CN105363472A - Low-carbon olefin catalyst made through dehydrogenation of low-carbon alkane and use method of low-carbon olefin catalyst - Google Patents
Low-carbon olefin catalyst made through dehydrogenation of low-carbon alkane and use method of low-carbon olefin catalyst Download PDFInfo
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- CN105363472A CN105363472A CN201410428896.3A CN201410428896A CN105363472A CN 105363472 A CN105363472 A CN 105363472A CN 201410428896 A CN201410428896 A CN 201410428896A CN 105363472 A CN105363472 A CN 105363472A
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Abstract
The invention relates to a low-carbon alkane dehydrogenation platinum catalyst and a use method thereof and mainly solves the problems that in an existing preparation method, the catalyst conversion rate is low, and the selectivity is lowered in the use process. According to the low-carbon alkane dehydrogenation platinum catalyst and the use method thereof, firstly, a coprecipitation method is adopted for introducing copper, nickel, manganese, cobalt and other transition metal elements into a zinc aluminate carrier, and a composite metal oxide carrier is obtained; then an impregnation method is adopted, platinum components are loaded, in other words, a water solution of soluble salt of platinum is dipped, and the platinum catalyst is obtained after drying, baking and stream treatment. Propane/iso-butane serve as raw materials, the raw materials are in contact with the catalyst in the conditions that the reaction temperature is 520-620 DEG C, the reaction pressure is 0-0.4 MPa, the alkane mass airspeed is 0.1-8.0 h<-1>, the H<2>O/C<n>H<2n+2> volume ratio is 1-18, a reaction is condnucted, and propane/iso-butane are generated, by means of the technical scheme, the problem is well solved, and the low-carbon alkane dehydrogenation platinum catalyst and the use method thereof can be used for industrial application of low-carbon olefin catalysts made through dehydrogenation of low-carbon alkane.
Description
Technical field
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins and using method thereof.
Background technology
Propylene/isobutene mainly from coproduction or the by-product of steam cracking and refinery factory fluid catalytic cracking process, can be widely used in synthetic polymer, gasoline additive, rubber and various chemical intermediate.Growing with low-carbon alkene demand, what traditional production process was difficult to meet the need of market increases rapidly.The a large amount of low-carbon alkanes obtained by oil plant are main components of liquefied petroleum gas, are mainly used as domestic fuel.Develop and opened up new alkene by low-carbon alkanes preparing low-carbon olefins process originate significant for making full use of low-carbon alkanes.At present, alkane catalytic dehydrogenation technology with the Catofin technique of the Oleflex technique of Uop Inc. and Lummus company for representative.The domestic process units still not having the dehydrogenating low-carbon alkane producing light olefins of independent intellectual property right.
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.The disclosed catalyst of Chinese patent (CN200710025372.X), be the preparation method of platinum-impregnated tin component on carrier at alumina modified mesoporous molecular sieve, conversion of propane is only 17%, Propylene Selectivity 93%; Chinese patent (CN200710023431.X) adopts the method for Hydrothermal Synthesis that tin is introduced ZSM-5 molecular sieve carrier, and by infusion process Supported Pt Nanoparticles component, after this catalyst runs 100 hours, conversion of propane is higher than 30%, Propylene Selectivity 99%, but this patent does not provide the stability data of coke-burning regeneration process.Chinese patent (CN200710020064.8) and (CN200710133324.2) disclose a kind of platinum-tin catalyst and react for dehydrogenating propane, have employed the preparation method of tin component and platinum component total immersion stain, carrier is that Y type, ZSM-5 etc. are containing Na molecular sieve, after catalyst runs 720 hours continuously, conversion of propane 30.5%, Propylene Selectivity 96.4%, but activity decrease half after twice coke-burning regeneration.U.S. patents disclose and adopt zinc aluminate spinel to be the aluminate carrier Pt catalyst (US3957688 that the auxiliary agent such as the Pt catalyst (US5430220) of carrier and Au, Ag promotes; US4041099; US5073662), all there is low conversion rate in catalyst, the problem of in use selective decline.
Above-mentioned catalyst all have employed the active component that aluminium oxide or aluminate carry out supported catalyst, and the activity of the catalyst in applied at elevated temperature process or after coke-burning regeneration is not high, and selectively in running declines gradually.The compound aluminate carrier with the transition metal modification close with zinc atom radius is adopted to have no report for the preparation of the document of dehydrogenating low-carbon alkane producing light olefins platinum-tin catalyst.
