CN103055871B - Method for preparing butadiene from C4 aliphatic hydrocarbons by oxidative dehydrogenation and catalyst used by same - Google Patents
Method for preparing butadiene from C4 aliphatic hydrocarbons by oxidative dehydrogenation and catalyst used by same Download PDFInfo
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- CN103055871B CN103055871B CN201110326316.6A CN201110326316A CN103055871B CN 103055871 B CN103055871 B CN 103055871B CN 201110326316 A CN201110326316 A CN 201110326316A CN 103055871 B CN103055871 B CN 103055871B
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Abstract
The invention relates to a method for preparing butadiene from C4 aliphatic hydrocarbons by oxidative dehydrogenation and a catalyst used by the same, belonging to the technical field of chemical engineering. C4 aliphatic hydrocarbons contact an oxidative dehydrogenation catalyst in the presence of oxygen and steam under the conditions of high air speed, proper oxygen-olefine ratio and water-olefine ratio and proper reaction temperature to obtain the butadiene, of which the olefine conversion rate is higher than 80%, the selectivity is higher than 90% and the yield is higher than 75%.
Description
Technical field:
The present invention relates to the method that butadiene is prepared in the oxidative dehydrogenation of a kind of C4 aliphatic hydrocarbon, belong to chemical technology field.
Background technology:
Butadiene is one of base stock of petrochemical industry, and its effect in petrochemical industry olefin feedstock is only second to ethene and propylene, is widely used in other Organic chemical products of synthetic rubber, synthetic resin and synthesis.As elastomeric monomer, the consumption of butadiene accounts for 60% of whole synthetic rubber consumption of raw materials, and the processing and utilization level of butadiene is an important symbol of whole petrochemical industry development level.
Butadiene industrially mainly from ethylene cracker by-product mixing C-4-fraction extracting obtain.In addition, can also be that raw material adopts the method for dehydrogenation to produce butadiene from butane and butylene.Typical butane dehydrogenation Butadiene Extraction Process is HoudryCatadiene technique, reaction temperature ~ 600 DEG C, based on butadiene yield ~ 65% of butane.Typical butylene oxidation-dehydrogenation method is the Oxo-D technique of Petro-Tex, butylene conversion per pass ~ 65%, butadiene selective ~ 93%, butadiene once through yield ~ 60%.
Produce the development experience of the raw material route of the butadiene process such as alcohol method, butylene or butane dehydrogenation and ethene coproduction carbon four solvent extraction process.Alcohol method is produced butadiene and is started from nineteen twenty-eight, and because technique falls behind, production cost is high, is progressively eliminated the fifties in last century.The commercial plant that nineteen forty-three produces butadiene by the catalytic dehydrogenation of oil gas butylene is gone into operation, and butadiene production device newly-built abroad afterwards almost all adopts oil gas B-B catalytic dehydrogenation route.But from the later stage sixties in last century, developing rapidly of cracking of ethylene technology, for butadiene industrial production provides the extremely abundant and by-product C 4 fraction of cheapness, since then, oxidative dehydrogenation device in succession close or replace by extraction process.
Along with constantly riseing of oil price, the sustainable growth of butadiene demand, breach between the butadiene and butadiene demand of cracking by-product will increase day by day, therefore except obtaining except butadiene from naphtha pyrolysis route, people also start to pay close attention to other butadiene production technology paths, particularly C 4 fraction production line.
China starts from early 1960s the research work that Oxidative Dehydrogenation of Butene gets butadiene, catalyst successively experienced by the P-Mo-Bi series catalysts of the first generation, second generation molybdenum series catalyst and third generation Fe-series catalyst, and catalytic activity is high, the selective high advantage of object product to only have Fe-series catalyst to have.
Patent 86108152.8 describes prepares Z by coprecipitation
naCr
cfe
do
4, Zn
amg
bcr
cfe
do
4, Zn
amg
bni
cfe
do
4, ZnaCrcFedO4 catalyst series, when this catalyst is used for fluidized-bed reactor, is 300 ~ 380 DEG C in reaction temperature, butylene air speed 250 ~ 500h
-1, oxygen ratio is 0.65 ~ 0.75 (mol ratio) water alkene ratio when being 8 ~ 12 (mol ratio), and butadiene yield is 62 ~ 68%, and butene conversion is 67 ~ 75%, and selective is 90 ~ 92%; Patent 91110590.5 describes prepares Zn by coprecipitation
aca
bfe
2o
4, Zn
amg
bfe
2o
4, Zn
ani
bfe
2o
4series is not containing Cr catalyst, and this catalyst is 66 ~ 75% for butadiene yield during fluidized-bed reactor, and butene conversion is 70 ~ 80%, and selective is 92 ~ 94%; Patent 96113127.6 describes prepares Zn by coprecipitation
ac
abCo
cfe
2o
4and Zn
aca
bni
cco
dfe
2o
4catalyst series, with addition of the components such as Co, Ni, and catalyst low-temperature activity is increased, and when reducing by 20 DEG C, some catalyst can reach the level of patent 91110590.5.
