regeneration can be adopted, regeneration temperature is 400 DEG C ~ 650 DEG C, and the recovery time is 1 ~ 10 hour, and regeneration atmosphere comprises at least one in oxygen, air, carbon dioxide or steam.
Compared with prior art, the present invention has significant advantage and high-lighting effect, and selected composite oxides to be carrier, vector stabilisation is high, and catalyst surface has suitable Acidity of Aikalinity, and catalyst performance is significantly improved; The alloy phase of Pt and other platinum group for independent Pt, there is higher catalytic activity and target alkene selective; The IB race element of trace, easily in catalyst surface enrichment, inhibits catalyst to the hydrogenolysis activity of Product olefins to a certain extent, thus improves olefin yields; Rare earth oxide and the catalysis dehydrogenation performance of IIIA race element oxide auxiliary agent to catalyst can play facilitation, appropriate auxiliary agent has the effect of dispersion, isolation active component barium oxide, significantly improve the decentralization of active component, also make catalyst have better anti-carbon deposition ability simultaneously; Sn oxide plays and improves catalyst activity and stability, improves the effect of active component decentralization, and Sn has the electronic effect of filling Pt element 5d track, and it can play minimizing carbon deposit, suppresses the effect of hydrogenolysis.This catalyst has the advantage that activity is higher, olefine selective is high, coking deactivation speed is slow, catalyst stability is high, reduces catalytic dehydrogenation processes cost.
Dehydrogenating low-carbon alkane reaction is carried out on the miniature catalyst reaction device of continuous-flow quartz tube reactor.Product analysis adopts HP-5890 gas chromatograph (HP-AL/S capillary column, 50m × 0.53mm × 15 μm; Fid detector) alkane in on-line analysis dehydrogenation product, olefin(e) centent calculate conversion ratio, the selective and yield of reaction.The catalyst using method provided by the invention to prepare reacts for dehydrogenating low-carbon alkane, and propane/iso-butane conversion ratio reaches 40%/50%, olefine selective is higher than 92%; Through 20 coke-burning regenerations, iso-butane conversion ratio remains on 50%, and olefine selective is higher than 90%, and catalyst performance is better and stability is high, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Weigh 96.5gMgAl
2o
4carrier joins containing 0.15g gold trichloride (AuCl
3), 6.23g lanthanum nitrate (La (NO
3)
36H
2o), 1.08g indium nitrate (In (NO
3)
3), 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.54g chloroplatinic acid (H again
2ptCl
66H
2and 0.17g palladium bichloride (PdCl O)
2) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.2% of catalyst weight, the load capacity of Pd is 0.1% of catalyst weight, the load capacity of Au is 0.1% of catalyst weight, the load capacity of La oxide is 2% of catalyst weight, the load capacity of In oxide is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst A.
[embodiment 2]
Weigh 96.4gMgAl
2o
4carrier joins containing 0.15g gold trichloride (AuCl
3), 6.23g lanthanum nitrate (La (NO
3)
36H
2o), 1.08g indium nitrate (In (NO
3)
3), 1.04g anhydrous stannic chloride (SnCl
4) and 0.27g sodium nitrate (NaNO
3) mixed ethanol solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.81g chloroplatinic acid (H again
2ptCl
66H
2o) in 60 DEG C of incipient impregnations 2 hours in ethanolic solution, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.3% of catalyst weight, the load capacity of Au is 0.1% of catalyst weight, the load capacity of La oxide is 2% of catalyst weight, the load capacity of In oxide is 0.5% of catalyst weight, the load capacity of Sn oxide is the load capacity of 0.6%, Na oxide of catalyst weight is 0.1% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst B.
[embodiment 3]
Weigh 99.83gSrAl
2o
4carrier joins containing 0.031g lanthanum nitrate (La (NO
3)
36H
2o), 0.216g indium nitrate (In (NO
3)
3), 0.087g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 10 DEG C of incipient impregnations 24 hours, then by the 90 DEG C of dryings 24 hours in an oven of the sample after dipping.The roasting 24 hours at 400 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.018g chloroplatinic acid (H again
2ptCl
66H
2and 0.006g palladium bichloride (PdCl O)
2) mixed aqueous solution in 10 DEG C of incipient impregnations 24 hours, then by the 90 DEG C of dryings 24 hours in an oven of the sample after dipping.The roasting 24 hours at 400 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 10 hours at 400 DEG C.
