CN104226350A - Iron spinel composite oxide catalyst and purpose thereof - Google Patents
Iron spinel composite oxide catalyst and purpose thereof Download PDFInfo
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- CN104226350A CN104226350A CN201310237119.6A CN201310237119A CN104226350A CN 104226350 A CN104226350 A CN 104226350A CN 201310237119 A CN201310237119 A CN 201310237119A CN 104226350 A CN104226350 A CN 104226350A
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Abstract
The invention relates to an iron spinel composite oxide catalyst and purpose thereof, and mainly solves the problem of low butadiene yield and high generation rate of byproduct alkynes in the prior art of dehydrogenation. The invention adopts a catalyst with a chemical composition formula of Fe2O3.MgO.ZnO.P2O5.MxOy, wherein M is at least one selected from the group consisting of Sc, M, Ti, V, Cr, Mn, Co, Ni and Cu, x and y are stoichiometry. The catalyst comprises 52-76% of Fe2O3, 12-28% of MgO, 10-25% of ZnO, 0.01-5.0% of P2O5 and 0.01-3.0% of MxOy. The technical scheme can well solve the problem, and can be used in industrial production of butadiene from butene oxidative dehydrogenation.
Description
Technical field
The present invention relates to a kind of iron system spinel composite oxide catalysts and uses 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.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, produces 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, water alkene than 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 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, but still there is conversion ratio, selective not high, the problem that in accessory substance, alkynes production rate is high.Petro-Tex company of the U.S. adopts adiabatic reactor reactor, and butadiene yield is only 60%, and selective 93%, and alkynes production rate is up to 0.26%, has higher requirement to the separation of product, and have influence on the safety and stability of whole system.
Summary of the invention
One of technical problem to be solved by this invention is that to there is butadiene yield in existing De-hydrogen Technology low, and the problem that alkynes accessory substance production rate is high, provides a kind of new iron system spinel composite oxide catalysts.Two of technical problem to be solved by this invention is to provide a kind of purposes of the catalyst corresponding with one of technical solution problem.This catalyst is used for Oxidative Dehydrogenation of Butene into Butadiene process, and have under high temperature and aqueous conditions, butadiene yield is high, and alkynes production rate is low, the advantage of good stability.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of iron system spinel composite oxide catalysts, and its 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%.
In technique scheme, preferably, M is selected from least one in V, Cr, Mn, Co or Ni.
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, described catalyst pore volume is 0.1 ~ 1.2 centimetre
3/ gram, specific area is 5 ~ 60 meters
2/ gram.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: described iron system spinel composite oxide catalysts is used for carbon four and above monoolefine oxidative dehydrogenation thereof and prepares in the reaction of conjugated diene.
One preferably embodiment be that, with carbon four or carbon more than four monoolefine for raw material, being diluent with water, take molecular oxygen as oxidant, reaction temperature 320 ~ 600 DEG C, reaction pressure 0 ~ 0.4MPa, monoolefine volume space velocity 200 ~ 500 hours
-1, H
2o/ monoolefine volume ratio is 6 ~ 20, O
2/ monoolefine volume ratio is under 0.4 ~ 1.0 condition, raw material and catalyst exposure, and reaction generates butadiene or carbon more than four conjugated diene.
In technique scheme, preferably, 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, H
2o/ monoolefine volume ratio is 8 ~ 18.
Preferably, O
2/ monoolefine volume ratio is 0.6 ~ 0.8.
Preferably, reaction raw materials is at least one in 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: adopt coprecipitation to be introduced by the composite assistants of phosphorus and period 3 transition metal and have in the Fe-series catalyst of spinel structure, carry out same order elements, obtain composite metal oxide, more namely obtain described catalyst through washing, drying, roasting.Concrete preparation method comprises the following steps:
1) preparation contains the aqueous solution I of the soluble-salt of Fe, Mg, Zn and auxiliary element;
2) prepare the aqueous solution II of the water soluble alkali of mass percent concentration scope 1 ~ 30%, water soluble alkali is selected from least one in NaOH, potassium hydroxide, ammoniacal liquor or ammonium carbonate;
3) solution I added in solution II, control ph 8 ~ 11, aged at room temperature 0 ~ 24 hour, filter, wash the sediment obtained, then add the phosphide of aequum, obtain presoma;
4) by presoma in 50 ~ 150 DEG C of oven dry, then 550 ~ 800 DEG C of roastings 1 ~ 24 hour, obtain described iron system spinel composite oxide catalysts.
Wherein, precipitation process can adopt along adding, the anti-dropping mode added or add altogether.Precipitation before or in coprecipitation process, in solution I, add the pore creating material of 0 ~ 15%, pore creating material is selected from the polyol agent such as active carbon, cellulose, high molecular polymer, glucose or plant amylum.Catalyst may be molded to the difform catalyst such as ball, cylinder, disk, annulus and trifolium-shaped.
