CN105478107A - Application of platinum catalyst in preparation of propylene by dimethylmethane - Google Patents

Application of platinum catalyst in preparation of propylene by dimethylmethane Download PDF

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CN105478107A
CN105478107A CN201510970983.6A CN201510970983A CN105478107A CN 105478107 A CN105478107 A CN 105478107A CN 201510970983 A CN201510970983 A CN 201510970983A CN 105478107 A CN105478107 A CN 105478107A
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propane
catalyst
tio
consumption
propylene
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CN105478107B (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
    • B01J35/61—
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses application of a platinum catalyst in preparation of propylene by dimethylmethane. The catalyst takes a TiO2-Al2O3 dual oxide as a carrier, a loaded active component is Pt, and the mass percentage composition of the Pt is 0.5-1.5 percent. The TiO2-Al2O3 dual oxide carrier is prepared by adopting a sol-gel method, and then the obtained carrier is steeped into a chloroplatinic acid solution, and is dried and calcined, thus obtaining the Pt/TiO2-Al2O3 catalyst. The catalyst is suitable for preparing the propylene by dimethylmethane dehydrogenation under a hydrogenation atmosphere; the addition of TiO2 changes the acting force of a product as well as a reactant with an active center, thus propylene selectivity and carbon deposition resistance are improved, and the catalyst is enabled to have better reaction stability under a high temperature condition.

Description

The application in propylene prepared by platinum catalyst at propane
The present patent application is the divisional application of parent application " a kind of be carried on platinum catalyst of double oxide complex carrier and its preparation method and application ", and the applying date of parent application is on July 14th, 2014, and the application number of parent application is 2014103338217.
Technical field
The present invention relates to a kind of loaded catalyst and its preparation method and application, specifically, relate to one and be carried on TiO 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 producing petrochemicals, mainly for the production of polypropylene, and acrylonitrile, expoxy propane, acrylic acid, methacrylaldehyde, the chemical products such as phenol and octyl alconyl.Current propylene is mainly derived from the by-product of petroleum cracking ethene and petroleum catalytic cracking, and owing to being subject to the factors such as oil supply and product distribution, traditional handicraft propylene 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 expanding propylene source mainly contains preparing propylene by dehydrogenating propane, and alkene transforms mutually, and low-carbon (LC) hydrocarbon cracking and preparing propylene from methanol etc., wherein preparing propylene by dehydrogenating propane is of greatest concern and the most promising approach.
The propane feed of cheapness can be converted into the olefin product with high value by dehydrogenating propane technique 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 uses is chromium-based catalysts, but has toxicity due to chromium, and be unfavorable for protection of the environment, therefore its use is subject to certain restrictions.Oleflex technique uses platinum group catalyst, and it has higher catalytic activity and Propylene Selectivity, environmental friendliness, but 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.Current propane dehydrogenation catalyst is mainly with Al 2o 3for carrier, take precious metals pt as active component, reduce carbon distribution by adding auxiliary agent or changing support, improve stability.[the Theeffectofreactionconditionsandtimeonstreamonthecokefor medduringpropanedehydrogenation.JournalofCatalyst such as BengtAndersson, 1996,164:44-53.] have studied the adding Pt/Al of Sn auxiliary agent 2o 3the effect of catalyst.Result shows that adding of Sn can impel Pt-Sn/Al 2o 3catalyst surface carbon distribution is deposited on carrier more, prolection center, thus improves the appearance charcoal amount of catalyst.At Pt-Sn/Al 2o 3the basis of catalyst is added alkaline assistant [PropanedehydrogenationoverPt-Sn/Rare-earth-dopedAl 2o 3: InfluenceofLa, Ce, orYontheformationandstabilityofPt-Snalloys.CatalysisToda y, 2011,164:214-220.], can in and the part acid site of carrier surface, before making carbon deposit, the conversion of unsaturated hydrocarbon molecule at support acidity center and the deposition at carrier surface are suppressed, thus enhance carbon accumulation resisting ability, improve stability.But this catalyst still inactivation is very fast, stablizes and still needs further raising.[the DehydrogenationofpropaneoverPt-SBA-15andPt-Sn-SBA-15:Eff ectofSnonthedispersionofPtandcatalyticbehavior.Catalysis Today such as M.SanthoshKumar, 2009,142:17-23.] to have studied a kind of take SBA-15 as the Pt series catalysts of carrier and the effect of Sn auxiliary agent.Result shows, Sn auxiliary agent add the reactivity and Propylene Selectivity that improve catalyst, and relative to Al 2o 3carrier, on SBA-15 carrier, acidic site amount is less, is conducive to improving stability.But the conversion of propane of this catalyst is on the low side, still need further raising.