Summary of the invention
It is not high that one of technical problem to be solved by this invention is that existing catalyst exists the activity of the catalyst in applied at elevated temperature process or after coke-burning regeneration, and in running the selective problem declined gradually; There is provided a kind of a kind of dehydrogenating low-carbon alkane platinum catalyst vector newly, this catalyst is used for dehydrogenating low-carbon alkane preparing low carbon olefin hydrocarbon, and have under high temperature and coke-burning regeneration condition, Catalyst Conversion is high, the advantage that selective maintenance is stable.Two of technical problem to be solved by this invention is to provide a kind of preparation method of the catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of dehydrogenating low-carbon alkane prepares the catalyst of low-carbon alkene, in catalyst weight percent, comprises following component:
A) be selected from least one in ruthenium in platinum metal, rhodium, palladium, osmium, iridium or platinum, count 0.01 ~ 1.5% of catalyst weight with simple substance;
B) be selected from least one element in the periodic table of elements I A or II A race or its compound, count 0.05 ~ 35.0% of catalyst weight with simple substance;
C) zinc aluminate carrier, carrier accounts for 63.5 ~ 94.9% of catalyst weight.
In technique scheme, carrier preferably forms coincidence formula: Zn
xm
yal
2o
4, wherein M is one or more in transition metal Ni, Cu, Co, Mn, Cr or Ge, and x+y=1,0.5≤x < 1; Carrier by weight percentage, comprises following component:
A) Al, counts 26.0 ~ 33.0% of vehicle weight with simple substance;
B) Zn, counts 10.0 ~ 35.0% of vehicle weight with simple substance;
C) M, counts 0.1 ~ 20.0% of vehicle weight with simple substance.
In technique scheme, the metal ion radius preferable range of M representative is 0.06 ~ 0.08nm; Preferred carrier has spinel structure; The carrier surface acidity adopting indicator method to record is preferably lower than 0.35mmol/g; M/Zn ratio be preferably 0 < M/Zn≤1; The pore volume preferable range of carrier is 0.06 ~ 0.8cm
3/ g, specific area preferable range is 20 ~ 220m
2/ g.
Carrier can make different shapes as required, as cylindric, spherical, sheet, tubular, Raschig ring or cellular etc., but cylindrical and spherical be reasonable selection, its effective diameter is at 1 ~ 6mm, so that commercial Application.
For solve the problems of the technologies described above two, the preparation method of catalyst comprises the following steps:
A) soluble compound of the nitric hydrate aluminium of aequum, nitric hydrate zinc and transition metal M is configured
Become the aqueous solution I, wherein M is selected from one of Ni, Cu, Co, Mn, Cr, Ge transition metal
Kind or several, Al:(Zn+M) amount of substance ratio is 1.5 ~ 2.5:1;
B) aqueous solution II of the water soluble alkali of configuration quality percent concentration scope 1 ~ 30%, water soluble alkali is selected from least one of NaOH, potassium hydroxide, ammoniacal liquor, carbonic acid ammonia;
C) under the precipitation temperature of 0 ~ 50 DEG C, solution I is added in solution II, after control ph 5.5 ~ 8.5 filtration, washing, this is deposited in 50 ~ 150 DEG C of oven dry under stirring condition, then 650 ~ 1000 DEG C of roastings 1 ~ 24 hour, obtains compound zinc aluminate carrier.
D) adopt infusion process load active component on complex carrier, the chloroplatinate of aequum is configured to the aqueous solution, on carrier, floods after 1 ~ 48 hour, after drying, obtain catalyst precarsor; Catalyst precarsor obtains dehydrogenating low-carbon alkane producing light olefins catalyst after roasting, reduction.。
In technique scheme, the preferable range of precipitation temperature is 15 ~ 40 DEG C; Under stirring condition, control ph preferable range is 6.5 ~ 8.0.
Dehydrogenating low-carbon alkane prepares a method for low-carbon alkene, adopts propane and/or iso-butane to be raw material, reaction temperature 520 ~ 620 DEG C, and reaction pressure 0 ~ 0.4MPa, alkane mass space velocity 0.1 ~ 8.0h
-1, H
2o/C
nh
2n+2volume ratio is under 1 ~ 18 condition, and described in raw material and technique scheme, catalyst exposure reacts and generates propylene and/or isobutene.
