CN104148060A - Platinum catalyst supported on double-oxide composite carrier and preparation method and application of platinum catalyst - Google Patents

Platinum catalyst supported on double-oxide composite carrier and preparation method and application of platinum catalyst Download PDF

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CN104148060A
CN104148060A CN201410333821.7A CN201410333821A CN104148060A CN 104148060 A CN104148060 A CN 104148060A CN 201410333821 A CN201410333821 A CN 201410333821A CN 104148060 A CN104148060 A CN 104148060A
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catalyst
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tio
platinum catalyst
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CN104148060B (en
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巩金龙
蒋锋
李水荣
刘刚
曾亮
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a platinum catalyst supported on a double-oxide composite carrier and a preparation method and an application of the platinum catalyst. The catalyst takes TiO2-Al2O3 double oxides as a carrier; the supported active component is Pt; the mass percentage content of Pt is 0.5-1.5%. The preparation method comprises the following steps: preparing the TiO2-Al2O3 double-oxide carrier by using a sol-gel method, subsequently dipping the obtained carrier into a chloroplatinic acid solution, drying and roasting, thereby obtaining the Pt/TiO2-Al2O3 catalyst. The catalyst disclosed by the invention is applicable to preparation of propylene by propane dehydrogenation in the presence of hydrogen atmosphere; and due to addition of TiO2, the acting forces between an active center and the product and a reactant are changed, so that the selectivity and the anti-carbon capability of propylene are improved, and relatively good reaction stability of the catalyst under the high temperature is ensured.

Description

A kind of platinum catalyst that is carried on double oxide complex carrier and its preparation method and application
Technical field
The present invention relates to a kind of loaded catalyst and its preparation method and application, specifically, relate to a kind of TiO of being carried on 2-Al 2o 3pt Catalysts and its preparation method on double oxide complex carrier and the application in preparing propylene by dehydrogenating propane.
Background technology
Propylene is adopted petrochemical materials the earliest, is also one of important alkene of producing petrochemicals, mainly for the production of polypropylene, and acrylonitrile, expoxy propane, acrylic acid, methacrylaldehyde, the chemical products such as phenol and fourth octanol.Propylene is mainly derived from the by-product of petroleum cracking ethene processed and petroleum catalytic cracking at present, and owing to being subject to the factors such as oil supply and product distribution, traditional handicraft propylene processed can not meet the existing market demand.And in recent years, along with the fast development of China's oil chemical industry, to propylene demand also day by day increase, there is huge breach in propylene market.The production technology that expands propylene source mainly contains preparing propylene by dehydrogenating propane, and alkene transforms mutually, low-carbon (LC) hydrocarbon cracking and preparing propylene from methanol etc., and wherein preparing propylene by dehydrogenating propane is of greatest concern and the most promising approach.
Dehydrogenating propane technique can be converted into cheap propane feed the olefin product with high value by catalytic process, product system is simple, and propene yield is high.Industrialized dehydrogenating propane technique has the Oleflex technique of Uop Inc., the Catofin technique of Lummus company, the Star technique of Phillips technique and Linden technique.Wherein, applying maximum, largest technique is Catofin technique and Oleflex technique.The catalyst that Catofin technique is used is chromium-based catalysts, but because chromium has toxicity, is unfavorable for protection of the environment, so its use is subject to certain restrictions.What Oleflex technique was used is platinum group catalyst, and it has higher catalytic activity and Propylene Selectivity, environmental friendliness, however platinum catalyst is expensive, easy carbon distribution inactivation in course of reaction, poor stability.
