CN103349988A - Platinoid bi-component catalyst as well as preparation method and application thereof - Google Patents
Platinoid bi-component catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a platinoid bi-component catalyst as well as a preparation method and application thereof. In the catalyst, gamma-Al203 is taken as a carrier, platinum is taken as an active component, and copper is taken as auxiliary agent. The preparation method includes the following steps: dipping the carrier gamma-Al203 powder in Cu(NO3)2 water solution, removing solvent, drying and roasting, placing the obtained copper-loaded catalyst in H2PtCl6 water solution for dipping, removing solvent, drying and roasting, wherein the platinoid bi-component catalyst can be used in propylene preparation through propane dehydrogenation. According to the invention, copper and platinum in the catalyst interact to change the interaction force between the reactant and the metal surface and between the product and the metal surface, so that better reaction stability at a high temperature in propylene preparation through propane dehydrogenation is guaranteed, the dimethylmethane conversion ratio is higher, the propylene selectivity is excellent; different components of the catalyst can be dipped through the step-by-step dipping method, contents of the components can be controlled easily, and the repeatability is excellent.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application, specifically, relate to a kind of Catalysts and its preparation method for preparing propylene by dehydrogenating propane and application.
Background technology
Propylene is one of most important petrochemicals, is widely used as the primary raw material of chemicals such as producing acrylonitrile, expoxy propane and acrylic acid.In recent years, be subjected to the pulling of the industry fast developments such as real estate, automobile, packing and textile garment, the huge scale of construction and breach appear in propylene market, and this makes propylene become at present the most promising large petroleum chemicals.Existing propylene is mainly derived from by-product or the coproduction such as traditional handicraft such as petroleum catalytic cracking and naphtha reforming.Traditional handicraft is subjected to the impact of the factors such as oil supply and product distribution, and propylene is supplied with can not satisfy the existing market demand, so the dehydrogenating propane technology is subject to researcher's extensive concern.
Dehydrogenating propane technique can change into the olefin product of high value by the gas-solid catalysis process with the propane feed of cheapness, and the product system is simple, and propene yield is higher.Abundant natural gas resource is contained in China can provide abundant cheap propane feed for dehydrogenating propane technique.In addition, the industrial production experience in existing 20 years of dehydrogenating propane technique, the total explained hereafter device that surpasses 20 covers in the whole world, technology is ripe.Consider the factors such as economy and technical maturity, dehydrogenating propane technique gets most of the attention.Industrialized dehydrogenating propane technique mainly contains the Oleflex technique of Uop Inc., the Catofin technique of Lummus company, Star technique, Linde technique and the FBD fluidized-bed process of Phillips company in the world.Wherein, the Oleflex technique of Uop Inc. is occupied and is surpassed 3/4ths the market share, is to use at present the technology that maximum dehydrogenating propanes is produced propylene.Use Pt/Al in the Oleflex technique of Uop Inc.
2O
3Catalyst, Pt/Al
2O
3Catalyst has higher catalytic activity and Propylene Selectivity, and environmental friendliness.Yet the Pt/Al2O3 catalyst is existent defect also: thus in reaction easily the carbon distribution inactivation reduced the yield of propylene.
