CN105597799A - Method for preparing iron catalyst for preparing butadiene from butylene oxidative dehydrogenation with heat insulation static bed - Google Patents
Method for preparing iron catalyst for preparing butadiene from butylene oxidative dehydrogenation with heat insulation static bed Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
Abstract
The invention relates to a method for preparing an iron catalyst for preparing butadiene from butylene oxidative dehydrogenation with a heat insulation static bed. The method for preparing the catalyst mainly comprises the following steps that firstly, a precipitating agent and an iron-containing solution are neutralized to form precipitate slurry, the precipitate slurry is aged and filtered, then washing is carried out, and a filter cake is obtained; secondly, the filter cake is added with deionized water to be prepared into slurry, the slurry is subjected to spray drying, and catalyst particles are obtained; thirdly, the catalyst particles obtained through the spray drying is subjected to flake beating forming and heat treatment, and the iron catalyst for preparing butadiene from butylene oxidative dehydrogenation is obtained. The catalyst is applied in the process of preparing butadiene from butylene oxidative dehydrogenation with a reactor of the heat insulation static bed. Compared with the prior art, the method for preparing the catalyst is small in number of processes, low in labor intensity and small in dust emission and energy consumption, the catalyst bulk density can be obviously reduced, and the heat insulation reaction performance of the catalyst can be improved.
Description
Technical field
The present invention relates to catalyst, the insulation fix bed iron that is specifically related to a kind of Oxidative Dehydrogenation of Butene into Butadiene is urgedThe preparation method of agent.
Background technology
Butadiene is mainly derived from naphtha steam cracking ethene processed and propylene unit, and in recent years, cracking stock becomesIn lighting, dehydrogenating propane and the commercialization of methanol-to-olefins technology make a breakthrough, and cause the growth slowdown of butadiene production capacity,Even occur structural shortage, along with the fast development of butadiene downstream industry, butadiene demand increases sharply, butyleneOxidative dehydrogenation butadiene technology processed more and more comes into one's own.
Oxidative Dehydrogenation of Butene into Butadiene mainly adopts iron catalyst at present, and reactor adopts fluid bed or adiabatic solidFixed bed. Under fluidized-bed reaction state, finely grained catalyst, in fluidized state, is easy to the efflorescence of wearing and tearing, Jin EryinPlaying after-treatment system stops up; Adopt insulation fix bedly, iron catalyst is fixed in reactor, therefore, and fixed bedLower to catalyst abrasion and requirement of strength, the pellet type catalyst of certain size can reach reaction requirement, secondly,Insulation fix bed have simple in structure, amplify the low and investment advantage such as lower of risk, according to industrialized unit,Become the optimization technique of butylene oxidation-dehydrogenation reaction.
Current insulation fix bed with iron catalyst preparation technology be ferrous metal after salpeter solution is dissolved, add itHis slaine forms mixed salt solution, then through precipitation neutralization, filtration washing, filtration cakes torrefaction, grinding, granulation,Granulation dry materials, beat the operations such as sheet moulding and heat treatment and make the pellet type catalyst of certain size, this technique is depositedProblem be: operation is many, grinding, granulation, plays sheet moulding and handling process can produce more serious dust dirtDye, cause that production material loss is high, environmental pollution is large, labour intensity is large and energy consumption is high; This explained hereafterCatalyst also exists catalyst bulk density high, reactivity and the selective problem such as low.
Summary of the invention
The object of the invention is exactly the defect existing in order to overcome above-mentioned prior art, and a kind of catalyst bulk density is providedLittle, heat-insulating property good, insulation fix bed iron catalyst preparation method easy to prepare.
