CN1034853C - Loading type butadiene catalyst made by butylene oxidation dehydrogen - Google Patents
Loading type butadiene catalyst made by butylene oxidation dehydrogen Download PDFInfo
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Abstract
The present invention relates to a supported iron series spinel composite oxide catalyst for preparing butadiene by butylene oxidation dehydrogenation, wherein the spinel composite oxide active constituents in the ferrum system are directly loaded on a carrier adopting mullite and/or sillimanite as the main phase. The present invention also relates to a preparation method of the supported iron series spinel composite oxide catalyst, which comprises: the carrier is immersed in metallic ionized water solution prepared according to the molar ratio of the required metallic elements of the active constituents, and then, the carrier is dried, roasted and activated. The present invention also relates to the application of the supported iron series spinel composite oxide catalyst to the industrial process of preparing butadiene by butylene oxidation dehydrogenation.
Description
The present invention relates to the catalyst of support type preparing butadiene with butylene oxo-dehydrogenation, comprise catalyst carrier, active component, preparation method and practical application.More particularly, the spinelle iron that the present invention relates to directly to be carried on mixture with sillimanite and mullite and be on the main thing carrier mutually is active constituent catalyst and preparation method thereof, with and as the application of butadiene catalyst made by butylene oxidation dehydrogen.
Butadiene is the base stock of petrochemical industry, for producing the important monomer of synthetic rubber and other high molecular synthetic material.At present, the source of butadiene mainly contains two kinds, i.e. extraction process that extracts from the pyrolysis product C-4-fraction and butylene oxidation-dehydrogenation method.Along with the increase to the butadiene demand, extraction process is produced butadiene and can not be satisfied the demand far away, and the butylene oxidation-dehydrogenation method has become the important technology route that comprehensive utilization C-4-fraction resource is produced butadiene.
The used catalyst of butylene oxidation-dehydrogenation system butadiene reaction has experienced the evolution of several stages, and at present widely used is the spinel-type Fe-series catalyst.Fe-series catalyst than before the catalyst of series such as molybdenum bismuth phosphorus, tin phosphorus lithium, have many remarkable advantages, as: reaction temperature is low; It is few to contain the oxygen accessory substance; Butadiene yield height; Water alkene is than low, or the like.
Since the iron few spar butadiene catalyst made by butylene oxidation dehydrogen invention of system [USP3270080], its performance is constantly improved and is improved.W.L.Kehl etc. find to introduce Cr
3+Can improve the stability [USP3450788] of catalyst.Zhou Wangyue etc. have invented the iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene [CN1033013] that is used for the shelf fluidized bed reactor.Yanshan Petrochemical company synthetic rubber plant has developed the B02 type catalyst that is used for insulation fix bed chromium-free iron series butylene oxidation-dehydrogenation system butadiene.
The load problem of composite oxides is concerned about by people always, but really do not achieve a solution yet so far [this Yu Fu of pine etc. openly specially permit communique (A), clear 61-234947].The butylene oxidation-dehydrogenation Fe-series catalyst of industrial present use does not have loadization, is to adopt coprecipitation to produce the catalyst activity component precursor, is shaped then, activates and make.During co-precipitation, exist certain component losing issue, this may have influence on the quality repeatability of Preparation of Catalyst.In addition, find in the production, be used for the not loading type iron series catalysts of fluidized-bed reactor, in use exist more serious efflorescence to run the damage problem.Therefore, though the Fe-series catalyst that uses has tangible advantage at present, but still need further improvement with perfect.
The purpose of this invention is to provide a kind of loading type butadiene catalyst made by butylene oxidation dehydrogen, this catalyst with the iron system spinel as active component.Another object of the present invention provides a kind of method for preparing this catalyst, comprising the preparation method of carrier and active component is directly loaded on method on the carrier, more particularly is exactly that iron system spinel active component is directly loaded on method on the mixture carrier of mullite and sillimanite.The catalyst that uses the inventive method to produce has the not advantage of load iron series catalysts, advantage such as have simultaneously that the preparation method is reliable and stable, the catalyst mechanical strength is breaking strength or scuff resistance height, Catalyst Production cost are low, loss is little when using.