Under study for action, generally by increasing auxiliary agent or designing the change support and reduce carbon distribution, suppress inactivation and also improve productivity of propylene.[the Effect of Ce addition on the Pt-Sn/ γ-Al2O3catalyst for propane dehydrogenation to propylene.Applied Catalysis A:General.2006 such as Yu Changlin, 315,58-67.] research tin and cerium auxiliary agent be to the effect of platinum/aluminium oxide catalyst.When reacting initial, Pt/Al catalyst conversion of propane is 34.10%, and Propylene Selectivity is 64.10%.Behind the reaction 150min, Pt/Al catalyst conversion of propane is 18.65%, and Propylene Selectivity is 88.18%.And after having added tin and cerium auxiliary agent, the initial conversion of propane of Pt-Sn/1.1Ce-Al catalyst is 43.78%, and initial Propylene Selectivity is 92.54%.Behind the reaction 150min, the conversion of propane of Pt-Sn/1.1Ce-Al catalyst is 39.76%, and Propylene Selectivity is 97.19%.By on can reach a conclusion, the adding of auxiliary agent has improved conversion ratio and the Propylene Selectivity of catalyst, thereby has promoted the propene yield of catalyst.But this catalyst activity reduction is very fast, and the stability of catalyst still remains to be improved.[Dehydrogenation of propane over Pt-SBA-15and Pt-Sn-SBA-15:Effect of Sn on the dispersion of Pt and catalytic behavior] such as M.Santhosh Kumar studied a kind of platinum group catalyst and effect of being embodied of tin auxiliary agent take SBA-15 as carrier in this system.The initial conversion of propane of Pt-SBA-15 catalyst is 13%, and initial Propylene Selectivity is 85%.Behind the reaction 220min, the conversion of propane of Pt-SBA-15 catalyst is 12%, and Propylene Selectivity is 78%.After adding auxiliary agent tin, the initial conversion of propane of Pt-Sn-SBA-15 catalyst is 16%, and initial Propylene Selectivity is 99%.Behind the reaction 220min, the conversion of propane of Pt-Sn-SBA-15 catalyst is 16%, and Propylene Selectivity is 99%.Hence one can see that, and the adding of tin auxiliary agent has improved conversion ratio and the Propylene Selectivity of catalyst.Auxiliary agent helps to improve the reactivity of catalyst, thereby has finally improved the conversion ratio of propylene.This mainly is with because compare aluminium oxide catalyst, and the SBA-15 catalyst has reduced the amount of acid activity position on the carrier, thereby has improved the stability of catalyst.But the conversion of propane of catalyst is lower, still awaits further raising.
Summary of the invention
What the present invention will solve is to be used at present the easy inactivation of platinum group catalyst of preparing propylene by dehydrogenating propane, the technical problem that propene yield is low, a kind of platinoid bicomponent catalyst and its preparation method and application is provided, this catalyst has preferably reaction stability, higher conversion of propane and Propylene Selectivity, thus higher productivity of propylene can be obtained.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical scheme:
A kind of platinoid bicomponent catalyst, this catalyst is with γ-Al
2O
3Be carrier, take platinum as active component, take the copper metal as auxiliary agent; Take the catalyst gross mass as benchmark, wherein platinum quality percentage composition is 0.3-1.0%, and the quality percentage composition of copper metal is 0.25-2.0%; And this catalyst adopts following method preparation:
(1) with carrier γ-Al
2O
3Powder places 9.84*10 under 40-80 ℃
-4M-3.15*10
-2Cu (the NO of M
3)
2Flood 4-8h in the aqueous solution, wherein said carrier quality and described Cu (NO
3)
2The ratio of aqueous solution volume is 1g:(10-40) ml;
(2) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the catalyst of copper load;
(3) with the catalyst of gained copper load under 40-80 ℃, place 3.84*10
-4M-5.13*10
-3The H of M
2PtCl
6Flood 4-8h in the aqueous solution, wherein said carrier quality and described H
2PtCl
6The ratio of aqueous solution volume is 1g:(10-40) ml;
(4) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the platinoid bicomponent catalyst.
A kind of preparation method of platinoid bicomponent catalyst, the method is carried out according to following steps:
(1) with carrier γ-Al
2O
3Powder places 9.84*10 under 40-80 ℃
-4M-3.15*10
-2Cu (the NO of M
3)
2Flood 4-8h in the aqueous solution, wherein said carrier quality and described Cu (NO
3)
2The ratio of aqueous solution volume is 1g:(10-40) ml;
(2) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the catalyst of copper load;
(3) with the catalyst of gained copper load under 40-80 ℃, place 3.84*10
-4M-5.13*10
-3The H of M
2PtCl
6Flood 4-8h in the aqueous solution, wherein said carrier quality and described H
2PtCl
6The ratio of aqueous solution volume is 1g:(10-40) ml;
(4) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the platinoid bicomponent catalyst.