In catalyst, the load capacity of Pt is 0.006% of catalyst weight, the load capacity of Pd is 0.004% of catalyst weight, the load capacity of La oxide is 0.01% of catalyst weight, the load capacity of In oxide is the load capacity of 0.1%, Sn oxide of catalyst weight is 0.05% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 400 DEG C, process 10 hours with steam, obtain catalyst C.
[embodiment 4]
Weigh 83gBaAl
2o
4carrier joins containing 1.5g gold trichloride (AuCl
3), 31.15g lanthanum nitrate (La (NO
3)
36H
2o), 2.16g indium nitrate (In (NO
3)
3), 6.93g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 80 DEG C of incipient impregnations 1 hour, then by the 150 DEG C of dryings 1 hour in an oven of the sample after dipping.The roasting 1 hour at 650 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 1.8g chloroplatinic acid (H again
2ptCl
66H
2and 0.57g palladium bichloride (PdCl O)
2) mixed aqueous solution in 80 DEG C of incipient impregnations 1 hour, then by the 150 DEG C of dryings 1 hour in an oven of the sample after dipping.The roasting 1 hour at 650 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 1 hour at 650 DEG C.
In catalyst, the load capacity of Pt is 0.6% of catalyst weight, the load capacity of Pd is 0.4% of catalyst weight, the load capacity of Au is 1.0% of catalyst weight, the load capacity of La oxide is 10% of catalyst weight, the load capacity of In oxide is the load capacity of 1.0%, Sn oxide of catalyst weight is 4.0% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 650 DEG C, process 1 hour with steam, obtain catalyst D.
[embodiment 5]
Weigh 99.49gMgAl
2o
4carrier joins containing 0.08g gold trichloride (AuCl
3), 0.31g lanthanum nitrate (La (NO
3)
36H
2o), 0.22g indium nitrate (In (NO
3)
3), 0.35g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.18g chloroplatinic acid (H again
2ptCl
66H
2and 0.06g palladium bichloride (PdCl O)
2) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.06% of catalyst weight, the load capacity of Pd is 0.04% of catalyst weight, the load capacity of Au is 0.01% of catalyst weight, the load capacity of La oxide is 0.1% of catalyst weight, the load capacity of In oxide is the load capacity of 0.1%, Sn oxide of catalyst weight is 0.2% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst E.
[embodiment 6]
Weigh 90.8gMgAl
2o
4carrier joins containing 1.5g gold trichloride (AuCl
3), 15.58g lanthanum nitrate (La (NO
3)
36H
2o), 1.728g indium nitrate (In (NO
3)
3), 2.77g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 1.44g chloroplatinic acid (H again
2ptCl
66H
2and 0.45g palladium bichloride (PdCl O)
2) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.53% of catalyst weight, the load capacity of Pd is 0.27% of catalyst weight, the load capacity of Au is 1.0% of catalyst weight, the load capacity of La oxide is 5.0% of catalyst weight, the load capacity of In oxide is the load capacity of 0.8%, Sn oxide of catalyst weight is 1.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst F.
[embodiment 7]
Weigh 96.5gZnAl
2o
4carrier joins containing 0.21g copper chloride (CuCl
2), 5.29g cerous nitrate (Ce (NO
3)
36H
2o), 1.36g gallium nitrate, 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.73g chloroplatinic acid (H again
2ptCl
66H
2and 0.06g ruthenium trichloride (RuCl O)
3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.27% of catalyst weight, the load capacity of Ru is 0.03% of catalyst weight, the load capacity of Cu is 0.1% of catalyst weight, the load capacity of Ce oxide is 2% of catalyst weight, the load capacity of Ga oxide is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst G.