Present invention employs coprecipitation and prepare compound zinc aluminate carrier, easily form MAl at the alumina support of the transition metal compound containing the metal such as magnesium, zinc
2o
4the spinel structure of type, there is a large amount of oxygen ion holes in the carrier of this structure, and after producing such lattice defect, the effect between platinum particle and alumina support strengthens, and is conducive to metallic decentralization is higher, distributes more even.But trivalent aluminium ion easily forms stronger Lewis acid centers, cause catalyst excessively strong to the activation of reactant in course of reaction, low conversion rate, also easily produces carbon deposit simultaneously, selectively while catalyst activity reduction also reduces.The acid site density (acidity) of carrier and the structure of catalyst, form relevant.The present invention makes the acidity of zinc aluminate carrier effectively reduce by the method for adding support modification auxiliary agent.Adopt the metal ion close with the ionic radius of zinc ion as the auxiliary agent of support modification, ionic radius close to making auxiliary agent more easily enter the lattice of ZnO, thus causes the imbalance of lattice deformability and distribution of charges, and causes the decline of acidity.
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.Adopt the catalyst that obtains of this method at 550 DEG C, normal pressure, iso-butane alkane mass space velocity 4.6 hours
-1, H
2o/C
4h
10for using under 8:1 condition, initial conversion is higher than 50%, and selective stable, higher than 94%, through repeatedly regenerating, metallic can maintain below 3nm, achieves good technique effect.
The catalyst prepared adopts Hammett indicator titration method measured surface acid site density (total acidity of different acid strength).The method measuring principle is as follows:
Represent the Hammett indicator of alkalescence with B, when it adsorbs on the surface of the catalyst, occurring to interact to the H+ on surface generates corresponding conjugate acid BH+:
B+H+＝＝＝＝BH+
Solid acid powder sample is suspended in non-water inert fluid, carries out titration by means of indicator alkali.Titration alkali used must be the alkali stronger than indicator, usually adopts pKa value to be about the n-butylamine of+10.First the alkali added be adsorbed on the strongest acidic site, and finally replace indicator molecules from solid.This experiment standard n-butylamine-cyclohexane solution titration solid acid, thus obtain acid amount.When certain indicator be adsorbed on solid acid becomes acid type look time, make indicator return to the titer of the n-butylamine needed for alkaline look, be the tolerance of solid acid acid site number on the surface.The overall result of B acid that what the method measured is and L acid.
Below by embodiment, the present invention is further elaborated.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction spectrogram of compound zinc aluminate carrier, its characteristic diffraction peak 2 θ=31.2 ± 0.2 °, 36.8 ± 0.2 °, 44.9 ± 0.2 °, 49.0 ± 0.2 °, 55.5 ± 0.2 °, 59.3 ± 0.2 °, 65.2 ± 0.2 °, 74.0 ± 0.2 °, 77.2 ± 0.2 °.
Detailed description of the invention
[embodiment 1]
Get 754.56g aluminum nitrate (Al (NO
3)
39H
2o), 245.81g zinc nitrate (Zn (NO
3)
26H
2o), 48.44g nickel nitrate (Ni (NO
3)
26H
2o) be dissolved in 2000ml deionized water; At 25 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 15% weight in this mixed aqueous solution, form precipitation, control ph is 6.5, after will being deposited in overnight at room temperature, filter, washing, in 110 DEG C of oven dry, pulverize, after sieving, 720 DEG C of roastings 18 hours, obtain compound zinc aluminate carrier.XRD characterizes (see Fig. 1) and illustrates that carrier has typical spinel structure, pore volume 0.34cm
3/ g, specific area 86m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of sodium nitrate (5.6g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as A.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 2]
Get 755.30g aluminum nitrate (Al (NO
3)
39H
2o), 167.51g zinc nitrate (Zn (NO
3)
26H
2o), 108.10g copper nitrate (Cu (NO
3)
26H
2o) be dissolved in 2000ml deionized water; At 20 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 16%wt. in this mixed aqueous solution, form precipitation, control ph is 7.5, after will being deposited in overnight at room temperature, filter, washing, in 100 DEG C of oven dry, pulverize, after sieving, 700 DEG C of roastings 10 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.32cm
3/ g, specific area 80m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of lithium nitrate (7.2g), then 80 DEG C of oven dry, 550 DEG C of roastings 3 hours in the air stream, then at 550 DEG C, 4 hours are processed with steam, finally logical dry air 550 DEG C process 1 hour.Gained catalyst is designated as B.
