CN107537512B - Butadiene catalyst made by butylene oxidation dehydrogen and method - Google Patents
Butadiene catalyst made by butylene oxidation dehydrogen and method Download PDFInfo
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Abstract
The present invention relates to a kind of butadiene catalyst made by butylene oxidation dehydrogen and methods, mainly solve the problem of that the high easy polymerization of acetaldehyde leads to reactor plugs in oxygen-containing by-product in existing preparing butadiene with butylene oxo-dehydrogenation technology.The present invention contains by using chemical composition: Fe2O3·ZnO·NiO·WO3The catalyst of M；Wherein, M Cr2O3Be selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3At least one of rare earth oxide mixture；By weight percentage, Fe2O3Dosage be 50.0~75.0%, ZnO dosage be 10.0~27.0%, NiO dosage be 1.0~10.0%, WO3Dosage be 1.0~8.0%, M dosage be 2.0~16.0% technical solution preferably solve the problems, such as this, 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 and methods.
Background technique
Butadiene is the important monomer of petrochemical industry base stock and production high molecular synthetic material, energy and multiple compounds
Various synthetic rubber and synthetic resin is made in copolymerization.Butadiene mainly has the extracting of refinery's preparing ethylene by steam cracking coproduction carbon four at present
Separation and two kinds of production methods of oxygenizement of butene.China's butadiene almost all is being passed through from the extracting separation of carbon four, the process
It is advantageous in Ji, but it is obtained as the by-product of refinery's cracker, as rubber industry is to the need of butadiene yield
Growth is asked, cracker production butadiene has been difficult to meet needs.Butylene oxidation-dehydrogenation is the mistake using butadiene as target product
Journey, can be the butadiene of high added value by the butenc that domestic fuel uses, which becomes more and more important.
Mo-Bi system, Sn-P-Li system, Fe silicate system are used equally for butylene oxidation-dehydrogenation to react.Though Mo-Bi system
Right water is relatively low 6~8, but selectivity is lower, generates a large amount of organic oxygen-containing by-products.Sn-P-Li system activity is high, but operates
Condition is more harsh, and water alkene is higher than up to 30 or more, energy consumption.Fe-series catalyst has clear advantage, if butadiene yield is high,
Oxidized byproduct is relatively fewer, water alkene than relatively low 12~16, current most widely used spinel-type Fe-series catalyst.
Since iron series butylene oxidation-dehydrogenation catalyst invention (USP3270080), the improvement in many generations have passed through, performance is not
It is disconnected to be improved.Cr3+Element can effectively improve the activity and stability (USP3450788) of Fe series catalysts.Chinese Academy of Sciences Lanzhou
Chemical Physics research institute invented can be used for fluidized bed butylene oxidation-dehydrogenation catalyst (CN86108152,
CN96113127.6).Synthetic rubber plant, Yanshan Petrochemical company has developed de- for insulation fix bed chromium-free iron series B02 oxidation
Hydrogen catalyst and the more superior B90 catalyst of performance.The iron series spinelle that white wave et al. discloses a kind of support type is compound
Oxide butylene oxidation-dehydrogenation catalyst has high mechanical strength, the good advantage of stability (CN92100436.2).
Iron series spinelle Oxydehydrogenation catalyst is although industrial application, and there are still water alkene than high, and energy consumption is high, by-product
The high problem of acetaldehyde in object.Current commercial plant, including Petro-Tex company, U.S. OXD-D technique, water are more equal than condition
12~16, so causing that energy consumption is high, production cost is high.And since acetaldehyde is high in product, it is easy to cause poly-
Conjunction leads to line clogging.
Summary of the invention
The first technical problem to be solved by the present invention is oxygen-containing by-product in preparing butadiene with butylene oxo-dehydrogenation technology
The problem of middle acetaldehyde is high, and easy polymerization leads to reactor plugs provides the new Oxidative Dehydrogenation of Butene into Butadiene of one kind and urges
Agent.The catalyst is reacted for Oxidative Dehydrogenation of Butene into Butadiene, can adapt to low-water ratio conditions, and have stability good
The characteristics of, the low feature of acetaldehyde by-products content.The second technical problem to be solved by the present invention is to provide a kind of new butylene
The method of oxidative dehydrogenation butadiene.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of Oxidative Dehydrogenation of Butene fourth
Diene catalyst, chemical composition contain:
Fe2O3·ZnO·NiO·WO3·M
Wherein, M Cr2O3Be selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3At least one of rare earth oxide mixing
Object；Fe by weight percentage2O3Dosage be 50.0~75.0%, ZnO dosage be 10.0~27.0%, NiO dosage be
1.0~10.0%, WO3Dosage be
The dosage of 1.0~8.0%, M are 2.0~16.0%.