Catalyst of the present invention is a kind of loaded catalyst, comprises the mixture carrier of iron system spinel active component and mullite and sillimanite, and described active component is expressed as with general formula:
(A
xA′
1－x)(B
yB′
1－y)
2O
4·zFe
2O
3
Wherein, A, A ' represent Zn
2+, Co
2+, Ni
2+, Mg
2+, Mn
2+, Cu
2+, Cd
2+Deng metal ion, Zn preferably
2+, Co
2+, Ni
2+, Mg
2+, Mn
2+Deng; B ' represents Cr
3+, Co
3+, Mn
3+, Ni
3+Plasma, preferably Cr
3+B is Fe
3+Ion; X=0～1.0; Y=0.4～1.0; Z=0～0.5.Wherein said active component forms and directly loads on the described carrier in original position on the described carrier.
Preparation of catalysts method of the present invention comprises, total concentration of metal ions of preparing according to the required metallic element mol ratio of described active component with the mixture carrier immersion of described mullite and sillimanite is in the metal ion soluble-salt aqueous solution of 1.0～3.0M, after dipping and the drying, in 400～8 00 ℃ of activation 2～16 hours, on carrier, generate iron system spinel active component, this active component directly loads on the mixture carrier of mullite and sillimanite, promptly makes described catalyst.
Catalyst of the present invention can be used for the process of butylene oxidation-dehydrogenation system butadiene, uses loading type iron system spinel catalyst of the present invention, and the butadiene yield is more than 70%, and the selectivity that generates butadiene is greater than 90%.
Detailed description of the present invention:
Catalyst of the present invention is the loading type iron system spinel catalyst that is used for butylene oxidation-dehydrogenation system butadiene.The catalyst activity component is iron system spinel composite oxides, is expressed as with general formula:
(A
xA′
1－x)(B
yB′
1－y)
2O
4·zFe
2O
3
Wherein, A, A ' represent Zn
2+, Co
2+, Ni
2+, Mg
2+, Mn
2+, Cu
2+, Cd
2+Deng metal ion, Zn preferably
2+, Co
2+, Ni
2+, Mg
2+, Mn
2+Deng; B ' represents Cr
3+, Co
3+, Mn
3+, Ni
3+Plasma, preferably Cr
3+B is Fe
3+Ion; X=0～1.0; Y=0.4～1.0; Z=0～0.5.
The carrier of catalyst of the present invention is the sial composite oxides, and its main thing is the mixture of mullite and sillimanite mutually, also with silicon remaining in the preparing carriers process, aluminum oxide and composite oxides thereof.Mullite and sillimanite are two kinds of crystal that structure is close, and mullite is the disordered structure of sillimanite.A large amount of experimental results show, in the roasting process of the oxide of silicon button aluminium, mullite and sillimanite are accompanied often, are difficult to clearly distinguish content and the ratio of the two.Because mullite has identical load effect in the present invention with sillimanite, so the present invention need not clearly to determine the mullite in the carrier of the present invention and the ratio and the content of sillimanite, therefore carrier of the present invention is referred to as the mixture carrier of mullite and sillimanite.Experiment shows, the mixture carrier of mullite of the present invention and sillimanite extremely helps iron system spinel type composite oxides active component, and load is thereon securely, and, help active component and give full play to its catalytic action not with the active component chemically reactive.
The preparation method of the mixture carrier of mullite of the present invention and sillimanite comprises:
1. the raw material with silicon oxide-containing and aluminium oxide mixes by metering, and being mixed with weight ratio is Al
2O
3: SiO
2=1.4～2.3, be preferably 1.55～1.90 mixture;
2. in mixture, add with the mixture weight ratio and be (0～10): 100, be preferably (1～5): 100 binding agent; And adding is (0～20) with the mixture weight ratio: 100, be preferably (5～15): 100 pore creating material and an amount of water, and aftershaping stirs;
3. after the article shaped oven dry with step 2, in high-temperature roasting, sintering temperature is 1200～1550 ℃, is preferably 1300～1500 ℃; Roasting time is 1～24 hour, is preferably 4～12 hours.
Wherein said binding agent is carboxymethyl cellulose and/or polyvinyl alcohol; Described pore creating material is made of the material that is selected from active carbon, high molecular polymer, shuck, grass-seed, cereal etc.