Sample is with hydrogen before dehydrogenation reaction, and 520 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 3]
Get 753.33g aluminum nitrate (Al (NO
3)
39H
2o), 154.65g zinc nitrate (Zn (NO
3)
26H
2o), 139.69g cobalt nitrate (Co (NO
3)
26H
2o) be dissolved in 2000ml deionized water; At 20 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 20%wt. in this mixed aqueous solution, form precipitation, control ph is 7.4, after will being deposited in overnight at room temperature, filter, washing, in 100 DEG C of oven dry, pulverize, after sieving, 750 DEG C of roastings 5 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.35cm
3/ g, specific area 51m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of lithium nitrate (6.3g), then 70 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as C.
Sample is with hydrogen before dehydrogenation reaction, and 520 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[comparative example 4]
Get 756.36g aluminum nitrate (Al (NO
3)
39H
2o), 278.63g zinc nitrate (Zn (NO
3)
26H
2o), 22.37g cobalt nitrate (Co (NO
3)
26H
2o) be dissolved in 2000ml deionized water; At 23 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 20%wt. in this mixed aqueous solution, form precipitation, control ph is 7.6, after will being deposited in overnight at room temperature, filter, washing, in 100 DEG C of oven dry, pulverize, after sieving, 750 DEG C of roastings 5 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.55cm
3/ g, specific area 151m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of lithium nitrate (9.1g), then 70 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as D.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 5]
Get 753.36g aluminum nitrate (Al (NO
3)
39H
2o), 223.20g zinc nitrate (Zn (NO
3)
26H
2o), 72.82g cobalt nitrate (Co (NO
3)
26H
2o) be dissolved in 2000ml deionized water; At 26 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 20%wt. in this mixed aqueous solution, form precipitation, control ph is 7.0, after will being deposited in overnight at room temperature, filter, washing, in 100 DEG C of oven dry, pulverize, after sieving, 750 DEG C of roastings 5 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.43cm
3/ g, specific area 117m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of lithium nitrate (8.0g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as E.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 6]
Get 754.33g aluminum nitrate (Al (NO
3)
39H
2o), 197.30g zinc nitrate (Zn (NO
3)
26H
2o), 86.34g manganese nitrate (Mn (NO
3)
24H
2o) be dissolved in 2000ml deionized water; At 25 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 22%wt. in this mixed aqueous solution, form precipitation, control ph is 6.5, after will being deposited in overnight at room temperature, filter, washing, in 70 DEG C of oven dry, pulverize, after sieving, 850 DEG C of roastings 3 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.15cm
3/ g, specific area 42m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of lithium nitrate (4.2g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as F.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 7]
Get 753.36g aluminum nitrate (Al (NO
3)
39H
2o), 205.26g zinc nitrate (Zn (NO
3)
26H
2o), 124.05g chromic nitrate (Cr (NO
3)
24H
2o) be dissolved in 2000ml deionized water; At 22 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 22%wt. in this mixed aqueous solution, form precipitation, control ph is 7.2, after will being deposited in overnight at room temperature, filter, washing, in 100 DEG C of oven dry, pulverize, after sieving, 850 DEG C of roastings 3 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.25cm
3/ g, specific area 68m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of calcium nitrate (8.2g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as G.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 8]
Get 752.15g aluminum nitrate (Al (NO
3)
39H
2o), 183.45g zinc nitrate (Zn (NO
3)
26H
2o), 38.86g germanium oxide (GeO
2) be dissolved in 2000ml deionized water; At 34 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 15%wt. in this mixed aqueous solution, form precipitation, control ph is 8.3, after will being deposited in overnight at room temperature, filter, washing, in 120 DEG C of oven dry, pulverize, after sieving, 750 DEG C of roastings 6 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.35cm
3/ g, specific area 98m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of lithium nitrate (6.6g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as H.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 9]
Get 753.36g aluminum nitrate (Al (NO
3)
39H
2o), 157.66g zinc nitrate (Zn (NO
3)
26H
