CN109608301A - A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene - Google Patents

A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene Download PDF

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CN109608301A
CN109608301A CN201710964985.3A CN201710964985A CN109608301A CN 109608301 A CN109608301 A CN 109608301A CN 201710964985 A CN201710964985 A CN 201710964985A CN 109608301 A CN109608301 A CN 109608301A
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dehydrogenation
catalyst
butylene
butanes
gallium
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CN109608301B (en
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张桥
徐勇
曹暮寒
刘其鹏
杨迪
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Suzhou University
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Abstract

The present invention provides a kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene, use the double activated component composite catalyst comprising zirconium and gallium, butane carries out efficient dehydrogenation, the selectivity of butadiene reaches 17% in product, the selectivity of total butylene reaches 81.5%, and catalyst shows good stability and reproducibility at high temperature.

Description

A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene
Technical field
The present invention relates to a kind of method for preparing butylene and butadiene, in particular to a kind of catalytic dehydrogenation of butanes prepares butylene With the method for butadiene.
Background technique
Butylene is basic petrochemical raw material, and status is only second to ethylene and propylene in petrochemical industry olefin feedstock, is to close At the important monomer of rubber and high molecular material.It is, in general, that butylene mainly has several isomers, such as n-butene (1- fourth Alkene), isobutene, cis- dibutene and four kinds of trans- dibutene.N-butene is mainly for the manufacture of methyl ethyl ketone, sec-butyl alcohol, ring Oxygen butane and butene polymers and copolymer.Isobutene is mainly for the manufacture of butyl rubber, Oppanol and various plastics. It is, in general, that 1- butylene and 2- butylene can carry out many important basic organic chemical industries of chemical process production together and produce without separation Product, such as hydration are sec-butyl alcohol and then produce methyl ethyl ketone, oxidative dehydrogenation butadiene, catalysis oxidation maleic anhydride with And acetic acid.In addition, butylene is also used as raw material manufacture butadiene.Butadiene is the basic material of petrochemical industry, in petroleum Status is only second to ethylene and propylene in work olefin feedstock, is the important monomer of synthetic rubber and high molecular material.Industrial butylene Production mainly by C-4-fraction separate obtain.Butylene quality is different in separate sources C-4-fraction.With China's oil Industry rapid development, oil price is high, and petroleum-based products manufacturing cost is excessively high, and butylene production capacity has lagged far behind reality The situation of demand, butylene supply and demand shortage is more serious, largely constrains the development of national economy.
In fact, scientist is just making great efforts the new technique for preparing butylene of exploitation, such as utilizes positive fourth since last century Alkane is raw material, corresponding butylene is prepared by way of dehydrogenation, and have been carried out industrialization.In recent years, with shale gas Constantly exploration, the minable shale gas total amount in the whole world are huge.Related data shows: the minable shale gas total amount in the whole world is up to 207 cubic metres, wherein the reserves height in China ranks first in the world, and total amount is up to 32 tcms.The main component of shale gas is first Alkane, ethane, propane and butane, these low-carbon alkanes can further synthesize other chemical intermediates by way of oxidative coupling, Therefore abundant and cheap raw material is provided for modernization industry.Therefore the technique of butylene is prepared by bigger by raw material of butane Concern.Process route there are two types of more popular at present: direct dehydrogenation and oxidative dehydrogenation.Although oxidative dehydrogenation is to a certain degree On can slow down carbon distribution generation, but the oxidant introduced tends to generate carbon monoxide and carbon dioxide, causes the choosing of butylene Selecting property is very low.And direct dehydrogenation can effectively avoid the generation of other OXO products, olefine selective may be up to 95% or more.Although Direct dehydrogenation generally requires higher temperature, this may result in the hydrocarbon that the excessive dehydrogenation of butane even chain rupture generates small molecule in this way Class, but can often realize that c h bond and C-C are selectively living by catalyst regulation.Furthermore the carbon deposit generated can pass through catalyst Regeneration is realized.Therefore butane direct dehydrogenation prepares butylene and receives extensive favor, and the technique has been carried out industrial metaplasia At.
Currently used butane dehydrogenation catalyst has following several: (1) Pt base catalyst, noble metal catalyst are anti-in dehydrogenation It should play the role of vital, but higher cost.Practical application has Uop Inc. and the oil company Philips, they Select Pt as catalyst activity component, by the way that auxiliary agent is added, carrier improves the stability of catalyst.It is wherein more famous to help Agent is exactly Sn, and commercialized catalyst is Pt-Sn-Al2O3 at present；(2) V-based catalyst, this catalyst are usually to use Vanadium oxide is supported on aluminium oxide or silica；(3) Cr base catalyst.Cr base catalyst is that another is important nonmetallic Catalyst, Catofin has been commercialized at present.Although the report at present about direct dehydrogenation catalyst is commonplace, It is that butane dehydrogenation still suffers from problems and challenge.For example, thermodynamically, direct dehydrogenation is a strong endothermic reaction, need It to carry out at high temperature.High temperature be easy to cause sintering of catalyst and inactivates, therefore it is required that catalyst has high stability.Another party Face, high temperature be easy to cause the excessive dehydrogenation of butane to form carbon deposit, thus to realize selective dehydrogenation to the design of catalyst it is also proposed that Higher requirement.For current industrial catalyst, Pt catalyst is easy carbon deposit, although high temperature regeneration can burn off carbon deposit, It is that high temperature easily causes Pt to be sintered and inactivate.Although regenerative process needs it was reported that addition Sn can effectively prevent Pt sintering Chlorination, this process have corrosiveness to equipment.Cr base catalyst is there is also similar problem, and Cr can move to load under hot conditions Active component is caused to lose in body aluminium oxide.Another aspect Cr's will also result in environmental pollution using the use of Cr.
In conclusion the exploitation of new catalyst is to realize that butane dehydrogenation prepares the committed step of alkene.Ideal catalysis Agent should have excellent C-H activity function, and can also shift intermediate product rapidly to avoid excessive dehydrogenation even chain rupture；This Outside, catalyst should have the anti-caking power of excellent high temperature, be able to maintain activity in circular regeneration in this way；But also it should focus on Based on base metal, environmental-friendly catalyst is developed, to embody bigger industrial value.
Summary of the invention
In view of the above problems in the prior art, the object of the present invention is to provide a kind of catalytic dehydrogenation of butanes to prepare butylene and fourth The method of diene realizes the Efficient Conversion of butane.
