CN104226352B - 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 method, mainly solve water alkene in existing preparing butadiene with butylene oxo-dehydrogenation technology higher, cause the problem that energy consumption is big, quantity of wastewater effluent is big.The present invention by using chemical composition formula is: Fe2O3·ZnO·CaO·P2O5The catalyst of M；Wherein, M is Cr2O3With selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In the mixture of at least one rare earth oxide；By weight percentage, Fe2O3Consumption be 55～76%, the consumption of ZnO is 10 ~ 27%, and the consumption of CaO is 1 ~ 10%, P2O5Consumption be 0.01 ~ 5.0%, the consumption of M be 0.01～6.0% technical scheme preferably solve this problem, can be used in the commercial 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 method.
Background technology
Butadiene is petrochemical industry base stock and the important monomer producing high molecular synthetic material, energy and multiple compounds
Various synthetic rubber and synthetic resin are made in copolymerization.Butadiene mainly has refinery's preparing ethylene by steam cracking coproduction carbon four extracting at present
Separate and two kinds of production methods of oxygenizement of butene.China's butadiene almost all derives from carbon four extracting and separates, and this process is at warp
Have superiority in Ji, but to be the by-product as refinery's cracker obtain, along with the rubber industry need to butadiene yield for it
Asking growth, cracker produces butadiene and has been difficult to meet needs.Butylene oxidation-dehydrogenation is the mistake with butadiene as target product
Journey, 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.Though Mo-Bi system
So water is than relatively low 6 ~ 8, but selectivity is relatively low, produces a large amount of organic oxygen-containing by-product.Sn-P-Li system activity is high, but operation
Condition is the harshest, and water alkene ratio up to more than 30, energy consumption are high.Fe-series catalyst has clear advantage, as butadiene yield is high,
Oxidized byproduct is few, water alkene than relatively low 12 ~ 16, current most widely used spinel-type Fe-series catalyst.
Since the butylene oxidation-dehydrogenation catalyst invention of ferrum system (USP3270080), have passed through the improvement in a lot of generation, performance is not
Break and be improved.Cr3+Element can be effectively improved activity and the stability (USP3450788) of Fe series catalysts.Chinese Academy of Sciences Lanzhou
Chemical Physics institute invented can be used for fluid bed butylene oxidation-dehydrogenation catalyst (CN86108152,
CN96113127.6).Synthetic rubber plant of Yanshan Petrochemical company have developed for insulation fix bed chromium-free iron series B02 oxidation de-
Hydrogen catalyst and the more superior B90 catalyst of performance.White wave et al. discloses the ferrum system spinel of a kind of support type and is combined
Oxide butylene oxidation-dehydrogenation catalyst, has mechanical strength high, the advantage (CN92100436.2) of good stability.
Though ferrum system spinel Oxydehydrogenation catalyst commercial Application, it is high to still suffer from water alkene ratio, and energy consumption is big, waste water
The problem that discharge capacity is big.Current commercial plant, including Petro-Tex company of U.S. OXD-D technique, water than condition all 12 ~
16, so causing energy consumption big, production cost remains high.Along with the maximization of butylene oxidation device, energy-saving and emission-reduction seem more to come
The most important, it is applicable to wait the low water ratio catalyst of hotbed in the urgent need to exploitation.
Summary of the invention
One of the technical problem to be solved is water alkene ratio in existing preparing butadiene with butylene oxo-dehydrogenation technology
Higher, cause the problem that energy consumption is big, quantity of wastewater effluent is big, it is provided that a kind of new butadiene catalyst made by butylene oxidation dehydrogen.Should
Catalyst reacts for Oxidative Dehydrogenation of Butene into Butadiene, it is possible to adapts to low-water ratio conditions, and has the feature of good stability.
The two of the technical problem to be solved are to provide a kind of method of new Oxidative Dehydrogenation of Butene into Butadiene.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of Oxidative Dehydrogenation of Butene fourth
Diene catalyst, its chemical composition formula is:
Fe2O3·ZnO·CaO·P2O5·M
Wherein, M is Cr2O3With selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In the mixing of at least one rare earth oxide
Thing；By weight percentage, Fe2O3Consumption be 55～76%, the consumption of ZnO is 10 ~ 27%, and the consumption of CaO is 1 ~ 10%, P2O5
Consumption be 0.01 ~ 5.0%, the consumption of M is 0.01～6.0%.
In technique scheme, it is preferable that by weight percentage, Fe2O3Consumption be 55.0 ~ 70.0 %.
Preferably, by weight percentage, the consumption of ZnO is 12.0 ~ 26.0 %.
Preferably, by weight percentage, the consumption of CaO is 3.0～9.0 %.
Preferably, by weight percentage, P2O5Consumption be 0.1～4.5 %.
Preferably, by weight percentage, the consumption of M is 2.0～5.0 %.