Object of the present invention can be achieved through the following technical solutions: a kind of for insulation fix bed butylene oxidationOxidative Dehydrogenation butadiene iron catalyst preparation method, is characterized in that, the method comprises the following steps:
(1) by precipitating reagent and iron-containing liquor and form sediment slurry, aging rear filtration, then washing obtains filter cake;
(2) step (1) gained filter cake and deionized water are mixed, and make slurries, then these slurries are enteredRow spraying is dry, under the condition of 100-200 DEG C of 180-350 DEG C of charging aperture temperature and discharge gate temperature, is urgedAgent particle;
(3) step (2) gained catalyst particle is beaten to sheet moulding and heat treatment, obtain butylene oxidation-dehydrogenationButadiene processed granular iron catalyst.
Described iron catalyst quality group becomes: iron (Fe) 51.67-64.43wt%, magnesium (Mg) 1.00-12.00Wt% and other elements 0.01-5.00wt%, all the other are oxygen (O) element.
Other described elements are selected from barium (Ba), calcium (Ca), nickel (Ni), cobalt (Co), copper (Cu), chromium(Cr), phosphorus (P), silicon (Si), aluminium (Al), vanadium (V), titanium (Ti), molybdenum (Mo), zinc (Zn), tin(Sn), one or more in antimony (Sb), zirconium (Zr), manganese (Mn) and rare earth.
The mode that described neutralization forms sediment slurry comprises that precipitating reagent is molten toward iron-containing liquor dropping, precipitating reagent and iron contentThe mode that the simultaneously past stillpot of liquid drips or iron-containing liquor drips toward precipitating reagent.
Described precipitating reagent comprise a kind of in ammoniacal liquor, ammonium bicarbonate soln, urea liquid or sodium hydroxide solution orMultiple mixed solution.
Described iron-containing liquor iron content, magnesium and other elements, other elements be barium (Ba), calcium (Ca), nickel (Ni),Cobalt (Co), copper (Cu), chromium (Cr), phosphorus (P), silicon (Si), aluminium (Al), vanadium (V), titanium (Ti),A kind of in molybdenum (Mo), zinc (Zn), tin (Sn), antimony (Sb), zirconium (Zr), manganese (Mn) and rare earth orMultiple.
Described catalyst heat treatment, its condition is under air atmosphere, processes 0.5-12.0h for 500.0-800.0 DEG C.
Described granular iron catalyst is cylindric or clover shape shape, and diameter is 3.0～7.0mm.
Described catalyst is applied to insulation fix bed, can be one section, two sections or multistage cold shock formula insulation fix bed.
Compared with prior art, beneficial effect of the present invention is embodied in: after washing, spray-dried, beat after filtrationSheet moulding and heat processing section can granulation shape catalyst, do not have traditional handicraft filtration cakes torrefaction, grind, makeThe workshop sections such as grain and granulation dry materials, thus catalyst manufacturing process reduced, reduce labour intensity, dust rowPut and energy consumption, and reach remarkable reduction catalyst bulk density, improve the object of catalyst adiabatic reaction performance.
Detailed description of the invention
Below embodiments of the invention are elaborated, the present embodiment enters under taking technical solution of the present invention as prerequisiteRow is implemented, and provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to downThe embodiment stating.
Embodiment 1
The insulation fix bed iron catalyst preparation of Oxidative Dehydrogenation of Butene into Butadiene, is specially: iron powder and magnesium metal are through nitreAcid solution adds ammonium dihydrogen phosphate (ADP) to form iron-containing liquor after dissolving completely, wherein, and iron-containing liquor concentration 0.50moLMg2+/ moLFe and 3.22 × 10-4moLPO4 3-/ moLFe, then ammonia spirit drops to and contains with certain speedFerrous solution precipitates, and fully stirs, and precipitation finishes rear continuation stirring aging, then sediment slurry is filtered alsoFully washing, gained filter cake is divided into two parts.
Adopt method for preparing catalyst of the present invention, a part of filter cake and deionized water mixing are made into slurries, send into sprayingDrying section, 180 DEG C of charging aperture temperature, sprays to slurries under the condition that discharge gate temperature is 100 DEG C dryDry, gained particle economy-combat sheet moulding and heat treatment, making diameter is 3mm clover shape beaded catalyst, numberingFor: NYZ01.