To solve the above-mentioned problems, technical scheme is as follows:
A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene, in the presence of dehydrogenation, by butane into Row dehydrogenation reaction, and butylene and butadiene are separated from obtained dehydrogenation product；The dehydrogenation includes in zirconium and gallium One or two are used as active component.
Further, the active component in the dehydrogenation accounts for the 1-10% of catalyst gross mass.
Preferably, the active component in the dehydrogenation accounts for the 3-5% of catalyst gross mass.
Preferably, the active component in the dehydrogenation is zirconium and gallium, and the mass ratio of zirconium and gallium is 0.1-10.
Preferably, the mass ratio of zirconium and gallium is 0.2-5 in the active component in the dehydrogenation.
Dehydrogenation includes active component zirconium and gallium, which is a kind of double activated component composite catalyst. The composite catalyst is acted synergistically by zirconium gallium based on base metal zirconium and gallium and is realized the efficient dehydrogenation of butane.Pass through regulation C h bond and the selection activation of C-C are realized, to improve the selectivity of butylene in the interface of composite catalyst.
Zirconium oxide and gallium oxide not only have excellent thermal stability, and it can generate a large amount of oxygen under hydrogen treat Vacancy can effectively facilitate c h bond activation.
Above-mentioned active component exists with metal or metal oxide form, can individually make dehydrogenation, can also bear It is loaded on carrier, the carrier is not particularly limited, it is preferable to use sial complex carrier, for example, ZSM Series Molecules Sieve, MCM Series Molecules sieve, beta-zeolite etc..It is total that active component in dehydrogenation described in loaded catalyst accounts for catalyst The 1-10% of quality, preferably 3-5%, particularly preferred 4.5%.
Above-mentioned dehydrogenation can be made according to existing various methods, such as a kind of specific implementation according to the present invention Mode, the dehydrogenation are prepared as follows:
1) it weighs the soluble-salt of a certain amount of zirconium and gallium and is configured to mixed solution；
2) by above-mentioned mixed solution incipient impregnation in sial complex carrier；
3) aging, drying after impregnating, high-temperature calcination is to get catalyst solid powder；
4) above-mentioned catalyst solid powder is passed through into H2/N2The processing of mixed gas high-temperature activation.
A kind of specific embodiment according to the present invention, catalytic dehydrogenation of butanes prepare the reaction condition of butylene and butadiene Are as follows: reaction temperature is 500-750 DEG C, reaction pressure 0-0.3Mpa, and volume space velocity is 20-300h when gas-1.The butane with Hydrogen is fed jointly, and wherein the molar ratio of hydrogen and butane is 0.1-10.
The concentration of inert gas dilution hydrogen and butane can also be used, during catalytic dehydrogenating reaction to slow down reaction Temperature in the process rises.The dosage of the inert gas controls reaction temperature subject within 500-750 DEG C, the inertia Gas can be one of nitrogen, helium and argon gas or a variety of.
Contain C3 following components and C4 component in the dehydrogenation product in the present invention.C4 component mainly contains butylene (packet Include 1- butylene, 2- butylene and isobutene), butadiene and unreacted butane.Art technology can be used in the present invention Method well known to personnel isolates n-butene and butadiene from dehydrogenation product.
Advantages of the present invention is as follows:
1) use base metal zirconium and gallium for the active component of catalyst, it is environmental-friendly, it is at low cost, there is bigger industry Value and application prospect.
2) the efficient dehydrogenation of butane is realized by zirconium gallium synergistic effect, the selectivity of butadiene reaches 17% or so in product, The selectivity of total butylene reaches 81.5%.
3) catalyst shows good stability and reproducibility at high temperature.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the catalyst of different activities constituent content provided in an embodiment of the present invention；
Fig. 2 is butane in the catalyst butane dehydrogenation reaction of different activities constituent content provided in an embodiment of the present invention Conversion ratio and selective figure；
Fig. 3 is the product distribution of the catalyst butane dehydrogenation of different activities constituent content provided in an embodiment of the present invention Figure；
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
Embodiment 1
A certain amount of zirconium nitrate is weighed, and is configured to solution, then incipient impregnation is in sial complex carrier.It is old after dipping Change to be subsequently placed in 100 DEG C of baking ovens for 1 hour and be dried overnight, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 1。
Zirconium mass fraction is 4.47% in the obtained catalyst of the present embodiment, the specific surface area of the catalyst, Kong Rong and Aperture is as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 2
It is 3.5:1 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 2.
The mass fraction of zirconium is 3.53% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 0.81%.It should The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 3
It is 2:2.5 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 3.
The mass fraction of zirconium is 1.89% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 2.23%.It should The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 4
It is 1:3.5 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 4.
The mass fraction of zirconium is 0.97% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 3.25%.It should The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 5
It is 0.5:4 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 5.
The mass fraction of zirconium is 0.51% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 3.34%.It should The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 6
It weighs a certain amount of gallium nitrate and is configured to solution, then incipient impregnation is in sial complex carrier.It is old after dipping Change to be subsequently placed in 100 DEG C of baking ovens for 1 hour and be dried overnight, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 6。
The mass fraction of gallium is 4.34% in the obtained catalyst of the present embodiment.The specific surface area of the catalyst, Kong Rong As shown in table 1 with aperture, X-ray diffractogram is as shown in Figure 1.
The chemical physical property of 1 different catalysts of table
Embodiment 7
Catalyst cat 1~cat 6 prepared by above-described embodiment 1 to embodiment 6 is after preparing, by tabletting Sieve selects the catalyst 0.4g of 60-80 mesh and quartz sand to be put into quartz reactor after mixing according to 1:3 mass ratio.
Catalyst is needed before the reaction by H2/N2(10%) it handles 30 minutes to 600 degrees Celsius.Then by butane, hydrogen It is introduced into reaction tube with nitrogen according to the volume ratio of 1:1:8, total flow 100ml/min.Reaction carries out under normal pressure, and temperature is 600 DEG C, volume space velocity is 20-300h when gas-1。
It is as shown in Figures 2 and 3 that product is subjected to gas phase analysis acquired results.The conversion ratio of butane as shown in Figure 2 reaches 90% Above, selectivity reaches as high as 60%；As shown in figure 3, the selectivity of butadiene is up to 17% or so in product, total butylene Selectivity be up to 81.5%.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention. Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.