Preferably, in mixture M, Cr2O3It is 0.05 ~ 4.0% with the weight ratio of rare earth oxide.It is highly preferred that Cr2O3With
The weight ratio of rare earth oxide is 0.3 ~ 2.0%.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of Oxidative Dehydrogenation of Butene fourth
The method of diene, uses and solves the catalyst that one of technical problem is described.
One is preferably carried out scheme and is, with butylene as raw material, with water as diluent, with molecular oxygen as oxidant, instead
Answer temperature 320 ~ 600 DEG C, reaction pressure 0 ~ 0.4MPa, 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 contacts with catalyst, and reaction generates butadiene.
In technique scheme, 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, 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 butadiene catalyst made by butylene oxidation dehydrogen of the present invention, its preparation uses dry pigmentation, comprises the following steps:
A) by the desired amount of solid Fe2O3、ZnO、CaO、P2O5、Cr2O3, 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 ball mill, and screening is more than 150 mesh (standards
Sieve) particle powder；
B) particle powder step a) obtained was 550～800 DEG C of roastings 1～36 hours, obtained described catalyst.
Wherein, solid Fe described in step a)2O3、ZnO、CaO、P2O5、Cr2O3, selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3
In at least one rare earth oxide, can by nitrate decompose obtain, it is also possible to by burning reaction obtain.
The catalyst of the present invention can be shaped to the difform catalyst such as ball, cylinder, annulus and trifolium-shaped.
Catalyst pore volume 0.1 ~ 1.2cm3/ g, specific surface area 5 ~ 60m2/g.After ball milling, screening is more than 150 mesh (standard screen) particle powder,
Preferably in 1 ~ 90 micrometer range.Pore creating material is selected from polyhydric alcohol such as activated carbon, high molecular polymer, glucose or plant amylums
Material.The addition of pore creating material is the 0 ~ 15% of metal oxide mixture weight.Step b) sintering temperature is 550～800 DEG C,
Roasting time is preferably 2 ~ 24 hours, more preferably 6 ~ 20 hours.
The a large amount of water vapour introduced during preparing butadiene with butylene oxo-dehydrogenation, relatively big mainly by specific heat of water,
Control reactor temperature rise, additionally, the blast area of system deviation butylene can be made after substantial amounts of steam dilution, it is ensured that equipment safety.
From the angle of catalyst performance, the existence of water vapour can promote the desorption of butadiene product, it is to avoid deep oxidation dehydrogenation, polymerization
Form carbon deposit, thus improve selectivity of catalyst and stability, under low-water ratio conditions, therefore to ensure catalyst performance,
It is accomplished by the desorption performance strengthening catalyst surface for product butadiene.A large number of experiments show that, in Fe-Zn-Ca-P catalytic body
The cloud density of active sites can be effectively strengthened after system adds Cr and rare earth elements, so that the butadiene of electron rich
Being easier to desorption, reducing by deep dehydrogenation is the probability of alkynes；Thus ensure that catalyst activity under low-water ratio conditions is with steady
Qualitative.Use the present invention catalyst at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8It is 0.7, water alkene ratio 7 ~ 11
Under the conditions of use, conversion ratio be higher than 76%, selectivity be higher than 92%, the inactive decline of stability experiment more than 2000 hours, obtain
Preferable technique effect.
Butylene dehydrogenation reaction is carried out on the flowing miniature catalyst reaction device of stainless steel reactor continuously.Product analysis uses
The Organic substances such as alkene in HP-6820 gas chromatograph (TCD, FID dual detector) on-line analysis dehydrogenation product, alkadienes and
The gas contents such as oxygen, carbon monoxide, carbon dioxide also calculate 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 ferrum oxide (Fe2O3), 8.0g zinc oxide (ZnO), 5.4g calcium oxide (CaO), 0.1g P2O5And
0.8g chromium oxide (Cr2O3) and 0.7gEu2O3、0.8gGd2O3Mixture, add 3.0g glucose, then in ball mill
Carry out mixing 120 minutes, screening 200 mesh powder (standard screen), 700 DEG C of roastings 6 hours, obtain composite oxide catalysts
A.The percentage by weight composition of gained catalyst is shown in Table 1.
[embodiment 2]
Take 24.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 2.5g calcium oxide (CaO), 1.7g P2O5And
0.4g chromium oxide (Cr2O3) and 0.3 g Pm2O3、0.5 g Gd2O3Mixture, add 3.0g polyvinyl alcohol, then at ball
Grinding machine is carried out mix 30 minutes, screening 200 mesh powder (standard screen), 700 DEG C of roastings 8 hours, obtain composite oxides and urge
Agent B.The percentage by weight composition of gained catalyst is shown in Table 1.
[embodiment 3]
Take 36.2g ferrum oxide (Fe2O3), 11.0g zinc oxide (ZnO), 1.6g calcium oxide (CaO), 1.5g P2O5And
0.4g chromium oxide (Cr2O3) and 0.4 g Eu2O3、0.6 g Pm2O3、0.2 g Dy2O3Mixture, 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.The percentage by weight composition of gained catalyst is shown in Table 1.
