CN106807453A - The method of preparing butadiene with butylene oxo-dehydrogenation catalyst - Google Patents
The method of preparing butadiene with butylene oxo-dehydrogenation catalyst Download PDFInfo
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- CN106807453A CN106807453A CN201710050539.1A CN201710050539A CN106807453A CN 106807453 A CN106807453 A CN 106807453A CN 201710050539 A CN201710050539 A CN 201710050539A CN 106807453 A CN106807453 A CN 106807453A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/84—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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of method of preparing butadiene with butylene oxo-dehydrogenation catalyst, it is non-ammonia or the alkaline precipitating agent of ammoniacal liquor to use precipitating reagent；Using ultra-fine grinding and secondary granulation and drying in granulating and drying.The present invention eradicated it is a large amount of in waste water ammonia nitrogen is exceeded is difficult process problem, while also obtaining qualified catalyst prod the problems such as overcome influence operating environment volatile due to ammonia, improve the environmental issue of ammonia-nitrogen sewage and the operating environment of improvement factory；By carrying out granulating and drying process ultra-fine grinding, secondary granulation, drying, and it is separately added into different expanding agents to improve catalyst both macro and micro diffusion problem in the application during raw material reaction proportioning, improves catalyst activity.
Description
Technical field
The present invention relates to a kind of method of preparing butadiene with butylene oxo-dehydrogenation catalyst.
Background technology
With flourishing for three big synthetic materials, as the important source material butadiene of synthetic rubber, oil is relied solely on
Refining and cracking separation product gained far can not meet demand, therefore produce fourth two by raw material of the butylene in the component of carbon four
The technology of alkene should be needed and given birth to.The key of Oxidative Dehydrogenation of Butene into Butadiene process is catalyst, now the life of the catalyst both at home and abroad
All, without report and patent using other precipitating reagents, mainly consider anti-using ammonia or ammoniacal liquor as precipitating reagent during product
Only introduce other ions remaining and influence the activity of catalyst.But brought in process of production as precipitating reagent using ammonia or ammoniacal liquor
Serious environmental issue, the volatility and smell of 10%-25% ammoniacal liquor cause the operative's environment for reacting and washing extremely
Badly.And substantial amounts of ammonia nitrogen is reclaimed and processing cost is extremely expensive in waste water.
Because butylene oxidation-dehydrogenation catalyst will typically be activated by compressing tablet high temperature (such as 650 DEG C), could be formed with work
The ferrite spinel product of property, its component elements oxide is through compressing tablet and high-temperature activation, the both macro and micro pore structure of product
Destroyed with gap, show as its specific surface very little or exhaust, the activated centre of catalyst in addition to surface almost
Can not play a role, cause catalyst activity very low.
The content of the invention
It is an object of the invention to provide a kind of method of preparing butadiene with butylene oxo-dehydrogenation catalyst, in having eradicated waste water
A large amount of ammonia nitrogens are exceeded to be difficult process problem, improves the environmental issue of ammonia-nitrogen sewage and the operating environment of improvement factory, improves catalysis
Agent both macro and micro diffusion problem in the application, improves catalyst activity.
A kind of method of preparing butadiene with butylene oxo-dehydrogenation catalyst of the present invention, use precipitating reagent for non-ammonia or
The alkaline precipitating agent of ammoniacal liquor；Using ultra-fine grinding and secondary granulation and drying in granulating and drying.
Non-ammonia or ammonia precipitation process agent are the compound of inorganic base, organic base or strong base-weak acid salt.
Non-ammonia or ammonia precipitation process agent are NaOH or potassium hydroxide.
Raw material adds expanding agent in preparing, granulate and drying；Addition twice is the 1%-10% of weight of iron.
Expanding agent is short fiber of plant, plant amylum, organic synthesis chopped fiber, synthetic resin and oligomer, carbon black or charcoal
Black and sucrose.
Plant amylum is field mountain valley with clumps of trees and bamboo powder, cornstarch or wheaten starch.
Iron, magnesium, Zn-ef ficiency are active component in catalyst；In copper, molybdenum, manganese, chlorine, cobalt, nickel, phosphorus, bismuth or chromium extremely
It is few a kind of for co-catalyst.
Iron in raw material：Magnesium：Zinc：The mol ratio of co-catalyst is 10:0.1‐9:0.2‐4:0.001‐3；The PH of precipitation reaction
Value control is in 8.5-10.
Granulation specifically includes granulation → drying → ultra-fine grinding → secondary granulation → redrying with drying.
Material fining smashes control between 150-800 mesh.
The method of preparing butadiene with butylene oxo-dehydrogenation catalyst of the present invention：The catalyst uses coprecipitation, and its is usual
Including 1. raw material prepare → be 2. co-precipitated with it is aging → 3. the granulation of filtration washing → 4. with dry → 5. the high temperature of compression molding → 6.
Activation → 7. finished product packing process.
