CN104226350B - Iron system spinel composite oxide catalysts and application thereof - Google Patents
Iron system spinel composite oxide catalysts and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of iron system spinel composite oxide catalysts and application thereof, mainly solve that existing De-hydrogen Technology exists butadiene yield low, the problem that alkynes accessory substance production rate is high.The present invention by using chemical composition formula is: Fe2O3·MgO·ZnO·P2O5·MxOyCatalyst, 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% technical scheme preferably solve 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 iron system spinel composite oxide catalysts and application thereof.
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., current most widely used 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 it is the highest to still suffer from conversion ratio, selectivity, the problem that in accessory substance, alkynes production rate is high.Petro-Tex company of the U.S. uses adiabatic reactor reactor, and butadiene yield is only 60%, selective 93%, and alkynes production rate is up to 0.26%, and the separation to product is had higher requirement, and has influence on the safety and stability of whole system.
Summary of the invention
One of the technical problem to be solved is that to there is butadiene yield in existing De-hydrogen Technology low, the problem that alkynes accessory substance production rate is high, it is provided that a kind of new iron system spinel composite oxide catalysts.The two of the technical problem to be solved are to provide the purposes of a kind of catalyst corresponding with solving one of technical problem.This catalyst is used for Oxidative Dehydrogenation of Butene into Butadiene process, has under high temperature and aqueous conditions, and butadiene yield is high, and alkynes production rate is low, the advantage of good stability.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of iron system spinel composite oxide catalysts, and its 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%.
In technique scheme, it is preferable that at least one in V, Cr, Mn, Co or Ni of M.
Preferably, 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, described catalyst pore volume is 0.1 ~ 1.2 centimetre3/ gram, specific surface area is 5 ~ 60 meters2/ gram.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: described iron system spinel composite oxide catalysts is prepared in the reaction of conjugated diene for carbon four and above monoolefine oxidative dehydrogenation thereof.
One is preferably carried out scheme and is, with carbon four or carbon more than four monoolefine as raw material, with water as diluent, with molecular oxygen as oxidant, at reaction temperature 320 ~ 600 DEG C, reaction pressure 0 ~ 0.4MPa, monoolefine volume space velocity 200 ~ 500 hours-1, H2O/ monoolefine volume ratio is 6 ~ 20, O2Under the conditions of/monoolefine volume ratio is 0.4 ~ 1.0, raw material contacts with catalyst, and reaction generates butadiene or carbon more than four conjugated diene.
In technique scheme, it is preferable that reaction temperature is 360 ~ 540 DEG C.
Preferably, reaction pressure is 0.05~0.2MPa.
Preferably, monoolefine volume space velocity is 260 ~ 450 hours-1。
Preferably, H2O/ monoolefine volume ratio is 8 ~ 18.
Preferably, O2/ monoolefine volume ratio is 0.6 ~ 0.8.
Preferably, at least one during reaction raw materials is butene-1, cis-butene-2 or trans-butene-2.
Preferably, oxidant is air or oxygen.
In the present invention, described pressure all refers to gauge pressure.
The preparation method of iron system spinel composite oxide catalysts of the present invention is: use coprecipitation to introduce in the Fe-series catalyst with spinel structure by the composite assistants of phosphorus with period 3 transition metal, carry out same order elements, obtain metal composite oxide, more scrubbed, dry, roasting i.e. obtains described catalyst.Concrete preparation method comprises the following steps:
1) preparation is containing Fe, Mg, Zn and the aqueous solution I of the soluble-salt of auxiliary element；
2) preparation mass percent concentration scope 1～the aqueous solution II of water soluble alkali of 30%, at least one in NaOH, potassium hydroxide, ammoniacal liquor or ammonium carbonate of water soluble alkali；
3) solution I is added in solution II, control ph 8～11, aged at room temperature 0 ~ 24 hour, filters, washs the sediment obtained, be subsequently adding the desired amount of phosphide, obtain presoma；
4) by presoma in 50～150 DEG C of drying, then 550～800 DEG C of roastings 1～24 hours, described iron system spinel composite oxide catalysts is obtained.
Wherein, precipitation process can to use along adding, the anti-dropping mode added or add altogether.Before precipitation or in coprecipitation process, adding the pore creating material of 0 ~ 15% in solution I, pore creating material is selected from polyol agent such as activated carbon, cellulose, high molecular polymer, glucose or plant amylums.Catalyst may be molded to the difform catalyst such as ball, cylinder, disk, annulus and trifolium-shaped.
In the iron system spinel composite oxide catalysts of the present invention, iron oxide easily with the bivalent metal ion formation MFe such as Mg, Zn2O4The spinel structure of type, and 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.