Summary of the invention
The present invention is to solve existing platinum group catalyst carbon distribution is serious, easy in 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 problem that deactivation rate is fast and Propylene Selectivity is low, thus improve 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; With catalyst gross mass for benchmark, wherein Pt metal mass percentage is 0.5-1.5%, TiO 2mass percentage is 5-20%.
Preferably, Pt metal mass percentage is 1-1.5%, TiO 2mass percentage is 10-15%.
Preferably, in described catalyst, Pt metal exists in granular 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 isopropyl alcohol jointly by aluminium secondary butylate (ATSB), butyl titanate (TTB) and surfactant softex kw (CTAB), fully stirs to mix, 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, mixed solution B is dripped again to be hydrolyzed in mixed solution A, the red fuming nitric acid (RFNA) of wherein said 65wt% to be mass percent be 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, and when dripping, select to dropwise in 5-10min, hydrolysis temperature is room temperature 20-25 degrees Celsius, and hydrolysis time is 0.5h at least, preferably 1-2h;
Step 3, the reaction system obtained through step 2 is left standstill aging 24-40h under room temperature 20-25 degrees Celsius, and after desolventizing, dry 20-24h at 70-90 DEG C of temperature, finally roasting 3-5h at 550-650 DEG C, obtains TiO 2-Al 2o 3composite oxides, as carrier;
Step 4, TiO prepared by step 3 2-Al 2o 3composite oxides impregnated in the chloroplatinic acid aqueous solution that concentration is 0.005-0.015g/ml, to make Payload element platinum, and wherein dip time at least 0.5h, preferably 1-2h;
Step 5, the TiO after step 4 is flooded 2-Al 2o 3composite oxides are dry 10-12h at 80-100 DEG C of temperature, then at 550-650 DEG C roasting 3-5h, finally at H 2fully reduce under atmosphere, obtain the platinum catalyst being carried on double oxide complex carrier, i.e. Pt/TiO 2-Al 2o 3catalyst, preferably, at H 2reduction 1-3h under atmosphere.
Under utilizing above-mentioned catalyst to carry out facing nitrogen atmosphere, propane prepares propylene, carries out according to following step:
Step 1, the catalyst of above-mentioned preparation is loaded fixed bed reactors, and pass into nitrogen and hydrogen mixture, at 500-550 DEG C of temperature, carry out reduction 1-2h to described catalyst, in nitrogen and hydrogen mixture, hydrogen volume ratio is 10-15%;
Step 2, to be restored complete after, control reactor batch temperature is 550-650 DEG C, with propane mass space velocity for 3-10h -1pass into reaction gas to 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 compressing tablet process, use to obtain 20-40 object pellet type catalyst.
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-ratio surface sum 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 changing product and reactant and activated centre, thus improve Propylene Selectivity and carbon accumulation resisting ability.
(2) under catalyst of the present invention is applicable to face nitrogen atmosphere, have good effect to preparing propylene by dehydrogenating propane, dehydrogenation activity is very high under the high temperature conditions, and Propylene Selectivity can reach 90%, and has good stability.
Accompanying drawing explanation
Fig. 1 is different Ti O 2the TiO of mass percentage 2-Al 2o 3the XRD spectra of carrier, wherein ▼ is Al 2o 3, be TiO 2.
Fig. 2 is different Ti O 2the Pt/TiO of mass percentage 2-Al 2o 3the XRD spectra of catalyst, wherein ▼ is Al 2o 3, be TiO 2.
Fig. 3 is gained Pt and TiO 2mass percentage is respectively the Pt/TiO of 1.0% and 10% 2-Al 2o 3the TEM figure of catalyst.