Adopt traditional handicraft method, another part filter cake drying, grinding, granulation, granulation dry materials, beat sheetThe workshop section such as moulding and heat treatment, making diameter is 3mm clover shape beaded catalyst, is numbered: CYZ01.
The catalyst of manufacturing according to the present invention and traditional handicraft, catalyst heat processing section condition is identical, is airThe lower 700.0 DEG C of heat treatment 6h of atmosphere. Quantitative elementary analysis shows, NYZ01 and CYZ01 catalyst composition oneCause, wherein, iron (Fe) 55.81wt%, magnesium (Mg) 12.17wt%, phosphorus (P) 0.01wt%, all the other areOxygen (O). From catalyst preparation process, adopt method for preparing catalyst of the present invention, with traditional preparation technologyCompare, reduced filtration cakes torrefaction in catalyst preparation process, grinding, granulation and granulation material drying process, therebyReach the object that reduces labour intensity, dust pollution and energy consumption.
NYZ01 and CYZ01 catalyst adiabatic reaction Calibration: adopt the insulation fix bed demarcation of single hop, it is exhaustedThermal response feed conditions is: n-butene air speed 400h-1, oxygen alkene is than 0.65, and water alkene is than 16.0, charging gauge pressurePower 0.060MPag, the physical property of catalyst and adiabatic reaction performance are as shown in table 1. Table 1 illustrates, adopts thisComparative catalyst's (numbering that catalyst (numbering NYZ01) bulk density of bright preparation is prepared lower than traditional handicraftCYZ01), and catalyst butadiene yield and butadiene prepared by the present invention be selectively better than comparative catalyst, itsReaction stability is able to obvious prolongation the duration of runs.
Embodiment 2
The insulation fix bed iron catalyst preparation of Oxidative Dehydrogenation of Butene into Butadiene, is specially: iron powder, magnesium metal, goldBelong to copper and metallic aluminium and add cerous nitrate to form iron-containing liquor after salpeter solution dissolves completely, wherein, iron-containing liquor is denseDegree 1.40moLMg2+/moLFe、1.22×10-2moLCu2+/moLFe、2.40×10-3moLCe3+/moLFeWith 1.87 × 10-3moLAl3+/ moLFe, then ammoniacal liquor and NaOH mixed solution drop to and contain with certain speedFerrous solution precipitates, and fully stirs, and precipitation finishes rear continuation stirring aging, then sediment slurry is filtered alsoFully washing, gained filter cake is divided into two parts.
Adopt method for preparing catalyst of the present invention, a part of filter cake and deionized water mixing are made into slurries, send into sprayingDrying section, 350 DEG C of charging aperture temperature, sprays to slurries under the condition that discharge gate temperature is 200 DEG C dryDry, gained particle economy-combat sheet moulding and heat treatment, making diameter is 7mm clover shape beaded catalyst, numberingFor: NYZ02.
Adopt traditional handicraft method, another part filter cake drying, grinding, granulation, granulation dry materials, beat sheetThe workshop section such as moulding and heat treatment, making diameter is 7mm clover shape beaded catalyst, is numbered: CYZ02.
The catalyst of manufacturing according to the present invention and traditional handicraft, catalyst heat processing section condition is identical, is airThe lower 800.0 DEG C of heat treatment 0.5h of atmosphere. Quantitative elementary analysis shows, NYZ02 and CYZ02 catalyst compositionUnanimously, wherein, iron (Fe) 61.46wt%, magnesium (Mg) 6.37wt%, copper (Cu) 0.17wt%, cerium (Ce)0.33wt%, aluminium (Al) 0.50%, all the other are oxygen (O). From catalyst preparation process, adopt the present inventionMethod for preparing catalyst, compared with traditional preparation technology, reduced filtration cakes torrefaction in catalyst preparation process, grinding,Granulation and granulation material drying process, thus reach the object that reduces labour intensity, dust pollution and energy consumption.