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-7820 gas chromatograph (TCD, FID dual detector) on-line analysis dehydrogenation product, alkadienes and calculates the conversion ratio of reaction, selectivity and yield.The catalyst of the present invention is at 380 DEG C, butylene volume space velocity 400 hours-1、O2/C4H8Be 0.7, water alkene ratio be to use under conditions of 12, conversion ratio is higher than 80%, selectively higher than 94%, the inactive decline of stability experiment more than 3000 hours, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Take 232.3g ferric nitrate (Fe (NO3)3
9H2O), 128.2g magnesium nitrate (Mg (NO3)2 6H2O), 29.4g zinc nitrate (Zn (NO3)2
6H2And 3.3g manganese nitrate (Mn (NO O)3)2) be dissolved in 400ml deionized water, adding 3.0g glucose and dissolve, then at 60 DEG C, be stirred vigorously down, the ammoniacal liquor of 20% is slowly dropped in this mixed aqueous solution, control ph is 9.5, forms precipitation, after being deposited in aged at room temperature 6 hours, filters.Then the solid that will filter out is washed with deionized 5 times, adds 1.1g H the last time in washing process3PO4, in 120 DEG C of drying, pulverize, after sieving, 700 DEG C of roastings 6 hours, obtain composite oxide catalysts A.
[embodiment 2]
Take 121.2g ferric nitrate (Fe (NO3)3
9H2O), 51.3g magnesium nitrate (Mg (NO3)2 6H2O), 36.7g zinc nitrate (Zn (NO3)2
6H2And 2.1g manganese nitrate (Mn (NO O)3)2) be dissolved in 400ml deionized water, adding 3.0g polyvinyl alcohol and dissolve, then in room temperature, be stirred vigorously down, this mixed aqueous solution is slowly dropped in the ammoniacal liquor of 12%, control ph is 8.0, forms precipitation, after being deposited in aged at room temperature 6 hours, filters.Then the solid that will filter out is washed with deionized 5 times, adds 2.8g the last time in washing process
H3PO4, in 110 DEG C of drying, pulverize, after sieving, 700 DEG C of roastings 6 hours, obtain composite oxide catalysts B.
[embodiment 3]
Take 182.6g ferric nitrate (Fe (NO3)3
9H2O), 51.3g magnesium nitrate (Mg (NO3)2 6H2O), 40.5g zinc nitrate (Zn (NO3)2
6H2And 1.7g manganese nitrate (Mn (NO O)3)2) be dissolved in 400ml deionized water, add 5.0g polyvinylpyrrolidone and dissolve, then at 60 DEG C, being stirred vigorously down, be simultaneously added dropwise by the ammoniacal liquor of this mixed aqueous solution and 18%, control ph is 9.0, form precipitation, after aged at room temperature being deposited in 6 hours, filter.Then the solid that will filter out is washed with deionized 5 times, adds 1.6g H the last time in washing process3PO4, in 120 DEG C of drying, pulverize, after sieving, 700 DEG C of roastings 6 hours, obtain composite oxide catalysts C.
[embodiment 4]
Take 328.3g ferric nitrate (Fe (NO3)3
9H2O), 76.9g magnesium nitrate (Mg (NO3)2 6H2O), 36.7g zinc nitrate (Zn (NO3)2
6H2And 3.7g copper nitrate (Cu (NO O)3)2 3 H2O) it is dissolved in 400ml deionized water, then adds mixed solution after the dissolving of 9.0g starch boiling.At room temperature, being stirred vigorously down, be slowly dropped in the ammoniacal liquor of 18% by this mixed aqueous solution, control ph is 9.0, forms precipitation, after being deposited in aged at room temperature 6 hours, filters.Then the solid that will filter out is washed with deionized 5 times, adds 2.8g H the last time in washing process3PO4, in 120 DEG C of drying, pulverize, after sieving, 600 DEG C of roastings 16 hours, obtain composite oxide catalysts D.
[embodiment 5]
Take 282.8g ferric nitrate (Fe (NO3)3
9H2O), 76.9g magnesium nitrate (Mg (NO3)2 6H2O), 36.7g zinc nitrate (Zn (NO3)2
6H2And 8.1g cobalt nitrate (Co (NO O)3)2 6H2O) it is dissolved in 400ml deionized water, adds 10.0g glucose and dissolve, then at 60 DEG C, being stirred vigorously down, be simultaneously added dropwise by the ammoniacal liquor of this mixed aqueous solution and 18%, control ph is 10.5, form precipitation, after aged at room temperature being deposited in 16 hours, filter.Then the solid that will filter out is washed with deionized 5 times, adds 2.8g H the last time in washing process3PO4, in 80 DEG C of drying, pulverize, after sieving, 650 DEG C of roastings 12 hours, obtain composite oxide catalysts E.
[embodiment 6]
Take 232.3g ferric nitrate (Fe (NO3)3
9H2O), 96.2g magnesium nitrate (Mg (NO3)2 6H2O), 36.1g zinc nitrate (Zn (NO3)2
6H2And 5.3g chromic nitrate ((Cr (NO O)3)3 9H2O) being dissolved in 400ml deionized water, add 4.0g glucose and dissolve, then at 60 DEG C, be stirred vigorously down, be simultaneously added dropwise by the ammoniacal liquor of this mixed aqueous solution and 18%, control ph is 9.0, forms precipitation, after being deposited in aged at room temperature 18 hours, filters.Then the solid that will filter out is washed with deionized 5 times, adds 2.8g H the last time in washing process3PO4, in 100 DEG C of drying, pulverize, after sieving, 650 DEG C of roastings 12 hours, obtain composite oxide catalysts F.
