CN107973690A - Catalyst and its method for Oxidative Dehydrogenation of Butene into Butadiene - Google Patents
Catalyst and its method for Oxidative Dehydrogenation of Butene into Butadiene Download PDFInfo
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- CN107973690A CN107973690A CN201610917080.6A CN201610917080A CN107973690A CN 107973690 A CN107973690 A CN 107973690A CN 201610917080 A CN201610917080 A CN 201610917080A CN 107973690 A CN107973690 A CN 107973690A
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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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C2523/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The present invention relates to a kind of catalyst and its method for Oxidative Dehydrogenation of Butene into Butadiene, mainly solve the problems, such as to be currently used for that Oxidative Dehydrogenation of Butene into Butadiene production process steam unit consumption is high, waste water yield is big, high energy consumption.The present invention includes following components by a kind of catalyst for being used for Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions, the catalyst：A) using molybdenum bismuth composite oxide as main active component；B) using chemical formula as AaBbCcThe oxide of combination is as auxiliary agent：Wherein A is selected from least one of Mn, Co, Ni or Fe；B is selected from least one of Al or Ti；C is selected from the technical solution of at least one of La or Ce, preferably solves the problems, such as this, efficiently, stably produces butadiene product, reduces energy consumption, reduce steam unit consumption and waste water yield, available in the industrial production of Oxidative Dehydrogenation of Butene into Butadiene.
Description
Technical field
The present invention relates to a kind of catalyst and its method for Oxidative Dehydrogenation of Butene into Butadiene；More particularly to one kind
Catalyst and its process for Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions.
Background technology
1,3- butadiene main application fields are the synthesis such as production butadiene rubber, butadiene-styrene rubber, ABS, SBS and nitrile rubber
Rubber, is additionally operable to other products such as production adiponitrile (nylon66 fiber monomer), sulfolane, anthraquinone, tetrahydrofuran.World's fourth in 2012
Diene consumption figure is about 1056.2 ten thousand tons.Butadiene has consequence in petrochemical industry olefin feedstock.
The production method of butadiene mainly has the extracting of preparing ethylene by steam cracking coproduction carbon four separation and butylene oxidation-dehydrogenation two
Kind production method.At present, the butadiene production capacity of world's overwhelming majority uses cracking c_4 extraction process.Since U.S.'s shale gas is removed from office
Life flourishes so that the ethylene cracker in the U.S. more using lighter hydrocarbons as cracking stock, north America region 60% with
On ethene production capacity use lightweight material.In order to reduce the cracking of ethylene of the Asia such as production cost, China in Recent Years, South Korea
Enterprise's also lighter hydrocarbons ratio in cracking stock is continuously improved, and Ethylene Unit Feedstocks lighting causes global butadiene supply
It is lasting tight slightly.As the fast development of synthetic rubber and resin industry, and butadiene purposes are more and more extensive, cause fourth two
The market demand sustainable growth of alkene, butadiene raw material are more in short supply.On the whole, it is contemplated that the coming years, world wide butadiene
Production capacity will be increased with the speed every year less than 3%, and butadiene consumption increase rate will be considerably beyond 3%, and demand growth is faster than
Expansible speed is produced, it will be normalization trend that supply falls short of demand within following one period.
In recent years, since the butadiene obtained using cracking c_4 extraction process cannot gradually meet the market demand, people
Begin to focus on the research of butylene oxidation-dehydrogenation technology.Contain substantial amounts of butylene in refinery's C-4-fraction, at present mainly as the people
Used with fuel, added value is relatively low, and butylene is converted into butadiene with high selectivity has significant economic benefit, for carbon four
The comprehensive utilization of cut resource is of great significance.The process route of Oxidative Dehydrogenation of Butene Into Butadiene has huge application
Prospect.
Butylene oxidation-dehydrogenation is strong exothermal reaction, in order to reach preferable catalytic effect, it usually needs into reaction raw materials
Substantial amounts of vapor is mixed as carrier gas and heat carrier.TPC groups of the U.S. (predecessor is Texas Petrochemical)
Oxo-D techniques and the O-X-D techniques of Philips companies are works representative in Oxidative Dehydrogenation of Butene into Butadiene technique
Skill.These techniques use ferrate catalyst, and the molar ratio of vapor and butylene is about 10：1.
