CN100413828C - Method for producing ethene and hexene through dismutation of butylene - Google Patents
Method for producing ethene and hexene through dismutation of butylene Download PDFInfo
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- CN100413828C CN100413828C CNB2005100287924A CN200510028792A CN100413828C CN 100413828 C CN100413828 C CN 100413828C CN B2005100287924 A CNB2005100287924 A CN B2005100287924A CN 200510028792 A CN200510028792 A CN 200510028792A CN 100413828 C CN100413828 C CN 100413828C
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- hexene
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- butylene
- disproportionation
- ethene
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Abstract
This invention relates to a method for manufacturing ethylene and hexane by butane disproportionation. The method uses at least one of Al2O3, SiO2 and TiO2 as the carrier, and at least one oxide of Re, Mo and Co as the catalyst to realize 1-butene disproportionation at low temperatures. The method avoids the problems of double bond isomerization of 1-butene during disproportionation, as well as low selectivity of ethylene and hexane in disproportionation products. The method can be used in ethylene and hexane industrial manufacture by butane disproportionation.
Description
Technical field
The present invention relates to the method for a kind of butylene disproportionation system ethene and hexene.
Background technology
As a kind of olefin product of high added value, the synthetic of hexene paid attention to very much.The conventional preparation method of present industrial hexene generates the 1-hexene by ethylene polymerization, and the catalyzer of employing is alkylating metal catalyst.In addition, by the olefin metathesis technology, also can be with superfluous, that added value is lower relatively C
4Conversion of olefines is the hexene and the ethene of high added value.React as follows:
But above-mentioned reaction often is accompanied by a certain amount of side reaction.This be because, in the disproportionation stage, double bond isomerization reaction will take place at catalyst surface and generate 2-butylene in 1-butylene simultaneously, 2-butylene and 1-butylene cross disproportionation, amylene that the output added value is lower and a certain amount of propylene cause the optionally reduction of ethene and hexene.Therefore, the key of this technology is to suppress the double-bond isomerization of raw material 1-butylene at catalyst surface.
WO02059600 has reported the automatic disproportionation technology of 1-butylene.The catalyzer that this technology adopts is that Tungsten oxide 99.999 is carried on the inert support silicon oxide, and under 200 ℃～350 ℃ temperature, 1-butylene self disproportionation on catalyzer generates ethene and 3-hexene.The 3-hexene is converted into the 1-hexene by isomerization reaction in flow process subsequently.This patent points out to reduce the pressure of reaction system, can reduce the duration of contact of raw material and disproportionation catalyst, suppresses the double-bond isomerization of 1-butylene to 2-butylene, improves the selectivity of reaction.
US6683019 has reported employing high purity SiO
2Inert support reduces the easy content that forms acidic site or basic sites element such as Al, Fe, Ca on the carrier, reduces the generation of isomerization reaction, improves the selectivity of ethene and hexene.
But above-mentioned several method suppresses limited to the double-bond isomerization phenomenon of 1-butylene; On the other hand, we notice that lower temperature of reaction helps suppressing the conversion of 1-butylene to 2-butylene, therefore, if can develop a kind of low temperature disproportionation technology, make 1-butylene at a lower temperature automatic disproportionation can take place, hexene and selectivity of ethylene are expected to improve greatly so.The research of this respect does not appear in the newspapers as yet.
Summary of the invention
Technical problem to be solved by this invention is the temperature of reaction height that in the past had butylene disproportionation in the document, poor catalyst activity, and product ethene and the low problem of hexene selectivity provide a kind of new butylene disproportionation system ethene and the method for hexene.This method is used for butylene disproportionation reaction, and to have temperature of reaction low, the characteristics that the productive rate of ethene and hexene and selectivity are high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of butylene disproportionation system ethene and hexene is a raw material with the butylene, is 0～200 ℃ in temperature of reaction, and reaction pressure is 0～10MPa, and the liquid phase air speed is 0.1～10 hour
-1Under the condition, raw material generates ethene and hexene by the fixed bed catalyst bed, and wherein used catalyzer comprises following component by weight percentage:
(a) 80～99% be selected from Al
2O
3, SiO
2Or TiO
2In the carrier of at least a oxide compound; With carry thereon
(b) 1～20% be selected from oxide compound at least a among Re, Mo or the Co.
In the technique scheme, the support of the catalyst preferred version is Al
2O
3, being selected from oxide compound preferred version at least a among Re, Mo or the Co is Re
2O
7The temperature of reaction preferable range is 0～100 ℃, and the reaction pressure preferable range is 0～5MPa.
The Preparation of catalysts method of using among the present invention: can select co-precipitation, ion-exchange, dipping, chemisorption, electroless plating, physical mixed for use, and under certain atmosphere, 350～700 ℃ of roastings 0.5～20 hour.Preferred version is impregnated on the inert support for the transistion metal compound aqueous solution, after the drying, and under dry air atmosphere, 500～700 ℃ of roastings 4～8 hours.Wherein, catalyzer need adopt spin, extruding slivering, method moulding such as compressing tablet.
To investigate reaction conditions be fixed-bed reactor to catalyzer in the technique scheme, is that 0～100 ℃, reaction pressure are 0～10MPa in temperature of reaction, and the liquid phase air speed is 0.1～10 hour
-1Condition under, 1-butylene carries out disproportionation reaction.
