CN105363473B - Dehydrogenating low-carbon alkane producing light olefins platinum catalyst - Google Patents
Dehydrogenating low-carbon alkane producing light olefins platinum catalyst Download PDFInfo
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- CN105363473B CN105363473B CN201410429000.3A CN201410429000A CN105363473B CN 105363473 B CN105363473 B CN 105363473B CN 201410429000 A CN201410429000 A CN 201410429000A CN 105363473 B CN105363473 B CN 105363473B
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Abstract
The present invention relates to a kind of dehydrogenating low-carbon alkane platinum catalyst and preparation method 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 ferrite carrier first, obtain metal composite oxide carrier, then infusion process Supported Pt Nanoparticles component is used, that is the aqueous solution of the soluble-salt of platinum-impregnated obtains platinum catalyst 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 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 one kind being used for dehydrogenating low-carbon alkane producing light olefins platinum catalyst.
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 mistake
The activity of catalyst in journey or after coke-burning regeneration is not high, and selectivity is gradually reduced in the process of running.Using novel multiple
The document that conjunction ferrite carrier is used to prepare dehydrogenating low-carbon alkane producing light olefins 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.A kind of new lower alkanes are provided
Hydrocarbon dehydrogenation platinum catalyst, the catalyst are used for dehydrogenating low-carbon alkane preparing low carbon olefin hydrocarbon, have in high temperature and coke-burning regeneration
Under the conditions of, Catalyst Conversion is high, and selectivity keeps stable advantage.The second technical problem to be solved by the present invention is to provide
It is a kind of with the preparation method for 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
Low-carbon alkene platinum catalyst, 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) it is selected from least one of I A of the periodic table of elements or II A races element or its compound, catalyst is calculated as with simple substance
The 0.05~35.0% of weight；
C) zinc ferrite carrier, carrier account for the 63.5~94.9% of catalyst weight.
In above-mentioned technical proposal, carrier preferably constitutes coincidence formula：ZnxMyFe2O4, wherein M be the periodic table of elements in Ni,
The divalent such as Cu, Co, Mn, Ce, Cr, Ge or trivalent metallic element are one or more of, and x+y=1,0.5≤x < 1, with weight hundred
Divide than meter, including following components：
A) Fe, 42.0~50.0% that vehicle weight is calculated as with simple substance；
B) Zn, 12.0~28.0% that vehicle weight is calculated as with simple substance；
C) M, 0.1~15.0% 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 between 0.060~0.080nm；Carrier is excellent
Choosing has spinel structure, uses the carrier surface acidity preferred scope that indicator method measures for less than 0.4mmol/g；M/Zn ratios
Value is between 0~1；The hole of carrier holds 0.08~0.8cm3/ g, 10~260m of specific surface area2/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 preparation method of catalyst includes the following steps：
A) soluble-salt of the desired amount of nitric hydrate iron, nitric hydrate zinc and transition metal M is configured to aqueous solution I,
Wherein M is selected from the one or more of the transition metal elements such as Ni, Cu, Co, Mn, Ce, Cr, Ge, Fe:(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, carbonic acid ammonia；
C) under 0~50 DEG C of precipitation temperature, solution I is added in solution II, control ph 7.0 under stirring condition~
10.5, this is deposited in 50~150 DEG C of drying after being filtered, washed, then roasts 1~24 hour, is answered at 650~1000 DEG C
Close zinc ferrite carrier；
D) infusion process load active component on complex carrier is used, the desired amount of chloroplatinate is configured to aqueous solution,
After being impregnated 1~48 hour on complex carrier, catalyst precarsor is obtained after dry；Catalyst precarsor obtains after roasting, restoring
To dehydrogenating low-carbon alkane 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 is 7.5~9.5.
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 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 generates propylene and/or isobutene with catalyst haptoreaction described in above-mentioned technical proposal.
