CN105363472B - Dehydrogenating low-carbon alkane producing light olefins catalyst and its application method - Google Patents
Dehydrogenating low-carbon alkane producing light olefins catalyst and its application method Download PDFInfo
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- CN105363472B CN105363472B CN201410428896.3A CN201410428896A CN105363472B CN 105363472 B CN105363472 B CN 105363472B CN 201410428896 A CN201410428896 A CN 201410428896A CN 105363472 B CN105363472 B CN 105363472B
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Abstract
The present invention relates to a kind of dehydrogenating low-carbon alkane platinum catalyst and its application method, mainly solves the problem of Catalyst Conversion is low, and selectivity declines in use in existing technology of preparing be present.The present invention is first introduced the transition metals such as copper, nickel, manganese, cobalt among zinc aluminate carrier using coprecipitation, obtain metal composite oxide carrier, then infusion process Supported Pt Nanoparticles component component is used, that is the aqueous solution of the soluble-salt of platinum-impregnated, platinum catalyst is obtained after drying, roasting, steam treatment.It is raw material by using propane/iso-butane, in 520~620 DEG C, 0~0.4MPa of reaction pressure of reaction temperature, 0.1~8.0h of alkane mass space velocity‑1, H2O/CnH2n+2Volume ratio be 1~18 under the conditions of, raw material contacts with catalyst, reaction generate propylene/isobutene technical scheme, preferably solve the problem, available for dehydrogenating low-carbon alkane producing light olefins catalyst it is industrially prepared in.
Description
Technical field
The present invention relates to a kind of catalyst and its application method for dehydrogenating low-carbon alkane producing light olefins.
Background technology
Coproduction or by-product of the propylene/isobutene essentially from steam cracking and refinery factory fluid catalytic cracking process, can be wide
It is general to be used for synthetic polymer, gasoline additive, rubber and various chemical intermediates.It is growing with low-carbon alkene demand,
Traditional production process is difficult to meet increasing rapidly for the market demand.The a large amount of low-carbon alkanes obtained by oil plant are liquefied petroleums
The main component of gas, is mainly used as domestic fuel.Exploitation is by low-carbon alkanes preparing low-carbon olefins process for making full use of low-carbon
It is significant that alkane opens up new alkene source.At present, alkane catalytic dehydrogenation technology is with the Oleflex techniques of Uop Inc.
Catofin techniques with Lummus companies are representative.The dehydrogenating low-carbon alkane low-carbon alkene of domestic still no independent intellectual property right
The process units of hydrocarbon.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, is developed high living
Property, the catalyst of high selectivity and high stability turn into the key of the technology.Chinese patent (CN200710025372.X) is open
Catalyst, alumina modified mesoporous molecular sieve be carrier on platinum-impregnated tin component preparation method, conversion of propane is only
For 17%, Propylene Selectivity 93%；Chinese patent (CN200710023431.X) is drawn tin using using the method for Hydrothermal Synthesiss
Enter ZSM-5 molecular sieve carrier, and with infusion process Supported Pt Nanoparticles component, after the catalyst is run 100 hours, conversion of propane is higher than
30%, Propylene Selectivity 99%, but the patent does not provide the stability data of coke-burning regeneration process.Chinese patent
(CN200710020064.8) and (CN200710133324.2) discloses a kind of platinum-tin catalyst and reacted for dehydrogenating propane, adopts
With tin component and the preparation method of platinum component co-impregnation, carrier is that molecular sieve containing Na, the catalyst such as Y types, ZSM-5 are continuously run
After 720 hours, conversion of propane 30.5%, Propylene Selectivity 96.4%, but activity decrease half after coke-burning regeneration twice.The U.S.
Patent discloses the aluminium for using zinc aluminate spinel to promote for auxiliary agents such as the Pt catalyst (US5430220) of carrier and Au, Ag
Hydrochlorate carrier Pt catalyst (US3957688；US4041099；US5073662), it is low all to there is conversion ratio in catalyst, was using
The problem of selectively declining in journey.
Above-mentioned catalyst employs aluminum oxide or aluminate carrys out the active component of supported catalyst, in applied at elevated temperature process
In or coke-burning regeneration after catalyst activity it is not high, and in the process of running selectivity be gradually reduced.Using having and zinc
The compound aluminate carrier that the close transition metal of atomic radius is modified is used to prepare dehydrogenating low-carbon alkane producing light olefins
The document of platinum-tin catalyst has no report.