A kind of described platinoid bicomponent catalyst is used for the method for preparing propylene by dehydrogenating propane, and the method is carried out according to following steps:
(1) with powder shaped platinoid bicomponent catalyst compressing tablet is 20-40 purpose graininess platinoid bicomponent catalyst;
(2) the described platinoid bicomponent catalyst behind the compressing tablet is packed in the fixed bed reactors, passes into hydrogen nitrogen mixed gas, under 500-600 ℃ to described platinoid bicomponent catalyst prereduction 1-3h; The volume content of hydrogen is 10% in the described hydrogen nitrogen mixed gas;
(3) control fixed bed reaction actuator temperature was to 500-700 ℃, with 3-10h after reduction was finished
-1The propane mass space velocity pass into reaction gas to fixed bed reactors and react, reaction gas is comprised of propane, hydrogen and nitrogen, wherein the flow-rate ratio of propane and hydrogen is 1:1, nitrogen is Balance Air.
The invention has the beneficial effects as follows:
(1) catalyst of the present invention is with γ-Al
2O
3Be carrier, have higher specific area and mesopore orbit, be beneficial to the even distribution of active component and auxiliary agent; Take platinum as active component, adopt the copper metal to make auxiliary agent, and can interact between copper metal and platinum, change the interaction force of reactant and product and metal surface, thereby when guaranteeing higher conversion of propane, improved the stability of Propylene Selectivity and reaction;
(2) method for preparing catalyst of the present invention adopts step impregnation method impregnated catalyst different component, and its constituent content is easily controlled, good reproducibility;
(3) catalyst of the present invention is used for preparing propylene by dehydrogenating propane, 500 ℃ of high temperature (〉) condition under preferably reaction stability is arranged, conversion of propane is higher, Propylene Selectivity is good.
The specific embodiment
The present invention is described in further detail below by specific embodiment, and following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
(1) with carrier γ-Al
2O
3Powder places 2.62*10 under 60 ℃
-3Cu (the NO of M
3)
2Flood 6h in the aqueous solution, the carrier quality is 1g:30ml with the liquor capacity ratio;
(2) eggplant-shape bottle connects Rotary Evaporators, and Rotary Evaporators links to each other with vavuum pump, usefulness Rotary Evaporators desolventizing water under the reduced pressure, and 120 ℃ of dry 12h, 550 ℃ of roasting 4h obtain the catalyst powder of copper load;
(3) under 60 ℃ of conditions, the catalyst fines of copper load of preparation is placed 8.54*10
-4The H of M
2PtCl
6Flood 6h in the aqueous solution, the carrier quality compares 1g:30ml with liquor capacity;
(4) eggplant-shape bottle connects Rotary Evaporators, and Rotary Evaporators links to each other with vavuum pump, uses Rotary Evaporators desolventizing water under the reduced pressure, dry 12h under 120 ℃ of temperature conditions, and roasting 4h under 550 ℃ of temperature conditions makes platinoid bicomponent catalyst powder.
Take platinoid bicomponent catalyst gross mass as benchmark, consist of: Pt0.5%, Cu0.5%.
(5) with the platinoid bicomponent catalyst powder compressing tablet for preparing to the platinoid bicomponent catalyst particle of particle diameter in 20-40 order scope;
(6) the platinoid bicomponent catalyst particle of preparation is packed in the fixed bed reactors, adopting hydrogen volume content is 10% hydrogen nitrogen mixed gas, with the flow of 50ml/min, under 550 ℃ of temperature conditions to platinoid bicomponent catalyst prereduction 2h;
(7) after reduction is finished, the fixed bed reaction actuator temperature is risen to 600 ℃, and pass into reaction gas in fixed bed reactors, reaction gas is comprised of propane, hydrogen and nitrogen, and wherein the propane mass space velocity is 3h
-1, the flow-rate ratio of propane and hydrogen is 1:1, N
2Be Balance Air.