In the traditional handicraft of butadiene is prepared, in addition to ferrate catalyst, molybdenum bismuth oxide is considered another kind of excellent
The catalyst of choosing.However, although molybdenum bismuth oxide has higher reactivity and butadiene yield, but there is also vapor to disappear
The problem of consumption is big.Ji Chul Jung etc. are in Catalytic performance of bismuth molybdate
catalysts in the oxidative dehydrogenation of C4raffinate-3to 1,3-butadiene
(catalytic performance of the bismuth molybdate catalysts in the reaction of -3 oxidative dehydrogenation butadiene of C4 mixed olefins raffinate), Applied
Catalysis A:General, 317, (2007), report butylene of the bismuth molybdate as catalyst in P244-249 articles
Oxidative dehydrogenation, in order to reach higher butadiene selective and relatively low by-product CO2Selectivity, have selected water alkene mole
Than the reaction condition for 15, water alkene is higher, and the butene conversion reacted is about 66%, and butadiene yield is about 60%.
Chinese patent CN103274887B discloses the side that a kind of tri- component composite oxide catalysts of Bi/Mo/Ce synthesize 1,3 butadiene
Method, tri- component composite oxide catalysts of Bi/Mo/Ce are obtained using the precipitation method, can be with by the content for adjusting Cerium in Catalysts
The high-selectivity catalyst for butadiene preparation process is obtained, the catalyst is used in butylene oxidation-dehydrogenation reaction, uses
Water alkene molar ratio be 5~15：1, water alkene is higher.These production technologies for being currently used for Oxidative Dehydrogenation of Butene into Butadiene are steamed
Gas unit consumption is big compared with high, waste water yield, energy consumption is higher, as environmental protection, the raising of energy-saving and emission-reduction requirement are, it is necessary to reduce to the greatest extent
The amount of vapor.However, research of the presently relevant patent literature to Oxidative Dehydrogenation of Butene into Butadiene low water ratio catalyst
It is also less.Exploitation high activity, the catalyst of low water ratio are the keys of low water ratio low energy consumption butylene oxidation-dehydrogenation technology.
The content of the invention
The technical problems to be solved by the invention are to be currently used for Oxidative Dehydrogenation of Butene into Butadiene production process steam list
A kind of the problem of consumption is high, waste water yield is big, high energy consumption, there is provided new Oxidative Dehydrogenation of Butene fourth being used under low-water ratio conditions
Diene catalyst, the method for preparing catalyst is easy, and butadiene production efficiently, is stably produced in butylene oxidation-dehydrogenation reaction
Thing, reduces energy consumption, reduces steam unit consumption and waste water yield, has that butadiene selective is high, catalyst activity and steady
Qualitative high advantage.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for fourth under low-water ratio conditions
The catalyst of alkene oxidative dehydrogenation butadiene, includes following components：
A) using molybdenum bismuth composite oxide as main active component；
B) using A, B, component C oxide as auxiliary agent, with molar ratio computing, be with molybdenum bismuth composite oxide constitutional chemistry formula
BiMoxAaBbCcOyComposition, wherein：
A is selected from least one of Mn, Co, Fe or Ni；
B is selected from least one of Al or Ti；
C is selected from least one of La or Ce；
The value range of a is 0.1~20；
The value range of b is 0~10；；
The value range of c is 0~5；
X is Mo total atom numbers in molybdate, and value range is 0.5~20；Y is to meet in catalyst needed for each element valence state
Oxygen atom sum.
In above-mentioned technical proposal, it is preferred that A is selected from least one of Ni, Co, Mn and Fe.
In above-mentioned technical proposal, it is preferred that A is selected from Ni and Fe.
In above-mentioned technical proposal, it is preferred that A is selected from Co and Fe.
