CN104226351B - Butadiene catalyst made by butylene oxidation dehydrogen preparation method - Google Patents
Butadiene catalyst made by butylene oxidation dehydrogen preparation method Download PDFInfo
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- CN104226351B CN104226351B CN201310237134.0A CN201310237134A CN104226351B CN 104226351 B CN104226351 B CN 104226351B CN 201310237134 A CN201310237134 A CN 201310237134A CN 104226351 B CN104226351 B CN 104226351B
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Abstract
The present invention relates to a kind of butadiene catalyst made by butylene oxidation dehydrogen preparation method, mainly solve that precipitation process prepared by existing catalyst exists component and be easy to run off, the problem of preparation poor reproducibility.The present invention is by using ball-milling method by the catalyst aid grinds of iron oxide, magnesia, zinc oxide and oxide form, obtain the mixture of metal composite oxide, the technical scheme obtaining preparing butadiene with butylene oxo-dehydrogenation Fe-series catalyst after high-temperature roasting preferably solves this problem, can be used in the industrial production of preparing butadiene with butylene oxo-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.Butadiene mainly has refinery's preparing ethylene by steam cracking coproduction carbon four extracting to separate and two kinds of production methods of oxygenizement of butene at present.China's butadiene almost all derives from carbon four extracting and separates, this process has superiority economically, but it is the accessory substance as refinery's cracker obtains, along with the rubber industry demand growth to butadiene yield, cracker produces butadiene and has been difficult to meet needs.Butylene oxidation-dehydrogenation is the process with butadiene as target product, and the butadiene that butenc is high added value that can be used by domestic fuel, this production technology route becomes more and more important.
Mo-Bi system, Sn-P-Li system, Fe silicate system are used equally to butylene oxidation-dehydrogenation reaction.But Mo-Bi system is the most relatively low, produces a large amount of organic oxygen-containing accessory substance.Sn-P-Li system activity is high, but operating condition is the harshest, water alkene than high, energy consumption is high.Fe-series catalyst has clear advantage, and as butadiene yield is high, oxidized byproduct is few, and water alkene ratio is low etc..The most most widely used is 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 continuously available raising.Cr3+Element can be effectively improved 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 the more superior B90 catalyst of insulation fix bed chromium-free iron series B02 Oxydehydrogenation catalyst and performance.White wave et al. discloses the iron system spinel composite oxides butylene oxidation-dehydrogenation catalyst of a kind of support type, has mechanical strength high, the advantage (CN92100436.2) of good stability.
Although iron system spinel Oxydehydrogenation catalyst commercial Application, but the preparation of existing catalyst is to use coprecipitation, there is component and is easy to run off, and prepares poor reproducibility, the uppity problem of catalyst quality.
Summary of the invention
The technical problem to be solved is to there is component in precipitation process prepared by existing catalyst to be easy to run off, the problem of preparation poor reproducibility, it is provided that a kind of new butadiene catalyst made by butylene oxidation dehydrogen preparation method.The catalyst prepared by the method is used for Oxidative Dehydrogenation of Butene into Butadiene process, has under high temperature and aqueous conditions, and active component not easily runs off, and butadiene yield is high, and alkynes production rate is low, the feature of good stability.
For solving above-mentioned technical problem, 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 formula is:
Fe2O3·MgO·ZnO·P2O5
·MxOy
Wherein, at least one in Sc, Ti, V, Cr, Mn, Co, Ni or Cu of M；X and y is stoichiometric proportion；By weight percentage, Fe2O3Consumption be 52～76%；The consumption of MgO is 12 ~ 28%；The consumption of ZnO is 10 ~ 25%；P2O5Consumption be 0.01 ~ 5.0%；MxOyConsumption be 0.01～3.0%；
Described preparation method comprises the following steps:
A) by the desired amount of solid Fe2O3、MgO、ZnO、P2O5
、MxOyAnd pore creating material, ball mill carrying out ball milling 0.5 ~ 6 hour, screening is more than the particle powder of 150 mesh standard sieves；
B) particle powder step a) obtained was 550～800 DEG C of roastings 2～36 hours, obtained described catalyst.
In technique scheme, it is preferable that by weight percentage, Fe2O3Consumption 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, P2O5Consumption be 0.1～3.0%.
Preferably, by weight percentage, MxOyConsumption be 1.0～2.8%.