Carrier of the present invention can be made different shape as required, generally be with the preparation compound by different forming method moulding after, with its oven dry, again 1200～1550 ℃ of following roastings 1～24 hour.As be used to prepare the carrier of fluid catalyst, and can adopt the spray drying technology preparation, behind the spray shaping, the carrier particle size range is 10～100 orders, and water absorption rate is 60～90%, and bulk density is 0.4～0.9 gram/cubic centimetre, and specific surface is 1.0～20 meters squared per gram.For being used to prepare the carrier of fixed bde catalyst, then can be made into shapes such as ball, cylinder, annulus, the pore volume of carrier is 0.2～0.7 a cubic centimetre/gram, and bulk density is 0.4～1.0 gram/cubic centimetre, and specific surface is 1.0～10 meters squared per gram.
Preparation of catalysts method of the present invention comprises: the raw material that will contain the required metallic element of active component is made into the aqueous solution, the aqueous solution of nitrate or acetate for example, make the concentration of each metal ion in the solution meet the stoichiometric relationship of contained each metallic element of active component, and make total concentration that GOLD FROM PLATING SOLUTION belongs to ion between 1～3M, 1.5～2.5M preferably.The mixture carrier of the mullite that makes and sillimanite added in the solution of being prepared flood, after the impregnated carrier oven dry, at 400～800 ℃, 450～650 ℃ roasting temperature 2～16 hours preferably, can on carrier, react generation iron system spinel active component, make catalyst of the present invention.Said process can repeat repeatedly, reaches required amount up to the active component that loads on the carrier.In the catalyst of the present invention, the weight ratio of active component and carrier is generally (5～20): 100, but in fact, reach (7～15): 100 o'clock, catalyst can have good catalytic performance.
Adopt impregnation-calcination preparation method of the present invention, by the metal ion solution that makes is flooded described carrier, can make and contain the activity component metal ion solution evenly attached to the surface of carrier, drying and calcination activation, active component can generate, and disperses equably and securely attached to the surface of carrier.In Preparation of catalysts process of the present invention, can in maceration extract, add citric acid, it helps to make active component more even and more firm with combining of carrier in the dispersion of carrier surface.The mol ratio that citric acid that is added and GOLD FROM PLATING SOLUTION belong to total ion concentration is (0.0～1.0): 1 o'clock, its consumption was comparatively suitable, preferably (0.4～0.8): 1.
The catalyst of method for preparing is the high selectivity and the high conversion catalyst of butylene oxidation-dehydrogenation system butadiene.During use, beds is passed through in butylene, empty G﹠W charging.Reaction temperature is 300～500 ℃, and optimum range is 320～400 ℃.Oxygen alkene is 0.5～1.0 than (mol ratio), and optimum range is 0.6～0.8.Water alkene is 8～15 than (mol ratio), optimum range 9～12.Butylene volume space velocity (GHSV) is 200～800hr
-1, optimum range is 300～600hr
-1Under optimum condition, use catalyst of the present invention, the yield of butadiene can reach more than 70%, and the selectivity that generates butadiene is greater than 90%.
The iron that the invention provides support type is butadiene catalyst made by butylene oxidation dehydrogen.By changing carrier form, can prepare the catalyst that is used for fixing bed and fluid bed.Adopt complexing dipping method of the present invention, can improve the quality stability of Catalyst Production, eliminate the quality destabilizing factor that exists when adopting coprecipitation method to produce at present.Catalyst of the present invention has higher mechanical strength, and particularly to fluid catalyst, the present invention can significantly improve the anti-wear performance of catalyst, reduces catalyst efflorescence in use and runs damage.By the fluid catalyst of the inventive method preparation, for the suitable microspherical catalyst of granularity, fluidizing performance is preferably arranged, can improve the fluidized state of the non-loaded catalyst of present use, help to improve the efficient of fluidized-bed reactor.Adopt method of the present invention, can also reduce catalyst production cost.