The content of the invention
One of technical problems to be solved by the invention are that existing catalyst is present during applied at elevated temperature or coke-burning regeneration
The problem of activity of catalyst afterwards is not high, and selectivity is gradually reduced in the process of running；There is provided a kind of new a kind of low
Carbon alkane dehydrogenation platinum catalyst vector, the catalyst are used for dehydrogenating low-carbon alkane preparing low carbon olefin hydrocarbon, have in high temperature and
Under the conditions of coke-burning regeneration, Catalyst Conversion is high, and selectivity is kept for the advantages of stable.The technical problems to be solved by the invention it
Two be to provide it is a kind of with solving the preparation method of the corresponding catalyst of one of technical problem.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：It is prepared by a kind of dehydrogenating low-carbon alkane
The catalyst of low-carbon alkene, in terms of catalyst weight percent, including following components：
A) at least one of ruthenium, rhodium, palladium, osmium, iridium or platinum in platinum metal, catalyst weight is calculated as with simple substance
0.01~1.5%；
B) at least one of the A of the periodic table of elements I or II A races element or its compound are selected from, catalyst is calculated as with simple substance
The 0.05~35.0% of weight；
C) zinc aluminate carrier, carrier account for the 63.5~94.9% of catalyst weight.
In above-mentioned technical proposal, carrier preferably constitutes coincidence formula：ZnxMyAl2O4, wherein M be transition metal Ni,
One or more in Cu, Co, Mn, Cr or Ge, and x+y=1,0.5≤x ＜ 1；Carrier by weight percentage, including with
Lower component：
A) Al, 26.0~33.0% that vehicle weight is calculated as with simple substance；
B) Zn, 10.0~35.0% that vehicle weight is calculated as with simple substance；
C) M, 0.1~20.0% that vehicle weight is calculated as with simple substance.
In above-mentioned technical proposal, the metal ion radius preferred scope that M is represented is 0.06~0.08nm；Preferable carrier tool
There is spinel structure；The carrier surface acidity measured using indicator method is preferably less than 0.35mmol/g；M/Zn ratios it is excellent
Elect 0 ＜ M/Zn≤1 as；The pore volume preferred scope of carrier is 0.06~0.8cm3/ g, specific surface area preferred scope are 20~220m2/
g。
Different shapes can be made as needed for carrier, such as cylindric, spherical, sheet, tubular, Raschig ring or cellular
Deng, but it is cylindrical and it is spherical be relatively good selection, its effective diameter is in 1~6mm, in order to commercial Application.
To solve the two of above-mentioned technical problem, the preparation method of catalyst comprises the following steps：
A) soluble compound of the desired amount of nitric hydrate aluminium, nitric hydrate zinc and transition metal M is configured
Into the aqueous solution I, wherein M is selected from the one of Ni, Cu, Co, Mn, Cr, Ge transition metal
Kind or several, Al:(Zn+M) the amount ratio of material 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 are selected from hydrogen-oxygen
Change sodium, potassium hydroxide, ammoniacal liquor, at least one of carbonic acid ammonia；
C) under 0~50 DEG C of precipitation temperature, solution I is added in solution II, control ph 5.5 under stirring condition~
This is deposited in 50~150 DEG C of drying after 8.5 filterings, washing, is then calcined 1~24 hour, obtains compound at 650~1000 DEG C
Zinc aluminate carrier.
D) infusion process load active component on complex carrier is used, the desired amount of chloroplatinate is configured to the aqueous solution,
On carrier, dipping obtains catalyst precarsor after 1~48 hour after drying；Catalyst precarsor obtains low after being calcined, reducing
Carbon alkane dehydrogenation producing light olefins catalyst..
In above-mentioned technical proposal, the preferred scope of precipitation temperature is 15~40 DEG C；The preferred model of control ph under stirring condition
Enclose for 6.5~8.0.
A kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, propane and/or iso-butane are used as raw material, in reaction temperature
520~620 DEG C, 0~0.4MPa of reaction pressure of degree, 0.1~8.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 1~18
Under the conditions of, raw material and the generation propylene of catalyst haptoreaction described in above-mentioned technical proposal and/or isobutene.