[embodiment 4]
Take 52.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 3.0g calcium oxide (CaO), 2.0g P2O5And
0.6g chromium oxide (Cr2O3) and 1.1g Pm2O3Mixture, add 9.2g activated carbon powder, then mix in ball mill
Close 95 minutes, screening 200 mesh powder (standard screen), 600 DEG C of roastings 16 hours, obtain composite oxide catalysts D.Gained
The percentage by weight composition of catalyst is shown in Table 1.
[embodiment 5]
Take 48.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 3.6g calcium oxide (CaO), 2.0g P2O5And
1.0g chromium oxide (Cr2O3) and 0.6g Eu2O3Mixture, add 10.0g glucose, then mix in ball mill
60 minutes, screening > 400 mesh powder (standard screen), 650 DEG C of roastings 12 hours, obtain composite oxide catalysts E.Gained is urged
The percentage by weight composition of agent is shown in Table 1.
[embodiment 6]
Take 46.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 4.0g calcium oxide (CaO), 2.0g P2O5And
1.6g chromium oxide (Cr2O3) and 0.4g Gd2O3Mixture, add 4.5g starch, then carry out mixing 240 in ball mill
Minute, screening > 200 mesh powder (standard screen), 680 DEG C of roastings 12 hours, obtain composite oxide catalysts F.Gained is catalyzed
The percentage by weight composition of agent is shown in Table 1.
[embodiment 7]
Take 46.0g ferrum oxide (Fe2O3), 8.0g zinc oxide (ZnO), 5.0g calcium oxide (CaO), 0.8g P2O5And
1.6g chromium oxide (Cr2O3) and 0.4g Dy2O3Mixture, add 8.3g cellulose, then mix in ball mill
300 minutes, screening > 500 mesh powder (standard screen), 700 DEG C of roastings 10 hours, obtain composite oxide catalysts G.Gained is urged
The percentage by weight composition of agent is shown in Table 1.
Table 1
[comparative example 1]
Method as disclosed in document CN86108152 prepares butylene oxidation-dehydrogenation catalyst, and catalyst consists of:
ZnCr0.5Fe2O4。
[embodiment 8]
Catalyst A ~ G at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8Being 0.7, water alkene ratio is the condition of 7 ~ 12
Under carry out performance evaluation, the results are shown in Table 2.
Table 2
Using the catalyst of the present invention, the catalyst performance under low-water ratio conditions significantly improves.
[embodiment 9]
By the condition evaluating catalyst B(embodiment 2 of [embodiment 8]) and [comparative example 1], contrast the steady of two catalyst
Qualitative, catalyst performance after 2000 hours is shown in Table 3.
Table 3
Claims (10)
1. a butadiene catalyst made by butylene oxidation dehydrogen, its chemical composition formula is:
Fe2O3·ZnO·CaO·P2O5·M
Wherein, M is Cr2O3With selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In the mixture of at least one rare earth oxide；With
Percentage by weight meter, Fe2O3Consumption be 55.0～76.0%, the consumption of ZnO is 10.0 ~ 27.0%, the consumption of CaO is 1.0 ~
10.0%, P2O5Consumption be 0.01 ~ 5.0%, the consumption of M is 0.01～6.0%.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage,
Fe2O3Consumption be 55.0 ~ 70.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage,
The consumption of ZnO is 12.0 ~ 26.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage,
The consumption of CaO is 3.0 ~ 9.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage,
P2O5Consumption be 0.1 ~ 4.5 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage, M
Consumption be 2.0 ~ 5.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that in mixture M, Cr2O3With
The weight ratio of rare earth oxide is 0.05 ~ 4.0%.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 7, it is characterised in that in mixture M, Cr2O3With
The weight ratio of rare earth oxide is 0.3 ~ 2%.
9. the method for an Oxidative Dehydrogenation of Butene into Butadiene, it is characterised in that use the arbitrary described catalysis of claim 1 ~ 8
Agent.
The method of Oxidative Dehydrogenation of Butene into Butadiene the most according to claim 9, it is characterised in that with butylene as raw material, with
Water is diluent, with molecular oxygen as oxidant, at reaction temperature 320 ~ 600 DEG C, reaction pressure 0 ~ 0.4MPa, 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 connects with catalyst
Touching, reaction generates butadiene.
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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 |
| EP1918312A1 (en) * | 2006-10-31 | 2008-05-07 | Ineos Europe Limited | Diene polymerisation |
| CN102974357A (en) * | 2011-09-06 | 2013-03-20 | 北京中石润达科技发展有限公司 | Lattice oxygen catalyst used for preparing butadiene through butylene oxidative dehydrogenation, and preparation method thereof |
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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 |
| EP1918312A1 (en) * | 2006-10-31 | 2008-05-07 | Ineos Europe Limited | Diene polymerisation |
| CN102974357A (en) * | 2011-09-06 | 2013-03-20 | 北京中石润达科技发展有限公司 | Lattice oxygen catalyst used for preparing butadiene through butylene oxidative dehydrogenation, and preparation method thereof |
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