CN105435856B - Dehydrogenating low-carbon alkane producing light olefins catalyst carrier and application thereof - Google Patents
Dehydrogenating low-carbon alkane producing light olefins catalyst carrier and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of low-carbon alkane dehydrogenation platinum-tin carrier and application thereof, mainly solve the problem of that there are the low selectivity in use of Catalyst Conversion to decline in existing technology of preparing.The present invention uses coprecipitation to introduce the transition metal elements such as copper, nickel, manganese, cobalt in zinc aluminate carrier first, obtains metal composite oxide carrier, then infusion process Supported Pt Nanoparticles component and tin component is used to obtain platinum-tin catalyst.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 is contacted with catalyst, reaction generation propylene/isobutene technical solution preferably solve the problems, such as this, can be used 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 carriers and application thereof 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.It is liquefied petroleum by a large amount of low-carbon alkanes that oil plant obtains
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
Alkane opens up new alkene source and is of great significance.Currently, alkane catalytic dehydrogenation technology is with the Oleflex techniques of Uop Inc.
Catofin techniques with Lummus companies are representative.The domestic process units still without dehydrogenating low-carbon alkane producing light olefins.
Dehydrogenating low-carbon alkane catalysis reaction carries out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, develops high living
Property, highly selective and high stability catalyst become the technology key.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
It is 17%, Propylene Selectivity 93%；Chinese patent (CN200710023431.X) is drawn tin using using the method for hydrothermal synthesis
Enter ZSM-5 molecular sieve carrier, after being used in combination infusion process Supported Pt Nanoparticles component, the catalyst to 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 is reacted for dehydrogenating propane, adopts
With the preparation method of tin component and platinum component co-impregnation, carrier is the molecular sieves containing Na such as Y types, ZSM-5, catalyst continuous operation
After 720 hours, conversion of propane 30.5%, Propylene Selectivity 96.4%, but active drop by 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 has been all made of aluminium 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 element of atomic radius is modified is used to prepare dehydrogenating low-carbon alkane producing light olefins
The document of platinum-tin catalyst has not been reported.
Invention content
The first technical problem to be solved by the present invention is existing catalyst, and there are 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.It is low to provide a kind of new one kind
Carbon alkane dehydrogenation platinum-tin catalyst carrier, the catalyst be used for dehydrogenating low-carbon alkane preparing low carbon olefin hydrocarbon, have high temperature with
And under the conditions of coke-burning regeneration, Catalyst Conversion is high, and selectivity keeps stable advantage.The technical problems to be solved by the invention
Two be to provide it is a kind of with preparation method that is solving the corresponding catalyst of one of technical problem.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of dehydrogenating low-carbon alkane preparation
The catalyst carrier of low-carbon alkene, carrier form coincidence formula：ZnxMyAl2O4, wherein M be the periodic table of elements in Ni, Cu, Co,
One or more of Mn, Cr or Ge, and x+y=1, 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, 0.1~20.0% that vehicle weight is calculated as with simple substance.
In above-mentioned technical proposal, the carrier of catalyst is compound zinc aluminate carrier；Preferably, 0.5≤x ＜ 1.
A kind of dehydrogenating low-carbon alkane prepares the catalyst of low-carbon alkene, by the catalysis in active component and above-mentioned technical proposal
Agent carrier forms, and wherein active component includes that IV A compounds are selected from least one of Sn or Ge in the periodic table of elements, with simple substance
It is calculated as the 1.0~2.0% of catalyst weight；Platinum metal be selected from Pt or Pd, with simple substance be calculated as catalyst weight 0.1~
1.0%；I A or II element A are selected from least one of Li, Na, K, Ca, Mg or Ba, be calculated as catalyst weight with simple substance 5.0
~35.0%.
In above-mentioned technical proposal, the metal ion radius preferred scope that M is represented is 0.06~0.10nm, more preferably ranging from
0.06~0.08nm；There is preferred carrier spinel structure, the carrier surface acidity measured using indicator method to be less than
0.044mmol/g, again more preferably less than 0.035mmol/g；M/Zn ratios are preferably 0~1；The hole of carrier holds preferred scope
0.08~0.6cm3/ g, specific surface area preferred scope are 20~200m2/g。
Different shapes can be made in carrier as needed, such as cylindric, spherical, sheet, tubular, Raschig ring or cellular
Deng, but cylindrical and spherical shape is relatively good selection, effective diameter is in 1~6mm, in order to commercial Application.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows, and the preparation method of catalyst includes
Following steps：
A) soluble-salt of the desired amount of nitric hydrate aluminium, nitric hydrate zinc and transition metal M is configured to aqueous solution I,
Wherein M is selected from one or more of Ni, Cu, Co, Mn, Cr or Ge, Al：(Zn+M) the amount ratio of substance is 1.5~2.5：1；
B) aqueous solution II of the water soluble alkali of configuration quality percent concentration range 1~30%, water soluble alkali are selected from hydrogen-oxygen
Change at least one of sodium, potassium hydroxide, ammonium hydroxide and carbonic acid ammonia；
C) solution I is added in solution II under stirring, control ph 5.5~8.5, after being filtered, washed, drying, roast
Obtain catalyst carrier；
D) infusion process load active component on a catalyst support is used：By the solvable of the desired amount of chloroplatinate and tin
Property salt be configured to mixed aqueous solution, after impregnating 1~48 hour on a catalyst support, catalyst precarsor is obtained after dry；Catalysis
Agent precursor obtains dehydrogenating low-carbon alkane producing light olefins catalyst in fired, reduction.