The key of dehydrogenating propane technique is that preparation has high activity, the catalyst of high stability.Propane dehydrogenation catalyst is mainly with Al at present 2o 3for carrier, take precious metals pt as active component, by adding auxiliary agent or changing support, reduce carbon distribution, improve stability.[the The effect of reaction conditions and time on stream on the coke formed during propane dehydrogenation.Journal of Catalyst such as Bengt Andersson, 1996,164:44-53.] studied the adding Pt/Al of Sn auxiliary agent 2o 3the effect of catalyst.Result shows can impel Pt-Sn/Al adding of Sn 2o 3catalyst surface carbon distribution is deposited on carrier more, prolection center, thus improved the appearance charcoal amount of catalyst.At Pt-Sn/Al 2o 3on the basis of catalyst, add alkaline assistant [Propane dehydrogenation over Pt-Sn/Rare-earth-doped Al 2o 3: Influence of La, Ce, or Y on the formation and stability of Pt-Sn alloys.Catalysis Today, 2011,164:214-220.], can in and the part acid site of carrier surface, unsaturated hydrocarbon molecule before carbon deposit is suppressed in the conversion at support acidity center and in the deposition of carrier surface, thereby strengthened carbon accumulation resisting ability, improved stability.But this catalyst still inactivation is very fast, stablizes and still need further raising.[the Dehydrogenation of propane over Pt-SBA-15and Pt-Sn-SBA-15:Effect of Sn on the dispersion of Pt and catalytic behavior.Catalysis Today such as M.Santhosh Kumar, 2009,142:17-23.] studied Pt series catalysts that a kind of SBA-15 of take is carrier and the effect of Sn auxiliary agent.Result shows, Sn auxiliary agent add reactivity and the Propylene Selectivity that has improved catalyst, and with respect to Al 2o 3carrier, on SBA-15 carrier, acidic site amount still less, is conducive to improve stability.But the conversion of propane of this catalyst is on the low side, still need further raising.
Summary of the invention
What the present invention will solve is that existing platinum group catalyst carbon distribution is serious, and easily inactivation and selective low technical problem, provide a kind of TiO 2-Al 2o 3double oxide carrier and support type Pt/TiO 2-Al 2o 3the preparation method of catalyst and the application in dehydrogenating propane, overcome Pt series catalysts carbon distribution serious, the fast and low problem of Propylene Selectivity of deactivation rate, thus improved propene yield.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical scheme:
Be carried on a platinum catalyst for double oxide complex carrier, described catalyst is with TiO 2-Al 2o 3composite oxides are carrier, take Pt metal as activated centre; Take catalyst gross mass as benchmark, and wherein Pt metal quality percentage composition is 0.5-1.5%, TiO 2quality percentage composition is 5-20%.
Preferably, Pt metal quality percentage composition is 1-1.5%, TiO 2quality percentage composition is 10-15%.
Preferably, in described catalyst, Pt metal exists with particle form, and the granular size of Pt metal, at 2-3nm, is disperseed comparatively even.
Above-mentioned catalyst is prepared according to following step:
Step 1, is dissolved in aluminium secondary butylate (ATSB), butyl titanate (TTB) and surfactant softex kw (CTAB) in isopropyl alcohol jointly, fully stirs to mix, and obtains mixed solution A; Wherein said aluminium secondary butylate consumption is 7.5-9.5 mass parts, and described butyl titanate consumption is 0.4-2 mass parts, and described surfactant softex kw consumption is 0.7-0.8 mass parts, and described isopropyl alcohol consumption is 10-12 mass parts; Preferably, described aluminium secondary butylate consumption is 7.7-9.2 mass parts, and described butyl titanate consumption is 0.43-1.72 mass parts, and described surfactant softex kw consumption is 0.75 mass parts, and described isopropyl alcohol consumption is 12 mass parts;
Step 2, the red fuming nitric acid (RFNA) of 65wt% and deionized water are mixed, obtain mixed solution B, in mixed solution A, drip mixed solution B to be hydrolyzed again, the red fuming nitric acid (RFNA) of wherein said 65wt% is that mass percent is 65% aqueous solution of nitric acid, consumption is 0.1-1.5 mass parts, preferably 0.1-1.41 mass parts; Described deionized water consumption is 2.5-12.5 mass parts, when dripping, is chosen in 5-10min and dropwises, and hydrolysis temperature is 20-25 degrees Celsius of room temperatures, and hydrolysis time is 0.5h at least, preferably 1-2h;
Step 3, by the reaction system obtaining through step 2 standing aging 24-40h under 20-25 degrees Celsius of room temperatures, except after desolventizing, dry 20-24h at 70-90 ℃ of temperature, finally roasting 3-5h at 550-650 ℃, obtains TiO 2-Al 2o 3composite oxides, as carrier;
Step 4, by the TiO of step 3 preparation 2-Al 2o 3composite oxides impregnated in the chloroplatinic acid aqueous solution that concentration is 0.005-0.015g/ml, so that load elements platinum, and at least 0.5h, preferably 1-2h of dip time wherein;
Step 5, by the TiO after step 4 dipping 2-Al 2o 3composite oxides are dry 10-12h at 80-100 ℃ of temperature, then at 550-650 ℃ roasting 3-5h, finally at H 2under atmosphere, fully reduce, obtain being carried on the platinum catalyst of double oxide complex carrier, i.e. Pt/TiO 2-Al 2o 3catalyst, preferred, at H 2under atmosphere, reduce 1-3h.