Present invention employs coprecipitations to prepare compound zinc ferrite carrier, multiple in the transition metal containing metals such as magnesium, zinc
The Iron oxide support of conjunction is easy to form MFe2O4The 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 ferric 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 ferrite carrier effectively reduce.Using the metal ion close with the ionic radius of iron ion
As the auxiliary agent of support modification, ionic radius is close to so that auxiliary agent is easier to enter oxide lattice, so as to cause lattice deformability
With 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 alkane mass space velocity 4.6 hours-1, H2O/C4H10It is 8:It is used under the conditions of 1, initial conversion is high
In 45%, selectivity is stablized, and is higher than 95%, through repeatedly regenerating, metallic can maintain 3nm hereinafter, achieving 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 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 is the XRD diffraction spectrograms of compound zinc ferrite carrier（Compound ferrous acid gahnite structure XRD spectra）, feature
2 θ=18.2 ± 0.2 ° of diffraction maximum, 29.9 ± 0.2 °, 35.3 ± 0.2 °, 42.8 ± 0.2 °, 53.1 ± 0.2 °, 56.6 ± 0.2 °,
62.2±0.2°。
Specific implementation mode
【Embodiment 1】
Take 807.14g ferric nitrates (Fe (NO3)39H2O), 247.62g zinc nitrates (Zn (NO3)26H2O), 48.29g nickel nitrates
(Ni(NO3)26H2O it) is dissolved in 2000ml deionized waters；It at 25 DEG C, is vigorously stirred down, 5%wt. ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, control ph is about 7.5, forms precipitation, at room temperature overnight by precipitation, 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 ferrite carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.29cm3/ g, specific surface area 76m2/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 (4.9g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 70 DEG C of drying roast 4 hours for 540 DEG C, it is small then to handle 4.5 at 540 DEG C with vapor in the air stream
When, finally lead to 540 DEG C of dry air and handles 1 hour.Gained catalyst is denoted as A.
Sample uses hydrogen, 520 DEG C of reduction activations 120 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 2】
Take 809.6g ferric nitrates (Fe (NO3)39H2O), 167.51g zinc nitrates (Zn (NO3)26H2O), 107.22g copper nitrates
(Cu(NO3)23H2O it) is dissolved in 2000ml deionized waters；It at 25 DEG C, is vigorously stirred down, 10% ammonium hydroxide is slowly dropped to this
In mixed aqueous solution, precipitation is formed, control ph is about 7.8, at room temperature overnight by precipitation, is filtered, washing, in 100 DEG C of bakings
It is dry, it crushes, after sieving, is roasted 8 hours at 750 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.39cm3/ 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 (5.2g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 60 DEG C of drying are roasted 3 hours for 530 DEG C, are then handled 4 hours at 530 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to 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 808.64g ferric nitrates (Fe (NO3)39H2O), 154.65g zinc nitrates (Zn (NO3)26H2O), 139.32g 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 8.8, at room temperature overnight by precipitation, is filtered, washing, in 100 DEG C of bakings
It is dry, it crushes, after sieving, is roasted 5 hours at 750 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.35cm3/ g, specific surface area 55m2/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 (6.1g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 90 DEG C of drying are roasted 3 hours for 530 DEG C, are then handled 4 hours at 530 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to 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.
【Comparative example 4】
Take 808.53g ferric nitrates (Fe (NO3)39H2O), 276.15g zinc nitrates (Zn (NO3)26H2O), 20.21g 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 9.2, at room temperature overnight by precipitation, is filtered, washing, in 100 DEG C of bakings
It is dry, it crushes, after sieving, is roasted 6 hours at 750 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has spinelle
Structure, hole hold 0.58cm3/ g, specific surface area 126m2/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 (4.6g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 80 DEG C of drying are roasted 3 hours for 530 DEG C, are then handled 4 hours at 530 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is denoted as D.
Sample uses hydrogen, 520 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 5】
Take 809.13g ferric nitrates (Fe (NO3)39H2O), 224.12g zinc nitrates (Zn (NO3)26H2O), 73.55g cobalt nitrates
(Co(NO3)26H2O it) is dissolved in 2000ml deionized waters；It at 20 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 9.5, after precipitation is stayed overnight at room temperature, is filtered, washing, in 100 DEG C
Drying crushes, after sieving, is roasted 4 hours at 750 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has point brilliant
Stone structure, hole hold 0.46cm3/ g, specific surface area 115m2/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 (6.4g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 90 DEG C of drying are roasted 4 hours for 550 DEG C, are then handled 4 hours at 550 DEG C with vapor in the air stream,
Finally lead to 550 DEG C of dry air to handle 1 hour.Gained catalyst is denoted as E.