NYZ02 and CYZ02 catalyst adiabatic reaction Calibration: adopt the insulation fix bed demarcation of single hop, it is exhaustedThermal response feed conditions is: n-butene air speed 400h-1, oxygen alkene is than 0.65, and water alkene is than 16.0, charging gauge pressurePower 0.060MPag, the physical property of catalyst and adiabatic reaction performance are as shown in table 1. Table 1 illustrates, adopts thisComparative catalyst's (numbering that catalyst (numbering NYZ02) bulk density of bright preparation is prepared lower than traditional handicraftCYZ02), and catalyst butadiene yield and butadiene prepared by the present invention be selectively better than comparative catalyst, itsReaction stability is able to obvious prolongation the duration of runs.
Embodiment 3
The insulation fix bed iron catalyst preparation of Oxidative Dehydrogenation of Butene into Butadiene, is specially: iron powder and metallic zinc are through nitreAcid solution forms iron-containing liquor after dissolving completely, wherein, and iron-containing liquor concentration 0.36moLMg2+/ moLFe and0.07moLZn2+/ moLFe, then sodium hydroxide solution drops to iron-containing liquor with certain speed and precipitates,And fully stir, precipitation finishes rear continuation stirring aging, then sediment slurry is filtered and fully washed, gained filterCake is divided into two parts.
Adopt method for preparing catalyst of the present invention, a part of filter cake and deionized water mixing are made into slurries, send into sprayingDrying section, 220 DEG C of charging aperture temperature, sprays to slurries under the condition that discharge gate temperature is 150 DEG C dryDry, gained particle economy-combat sheet moulding and heat treatment, making diameter is 6mm cylindrical pellet catalyst, is numbered:NYZ03。
Adopt traditional handicraft method, another part filter cake drying, grinding, granulation, granulation dry materials, beat sheetThe workshop section such as moulding and heat treatment, making diameter is 6mm cylindrical pellet catalyst, is numbered: CYZ03.
The catalyst of manufacturing according to the present invention and traditional handicraft, catalyst heat processing section condition is identical, is airThe lower 500.0 DEG C of heat treatment 12h of atmosphere. Quantitative elementary analysis shows, NYZ03 and CYZ03 catalyst composition oneCause, wherein, iron (Fe) 64.43%, magnesium (Mg) 0.93wt%, zinc (Zn) 5.03wt%, all the other are oxygen(O). From catalyst preparation process, adopt method for preparing catalyst of the present invention, with traditional preparation technology's phaseRatio, has reduced filtration cakes torrefaction in catalyst preparation process, grinding, granulation and granulation material drying process, thereby has reachedTo the object that reduces labour intensity, dust pollution and energy consumption.
NYZ03 and CYZ03 catalyst adiabatic reaction Calibration: adopt the insulation fix bed demarcation of single hop, it is exhaustedThermal response feed conditions is: n-butene air speed 400h-1, oxygen alkene is than 0.65, and water alkene is than 16.0, charging gauge pressurePower 0.060MPag, the physical property of catalyst and adiabatic reaction performance are as shown in table 1. Table 1 illustrates, adopts thisComparative catalyst's (numbering that catalyst (numbering NYZ03) bulk density of bright preparation is prepared lower than traditional handicraftCYZ03), and catalyst butadiene yield and butadiene prepared by the present invention be selectively better than comparative catalyst, itsReaction stability is able to obvious prolongation the duration of runs.
Embodiment 4
The insulation fix bed iron catalyst preparation of Oxidative Dehydrogenation of Butene into Butadiene, is specially: iron powder is molten through salpeter solutionAfter separating completely, add cobalt nitrate to form iron-containing liquor, wherein, iron-containing liquor concentration 0.54moLMg2+/moLFeAnd 0.087moLCo2+/ moLFe, then ammoniacal liquor, urea and carbon ammonium mixed solution drop to and contain with certain speedFerrous solution precipitates, and fully stirs, and precipitation finishes rear continuation stirring aging, then sediment slurry is filtered alsoFully washing, gained filter cake is divided into two parts.