Utilize above-mentioned catalyst to face propane under nitrogen atmosphere and prepare propylene, according to following step, carry out:
Step 1, packs the catalyst of above-mentioned preparation into fixed bed reactors, passes into nitrogen and hydrogen mixture, at 500-550 ℃ of temperature, described catalyst is reduced to 1-2h, and in nitrogen and hydrogen mixture, hydrogen volume ratio is 10-15%;
Step 2, after to be restored completing, control reactor batch temperature is 550-650 ℃, take propane mass space velocity as 3-10h -1pass into reaction gas and react, wherein propane and hydrogen mol ratio are 1:1, and Balance Air is nitrogen.
In above-mentioned use procedure, the catalyst of above-mentioned preparation is carried out to compressing tablet processing, to obtain 20-40 object pellet type catalyst, use.
Compared with prior art, technical scheme of the present invention has following beneficial effect:
(1) catalyst of the present invention is with TiO 2-Al 2o 3double oxide is carrier, has high-specific surface area and mesopore orbit, is conducive to active component and is uniformly distributed and gas molecular diffusion; Take Pt as active component, adopt TiO 2-Al 2o 3for carrier, TiO 2add the active force that has changed product and reactant and activated centre, thereby improved Propylene Selectivity and carbon accumulation resisting ability.
(2) catalyst of the present invention is applicable to face under nitrogen atmosphere, and preparing propylene by dehydrogenating propane is had to good effect, and under hot conditions, dehydrogenation activity is very high, and Propylene Selectivity can reach 90%, and has good stability.
Accompanying drawing explanation
Fig. 1 is different Ti O 2the TiO of quality percentage composition 2-Al 2o 3the XRD spectra of carrier, wherein ▼ is Al 2o 3, ★ is TiO 2.
Fig. 2 is different Ti O 2the Pt/TiO of quality percentage composition 2-Al 2o 3the XRD spectra of catalyst, wherein ▼ is Al 2o 3, ★ is TiO 2.
Fig. 3 is gained Pt and TiO 2quality percentage composition is respectively 1.0% and 10% Pt/TiO 2-Al 2o 3the TEM figure of catalyst.
The specific embodiment
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
(1) get 8.7g aluminium secondary butylate (ATSB), 0.86g butyl titanate (TTB) and 0.75gCTAB are dissolved in 12g isopropyl alcohol jointly, and rotor stirs 2h;
(2) get the red fuming nitric acid (RFNA) 0.705g of 65wt% and deionized water 12.5g and mix, to dripping mixed solution in precursor solution, be hydrolyzed, hydrolysis time is 0.5h;
(3) by the standing aging 24h of gel generating, then except desolventizing, dry 20h at 70 ℃ of temperature, roasting 3h at 600 ℃, obtains TiO 2-Al 2o 3complex carrier;
(4) by TiO 2-Al 2o 3complex carrier impregnated in the platinum acid chloride solution that concentration is 0.01g/ml, ultrasonic 0.5h, dry 12h under room temperature condition;
Dry 12h at (5) 90 ℃ of temperature, roasting 3h at 600 ℃, that obtain is PtO 2/ TiO 2-Al 2o 3catalyst; Finally at H 2under atmosphere, reduce 1h, obtain Pt/TiO 2-Al 2o 3catalyst.