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 is 6.5~8.0.
A kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, uses propane and/or iso-butane for raw material, in reaction temperature
520~620 DEG C of degree, 0~0.4MPa of reaction pressure；0.1~8.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 1~18
Under the conditions of, raw material generates propylene and/or isobutene with catalyst haptoreaction described in above-mentioned technical proposal.
In above-mentioned technical proposal, the preferred scope of reaction temperature is 550~610 DEG C；The preferred scope of reaction pressure is 0.1
~0.3MPa；The preferred scope of reaction velocity is 1.4~7.2h-1；H2O/CnH2n+2Volume ratio preferred scope is 2~16.
Present invention employs coprecipitations to prepare compound zinc aluminate carrier, multiple in the transition metal containing metals such as magnesium, zinc
The alumina support of conjunction is easy to form MAl2O4The spinel structure of type, there are a large amount of oxonium ions on the carrier of this structure
Hole, after generating such lattice defect, the effect enhancing between platinum particle and alumina support is conducive to obtain clipped wire
Sub- dispersion degree higher, distribution are more uniform.But trivalent aluminium ion is easy to form stronger Lewis acid centers, and catalyst is caused to exist
Reaction process is too strong to the activation of reactant, and conversion ratio is low, while being also easy to generate carbon deposit, and catalyst activity reduction while is selected
Selecting property also reduces.The acid site density (acidity) of carrier is related with the structure of catalyst, composition.The present invention is changed by adding carrier
The method of property auxiliary agent makes the acidity of zinc aluminate carrier effectively reduce.Using the metal ion close with the ionic radius of zinc ion
As the auxiliary agent of support modification, ionic radius close to so that auxiliary agent is easier the lattice into ZnO, so as to cause lattice deformability and
The imbalance of distribution of charges, and lead to the decline of acidity.
Dehydrogenating low-carbon alkane reaction carries out on the continuously 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 is de-
Alkane, olefin(e) centent in hydrogen product and conversion ratio, selectivity and the yield for calculating reaction.The catalysis obtained using this method
Agent is at 550 DEG C, normal pressure, iso-butane mass space velocity 4.6 hours-1, H2O/C4H10It is 8:It is used under the conditions of 1, initial conversion is higher than
50%, selectivity is stablized, and is higher than 94%, through repeatedly regenerating, metallic can maintain 3nm hereinafter, achieving good technology
Effect.The catalyst being prepared uses indicator titration method measurement surface acid site density (acidity).
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 that alkalinity is represented with B is sent out when it is adsorbed on the surface of the catalyst 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, is titrated with alkali by means of indicator.Titration institute
Alkali must be alkali more stronger than indicator, and generally use pKa value is about+10 n-butylamine.The alkali of addition is adsorbed on first
On strongest acidic site, and finally replace indicator molecules from solid.This experiment standard n-butylamine-cyclohexane solution
Solid acid is titrated, is measured so as to find out acid.When certain indicator, which is adsorbed on solid acid, becomes acid type color, indicator is made to be restored 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 measured is B acid
With the overall result of L acid.
Below by embodiment, the present invention is further elaborated.