In above-mentioned technical proposal, it is preferred that A is selected from Mn and Fe.
In above-mentioned technical proposal, it is furthermore preferred that the molar ratio of the and Fe in Ni, Co, Mn a kind of is (3：1)~(1:11)；
In above-mentioned technical proposal, it is furthermore preferred that the molar ratio of the and Fe in Ni, Co, Mn a kind of is (2：1)~(1:5).
In above-mentioned technical proposal, the value range of a is 0.5~15；The value of a more preferably scope is 0.5~5.
In above-mentioned technical proposal, the value range of b is to be less than or equal to 10 more than 0；The value preferred scope of b is 0.5~5.
In above-mentioned technical proposal, the value range of c is to be less than or equal to 5 more than 0.
In above-mentioned technical proposal, the value range of c is to be less than or equal to 2 more than 0；The value preferred scope of c is 0~2.
A kind of preparation for being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions according to the present invention
Method, comprises the steps of：
A) salt of bismuth nitrate and the component containing catalyst promoter is dissolved in the water of nitric acid acidifying；
B) under agitation, above-mentioned solution is added in the solution containing ammonium molybdate；
C) solution is obtained into solid chemical compound through spray-on process, coprecipitation, infusion process or sol-gal process.
D) gained sample is roasted.
In above-mentioned technical proposal, calcination temperature is 400 DEG C~650 DEG C, when roasting time is 1~24 small.
Application of the catalyst according to the present invention in Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions, can use
Include following processing step：
Using butylene, air or oxygen, vapor gaseous mixture as raw material, reaction inlet temperature be 300 DEG C~500 DEG C, fourth
Alkene mass space velocity is 1.0~6.0h-1, raw material after catalyst haptoreaction with obtaining butadiene.
Butylene in reactant：Oxygen：The volume ratio of vapor is 1：(0.5~5)：(1~10), water enter reactor it
It is preceding to be heated as vapor in advance and be sufficiently mixed with unstripped gas.
In above-mentioned technical proposal, butylene：The volume ratio preferred solution of vapor is 1：(1~4), more preferably scheme are 1：(1
~3).
Catalyst according to the present invention can be molded in different ways, in fixed bed or fluidized-bed reactor.
Compared with prior art, the present invention has the advantages that notable and high-lighting effect.Traditional butylene oxidation-dehydrogenation catalysis
Agent needs higher water alkene molar ratio, and catalytic performance significantly reduces under low-water ratio conditions.Butylene dehydrogenation reaction follows Mars-
Van Krevelen mechanism, the mobility of oxygen and the power of butylene dehydrogenation chain carrier are to determine molybdenum bismuth system in catalyst
Catalyst is in butylene oxidation-dehydrogenation reaction an important factor for reactivity worth.Meanwhile the stronger catalyst of hydrophily can improve
To the utilization ratio of vapor, it may be possible to the reactivity of catalyst is improved by stronger aquation, so as to reduce water
The dosage of steam, achieves energy-saving and emission reduction purposes.The present invention uses multi-component composite oxide catalysts, the activity of catalyst
It is significantly increased with butadiene selective.The addition of auxiliary agent can form redox couple, be conducive to improve in reaction process
Electron transporting properties, are conducive to the reactivity of catalyst and promote the recovery of catalyst activity state；Catalyst is promoted to be formed
Stable structure；Form lattice defect.Adjuvant component makes catalyst have preferable hydrophily at the same time, promotes catalyst surface
Hydroxylating, improves the utilization ratio to vapor, can further reduce vapor dosage.Pass through catalyst composition and component
Between ratio adjusting and optimization, catalyst be applicable not only to higher water than under butylene oxidation-dehydrogenation reaction, be also highly adaptable for
Oxidative Dehydrogenation of Butene into Butadiene reaction under low-water ratio conditions.The method for preparing catalyst is easy, has butadiene selective
Height, catalyst activity, the advantages of stability is high, reduces steam unit consumption and waste water yield, reduces energy consumption.