The TiO obtaining 2-Al 2o 3as shown in Figure 1, reduction is gained Pt/TiO afterwards for the XRD spectra of carrier 2-Al 2o 3(XRD adopts the RigakuD/max-2500 of Rigaku company shape diffractometer to the XRD spectra of catalyst, and the Cu/K alpha ray of take is measured as light source as shown in Figure 2.Target is copper target, and 2 θ measurable angle ranges are 20～80 °, and sweep speed is 4 °/min, and test sample is the powder after grinding, lower same).Gained Pt/TiO after reduction 2-Al 2o 3the TEM figure of catalyst is (TEM adopt be the JEM-2100F model field transmission electron microscope of company of NEC) as shown in Figure 3.Can find out that in the catalyst of method gained thus, Pt metal exists with particle form, the granular size of Pt, in 2-3nm left and right, is disperseed comparatively even.
Take catalyst gross mass as benchmark, and the quality percentage composition of Pt is 1%, TiO 2quality percentage composition be 10%.
(6) by Pt/TiO 2-Al 2o 3fine catalyst compressing tablet is 20-40 object pellet type catalyst;
(7) by the Pt/TiO after compressing tablet 2-Al 2o 3catalyst packs fixed bed reactors into, passes into nitrogen and hydrogen mixture, and at 500 ℃ of temperature, to described catalyst prereduction 1h, in nitrogen and hydrogen mixture, hydrogen volume ratio is 10%;
(8) having reduced rear control reactor batch temperature is 600 ℃, take propane mass space velocity as 10h -1pass into reaction gas, wherein propane and hydrogen mol ratio are 1:1, and Balance Air is nitrogen.
Conversion of propane, Propylene Selectivity and propene yield are with following various calculating:
Conversion ratio: Conv ( % ) = [ F C 3 H 8 ] in - [ F C 3 H 8 ] out [ F C 3 H 8 ] in ×100
Selective: Sel ( % ) = 3 × [ F C 3 H 6 ] out 3 × [ F C 3 H 6 ] out + 2 × [ F C 2 H 4 ] out + 2 × [ F C 2 H 6 ] out + [ F CH 4 ] out × 100
Yield: Yield ( % ) = Conv ( % ) × Sel ( % ) 100
Product adopts gas chromatograph on-line analysis, conversion of propane, and the relation of Propylene Selectivity and propene yield and time is as shown in table 1.
The conversion of propane of table 1, differential responses time, Propylene Selectivity and propene yield
Reaction time (h) Conversion of propane (%) Propylene Selectivity (%) Propene yield (%)
1 42.3 83.4 35.3
5 32.2 89.4 28.8
10 25.9 90.4 23.4
From table 1, this catalyst has higher activity and Propylene Selectivity, and has embodied good stability.The continuous inactivation of catalyst is to cause owing to reacting the carbon distribution producing.
Embodiment 2:
Adopt embodiment 1 method to react, its difference is only that in step (1), aluminium secondary butylate (ATSB) consumption is 9.2g, and butyl titanate (TTB) consumption is 0.43g, TiO in gained catalyst 2quality percentage composition is 5%.The TiO of gained 2-Al 2o 3as shown in Figure 1, reduction is gained Pt/TiO afterwards for the XRD spectra of carrier 2-Al 2o 3the XRD spectra of catalyst as shown in Figure 2.
Embodiment 3:
Adopt embodiment 1 method to react, its difference is only that in step (1), aluminium secondary butylate (ATSB) consumption is 7.7g, and butyl titanate (TTB) consumption is 1.72g, TiO in gained catalyst 2quality percentage composition is 20%.The TiO obtaining 2-Al 2o 3as shown in Figure 1, reduction is gained Pt/TiO afterwards for the XRD spectra of carrier 2-Al 2o 3the XRD spectra of catalyst as shown in Figure 2.
The composition of the carrier obtaining as can be seen from Figure 1, is TiO 2and Al 2o 3, be verified as double oxide complex carrier; Work as TiO 2when percentage composition is 5%, without TiO 2peak occurs, works as TiO 2when quality percentage composition reaches 10%, there is TiO 2diffraction maximum and its peak are by force with TiO 2quality percentage composition increase and constantly strengthen, and Al 2o 3peak constantly weaken by force thereupon, prove thus TiO 2be distributed in Al 2o 3surface, and high degree of dispersion.
By Fig. 2, found out, adding of Pt do not affect TiO 2-Al 2o 3the structure of carrier and TiO 2at Al 2o 3the dispersion on surface; And the diffraction maximum of Pt in spectrogram, do not detected, prove that Pt particle high degree of dispersion is at carrier surface.