[embodiment 7]
Take 232.3g ferric nitrate (Fe (NO3)3
9H2O), 128.2g magnesium nitrate (Mg (NO3)2 6H2O), 29.4g zinc nitrate (Zn (NO3)2
6H2O), 0.6g ammonium metavanadate (NH4VO3) and 3.3g manganese nitrate (Mn (NO3)2) be dissolved in 400ml deionized water, adding 8.0g glucose and dissolve, then at 60 DEG C, be stirred vigorously down, the ammoniacal liquor of this mixed aqueous solution and 18% is simultaneously added dropwise, control ph is 9.0, forms precipitation, after being deposited in aged at room temperature 12 hours, filters.Then the solid that will filter out is washed with deionized 5 times, adds 1.1g H the last time in washing process3PO4, in 120 DEG C of drying, pulverize, after sieving, 700 DEG C of roastings 10 hours, obtain composite oxide catalysts G.
[comparative example 1]
Composite oxide catalysts is prepared by the method for [embodiment 1], different without P elements and manganese nitrate (Mn (NO3)2) etc. period 3 metallic element auxiliary agent.
[embodiment 8]
By the catalyst of [embodiment 1～7] at 380 DEG C, butylene volume space velocity 400 hours-1、O2/C4H8It is 0.7, under conditions of water alkene ratio is 12, carries out performance evaluation, the results are shown in Table 1.
[comparative example 2]
The performance of catalyst according to the method evaluation [comparative example 1] of [embodiment 8].The results are shown in Table 1.
Table 1
From table 1, using the catalyst of the present invention, performance is significantly improved, and gas phase alkynes product substantially reduces.
[embodiment 9]
By the condition evaluating catalyst C([embodiment 3 of [embodiment 8]]) the operation performance of 3000 hours.The results are shown in Table 2.
[comparative example 3]
Catalyst by the condition evaluating [comparative example 1] of [embodiment 8] runs the performance of 3000 hours.The results are shown in Table 2.
Table 2
Claims (9)
1. an iron system spinel composite oxide catalysts, its chemical composition formula is:
Fe2O3·MgO·ZnO·P2O5·MxOy
Wherein, during M is selected from Sc, Ti, V, Cr, Mn, Co, Ni or Cu at least
A kind of；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%；P2O5Use
Amount is 0.01～5.0%；MxOyConsumption be 0.01～3.0%；
Described catalyst pore volume is 0.1～1.2 centimetre3/ gram, specific surface area is 5～60 meters2/ gram.
Iron system spinel composite oxide catalysts the most according to claim 1, its
It is characterised by least one that M is selected from V, Cr, Mn, Co or Ni.
Iron system spinel composite oxide catalysts the most according to claim 1, its
It is characterised by by weight percentage, Fe2O3Consumption be 55～70%.
Iron system spinel composite oxide catalysts the most according to claim 1, its
Being characterised by by weight percentage, the consumption of MgO is 14.0～25.0%.
Iron system spinel composite oxide catalysts the most according to claim 1, its
Being characterised by by weight percentage, the consumption of ZnO is 12.0～22.0%.
Iron system spinel composite oxide catalysts the most according to claim 1, its
It is characterised by by weight percentage, P2O5Consumption be 0.1～3.0%.
Iron system spinel composite oxide catalysts the most according to claim 1, its
It is characterised by by weight percentage, MxOyConsumption be 1.0～2.8%.
8. iron system spinel composite oxide catalysts described in claim 1 for carbon four and
Its above monoolefine oxidative dehydrogenation is prepared in the reaction of conjugated diene.
The purposes of iron system spinel composite oxide catalysts the most according to claim 8,
It is characterized in that with carbon four or carbon more than four monoolefine as raw material, with water as diluent, with point
Sub-oxygen is oxidant, reaction temperature 320～600 DEG C, and reaction pressure 0～0.4MPa, single
Alkene volume space velocity 200～500 hours-1, H2O/ monoolefine volume ratio is 6～20, O2/ mono-
Under the conditions of alkene volume ratio is 0.4～1.0, raw material contacts with catalyst, and reaction generates fourth two
Alkene or carbon more than four conjugated diene.
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| CN106881099B (en) * | 2015-12-16 | 2020-02-18 | 上海华谊新材料有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene, preparation method and application thereof |
| CN111054407A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene |
| CN111054406A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and method thereof |
| CN111054405A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103962062A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Filling method for isothermal reactor catalyst |
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| 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 |
| CN103962062A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Filling method for isothermal reactor catalyst |
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