Sample uses hydrogen, 500 DEG C of reduction activations 120 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 6】
Take 808.64g ferric nitrates (Fe (NO3)39H2O), 196.02g zinc nitrates (Zn (NO3)26H2O), 85.56g 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 10.2, after precipitation is stayed overnight at room temperature, is filtered, washing, in 60 DEG C
Drying crushes, after sieving, is roasted 3 hours at 850 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has point brilliant
Stone structure, hole hold 0.16cm3/ g, specific surface area 45m2/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 (5.5g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 80 DEG C of drying are roasted 3 hours for 530 DEG C, are then handled 4 hours at 530 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to 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 807.56g ferric nitrates (Fe (NO3)39H2O), 204.14g zinc nitrates (Zn (NO3)26H2O), 123.98g 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 8.5, 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 ferrite carrier.XRD characterization illustrates that carrier has point brilliant
Stone structure, hole hold 0.28cm3/ g, specific surface area 76m2/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 (6.0g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 60 DEG C of drying are roasted 3 hours for 530 DEG C, are then handled 4 hours at 530 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to 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 808.41g ferric nitrates (Fe (NO3)39H2O), 183.69g zinc nitrates (Zn (NO3)26H2O), 38.76g germanium oxides
(GeO2) be dissolved in 2000ml deionized waters；It at 35 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 10.0, at room temperature overnight by precipitation, is filtered, washing, in 120 DEG C of drying, is crushed,
After sieving, is roasted 6 hours at 750 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has spinel structure, Kong Rong
0.36cm3/ g, specific surface area 94m2/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 (7.9g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 80 DEG C of drying are roasted 3 hours for 530 DEG C, are then handled 4 hours at 530 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is denoted as H.
Sample uses hydrogen, 550 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 9】
Take 808.10g ferric nitrates (Fe (NO3)39H2O), 157.11g zinc nitrates (Zn (NO3)26H2O), 62.35g manganese nitrates
(Mn(NO3)24H2O), 64.12g 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 9.8, 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 ferrite load
Body.XRD characterization illustrates that there is carrier spinel structure, hole to hold 0.33cm3/ g, specific surface area 114m2/g.Carrier forms and acidity
It 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 (6.7g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 90 DEG C of drying are roasted 3 hours for 530 DEG C, are then handled 4 hours at 530 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is denoted as I.
Sample uses hydrogen, 550 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 10】
Take 808.33g ferric nitrates (Fe (NO3)39H2O), 182.15g zinc nitrates (Zn (NO3)26H2O), 93.24g cadmium nitrates
(Cd(NO3)2) be dissolved in 2000ml deionized waters；It at 26 DEG C, is vigorously stirred down, 15% ammonium hydroxide is slowly dropped to the mixing
In aqueous solution, precipitation is formed, control ph is about 9.8, after precipitation is stayed overnight at room temperature, is filtered, and washing is dried in 120 DEG C,
It crushes, after sieving, is roasted 8 hours at 750 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has spinelle knot
Structure, hole hold 0.37cm3/ g, specific surface area 106m2/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 (6.4g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 90 DEG C of drying are roasted 3 hours for 560 DEG C, are then handled 4 hours at 560 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is denoted as J.
Sample uses hydrogen, 550 DEG C of reduction activations 90 minutes to be reacted for dehydrogenation of isobutane before dehydrogenation reaction.
【Embodiment 11】
Take 810.16g ferric nitrates (Fe (NO3)39H2O), 99.84g zinc nitrates (Zn (NO3)26H2O), 163.80g copper nitrates
(Cu(NO3)2) be dissolved in 2000ml deionized waters；It at 26 DEG C, is vigorously stirred down, 15% ammonium hydroxide is slowly dropped to the mixing
In aqueous solution, precipitation is formed, control ph is about 9.8, after precipitation is stayed overnight at room temperature, is filtered, and washing is dried in 120 DEG C,
It crushes, after sieving, is roasted 8 hours at 750 DEG C, obtain compound zinc ferrite carrier.XRD characterization illustrates that carrier has spinelle knot
Structure, hole hold 0.32cm3/ g, specific surface area 112m2/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 (5.5g) 24 hours (metal platinum carrying capacity of aqueous solution (10ml)
0.4%), then 90 DEG C of drying are roasted 3 hours for 560 DEG C, are then handled 4 hours at 560 DEG C with vapor in the air stream,
Finally lead to 530 DEG C of dry air to handle 1 hour.Gained catalyst is denoted as K.
Sample uses hydrogen, 550 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, XRD characterization illustrates that carrier has typical spinel structure,
Different carrier precipitation processes be added without modified additive component.
Table 1
After metal promoter is added, catalyst surface acidity declines apparent.
【Embodiment 10~21】
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/C3H8For
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.
【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
Claims (7)
1. a kind of dehydrogenating low-carbon alkane prepares low-carbon alkene platinum catalyst, 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) it is selected from least one of I A of the periodic table of elements or II A races element or its compound, catalyst weight is calculated as with simple substance
0.05~35.0%；
C) zinc ferrite carrier, carrier account for the 63.5~94.9% of catalyst weight, and the support acidity measured using indicator method is low
In 0.4mmol/g；
Carrier forms coincidence formula：ZnxMyFe2O4, wherein M is in transition metal element Ni, Cu, Co, Mn, Ce, Cr or Ge
One or more, and x+y=1；0.5≤x < 1；By weight percentage, including following components：
A) Fe, 42.0~50.0% that vehicle weight is calculated as with simple substance；
B) Zn, 12.0~28.0% that vehicle weight is calculated as with simple substance；
C) M, 0.1~15.0% that vehicle weight is calculated as with simple substance.
