CN104226351A - Preparation method of catalyst for butylene oxidative dehydrogenation to produce butadiene - Google Patents
Preparation method of catalyst for butylene oxidative dehydrogenation to produce butadiene Download PDFInfo
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- CN104226351A CN104226351A CN201310237134.0A CN201310237134A CN104226351A CN 104226351 A CN104226351 A CN 104226351A CN 201310237134 A CN201310237134 A CN 201310237134A CN 104226351 A CN104226351 A CN 104226351A
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- butylene
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Abstract
The invention relates to a preparation method of a catalyst for butylene oxidative dehydrogenation to produce butadiene, and mainly solves the problems of easy loss of components in precipitation process and poor reproducibility in the existing preparation of the catalyst. The invention adopts ball milling method to grind iron oxide, magnesium oxide, zinc oxide and a catalytic promoter in the form of oxides into powder, so as to obtain a mixture of complex metal oxides, the mixture is subjected to high-temperature calcination to obtain butylene, and butylene is subjected to oxidative dehydrogenation to obtain butadiene. The technical scheme well solves the problem, and can be used in industrial production of butadiene from butylene oxidative dehydrogenation.
Description
Technical field
The present invention relates to a kind of butadiene catalyst made by butylene oxidation dehydrogen method for preparing catalyst.
Background technology
Butadiene is petrochemical industry base stock and the important monomer producing high molecular synthetic material, can make various synthetic rubber and synthetic resin with multiple compounds copolymerization.Current butadiene mainly contains refinery's preparing ethylene by steam cracking coproduction carbon four extracting separation and oxygenizement of butene two kinds of production methods.China's butadiene almost all derives from carbon four extracting and is separated, this process has superiority economically, but it obtains as the accessory substance of refinery's cracker, and along with rubber industry is to the demand growth of butadiene output, cracker is produced butadiene and has been difficult to satisfy the demand.Butylene oxidation-dehydrogenation take butadiene as the process of target product, and the butadiene that the butenc that domestic fuel can be used be high added value, this production technology route becomes more and more important.
Mo-Bi system, Sn-P-Li system, Fe silicate system all can be used for butylene oxidation-dehydrogenation reaction.But Mo-Bi system is selective lower, produce a large amount of organic oxygen-containing accessory substance.Sn-P-Li system activity is high, but operating condition is comparatively harsh, water alkene than high, energy consumption is high.Fe-series catalyst has obvious advantage, and as butadiene yield is high, oxidized byproduct is few, and water alkene is than low etc.Most widely used is at present spinel-type Fe-series catalyst.
Since the butylene oxidation-dehydrogenation catalyst invention of iron system (USP3270080), have passed through the improvement in a lot of generation, performance is constantly improved.Cr
3+element effectively can improve activity and the stability (USP3450788) of Fe series catalysts.The butylene oxidation-dehydrogenation catalyst (CN86108152, CN96113127.6) that can be used for fluid bed has been invented by Lanzhou Chemical Physics research institute of the Chinese Academy of Sciences.Synthetic rubber plant of Yanshan Petrochemical company have developed for insulation fix bed chromium-free iron series B02 Oxydehydrogenation catalyst and the more superior B90 catalyst of performance.The people such as white wave disclose a kind of iron system spinel composite oxides butylene oxidation-dehydrogenation catalyst of support type, have mechanical strength high, the advantage (CN92100436.2) of good stability.
Although iron system spinel Oxydehydrogenation catalyst commercial Application, the preparation of existing catalyst adopts coprecipitation, there is component and easily run off, preparation poor reproducibility, the uppity problem of catalyst quality.
Summary of the invention
Technical problem to be solved by this invention there is component in the precipitation process of existing catalyst preparing easily to run off, and the problem of preparation poor reproducibility, provides a kind of new butadiene catalyst made by butylene oxidation dehydrogen preparation method.The catalyst obtained by the method is used for Oxidative Dehydrogenation of Butene into Butadiene process, and have under high temperature and aqueous conditions, active component not easily runs off, and butadiene yield is high, and alkynes production rate is low, the feature of good stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of butadiene catalyst made by butylene oxidation dehydrogen preparation method, and described catalyst chemical composition general formula is:
Fe
2O
3·MgO·ZnO·P
2O
5?·M
xO
y
Wherein, M is selected from least one in Sc, Ti, V, Cr, Mn, Co, Ni or Cu; X and y is stoichiometric proportion; By weight percentage, Fe
2o
3consumption be 52 ~ 76%; The consumption of MgO is 12 ~ 28%; The consumption of ZnO is 10 ~ 25%; P
2o
5consumption be 0.01 ~ 5.0%; M
xo
yconsumption be 0.01 ~ 3.0%;
Described preparation method comprises the following steps:
A) by the solid Fe of aequum
2o
3, MgO, ZnO, P
2o
5, M
xo
yand pore creating material, in ball mill, carry out ball milling 0.5 ~ 6 hour, screening is greater than the particle powder of 150 mesh standard sieves;
B) particle powder step a) obtained, 550 ~ 800 DEG C of roastings 2 ~ 36 hours, obtains described catalyst.
