CN1088627C - Preparing catalyst cantaining group eight metal and non-acidic promoter dispersed on support via simultaneous impregnation - Google Patents
Preparing catalyst cantaining group eight metal and non-acidic promoter dispersed on support via simultaneous impregnation Download PDFInfo
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- CN1088627C CN1088627C CN96100635A CN96100635A CN1088627C CN 1088627 C CN1088627 C CN 1088627C CN 96100635 A CN96100635 A CN 96100635A CN 96100635 A CN96100635 A CN 96100635A CN 1088627 C CN1088627 C CN 1088627C
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Abstract
First aqueous solution is prepared and heated to 80 DEG C to a boiling point, and then is mixed with second aqueous solution. Mixed solution is immersed and is used for preparing a catalyst containing VIII family metal and non acidic accelerator simultaneously. The first aqueous solution contains a chelating agent (such as ethylenediamine tetraacetic acid (EDTA)) and a metal salt catalyst. The second aqueous solution contains a VIII family metal compound. The obtained mixed solution is aged under 40 to 100 DEG C and then is used to immerse a carrier, such as an alumina ball. Then, the immersed carrier is dried, sintered and reduced by hydrogen gas. Before reduction, chlorine gas or chloride gas flow can be optionally selected to treat the catalyst.
Description
The catalyst that contains VIII family metal and modifier (as alkali metal, tin, germanium, lead, indium, gallium etc.) is well-known in the present technique field.For example, US-A-4914075 discloses a kind of dehydrogenation, and it comprises a kind of VIII family metal component, a kind of alkali metal or alkaline earth metal component and a kind of component that is selected from tin, germanium, lead, indium, gallium, thallium or its mixture.This catalyst is by making with required component impregnated carrier.Also known available chelatingligand with metal impregnation to carrier.For example, US-A-4719196 discloses and has used a kind of formulations prepared from solutions catalyst that contains ethylenediamine tetra-acetic acid (EDTA), noble metal and ammonia.
Have now found that a kind of method for preparing catalyst, it relates to uses chelatingligand to flood VIII family metal and nonacid metallic promoter agent simultaneously.This method comprises a kind of solution that contains chelatingligand (as EDTA) and metallic promoter agent of preparation.Heat this solution, mix aging resulting mixed solution with a kind of VIII of containing family solution of metal compound then.Solution that this is aging is used for flooding a kind of refractory oxide carrier (as θ-aluminium oxide), calcines then and reduces, and obtains metallic promoter agent and VIII family metal and all is scattered in expectation catalyst on the carrier.
The present invention relates to a kind of method for preparing catalyst of flooding through simultaneously.This catalyst comprises the VIII family metal that is scattered on the solid-state refractory oxide carrier and the catalyst of nonacid metal modifiers.Therefore, one embodiment of the invention comprise a kind of method that comprises following steps: a) mix first and second aqueous solution, obtain mixed solution, first solution contains a kind of chelating agent and at least a metal salt promoter, described first solution has been heated to 80 ℃ of temperature to its boiling point, and second solution contains at least a VIII family metallic compound; B) aging this mixed solution 5 minutes to 4 hours under 40-100 ℃ temperature; C) mixed solution with described ageing is impregnated on a kind of solid-state refractory oxide carrier the solid-state carrier that obtains flooding; D) 300-850 ℃ temperature lower calcination should dipping solid-state carrier 10 minutes to 8 hours, obtain a kind of catalyst of calcining; And e) catalyst of this calcining of reduction under 300-850 ℃ temperature is 30 minutes to 8 hours, thereby obtains described catalyst.
In another embodiment, under 300-850 ℃ of temperature, handle by the catalyst of method for preparing 30 minutes to 8 hours with hydrogen chloride/chlorine air-flow.
In yet another embodiment, also aluminium chloride can be deposited on the described catalyst.