For being illustrated more clearly in the present invention, enumerate following example.Below in each example, remove and indicate the person in addition, activity of such catalysts and optionally mensuration all be in 10 milliliters of thermostatic type fixed bed reactors, to carry out, reaction temperature is 370 ℃, butylene volume space velocity 500hr
-1, oxygen alkene is 0.7 than (mol ratio), water alkene is 10 than (mol ratio).Raw materials used chemical pure or the industrial raw material of being.Following example not delimit the scope of the invention.Example 1 contains Al with 85 kilograms
2O
3The aluminium glue of 70% (weight) and 33 kilograms contain SiO
2The silica gel of 91% (weight) grinds mixing, adds 2.2 kilograms polyvinyl alcohol and 170 premium on currency, making beating, and spray drying forming gets 10～100 purpose microballoons.Microballoon 1450 ℃ of following roastings 8.5 hours, is obtained the microspheric carrier.This carrier Main Ingredients and Appearance is sillimanite and/or mullite, and the two total amount is greater than 90%.The water absorption rate of this carrier is 78% (weight), and bulk density is 0.75 gram/cubic centimetre, and specific surface is 5.7 meters squared per gram.Example 2 contains Al with 7.9 kilograms
2O
3The aluminium glue of 70% (weight) and 3.6 kilograms contain SiO
2The silica gel of 91% (weight) grinds mixing, adds 0.20 kilogram carboxymethyl cellulose, and 1.5 kilograms of granular activated carbons and 7.0 premium on currency stir, and extruded moulding is 5 millimeters of diameters, grow 5 millimeters small column.After the oven dry,, obtain the column type carrier in 1450 ℃ of following roastings 8.5 hours.This carrier Main Ingredients and Appearance is sillimanite and/or mullite, and the two total amount is greater than 90%.The pore volume of this carrier is 0.27 a cubic centimetre/gram, and bulk density is 0.55 gram/cubic centimetre, and specific surface is 3.5 meters squared per gram.Example 3 weighings 14.0 gram Zn (NO
3)
26H
2O, 3.4 gram Co (NO
3)
26H
2O, 33.3 gram Fe (NO
3)
39H
2O and 23.5 gram Cr (NO
3)
39H
2O is dissolved in and is made into 100 ml solns in certain water gaging, adds the citric acids of 28.0 grams then, the heating stirring and dissolving.The carrier of getting in the 70 gram examples 2 adds above-mentioned solution, soaks half an hour, after the taking-up oven dry, in 500 ℃ of activation 2 hours, makes catalyst.With above-mentioned catalyst breakage, get 10～30 purpose samples, estimate it to butylene oxidation-dehydrogenation system butadiene reactive activity, the result is, butadiene yield 76.5%, butene conversion 82.5%, the selectivity that generates butadiene is 92.8%.Example 4 weighings 14.0 gram Zn (NO
3)
26HO, 3.4 gram Co (NO
3)
26H
2O, 33.3 gram Fe (NO
3)
39H
2O and 23.5 gram Cr (NO
3)
39H
2O is dissolved in and is made into 100 ml solns in certain water gaging, adds the citric acids of 28.0 grams then, the heating stirring and dissolving.The carrier of getting in the 70 gram examples 1 adds above-mentioned solution, soaks half an hour, after the taking-up oven dry, in 500 ℃ of activation 2 hours, makes catalyst.Above-mentioned catalyst generates the butadiene reactive activity to butylene oxidation-dehydrogenation, butadiene yield 83.9%, and butene conversion 93.1%, the selectivity that generates butadiene is 90.1%.Example 5 weighings 14.0 gram Zn (NO
3)
26H
2O, 3.4 gram Co (NO
3)
26H
2O, 33.3 gram Fe (NO
3)
39H
2O and 23.5 gram Cr (NO
3)
39H
2O is dissolved in and is made into 100 ml solns in certain water gaging, adds the citric acids of 28.0 grams then, the heating stirring and dissolving.The carrier of getting in the 70 gram examples 2 adds above-mentioned solution, soaks half an hour, after the taking-up oven dry, in 600 ℃ of activation 2 hours, makes catalyst.With above-mentioned catalyst breakage, get 10～30 purpose samples, estimate it to butylene oxidation-dehydrogenation system butadiene reactive activity, the result is, butadiene yield 69.0%, butene conversion 75.1%, the selectivity of butadiene are 91.9%.Example 6 weighings 14.0 gram Zn (NO