Embodiment 4:
Adopt embodiment 1 method to react, its difference is only that the red fuming nitric acid (RFNA) consumption of step (2) is 0g.
Embodiment 5:
Adopt embodiment 1 method to react, its difference is only that the red fuming nitric acid (RFNA) consumption of step (2) is 1.41g.
Embodiment 6:
Adopt embodiment 1 method to react, its difference is only that the deionized water consumption of step (2) is 2.5g.
Embodiment 7:
Adopt embodiment 1 method to react, its difference is only that the deionized water consumption of step (2) is 7.5g.
Embodiment 8:
Adopt embodiment 1 method to react, its difference is only that the baking temperature of step (3) is 80 ℃.
Embodiment 9:
Adopt embodiment 1 method to react, its difference is only that the baking temperature of step (3) is 90 ℃.
Embodiment 10:
Adopt embodiment 2 methods to react, its difference is only that the sintering temperature of step (3) and step (5) is 550 ℃.
Embodiment 11:
Adopt embodiment 3 methods to react, its difference is only that the sintering temperature of step (3) and step (5) is 650 ℃.
Embodiment 12:
Adopt embodiment 4 methods to react, its difference is only that the chloroplatinic acid concentration in step (4) is 0.005g/ml, and in the catalyst obtaining, Pt quality percentage composition is 0.5%.
Embodiment 13:
Adopt embodiment 1 method to react, its difference is only that the chloroplatinic acid concentration in step (4) is 0.015g/ml, and in the catalyst obtaining, Pt quality percentage composition is 1.5%.
Embodiment 14:
Adopt embodiment 1 method to react, its difference is only that the baking temperature of step (5) is 80 ℃.
Embodiment 15:
Adopt embodiment 1 method to react, its difference is only that the baking temperature of step (5) is 100 ℃.
Embodiment 16:
Adopt embodiment 1 method to react, its difference is only that the reaction temperature of step (8) is 550 ℃.
Embodiment 17:
Adopt embodiment 1 method to react, its difference is only that the reaction temperature of step (8) is 650 ℃.
Embodiment 18:
Adopt embodiment 1 method to react, its difference is only that the propane mass space velocity of step (8) is 3h -1.
Embodiment 19:
Adopt embodiment 1 method to react, its difference is only that the propane mass space velocity of step (8) is 7h -1.
About above-described embodiment result and data, all adopt the activity data of the rear 5h of reaction to contrast, to investigate the impact of different parameters on catalyst reaction performance.
(1) TiO 2the impact of quality percentage composition on catalyst reaction activity, referring to table 2.Reaction condition is with embodiment 1,2,3.
Table 2, TiO 2the impact of quality percentage composition on catalyst reaction activity and Propylene Selectivity
TiO 2Quality percentage composition (%) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
5 28.7 88.3 25.3
10 32.2 89.4 28.8
20 25.6 92.7 23.7
From above result, can see, along with TiO 2content increase, the selective of propylene constantly increases, but the conversion ratio of propane occurs first increasing the trend reducing afterwards, and the rule that first rises and decline afterwards also appears in the yield of propylene.Visible, TiO 2mass content while being 10%, conversion of propane is 32.2%, Propylene Selectivity is 89.4%.Propene yield reaches 28.8%, has reached optimal value.
(2) impact of the quality percentage composition of Pt on catalyst reaction activity, referring to table 3.Reaction condition is with embodiment 1,12,13.
The impact of the quality percentage composition of table 3, Pt on catalyst reaction activity and Propylene Selectivity
Pt quality percentage composition (%) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
0.5 25.6 91.3 23.4
1.0 32.2 89.4 28.8
1.5 33.1 85.5 28.3
As can be seen from the above results, along with the increase of Pt content, conversion of propane increases gradually, but when Pt content increases to 1.5% by 1.0%, conversion ratio increase is not obvious, starts to tend towards stability; And the increase of Pt content causes Propylene Selectivity constantly to lower, there is first increasing the trend reducing afterwards in propene yield.When Pt quality percentage composition is 1.0%, propene yield is best.
(3) TiO 2-Al 2o 3the impact of red fuming nitric acid (RFNA) consumption on catalyst reaction activity and Propylene Selectivity in preparation process, referring to table 4.Reaction condition is with embodiment 1,4,5.