Comprise a kind of solid-state refractory oxide carrier that has been dispersed with at least a VIII family's metal and a kind of nonacid metallic promoter agent on it by the catalyst of the present invention preparation.This carrier can be any in many carriers that present technique field crowd knows, these known carriers comprise aluminium oxide, silica/alumina, silica, titanium dioxide, zirconia and zeolite.The aluminium oxide that can be used as carrier comprises gama-alumina, θ-aluminium oxide, δ-aluminium oxide and Alpha-alumina, preferred gama-alumina and θ-aluminium oxide.Containing modifier such as tin, zirconium, titanium and phosphatic aluminium oxide is also included within these aluminium oxide.Spendable zeolite comprises: faujasite, beta-zeolite, L-zeolite, ESM-5, ZSM-8, ZSM-11, ZSM-12 and ZSM-35.Carrier can any desired shape be made, and as ball, ball, cake, extrudate, powder, particle etc., and they can any granular size use.Preferred shape is spherical, and preferred granular size is about 1.59 millimeters an of diameter, but also can use little of 0.79 millimeter or littler particle.
A kind of method of preparation ball-aluminium oxide carrier is well-known oil drop method, and this method has description in US-A-2620314, and this patent is hereby incorporated by reference.Oil drop method comprises that by arbitrary technology well known in the prior art preferably the reaction by metallic aluminium and hydrochloric acid prepares the aluminium hydrosol; This hydrosol is mixed with suitable gelling agent; With the gained mixture is splashed in the high temperature oil bath.Mixture droplets remains in the oil bath up to them solidifies and forms hydrogel sphere.From oil bath, take out these balls then continuously, and typically in the solution of oil and ammonia, wear out uniquely and dry the processing, with further its physical characteristic of improving.The ball of the aging and gelling that produced of washing then, and under 80-260 ℃ lower temperature drying, again 455-705 ℃ temperature lower calcination 1-20 hour.This processing makes hydrogel be converted into corresponding crystalline state gama-alumina.θ-aluminium oxide if desired is so just 950-1100 ℃ of temperature lower calcination hydrogel sphere.
VIII family metal is distributed on the carrier of expectation as follows.At first, the aqueous solution for preparing a kind of chelatingligand and at least a nonacid promoter salts.The chelatingligand that can be used in the inventive method is included in the amino acid that can not stay when decomposing the harmful component (as sulphur) of carrier.These amino acid whose object lessons comprise ethylenediamine tetra-acetic acid, NTA, N-methylamino oxalic acid, iminodiacetic acid, amion acetic acid, alanine, methyl amimoacetic acid, α-An Jiyidingsuan, N, N-dimethylamino acetate, α, β-diaminopropionic acid, aspartic acid, glutamic acid, histidine and methionine.
The necessary component of another of this first solution is the salt of non-acid metal promoter.This metallic promoter agent is selected from alkali metal or alkaline-earth metal.The example of the salt of spendable these metallic promoter agent comprises potassium hydroxide, lithium hydroxide, NaOH, cesium hydroxide, magnesium hydroxide etc.Gained solution is heated to about 80 ℃ of temperature to its boiling point, preferred 90-102 ℃.The ratio of chelatingligand and slaine is 1-8, preferred 1.5-4.
Second aqueous solution that now first solution and one is contained at least a VIII family metallic compound.In the VIII family metal on the carrier that can be scattered in expectation, preferred metal is rhodium, palladium, platinum, nickel, cobalt and iron, more preferably rhodium, palladium and platinum, most preferably platinum.The example that can be used for VIII of the present invention family metallic compound is that chloroplatinic acid, positive palladium acid, tetramine close platinum chloride, tetramine closes palladium bichloride, bromoplatinic acid, rhodium chloride, ruthenic chloride, gallium nitrate, nickel chloride, nickel nitrate, cobalt nitrate, ferric nitrate and iron chloride.
The mixing of first and second solution causes forming complex between VIII family metal and the chelatingligand.Metallic promoter agent also can be the part of complex.In order to form this complex, the ratio of chelatingligand and VIII family metal is 0.5-30, preferred 5-13.This ratio depends on metallic promoter agent and VIII family concentration of metal, and ratio is high more, requires concentration of metal high more.The concentration of VIII family metal and metallic promoter agent can alter a great deal, and makes its concentration on carrier be respectively 0.2-1wt% and 0.5-3wt% by the percetage by weight that this metal accounts for carrier but be typically chosen in.