Adopt method for preparing catalyst of the present invention, a part of filter cake and deionized water mixing are made into slurries, send into sprayingDrying section, 250 DEG C of charging aperture temperature, sprays to slurries under the condition that discharge gate temperature is 180 DEG C dryDry, gained particle economy-combat sheet moulding and heat treatment, making diameter is 5.5mm cylindrical pellet catalyst, numberingFor: NYZ04.
Adopt traditional handicraft method, another part filter cake drying, grinding, granulation, granulation dry materials, beat sheetThe workshop section such as moulding and heat treatment, making diameter is 5.5mm cylindrical pellet catalyst, is numbered: CYZ04.
The catalyst of manufacturing according to the present invention and traditional handicraft, catalyst heat processing section condition is identical, is airThe lower 550.0 DEG C of heat treatment 10h of atmosphere. Quantitative elementary analysis shows, NYZ04 and CYZ04 catalyst composition oneCause, wherein, iron (Fe) 51.36wt%, magnesium (Mg) 12.03wt%, cobalt (Co) 4.70wt%, all the otherFor oxygen (O). From catalyst preparation process, adopt method for preparing catalyst of the present invention, prepare work with traditionSkill is compared, and has reduced filtration cakes torrefaction in catalyst preparation process, grinding, granulation and granulation material drying process, fromReduce the object of labour intensity, dust pollution and energy consumption and reach.
NYZ04 and CYZ04 catalyst adiabatic reaction Calibration: adopt the insulation fix bed demarcation of single hop, it is exhaustedThermal response feed conditions is: n-butene air speed 400h-1, oxygen alkene is than 0.65, and water alkene is than 16.0, charging gauge pressurePower 0.060MPag, the physical property of catalyst and adiabatic reaction performance are as shown in table 1. Table 1 illustrates, adopts thisComparative catalyst's (numbering that catalyst (numbering NYZ04) bulk density of bright preparation is prepared lower than traditional handicraftCYZ04), and catalyst butadiene yield and butadiene prepared by the present invention be selectively better than comparative catalyst, itsReaction stability is able to obvious prolongation the duration of runs.
Table 1 catalyst physical property and adiabatic reaction performance
In table 1, physical quantity definition refers to:
N-butene air speed: pass through n-butene volume under the standard state of per volume of catalyst bed in the unit interval;
Oxygen alkene ratio: the ratio of the oxygenous mole of reaction feed air institute and reaction feed n-butene mole;Water alkene ratio: the ratio of reaction feed water mole and reaction feed n-butene mole;
Butadiene yield and be selectively the mean value in reaction stability duration of runs.
Claims (9)
1. for an insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron catalyst preparation method, its featureBe, this preparation method comprises the following steps:
(1) by precipitating reagent and iron-containing liquor and form sediment slurry, aging rear filtration, then washing obtains filter cake;
(2) step (1) gained filter cake and deionized water are mixed, and make slurries, then these slurries are enteredRow spraying is dry, under the condition of 100-200 DEG C of 180-350 DEG C of charging aperture temperature and discharge gate temperature, is urgedAgent particle;
(3) step (2) gained catalyst particle is beaten to sheet moulding and heat treatment, obtain butylene oxidation-dehydrogenationButadiene processed granular iron catalyst.
2. as claimed in claim 1 for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron catalyst systemPreparation Method, is characterized in that, described iron catalyst quality group becomes: iron (Fe) 51.67-64.43wt%, magnesium(Mg) 1.00-12.00wt% and other elements 0.01-5.00wt%, all the other are oxygen (O) element.
3. according to claim 2 for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron catalystPreparation method, is characterized in that, other described elements be selected from barium (Ba), calcium (Ca), nickel (Ni), cobalt (Co),Copper (Cu), chromium (Cr), phosphorus (P), silicon (Si), aluminium (Al), vanadium (V), titanium (Ti), molybdenum (Mo),One or more in zinc (Zn), tin (Sn), antimony (Sb), zirconium (Zr), manganese (Mn) and rare earth.