Table 4, TiO 2-Al 2o 3the impact of red fuming nitric acid (RFNA) consumption on catalyst reaction activity and Propylene Selectivity in preparation process
Red fuming nitric acid (RFNA) consumption (g) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
0 30.4 87.3 26.5
0.705 32.2 89.4 28.8
1.41 31.0 89.8 27.8
Result from table can find out, along with the increase of red fuming nitric acid (RFNA) consumption, Propylene Selectivity increases gradually, but when red fuming nitric acid (RFNA) consumption increases to 1.41g by 0.705g, and selective increase is not obvious, starts to tend towards stability; And the increase of red fuming nitric acid (RFNA) consumption makes transformation of propane take the lead in increasing rear reduction, thereby impel propene yield first to rise and decline afterwards.Therefore best red fuming nitric acid (RFNA) consumption is than being 0.705g.
(4) TiO 2-Al 2o 3the impact of the consumption of deionized water on catalyst reaction activity and Propylene Selectivity in preparation process, referring to table 5.Reaction condition is with embodiment 1,6,7.
Table 5, TiO 2-Al 2o 3the impact of the consumption of deionized water on catalyst reaction activity and Propylene Selectivity in preparation process
Deionized water consumption (g) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
2.5 27.8 90.3 25.1
7.5 29.6 91.5 27.1
12.5 32.2 89.4 28.8
Result from table can find out, along with deionized water consumption increases, conversion of propane constantly increases, and Propylene Selectivity first increases rear reduction, but changes faintly, and propene yield constantly raises along with the increase of water consumption.
(5) TiO 2-Al 2o 3the impact of baking temperature (step 3) on catalyst reaction activity and Propylene Selectivity in preparation process, referring to table 6.Reaction condition is with embodiment 1,8,9.
Table 6, TiO 2-Al 2o 3the impact of baking temperature on catalyst reaction activity and Propylene Selectivity in preparation process
Baking temperature (℃) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
70 32.2 89.4 28.8
80 30.5 90.1 27.5
90 28.9 90.6 26.2
Result from above-mentioned table can find out, along with the rising of baking temperature, conversion of propane constantly reduces, and that Propylene Selectivity changes is very little, and propene yield constantly reduces along with the rising of baking temperature.Therefore, in carrier preparation process, optimum drying temperature is 70 ℃.
(6) impact of sintering temperature on catalyst reaction activity and Propylene Selectivity in carrier and catalyst preparation process, referring to table 7.Reaction condition is with embodiment 1,10,11.
The impact of sintering temperature on catalyst reaction activity and Propylene Selectivity in table 7, carrier and catalyst preparation process
Sintering temperature (℃) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
550 30.1 90.6 27.3
600 32.2 89.4 28.8
650 27.8 91.3 25.4
Result from table can be found out, along with the rising of sintering temperature, reduce, and Propylene Selectivity Changing Pattern is contrary after transformation of propane takes the lead in raising, and first reducing increases afterwards, and propene yield presents the trend that first raises and reduce afterwards along with the rising of sintering temperature.Therefore, optimum calcination temperature is 600 ℃.
(7) impact of baking temperature on catalyst reaction activity and Propylene Selectivity in catalyst preparation process (step 5), referring to table 8.Reaction condition is with embodiment 1,14,15.
The impact of baking temperature on catalyst reaction activity and Propylene Selectivity in table 8, catalyst preparation process
Baking temperature (℃) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
80 32.7 86.5 28.3
90 32.2 89.4 28.8
100 30.5 91.3 27.8
Result from above-mentioned table can find out, along with the rising of baking temperature, conversion of propane constantly reduces, and Propylene Selectivity rises gradually, and propene yield constantly reduces along with the rising of baking temperature.Therefore, in catalyst preparation process, optimum drying temperature is 90 ℃.
(8) impact of reaction temperature on catalyst reaction activity and Propylene Selectivity, referring to table 9.Reaction condition is with embodiment 1,16,17.