Fe-series catalyst involved in above-mentioned three patents, all the composite oxides with spinel structure, and also containing more than one other metallic element, but its performance is not very stable, catalyst wherein containing Cr can improve its stability effectively, but the existence of Cr has bad impact to human and environment, above-mentioned catalyst is all adapted to use in the dehydrogenation reactor of deflector apron fluid bed.And because adding other active metallic element in above patent, and cost increase, in addition, also just rest on the lab scale stage in laboratory, catalytic performance has no long test result data, whether can still have good effect in long industrialization is used still unknown.
Summary of the invention:
One object of the present invention is to provide and is applicable to the oxidative dehydrogenation of C4 aliphatic hydrocarbon and prepares iron acid zinc catalyst in the method for butadiene, can carry out large-scale industrial applications, and have environmental protection, the feature that catalytic efficiency is high.
Another object of the present invention is to provide the oxidative dehydrogenation of a kind of C4 aliphatic hydrocarbon to prepare the method for butadiene, under above-mentioned catalyst existent condition, under suitable process conditions, obtain higher butene conversion, selective and butadiene yield.
The present invention's iron acid zinc catalyst used, general structure is ZnFe
2o
4χ (α-Fe
2o
3), wherein χ is α-Fe
2o
3account for the mass percent of composite oxides: 30 ~ 60%, the main activity that described catalyst has spinel structure is ZnFe mutually
2o
4, secondary activity is α-Fe mutually
2o
3.
Described spinel structure is face-centered cube configuration.
Described iron acid zinc catalyst, χ is particularly preferably the mass percent of 35 ~ 45%.
Adopt the method for above-mentioned catalyst preparing butadiene to be, by account for C4 aliphatic hydrocarbon percent by volume be 50 ~ 100% n-butene to contact under oxygen exists with water vapour with catalyst and carry out oxidative dehydrogenation; Described catalyst is iron acid zinc catalyst, and general structure is ZnFe
2o
4χ (α-Fe
2o
3), wherein χ is the mass percent of 30 ~ 60%, and described catalyst has spinel structure, and its main activity is ZnFe mutually
2o
4, secondary activity is α-Fe mutually
2o
3; The process conditions of oxidative dehydrogenation are: air speed is 220 ~ 450h
-1, reaction temperature is 300 ~ 420 DEG C, and reaction oxygen alkene ratio is 0.5 ~ 0.8, and vapour alkene ratio is 8 ~ 18, synthesis under normal pressure.
Wherein said oxygen can be pure oxygen or air.
The present invention compared with prior art, catalyst of the present invention is without the need to adding other active metallic element artificially, still there is good stability, and higher activity and selectivity, catalyst of the present invention through the continuous running of 1000 hours, but still can have higher catalytic activity, therefore, the condition of oxidative dehydrogenation of the present invention is well-to-do, has higher butene conversion, selective and object product yield.In addition, catalyst of the present invention can be adapted to radial adiabatic fixed bed preferably.Fixed bed reactors structure is simple, and easy to operate, in bed, catalyst is fixed, and generate not containing dust in gas, its linear speed can regulate in the larger context, and the erosion problem of the loss of fluid catalyst and equipment is comparatively serious.
Of the present invention adopted catalyst is a kind of without Cr, the iron acid zinc catalyst with spinelle (face-centered cube configuration) structure, and its main activity is ZnFe mutually
2o
4, secondary activity is α-Fe mutually
2o
3, general structure is ZnFe
2o
4χ (α-Fe
2o
3), wherein χ=30 ~ 60% (quality).Due to, have the pure ferrite of perfect crystal phase structure, spinel structure is more intact, reactivity is poorer, how being organically combined mutually with bloodstone by Spinel, inventor finds in catalyst of the present invention by repeatedly attempting research, and χ is limited to 30 ~ 60%.Be particularly preferably in the scope of 35 ~ 45%, relatively unordered ferrate catalyst can be made can to obtain excellent result, its catalytic performance is the joint effect by two kinds of crystalline phases.