2. dehydrogenating low-carbon alkane according to claim 1 prepares low-carbon alkene platinum catalyst, it is characterised in that the gold that M is represented
Belong to ionic radius between 0.06~0.09nm.
3. dehydrogenating low-carbon alkane according to claim 1 prepares low-carbon alkene platinum catalyst, it is characterised in that 0 < M/Zn≤
1。
4. dehydrogenating low-carbon alkane according to claim 1 prepares low-carbon alkene platinum catalyst, it is characterised in that the hole of carrier
Hold 0.08~0.8cm3/ g, 10~260m of specific surface area2/g。
5. Claims 1 to 4 any one of them dehydrogenating low-carbon alkane prepares the preparation method of low-carbon alkene platinum catalyst, including
Following steps：
A) soluble-salt of the desired amount of nitric hydrate iron, nitric hydrate zinc and transition metal M is configured to aqueous solution I, wherein M
One or more selected from Ni, Cu, Co, Mn, Ce, Cr, Ge transition metal element, Fe:(Zn+M) the amount ratio of substance be 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, carbonic acid ammonia；
C) under 0~50 DEG C of precipitation temperature, solution I is added in solution II, control ph 7.0~10.5 under stirring condition,
This is deposited in 50~150 DEG C of drying after being filtered, washed, is then roasted 1~24 hour at 650~1000 DEG C, obtains compound iron
Sour zinc carrier；
D) use infusion process in compound zinc ferrite supported on carriers active component, by the desired amount of chloroplatinate and selected from element week
The nitrate of at least one of I A of phase table or II A races element is configured to aqueous solution, and 1~48 is impregnated on compound zinc ferrite carrier
After hour, catalyst precarsor is obtained after dry；Catalyst precarsor is fired, reduction obtains dehydrogenating low-carbon alkane producing light olefins and urges
Agent.
6. dehydrogenating low-carbon alkane according to claim 5 prepares the preparation method of low-carbon alkene platinum catalyst, feature exists
In precipitation process pH value 7.5~9.5, precipitation temperature is at 10~45 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 4 the catalyst haptoreaction generate propylene and/or isobutene.
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| 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 |
| CN114797874A (en) * | 2022-05-31 | 2022-07-29 | 西安交通大学 | Spinel ferrite catalyst doped with metallic copper, preparation method and application |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3737473A (en) * | 1970-07-27 | 1973-06-05 | Phillips Petroleum Co | Two-stage dehydrogenation process |
| FI942019A (en) * | 1993-05-03 | 1994-11-04 | Phillips Petroleum Co | Platinum and tin containing catalyst and its use in alkane dehydrogenation |
| CN1317467A (en) * | 2000-04-07 | 2001-10-17 | 中国石油化工集团公司 | Process for processing low-carbon paraffin |
| CN1371304A (en) * | 1999-08-27 | 2002-09-25 | 胡茨曼石油化学公司 | Advances in dehydrogenation catalysis |
| CN101773850A (en) * | 2010-01-28 | 2010-07-14 | 清华大学 | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof |
| CN102247843A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Improvement method for stability of platinum-based catalyst for cycloparaffin dehydrogenation |
| 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 |
| CN103079695A (en) * | 2010-09-02 | 2013-05-01 | 沙特基础工业公司 | Modified zinc ferrite catalyst and method of preparation and use |
-
2014
- 2014-08-27 CN CN201410429000.3A patent/CN105363473B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3737473A (en) * | 1970-07-27 | 1973-06-05 | Phillips Petroleum Co | Two-stage dehydrogenation process |
| FI942019A (en) * | 1993-05-03 | 1994-11-04 | Phillips Petroleum Co | Platinum and tin containing catalyst and its use in alkane dehydrogenation |
| CN1371304A (en) * | 1999-08-27 | 2002-09-25 | 胡茨曼石油化学公司 | Advances in dehydrogenation catalysis |
| CN1317467A (en) * | 2000-04-07 | 2001-10-17 | 中国石油化工集团公司 | Process for processing low-carbon paraffin |
| CN101773850A (en) * | 2010-01-28 | 2010-07-14 | 清华大学 | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof |
| CN102247843A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Improvement method for stability of platinum-based catalyst for cycloparaffin dehydrogenation |
| CN103079695A (en) * | 2010-09-02 | 2013-05-01 | 沙特基础工业公司 | Modified zinc ferrite catalyst and method of preparation and use |
| 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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