4. arbitrary described for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron according to claim 1～3Method for preparing catalyst, is characterized in that, the mode that described neutralization forms sediment slurry comprises that precipitating reagent is toward iron contentThe mode that the simultaneously past stillpot of solution dropping, precipitating reagent and iron-containing liquor drips or iron-containing liquor drips toward precipitating reagent.
5. arbitrary described for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron according to claim 1～3Method for preparing catalyst, is characterized in that, described precipitating reagent comprises ammoniacal liquor, ammonium bicarbonate soln, urea liquidOr one or more mixed solutions in sodium hydroxide solution.
6. arbitrary described for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron according to claim 1～3Method for preparing catalyst, is characterized in that, described iron-containing liquor iron content, magnesium and other elements, and other elements areBarium (Ba), calcium (Ca), nickel (Ni), cobalt (Co), copper (Cu), chromium (Cr), phosphorus (P), silicon (Si),Aluminium (Al), vanadium (V), titanium (Ti), molybdenum (Mo), zinc (Zn), tin (Sn), antimony (Sb), zirconium (Zr),One or more in manganese (Mn) and rare earth.
7. arbitrary described for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron according to claim 1～3Method for preparing catalyst, is characterized in that, the described heat treated condition of step (3) is under air atmosphere,500.0-800.0 DEG C processing 0.5-12.0h.
8. arbitrary described for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron according to claim 1～3Method for preparing catalyst, is characterized in that, described granular iron catalyst is cylindric or clover shape shape,External diameter is 3.0～7.0mm.
9. as claimed in claim 8 for insulation fix bed Oxidative Dehydrogenation of Butene into Butadiene iron catalyst systemPreparation Method, described catalyst is applied to insulation fix bed, can be that one section, two sections or multistage cold shock formula are adiabatic solidFixed bed.
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| CN201610061574.9A Pending CN105597799A (en) | 2016-01-28 | 2016-01-28 | Method for preparing iron catalyst for preparing butadiene from butylene oxidative dehydrogenation with heat insulation static bed |
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Cited By (3)
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| CN107308942A (en) * | 2016-06-12 | 2017-11-03 | 中国石油化工股份有限公司 | The catalyst and its method of preparing butadiene with butylene oxo-dehydrogenation |
| CN112675807A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Adsorbent for removing carbon monoxide in gas, preparation method and application |
| CN114425364A (en) * | 2020-10-15 | 2022-05-03 | 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 thereof |
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| CN103752316A (en) * | 2014-01-26 | 2014-04-30 | 惠生工程（中国）有限公司 | Iron catalyst for preparing butadiene through n-butene oxydehydrogenation and preparation method and application of iron catalyst |
| CN104968434A (en) * | 2012-12-06 | 2015-10-07 | 巴斯夫欧洲公司 | Catalyst and method for oxidative dehydrogenation of N-butenes to give butadiene |
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| CN103055890A (en) * | 2013-01-07 | 2013-04-24 | 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 |
| CN103316688A (en) * | 2013-07-03 | 2013-09-25 | 王伟跃 | Catalyst for preparing butadiene from mixed C4 and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107308942A (en) * | 2016-06-12 | 2017-11-03 | 中国石油化工股份有限公司 | The catalyst and its method of preparing butadiene with butylene oxo-dehydrogenation |
| CN112675807A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Adsorbent for removing carbon monoxide in gas, preparation method and application |
| CN112675807B (en) * | 2019-10-18 | 2023-07-04 | 中国石油化工股份有限公司 | Adsorbent for removing carbon monoxide in gas, preparation method and application |
| CN114425364A (en) * | 2020-10-15 | 2022-05-03 | 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 thereof |
| 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 |
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Application publication date: 20160525 |