Butylene oxidation-dehydrogenation reaction is continuously carrying out on the flowing miniature catalyst reaction device of quartz tube reactor.Product analysis
Using HP-5890 gas chromatographs (HP-AL/S capillary columns, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis takes off
The content of alkane, alkene, butadiene in hydrogen product etc. and the conversion ratio and selectivity of product for calculating reaction.Use the present invention
Catalyst prepared by the method for offer is reacted for butylene oxidation-dehydrogenation, in butylene：The molar ratio of vapor is only 1：(1~4)
Low water alkene ratio under the conditions of can keep high-performance, butene conversion is higher than 75%, and butadiene selective is higher than 90%, catalyst performance
Energy is preferably and stability is high, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
Weigh 48.5g Bi (NO3)3·5H2O、87.3g Co(NO3)2·6H2O、161.6g Fe(NO3)3·9H2O、
37.5g Al(NO3)3·9H2O、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as A
Solution.In 80 DEG C of water-baths, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.
Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continued under 80 DEG C of water-baths fully
2h is stirred, obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then
When roasting 4 is small at 600 DEG C in the tube furnace being connected with oxygen atmosphere, obtains catalyst A and be used for evaluating catalyst.Catalyst
The element constitutive molar ratio example of A is BiMo12Co3Fe4Al1Ce1.5, remaining is O.
【Embodiment 2】
Weigh 48.5g Bi (NO3)3·5H2O、14.6g Co(NO3)2·6H2O、20.2g Fe(NO3)3·9H2O、7.5g
Al(NO3)3·9H2O、8.7g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A.
In 80 DEG C of water-baths, by 17.7g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Acutely stirring
Under the conditions of mixing, above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths,
Obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then are being connected with oxygen
When roasting 8 is small at 500 DEG C in tube furnace under gas atmosphere, obtains catalyst B and be used for evaluating catalyst.The element of catalyst B
Constitutive molar ratio example is BiMo1Co0.5Fe0.5Al0.2Ce 0.2, remaining is O.
【Embodiment 3】
Weigh 48.5g Bi (NO3)3·5H2O、145.5g Co(NO3)2·6H2O、202g Fe(NO3)3·9H2O、
187.5g Al(NO3)3·9H2O、86.8g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as A
Solution.In 80 DEG C of water-baths, by 264.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.
Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continued under 80 DEG C of water-baths fully
2h is stirred, obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then
When roasting 4 is small at 600 DEG C in the tube furnace being connected with oxygen atmosphere, obtains catalyst C and be used for evaluating catalyst.Catalyst
The element constitutive molar ratio example of C is BiMo15Co5Fe5Al5Ce 2, remaining is O.
【Embodiment 4】
Weigh 48.5g Bi (NO3)3·5H2O、2.9g Co(NO3)2·6H2O、4.0g Fe(NO3)3·9H2O is dissolved in 1L and contains
In 5% salpeter solution, which is labeled as solution A.In 80 DEG C of water-baths, by 8.9g (NH4)6Mo7O24·4H2O is dissolved in 2L and goes
In ionized water, which is labeled as B solution.Under intense agitation, above-mentioned solution A is added in B solution, be added dropwise
After, continue to be sufficiently stirred 2h under 80 DEG C of water-baths, obtained solution carries out spray shaping, obtains solid chemical compound.Solid
It is ground into 40~60 mesh particles after tabletting, then when roasting 10 is small at 400 DEG C in the tube furnace being connected with oxygen atmosphere, obtains
Catalyst D is used for evaluating catalyst.The element constitutive molar ratio example of catalyst D is BiMo0.5Co0.1Fe0.1, remaining is O.
【Embodiment 5】
Weigh 48.5g Bi (NO3)3·5H2O、291.0g Co(NO3)2·6H2O、404.0g Fe(NO3)3·9H2O、
375g Al(NO3)3·9H2O、217.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as A
Solution.In 80 DEG C of water-baths, by 253g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.
Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continues fully to stir under 80 DEG C of water-baths
2h is mixed, obtained solution carries out spray shaping, obtains solid chemical compound.It is ground into 40~60 mesh particles after solid preform, then
Be connected with the tube furnace under oxygen atmosphere at 650 DEG C roasting 4 it is small when, obtain catalyst E and be used for evaluating catalyst.Catalyst E
Element constitutive molar ratio example be BiMo20Co10Fe10Al10Ce 5, remaining is O.
【Embodiment 6】
Weigh 48.5g Bi (NO3)3·5H2O、87.3g Co(NO3)2·6H2O、87.3g Ni(NO3)2·6H2O、40.4g
Fe(NO3)3·9H2O、37.5g Al(NO3)3·9H2O、65.1g Ce(NO3)3·6H2O is dissolved in the salpeter solution that 1L contains 5%,
The solution is labeled as solution A.In 80 DEG C of water-baths, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, this is molten
Liquid is labeled as B solution.Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continued
2h is sufficiently stirred under 80 DEG C of water-baths, obtained solution carries out spray shaping, obtains solid chemical compound.40 are ground into after solid preform
~60 mesh particles, then in the tube furnace being connected with oxygen atmosphere at 600 DEG C roasting 4 it is small when, obtain catalyst F be used for be catalyzed
Agent is evaluated.The element constitutive molar ratio example of catalyst F is BiMo12Co3Ni3Fe1Al1Ce1.5, remaining is O.
【Embodiment 7】
Weigh 48.5g Bi (NO3)3·5H2O、484.8g Fe(NO3)3·9H2O、75.9g TiCl4、65.1g Ce
(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A.In 80 DEG C of water-baths, by 211.8g
(NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Under intense agitation, it is above-mentioned A is molten
Drop is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths, obtained solution is sprayed
Shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then in the tube furnace being connected with oxygen atmosphere
When roasting 4 is small at 600 DEG C, obtains catalyst G and be used for evaluating catalyst.The element constitutive molar ratio example of catalyst G is
BiMo12Fe12Ti4Ce1.5, remaining is O.
【Embodiment 8】
Weigh 48.5g Bi (NO3)3·5H2O、225.9g Mn(NO3)2·4H2O、121.2g Fe(NO3)3·9H2O、
150.0g Al(NO3)3·9H2O、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as A
Solution.In 80 DEG C of water-baths, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.
Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continued under 80 DEG C of water-baths fully
2h is stirred, obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then
When roasting 4 is small at 600 DEG C in the tube furnace being connected with oxygen atmosphere, obtains catalyst H and be used for evaluating catalyst.Catalyst
The element constitutive molar ratio example of H is BiMo12Mn9Fe3Al4Ce1.5, remaining is O.
【Embodiment 9】
Weigh 48.5g Bi (NO3)3·5H2O、29.1g Ni(NO3)2·6H2O、404.0g Fe(NO3)3·9H2O、
75.9g TiCl4、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A.80
In DEG C water-bath, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Acutely stirring
Under the conditions of mixing, above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths,
Obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then are being connected with oxygen
When roasting 4 is small at 600 DEG C in tube furnace under gas atmosphere, obtains catalyst I and be used for evaluating catalyst.The element of catalyst I
Constitutive molar ratio example is BiMo12Ni1Fe10Ti4Ce1.5, remaining is O.
【Embodiment 10】
Weigh 48.5g Bi (NO3)3·5H2O、232.8g Co(NO3)2·6H2O、161.6g Fe(NO3)3·9H2O、
75.9g TiCl4、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A.80
In DEG C water-bath, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Acutely stirring
Under the conditions of mixing, above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths,
Obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then are being connected with oxygen
When roasting 4 is small at 600 DEG C in tube furnace under gas atmosphere, obtains catalyst J and be used for evaluating catalyst.The element of catalyst J
Constitutive molar ratio example is BiMo12Co8Fe4Ti4Ce1.5, remaining is O.