Reaction end gas adopts gas chromatograph to carry out on-line analysis, relation such as the table 1 of conversion of propane and Propylene Selectivity and time.
The conversion of propane of table 1 differential responses time and Propylene Selectivity and propene yield
As seen, this catalyst has very high conversion of propane and higher Propylene Selectivity, and catalyst has also embodied preferably reaction stability simultaneously.Along with the variation in reaction time, conversion of propane descends gradually, and Propylene Selectivity increases gradually, and this mainly is because the inactivation of catalyst causes, and the minimizing of active sites then causes resolving weakening of bond energy power, thereby makes selectively increasing to some extent of propylene.When being reacted to 4h, this catalyst still embodies higher conversion of propane (42.8%) and Propylene Selectivity (90.4%), thereby preferably productivity of propylene (38.7%) is arranged, and has embodied preferably reaction stability of this platinoid bicomponent catalyst.
Embodiment 2:
Adopt embodiment 1 method to react, its difference only is that the dipping temperature of step (1) and step (3) is 40 ℃.
Embodiment 3:
Adopt embodiment 1 method to react, its difference only is that the dipping temperature of step (1) and step (3) is 80 ℃.
Embodiment 4:
Adopt embodiment 1 method to react, its difference only is that the carrier quality of step (1) and step (3) and copper nitrate solution volume ratio, carrier quality and platinum acid chloride solution volume ratio are 1:10(g/ml), copper nitrate solution concentration is 3.15*10
-2M, platinum acid chloride solution concentration is 5.13*10
-3M.
Embodiment 5:
Adopt embodiment 1 method to react, its difference only is that the carrier quality of step (1) and step (3) and copper nitrate solution volume ratio, carrier quality and platinum acid chloride solution volume ratio are 1:40(g/ml), copper nitrate solution concentration is 9.84*10
-4, platinum acid chloride solution concentration is 3.84*10
-4
Embodiment 6:
Adopt embodiment 1 method to react, its difference only is that the carrier quality of step (1) and step (3) and copper nitrate solution volume ratio, carrier quality and platinum acid chloride solution volume ratio are 1:10(g/ml), copper nitrate solution concentration is 7.87*10
-3M, platinum acid chloride solution concentration is 2.56*10
-3M.
Embodiment 7:
Adopt embodiment 1 method to react, its difference only is that the carrier quality of step (1) and step (3) and copper nitrate solution volume ratio, carrier quality and platinum acid chloride solution volume ratio are 1:40(g/ml), copper nitrate solution concentration is 1.97*10
-3, platinum acid chloride solution concentration is 6.41*10
-4M.
Embodiment 8:
Adopt embodiment 1 method to react, its difference only is that the dip time of step (1) and step (3) is 4h.
Embodiment 9:
Adopt embodiment 1 method to react, its difference only is that the dip time of step (1) and step (3) is 8h.
Embodiment 10:
Adopt embodiment 1 method to react, its difference only is that the baking temperature of step (2) and step (4) is 100 ℃.
Embodiment 11:
Adopt embodiment 1 method to react, its difference only is that the baking temperature of step (2) and step (4) is 140 ℃.
Embodiment 12:
Adopt embodiment 1 method to react, its difference only is that be 8h the drying time of step (2) and step (4).
Embodiment 13:
Adopt embodiment 1 method to react, its difference only is that be 10h the drying time of step (2) and step (4).
Embodiment 14:
Adopt embodiment 1 method to react, its difference only is that the sintering temperature of step (2) and step (4) is 400 ℃.
Embodiment 15:
Adopt embodiment 1 method to react, its difference only is that the sintering temperature of step (2) and step (4) is 600 ℃.