Table 9, the impact of reaction temperature on catalyst reaction activity and Propylene Selectivity
Baking temperature (℃) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
550 19.8 94.3 18.7
600 32.2 89.4 28.8
650 42.7 56.8 24.3
As can be seen from the results, because dehydrogenating propane is the endothermic reaction, along with the rising of reaction temperature, conversion of propane constantly raises, however but sharply decline of Propylene Selectivity, and propene yield is along with the rising of reaction temperature first increases then reduction.Therefore, dehydrogenating propane optimal reaction temperature is 600 ℃.
(9) impact of propane mass space velocity on catalyst reaction activity and Propylene Selectivity, referring to table 10.Reaction condition is with embodiment 1,18,19.
Table 10, the impact of propane mass space velocity on catalyst reaction activity and Propylene Selectivity
Propane mass space velocity (h -1) Conversion of propane (%) Propylene Selectivity (%) Propane yield (%)
3 36.3 76.8 27.9
7 34.5 81.4 28.1
10 32.2 89.4 28.8
As can be seen from the above results, along with the rising of propane mass space velocity, conversion of propane constantly reduces, and Propylene Selectivity raises, and propene yield also constantly rises.Best propane mass space velocity is 10h -1.
Above the present invention has been done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.

Claims (10)

1. a platinum catalyst that is carried on double oxide complex carrier, is characterized in that, described catalyst is with TiO 2-Al 2o 3composite oxides are carrier, take Pt metal as activated centre; Take catalyst gross mass as benchmark, and in described catalyst, Pt metal exists with particle form, and the granular size of Pt metal, at 2-3nm, is uniformly dispersed, and wherein Pt metal quality percentage composition is 0.5-1.5%, TiO 2quality percentage composition is 5-20%, and is prepared according to following step:
Step 1, is dissolved in aluminium secondary butylate, butyl titanate and surfactant softex kw in isopropyl alcohol jointly, fully stirs to mix, and obtains mixed solution A; Wherein said aluminium secondary butylate consumption is 7.5-9.5 mass parts, and described butyl titanate consumption is 0.4-2 mass parts, and described surfactant softex kw consumption is 0.7-0.8 mass parts, and described isopropyl alcohol consumption is 10-12 mass parts;
Step 2, the red fuming nitric acid (RFNA) of 65wt% and deionized water are mixed, obtain mixed solution B, then drip mixed solution B to be hydrolyzed in mixed solution A, the red fuming nitric acid (RFNA) of wherein said 65wt% is that mass percent is 65% aqueous solution of nitric acid, and consumption is 0.1-1.5 mass parts; Described deionized water consumption is 2.5-12.5 mass parts, when dripping, is chosen in 5-10min and dropwises, and hydrolysis temperature is 20-25 degrees Celsius of room temperatures, and hydrolysis time is 0.5h at least;
Step 3, by the reaction system obtaining through step 2 standing aging 24-40h under 20-25 degrees Celsius of room temperatures, except after desolventizing, dry 20-24h at 70-90 ℃ of temperature, finally roasting 3-5h at 550-650 ℃, obtains TiO 2-Al 2o 3composite oxides, as carrier;
Step 4, by the TiO of step 3 preparation 2-Al 2o 3composite oxides impregnated in the chloroplatinic acid aqueous solution that concentration is 0.005-0.015g/ml, so that load elements platinum, and dip time 0.5h at least wherein;
Step 5, by the TiO after step 4 dipping 2-Al 2o 3composite oxides are dry 10-12h at 80-100 ℃ of temperature, then at 550-650 ℃ roasting 3-5h, finally at H 2under atmosphere, fully reduce, obtain being carried on the platinum catalyst of double oxide complex carrier, i.e. Pt/TiO 2-Al 2o 3catalyst.
2. a kind of platinum catalyst that is carried on double oxide complex carrier according to claim 1, is characterized in that, Pt metal quality percentage composition is 1-1.5%, TiO 2quality percentage composition is 10-15%.
3. a kind of platinum catalyst that is carried on double oxide complex carrier according to claim 1, it is characterized in that, in step 1, described aluminium secondary butylate consumption is 7.7-9.2 mass parts, described butyl titanate consumption is 0.43-1.72 mass parts, described surfactant softex kw consumption is 0.75 mass parts, and described isopropyl alcohol consumption is 12 mass parts.
4. a kind of platinum catalyst that is carried on double oxide complex carrier according to claim 1, is characterized in that, in step 2, the red fuming nitric acid (RFNA) consumption of described 65wt% is 0.1-1.41 mass parts; Hydrolysis time 1-2h.