Detailed description of the invention
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 red fuming nitric acid (RFNA) 0.705g and the deionized water 12.5g mixing of 65wt%, in precursor solution, drip mixed solution be hydrolyzed, hydrolysis time is 0.5h;
(3) gel of generation is left standstill aging 24h, then except desolventizing, dry 20h at 70 DEG C of temperature, at 600 DEG C, roasting 3h, 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 DEG C of temperature, roasting 3h at 600 DEG C, that obtain is PtO 2/ TiO 2-Al 2o 3catalyst; Last at H 2reduce 1h under atmosphere, obtain Pt/TiO 2-Al 2o 3catalyst.
The TiO obtained 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 Rigaku company RigakuD/max-2500 shape diffractometer to the XRD spectra of catalyst, with Cu/K alpha ray for light source measures 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 as shown in Figure 3 (TEM adopt be the JEM-2100F model Flied emission transmission electron microscope of company of NEC).Can find out that in the catalyst of method gained thus, Pt metal exists in granular form, the granular size of Pt, at about 2-3nm, is disperseed comparatively even.
With catalyst gross mass for benchmark, the mass percentage of Pt is 1%, TiO 2mass percentage 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 loads fixed bed reactors, and pass into nitrogen and hydrogen mixture, to described catalyst prereduction 1h at 500 DEG C of temperature, in nitrogen and hydrogen mixture, hydrogen volume ratio is 10%;
(8) the rear control reactor batch temperature that reduced is 600 DEG C, with propane mass space velocity for 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 variously to calculate with following:
Conversion ratio: C o n v ( % ) = [ F C 3 H 8 ] i n - [ F C 3 H 8 ] o u t [ F C 3 H 8 ] i n × 100
Selective: S e l ( % ) = 3 × [ F C 3 H 6 ] o u t 3 × [ F C 3 H 6 ] o u t + 2 × [ F C 2 H 4 ] o u t + 2 × [ F C 2 H 6 ] o u t + [ F CH 4 ] o u t × 100
Y i e l d ( % ) = C o n v ( % ) × S e l ( % ) 100
Product adopts gas chromatograph on-line analysis, and conversion of propane, the relation of Propylene Selectivity and propene yield and time is as shown in table 1.
Table 1, the conversion of propane of 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 embodies good stability.The continuous inactivation of catalyst causes owing to reacting the carbon distribution produced.
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 2mass percentage 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 2mass percentage is 20%.The TiO obtained 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.
As can be seen from Figure 1, the composition of the carrier obtained 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 mass percentage reaches 10%, there is TiO 2diffraction maximum and its peak are by force with TiO 2mass percentage increase and constantly strengthen, and Al 2o 3peak constantly weaken by force thereupon, prove TiO thus 2be distributed in Al 2o 3surface, and high degree of dispersion.
Found out by Fig. 2, adding of Pt does 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 is highly dispersed 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 DEG C.
Embodiment 9:
Adopt embodiment 1 method to react, its difference is only that the baking temperature of step (3) is 90 DEG C.
Embodiment 10:
Adopt embodiment 2 method to react, its difference is only that the sintering temperature of step (3) and step (5) is 550 DEG C.
Embodiment 11:
Adopt embodiment 3 method to react, its difference is only that the sintering temperature of step (3) and step (5) is 650 DEG C.
Embodiment 12:
Adopt embodiment 4 method to react, its difference is only that the chloroplatinic acid concentration in step (4) is 0.005g/ml, and in the catalyst obtained, Pt mass percentage 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 obtained, Pt mass percentage is 1.5%.
Embodiment 14:
Adopt embodiment 1 method to react, its difference is only that the baking temperature of step (5) is 80 DEG C.
Embodiment 15:
Adopt embodiment 1 method to react, its difference is only that the baking temperature of step (5) is 100 DEG C.
Embodiment 16:
Adopt embodiment 1 method to react, its difference is only that the reaction temperature of step (8) is 550 DEG C.
Embodiment 17:
Adopt embodiment 1 method to react, its difference is only that the reaction temperature of step (8) is 650 DEG C.
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, after all adopting reaction, the activity data of 5h contrasts, to investigate the impact of different parameters on catalyst reaction performance.
(1) TiO 2mass percentage on the impact of catalyst reaction activity, see table 2.Reaction condition is with embodiment 1,2,3.