Embodiment 16:
Adopt embodiment 1 method to react, its difference only is that the roasting time of step (2) and step (4) is 2h.
Embodiment 17:
Adopt embodiment 1 method to react, its difference only is that the roasting time of step (2) and step (4) is 6h.
Embodiment 18:
Adopt embodiment 1 method to react, its difference only is that the reduction temperature of step (6) is 500 ℃.
Embodiment 19:
Adopt embodiment 1 method to react, its difference only is that the reduction temperature of step (6) is 600 ℃.
Embodiment 20:
Adopt embodiment 1 method to react, its difference only is that the recovery time of step (6) is 1h.
Embodiment 21:
Adopt embodiment 1 method to react, its difference only is that the recovery time of step (6) is 3h.
Embodiment 22:
Adopt embodiment 1 method to react, its difference only is that the reaction temperature of step (7) is 500 ℃.
Embodiment 23:
Adopt embodiment 1 method to react, its difference only is that the reaction temperature of step (7) is 700 ℃.
Embodiment 24:
Adopt embodiment 1 method to react, its difference only is that the reaction velocity of step (7) is 5h
-1
Embodiment 25:
Adopt embodiment 1 method to react, its difference only is that the reaction velocity of step (7) is 10h
-1
About above-described embodiment 2-25 result and data discussion:
In the following discussion, all adopt the activity data of the rear 4h of reaction to do contrast, to investigate the different condition parameter to the impact of catalyst reaction performance.
(1) solution concentration, carrier quality and liquor capacity are compared to the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 2.Reaction condition is with embodiment 1,4,5,6,7.
Table 2, solution concentration, carrier quality and liquor capacity are compared to the impact of platinoid bicomponent catalyst reactivity
Can find out from the above results contrast, the carrier quality affects the catalyst activity of preparing with liquor capacity than meeting, be 1:30(g/ml at carrier quality and liquor capacity ratio) time, conversion of propane is 42.8%, Propylene Selectivity is 90.4%, propene yield is 38.7%, has embodied best propene yield.In addition, the resulting different catalyst activity of different content of metal is also listed in the table, and Pt and Cu mass fraction are respectively 0.5% catalyst and have embodied optimum propene yield.
(2) dipping temperature is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 3.Reaction condition is with embodiment 1,2,3.
Table 3, dipping temperature are for the impact of platinoid bicomponent catalyst reactivity
| Dipping temperature (℃) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 40 | 40.1 | 91.2 | 36.6 | 2 |
| 60 | 42.8 | 90.4 | 38.7 | 1 |
| 80 | 44.7 | 85.1 | 38.0 | 3 |
Can see that from above result along with dipping temperature raises, conversion of propane can rise, but Propylene Selectivity can descend downward trend after productivity of propylene has also embodied and risen first.From above-mentioned three examples, during 60 ℃ dipping temperature, conversion of propane is 42.8%, and Propylene Selectivity is 90.4%, and productivity of propylene is 38.7%, has embodied best productivity of propylene.
(3) dip time is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 4.Reaction condition is with embodiment 1,8,9.
Table 4, dip time are for the impact of platinoid bicomponent catalyst reactivity
| Dip time (h) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 4 | 40.5 | 91.0 | 36.9 | 8 |
| 6 | 42.8 | 90.4 | 38.7 | 1 |
| 8 | 42.5 | 90.8 | 38.6 | 9 |
Can see that from above result along with the increase of dip time, conversion of propane can rise first, rear maintenance is stablized constant.Stable trend after productivity of propylene has also embodied and risen first.
(4) baking temperature is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 5.Reaction condition is with embodiment 1,10,11.