3)
26H
2O, 3.4 gram Ni (NO
3)
26H
2O, 33.3 gram Fe (NO
3)
39H
2O and 23.5 gram Cr (NO
3)
39H
2O is dissolved in and is made into 100 ml solns in certain water gaging, adds the citric acids of 28.0 grams then, the heating stirring and dissolving.The carrier of getting in the 70 gram examples 2 adds above-mentioned solution, soaks half an hour, after the taking-up oven dry, in 500 ℃ of activation 2 hours, makes catalyst.With above-mentioned catalyst breakage, get 10～30 purpose samples, estimate it to butylene oxidation-dehydrogenation system butadiene reactive activity, the result is, butadiene yield 71.0%, butene conversion 78.2%, the selectivity that generates butadiene is 90.8%.Example 7 weighings 6.0 gram Zn (NO
3)
26H
2O, 5.2 gram Mg (NO
3)
26H
2O, 23.0 gram Fe (NO
3)
39H
2O and 16.2 gram Cr (NO
3)
39H
2O is dissolved in and is made into 60 ml solns in certain water gaging, adds the citric acids of 14.5 grams then, the heating stirring and dissolving.The carrier of getting in the 30 gram examples 2 adds above-mentioned solution, soaks half an hour, after the taking-up oven dry, in 500 ℃ of activation 2 hours, makes catalyst.With above-mentioned catalyst breakage, get 10～30 purpose samples, estimate it to butylene oxidation-dehydrogenation system butadiene reactive activity, the result is, butadiene yield 64.3%, butene conversion 75.6%, the selectivity that generates butadiene is 85.0%.Example 8 weighings 5.7 gram Zn (NO
3)
26H
2O, 3.7 gram Co (NO
3)
26H
2O, 25.7 gram Fe (NO
3)
39H
2O and 5.1 gram Cr (NO
3)
39H
2O is dissolved in and is made into 60 ml solns in certain water gaging, adds the citric acids of 11.3 grams then, the heating stirring and dissolving.The carrier of getting in the 30 gram examples 2 adds above-mentioned solution, soaks half an hour, takes out oven dry, in 500 ℃ of activation 2 hours, makes catalyst.With above-mentioned catalyst breakage, get 10～30 purpose samples, estimate it to butylene oxidation-dehydrogenation system butadiene reactive activity, the result is, butadiene yield 64.0%, butene conversion 75.4%, the selectivity that generates butadiene is 84.8%.Example 9 weighings 8.0 gram Zn (NO
3)
26H
2O, 2.0 gram Co (NO
3)
26H
2O and 32.5 gram Fe (NO
3)
39H
2O is dissolved in and is made into 60 ml solns in certain water gaging, adds the citric acids of 16.0 grams then, the heating stirring and dissolving.The carrier of getting in the 30 gram examples 2 adds above-mentioned solution, soaks half an hour, after the taking-up oven dry, in 500 ℃ of activation 2 hours, makes catalyst.With above-mentioned catalyst breakage, get 10～30 purpose samples, estimate it to butylene oxidation-dehydrogenation system butadiene reactive activity, the result is, butadiene yield 63.9%, butene conversion 72.3%, the selectivity that generates butadiene is 88.4%.Example 10 weighings 7.5 gram Zn (NO
3)
26H
2O, 1.8 gram Co (NO
3)
26H
2O, 14.8 gram Fe (NO
3)
39H
2O and 12.7 gram Cr (NO
3)
39H
2O is dissolved in and is made into 50 ml solns in certain water gaging, adds the citric acids of 14.0 grams then, the heating stirring and dissolving.The carrier of getting in the 25 gram examples 2 adds above-mentioned solution, soaks half an hour, after the taking-up oven dry, in 500 ℃ of activation 2 hours, makes catalyst.With above-mentioned catalyst breakage, get 10～30 purpose samples, estimate it to butylene oxidation-dehydrogenation system butadiene reactive activity, the result is, butadiene yield 81.7%, butene conversion 90.2%, the selectivity that generates butadiene is 90.6%.