Above-mentioned first solution also can contain a kind of following alkali compounds that is selected from: ammonium hydroxide and general formula NR
1R
2R
3R
4 +X
-Quaternary ammonium compound (R wherein
1, R
2, R
3, R
4Respectively be methyl, ethyl, propyl group, butyl or normal-butyl, X is a hydroxyl).The purpose that adds one or more these alkali compounds is to adjust the pH value of this solution, to change the distribution of metal.That is to say, may wish being evenly distributed of metal in some cases, and it is bigger to wish that in other cases concentration is gone up on the surface.In addition, the distribution of VIII family metal can be different from the distribution of metallic promoter agent.
Although the arbitrary theory of hopeless usefulness connects, appear to have relation between the pH of isoelectric point of carrier (IEp) and dipping solution.Therefore, if the EIP height, as 8, and pH low (1-2), strong bonding or chemisorbed may cause the metallic surface dipping so.Increase pH to 6-9, will obtain basic distribution uniformly.Equally, if IEP and pH are low, so with metallic even distribution.
After obtaining mixed solution, it was worn out 5 minutes to 4 hours under 40-100 ℃ temperature.By many in the art methods of knowing, use this aging mixed solution that metal is deposited on the carrier.The example of described method comprises spray immersion method and evaporation infusion process.The spray immersion method comprises taking-up mixed with little amount solution and it is sprayed on the carrier when carrier moves.AEI After End of Injection is transferred to the device that other are used for drying or arrangement step with moistening carrier.
A kind of specific process of evaporation dipping comprises a kind of steam cover of use rotary dryer.In the method, carrier immerses has inserted in the dipping solution of drier, and rotatablely moving and rotate with drier.Quicken the evaporation of the solution that contacts with the carrier that rotates by infeed steam to the drier chuck.The carrier of dry dipping under the about 300 ℃ temperature of 60-then, again 300-850 ℃ temperature lower calcination 30 minutes to 8 hours, the catalyst that obtains calcining.At last, by at reducing atmosphere, under the preferred dry hydrogen, the catalyst 30 minutes to 8 hours of this calcining of heating under 300-850 ℃ temperature and make it reduction.This has guaranteed that VIII family metal is metallic state or zero-valent state.
An optional step in the methods of the invention is included in before the reduction step oxychlorination to the catalyst of above-mentioned calcining.If wish to have this step, then the catalyst of calcining is inserted in the reactor, make the air-flow flow velocity with 0.91-18.18 kilogram/hr under 300-850 ℃ of temperature that contains chloride or chlorine flow through this catalyst 10 minutes to 6 hours.This air-flow can be hydrogen chloride/cl gas flow, water/Hcl air-flow, water/Cl
2Air-flow or cl gas flow.The purpose of this step provides the optimum dispersion of VIII family metal and provide a certain amount of chloride on final catalyst.
Except that above-mentioned catalyst component, also can add other components in this catalyst.For example, can be selected from the second following metal modifiers toward adding in this catalyst: tin, germanium, lead, indium, gallium, thallium and composition thereof.Second metal modifiers or add in the preparing carriers process in the carrier for example by this solution of metal compound is added in the hydrosol, perhaps was impregnated on the carrier before or after flooding with VIII family metal and nonacid promoter.Impregnated on the carrier is to be undertaken by the suitable dipping solution of the mode that is similar to aforesaid way with second metal modifiers.
If this catalyst is used for alkylation, this catalyst also will contain the metal halide of a kind of Fei Ruide of having-Ke Lai Ford activity so.The alkylation here is meant that the alkane of using 4-6 carbon is to C
2-C
6The alkylation of alkene.This class alkylation typically refers to the engine fuel alkylation.This metal halide is calcined at catalyst, randomly deposits on this catalyst after oxychlorination and the reduction.Metal with Fei Ruide-Ke Lai Ford activity comprises aluminium, zirconium, tin, tantalum, titanium, gallium, antimony and composition thereof.Preferred metal is aluminium, gallium, boron and composition thereof.Suitable halide is fluoride, chloride and bromide.The representative of this type of metal halide comprises aluminium chloride, aluminium bromide, iron chloride, ferric bromide, zirconium chloride, zirconium bromide, boron trifluoride, titanium tetrachloride, gallium chloride, butter of tin, antimony fluoride, chlorination button, fluoridizes button etc.Wherein preferred aluminum halide, especially aluminium chloride.Except that boron trifluoride, the normally preferred halide of chloride.