Table 2, TiO 2the impact of mass percentage active on catalyst reaction in Propylene Selectivity
TiO 2Mass percentage (%) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
5 28.7 88.3 25.3
10 32.2 89.4 28.8
20 25.6 92.7 23.7
Can see, along with TiO from above result 2content increase, the selective continuous increase of propylene, but the conversion ratio of propane occurs first increasing the trend reduced afterwards, and also there is the rule declined afterwards that first rises in the yield of propylene.Visible, TiO 2mass content when being 10%, conversion of propane is 32.2%, and Propylene Selectivity is 89.4%.Propene yield reaches 28.8%, reaches optimal value.
(2) mass percentage of Pt is on the impact of catalyst reaction activity, see table 3.Reaction condition is with embodiment 1,12,13.
The impact of the mass percentage of table 3, Pt active on catalyst reaction in Propylene Selectivity
Pt mass percentage (%) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
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, propene yield occurs first increasing the trend reduced afterwards.When Pt mass percentage is 1.0%, propene yield is best.
(3) TiO 2-Al 2o 3the impact of red fuming nitric acid (RFNA) consumption active on catalyst reaction in Propylene Selectivity in preparation process,
See 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 active on catalyst reaction in Propylene Selectivity in preparation process
Red fuming nitric acid (RFNA) consumption (g) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
0 30.4 87.3 26.5
0.705 32.2 89.4 28.8
1.41 31.0 89.8 27.8
Result as can be seen from table, 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, 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, thus impel propene yield first to rise to 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 active on catalyst reaction in Propylene Selectivity in preparation process, see table 5.Reaction condition is with embodiment 1,6,7.
Table 5, TiO 2-Al 2o 3the impact of the consumption of deionized water active on catalyst reaction in Propylene Selectivity in preparation process
Deionized water consumption (g) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
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 as can be seen from table, along with deionized water consumption increases, conversion of propane constantly increases, and Propylene Selectivity first increases rear reduction, but changes faint, and propene yield constantly raises along with the increase of water consumption.
(5) TiO 2-Al 2o 3the impact of baking temperature (step 3) active on catalyst reaction in Propylene Selectivity in preparation process, see table 6.Reaction condition is with embodiment 1,8,9.
Table 6, TiO 2-Al 2o 3the impact of baking temperature active on catalyst reaction in Propylene Selectivity in preparation process
Result as can be seen from above-mentioned table, along with the rising of baking temperature, conversion of propane constantly reduces, and Propylene Selectivity change 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 DEG C.
(6) impact of sintering temperature active on catalyst reaction in Propylene Selectivity in carrier and catalyst preparation process, see table 7.Reaction condition is with embodiment 1,10,11.
The impact of sintering temperature active on catalyst reaction in Propylene Selectivity in table 7, carrier and catalyst preparation process
Sintering temperature (DEG C) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
550 30.1 90.6 27.3
600 32.2 89.4 28.8
650 27.8 91.3 25.4
Result as can be seen from table, along with the rising of sintering temperature, transformation of propane takes the lead in raising rear reduction, and Propylene Selectivity Changing Pattern is contrary, and first reducing increases afterwards, and propene yield presents the trend first raising and reduce afterwards along with the rising of sintering temperature.Therefore, optimum calcination temperature is 600 DEG C.
(7) impact of baking temperature active on catalyst reaction in Propylene Selectivity in catalyst preparation process (step 5), see table 8.Reaction condition is with embodiment 1,14,15.
The impact of baking temperature active on catalyst reaction in Propylene Selectivity in table 8, catalyst preparation process
Baking temperature (DEG C) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
80 32.7 86.5 28.3
90 32.2 89.4 28.8
100 30.5 91.3 27.8
Result as can be seen from above-mentioned table, 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 DEG C.
(8) impact of reaction temperature active on catalyst reaction in Propylene Selectivity, see table 9.Reaction condition is with embodiment 1,16,17.
The impact of table 9, reaction temperature active on catalyst reaction in Propylene Selectivity
Baking temperature (DEG C) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
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, but Propylene Selectivity but sharply declines, and propene yield then reduces along with the rising of reaction temperature first increases.Therefore, dehydrogenating propane optimal reaction temperature is 600 DEG C.