In above-mentioned technical proposal, it is preferable that by weight percentage, Fe2O3Dosage be 55.0~70.0%.
Preferably, by weight percentage, the dosage of ZnO is 12.0~26.0%.
Preferably, by weight percentage, the dosage of NiO is 2.0~8.0%.
Preferably, by weight percentage, WO3Dosage be 2.0~6.0%.
Preferably, by weight percentage, the dosage of M is 3.0~15.0%.
Preferably, in mixture M, Cr2O3Weight ratio with rare earth oxide is 0.5~4.0.It is highly preferred that Cr2O3With
The weight ratio of rare earth oxide is 1.0~3.0.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of Oxidative Dehydrogenation of Butene fourth
The method of diene uses catalyst described in one of solution technical problem.
One is preferably carried out scheme and is, using butylene as raw material, using water as diluent, using molecular oxygen as oxidant, anti-
Answer 320~600 DEG C of temperature, 0~0.4MPa of reaction pressure, butylene volume space velocity 200~500 hours-1, H2O/ butylene volume ratio is
6~20, O2Under the conditions of/butylene volume ratio is 0.4~1.0, raw material is contacted with catalyst, and reaction generates butadiene.
In above-mentioned technical proposal, it is preferable that reaction temperature is 360~540 DEG C.
Preferably, reaction pressure is 0.05~0.2MPa.
Preferably, butylene volume space velocity is 260~450 hours-1。
Preferably, H2O/ butylene volume ratio is 8~18.
Preferably, O2/ butylene volume ratio is 0.6~0.8.
Preferably, reaction raw materials are at least one of butene-1, cis-butene-2 or trans-butene-2.
Preferably, oxidant is air or oxygen.
In the present invention, the pressure all refers to gauge pressure.
Butadiene catalyst made by butylene oxidation dehydrogen of the invention, preparation use dry pigmentation, comprising the following steps:
A) by the desired amount of solid Fe2O3、ZnO、NiO、WO3、Cr2O3, be selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In
At least one rare earth oxide and pore creating material carry out ball milling 0.5~6 hour in the ball mill, and screening is greater than 150 mesh (standards
Sieve) particle powder；
B) particle powder for obtaining step a) roasts 1~36 hour at 550~800 DEG C to get the catalyst.
Wherein, solid Fe described in step a)2O3、ZnO、NiO、WO3、Cr2O3, be selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3
At least one of rare earth oxide, can decompose to obtain by nitrate, can also be obtained by metal oxidation reaction.
Catalyst of the invention can be shaped to the catalyst of different shapes such as ball, cylinder, annulus and trifolium-shaped.
Catalyst pores hold 0.1~1.8cm3/ g, 5~80m of specific surface area2/g.After ball milling, less than 110 microns (> 150 mesh standard sieve) is screened
Particle powder, preferably in 1~90 micron range.Pore creating material is selected from active carbon, high molecular polymer, glucose or plant and forms sediment
The polyol agents such as powder.The additional amount of pore creating material is the 0~15% of metal oxide mixture weight.Step b) maturing temperature is
550~800 DEG C, calcining time is preferably 2~24 hours, and more preferably 6~20 hours.
The a large amount of water vapours introduced during preparing butadiene with butylene oxo-dehydrogenation, it is mainly larger using the specific heat of water,
Reactor temperature rise is controlled, in addition, system can be made to deviate the blast area of butylene after a large amount of steam dilution, guarantees equipment safety.
From the angle of catalyst performance, the presence of water vapour can promote the desorption of butadiene product, avoid deep oxidation dehydrogenation, polymerization
Carbon deposit is formed, to improve the selectivity and stability of catalyst, therefore to guarantee catalyst performance under low-water ratio conditions,
Just need to enhance catalyst surface for the desorption performance of product butadiene.A large number of experiments show that in Fe-Zn-Ca-P catalytic body
The cloud density of active sites can effectively be enhanced after adding Cr and middle rare earth element in system, to make the butadiene of electron rich
It is more easily desorbed, reduces the probability by deep dehydrogenation for alkynes；To guarantee that catalyst is active and steady under low-water ratio conditions
It is qualitative.Using catalyst of the invention at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8It is 0.7, water alkene is than 7~11
Under the conditions of use, high conversion rate is in 76%, and selectivity is higher than 92%, and acetaldehyde by-product selectivity is small more than 2000 less than 0.7%
When the inactive decline of stability experiment, achieve preferable technical effect.