Present invention employs coprecipitation to prepare compound zinc aluminate carrier, is answered in the transition metal containing metals such as magnesium, zinc
The alumina support of conjunction easily forms MAl2O4The spinel structure of type, substantial amounts of oxonium ion on the carrier of this structure be present
Hole, after lattice defect as generation, the effect enhancing between platinum particle and alumina support, be advantageous to obtain clipped wire
Sub- decentralization is higher, and distribution is more uniform.But trivalent aluminium ion easily forms stronger Lewis acid centers, causes catalyst to exist
Activation of the course of reaction to reactant is too strong, and conversion ratio is low, while is also easy to produce carbon deposit, selects while catalyst activity reduction
Selecting property also reduces.The acid site density (acidity) of carrier is relevant with the structure of catalyst, composition.The present invention is changed by adding carrier
The method of property auxiliary agent causes the acidity of zinc aluminate carrier effectively to reduce.Using the metal ion close with the ionic radius of zinc ion
As the auxiliary agent of support modification, ionic radius close to causing auxiliary agent to be easier the lattice into ZnO, so as to cause lattice deformability and
The imbalance of distribution of charges, and cause the decline of acidity.
Dehydrogenating low-carbon alkane reaction is continuously being carried out on the flowing miniature catalyst reaction device of quartz tube reactor.Product analysis
Using HP-5890 gas chromatographs (HP-AL/S capillary columns, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis takes off
Alkane, olefin(e) centent in hydrogen product simultaneously calculate conversion ratio, selectivity and the yield of reaction.The catalysis obtained using this method
Agent is at 550 DEG C, normal pressure, iso-butane alkane mass space velocity 4.6 hours-1, H2O/C4H10For 8:Used under the conditions of 1, initial conversion is high
In 50%, selectivity is stable, higher than 94%, can maintain below 3nm through repeatedly regeneration, metallic, achieve good skill
Art effect.
The catalyst being prepared uses Hammett indicator titration method measurement surfaces acid site density (different acid strengths
Total acidity).This method measuring principle is as follows：
The Hammett indicator of alkalescence is represented with B, when it is adsorbed on the surface of the catalyst, is sent out with the H+ on surface
Raw interaction generates corresponding conjugate acid BH+：
B+H+====BH+
Solid acid powder sample is suspended in non-aqueous inert fluid, titrated by means of indicator with alkali.Titration institute
Alkali must be the alkali more stronger than indicator, and generally use pKa value is about+10 n-butylamine.The alkali of addition adsorbs first
On most strong acidic site, and finally substitute indicator molecules from solid.This experiment standard n-butylamine-cyclohexane solution
Solid acid is titrated, so as to obtain sour amount.When the absorption of certain indicator is becoming acid type color on solid acid, indicator is set to return to alkali
The titer of n-butylamine needed for type color, the measurement of acid site number as on solid acid surfaces.What this method was determined is B acid
With the overall result of L acid.
Below by embodiment, the present invention is further elaborated.
Brief description of the drawings
Fig. 1 be compound zinc aluminate carrier XRD diffraction spectrograms, its θ=31.2 ± 0.2 ° of characteristic diffraction peak 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°。
Embodiment
【Embodiment 1】
Take 754.56g aluminum nitrates (Al (NO3)39H2O), 245.81g zinc nitrates (Zn (NO3)26H2O), 48.44g nickel nitrates
(Ni(NO3)26H2O) it is dissolved in 2000ml deionized waters；At 25 DEG C, it is stirred vigorously down, the ammoniacal liquor of 15% weight is slowly added dropwise
Into the mixed aqueous solution, precipitation is formed, control ph 6.5, after precipitation is stayed overnight at room temperature, is filtered, washing, in 110
DEG C drying, crush, after sieving, 720 DEG C be calcined 18 hours, obtain compound zinc aluminate carrier.XRD is characterized to be illustrated to carry (see Fig. 1)
Body has typical spinel structure, pore volume 0.34cm3/ g, specific surface area 86m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and sodium nitrate (5.6g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as A.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 2】
Take 755.30g aluminum nitrates (Al (NO3)39H2O), 167.51g zinc nitrates (Zn (NO3)26H2O), 108.10g copper nitrates
(Cu(NO3)26H2O) it is dissolved in 2000ml deionized waters；At 20 DEG C, it is stirred vigorously down, 16%wt. ammoniacal liquor is slowly dropped to
In the mixed aqueous solution, precipitation is formed, control ph 7.5, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying, crush, after sieving, be calcined 10 hours at 700 DEG C, obtain compound zinc aluminate carrier.XRD, which characterizes explanation carrier, has typical case
Spinel structure, pore volume 0.32cm3/ g, specific surface area 80m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and lithium nitrate (7.2g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 80 DEG C of drying, 550 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 550 DEG C with vapor,
Finally lead to 550 DEG C of dry air to handle 1 hour.Gained catalyst is designated as B.