In technique scheme, preferably, by weight percentage, Fe
2o
3consumption be 55 ~ 70 %.
Preferably, by weight percentage, the consumption of MgO is 14.0 ~ 25.0%.
Preferably, by weight percentage, the consumption of ZnO is 12.0 ~ 22.0%.
Preferably, by weight percentage, P
2o
5consumption be 0.1 ~ 3.0%.
Preferably, by weight percentage, M
xo
yconsumption be 1.0 ~ 2.8%.
Preferably, M is selected from least one in Mn, Cu, Co or Cr,
Preferably, described particle powder diameter is 0.1 micron ~ 100 microns.
Preferably, described pore creating material is selected from least one in active carbon, polyvinyl alcohol, glucose, cellulose or plant amylum, and the addition of pore creating material is 0 ~ 15% of metal oxide mixture weight.
Preferably, sintering temperature is 600 ~ 780 DEG C, and roasting time is 6 ~ 20 hours.
Preferably, catalyst may be molded to the difformities such as ball, cylinder, disk, annulus and trifolium-shaped.Catalyst pore volume 0.1 ~ 1.2 centimetre
3/ gram, specific area 5 ~ 60 meters
2/ gram.
Catalyst prepared by the present invention reacts for butylene oxidation-dehydrogenation, and reaction condition is: be raw material with butylene, and being diluent with water, take molecular oxygen as oxidant, and reaction temperature is 320 ~ 600 DEG C, and reaction pressure is 0 ~ 0.4MPa, and butylene volume space velocity is 200 ~ 500 hours
-1, H
2o/ butylene volume ratio is 6 ~ 20, O
2/ butylene volume ratio is 0.4 ~ 1.0.
Present invention employs mixing method and prepare composite oxide catalysts, iron oxide easily and the bivalent metal ion such as Mg, Zn form MFe
2o
4the spinel structure of type, the at least one auxiliary element be selected from Sc, Ti, V, Cr, Mn, Co, Ni or Cu can enter spinel structure generation same order elements, the effect of the active sites performance changing catalyst can be played, especially the electronics of its 4S electronic shell easily offsets, the cloud density of enhanced activity position, thus make the easier desorption of the butadiene of electron rich, reducing by deep dehydrogenation is the probability of alkynes; And adding of P element effectively can improve the activation capacity of catalyst surface to oxygen molecule, reduce the Fe caused because activating oxygen molecule reduces
3+ion is reduced into Fe
2+, effectively improve the stability of catalyst.Adopt mixing method Kaolinite Preparation of Catalyst, avoid the precipitation process of influence factor complexity, and do not relate to washing, effectively reduce the loss of component in washing process.And adopt stay-in-grade oxide as active component presoma, simple to operate, influence factor is few, and what improve catalyst well prepares Repeatability.Adopt the catalyst that obtains of this method at 380 DEG C, butylene volume space velocity 400 hours
-1, O
2/ C
4h
8be 0.7, water alkene than be 12 condition under use, conversion ratio is higher than 80%, selective higher than 94%, declines, achieve good technique effect more than 4000 hours stability experiment non-activities.
Butylene oxidation-dehydrogenation reaction is carried out on the miniature catalyst reaction device of continuous-flow stainless steel reactor.Product analysis adopts the gas contents such as the organic matter such as alkene, alkadienes in HP-6820 gas chromatograph (TCD, FID dual detector) on-line analysis dehydrogenation product and oxygen, carbon monoxide, carbon dioxide and calculates conversion ratio, the selective and yield of reaction.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Get 46.0g iron oxide (Fe
2o
3), 20.0g magnesia (MgO), 8.0g zinc oxide (ZnO), 1.6g manganese oxide (MnO
2) and 0.8g P
2o
5, then add 3.0g glucose, then in ball mill, carry out mixing 120 minutes, screening >200 order powder (standard screen), 700 DEG C of roastings 6 hours, obtains composite oxide catalysts A.