The hydroxyl reaction that combines of these metal halides and carrier.Therefore, for this alkylation catalyst, carrier must have the hydroxyl of combination.Metal halide combines the reaction of hydroxyl easily by for example metal halide being distilled or distilling carrier particle surface and finish with the surface of carrier.This reaction makes every mole of metal halide that is adsorbed on the carrier eliminate the hydrogen halides of 0.5-2.0 mole.Reaction temperature depends on following variable: the reactivity of metal halide and sublimation temperature thereof or boiling point, because metal halide is to react, also depend on the character of carrier in gas phase.For example, when as shown in embodiment, using aluminium chloride and aluminium oxide, be easy to take place at 190-600 ℃ of scope internal reaction.
The metal halide amount that combines hydroxyl reaction with the surface of carrier accounts for the percetage by weight of this complex by Fei Ruide-Ke Lai Ford metal usually.This amount with the surface of used carrier, carrier in conjunction with hydroxyl relative value (may be relevant), used concrete Friedel-Craft metal halide and be used for making Friedel-Craft type metal halide and surface to change in conjunction with the concrete grammar of hydroxyl reaction with used particular oxides phase.According to the initial experience that is used for the aluminium chloride on the aluminium oxide, for example, the aluminium chloride amount of reaction is expressed as 0.1-2.5% by the percetage by weight of aluminium in resulting composite, and this value mainly is the function of carrier upper surface in conjunction with hydroxyl value.
Various catalyst by the inventive method preparation can be used for many hydrocarbon conversion process.For example, contain VIII family metal (especially platinum), the catalyst of first metal modifiers (especially potassium) and second metal modifiers (especially tin) is as dehydrogenation.But the dehydrogenation of hydrocarbon comprises in the dehydrogenation zone of hydrocarbon under remaining on dehydrogenation condition that makes catalyst and dehydrogenation and contacting.This contact can be used fixed catalyst bed system, moving catalyst bed system, fluidized system or finish in batch system, preferred fixed bed system.But the hydrocarbon of dehydrogenation comprises the dehydrogenatable hydrocarbon with 2-30 or more carbon atoms, comprises alkane, alkylaromatic hydrocarbon, cycloalkane and alkene.Especially preferred is C
2-C
6Alkane mainly is propane and butane.
Dehydrogenation condition comprises that temperature is that 400-900 ℃, pressure are that 1-1013KPa (0.01-10 absolute atmosphere) and liquid hourly space velocity (LHSV) are 0.1-100hr
-1Carrying out other conditions of dehydrogenation reaction and common condition is well-known in the present technique field, and description is for example arranged in US-A-4914075, and this patent is incorporated herein for referencial use.
Add after the functional metal halide, catalyst of the present invention also can be used for the alkylation of engine fuel oil.The alkylation of engine fuel oil by taking out alkane and olefine raw mix and make it and the catalyst expected reacts under alkylation conditions and carries out.Alkylation conditions comprises that temperature is low to moderate-10 ℃, high to 100 ℃, and this depends on the used concrete raw material and the essence of catalyst.Preferred temperature is 10-50 ℃.Being reflected at pressure is enough to make reactant to maintain to carry out under liquid.Alkylation reaction zone uses the catalyst bed of expectation usually, and liquid reaction mixture is with 0.1-5.0hr
-1LHSV flow through this bed.
Embodiment 1
Prepare a solution by in flask, mixing 262.5g deionized water, 22.3g potassium hydroxide solution (39.5%KOH) and 11.6gEDTA.Heat this solution to boiling, be transferred to then in the rotary evaporator that is controlled at 70 ℃.In this evaporimeter, add and contain second solution that 79.1g deionized water and 86g contain the solution (2.92%Pt) of chloroplatinic acid.Aging this mixed solution is 45 minutes in evaporimeter.
Add 283.5g gama-alumina ball in aging solution, it contains the tin of 0.3wt% and described and prepare by US-A-4914075 (embodiment 1).Be warming up to 100 ℃ and carrier rotated 5 hours.
In dry air, the carrier that floods is heated to 565 ℃ then.When reaching this temperature, make to contain Hcl and Cl
2Air stream flow through this catalyst 6 hours.
At last, by making purified hydrogen under 562 ℃ of temperature, reduce it in 2.5 hours by this catalyst.