Iron acid zinc catalyst of the present invention contains the zinc of combination, iron and oxygen as its active ingredient; Its obtained reaction by the reactive compound of iron and the reactive compound of zinc generates.Reactive compound to react the compound generating ferrite, generally refers to oxide or forming the compound being converted into oxide in ferrite process, such as organic and inorganic salts or hydroxide.The reactive compound of iron and zinc comprises nitrate, hydroxide, hydrate, carbonate, acetate, oxide etc.The slaine generated (as ammoniacal liquor, ammonium carbonate etc.) can be separated out by co-precipitation in alkaline precipitating agent, the inert binder (as sesbania powder, starch, silica gel etc.) of appropriate (1 ~ 6% mass ratio) is added before precipitation, and adopting moving air air-flow roasting mode process catalyst of 8 ~ 12 hours at 620 ~ 670 DEG C, XRD (X-ray diffraction) spectrogram after process shows that its crystal phase structure is the compound of zinc ferrite Spinel and bloodstone phase.
Raw material that the present invention adopts is C4 aliphatic hydrocarbon, and wherein n-butene content is 50 ~ 100% (percents by volume), and the content of isobutene is less than 0.5% (percent by volume).
The concrete embodiment of the present invention is
By Catalyst packing of the present invention in fixed bed reactors, the device adopted forms by primarily of control section, reactive moieties, product gas-liquid separation, analysis part.Reactive moieties is made up of fixed bed reactors, heating furnace, reacting furnace temperature control and beds temperature measuring equipment.Water is vaporized afterwards and C4 aliphatic hydrocarbon, oxygen mix in heating furnace, enter reactor generation oxidative dehydrogenation, reacted product flows out from reactor bottom and enters condensing unit, carries out gas-liquid separation, gaseous product delivers to gas chromatographic analysis through dewatering further, and condensed fluid is all collected.Byproduct of reaction is CO, CO
2and the organic oxygen-containing compound such as acetaldehyde, acetone.
The process regulation of oxidative dehydrogenation is: air speed is 220 ~ 450h
-1, reaction temperature is 300 ~ 420 DEG C, and reaction oxygen is 0.5 ~ 0.8 with n-butene ratio (mol ratio), and water vapour is 8 ~ 18 with n-butene ratio (mol ratio), synthesis under normal pressure.
Olefin conversion of the present invention can up to 91.1%, and the selective of butadiene can up to 95.1%, and the yield of butadiene can reach 80.5%.
Accompanying drawing explanation
Accompanying drawing 1 is the structure cell of face-centered cube lattice and the Mathematical Model of heaped-up of atom of catalyst of the present invention.
Accompanying drawing 2 is the XRD spectra of air-flow calcination process catalyst.
The flow process of a kind of preparation method of butadiene of accompanying drawing 3 for the present invention relates to.
Detailed description of the invention
Following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1:
C4 aliphatic hydrocarbon air speed 400h
-1, reaction bed temperature is 406 DEG C, and vapour alkene ratio is 12, and oxygen alkene ratio is 0.6, and catalyst is for containing ZnFe
2o
465%, α-Fe
2o
335%, reaction result is in table 1.
Table 1 reaction result
Embodiment 2:
C4 aliphatic hydrocarbon air speed 400h
-1, reaction bed temperature is 404 DEG C, and vapour alkene ratio is 12, and oxygen alkene ratio is 0.8, and catalyst is for containing ZnFe
2o
465%, α-Fe
2o
335%, reaction result is in table 2.
Table 2 reaction result
Embodiment 3:
C4 aliphatic hydrocarbon air speed 400h
-1, reaction bed temperature is 387 DEG C, and vapour alkene ratio is 9, and oxygen alkene ratio is 0.6, and catalyst is for containing ZnFe
2o
465%, α-Fe
2o
335%, reaction result is in table 3.
Table 3 reaction result
Embodiment 4:
C4 aliphatic hydrocarbon air speed 389h
-1, reaction bed temperature is 406 DEG C, and vapour alkene ratio is 12, and oxygen alkene ratio is 0.6, and when substituting oxygen as oxidant with air, catalyst is for containing ZnFe
2o
465%, α-Fe
2o
335%, reaction result is in table 4.
Table 4 reaction result
Embodiment 5:
C4 aliphatic hydrocarbon air speed 400h
-1, reaction bed temperature is 406 DEG C, and vapour alkene ratio is 12, and oxygen alkene ratio is 0.6, and catalyst is for containing ZnFe
2o
465%, α-Fe
2o
335%, reaction result is in table 5.