Sample uses hydrogen before dehydrogenation reaction, 520 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 3】
Take 753.33g aluminum nitrates (Al (NO3)39H2O), 154.65g zinc nitrates (Zn (NO3)26H2O), 139.69g cobalt nitrates
(Co(NO3)26H2O) it is dissolved in 2000ml deionized waters；At 20 DEG C, it is stirred vigorously down, 20%wt. ammoniacal liquor is slowly dropped to
In the mixed aqueous solution, precipitation is formed, control ph 7.4, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying, crush, after sieving, be calcined 5 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD, which characterizes explanation carrier, has typical case
Spinel structure, pore volume 0.35cm3/ g, specific surface area 51m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and lithium nitrate (6.3g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 70 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as C.
Sample uses hydrogen before dehydrogenation reaction, 520 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Comparative example 4】
Take 756.36g aluminum nitrates (Al (NO3)39H2O), 278.63g zinc nitrates (Zn (NO3)26H2O), 22.37g cobalt nitrates
(Co(NO3)26H2O) it is dissolved in 2000ml deionized waters；At 23 DEG C, it is stirred vigorously down, 20%wt. ammoniacal liquor is slowly dropped to
In the mixed aqueous solution, precipitation is formed, control ph 7.6, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying, crush, after sieving, be calcined 5 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD, which characterizes explanation carrier, has typical case
Spinel structure, pore volume 0.55cm3/ g, specific surface area 151m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and lithium nitrate (9.1g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 70 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as D.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 5】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 223.20g zinc nitrates (Zn (NO3)26H2O), 72.82g cobalt nitrates
(Co(NO3)26H2O) it is dissolved in 2000ml deionized waters；At 26 DEG C, it is stirred vigorously down, 20%wt. ammoniacal liquor is slowly dropped to
In the mixed aqueous solution, precipitation is formed, control ph 7.0, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying, crush, after sieving, be calcined 5 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD, which characterizes explanation carrier, has typical case
Spinel structure, pore volume 0.43cm3/ g, specific surface area 117m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and lithium nitrate (8.0g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as E.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 6】
Take 754.33g aluminum nitrates (Al (NO3)39H2O), 197.30g zinc nitrates (Zn (NO3)26H2O), 86.34g manganese nitrates
(Mn(NO3)24H2O) it is dissolved in 2000ml deionized waters；At 25 DEG C, it is stirred vigorously down, 22%wt. ammoniacal liquor is slowly dropped to
In the mixed aqueous solution, precipitation is formed, control ph 6.5, after precipitation is stayed overnight at room temperature, is filtered, washing, in 70 DEG C of bakings
It is dry, crush, after sieving, be calcined 3 hours at 850 DEG C, obtain compound zinc aluminate carrier.XRD, which characterizes explanation carrier, to be had typically
Spinel structure, pore volume 0.15cm3/ g, specific surface area 42m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and lithium nitrate (4.2g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as F.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 7】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 205.26g zinc nitrates (Zn (NO3)26H2O), 124.05g chromic nitrates
(Cr(NO3)24H2O) it is dissolved in 2000ml deionized waters；At 22 DEG C, it is stirred vigorously down, 22%wt. ammoniacal liquor is slowly dropped to
In the mixed aqueous solution, precipitation is formed, control ph 7.2, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying, crush, after sieving, be calcined 3 hours at 850 DEG C, obtain compound zinc aluminate carrier.XRD, which characterizes explanation carrier, has typical case
Spinel structure, pore volume 0.25cm3/ g, specific surface area 68m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and calcium nitrate (8.2g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as G.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 8】
Take 752.15g aluminum nitrates (Al (NO3)39H2O), 183.45g zinc nitrates (Zn (NO3)26H2O), 38.86g germanium oxides
(GeO2) be dissolved in 2000ml deionized waters；At 34 DEG C, it is stirred vigorously down, 15%wt. ammoniacal liquor is slowly dropped to the mixing
In the aqueous solution, precipitation is formed, control ph 8.3, after precipitation is stayed overnight at room temperature, is filtered, washing, in 120 DEG C of drying, powder
It is broken, after sieving, it is calcined 6 hours at 750 DEG C, obtains compound zinc aluminate carrier.XRD, which characterizes explanation carrier, has typical spinelle