[embodiment 8]
Weigh 96.5gCaAl
2o
4carrier joins containing 0.21g copper chloride (CuCl
2), 5.29g cerous nitrate (Ce (NO
3)
36H
2o), 1.36g gallium nitrate and 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.68g chloroplatinic acid (H again
2ptCl
66H
2and 0.10g rhodium chloride (RhCl O)
3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.25% of catalyst weight, the load capacity of Rh is 0.05% of catalyst weight, the load capacity of Cu is 0.1% of catalyst weight, the load capacity of Ce oxide is 2% of catalyst weight, the load capacity of Ga oxide is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst H.
[embodiment 9]
Weigh 96.5gFeAl
2o
4carrier joins containing 0.13g silver chlorate (AgCl), 13.03g neodymium nitrate (Nd (NO
3)
36H
2o), 0.63g thallous nitrate (TlNO
3), 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.61g chloroplatinic acid (H again
2ptCl
66H
2and 0.12g osmium chloride (OsCl O)
3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.225% of catalyst weight, the load capacity of Os is 0.075% of catalyst weight, the load capacity of Ag is 0.1% of catalyst weight, the load capacity of Nd oxide is 2% of catalyst weight, the load capacity of Tl oxide is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst I.
[embodiment 10]
Weigh 96.5gCoAl
2o
4carrier joins containing 0.13g silver chlorate (AgCl), 13.03g neodymium nitrate (Nd (NO
3)
36H
2o), 1.36g gallium nitrate, 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.41g chloroplatinic acid (H again
2ptCl
66H
2o) and 0.41
gchloro-iridic acid (H
2irCl
66H
2o) in 60 DEG C of incipient impregnations 2 hours in mixed aqueous solution, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.15% of catalyst weight, the load capacity of Ir is 0.15% of catalyst weight, the load capacity of Ag is 0.1% of catalyst weight, the load capacity of Nd oxide is 2% of catalyst weight, the load capacity of Ga oxide is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst J.
[embodiment 11]
Weigh 96.5gZnAl
2o
4carrier joins containing 0.15g gold trichloride (AuCl
3), 6.23g lanthanum nitrate (La (NO
3)
36H
2o), 1.08g indium nitrate (In (NO
3)
3), 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.27g chloroplatinic acid (H again
2ptCl
66H
2and 0.40g rhodium chloride (RhCl O)
3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.1% of catalyst weight, the load capacity of Rh is 0.2% of catalyst weight, the load capacity of Au is 0.1% of catalyst weight, the load capacity of La oxide is 2% of catalyst weight, the load capacity of In oxide is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst K.
[embodiment 12]
Weigh 96.5gZnAl
2o
4carrier joins containing 0.15g gold trichloride (AuCl
3), 5.29g cerous nitrate (Ce (NO
3)
36H
2o), 1.08g indium nitrate (In (NO
3)
3), 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.54g chloroplatinic acid (H again
2ptCl
66H
2and 0.17g palladium bichloride (PdCl O)
2) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.2% of catalyst weight, the load capacity of Pd is 0.1% of catalyst weight, the load capacity of Au is 0.1% of catalyst weight, the load capacity of Ce oxide is 2% of catalyst weight, the load capacity of In oxide is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst L.
[comparative example 1]
Weigh 98.6g γ-Al
2o
3carrier joins containing 1.04g anhydrous stannic chloride (SnCl
4) and 1.35g sodium nitrate (NaNO
3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.81g chloroplatinic acid (H again
2ptCl
66H
2o) in 60 DEG C of incipient impregnations 2 hours in the aqueous solution, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of the load capacity of Pt to be the load capacity of 0.3%, Sn oxide of catalyst weight be 0.6%, Na oxide of catalyst weight is 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst M.
[comparative example 2]
Weigh 96.6gMgAl
2o
4carrier joins containing 6.23g lanthanum nitrate (La (NO
3)
36H
2o), 1.08g indium nitrate (In (NO
3)
3), 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.81g chloroplatinic acid (H again
2ptCl
66H
2o) in 60 DEG C of incipient impregnations 2 hours in the aqueous solution, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of the load capacity of Pt to be the load capacity of 0.3%, La oxide of catalyst weight be 2%, In oxide of catalyst weight is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst n.