Table 5, baking temperature are for the impact of platinoid bicomponent catalyst reactivity
| Baking temperature (℃) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 100 | 35.1 | 93.0 | 32.6 | 10 |
| 120 | 42.8 | 90.4 | 38.7 | 1 |
| 140 | 32.8 | 92.4 | 30.3 | 11 |
Can see that from above result along with baking temperature raises, conversion of propane can rise, but selectively can descend, productivity of propylene raises with temperature.
(5) drying time is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 6.Reaction condition is with embodiment 1,12,13.
Table 6, drying time are for the impact of platinoid bicomponent catalyst reactivity
| Drying time (h) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 8 | 40.1 | 91.2 | 36.6 | 12 |
| 10 | 39.8 | 90.7 | 36.1 | 13 |
| 12 | 42.8 | 90.4 | 38.7 | 1 |
Can see that from above result along with the increase of drying time, conversion of propane can rise, but selective slightly decline.Under the condition of dry 12h, obtained best propane yield.
(6) sintering temperature is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 7.Reaction condition is with embodiment 1,14,15.
Table 7, sintering temperature are for the impact of platinoid bicomponent catalyst reactivity
| Sintering temperature (℃) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 400 | 34.1 | 92.3 | 31.5 | 14 |
| 550 | 42.8 | 90.4 | 38.7 | 1 |
| 600 | 42.5 | 89.8 | 38.2 | 15 |
Can see from above result, along with the rising of sintering temperature, substantially keep stable after conversion of propane and productivity of propylene increase first.When sintering temperature was 400 ℃, the conversion ratio of propane was lower.This is because cause a little less than the interaction between carrier and active component slightly.In the time of 550 ℃.The conversion of propane of catalyst has had higher lifting, and propylene selective be because good catalytic activity and lower slightly, and productivity of propylene has had preferably compared to 400 ℃ and promotes.
(7) roasting time is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 8.Reaction condition is with embodiment 1,16,17.
Table 8, roasting time are for the impact of platinoid bicomponent catalyst reactivity
| Roasting time (h) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 2 | 36.4 | 85.9 | 31.3 | 16 |
| 4 | 42.8 | 90.4 | 38.7 | 1 |
| 6 | 43.9 | 87.1 | 38.2 | 17 |
Can see that from above result along with the increase of roasting time, conversion of propane constantly raises, the Propylene Selectivity rear decline that then raises is kept stable substantially after productivity of propylene increases first.
Contrast the preparation parameter condition that the platinoid bicomponent catalyst is investigated in above-described embodiment in preparation process, by the activity data of comparing embodiment, can obtain each Parameter Conditions to the impact of catalyst performance.
And among the following embodiment, the difference of the catalyst activity that then different conditions causes in the emphasis contrast preparing propylene by dehydrogenating propane application process.
(8) reduction temperature is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 9.Reaction condition is with embodiment 1,18,19.
Table 9, reduction temperature are for the impact of platinoid bicomponent catalyst reactivity
| Reduction temperature (℃) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 500 | 33.8 | 92.0 | 31.1 | 18 |
| 550 | 42.8 | 90.4 | 38.7 | 1 |
| 600 | 43.1 | 90.0 | 38.8 | 19 |
Can see from above result, along with the increase of reduction temperature, substantially keep stablely after conversion of propane and productivity of propylene raise first, keep stable after Propylene Selectivity then descends.
(9) recovery time is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 10.Reaction condition is with embodiment 1,20,21.
Table 10, recovery time are for the impact of platinoid bicomponent catalyst reactivity
| Recovery time (h) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 1 | 30.6 | 92.3 | 28.2 | 20 |
| 2 | 42.8 | 90.4 | 38.7 | 1 |
| 3 | 41.9 | 90.9 | 38.1 | 21 |
Can see that from above result the recovery time has been obtained best conversion of propane and productivity of propylene when being 2h, propylene selectively more than 90%.
(10) reaction temperature is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 11.Reaction condition is with embodiment 1,22,23.