Butylene dehydrogenation reaction carries out on the continuously flowing miniature catalyst reaction device of stainless steel reactor.Product analysis uses
The organic matters such as alkene, alkadienes in HP-6820 gas chromatograph (TCD, FID dual detector) on-line analysis dehydrogenation product and
The gas contents such as oxygen, carbon monoxide, carbon dioxide and conversion ratio, selectivity and the yield for calculating reaction.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Take 121.7g iron oxide (Fe2O3), 26.00g zinc oxide (ZnO), 8.7g nickel oxide (NiO), 2.7g tungsten oxide
(WO3) and 8.2g chromium oxide (Cr2O3) and 6.2g Eu2O3、6.9g Gd2O3Mixture, add 8.0g glucose, then
Mixing 120 minutes is carried out in the ball mill, screens > 180 mesh powder (standard screen), is roasted 5 hours at 720 DEG C, is obtained composite oxygen
Compound catalyst A.The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 2]
Take 115.2g iron oxide (Fe2O3), 50.7g zinc oxide (ZnO), 12.7g nickel oxide (NiO), 8.6g tungsten oxide
(WO3) and 8.7g chromium oxide (Cr2O3) and 2.0g Pm2O3、2.1g Gd2O3Mixture, add 6.5g polyvinyl alcohol, so
It carries out mixing 40 minutes in the ball mill afterwards, screens > 200 mesh powder (standard screen), roasted 7 hours at 700 DEG C, obtain composite oxygen
Compound catalyst B.The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 3]
Take 130.8g iron oxide (Fe2O3), 42.0g zinc oxide (ZnO), 6.2g nickel oxide (NiO), 4.4g tungsten oxide (WO3)
And 10.24g chromium oxide (Cr2O3) and 2.0g Eu2O3、3.3g Pm2O3、1.2g Dy2O3Mixture, add 9.0g grape
Then sugar carries out mixing 60 minutes in the ball mill, screen > 160 mesh amount of powder (standard screen), roasts 6 hours at 750 DEG C,
Obtain composite oxide catalysts C.The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 4]
Take 137.9g iron oxide (Fe2O3), 33.1g zinc oxide (ZnO), 0.05g titanium oxide (TiO2), 11.7g nickel oxide
(NiO), 7.3g tungsten oxide (WO3) and 6.5g chromium oxide (Cr2O3) and 3.6g Pm2O3Mixture, add 11.2g activity
Then carbon dust carries out mixing 80 minutes in the ball mill, screen > 220 mesh powder (standard screen), roasts 12 hours, obtains at 650 DEG C
To composite oxide catalysts D.The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 5]
Take 122.5g iron oxide (Fe2O3), 30.7g zinc oxide (ZnO), 11.0g nickel oxide (NiO), 14.7g tungsten oxide
(WO3) and 15.4g chromium oxide (Cr2O3) and 5.8g Eu2O3Mixture, 10.0g glucose is added, then in ball mill
In carry out mixing 60 minutes, screen > 350 mesh powder (standard screen), 660 DEG C roast 12 hours, obtain composite oxide catalytic
Agent E.The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 6]
Take 140.4g iron oxide (Fe2O3), 20.7g zinc oxide (ZnO), 15.1g nickel oxide (NiO), 2.6g tungsten oxide
(WO3) and 12.1g chromium oxide (Cr2O3) and 9.1g Dy2O3Mixture, 12.6g cellulose is added, then in ball mill
In carry out mixing 260 minutes, screen > 450 mesh powder (standard screen), 720 DEG C roast 8 hours, obtain composite oxide catalytic
Agent F.The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 7]
Take 125.2g iron oxide (Fe2O3), 35.8g zinc oxide (ZnO), 12.3g nickel oxide (NiO), 8.1g tungsten oxide
(WO3) and 9.4g chromium oxide (Cr2O3) and 9.3g Gd2O3Mixture, add 9.0g starch, then in the ball mill into
Row mixing 200 minutes, screens > 200 mesh powder (standard screen), roasts 10 hours at 680 DEG C, obtains composite oxide catalysts G.
The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 8]
Take 125.2g iron oxide (Fe2O3), 35.8g zinc oxide (ZnO), 12.3g nickel oxide (NiO), 8.1g tungsten oxide
(WO3) and 13.4g chromium oxide (Cr2O3) and 5.3g Gd2O3Mixture, add 9.0g starch, then in the ball mill into
Row mixing 200 minutes, screens > 200 mesh powder (standard screen), roasts 10 hours at 680 DEG C, obtains composite oxide catalysts H.
The weight percent composition of gained catalyst is shown in Table 1.
[embodiment 9]
Take 125.2g iron oxide (Fe2O3), 35.8g zinc oxide (ZnO), 12.3g nickel oxide (NiO), 8.1g tungsten oxide
(WO3) and 7.4g chromium oxide (Cr2O3) and 11.3g Gd2O3Mixture, add 9.0g starch, then in the ball mill into
Row mixing 200 minutes, screens > 200 mesh powder (standard screen), roasts 10 hours at 680 DEG C, obtains composite oxide catalysts I.
The weight percent composition of gained catalyst is shown in Table 1.