Table 5 reaction result
Claims (8)
1. an iron acid zinc catalyst used in butadiene is prepared in the oxidative dehydrogenation of C4 aliphatic hydrocarbon, and general structure is ZnFe
2o
4χ (α-Fe
2o
3), wherein χ is α-Fe
2o
3account for the mass percent of composite oxides: 30 ~ 60%, described catalyst has the main active phase ZnFe of spinel structure
2o
4, secondary active phase α-Fe
2o
3; Described iron acid zinc catalyst is reacted by the reactive compound of iron and the reactive compound of zinc and generates; The slaine generated is separated out by co-precipitation in alkaline precipitating agent, the inert binder added before precipitation, and adopts the roasting mode process of 8 ~ 12 hours at 620 ~ 670 DEG C of flowing steam-air draught to obtain described iron acid zinc catalyst; The iron acid zinc catalyst obtained is zinc ferrite Spinel and the compound of bloodstone phase; Described iron and the reactive compound of zinc comprise nitrate, hydroxide, hydrate, carbonate, acetate, oxide; Inert binder is sesbania powder, starch or silica gel.
2. iron acid zinc catalyst according to claim 1, described spinel structure is face-centered cube configuration.
3. iron acid zinc catalyst according to claim 1 and 2, χ is the mass percent of 35 ~ 45%.
4. catalyst according to claim 1 is used for the oxidative dehydrogenation of C4 aliphatic hydrocarbon and prepares the method for butadiene, by account for C4 aliphatic hydrocarbon percent by volume be 50 ~ 100% n-butene to contact under oxygen exists with water vapour with described catalyst and carry out oxidative dehydrogenation; The process conditions of oxidative dehydrogenation are: air speed is 220 ~ 450h
-1, reaction temperature is 300 ~ 420 DEG C, and the mol ratio of reaction oxygen and n-butene is 0.5 ~ 0.8, and the mol ratio of water vapour and n-butene is 8 ~ 18, synthesis under normal pressure.
5. method according to claim 4, described spinel structure is face-centered cube configuration.
6. the method according to claim 4 or 5, is characterized in that wherein said oxygen can be pure oxygen or air.
7. the method according to claim 4 or 5, χ is the mass percent of 35 ~ 45%.
8. the method according to claim 4 or 5, loads in radial adiabatic fixed bed by catalyst, carry out catalytic reaction.
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| CN201110326316.6A CN103055871B (en) | 2011-10-24 | 2011-10-24 | Method for preparing butadiene from C4 aliphatic hydrocarbons by oxidative dehydrogenation and catalyst used by same |
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Cited By (1)
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|---|---|---|---|---|
| WO2017150830A1 (en) * | 2016-03-04 | 2017-09-08 | (주) 엘지화학 | Ferrite-based catalyst composite, method for preparing same, and method for preparing butadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3019458B1 (en) * | 2013-07-10 | 2017-04-05 | Basf Se | Method for the oxidative dehydrogenation of n-butenes to butadiene |
| WO2017122103A1 (en) | 2016-01-11 | 2017-07-20 | Sabic Global Technologies B.V. | Methods for the oxidative dehydrogenation of butene to produce butadiene |
| KR101973614B1 (en) * | 2016-03-18 | 2019-04-30 | 주식회사 엘지화학 | Method of preparing catalyst for oxidative dehydrogenation |
| KR102353147B1 (en) * | 2018-03-13 | 2022-01-18 | 주식회사 엘지화학 | Method for preparing ferrite-based coating catalysts and method for butadiene using the same |
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| CN1088624C (en) * | 1996-09-25 | 2002-08-07 | 中国科学院兰州化学物理研究所 | Iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene |
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| US3856880A (en) * | 1970-03-02 | 1974-12-24 | Petro Tex Chem Corp | Oxidative dehydrogenation catalyzed with promoted zinc ferrite |
| CN1013247B (en) * | 1986-11-27 | 1991-07-24 | 中国科学院兰州化学物理研究所 | Butylene oxidation-dehydrogenation catalyst |
| CN101367702A (en) * | 2008-09-26 | 2009-02-18 | 淄博齐翔腾达化工股份有限公司 | Method for preparing butadiene with butylene oxo-dehydrogenation of axially-located bed |
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Cited By (1)
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| WO2017150830A1 (en) * | 2016-03-04 | 2017-09-08 | (주) 엘지화학 | Ferrite-based catalyst composite, method for preparing same, and method for preparing butadiene |
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