Table 11, reaction temperature are for the impact of platinoid bicomponent catalyst reactivity
| Reaction temperature (℃) | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 500 | 15.7 | 95.3 | 15.0 | 22 |
| 600 | 42.8 | 90.4 | 38.7 | 1 |
| 700 | 71.3 | 51.9 | 37.0 | 23 |
Can see that from above result along with the rising of reaction temperature, conversion of propane constantly raises, Propylene Selectivity then descends, and productivity of propylene increases.Because the dehydrogenating propane reaction is subjected to the restriction of thermodynamical equilibrium for reversible reaction.In the time of 500 ℃, conversion of propane is very low, and along be elevated to 600 ℃ of temperature, conversion of propane is greatly improved.In the time of 700 ℃, conversion of propane reaches 71.3%, but Propylene Selectivity decline is more.600 ℃ reaction temperature has embodied the highest productivity of propylene.
(11) propane mass space velocity is for the impact of platinoid bi-component propane dehydrogenation catalyst reactivity, referring to table 12.Reaction condition is with embodiment 1,24,25.
Table 12, propane mass space velocity are for the impact of platinoid bicomponent catalyst reactivity
| Propane mass space velocity (h -1） | Conversion of propane (%) | Propylene Selectivity (%) | Productivity of propylene (%) | Embodiment |
| 3 | 42.8 | 90.4 | 38.7 | 24 |
| 5 | 35.1 | 93.7 | 32.9 | 1 |
| 10 | 27.5 | 94.3 | 25.9 | 25 |
Can see that from above result along with the rising of propane mass space velocity, conversion of propane constantly descends, Propylene Selectivity then raises, and productivity of propylene descends.
Although the above is described the preferred embodiments of the present invention; but the present invention is not limited to the above-mentioned specific embodiment; the above-mentioned specific embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, can also make the concrete conversion of a lot of forms, these all belong within protection scope of the present invention.
Claims (6)
1. platinoid bicomponent catalyst, this catalyst is with γ-Al
2O
3Be carrier, it is characterized in that, take platinum as active component, take the copper metal as auxiliary agent; Take the catalyst gross mass as benchmark, wherein platinum quality percentage composition is 0.3-1.0%, and the quality percentage composition of copper metal is 0.25-2.0%; And this catalyst adopts following method preparation:
(1) with carrier γ-Al
2O
3Powder places 9.84*10 under 40-80 ℃
-4M-3.15*10
-2Cu (the NO of M
3)
2Flood 4-8h in the aqueous solution, wherein said carrier quality and described Cu (NO
3)
2The ratio of aqueous solution volume is 1g:(10-40) ml;
(2) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the catalyst of copper load;
(3) with the catalyst of gained copper load under 40-80 ℃, place 3.84*10
-4M-5.13*10
-3The H of M
2PtCl
6Flood 4-8h in the aqueous solution, wherein said carrier quality and described H
2PtCl
6The ratio of aqueous solution volume is 1g:(10-40) ml;
(4) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the platinoid bicomponent catalyst.
2. a kind of platinoid bicomponent catalyst according to claim 1 is characterized in that, described platinum quality percentage composition is 0.5%, and the quality percentage composition of described copper metal is 0.5%; And this catalyst adopts following method preparation:
(1) with carrier γ-Al
2O
3Powder places 2.62*10 under 60 ℃
-3Cu (the NO of M
3)
2Flood 6h in the aqueous solution, wherein said carrier quality and described Cu (NO
3)
2The ratio of aqueous solution volume is 1g:30ml;
(2) desolventizing, 120 ℃ of dry 12h, 550 ℃ of roasting 4h obtain the catalyst of copper load;
(3) with the catalyst of gained copper load under 60 ℃, place 8.54*10
-4The H of M
2PtCl
6Flood 6h in the aqueous solution, wherein said carrier quality and described H
2PtCl
6The ratio of aqueous solution volume is 1g:30ml;
(4) desolventizing, 120 ℃ of dry 12h, 550 ℃ of roasting 4h obtain the platinoid bicomponent catalyst.