Table 1
[comparative example 1]
It is prepared by business butylene oxidation-dehydrogenation catalyst.Catalyst composition are as follows: ZnCr0.5Fe2O4(Chinese patent:
CN86108152)
[comparative example 2]
Catalyst is prepared as described in Example 7, the difference is that not adding tungsten oxide component.
[embodiment 10]
Catalyst A~I is at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8It is 0.7, water alkene is than the item for 7~12
Performance evaluation is carried out under part, the results are shown in Table 2.
Table 2
| Catalyst | Water ratio (volume ratio) | Conversion ratio % | Selective % | Acetaldehyde selectivity % |
| A | 8.5 | 73.3 | 92.6 | 0.56 |
| B | 8.5 | 77.2 | 92.2 | 0.36 |
| C | 8.5 | 76.2 | 93.5 | 0.44 |
| D | 8.5 | 75.6 | 91.4 | 0.63 |
| E | 8.5 | 74.1 | 91.8 | 0.66 |
| F | 8.5 | 73.2 | 91.9 | 0.62 |
| G | 8.5 | 77.5 | 92.9 | 0.48 |
| G | 7.0 | 72.7 | 92.0 | 0.53 |
| G | 10.0 | 78.0 | 93.2 | 0.61 |
| G | 12.0 | 78.4 | 93.1 | 0.55 |
| H | 8.5 | 78.8 | 93.6 | 0.40 |
| I | 8.5 | 76.5 | 93.0 | 0.76 |
| Comparative example 1 | 8.5 | 64.8 | 90.2 | 1.02 |
| Comparative example 2 | 8.5 | 65.2 | 90.1 | 0.90 |
Using catalyst of the invention, the catalyst performance under low-water ratio conditions is significantly improved, the selection of acetaldehyde by-product
Property is substantially reduced.
[embodiment 11]
By the condition evaluating catalyst B (embodiment 2) and [comparative example 1] of [embodiment 10], two catalyst are compared
Stability, the performance after catalyst 2000 hours are shown in Table 2.
Table 2
Claims (10)
1. a kind of butadiene catalyst made by butylene oxidation dehydrogen, chemical composition contain:
Fe2O3·ZnO·NiO·WO3·M
Wherein, M Cr2O3Be selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3At least one of rare earth oxide mixture；With
Weight percent meter, Fe2O3Dosage be 50.0~75.0%, ZnO dosage be 10.0~27.0%, NiO dosage be 1.0
~10.0%, WO3Dosage be 1.0~8.0%, M dosage be 2.0~16.0%.
2. butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterised in that by weight percentage,
Fe2O3Dosage be 55.0~70.0%.
3. butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterised in that by weight percentage,
The dosage of ZnO is 12.0~26.0%.
4. butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterised in that by weight percentage,
The dosage of NiO is 2.0~8.0%.
5. butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterised in that by weight percentage, WO3
Dosage be 2.0~6.0%.
6. butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterised in that by weight percentage, M
Dosage be 2.0~16.0%.
7. butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterised in that in mixture M, Cr2O3With
The weight ratio of rare earth oxide is 0.5~4.0.
8. butadiene catalyst made by butylene oxidation dehydrogen according to claim 7, it is characterised in that in mixture M, Cr2O3With
The weight ratio of rare earth oxide is 1.0~3.0.
9. a kind of method of Oxidative Dehydrogenation of Butene into Butadiene, it is characterised in that use any catalysis of claim 1~8
Agent.
10. the method for Oxidative Dehydrogenation of Butene into Butadiene according to claim 9, it is characterised in that using butylene as raw material, with
Water is diluent, and using molecular oxygen as oxidant, at 320~600 DEG C of reaction temperature, 0~0.4MPa of reaction pressure, butylene volume is empty
Speed 200~500 hours-1, H2O/ butylene volume ratio is 6~20, O2/ butylene volume ratio be 0.4~1.0 under the conditions of, raw material with urge
Agent contact, reaction generate butadiene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010052191A3 (en) * | 2008-11-04 | 2010-12-23 | Universitetet I Oslo | Coated solid pliant materials |
| CN103657680A (en) * | 2012-09-26 | 2014-03-26 | 上海华谊丙烯酸有限公司 | Ferrate catalyst, preparation method and application of ferrate catalyst |
| CN104226352A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for butylene oxidative dehydrogenation to produce butadiene and a preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010052191A3 (en) * | 2008-11-04 | 2010-12-23 | Universitetet I Oslo | Coated solid pliant materials |
| CN103657680A (en) * | 2012-09-26 | 2014-03-26 | 上海华谊丙烯酸有限公司 | Ferrate catalyst, preparation method and application of ferrate catalyst |
| CN104226352A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for butylene oxidative dehydrogenation to produce butadiene and a preparation method thereof |
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