Catalyst be the analysis showed that it contains 0.75wt%Pt and 2.2wt%K.Platinum is evenly distributed on the whole carrier, and potassium has slight gradient (surface is higher) from the surface to inside.This catalyst is decided to be catalyst A.
Embodiment 2
Prepare a solution by in flask, mixing 276.7g deionized water, 8.1g potassium hydroxide solution (39.5%KOH) and 4.2gEDTA.Heat this solution to boiling, be transferred to then in the rotary evaporator that is controlled at 70 ℃.In this evaporimeter, add second solution contain the solution (2.92%Pt) that 102.7g deionized water and 62.4 contains chloroplatinic acid.Aging this mixed solution is 45 minutes in evaporimeter.
Add 310.5g θ-alumina balls in aging solution, it contains the tin of 0.3wt% and by at first preparing in 2 hours at this carrier of 565 ℃ of temperature lower calcinations then by US-A-4914075 (embodiment 1) described preparation gama-alumina ball (containing Sn).Be warming up to 100 ℃ and carrier rotated 5 hours.
In dry air, the carrier that floods is heated to 565 ℃ then.When reaching this temperature, make to contain Hcl and Cl
2Air stream flow through this catalyst 6 hours.
At last, by making purified hydrogen under 562 ℃ of temperature, reduce it in 2.5 hours by this catalyst.
Catalyst be the analysis showed that it contains 0.60wt%Pt and 0.73wt%K.This catalyst is decided to be catalyst B.Platinum is evenly distributed in this catalyst, and potassium is at the surface concentration height.
Embodiment 3
Prepare a solution by mixing 276.8g deionized water, 7.9g potassium hydroxide solution (39.5%KOH) and 4.17gEDTA and 4.0g TMAH in flask.Heat this solution to boiling, be transferred to then in the rotary evaporator that is controlled at 70 ℃.In this evaporimeter, add second solution contain the solution (2.92%Pt) that 102.34g deionized water and 62.8 contains chloroplatinic acid.Aging this mixed solution is 45 minutes in evaporimeter.
Add 310.5g θ-alumina balls in aging solution, it contains the tin of 0.3wt% and by at first preparing in about 2 hours at 1037 ℃ of these carriers of temperature lower calcination then by US-A-4914075 (embodiment 1) described preparation gama-alumina ball (containing Sn).Be warming up to 100 ℃ and carrier rotated 5 hours.
In dry air, the carrier that floods is heated to 565 ℃ then.When reaching this temperature, make to contain Hcl and Cl
2Air stream flow through this catalyst 6 hours.
At last, by making purified hydrogen under 562 ℃ of temperature, reduce it in 2.5 hours by this catalyst.
Catalyst be the analysis showed that it contains 0.6wt%Pt and 0.7wt%K.Platinum and potassium all are uniformly distributed on the whole carrier.This catalyst is decided to be catalyst C.
Embodiment 4
The dehydrogenation activity of detecting catalyst A, B and C as follows.In a vertical reactor, insert 20 milliliters and be heated to about 532 ℃ catalyst.The feed stream of being made up of iso-butane and hydrogen is with the H of 1.0 moles/mole
2/ HC ratio and 20hr
-1LHSV flow through this reactor.Measure the conversion ratio of air-flow to the time.Each catalyst the results are shown in following table in this test.
Table
Data show that the equally distributed catalyst C of platinum and potassium has best conversion ratio and selectivity.
| Catalyst | Conversion ratio | Selectivity | ||
| Initially | Finally | Initially | Finally | |
| A B C | 36 41 41 | 31 35 35 | 92 92.5 95 | 92 94 95 |
Claims (11)
1. comprise the VIII family metal that is scattered on the solid-state refractory oxide carrier and the Preparation of catalysts method of nonacid promoter, this method comprises the steps:
A) mix first and second aqueous solution to obtain mixed solution, this first solution contains a kind of chelating agent and at least a metal salt promoter, described first solution has been heated to 80 ℃ of temperature to its boiling point, and described second solution contains at least a VIII family metallic compound;
B) aging this mixed solution 5 minutes to 4 hours under 40-100 ℃ temperature;
C) described aging mixed solution is impregnated on a kind of solid-state refractory oxide carrier to obtain the solid-state carrier of a dipping;
D) the solid-state carrier of this dipping of temperature lower calcination of 300-850 ℃ 10 minutes to 8 hours to obtain a kind of catalyst of calcining; With
E) catalyst of reduction calcining under 300 ℃ to 850 ℃ temperature is 30 minutes to 8 hours, thereby obtains described catalyst.