Preferably, at least one in Mn, Cu, Co or Cr of M,
Preferably, a diameter of 0.1 micron ~ 100 microns of described particle powder.
Preferably, at least one in activated carbon, polyvinyl alcohol, glucose, cellulose or plant amylum of described pore creating material, the addition of pore creating material is the 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 centimetre3/ gram, specific surface area 5 ~ 60 meters2/ gram.
Catalyst prepared by the present invention reacts for butylene oxidation-dehydrogenation, and reaction condition is: with butylene as raw material, with water as diluent, with 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, H2O/ butylene volume ratio is 6 ~ 20, O2/ butylene volume ratio is 0.4 ~ 1.0.
Present invention employs mixing method and prepare composite oxide catalysts, iron oxide easily with the bivalent metal ion formation MFe such as Mg, Zn2O4The spinel structure of type, at least one auxiliary element in 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, the especially electronics of its 4S electronic shell is susceptible to skew, strengthen the cloud density of active sites, so that the butadiene of electron rich is easier to desorption, reducing by deep dehydrogenation is the probability of alkynes；And the addition of P element can be effectively improved the catalyst surface activation capacity to oxygen molecule, reduce the Fe caused because activating oxygen molecule reduces3+Ion is reduced into Fe2+, it is effectively increased the stability of catalyst.Use mixing method to prepare catalyst, it is to avoid the precipitation process that influence factor is complicated, and be not related to washing, effectively reduce the loss of component in washing process.And use stay-in-grade oxide as active component presoma, simple to operate, influence factor is few, and improve catalyst well prepares Repeatability.Use the catalyst that obtains of this method at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8Being 0.7, water alkene ratio is use under conditions of 12, and conversion ratio is higher than 80%, selectively higher than 94%, and the inactive decline of stability experiment more than 4000 hours, achieve preferable technique effect.
Butylene oxidation-dehydrogenation reaction is carried out on the flowing miniature catalyst reaction device of stainless steel reactor continuously.Product analysis uses the gas contents such as organic matter and oxygen, carbon monoxide, carbon dioxide such as the alkene in HP-6820 gas chromatograph (TCD, FID dual detector) on-line analysis dehydrogenation product, alkadienes and calculates the conversion ratio of reaction, selectivity and yield.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Take 46.0g iron oxide (Fe2O3), 20.0g magnesia (MgO), 8.0g zinc oxide (ZnO), 1.6g manganese oxide (MnO2)
And 0.8g P2O5, add 3.0g glucose, then carry out mixing in ball mill 120 minutes, screening > 200 mesh powder (standard screen), 700 DEG C of roastings 6 hours, obtain composite oxide catalysts A.
[embodiment 2]
Take 24.0g iron oxide (Fe2O3), 8.0g magnesia (MgO), 10.0g zinc oxide (ZnO), 1.0g manganese oxide (MnO2)
And 2.0g P2O5, add 3.0g polyvinyl alcohol, then carry out mixing in ball mill 30 minutes, screening > 200 mesh powder (standard screen), 700 DEG C of roastings 8 hours, obtain composite oxide catalysts B.
[embodiment 3]
Take 36.2g iron oxide (Fe2O3), 8.0g magnesia (MgO), 11.0g zinc oxide (ZnO), 1.0g manganese oxide (MnO2)
And 2.0g P2O5, add 5.0g glucose, then carry out mixing in ball mill 60 minutes, screening > 150 mesh amount of powder (standard screen), 750 DEG C of roastings 6 hours, obtain composite oxide catalysts C.
[embodiment 4]
Take 65.0g iron oxide (Fe2O3), 12.1g magnesia (MgO), 10.2g zinc oxide (ZnO), 2.0g cupric oxide (CuO) and 2.1g P2O5, add 9.2g activated carbon powder, then carry out mixing in ball mill 95 minutes, screening > 200 mesh amount of powder (standard screen), 600 DEG C of roastings 16 hours, obtain composite oxide catalysts D.
[embodiment 5]
Take 56.0g iron oxide (Fe2O3), 12.2g magnesia (MgO), 10.1g zinc oxide (ZnO), 3.3g cobalt oxide (Co2O3) and 2.1g P2O5, add 10.0g glucose, then carry out mixing in ball mill 60 minutes, screening > 400 mesh amount of powder (standard screen), 650 DEG C of roastings 12 hours, obtain composite oxide catalysts E.