Structure, pore volume 0.35cm3/ g, specific surface area 98m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and lithium nitrate (6.6g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as H.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 9】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 157.66g zinc nitrates (Zn (NO3)26H2O), 62.75g manganese nitrates
(Mn(NO3)24H2O), 64.03g cobalt nitrates (Co (NO3)26H2O) it is dissolved in 2000ml deionized waters；At 26 DEG C, it is stirred vigorously
Under, 15 weight % ammoniacal liquor is slowly dropped in the mixed aqueous solution, precipitation is formed, control ph 7.6, room will be deposited in
Temperature it is lower overnight after, filter, washing, in 120 DEG C of drying, crush, after sieving, be calcined 8 hours at 750 DEG C, obtain compound zinc aluminate
Carrier.XRD, which characterizes explanation carrier, has typical spinel structure, pore volume 0.36cm3/ g, specific surface area 108m2/g.Vehicle group
Into and acidity be shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and sodium nitrate (7.0g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as I.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 10】
Take 752.20g aluminum nitrates (Al (NO3)39H2O), 181.21g zinc nitrates (Zn (NO3)26H2O), 92.26g cadmium nitrates
(Cd(NO3)2) be dissolved in 2000ml deionized waters (HCl containing 0.001mol/L)；At 26 DEG C, it is stirred vigorously down, by 15 weight %
Ammoniacal liquor be slowly dropped in the mixed aqueous solution, formed precipitation, control ph 7.4, will precipitation at room temperature overnight after, mistake
Filter, washing, in 120 DEG C of drying, crush, after sieving, be calcined 8 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD is characterized and said
Bright carrier has typical spinel structure, pore volume 0.30cm3/ g, specific surface area 92m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and sodium nitrate (5.1g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as J.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Embodiment 11】
Take 752.27g aluminum nitrates (Al (NO3)39H2O), 98.17g zinc nitrates (Zn (NO3)26H2O), 161.87g copper nitrates
(Cu(NO3)2) be dissolved in 2000ml deionized waters；At 26 DEG C, it is stirred vigorously down, 15 weight % ammoniacal liquor is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph 7.0, after precipitation is stayed overnight at room temperature, is filtered, washing, in 120 DEG C of bakings
It is dry, crush, after sieving, be calcined 8 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD, which characterizes explanation carrier, to be had typically
Spinel structure, pore volume 0.42cm3/ g, specific surface area 125m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier is contained with the carrier 15.0g dippings of gained at room temperature using the upper platinum component of dipping technique load
Chloroplatinic acid (H2PtCl66H2O, 0.16g) and calcium nitrate (10.2g) 24 hours (metal platinum carrying capacity of the aqueous solution (10ml)
0.4%), then 60 DEG C of drying, 530 DEG C are calcined 3 hours in the air stream, are then handled 4 hours at 530 DEG C with vapor,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is designated as K.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for dehydrogenation of isobutane.
【Comparative example 1】
Carrier and catalyst are prepared as described in Example 1, and different carrier precipitation processes is added without modified additive group
Point.
Table 1
After adding metal promoter, catalyst surface acidity declines obvious.
【Embodiment 10~18】
Catalyst obtained by embodiment 1~9 is at 550 DEG C, normal pressure, iso-butane mass space velocity 4.6 hours-1, H2O/C3H8Body
Product is than being 8:Evaluated under the conditions of 1, 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 |
The platinum-tin catalyst prepared using common zinc aluminate, acidity is higher, and performance is more unstable, and selectivity declines within 10 hours
Subtract the catalyst performance and stability substantially, prepared using complex carrier to significantly improve, and selectivity slightly carries after operation
It is high.
【Embodiment 20】
Catalyst is prepared by each Step By Condition in embodiment 1 and examination catalyst, sample are used before dehydrogenation reaction
Hydrogen, 500 DEG C of reduction activations 90 minutes, reacted for dehydrogenation of isobutane.Catalyst is at 550 DEG C, normal pressure, iso-butane mass space velocity
4.6 hour-1, H2O/C4H10For 8:After being reacted 10 hours under the conditions of 1, being made charcoal 60 minutes at 500 DEG C using 1% air makes catalysis
Agent regenerates, and the initial performance after catalyst repeatedly regenerates is as shown in table 3.
Table 3
【Embodiment 21~26】
Embodiment 5 is subjected to performance evaluation under differential responses process conditions, the results are shown in Table 4.