Claims (14)
1. a loaded catalyst is made up of the mixture carrier of iron system spinel type active component and mullite and sillimanite, and described active component general formula is:
(A
xA′
1－x)(ByB′
1－y)
2O
4·zFe
2O
3
A in the formula, A ' are respectively and are selected from Zn
2+, Co
2+, Ni
2+, Mg
2+, Mn
2+, Cu
2+And Cd
2+Metal ion; B is Fe
3+B ' is for being selected from Cr
3+, Co
3+, Ni
3+And Mn
3+Metal ion; And x=0～1.0; Y=0.4～1.0; Z=0～0.5; It is characterized in that wherein said active component forms and directly loads on the described carrier in original position on the mixture carrier of described mullite and sillimanite.
2. catalyst according to claim 1 is characterized in that, A, A ' are respectively and are selected from Zn in the formula
2+, Co
2+, Ni
2+, Mg
2+, Mn
2+Metal ion; And B ' is Cr
3+
3. catalyst according to claim 1 is characterized in that, the weight ratio of wherein said active component and carrier is (5～20): 100.
4. catalyst according to claim 1 is characterized in that wherein said carrier is shaped to microballoon, and granularity is 10～100 orders, and bulk density is 0.4～0.9 gram/cubic centimetre, specific surface be 1.0～20 square metres/exempt from, water absorption rate is 60～90%.
5. catalyst according to claim 1 is characterized in that wherein said carrier is shaped to ball, cylinder or annulus, and pore volume is 0.2～0.7 a cubic centimetre/gram, and bulk density is 0.4～1.0 gram/cubic centimetre, and specific surface is 1.0～10 meters squared per gram.
6. method for preparing the described loaded catalyst of claim 1, it is characterized in that, immerse in the aqueous solution of metal ion soluble-salt that total concentration of metal ions according to the required metallic element mol ratio preparation of described active component is 1.0～3.0M with the mixture carrier of described mullite and sillimanite, after dipping and the drying, in 400～800 ℃ of calcination activations 2～16 hours, the iron system spinel active component that generates directly is carried on mullite and the sillimanite mixture carrier, promptly makes described catalyst.
7. method according to claim 6, it is characterized in that, wherein the metal ion total concentration of the soluble-salt aqueous solution is 1.5～2.5M, the calcination activation temperature is 450～650 ℃, the calcination activation time is 2～16 hours, water-soluble metal salt is nitrate and acetate, and the weight ratio of active component and carrier is (5～20): 100.
8. method according to claim 6 is characterized in that, needs in the soluble-salt aqueous solution to add citric acid, and the mol ratio of citric acid and metal ion total amount is (0.0～1.0): 1.
9. method according to claim 6 is characterized in that, the A in the wherein said general formula, A ' are respectively and are selected from Zn
2+, Co
2+, Ni
2+, Mg
2+, Mn
2+Metal ion; And B ' is Cr
3+
10. method according to claim 6 is characterized in that, wherein said carrier prepares as follows:
(1) salic and raw material silica are pressed Al
2O
3: SiO
2=1.4～2.3 weight ratio is mixed with compound;
(2) add the binding agent account for compound weight 0～10%, 0～20% pore creating material and an amount of water in compound, aftershaping stirs;
(3),, promptly make described carrier 1200～1550 ℃ of calcination activations 1～24 hour with after the article shaped of (2) oven dry;
Wherein said pore creating material is made of the material that is selected from active carbon, high molecular polymer, shuck, grass-seed, cereal etc.; Described binding agent is carboxymethyl cellulose and/or polyvinyl alcohol.
11. method according to claim 10 is characterized in that, in weight ratio, and Al wherein
2O
3: SiO
2=1.55～1.90.
12. method according to claim 10 is characterized in that, wherein said carrier is shaped to microballoon, and granularity is 10～100 orders, and bulk density is 0.4～0.9 gram/cubic centimetre, and specific surface is 1.0～20 meters squared per gram, and water absorption rate is 60～90%.
13. method according to claim 10 is characterized in that, wherein said carrier is shaped to ball, cylinder or annulus, and pore volume is 0.2～0.7 a cubic centimetre/gram, and bulk density is 0.4～1.0 gram/cubic centimetre, and specific surface is 1.0～10 meters squared per gram.