[embodiment 2]
Get 24.0g iron oxide (Fe
2o
3), 8.0g magnesia (MgO), 10.0g zinc oxide (ZnO), 1.0g manganese oxide (MnO
2) and 2.0g P
2o
5, then add 3.0g polyvinyl alcohol, then in ball mill, carry out mixing 30 minutes, screening >200 order powder (standard screen), 700 DEG C of roastings 8 hours, obtains composite oxide catalysts B.
[embodiment 3]
Get 36.2g iron oxide (Fe
2o
3), 8.0g magnesia (MgO), 11.0g zinc oxide (ZnO), 1.0g manganese oxide (MnO
2) and 2.0g P
2o
5, then add 5.0g glucose, then in ball mill, carry out mixing 60 minutes, screening >150 order amount of powder (standard screen), 750 DEG C of roastings 6 hours, obtains composite oxide catalysts C.
[embodiment 4]
Get 65.0g iron oxide (Fe
2o
3), 12.1g magnesia (MgO), 10.2g zinc oxide (ZnO), 2.0g cupric oxide (CuO) and 2.1g P
2o
5, then add 9.2g activated carbon powder, then in ball mill, carry out mixing 95 minutes, screening >200 order amount of powder (standard screen), 600 DEG C of roastings 16 hours, obtains composite oxide catalysts D.
[embodiment 5]
Get 56.0g iron oxide (Fe
2o
3), 12.2g magnesia (MgO), 10.1g zinc oxide (ZnO), 3.3g cobalt oxide (Co
2o
3) and 2.1g P
2o
5, then add 10.0g glucose, then in ball mill, carry out mixing 60 minutes, screening >400 order amount of powder (standard screen), 650 DEG C of roastings 12 hours, obtains composite oxide catalysts E.
[embodiment 6]
Get 46.4g iron oxide (Fe
2o
3), 15.1g magnesia (MgO), 10.0g zinc oxide (ZnO), 1.0g chromium oxide (Cr
2o
3) and 2.2g P
2o
5, then add 4.5g starch, then in ball mill, carry out mixing 240 minutes, screening >200 order amount of powder (standard screen), 680 DEG C of roastings 12 hours, obtains composite oxide catalysts F.
[embodiment 7]
Get 46.0g iron oxide (Fe
2o
3), 20.0g magnesia (MgO), 8.4g zinc oxide (ZnO), 2.0g manganese oxide (MnO
2) and 1.1g P
2o
5, 1.1g vanadic anhydride (V
2o
5), then add 8.3g cellulose, then in ball mill, carry out mixing 300 minutes, screening >500 order amount of powder (standard screen), 700 DEG C of roastings 10 hours, obtains composite oxide catalysts G.
[comparative example 1]
Prepare composite oxide catalysts by the method for [embodiment 1], adopt coprecipitation preparation.
[embodiment 8]
Catalyst A ~ G at 380 DEG C, butylene volume space velocity 400 hours
-1, O
2/ C
4h
8be 0.7, water alkene than be 12 condition under carry out performance evaluation, the results are shown in Table 1.
Table 1
| Catalyst | Conversion ratio % | Selective % | Gas phase alkynes ppm | Yield % |
| A | 77.2 | 93.5 | 1244 | 96.1 |
| B | 79.2 | 92.3 | 789 | 94.3 |
| C | 81.5 | 93.5 | 673 | 94.2 |
| D | 77.6 | 93.0 | 689 | 97.5 |
| E | 75.2 | 92.5 | 435 | 96.6 |
| F | 83.0 | 93.1 | 853 | 95.4 |
| G | 82.6 | 92.5 | 685 | 94.1 |
| Comparative example 1 | 77.1 | 92.8 | 1187 | 75.2 |
Adopt the catalyst that the present invention obtains, yield significantly improves, and gas phase alkynes product obviously reduces.
[embodiment 9]
Condition evaluating catalyst C(embodiment 3 by [embodiment 8]) and [comparative example 1], the stability of contrast two catalyst, the performance of catalyst after 4000 hours is in table 2.
Table 2
Claims (9)
1. a butadiene catalyst made by butylene oxidation dehydrogen preparation method, described catalyst chemical composition general formula is:
Fe
2O
3·MgO·ZnO·P
2O
5?·M
xO
y
Wherein, M is selected from least one in Sc, Ti, V, Cr, Mn, Co, Ni or Cu; X and y is stoichiometric proportion; By weight percentage, Fe
2o
3consumption be 52 ~ 76%; The consumption of MgO is 12 ~ 28%; The consumption of ZnO is 10 ~ 25%; P
2o
5consumption be 0.01 ~ 5.0%; M
xo
yconsumption be 0.01 ~ 3.0%;
Described preparation method comprises the following steps:
A) by the solid Fe of aequum
2o
3, MgO, ZnO, P
2o
5, M
xo
yand pore creating material, in ball mill, carry out ball milling 0.5 ~ 6 hour, screening is greater than the particle powder of 150 mesh standard sieves;
B) particle powder step a) obtained, 550 ~ 800 DEG C of roastings 2 ~ 36 hours, obtains described catalyst.
2. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, is characterized in that by weight percentage, Fe
2o
3consumption be 55 ~ 70 %.
3. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, it is characterized in that by weight percentage, the consumption of MgO is 14.0 ~ 25.0%.
4. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, it is characterized in that by weight percentage, the consumption of ZnO is 12.0 ~ 22.0%.
5. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, is characterized in that by weight percentage, P
2o
5consumption be 0.1 ~ 3.0%.
6. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, is characterized in that by weight percentage, M
xo
yconsumption be 1.0 ~ 2.8%; M is selected from least one in Mn, Cu, Co or Cr.
7. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, is characterized in that described particle powder diameter is 0.1 micron ~ 100 microns.
8. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, it is characterized in that described pore creating material is selected from least one in active carbon, polyvinyl alcohol, glucose, cellulose or plant amylum, the addition of pore creating material is 0 ~ 15% of metal oxide mixture weight.
9. butadiene catalyst made by butylene oxidation dehydrogen preparation method according to claim 1, it is characterized in that sintering temperature is 600 ~ 780 DEG C, roasting time is 6 ~ 20 hours.
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| CN104226351B CN104226351B (en) | 2016-09-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772015A (en) * | 2014-12-26 | 2016-07-20 | 上海华谊新材料有限公司 | Molybdenum-series composite oxide catalyst, and preparation method and use of molybdenum-series composite oxide catalyst |
| CN105772001A (en) * | 2014-12-25 | 2016-07-20 | 上海华谊新材料有限公司 | Preparation method and application of ferrite catalyst |
| CN109046361A (en) * | 2018-08-28 | 2018-12-21 | 山东泰和水处理科技股份有限公司 | A kind of fatty alcohol TERTIARY AMINATING CATALYST and the preparation method and application thereof |
| CN110302753A (en) * | 2019-06-24 | 2019-10-08 | 大连理工大学 | A kind of preparation method of magnesia-carbon complex microsphere |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862910A (en) * | 1971-01-22 | 1975-01-28 | Phillips Petroleum Co | Oxidative dehydrogenation catalyst and process of preparation thereof |
| CN1033013A (en) * | 1986-11-27 | 1989-05-24 | 锦州石油化工公司锦州炼油厂 | Butylene oxidation-dehydrogenation catalyst |
| CN103071544A (en) * | 2013-01-30 | 2013-05-01 | 中国石油化工股份有限公司 | In-situ regeneration method of butylene oxy-dehydrogenation catalyst |
-
2013
- 2013-06-17 CN CN201310237134.0A patent/CN104226351B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862910A (en) * | 1971-01-22 | 1975-01-28 | Phillips Petroleum Co | Oxidative dehydrogenation catalyst and process of preparation thereof |
| CN1033013A (en) * | 1986-11-27 | 1989-05-24 | 锦州石油化工公司锦州炼油厂 | Butylene oxidation-dehydrogenation catalyst |
| CN103071544A (en) * | 2013-01-30 | 2013-05-01 | 中国石油化工股份有限公司 | In-situ regeneration method of butylene oxy-dehydrogenation catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772001A (en) * | 2014-12-25 | 2016-07-20 | 上海华谊新材料有限公司 | Preparation method and application of ferrite catalyst |
| CN105772001B (en) * | 2014-12-25 | 2019-07-26 | 上海华谊新材料有限公司 | A kind of preparation method and purposes of ferrate catalyst |
| CN105772015A (en) * | 2014-12-26 | 2016-07-20 | 上海华谊新材料有限公司 | Molybdenum-series composite oxide catalyst, and preparation method and use of molybdenum-series composite oxide catalyst |
| CN105772015B (en) * | 2014-12-26 | 2018-09-28 | 上海华谊新材料有限公司 | Molybdenum system composite oxide catalysts and its preparation method and application |
| CN109046361A (en) * | 2018-08-28 | 2018-12-21 | 山东泰和水处理科技股份有限公司 | A kind of fatty alcohol TERTIARY AMINATING CATALYST and the preparation method and application thereof |
| CN110302753A (en) * | 2019-06-24 | 2019-10-08 | 大连理工大学 | A kind of preparation method of magnesia-carbon complex microsphere |
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|---|---|
| CN104226351B (en) | 2016-09-07 |
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