3. the preparation method of a platinoid bicomponent catalyst is characterized in that, the method is carried out according to following steps:
(1) with carrier γ-Al
2O
3Powder places 9.84*10 under 40-80 ℃
-4M-3.15*10
-2Cu (the NO of M
3)
2Flood 4-8h in the aqueous solution, wherein said carrier quality and described Cu (NO
3)
2The ratio of aqueous solution volume is 1g:(10-40) ml;
(2) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the catalyst of copper load;
(3) with the catalyst of gained copper load under 40-80 ℃, place 3.84*10
-4M-5.13*10
-3The H of M
2PtCl
6Flood 4-8h in the aqueous solution, wherein said carrier quality and described H
2PtCl
6The ratio of aqueous solution volume is 1g:(10-40) ml;
(4) desolventizing, 100-140 ℃ of dry 8-12h, 400-600 ℃ of roasting 2-6h obtains the platinoid bicomponent catalyst.
4. the preparation method of a kind of platinoid bicomponent catalyst according to claim 3 is characterized in that, the method is carried out according to following steps:
(1) with carrier γ-Al
2O
3Powder places 2.62*10 under 60 ℃
-3Cu (the NO of M
3)
2Flood 6h in the aqueous solution, wherein said carrier quality and described Cu (NO
3)
2The ratio of aqueous solution volume is 1g:30ml;
(2) desolventizing, 120 ℃ of dry 12h, 550 ℃ of roasting 4h obtain the catalyst of copper load;
(3) with the catalyst of gained copper load under 60 ℃, place 8.54*10
-4The H of M
2PtCl
6Flood 6h in the aqueous solution, wherein said carrier quality and described H
2PtCl
6The ratio of aqueous solution volume is 1g:30ml;
(4) desolventizing, 120 ℃ of dry 12h, 550 ℃ of roasting 4h obtain the platinoid bicomponent catalyst.
One kind as claimed in claim 1 the platinoid bicomponent catalyst be used for the method for preparing propylene by dehydrogenating propane, it is characterized in that the method is carried out according to following steps:
(1) with powder shaped platinoid bicomponent catalyst compressing tablet is 20-40 purpose graininess platinoid bicomponent catalyst;
(2) the described platinoid bicomponent catalyst behind the compressing tablet is packed in the fixed bed reactors, passes into hydrogen nitrogen mixed gas, under 500-600 ℃ to described platinoid bicomponent catalyst prereduction 1-3h; The volume content of hydrogen is 10% in the described hydrogen nitrogen mixed gas;
(3) control fixed bed reaction actuator temperature was to 500-700 ℃, with 3-10h after reduction was finished
-1The propane mass space velocity pass into reaction gas to fixed bed reactors and react, reaction gas is comprised of propane, hydrogen and nitrogen, wherein the flow-rate ratio of propane and hydrogen is 1:1, nitrogen is Balance Air.
6. platinoid bicomponent catalyst according to claim 5 is used for the method for preparing propylene by dehydrogenating propane, it is characterized in that the method is carried out according to following steps:
(1) with powder shaped platinoid bicomponent catalyst compressing tablet is 20-40 purpose graininess platinoid bicomponent catalyst;
(2) the described platinoid bicomponent catalyst behind the compressing tablet is packed in the fixed bed reactors, passes into hydrogen nitrogen mixed gas, under 550 ℃ to described platinoid bicomponent catalyst prereduction 2h; The volume content of hydrogen is 10% in the described hydrogen nitrogen mixed gas;
(3) control fixed bed reaction actuator temperature to 600 ℃ after reduction is finished is with 3h
-1The propane mass space velocity pass into reaction gas to fixed bed reactors and react, reaction gas is comprised of propane, hydrogen and nitrogen, wherein the flow-rate ratio of propane and hydrogen is 1:1, nitrogen is Balance Air.
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