5. a kind of platinum catalyst that is carried on double oxide complex carrier according to claim 1, is characterized in that, in step 4, and dip time 1-2h; In step 5, at H 2under atmosphere, reduce 1-3h.
6. a preparation method who is carried on the platinum catalyst of double oxide complex carrier, is characterized in that, according to following step, is prepared:
Step 1, is dissolved in aluminium secondary butylate, butyl titanate and surfactant softex kw in isopropyl alcohol jointly, fully stirs to mix, and obtains mixed solution A; Wherein said aluminium secondary butylate consumption is 7.5-9.5 mass parts, and described butyl titanate consumption is 0.4-2 mass parts, and described surfactant softex kw consumption is 0.7-0.8 mass parts, and described isopropyl alcohol consumption is 10-12 mass parts;
Step 2, the red fuming nitric acid (RFNA) of 65wt% and deionized water are mixed, obtain mixed solution B, then drip mixed solution B to be hydrolyzed in mixed solution A, the red fuming nitric acid (RFNA) of wherein said 65wt% is that mass percent is 65% aqueous solution of nitric acid, and consumption is 0.1-1.5 mass parts; Described deionized water consumption is 2.5-12.5 mass parts, when dripping, is chosen in 5-10min and dropwises, and hydrolysis temperature is 20-25 degrees Celsius of room temperatures, and hydrolysis time is 0.5h at least;
Step 3, by the reaction system obtaining through step 2 standing aging 24-40h under 20-25 degrees Celsius of room temperatures, except after desolventizing, dry 20-24h at 70-90 ℃ of temperature, finally roasting 3-5h at 550-650 ℃, obtains TiO 2-Al 2o 3composite oxides, as carrier;
Step 4, by the TiO of step 3 preparation 2-Al 2o 3composite oxides impregnated in the chloroplatinic acid aqueous solution that concentration is 0.005-0.015g/ml, so that load elements platinum, and dip time 0.5h at least wherein;
Step 5, by the TiO after step 4 dipping 2-Al 2o 3composite oxides are dry 10-12h at 80-100 ℃ of temperature, then at 550-650 ℃ roasting 3-5h, finally at H 2under atmosphere, fully reduce, obtain being carried on the platinum catalyst of double oxide complex carrier, i.e. Pt/TiO 2-Al 2o 3catalyst.
7. a kind of preparation method who is carried on the platinum catalyst of double oxide complex carrier according to claim 6, it is characterized in that, in step 1, described aluminium secondary butylate consumption is 7.7-9.2 mass parts, described butyl titanate consumption is 0.43-1.72 mass parts, described surfactant softex kw consumption is 0.75 mass parts, and described isopropyl alcohol consumption is 12 mass parts; In step 2, the red fuming nitric acid (RFNA) consumption of described 65wt% is 0.1-1.41 mass parts; Hydrolysis time 1-2h.
8. a kind of preparation method who is carried on the platinum catalyst of double oxide complex carrier according to claim 6, is characterized in that, in step 4, and dip time 1-2h; In step 5, at H 2under atmosphere, reduce 1-3h.
9. the propane under facing nitrogen atmosphere of the platinum catalyst that is carried on double oxide complex carrier as described in one of claim 1-5 is prepared the application in propylene, it is characterized in that, according to following step, carries out:
Step 1, packs the platinum catalyst catalyst that is carried on double oxide complex carrier into fixed bed reactors, passes into nitrogen and hydrogen mixture, at 500-550 ℃ of temperature, described catalyst is reduced to 1-2h, and in nitrogen and hydrogen mixture, hydrogen volume ratio is 10-15%;
Step 2, after to be restored completing, control reactor batch temperature is 550-650 ℃, take propane mass space velocity as 3-10h -1pass into reaction gas and react, wherein propane and hydrogen mol ratio are 1:1, and Balance Air is nitrogen.
10. the platinum catalyst propane under facing nitrogen atmosphere that is carried on double oxide complex carrier according to claim 9 is prepared the application in propylene, it is characterized in that, catalyst is carried out to compressing tablet processing, to obtain 20-40 object pellet type catalyst, uses.
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