14. each described loaded catalyst is as the Application of Catalyst of preparing butadiene with butylene oxo-dehydrogenation in the claim 1～5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100436A CN1034853C (en) | 1992-01-24 | 1992-01-24 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100436A CN1034853C (en) | 1992-01-24 | 1992-01-24 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
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| Publication Number | Publication Date |
|---|---|
| CN1074631A CN1074631A (en) | 1993-07-28 |
| CN1034853C true CN1034853C (en) | 1997-05-14 |
Family
ID=4938582
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|---|---|---|---|
| CN92100436A Expired - Fee Related CN1034853C (en) | 1992-01-24 | 1992-01-24 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8551443B2 (en) | 2010-09-02 | 2013-10-08 | Saudi Basic Industries Corporation | Modified zinc ferrite catalyst and method of preparation and use |
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| KR100888133B1 (en) * | 2007-10-02 | 2009-03-13 | 에스케이에너지 주식회사 | Method of preparing multicomponent bismuth molybdate catalysts comprising four metal components and method of preparing 1,3-butadiene using said catalysts |
| CN102259034A (en) * | 2011-06-24 | 2011-11-30 | 淄博齐茂催化剂有限公司 | Method for producing finished product of supported catalyst |
| CN102580749B (en) * | 2012-02-02 | 2013-07-31 | 中石油东北炼化工程有限公司锦州设计院 | Preparation technology of butadiene catalyst by oxidative dehydrogenation of butene |
| US20130217568A1 (en) * | 2012-02-20 | 2013-08-22 | Saudi Basic Industries Corporation | Oxidative dehydrogenation of olefins catalyst and methods of making and using the same |
| CN102824914B (en) * | 2012-09-18 | 2014-07-02 | 陕西煤业化工技术研究院有限责任公司 | Catalyst and method used for preparing 1,3-butadiene by oxidative dehydrogenation of n-butene |
| CN103055890B (en) * | 2013-01-07 | 2015-06-03 | 惠生工程（中国）有限公司 | Iron catalyst used in butadiene production through n-butylene oxidation dehydrogenation, and preparation method and application thereof |
| CN103071541B (en) * | 2013-01-18 | 2015-10-28 | 中国科学院广州能源研究所 | A kind of preparation method of load type metal catalyst of highly disperse active center |
| CN103962062B (en) * | 2013-01-30 | 2016-08-24 | 中国石油化工股份有限公司 | The packing method of isothermal reactor catalyst |
| CN104028278B (en) * | 2013-03-04 | 2016-05-11 | 上海碧科清洁能源技术有限公司 | A kind of Catalysts and its preparation method for Oxidative Dehydrogenation of Butene into Butadiene and purposes |
| KR101507686B1 (en) * | 2013-05-06 | 2015-03-31 | 주식회사 엘지화학 | Mesoporous complex oxide catalyst, method for preparing the catalyst, and method for preparing 1,3-butadiene using thereof |
| KR102115299B1 (en) | 2016-06-07 | 2020-05-26 | 주식회사 엘지화학 | Catalyst for oxidative dehydrogenation and method for preparing the catalyst |
| CN109201070B (en) * | 2017-06-30 | 2021-05-04 | 中国石油化工股份有限公司 | Catalyst for preparing 1, 3-butadiene from butylene |
| CN114425364B (en) * | 2020-10-15 | 2024-03-29 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene, preparation method and application |
| CN114260007B (en) * | 2021-12-13 | 2023-03-28 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by high mechanical strength propane dehydrogenation and preparation method thereof |
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|---|---|---|---|---|
| US3450788A (en) * | 1968-05-21 | 1969-06-17 | Goodrich Gulf Chem Inc | Dehydrogenation process |
| US3595810A (en) * | 1969-06-24 | 1971-07-27 | Gulf Research & Chemical Co | Zinc chromium ferrite catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3450788A (en) * | 1968-05-21 | 1969-06-17 | Goodrich Gulf Chem Inc | Dehydrogenation process |
| US3595810A (en) * | 1969-06-24 | 1971-07-27 | Gulf Research & Chemical Co | Zinc chromium ferrite catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8551443B2 (en) | 2010-09-02 | 2013-10-08 | Saudi Basic Industries Corporation | Modified zinc ferrite catalyst and method of preparation and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1074631A (en) | 1993-07-28 |
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