Description of the drawings
Fig. 1 be compound zinc aluminate carrier XRD diffraction spectrograms, 2 θ=31.2 ± 0.2 ° of characteristic diffraction peak, 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°。
Specific implementation mode
【Embodiment 1】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 246.91g zinc nitrates (Zn (NO3)26H2O), 49.44g nickel nitrates
(Ni(NO3)26H2O it) is dissolved in 2000ml deionized waters；It at 20 DEG C, is vigorously stirred down, 5% ammonium hydroxide, which is slowly dropped to this, to be mixed
In Heshui solution, precipitation is formed, control ph is about 6.8, after precipitation is stayed overnight at room temperature, is filtered, washing, in 120 DEG C of bakings
It is dry, it crushes, after sieving, is roasted 16 hours at 700 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.32cm3/ g, specific surface area 89m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.22g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as A.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 2】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 166.59g zinc nitrates (Zn (NO3)26H2O), 106.30g copper nitrates
(Cu(NO3)26H2O it) is dissolved in 2000ml deionized waters；It at 20 DEG C, is vigorously stirred down, 15% ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph is about 7.8, after precipitation is stayed overnight at room temperature, is filtered, washing, in 90 DEG C of bakings
It is dry, it crushes, after sieving, is roasted 8 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.28cm3/ g, specific surface area 74m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.22g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as B.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 3】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 154.69g zinc nitrates (Zn (NO3)26H2O), 139.70g cobalt nitrates
(Co(NO3)26H2O it) is dissolved in 2000ml deionized waters；It at 26 DEG C, is vigorously stirred down, 20% ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph is about 7.2, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying crushes, after sieving, is roasted 5 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has point brilliant
Stone structure, hole hold 0.33cm3/ g, specific surface area 51m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.22g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as C.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 4】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 276.66g zinc nitrates (Zn (NO3)26H2O), 20.37g cobalt nitrates
(Co(NO3)26H2O it) is dissolved in 2000ml deionized waters；It at 26 DEG C, is vigorously stirred down, 20% ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph is about 7.2, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying crushes, after sieving, is roasted 5 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has point brilliant
Stone structure, hole hold 0.52cm3/ g, specific surface area 149m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.66g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：6), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as D.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 5】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 223.11g zinc nitrates (Zn (NO3)26H2O), 72.76g cobalt nitrates
(Co(NO3)26H2O it) is dissolved in 2000ml deionized waters；It at 26 DEG C, is vigorously stirred down, 20% ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph is about 7.2, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying crushes, after sieving, is roasted 5 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has point brilliant
Stone structure, hole hold 0.42cm3/ g, specific surface area 115m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.25g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as E.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 6】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 196.34g zinc nitrates (Zn (NO3)26H2O), 85.34g manganese nitrates
(Mn(NO3)24H2O it) is dissolved in 2000ml deionized waters；It at 20 DEG C, is vigorously stirred down, 22% ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph is about 6.5, after precipitation is stayed overnight at room temperature, is filtered, washing, in 60 DEG C of bakings
It is dry, it crushes, after sieving, is roasted 3 hours at 850 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.12cm3/ g, specific surface area 43m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.21g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as F.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【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；It at 22 DEG C, is vigorously stirred down, 22% ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph is about 7.2, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying crushes, after sieving, is roasted 3 hours at 850 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has point brilliant
Stone structure, hole hold 0.25cm3/ g, specific surface area 68m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.21g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as G.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 8】
Take 753.36g aluminum nitrates (Al (NO3)39H2O), 184.44g zinc nitrates (Zn (NO3)26H2O), 39.76g germanium oxides
(GeO2) be dissolved in 2000ml deionized waters；It at 34 DEG C, is vigorously stirred down, it is water-soluble that 15% ammonium hydroxide is slowly dropped to the mixing
In liquid, precipitation is formed, control ph is about 8.2, after precipitation is stayed overnight at room temperature, is filtered, washing, in 120 DEG C of drying, powder
It is broken, after sieving, is roasted 6 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has spinel structure,
Hole holds 0.33cm3/ g, specific surface area 94m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.21g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as H.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【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 vigorously stirred
Under, 15% ammonium hydroxide is slowly dropped in the mixed aqueous solution, forms precipitation, control ph is about 7.6, will be deposited in room temperature
It after staying overnight down, filters, washing, in 120 DEG C of drying, crushing after sieving, roasts 8 hours at 750 DEG C, obtains compound zinc aluminate load
Body.XRD characterization illustrates that there is carrier spinel structure, hole to hold 0.36cm3/ g, specific surface area 108m2/g.Carrier forms and acidity
It is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.21g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as G.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 10】
Take 751.28g aluminum nitrates (Al (NO3)39H2O), 181.46g zinc nitrates (Zn (NO3)26H2O), 92.20g cadmium nitrates
(Cd(NO3)2) be dissolved in 2000ml deionized waters (HCl containing 0.001mol/L)；It at 26 DEG C, is vigorously stirred down, by 15 weight %
Ammonium hydroxide be slowly dropped in the mixed aqueous solution, formed precipitation, control ph 7.2, will precipitation at room temperature overnight after, mistake
Filter, washing crush in 120 DEG C of drying, after sieving, are roasted 8 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD characterization is said
There is bright carrier spinel structure, hole to hold 0.29cm3/ g, specific surface area 93m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.21g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as J.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【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；It at 26 DEG C, is vigorously stirred down, the ammonium hydroxide of 15 weight % is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph 7.0 after staying overnight precipitation at room temperature, filters, washing, in 120 DEG C of bakings
It is dry, it crushes, after sieving, is roasted 8 hours at 750 DEG C, obtain compound zinc aluminate carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.42cm3/ g, specific surface area 125m2/g.Carrier forms and acidity is shown in Table 1.