【Embodiment 11】
Weigh 48.5g Bi (NO3)3·5H2O、50.2g Mn(NO3)2·4H2O、404.0g Fe(NO3)3·9H2O、
75.9g TiCl4、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A.80
In DEG C water-bath, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Acutely stirring
Under the conditions of mixing, above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths,
Obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then are being connected with oxygen
When roasting 4 is small at 600 DEG C in tube furnace under gas atmosphere, obtains catalyst K and be used for evaluating catalyst.The element of catalyst K
Constitutive molar ratio example is BiMo12Mn2Fe10Ti4Ce1.5, remaining is O.
【Embodiment 12】
Weigh 48.5g Bi (NO3)3·5H2O、29.1g Ni(NO3)2·6H2O、444.5g Fe(NO3)3·9H2O、
75.9g TiCl4、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A.80
In DEG C water-bath, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Acutely stirring
Under the conditions of mixing, above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths,
Obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then are being connected with oxygen
When roasting 4 is small at 600 DEG C in tube furnace under gas atmosphere, obtains catalyst L and be used for evaluating catalyst.The element of catalyst L
Constitutive molar ratio example is BiMo12Ni1Fe11Ti4Ce1.5, remaining is O.
【Embodiment 13】
Weigh 48.5g Bi (NO3)3·5H2O、29.1g Ni(NO3)2·6H2O、202.0g Fe(NO3)3·9H2O、
150.0g Al(NO3)3·9H2O、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as A
Solution.In 80 DEG C of water-baths, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.
Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continued under 80 DEG C of water-baths fully
2h is stirred, obtained solution carries out spray shaping, obtains solid chemical compound.40~60 mesh particles are ground into after solid preform, then
When roasting 4 is small at 600 DEG C in the tube furnace being connected with oxygen atmosphere, obtains catalyst M and be used for evaluating catalyst.Catalyst
The element constitutive molar ratio example of M is BiMo12Ni1Fe5Al4Ce1.5, remaining is O.
【Embodiment 14】
Weigh 48.5g Bi (NO3)3·5H2O、87.3g Co(NO3)2·6H2O、161.6g Fe(NO3)3·9H2O、
150.0g Al(NO3)3·9H2O、65.0g La(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as A
Solution.In 80 DEG C of water-baths, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.
Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continued under 80 DEG C of water-baths fully
2h is stirred, obtained solution is impregnated into the SiO of 40~60 mesh2On particle, then in 600 in the tube furnace being connected with oxygen atmosphere
When roasting 4 is small at DEG C, obtains catalyst n and be used for evaluating catalyst.Carrier S iO in catalyst n2Mass content be 60%, urge
The molar ratio for changing component is BiMo12Co3Fe4Al4La1.5, remaining is O.
【Embodiment 15】
Weigh 48.5g Bi (NO3)3·5H2O、87.3g Ni(NO3)2·6H2O、75.3g Mn(NO3)2·4H2O、
161.6g Fe(NO3)3·9H2O、75.9g TiCl4、65.0g La(NO3)3·6H2O、2.6g Mg(NO3)2·6H2O is dissolved in 1L
In salpeter solution containing 5%, which is labeled as solution A.In 80 DEG C of water-baths, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in
In 2L deionized waters, which is labeled as B solution.Under intense agitation, above-mentioned solution A is added in B solution,
After being added dropwise, continue to be sufficiently stirred 2h under 80 DEG C of water-baths, obtained solution and the ammonium hydroxide of 15w.t.% is co-precipitated, pH
=3,1h is vigorously mixed at room temperature for, is then filtered, solid is obtained and is dried.40~60 mesh are ground into after solid preform
Grain, then in the tube furnace being connected with oxygen atmosphere at 600 DEG C roasting 4 it is small when, obtain catalyst O and be used for evaluating catalyst.
The element constitutive molar ratio example of catalyst O is BiMo12Ni3Mn3Fe4Ti4La1.5Mg0.1, remaining is O.