In iron system spinel composite oxide catalysts of the present invention, iron oxide easily and the bivalent metal ion such as Mg, Zn form MFe
2o
4the spinel structure of type, and 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.
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-7820 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.Catalyst of the present invention is 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 3000 hours stability experiment non-activities.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Get 232.3g ferric nitrate (Fe (NO
3)
39H
2o), 128.2g magnesium nitrate (Mg (NO
3)
26H
2o), 29.4g zinc nitrate (Zn (NO
3)
26H
2and 3.3g manganese nitrate (Mn (NO O)
3)
2) be dissolved in 400ml deionized water, then add the dissolving of 3.0g glucose, then at 60 DEG C, under vigorous stirring, be slowly added drop-wise to by the ammoniacal liquor of 20% in this mixed aqueous solution, control ph is 9.5, forms precipitation, will be deposited in aged at room temperature after 6 hours, filters.Then the solid filtered out is spent deionized water 5 times, add 1.1g H in washing process the last time
3pO
4, in 120 DEG C of oven dry, pulverize, after sieving, 700 DEG C of roastings 6 hours, obtain composite oxide catalysts A.
[embodiment 2]
Get 121.2g ferric nitrate (Fe (NO
3)
39H
2o), 51.3g magnesium nitrate (Mg (NO
3)
26H
2o), 36.7g zinc nitrate (Zn (NO
3)
26H
2and 2.1g manganese nitrate (Mn (NO O)
3)
2) be dissolved in 400ml deionized water, then add 3.0g polyvinyl alcohol dissolution, then in room temperature, under vigorous stirring, be slowly added drop-wise in the ammoniacal liquor of 12% by this mixed aqueous solution, control ph is 8.0, forms precipitation, will be deposited in aged at room temperature after 6 hours, filters.Then the solid filtered out is spent deionized water 5 times, add 2.8g H in washing process the last time
3pO
4, in 110 DEG C of oven dry, pulverize, after sieving, 700 DEG C of roastings 6 hours, obtain composite oxide catalysts B.
[embodiment 3]
Get 182.6g ferric nitrate (Fe (NO
3)
39H
2o), 51.3g magnesium nitrate (Mg (NO
3)
26H
2o), 40.5g zinc nitrate (Zn (NO
3)
26H
2and 1.7g manganese nitrate (Mn (NO O)
3)
2) be dissolved in 400ml deionized water, then add the dissolving of 5.0g polyvinylpyrrolidone, then at 60 DEG C, under vigorous stirring, dripped by the ammoniacal liquor of this mixed aqueous solution and 18%, control ph is 9.0 simultaneously, form precipitation, aged at room temperature will be deposited in after 6 hours, filter.Then the solid filtered out is spent deionized water 5 times, add 1.6g H in washing process the last time
3pO
4, in 120 DEG C of oven dry, pulverize, after sieving, 700 DEG C of roastings 6 hours, obtain composite oxide catalysts C.
[embodiment 4]
Get 328.3g ferric nitrate (Fe (NO
3)
39H
2o), 76.9g magnesium nitrate (Mg (NO
3)
26H
2o), 36.7g zinc nitrate (Zn (NO
3)
26H
2and 3.7g copper nitrate (Cu (NO O)
3)
23 H
2o) be dissolved in 400ml deionized water, then add mixed solution after being dissolved by 9.0g starch boiling.At room temperature, under vigorous stirring, be slowly added drop-wise in the ammoniacal liquor of 18% by this mixed aqueous solution, control ph is 9.0, forms precipitation, will be deposited in aged at room temperature after 6 hours, filters.Then the solid filtered out is spent deionized water 5 times, add 2.8g H in washing process the last time
3pO
4, in 120 DEG C of oven dry, pulverize, after sieving, 600 DEG C of roastings 16 hours, obtain composite oxide catalysts D.
[embodiment 5]
Get 282.8g ferric nitrate (Fe (NO
3)
39H
2o), 76.9g magnesium nitrate (Mg (NO
3)
26H
2o), 36.7g zinc nitrate (Zn (NO
3)
26H
2and 8.1g cobalt nitrate (Co (NO O)
3)
26H
2o) be dissolved in 400ml deionized water, then add the dissolving of 10.0g glucose, then at 60 DEG C, under vigorous stirring, dripped by the ammoniacal liquor of this mixed aqueous solution and 18%, control ph is 10.5 simultaneously, form precipitation, aged at room temperature will be deposited in after 16 hours, filter.Then the solid filtered out is spent deionized water 5 times, add 2.8g H in washing process the last time
3pO
4, in 80 DEG C of oven dry, pulverize, after sieving, 650 DEG C of roastings 12 hours, obtain composite oxide catalysts E.