Obtained carrier uses the carrier 15.0g dippings of gained at room temperature using the upper platinum of dipping technique load, tin component
Containing chloroplatinic acid (H2PtCl66H2O, 0.16g) and stannic chloride (SnCl45H2O, 0.21g) 24 hours (metals of aqueous solution (10ml)
Platinum carrying capacity 0.4%, Pt：Sn=1：2), then 60 DEG C of drying roast 3 hours for 530 DEG C, are then existed with vapor in the air stream
It is handled at 530 DEG C 4 hours, finally leads to 530 DEG C of dry air and handle 1 hour.Gained catalyst is denoted as K.
Sample uses hydrogen, 500 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【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 metal promoter is added, catalyst surface acidity declines apparent.
【Embodiment 10~18】
The obtained catalyst of Examples 1 to 9 is at 550 DEG C, normal pressure, iso-butane mass space velocity 4.6 hours-1, H2O/C3H8
Volume ratio is 8:It is evaluated under the conditions of 1, the results are shown in Table 2.
Table 2*
The platinum-tin catalyst prepared using common zinc aluminate, acidity higher, performance is more unstable, and selectivity declines within 10 hours
Subtract the catalyst performance and stability obviously, 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 are reacted for dehydrogenation of isobutane.Catalyst is at 550 DEG C, normal pressure, iso-butane mass space velocity
4.6 hour-1, H2O/C4H10It is 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 (7)
1. a kind of dehydrogenating low-carbon alkane prepares the catalyst of low-carbon alkene, it is made of active component and carrier, the composition symbol of carrier
Close formula：ZnxMyAl2O4, wherein M be selected from one or more of transition metal element Ni, Cu, Co, Mn, Cr or Ge, and
X+y=1,0.5≤x ＜ 1；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；
0.44mmol/g is less than using the support acidity that indicator method measures；
Wherein active component include in the periodic table of elements IV A compounds be selected from least one of Sn or Ge, be calculated as urging with simple substance
The 1.0~2.0% of agent weight；Platinum metal is selected from Pt or Pd, be calculated as catalyst weight with simple substance 0.1~1.0%；I A or
II element A is selected from least one of Li, Na, K, Ca, Mg or Ba, be calculated as catalyst weight with simple substance 5.0~35.0%.
2. 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 0.06~0.10nm.
3. dehydrogenating low-carbon alkane according to claim 1 prepares the catalyst of low-carbon alkene, it is characterised in that 0 ＜ M/Zn≤
1。
4. claims 1 to 3 any one of them dehydrogenating low-carbon alkane 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 aqueous solution I, wherein M
Selected from one or more of Ni, Cu, Co, Mn, Cr or Ge, Al：(Zn+M) the amount ratio of substance is 1.5~2.5：1；
B) aqueous solution II of the water soluble alkali of configuration quality percent concentration range 1~30%, water soluble alkali be selected from sodium hydroxide,
At least one of potassium hydroxide, ammonium hydroxide and carbonic acid ammonia；
C) at a temperature of 0~50 DEG C, solution I is added in solution II, control ph 5.5~8.5 under stirring condition were passed through
Catalyst carrier is obtained after filter, washing, drying, roasting；
D) infusion process load active component on a catalyst support is used：By the desired amount of chloroplatinate and the soluble-salt of tin
It is configured to mixed aqueous solution, after impregnating 1~48 hour on a catalyst support, catalyst precarsor is obtained after dry；Before catalyst
Body obtains dehydrogenating low-carbon alkane producing light olefins catalyst in fired, reduction.
5. dehydrogenating low-carbon alkane according to claim 4 prepares the preparation method of the catalyst of low-carbon alkene, feature exists
In precipitation process pH value be 6.5~8.0.
6. dehydrogenating low-carbon alkane according to claim 4 prepares the preparation method of the catalyst of low-carbon alkene, feature exists
In precipitation temperature be 15~40 DEG C.
7. a kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene uses propane and/or iso-butane for 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 3 the catalyst haptoreaction generate propylene and/or isobutene.
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| CN110496618B (en) * | 2018-05-17 | 2021-11-19 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
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| CN103055857A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for low-carbon alkane dehydrogenation and preparation method thereof |
| CN103998126A (en) * | 2011-12-22 | 2014-08-20 | 沙特基础工业公司 | Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation |
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| CN103055857A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for low-carbon alkane dehydrogenation and preparation method thereof |
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