【Embodiment 16】
Weigh 48.5g Bi (NO3)3·5H2O、75.3g Mn(NO3)2·4H2O、161.6g Fe(NO3)3·9H2O、
65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A., will in 80 DEG C of water-baths
211.8g(NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Under intense agitation, will
Above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths, obtained solution into
Row spray shaping, obtains solid chemical compound.40~60 mesh particles, then the pipe in the case where being connected with oxygen atmosphere are ground into after solid preform
When roasting 4 is small at 600 DEG C in formula stove, obtains catalyst P and be used for evaluating catalyst.The element constitutive molar ratio example of catalyst P
For BiMo12Mn3Fe4Ce1.5, remaining is O.
【Embodiment 17】
Weigh 48.5g Bi (NO3)3·5H2O、87.3g Co(NO3)2·6H2O、161.6g Fe(NO3)3·9H2O、
37.5g Al(NO3)3·9H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A., will in 80 DEG C of water-baths
211.8g(NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, which is labeled as B solution.Under intense agitation, will
Above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths, obtained solution into
Row spray shaping, obtains solid chemical compound.40~60 mesh particles, then the pipe in the case where being connected with oxygen atmosphere are ground into after solid preform
When roasting 4 is small at 600 DEG C in formula stove, obtains catalyst Q and be used for evaluating catalyst.The element constitutive molar ratio example of catalyst Q
For BiMo12Co3Fe4Al1, remaining is O.
【Comparative example 1】
Weigh 24.3g Bi (NO3)3·5H2O is dissolved in 1L containing in 5% salpeter solution, which is labeled as solution A.80
In DEG C water-bath, by 17.7g (NH4)6Mo7O24·4H2O is dissolved in 1L deionized waters, which is labeled as B solution.It is being vigorously stirred
Under the conditions of, above-mentioned solution A is added in B solution, after being added dropwise, continues to be sufficiently stirred 2h under 80 DEG C of water-baths, obtains
To solution and the ammonium hydroxide of 15w.t.% be co-precipitated, pH=3, is vigorously mixed at room temperature for 1h, then filters, obtain solid
It is dried.40~60 mesh particles are ground into after solid preform, then are roasted in the tube furnace being connected with oxygen atmosphere at 600 DEG C
Burn 4 it is small when, obtain catalyst R and be used for evaluating catalyst.The element constitutive molar ratio example of catalyst R is BiMo2, remaining is O.
【Comparative example 2】
Weigh 48.5g Bi (NO3)3·5H2O、65.1g Ce(NO3)3·6H2O is dissolved in 1L containing in 5% salpeter solution, is somebody's turn to do
Solution is labeled as solution A.In 80 DEG C of water-baths, by 211.8g (NH4)6Mo7O24·4H2O is dissolved in 2L deionized waters, the solution
Labeled as B solution.Under intense agitation, above-mentioned solution A is added in B solution, after being added dropwise, continued 80
2h is sufficiently stirred under DEG C water-bath, obtained solution carries out spray shaping, obtains solid chemical compound.It is ground into 40 after solid preform~
60 mesh particles, then in the tube furnace being connected with oxygen atmosphere at 600 DEG C roasting 4 it is small when, obtain catalyst S and be used for catalyst
Evaluation.The element constitutive molar ratio example of catalyst S is BiMo12Ce1.5, remaining is O.
【Embodiment 18】
0.5g catalyst A~S is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas are the mixing of butylene, oxygen, vapor
Thing, wherein butylene：Oxygen：The constitutive molar ratio of water is 1：0.75：2, first unstrpped gas is sufficiently mixed, is re-introduced into anti-
Answer and oxidative dehydrogenation is carried out in device.Reactor inlet temperatures are 420 DEG C；Reaction pressure is normal pressure；Butylene air speed (GHSV) is
300h-1.Catalytic reaction is carried out under above-mentioned condition, reaction product is analyzed with gas chromatography.Reaction result is listed in table 1.
Table 1*
* butene conversion and butadiene selective when reaction 10 is small
【Embodiment 19】
0.5g catalyst A, R is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas are butylene, oxygen, the mixture of vapor,
Wherein butylene：Oxygen：The constitutive molar ratio of water is 1：0.75：2, first unstrpped gas is sufficiently mixed, is re-introduced into reaction
Oxidative dehydrogenation is carried out in device.Reactor inlet temperatures are 420 DEG C；Reaction pressure is normal pressure；Butylene air speed (GHSV) is
300h-1.Catalytic reaction is carried out under above-mentioned condition, reaction product is analyzed with gas chromatography.Reaction result is listed in table 2.