[embodiment 6]
Take 46.4g iron oxide (Fe2O3), 15.1g magnesia (MgO), 10.0g zinc oxide (ZnO), 1.0g chromium oxide (Cr2O3)
And 2.2g P2O5, add 4.5g starch, then carry out mixing in ball mill 240 minutes, screening > 200 mesh amount of powder (standard screen), 680 DEG C of roastings 12 hours, obtain composite oxide catalysts F.
[embodiment 7]
Take 46.0g iron oxide (Fe2O3), 20.0g magnesia (MgO), 8.4g zinc oxide (ZnO), 2.0g manganese oxide (MnO2)
And 1.1g P2O5, 1.1g vanadic anhydride (V2O5), add 8.3g cellulose, then carry out mixing in ball mill 300 minutes, screening > 500 mesh amount of powder (standard screen), 700 DEG C of roastings 10 hours, obtain composite oxide catalysts G.
[comparative example 1]
Prepare composite oxide catalysts by the method for [embodiment 1], use coprecipitation to prepare.
[embodiment 8]
Catalyst A ~ G at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8Being 0.7, water alkene ratio is to carry out performance evaluation under conditions of 12, 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 |
Using the catalyst obtained by the present invention, yield significantly improves, and gas phase alkynes product substantially reduces.
[embodiment 9]
By the condition evaluating catalyst C(embodiment 3 of [embodiment 8]) and [comparative example 1], the stability of two catalyst of contrast, catalyst performance after 4000 hours is shown in Table 2.
Table 2
Claims (9)
1. a butadiene catalyst made by butylene oxidation dehydrogen preparation method, described catalyst chemical composition formula is:
Fe2O3·MgO·ZnO·P2O5 ·MxOy
Wherein, at least one in Sc, Ti, V, Cr, Mn, Co, Ni or Cu of M；X and y is stoichiometric proportion；By weight percentage, Fe2O3Consumption be 52～76%；The consumption of MgO is 12 ~ 28%；The consumption of ZnO is 10 ~ 25%；P2O5Consumption be 0.01 ~ 5.0%；MxOyConsumption be 0.01～3.0%；
Described preparation method comprises the following steps:
A) by the desired amount of solid Fe2O3、MgO、ZnO、P2O5 、MxOyAnd pore creating material, ball mill carrying out ball milling 0.5 ~ 6 hour, screening is more than the particle powder of 150 mesh standard sieves；
B) particle powder step a) obtained was 550～800 DEG C of roastings 2～36 hours, obtained described catalyst.
Butadiene catalyst made by butylene oxidation dehydrogen preparation method the most according to claim 1, it is characterised in that by weight percentage, Fe2O3Consumption be 55 ~ 70 %.
The most according to claim 1, butadiene catalyst made by butylene oxidation dehydrogen preparation method, it is characterised in that by weight percentage, the consumption of MgO is 14.0 ~ 25.0%.
The most according to claim 1, butadiene catalyst made by butylene oxidation dehydrogen preparation method, it is characterised in that by weight percentage, the consumption of ZnO is 12.0 ~ 22.0%.
Butadiene catalyst made by butylene oxidation dehydrogen preparation method the most according to claim 1, it is characterised in that by weight percentage, P2O5Consumption be 0.1～3.0%.
Butadiene catalyst made by butylene oxidation dehydrogen preparation method the most according to claim 1, it is characterised in that by weight percentage, MxOyConsumption be 1.0～2.8%；At least one in Mn, Cu, Co or Cr of M.
Butadiene catalyst made by butylene oxidation dehydrogen preparation method the most according to claim 1, it is characterised in that a diameter of 0.1 micron ~ 100 microns of described particle powder.
Butadiene catalyst made by butylene oxidation dehydrogen preparation method the most according to claim 1, it is characterized in that at least one in activated carbon, polyvinyl alcohol, glucose, cellulose or plant amylum of described pore creating material, the addition of pore creating material is the 0 ~ 15% of metal oxide mixture weight.
The most according to claim 1, butadiene catalyst made by butylene oxidation dehydrogen preparation method, it is characterised in that sintering temperature is 600～780 DEG C, roasting time is 6 ~ 20 hours.
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| 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 |
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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 |
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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 |
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