[embodiment 6]
Get 232.3g ferric nitrate (Fe (NO
3)
39H
2o), 96.2g magnesium nitrate (Mg (NO
3)
26H
2o), 36.1g zinc nitrate (Zn (NO
3)
26H
2and 5.3g chromic nitrate ((Cr (NO O)
3)
39H
2o) be dissolved in 400ml deionized water, then add the dissolving of 4.0g glucose, then at 60 DEG C, under vigorous stirring, dripped by the ammoniacal liquor of this mixed aqueous solution and 18%, control ph is 9.0 simultaneously, form precipitation, aged at room temperature will be deposited in after 18 hours, filter.Then the solid filtered out is spent deionized water 5 times, add 2.8g H in washing process the last time
3pO
4, in 100 DEG C of oven dry, pulverize, after sieving, 650 DEG C of roastings 12 hours, obtain composite oxide catalysts F.
[embodiment 7]
Get 232.3g ferric nitrate (Fe (NO
3)
39H
2o), 128.2g magnesium nitrate (Mg (NO
3)
26H
2o), 29.4g zinc nitrate (Zn (NO
3)
26H
2o), 0.6g ammonium metavanadate (NH
4vO
3) and 3.3g manganese nitrate (Mn (NO
3)
2) be dissolved in 400ml deionized water, then add the dissolving of 8.0g glucose, then at 60 DEG C, under vigorous stirring, dripped by the ammoniacal liquor of this mixed aqueous solution and 18%, control ph is 9.0 simultaneously, forms precipitation, will be deposited in aged at room temperature after 12 hours, filters.Then the solid filtered out is spent deionized water 5 times, add 1.1g H in washing process the last time
3pO
4, in 120 DEG C of oven dry, pulverize, after sieving, 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], difference does not add P elements and manganese nitrate (Mn (NO
3)
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, 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.
[comparative example 2]
According to the performance of the catalyst of the method evaluation [comparative example 1] of [embodiment 8].The results are shown in Table 1.
Table 1
From table 1, adopt catalyst of the present invention, performance is significantly improved, and gas phase alkynes product obviously reduces.
[embodiment 9]
Condition evaluating catalyst C([embodiment 3 by [embodiment 8]]) the operation performance of 3000 hours.The results are shown in Table 2.
[comparative example 3]
The performance of 3000 hours is run by the catalyst of the condition evaluating [comparative example 1] of [embodiment 8].The results are shown in Table 2.
Table 2
Claims (10)
1. an iron system spinel composite oxide catalysts, its 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%.
2. iron system spinel composite oxide catalysts according to claim 1, is characterized in that M is selected from least one in V, Cr, Mn, Co or Ni.
3. iron system spinel composite oxide catalysts according to claim 1, is characterized in that by weight percentage, Fe
2o
3consumption be 55 ~ 70 %.
4. iron system spinel composite oxide catalysts according to claim 1, is characterized in that by weight percentage, and the consumption of MgO is 14.0 ~ 25.0 %.
5. iron system spinel composite oxide catalysts according to claim 1, is characterized in that by weight percentage, and the consumption of ZnO is 12.0 ~ 22.0%.
6. iron system spinel composite oxide catalysts according to claim 1, is characterized in that by weight percentage, P
2o
5consumption be 0.1 ~ 3.0%.
7. iron system spinel composite oxide catalysts according to claim 1, is characterized in that by weight percentage, M
xo
yconsumption be 1.0 ~ 2.8%.
8. iron system spinel composite oxide catalysts according to claim 1, is characterized in that described catalyst pore volume is 0.1 ~ 1.2 centimetre
3/ gram, specific area is 5 ~ 60 meters
2/ gram.
9. iron system spinel composite oxide catalysts described in claim 1 is prepared in the reaction of conjugated diene for carbon four and above monoolefine oxidative dehydrogenation thereof.
10. the purposes of iron system spinel composite oxide catalysts according to claim 9, it is characterized in that with carbon four or carbon more than four monoolefine for raw material, take water as diluent, take molecular oxygen as oxidant, reaction temperature 320 ~ 600 DEG C, reaction pressure 0 ~ 0.4MPa, monoolefine volume space velocity 200 ~ 500 hours
-1, H
2o/ monoolefine volume ratio is 6 ~ 20, O
2/ monoolefine volume ratio is under 0.4 ~ 1.0 condition, raw material and catalyst exposure, and reaction generates butadiene or carbon more than four conjugated diene.
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|---|---|---|---|
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| CN104226350B CN104226350B (en) | 2016-09-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881099A (en) * | 2015-12-16 | 2017-06-23 | 上海华谊新材料有限公司 | The catalyst of preparing butadiene with butylene oxo-dehydrogenation, Preparation Method And The Use |
| 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 |
| 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 |
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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 |
| JP2010069335A (en) * | 2010-01-06 | 2010-04-02 | Sankyo Co Ltd | Game machine |
| 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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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2010069335A (en) * | 2010-01-06 | 2010-04-02 | Sankyo Co Ltd | Game machine |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881099A (en) * | 2015-12-16 | 2017-06-23 | 上海华谊新材料有限公司 | The catalyst of preparing butadiene with butylene oxo-dehydrogenation, Preparation Method And The Use |
| 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 |
| 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 |
| 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 |
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