2. according to the process of claim 1 wherein that nonacid promoter is selected from alkali metal or alkali salt, and VIII family metal is selected from platinum, palladium, rhodium, ruthenium, cobalt, nickel and iron.
3. according to the method for claim 2, wherein said VIII family metal is a platinum, and described promoter is potassium.
4. be selected from following a kind of alkali compounds according to the process of claim 1 wherein that described first solution contains: ammonium hydroxide and have a general formula NR
1R
2R
3R
4 +X
-Quaternary ammonium compound, R wherein
1, R
2, R
3, R
4Be methyl, ethyl, propyl group, butyl or normal-butyl respectively, and X is a hydroxyl.
5. according to the process of claim 1 wherein that described catalyst is with being selected from HCl/Cl in step (d) afterwards
2, water/HCl, water/Cl
2And Cl
2Air-flow with the 0.91-18.18 kilogram/hour speed under 300 ℃ to 850 ℃ temperature, handled 10 minutes to 6 hours.
6. according to the process of claim 1 wherein afterwards, a kind ofly have the metal halide of Friedel-Craft activity and combine hydroxyl reaction with surface in the described carrier and make it to be deposited on the described carrier surface by making in step (e).
7. according to the method for claim 6, wherein said metal halide is halide of aluminium, gallium, boron and composition thereof.
8. according to the process of claim 1 wherein that described chelating agent and the metal salt promoter ratio in described first solution is 1-8.
9. according to the process of claim 1 wherein that described refractory oxide carrier contains a kind of metal modifiers that is selected from tin, germanium, lead, indium, gallium, thallium and composition thereof.
10. according to the method for claim 1, the chelating agent that wherein is used for described first solution is selected from ethylenediamine tetra-acetic acid, NTA, N-methylamino oxalic acid, iminodiacetic acid, amion acetic acid, alanine, methyl amimoacetic acid, α-An Jiyidingsuan, N, N-dimethylamino acetate, α, β-diaminopropionic acid, aspartic acid, glutamic acid, histidine and methionine.
11. the catalyst of each method preparation among the claim 1-10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100635A CN1088627C (en) | 1996-01-08 | 1996-01-08 | Preparing catalyst cantaining group eight metal and non-acidic promoter dispersed on support via simultaneous impregnation |
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|---|---|---|---|
| CN96100635A CN1088627C (en) | 1996-01-08 | 1996-01-08 | Preparing catalyst cantaining group eight metal and non-acidic promoter dispersed on support via simultaneous impregnation |
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| CN1154269A CN1154269A (en) | 1997-07-16 |
| CN1088627C true CN1088627C (en) | 2002-08-07 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5137859A (en) * | 1990-03-30 | 1992-08-11 | Cosmo Research Institute | Process for producing catalyst composition for use in hydrodesulfurization of hydrocarbon oil |
| US5248412A (en) * | 1990-03-30 | 1993-09-28 | Cosmo Research Institute | Process for producing catalyst composition for use in hydrodesulfurization of hydrocarbon oil and process for hydrodesulfurizing hydrocarbon oil |
| US5344805A (en) * | 1993-05-03 | 1994-09-06 | Phillips Petroleum Company | Platinum and tin-containing catalyst and use thereof in alkane dehydrogenation |
-
1996
- 1996-01-08 CN CN96100635A patent/CN1088627C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5137859A (en) * | 1990-03-30 | 1992-08-11 | Cosmo Research Institute | Process for producing catalyst composition for use in hydrodesulfurization of hydrocarbon oil |
| US5248412A (en) * | 1990-03-30 | 1993-09-28 | Cosmo Research Institute | Process for producing catalyst composition for use in hydrodesulfurization of hydrocarbon oil and process for hydrodesulfurizing hydrocarbon oil |
| US5344805A (en) * | 1993-05-03 | 1994-09-06 | Phillips Petroleum Company | Platinum and tin-containing catalyst and use thereof in alkane dehydrogenation |
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