Table 4
Claims (8)
1. a kind of dehydrogenating low-carbon alkane prepares the catalyst of low-carbon alkene, in terms of catalyst weight percent, including following components：
A) at least one of ruthenium, rhodium, palladium, osmium, iridium or platinum in platinum metal, 0.01 that catalyst weight is calculated as with simple substance
~1.5%；
B) at least one of the A of the periodic table of elements I or II A races element or its compound are selected from, catalyst weight is calculated as with simple substance
0.05~35.0%；
C) zinc aluminate carrier, carrier account for the 63.5~94.9% of catalyst weight；
Wherein, the carrier composition coincidence formula：ZnxMyAl2O4, wherein M is selected from transition metal Ni, Cu, Co, Mn, Cr
Or the one or more in Ge, and x+y=1；Carrier by weight percentage, including following components：
A) Al, 26.0~33.0% that vehicle weight is calculated as with simple substance；
B) Zn, 10.0~35.0% that vehicle weight is calculated as with simple substance；
C) M, 2.3~20.0% that vehicle weight is calculated as with simple substance；
Wherein, the support acidity measured using indicator method is less than 0.35mmol/g.
2. dehydrogenating low-carbon alkane according to claim 1 prepares the catalyst of low-carbon alkene, it is characterised in that 0.5≤x ＜
1。
3. dehydrogenating low-carbon alkane according to claim 1 prepares the catalyst of low-carbon alkene, it is characterised in that the gold that M is represented
Belong to ionic radius between 0.060~0.080nm.
4. dehydrogenating low-carbon alkane according to claim 1 prepares the catalyst of low-carbon alkene, it is characterised in that 0 ＜ M/Zn≤
1。
5. dehydrogenating low-carbon alkane according to claim 1 prepares the catalyst of low-carbon alkene, it is characterised in that the hole of carrier
Hold 0.08~0.6cm3/ g, 20~220m of specific surface area2/g。
6. the dehydrogenating low-carbon alkane described in any one of Claims 1 to 5 prepares the preparation method of the catalyst of low-carbon alkene, including
Following steps：
A) soluble-salt of the desired amount of nitric hydrate aluminium, nitric hydrate zinc and transition metal M is configured to the aqueous solution I, wherein M
One or more in Ni, Cu, Co, Mn, Cr or Ge, Al：(Zn+M) the amount ratio of material 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 be selected from sodium hydroxide,
At least one of potassium hydroxide, ammoniacal liquor or carbonic acid ammonia；
C) under 0~50 DEG C of precipitation temperature, solution I is added in solution II, control ph 5.5~8.5 under stirring condition, mistake
This is deposited in 50~150 DEG C of drying after filter, washing, is then calcined 1~24 hour at 650~1000 DEG C, obtains compound aluminic acid
Zinc carrier；
D) infusion process load active component on complex carrier is used, the desired amount of chloroplatinate is configured to the aqueous solution, carried
On body, dipping obtains catalyst precarsor after 1~48 hour after drying；Low-carbon alkanes are obtained after catalyst precarsor roasting, reduction to take off
Hydrogen producing light olefins catalyst.
7. the dehydrogenating low-carbon alkane described in claim 6 prepares the preparation method of the catalyst of low-carbon alkene, it is characterised in that heavy
The pH value of shallow lake process is 6.5~8.0；Precipitation temperature is at 15~40 DEG C.
8. a kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, propane and/or iso-butane are used as raw material, in reaction temperature
520~620 DEG C, 0~0.4MPa of reaction pressure, 0.1~8.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 1~18
Under part, any one of raw material and Claims 1 to 5 the catalyst haptoreaction generation propylene and/or isobutene.
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| CN107537462A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Butane dehydrogenation butylene/butadiene catalyst and purposes |
| CN107537534A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Normal butane dehydrogenation butylene/butadiene catalyst and purposes |
| CN107970920B (en) * | 2016-10-21 | 2021-03-30 | 中国石油化工股份有限公司 | High-dispersion metal material and use |
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| CN109603821A (en) * | 2018-12-19 | 2019-04-12 | 沈阳师范大学 | A kind of propane catalytic dehydrogenation catalyst of high activity and preparation method thereof |
| CN113828327B (en) * | 2020-06-24 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof, and method for preparing olefin by alkane dehydrogenation |
| CN113877577B (en) * | 2020-07-02 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for improving alkane conversion rate |
| CN114656320A (en) * | 2022-03-14 | 2022-06-24 | 厦门中科易工化学科技有限公司 | Method for preparing low-carbon olefin by oxidative dehydrogenation and application of antimony oxide |
| CN115254136A (en) * | 2022-07-08 | 2022-11-01 | 润和科华催化剂(上海)有限公司 | Rare earth metal and alkaline earth metal modified low-carbon alkane dehydrogenation catalyst and preparation method and application thereof |
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