The preferred strong basicity inorganic alkali compound of precipitating reagent, more preferred NaOH, potassium hydroxide.
Process 1., 4. in preferably use plant amylum, the preferred field mountain valley with clumps of trees and bamboo powder of plant amylum, cornstarch, wheaten starch, and
In process 5. middle use graphite.
The present invention except adding the graphite, graphite can to play a part of lubricant and expanding agent in compressing tablet, also in precipitation
Expanding agent is added as the crystal seed for precipitating particle during reaction, is made to be deposited in seed surface and is grown up；Simultaneously secondary granulation at again
Secondary to add expanding agent, these expanding agents are broken down and oxidized to form gas and go out in catalyst in catalyst high-temperature activation
Portion's particle, so as to form the interstitial channels of insertion, while catalyst specific surface is improved, material is easy to expand in making course of reaction
Dissipate, improve the utilization rate of catalyst active center, also just improve the activity of catalyst.
Repeatedly the species of addition expanding agent can be with identical, it is also possible to different.
The process of preparing butadiene with butylene oxo-dehydrogenation is macroscopically showing as spreading control.Based on above-mentioned same original
Reason, to improve the specific surface area of catalyst, for fine particle hardened after enabling precipitation to dry is separated after filtration cakes torrefaction, adopts
With ultra-fine grinding and then granulating and drying again, the specific surface area of finished catalyst is also improved.
The method of preparing butadiene with butylene oxo-dehydrogenation catalyst of the present invention, it is heavy by using non-ammonia or ammoniacal liquor
Shallow lake agent come improve ammonia-nitrogen sewage environmental issue and improve factory operating environment；Superfine powder is carried out by granulating and drying process
It is broken, secondary granulation and drying, and be separately added into not during raw material reaction matches process, secondary granulation process and compression molding
Same expanding agent reaches the purpose for improving catalyst activity to improve catalyst both macro and micro diffusion problem in the application.
Compared with prior art, the invention has the advantages that：
The method of preparing butadiene with butylene oxo-dehydrogenation catalyst of the present invention, has eradicated that a large amount of in waste water ammonia nitrogen is exceeded is difficult
Process problem, overcomes the problems such as influenceing operating environment because ammonia is volatile while also obtaining qualified catalyst prod, improves
The environmental issue of ammonia-nitrogen sewage and the operating environment of improvement factory；By carrying out to granulating and drying process ultra-fine grinding, secondary making
Grain, drying, and be separately added into different expanding agents to improve catalyst macroscopic view in the application during raw material reaction proportioning
With microcosmic diffusion problem, catalyst activity is improved.
Specific embodiment
In order to further illustrate said process and effect, comparative illustration is carried out with following example, but this patent protection
Not only it is only applicable to following example.
Embodiment 1
Weigh ferric nitrate Fe (NO3)3.9H2O169.5g, magnesium nitrate Mg (NO3)2·6H2O18.2g, zinc chloride
ZnCl222.2g, manganese nitrate Mn (NO3)2·4H2O2.0g, 11.5 grams of cobalt nitrate hexahydrate, 4g starch, the NaOH with 2.5M is molten
Liquid cocurrent neutralization precipitation to PH=8.67, aging 1.5 hours, then washed six times with 1500ml deionized waters, filtration cakes torrefaction granulation,
Plus compressing tablet is φ 6x6 after graphite 1.5%, 660 DEG C are calcined 8 hours under air ambient, measure STableIt is 13.8m2/g.It is crushed to
40-80 mesh.370 degree of conversion ratios 71.3%, selective 91.5%. under the same appreciation condition of comparative example 1
Embodiment 2
Weigh ferric nitrate Fe (NO3)3.9H2O 603.7g, magnesium nitrate Mg (NO3)2·6H2O 165.0g, zinc nitrate Zn
(NO3)2.6H2O 33.1g, manganese chloride MnCl215.4g, plus 12.7g sucrose, with 2.0MNaOH solution parallel-flow precipitations and PH=
9.82, aging 45 minutes, then distill water washing five times with 2500ml, filter cake is first dried, then crushes at least 300 mesh, is steamed with 60ml
Distilled water adjusts after 8.2g starch that compressing tablet is φ 6x6 after granulating and drying, plus graphite 1.5% again, 680 DEG C of roastings 6 under air ambient
Hour, measure STableIt is 27.7m2/ g, is crushed to 40-80 mesh.365 degree of conversion ratios under the same appreciation condition of comparative example 1
80.1%, selectivity 92.7%.
Embodiment 3
Weigh ferric nitrate Fe (NO3)3.9H2O 143.5g, magnesium nitrate Mg (NO3)2·6H2O 40.0g, zinc nitrate Zn
(NO3)2.6H2O 33.1g, manganese nitrate Mn (NO3)2·4H2O 3.1g, 6.2 grams of polyvinyl alcohol is neutralized with the potassium hydroxide of 1.5M
To PH=9.78, aging 1 hour, then washed five times with 1000ml deionized waters, filter cake is first dried, then is crushed to 400 mesh, is used
15ml water adds 2.0 grams of nickel chloride wiring solution-formings, and compressing tablet is straight after adding after 2.8g starch granulating and drying, plus graphite 1.5% again
Footpath is 5 millimeters of cylinders, and 690 DEG C are calcined 6 hours under air ambient, measure STableIt is 22.6m2/ g, is crushed to 40-80 mesh.