[comparative example 3]
Weigh 98.5gZnAl
2o
4carrier joins containing 0.15g gold trichloride (AuCl
3), 1.08g indium nitrate (In (NO
3)
3), 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.81g chloroplatinic acid (H again
2ptCl
66H
2o) in 60 DEG C of incipient impregnations 2 hours in the aqueous solution, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of the load capacity of Pt to be the load capacity of 0.3%, Au of catalyst weight be 0.1%, In oxide of catalyst weight is the load capacity of 0.5%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst O.
[comparative example 4]
Weigh 97.0gMgAl
2o
4carrier joins containing 0.15g gold trichloride (AuCl
3), 6.23g lanthanum nitrate (La (NO
3)
36H
2o), 1.04g anhydrous stannic chloride (SnCl
4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.54g chloroplatinic acid (H again
2ptCl
66H
2and 0.17g palladium bichloride (PdCl O)
2) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.2% of catalyst weight, the load capacity of Pd is 0.1% of catalyst weight, the load capacity of the load capacity of Au to be the load capacity of 0.1%, La oxide of catalyst weight be 2%, Sn oxide of catalyst weight is 0.6% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst P.
[comparative example 5]
Weigh 97.1gMgAl
2o
4carrier joins containing 0.15g gold trichloride (AuCl
3), 6.23g lanthanum nitrate (La (NO
3)
36H
2o), 1.08g indium nitrate (In (NO
3)
3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample.
Products obtained therefrom is joined 0.54g chloroplatinic acid (H again
2ptCl
66H
2and 0.17g palladium bichloride (PdCl O)
2) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 hours in an oven of the sample after dipping.The roasting 4 hours at 600 DEG C in Muffle furnace again of dried sample, then through hydrogen reducing 2 hours at 500 DEG C.
In catalyst, the load capacity of Pt is 0.2% of catalyst weight, the load capacity of Pd is 0.1% of catalyst weight, the load capacity of the load capacity of Au to be the load capacity of 0.1%, La oxide of catalyst weight be 2%, In oxide of catalyst weight is 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, at 500 DEG C, process 2 hours with steam, obtain catalyst Q.
[embodiment 13]
Take 0.5g catalyst A and carry out dehydrogenating propane evaluation.Feeding gas is propane/H
2o=5/3 (vol/vol); Temperature 550 DEG C; Reaction pressure is normal pressure; Alkane mass space velocity is 4.6h
-1carry out activity rating under condition, test result lists in table 1.
Table 1*
| Reaction time (h) | Conversion of propane (%) | Propylene Selectivity (%) |
| 6 | 41.8(30.5) | 93.5(82.3) |
| 10 | 41.7(29.7) | 93.5(80.4) |
| 40 | 40.4(27.1) | 93.1(75.1) |
* be catalyst M data in bracket
[embodiment 14]
Take 0.5g catalyst A ~ Q and carry out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane/H
2=5/2 (vol/vol); Temperature 560 DEG C; Reaction pressure is normal pressure; Alkane mass space velocity is 4.6h
-1carry out activity rating under condition, test result lists in table 2.
Table 2*
| Catalyst | Iso-butane conversion ratio (%) | Selective isobutene (%) |
| A | 51.2 | 92.8 |
| B | 50.3 | 91.7 |
| C | 44.6 | 85.7 |
| D | 52.2 | 85.1 |
| E | 45.7 | 87.5 |
| F | 53.8 | 87.3 |
| G | 51.0 | 92.5 |
[0101]
| H | 50.3 | 92.4 |
| I | 48.7 | 90.1 |
| J | 48.9 | 90.0 |
| K | 50.7 | 91.5 |
| L | 51.0 | 92.2 |
| Comparative example 1 (M) | 32.3 | 81.5 |
| Comparative example 2 (N) | 44.8 | 85.1 |
| Comparative example 3 (O) | 42.8 | 84.2 |
| Comparative example 4 (P) | 45.3 | 82.6 |
| Comparative example 5 (Q) | 41.3 | 83.9 |
* iso-butane conversion ratio and the selective isobutene of 6 hours is reacted
[comparative example 6]
Catalyst regeneration stability contrasts
Take 0.5g catalyst A respectively, 0.5g catalyst M carries out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane/H
2=5/2 (vol/vol); Temperature 560 DEG C; Reaction pressure is normal pressure; Alkane mass space velocity is 4.6h
-1carry out catalytic dehydrogenation activity rating under condition, charging is after 40 hours, regenerates 5 hours at 560 DEG C under air atmosphere, and the catalyst reaction performance after circular response/regeneration 20 times lists in table 3.