Compared with prior art, among the present invention owing to adopt that to be selected from oxide compound at least a among Re, Mo or the Co be the catalytic activity component, and adopt low temperature disproportionation technology, the double-bond isomerization that has suppressed 1-butylene, reduced the generation of side reaction, thereby improved the reactivity worth of olefin metathesis, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
In length is 60 centimetres, and internal diameter is that 1.8 centimetres reactor lower curtate adding volume is 80 cubic centimetres, and granularity is 10～20 order glass sphere fillers; With 2 gram Re
2O
7/ Al
2O
3Catalyzer adds reactor, and the catalyzer upper end adds 30 cubic centimetres again, and granularity is 10～20 order glass sphere fillers.Be warming up to 550 ℃ under the condition of nitrogen gas that the reactor feeding is 10 liters/hour, and after keeping 2 hours under this temperature, reduce to 40 ℃ of temperature of reaction.
Reactor stops to feed nitrogen, and feeds the 99.5%1-butene feedstock from reactor upper end, and raw material flow rate is the variable valve control by reactor outlet of 10 milliliters/hour, reaction system pressure, and pressure-controlling is at 3MPa.Reaction product after release by the gas-chromatography on-line analysis.Reaction result such as table 1.
Table 1 different catalysts 1-butylene disproportionation reaction result
[comparative example 1]
Adding volume by the reactor lower curtate shown in the embodiment 2 is 80 cubic centimetres, and granularity is 10～20 order glass sphere fillers; With 2 gram WO
3/ SiO
2Catalyzer adds reactor, and the catalyzer upper end adds 30 cubic centimetres again, and granularity is 10～20 order glass sphere fillers.Reactor feeds under the condition of nitrogen gas of 10 liter per hours and is warming up to 550 ℃, and after keeping 2 hours under this temperature, reduces to 350 ℃ of temperature of reaction.
Reactor stops to feed nitrogen, and feeds the 99.5%1-butene feedstock from reactor upper end, raw material flow rate be 24 milliliters per hour, reaction system pressure is by the variable valve control of reactor outlet, pressure-controlling is at 0.49MPa.Reaction product after release by the gas-chromatography on-line analysis.React and reach balance, reaction result such as table 1 after 10 hours.
[embodiment 2～4]
The automatic disproportionation reaction of butylene---the influence of temperature of reaction
Carry out catalyst loading and pre-treatment by the program shown in the embodiment 1, temperature of reaction is controlled at 20 ℃ respectively, 40 ℃, 60 ℃.
Other reaction conditionss such as embodiment 1.Reaction result such as table 2.
1-butylene disproportionation reaction result under table 2 differing temps
[embodiment 5～7]
The automatic disproportionation reaction of butylene---the influence of reaction pressure
Carry out catalyst loading, pre-treatment and butylene disproportionation reaction by the program shown in the embodiment 1, reaction pressure is controlled at 2MPa, 3MPa, 4MPa respectively.Reaction result such as table 3.
1-butylene disproportionation reaction result under table 3 different pressures
Claims (5)
1. the method for butylene disproportionation system ethene and hexene is a raw material with the butylene, is 0～200 ℃ in temperature of reaction, and reaction pressure is 0～10MPa, and the liquid phase air speed is 0.1～10 hour
-1Under the condition, raw material generates ethene and hexene by the fixed bed catalyst bed, and wherein used catalyzer comprises following component by weight percentage:
(a) 80～99% be selected from Al
2O
3, SiO
2Or TiO
2In the carrier of at least a oxide compound; With carry thereon
(b) 1～20% be selected from oxide compound at least a among Re, Mo or the Co.
2. according to the method for described butylene disproportionation system ethene of claim 1 and hexene, it is characterized in that support of the catalyst is Al
2O
3
3. according to the method for described butylene disproportionation system ethene of claim 1 and hexene, it is characterized in that being selected from oxide compound at least a among Re, Mo or the Co is Re
2O
7
4. according to the method for described butylene disproportionation system ethene of claim 1 and hexene, it is characterized in that temperature of reaction is 0～100 ℃.
5. according to the method for described butylene disproportionation system ethene of claim 1 and hexene, it is characterized in that reaction pressure is 0～5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100287924A CN100413828C (en) | 2005-08-15 | 2005-08-15 | Method for producing ethene and hexene through dismutation of butylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100287924A CN100413828C (en) | 2005-08-15 | 2005-08-15 | Method for producing ethene and hexene through dismutation of butylene |
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| Publication Number | Publication Date |
|---|---|
| CN1915938A CN1915938A (en) | 2007-02-21 |
| CN100413828C true CN100413828C (en) | 2008-08-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100287924A Active CN100413828C (en) | 2005-08-15 | 2005-08-15 | Method for producing ethene and hexene through dismutation of butylene |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030513B (en) * | 2011-09-29 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing hexene by butylene disproportionation reaction |
| CN103769084B (en) * | 2012-10-25 | 2015-12-16 | 中国石油化工股份有限公司 | The catalyst of olefin(e) disproportionation hexene |
| CN103772116B (en) * | 2012-10-25 | 2015-12-16 | 中国石油化工股份有限公司 | For the method for preparing hexane by disproportionating butylene |
| CN108059580B (en) * | 2016-11-09 | 2020-01-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing hexene/ethylene by self-disproportionation of 1-butene and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3448163A (en) * | 1965-04-23 | 1969-06-03 | British Petroleum Co | Disproportionation of olefins |
| US4709115A (en) * | 1986-05-15 | 1987-11-24 | The Dow Chemical Company | Disproportionation of alkenes |
-
2005
- 2005-08-15 CN CNB2005100287924A patent/CN100413828C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3448163A (en) * | 1965-04-23 | 1969-06-03 | British Petroleum Co | Disproportionation of olefins |
| US4709115A (en) * | 1986-05-15 | 1987-11-24 | The Dow Chemical Company | Disproportionation of alkenes |
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|---|---|
| CN1915938A (en) | 2007-02-21 |
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