Claims (8)

1. a kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene, it is characterised in that: in the presence of dehydrogenation, Butane is subjected to dehydrogenation reaction, and separates butylene and butadiene from obtained dehydrogenation product；The dehydrogenation includes zirconium Active component is used as with one or both of gallium.
2. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: the dehydrogenation Active component in catalyst accounts for the 1-10% of catalyst gross mass.
3. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 2, it is characterised in that: the dehydrogenation Active component in catalyst accounts for the 3-5% of catalyst gross mass.
4. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: the dehydrogenation Active component in catalyst is zirconium and gallium, and the mass ratio of zirconium and gallium is 0.1-10.
5. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 4, it is characterised in that: the dehydrogenation The mass ratio of zirconium and gallium is 0.2-5 in active component in catalyst.
6. the method that any one of -5 catalytic dehydrogenation of butanes prepare butylene and butadiene according to claim 1, which is characterized in that The dehydrogenation is prepared as follows:
1) it weighs the soluble-salt of a certain amount of zirconium and gallium and is configured to mixed solution；
2) by above-mentioned mixed solution incipient impregnation in sial complex carrier；
3) aging, drying after impregnating, high-temperature calcination is to get catalyst solid powder；
4) above-mentioned catalyst solid powder is passed through into H2/N2The processing of mixed gas high-temperature activation.
7. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: the butane It is fed jointly with hydrogen, wherein the molar ratio of hydrogen and butane is 0.1-10.
8. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: reaction temperature It is 500-750 DEG C, reaction pressure 0-0.3Mpa, volume space velocity is 20-300h when gas-1。
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