(9) impact of propane mass space velocity active on catalyst reaction in Propylene Selectivity, see table 10.Reaction condition is with embodiment 1,18,19.
The impact of table 10, propane mass space velocity active on catalyst reaction in Propylene Selectivity
Propane mass space velocity (h -1) Conversion of propane (%) Propylene Selectivity (%) Propane recovering rate (%)
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 then raises, and propene yield also constantly rises.Best propane mass space velocity is 10h -1.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.

Claims (9)

1. the application in propylene prepared by platinum catalyst at propane, it is characterized in that, described platinum catalyst is with TiO 2-Al 2o 3composite oxides are carrier, take Pt metal as activated centre; With catalyst gross mass for benchmark, in described catalyst, Pt metal exists in granular form, and the granular size of Pt metal, at 2-3nm, is uniformly dispersed, and wherein Pt metal mass percentage is 0.5-1.5%, TiO 2mass percentage is 5-20%, and is prepared according to following step:
Step 1, is dissolved in isopropyl alcohol jointly by aluminium secondary butylate, butyl titanate and surfactant softex kw, fully stirs to mix, 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, obtains mixed solution B, then in mixed solution A, drip mixed solution B to be hydrolyzed, the red fuming nitric acid (RFNA) of wherein said 65wt% to be mass percent be 65% aqueous solution of nitric acid, consumption is 0.1-1.5 mass parts; Described deionized water consumption is 2.5-12.5 mass parts, and when dripping, select to dropwise in 5-10min, hydrolysis temperature is room temperature 20-25 degrees Celsius, and hydrolysis time is 0.5h at least;
Step 3, the reaction system obtained through step 2 is left standstill aging 24-40h under room temperature 20-25 degrees Celsius, and after desolventizing, dry 20-24h at 70-90 DEG C of temperature, finally roasting 3-5h at 550-650 DEG C, obtains TiO 2-Al 2o 3composite oxides, as carrier;
Step 4, TiO prepared by step 3 2-Al 2o 3composite oxides impregnated in the chloroplatinic acid aqueous solution that concentration is 0.005-0.015g/ml, to make Payload element platinum, and wherein dip time at least 0.5h;
Step 5, the TiO after step 4 is flooded 2-Al 2o 3composite oxides are dry 10-12h at 80-100 DEG C of temperature, then at 550-650 DEG C roasting 3-5h, finally at H 2fully reduce under atmosphere, obtain the platinum catalyst being carried on double oxide complex carrier, i.e. Pt/TiO 2-Al 2o 3catalyst.
2. the application in propylene prepared by platinum catalyst according to claim 1 at propane, it is characterized in that, prepares propylene facing under nitrogen atmosphere, carry out according to following step with propane:
Step 1, the platinum catalyst being carried on double oxide complex carrier is loaded fixed bed reactors, and pass into nitrogen and hydrogen mixture, at 500-550 DEG C of temperature, carry out reduction 1-2h to described catalyst, in nitrogen and hydrogen mixture, hydrogen volume ratio is 10-15%;
Step 2, to be restored complete after, control reactor batch temperature is 550-650 DEG C, with propane mass space velocity for 3-10h -1pass into reaction gas to react, wherein propane and hydrogen mol ratio are 1:1, and Balance Air is nitrogen.
3. the application in propylene prepared by platinum catalyst according to claim 1 at propane, it is characterized in that, catalyst is carried out compressing tablet process, uses to obtain 20-40 object pellet type catalyst.
4. the application in propylene prepared by platinum catalyst according to claim 1 at propane, it is characterized in that, Pt metal mass percentage is 1-1.5%.
5. the application in propylene prepared by platinum catalyst according to claim 1 at propane, it is characterized in that, TiO 2mass percentage is 10-15%.
6. the application in propylene prepared by platinum catalyst according to claim 1 at propane, 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.
7. the application in propylene prepared by platinum catalyst according to claim 1 at propane, it 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.
8. the application in propylene prepared by platinum catalyst according to claim 1 at propane, it is characterized in that, in step 4, and dip time 1-2h.
9. the application in propylene prepared by platinum catalyst according to claim 1 at propane, it is characterized in that, in steps of 5, at H 2reduction 1-3h under atmosphere.
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