360 degree of conversion ratios 78.3% under the same appreciation condition of comparative example 1, selectivity 93.2%.
Comparative example 1
Weigh ferric nitrate Fe (NO3)3.9H2O 289g, magnesium nitrate Mg (NO3)2·6H2O 83.8g, zinc nitrate Zn (NO3)2.6H2O 33.1g, zinc chloride ZnCl215.2g, manganese nitrate Mn (NO3)2·4H2O 4.1g, are made into mixed solution 1000ml, use
17% ammoniacal liquor cocurrent neutralization precipitation PH is 9.95, aging 1 hour, then wash three times, filter cake with the ammoniacal liquor 1500ml that pH value is 9.5
Drying-granulating, plus the compressing tablet of graphite 1.5% is φ 6x6, and 650 DEG C are calcined 10 hours under air ambient.
S tables are measured for 8.3m2/ g, is crushed to 40-80 mesh, in butylene air speed 300h‐1Oxygen/alkene is 0.65, and water alkene compares 16, list
Evaluated in pipe flow reactor, 385 degree of conversion ratios 62.3%, selectivity 88.8%.
Claims (10)
1. a kind of method of preparing butadiene with butylene oxo-dehydrogenation catalyst, it is characterised in that it is non-ammonia or ammonia to use precipitating reagent
The alkaline precipitating agent of water；Granulate and use ultra-fine grinding, secondary granulation and drying in drying.
2. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 1, it is characterised in that non-ammonia or
Ammonia precipitation process agent is the compound of inorganic base, organic base or strong base-weak acid salt.
3. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 2, it is characterised in that non-ammonia or
Ammonia precipitation process agent is NaOH or potassium hydroxide.
4. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 1, it is characterised in that raw material is accurate
Expanding agent is added in standby and granulation and drying；Expanding agent addition twice is the 1%-10% of weight of iron.
5. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 4, it is characterised in that expanding agent
It is short fiber of plant, plant amylum, organic synthesis chopped fiber, synthetic resin and oligomer, carbon black or sucrose.
6. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 5, it is characterised in that plant is formed sediment
Powder is field mountain valley with clumps of trees and bamboo powder, cornstarch or wheaten starch.
7. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 1, it is characterised in that catalyst
Middle iron, magnesium, Zn-ef ficiency are active component；At least one in copper, molybdenum, manganese, chlorine, cobalt, nickel, phosphorus, bismuth or chromium is co-catalysis
Agent.
8. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 7, it is characterised in that in raw material
Iron：Magnesium：Zinc：The mol ratio of co-catalyst is 10:0.1-9:0.2-4:0.001-3；The pH value of precipitation reaction is controlled in 8.5-10.
9. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 1, it is characterised in that granulation with
Drying specifically includes granulation → drying → ultra-fine grinding → secondary granulation → redrying.
10. the method for preparing butadiene with butylene oxo-dehydrogenation catalyst according to claim 9, it is characterised in that material
Size controlling is between 150-800 mesh after ultra-fine smashing.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144197A (en) * | 1977-04-14 | 1979-03-13 | Shell Oil Company | Dehydrogenation catalyst |
| CN1184705A (en) * | 1996-09-25 | 1998-06-17 | 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 |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| 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 |
| CN105562007A (en) * | 2014-10-13 | 2016-05-11 | 上海碧科清洁能源技术有限公司 | Fe-based metal oxide catalyst, and preparation method and application thereof |
| CN105749929A (en) * | 2014-12-15 | 2016-07-13 | 中国石油天然气股份有限公司 | Supported catalyst used for butylene oxidative dehydrogenation, and preparation method thereof |
-
2017
- 2017-01-23 CN CN201710050539.1A patent/CN106807453A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144197A (en) * | 1977-04-14 | 1979-03-13 | Shell Oil Company | Dehydrogenation catalyst |
| CN1184705A (en) * | 1996-09-25 | 1998-06-17 | 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 |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| 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 |
| CN105562007A (en) * | 2014-10-13 | 2016-05-11 | 上海碧科清洁能源技术有限公司 | Fe-based metal oxide catalyst, and preparation method and application thereof |
| CN105749929A (en) * | 2014-12-15 | 2016-07-13 | 中国石油天然气股份有限公司 | Supported catalyst used for butylene oxidative dehydrogenation, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 朱洪法: "《催化剂制备及应用技术》", 30 June 2011, 中国石化出版社 * |
| 马世昌: "《化学物质辞典》", 30 April 1999, 陕西科学技术出版社 * |
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Application publication date: 20170609 |