Table 2
【Embodiment 20】
0.5g catalyst A is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas are butylene, oxygen, the mixture of vapor, its
Middle butylene：The constitutive molar ratio of oxygen is 1：0.75, water：The constitutive molar ratio of butylene is listed in table 3, is first filled unstrpped gas
Divide mixing, be re-introduced into reactor and carry out oxidative dehydrogenation.Reactor inlet temperatures are 420 DEG C；Reaction pressure is normal pressure；
Butylene air speed (GHSV) is 300h-1.Catalytic reaction is carried out under above-mentioned condition, reaction product is analyzed with gas chromatography.Instead
Should the results are shown in table 3.
Table 3
| Water alkene ratio (mol) | Butene conversion (%) | Butadiene selective (%) |
| 1 | 61.8 | 85.2 |
| 2 | 75.5 | 94.1 |
| 3 | 76.2 | 94.5 |
| 4 | 78.1 | 94.8 |
| 8 | 77.6 | 95.3 |
Claims (10)
1. a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene, includes following components：
A) using molybdenum bismuth composite oxide as main active component；
B) using A, B, component C oxide as auxiliary agent, with molar ratio computing, be with molybdenum bismuth composite oxide constitutional chemistry formula
BiMoxAaBbCcOyComposition, wherein：
A is selected from least one of Mn, Co, Fe or Ni；
B is selected from least one of Al or Ti；
C is selected from least one of La or Ce；
The value range of a is 0.1~20；
The value range of b is 0~10；
The value range of c is 0~5；
X is Mo total atom numbers in molybdate, and value range is 0.5~20；Y is the oxygen met in catalyst needed for each element valence state
Total atom number.
2. it is used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that A is selected from Co, Ni
Or at least one of Fe.
3. it is used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the value range of a
For 0.5~15.
4. it is used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the value range of b
For 0.1~10.
5. it is used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 4, it is characterised in that the value range of b
For 0.5~5.
6. it is used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the value range of c
For 0~2.
7. being used for the preparation method of the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, following step is included
Suddenly：
A) salt of bismuth nitrate and the component containing catalyst promoter is dissolved in the water of nitric acid acidifying；
B) under agitation, above-mentioned solution is added in the solution containing ammonium molybdate；
C) solution is obtained into solid chemical compound through spray-on process, coprecipitation, infusion process or sol-gal process.
D) gained sample is roasted.
8. it is a kind of be used for low-water ratio conditions under Oxidative Dehydrogenation of Butene into Butadiene catalyst method, with butylene, oxygen-containing gas,
The gaseous mixture of vapor is raw material, and reaction inlet temperature is 300 DEG C~500 DEG C, and butylene mass space velocity is 1.0~6.0h-1, raw material
With obtaining butadiene after claim 1~6 any one of them catalyst haptoreaction.
9. it is used for the method for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions according to claim 8, instead
Answer butylene in thing：Oxygen：The volume ratio of vapor is 1：(0.5~5)：(1~10).
10. it is used for the side of the catalyst of Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions according to claim 8 or claim 9
Method, butylene in reactant：The volume ratio of vapor is 1：(1~4).
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| CN114425447A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Heteropolyacid modified catalyst, preparation method and application thereof, and butylene oxidative dehydrogenation method |
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| CN101678328A (en) * | 2007-05-30 | 2010-03-24 | Sk能源株式会社 | A method of preparing multicomponent bismuth molybdate catalysts with controlling ph and a method of preparing 1,3-butadiene using thereof |
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| CN114425447B (en) * | 2020-10-15 | 2024-01-30 | 中国石油化工股份有限公司 | Heteropoly acid modified catalyst, preparation method and application thereof and butene oxidative dehydrogenation method |
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