2o), 62.75g manganese nitrate (Mn (NO
3)
24H
2o), 64.03g cobalt nitrate (Co (NO
3)
26H
2o) be dissolved in 2000ml deionized water; At 26 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 15 % by weight in this mixed aqueous solution, form precipitation, control ph is 7.6, after will being deposited in overnight at room temperature, filter, washing, in 120 DEG C of oven dry, pulverize, after sieving, 750 DEG C of roastings 8 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.36cm
3/ g, specific area 108m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of sodium nitrate (7.0g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as I.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 10]
Get 752.20g aluminum nitrate (Al (NO
3)
39H
2o), 181.21g zinc nitrate (Zn (NO
3)
26H
2o), 92.26g cadmium nitrate (Cd (NO
3)
2) be dissolved in (containing 0.001mol/LHCl) in 2000ml deionized water; At 26 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 15 % by weight in this mixed aqueous solution, form precipitation, control ph is 7.4, after will being deposited in overnight at room temperature, filter, washing, in 120 DEG C of oven dry, pulverize, after sieving, 750 DEG C of roastings 8 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.30cm
3/ g, specific area 92m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of sodium nitrate (5.1g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as J.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[embodiment 11]
Get 752.27g aluminum nitrate (Al (NO
3)
39H
2o), 98.17g zinc nitrate (Zn (NO
3)
26H
2o), 161.87g copper nitrate (Cu (NO
3)
2) be dissolved in 2000ml deionized water; At 26 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 15 % by weight in this mixed aqueous solution, form precipitation, control ph is 7.0, after will being deposited in overnight at room temperature, filter, washing, in 120 DEG C of oven dry, pulverize, after sieving, 750 DEG C of roastings 8 hours, obtain compound zinc aluminate carrier.XRD characterizes and illustrates that carrier has typical spinel structure, pore volume 0.42cm
3/ g, specific area 125m
2/ g.Carrier composition and acidity are in table 1.
The carrier obtained adopts platinum component in dipping technique load, namely at room temperature floods containing chloroplatinic acid (H with the carrier 15.0g of gained
2ptCl
66H
2o, 0.16g) and the aqueous solution (10ml) 24 hours (metal platinum carrying capacity 0.4%) of calcium nitrate (10.2g), then 60 DEG C of oven dry, 530 DEG C of roastings 3 hours in the air stream, then at 530 DEG C, 4 hours are processed with steam, finally logical dry air 530 DEG C process 1 hour.Gained catalyst is designated as K.
Sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.
[comparative example 1]
Prepare carrier and catalyst by the method for embodiment 1, difference carrier precipitation process does not add modified additive component.
Table 1
After adding metal promoter, catalyst surface acidity declines obviously.
[embodiment 10 ~ 18]
The catalyst that embodiment 1 ~ 9 obtains at 550 DEG C, normal pressure, iso-butane mass space velocity 4.6 hours
-1, H
2o/C
3h
8volume ratio is evaluate under 8:1 condition, the results are shown in Table 2.
Table 2*
| Embodiment | Catalyst | 1 hour | 10 hours |
| Conversion ratio % | Selective % | Conversion ratio % | Selective % | ||
| 10 | A | 40.6 | 92.6 | 30.4 | 93.5 |
| 11 | B | 43.6 | 93.8 | 32.9 | 95.6 |
| 12 | C | 51.8 | 94.0 | 42.3 | 95.0 |
| 13 | D | 44.3 | 93.2 | 33.2 | 94.9 |
| 14 | E | 49.9 | 93.1 | 38.3 | 95.1 |
| 15 | F | 43.8 | 93.0 | 34.4 | 95.7 |
| 16 | G | 46.2 | 93.0 | 36.4 | 95.4 |
| 17 | H | 47.3 | 93.7 | 35.8 | 95.9 |
| 18 | I | 48.1 | 94.2 | 36.4 | 95.6 |
| 19 | J | 34.3 | 92.1 | 25.2 | 94.3 |
| 20 | K | 32.5 | 94.5 | 21.6 | 95.9 |
| 21 | Comparative example | 30.5 | 91.6 | 15.1 | 86.4 |
Adopt platinum-tin catalyst prepared by common zinc aluminate, acidity is higher, and performance is more unstable, and 10 hours selective attenuations are obvious, and the catalyst performance adopting complex carrier to prepare and stability significantly improve, and selectively slightly improves after operation.
[embodiment 20]
By each Step By Condition Kaolinite Preparation of Catalyst in embodiment 1 and examination catalyst, sample is with hydrogen before dehydrogenation reaction, and 500 DEG C of reduction activations 90 minutes, react for dehydrogenation of isobutane.Catalyst at 550 DEG C, normal pressure, iso-butane mass space velocity 4.6 hours
-1, H
2o/C
4h
10after reacting 10 hours under 8:1 condition, adopt 1% air to make charcoal at 500 DEG C and make catalyst regeneration in 60 minutes, the initial performance after catalyst repeatedly regenerates is as shown in table 3.