Table 3*
* iso-butane conversion ratio and the selective isobutene of 6 hours is reacted.
Claims (10)
1., for a catalyst for dehydrogenating low-carbon alkane producing light olefins, comprise following component by weight percentage:
A) with MO-Al
2o
3the composite oxides of structure are carrier, and wherein M has the+metal of divalent, and carrier is 83 ~ 99.83% of catalyst weight;
B) with one or both in platinum group for active component, described active component is 0.01 ~ 1.0% of catalyst weight;
C) with IB race element for auxiliary agent, described IB race element is 0 ~ 1.0% of catalyst weight;
D) with the oxide of rare earth element for auxiliary agent, described rare earth oxide is 0.01 ~ 10% of catalyst weight;
E) with IIIA race element oxide for auxiliary agent, described IIIA race element oxide is 0.1 ~ 1.0% of catalyst weight;
F) with the oxide of Sn for auxiliary agent, described Sn oxide is 0.05 ~ 4.0% of catalyst weight.
2., according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that described low-carbon alkanes comprises propane and iso-butane.
3., according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that described composite oxide carrier is selected from MgAl
2o
4, ZnAl
2o
4, FeAl
2o
4, CoAl
2o
4, CaAl
2o
4, BaAl
2o
4or SrAl
2o
4in one.
4. according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that in active component, a kind of platinum group is Pt, another kind of platinum group is selected from the one in Ru, Rh, Pd, Os or Ir, and the percentage by weight that active component accounts for catalyst is 0.1 ~ 0.8%.
5., according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that described IB race element is selected from the one in Cu, Ag or Au, IB race element is 0.01 ~ 1.0% of catalyst weight.
6., according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that described rare earth oxide auxiliary agent is selected from the one in La, Ce or Nd, rare earth oxide auxiliary agent is 0.1 ~ 5% of catalyst weight.
7., according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that described IIIA race element auxiliary agent is selected from the one in Ga, In or Tl, the oxide of IIIA race element is 0.1 ~ 0.8% of catalyst weight.
8., according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that the oxide of described Sn is 0.2 ~ 1.6% of catalyst weight.
9., according to claim 1 for the catalyst of dehydrogenating low-carbon alkane producing light olefins, it is characterized in that the preparation method of catalyst comprises following steps:
1) solution of described adjuvant component and described carrier incipient impregnation will be contained, dipping temperature is 10 DEG C ~ 80 DEG C, dip time is 1 ~ 24 hour, drying, roasting is carried out after dipping, baking temperature is 90 DEG C ~ 150 DEG C, drying time is 1 ~ 24 hour, and sintering temperature is 400 DEG C ~ 650 DEG C, and roasting time is 1 ~ 24 hour;
2) solution of active component platinum group and described carrier incipient impregnation will be contained, dipping temperature is 10 DEG C ~ 80 DEG C, dip time is 1 ~ 24 hour, drying, roasting is carried out after dipping, baking temperature is 90 DEG C ~ 150 DEG C, and drying time is 1 ~ 24 hour, and sintering temperature is 400 DEG C ~ 650 DEG C, roasting time is 1 ~ 24 hour, then through hydrogen 400 DEG C ~ 650 DEG C reduction treatments 1 ~ 10 hour.
10. a method for dehydrogenating low-carbon alkane producing light olefins, with low-carbon alkanes and H
2or the gaseous mixture of steam is raw material, reaction temperature is 400 DEG C ~ 600 DEG C, and reaction pressure is 0.08MPa ~ 0.12MPa, and alkane mass space velocity is 3.0 ~ 8.0h
-1, raw material obtains low-carbon alkene with after the catalyst exposure reaction described in any one of claim 1 ~ 8.
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