Table 3
[embodiment 21 ~ 26]
Embodiment 5 is carried out performance evaluation under differential responses process conditions, the results are shown in Table 4.
Table 4
Claims (10)
1. dehydrogenating low-carbon alkane prepares a catalyst for low-carbon alkene, in catalyst weight percent, comprises following component:
A) be selected from least one in ruthenium in platinum metal, rhodium, palladium, osmium, iridium or platinum, count 0.01 ~ 1.5% of catalyst weight with simple substance;
B) be selected from least one element in the periodic table of elements I A or II A race or its compound, count 0.05 ~ 35.0% of catalyst weight with simple substance;
C) zinc aluminate carrier, carrier accounts for 63.5 ~ 94.9% of catalyst weight.
2. dehydrogenating low-carbon alkane according to claim 1 prepares the catalyst of low-carbon alkene, it is characterized in that described carrier composition coincidence formula: Zn
xm
yal
2o
4, wherein M is selected from one or more in transition metal Ni, Cu, Co, Mn, Cr or Ge, and x+y=1; Carrier by weight percentage, comprises following component:
A) Al, counts 26.0 ~ 33.0% of vehicle weight with simple substance;
B) Zn, counts 10.0 ~ 35.0% of vehicle weight with simple substance;
C) M, counts 0.1 ~ 20.0% of vehicle weight with simple substance.
3. dehydrogenating low-carbon alkane according to claim 2 prepares the catalyst of low-carbon alkene, it is characterized in that 0.5≤x < 1.
4. dehydrogenating low-carbon alkane according to claim 2 prepares the catalyst of low-carbon alkene, it is characterized in that metal ion radius that M represents is between 0.060 ~ 0.080nm.
5. dehydrogenating low-carbon alkane according to claim 2 prepares the catalyst of low-carbon alkene, it is characterized in that the support acidity adopting indicator method to record is lower than 0.35mmol/g.
6. dehydrogenating low-carbon alkane according to claim 2 prepares the catalyst of low-carbon alkene, it is characterized in that 0 < M/Zn≤1.
7. dehydrogenating low-carbon alkane according to claim 2 prepares the catalyst of low-carbon alkene, it is characterized in that the pore volume 0.08 ~ 0.6cm of carrier
3/ g, specific area 20 ~ 220m
2/ g.
8. the dehydrogenating low-carbon alkane described in any one of claim 1 ~ 7 prepares the preparation method of the catalyst of low-carbon alkene, comprises the following steps:
A) soluble-salt of the nitric hydrate aluminium of aequum, nitric hydrate zinc and transition metal M is configured to the aqueous solution I, wherein M is selected from one or more in Ni, Cu, Co, Mn, Cr or Ge, Al:(Zn+M) amount of substance ratio is 1.5 ~ 2.5:1;
B) aqueous solution II of the water soluble alkali of configuration quality percent concentration scope 1 ~ 30%, water soluble alkali is selected from least one in NaOH, potassium hydroxide, ammoniacal liquor or carbonic acid ammonia;
C) under the precipitation temperature of 0 ~ 50 DEG C, solution I is added in solution II, control ph 5.5 ~ 8.5 under stirring condition, after filtration, washing, this is deposited in 50 ~ 150 DEG C of oven dry, then 650 ~ 1000 DEG C of roastings 1 ~ 24 hour, compound zinc aluminate carrier is obtained;
D) adopt infusion process load active component on complex carrier, the chloroplatinate of aequum is configured to the aqueous solution, on carrier, floods after 1 ~ 48 hour, after drying, obtain catalyst precarsor; Dehydrogenating low-carbon alkane producing light olefins catalyst is obtained after catalyst precarsor roasting, reduction.
9. dehydrogenating low-carbon alkane according to claim 8 prepares the preparation method of the catalyst of low-carbon alkene, it is characterized in that the pH value of precipitation process is 6.5 ~ 8.0; Precipitation temperature is at 15 ~ 40 DEG C.
10. dehydrogenating low-carbon alkane prepares a method for low-carbon alkene, adopts propane and/or iso-butane to be raw material, reaction temperature 520 ~ 620 DEG C, and reaction pressure 0 ~ 0.4MPa, alkane mass space velocity 0.1 ~ 8.0h
-1, H
2o/C
nh
2n+2volume ratio is under 1 ~ 18 condition, and described in raw material and any one of claim 1 ~ 7, catalyst exposure reacts and generates propylene and/or isobutene.
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