CN1915492A - Catalyst for preparing ethane and hexane through butene disproportionation - Google Patents
Catalyst for preparing ethane and hexane through butene disproportionation Download PDFInfo
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- CN1915492A CN1915492A CNA2005100287939A CN200510028793A CN1915492A CN 1915492 A CN1915492 A CN 1915492A CN A2005100287939 A CNA2005100287939 A CN A2005100287939A CN 200510028793 A CN200510028793 A CN 200510028793A CN 1915492 A CN1915492 A CN 1915492A
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- China
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- catalyst
- reaction
- hexene
- butylene
- ethene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A catalyst for dismutating butene to prepare ethene and hexene with high selectivity and the ability to suppress the double-bond isomerizing reaction of 1-buten is composed of the carrier chosen from Al2O3, SiO2 and TiO2 and the active component chosen from Re, Mo and Co.
Description
Technical field
The present invention relates to the catalyst of a kind of butylene disproportionation system ethene and hexene.
Background technology
The 1-hexene is the important additives of synthesizing linear low-density polyethylene, has very high added value; Butylene is the byproduct of naphtha steam cracking, generally as liquefied petroleum gas consumption.By self disproportionated reaction and olefin isomerization of butylene, superfluous, that added value is lower relatively butylene can be converted into the hexene and the ethene of high added value.Reaction equation is as follows
The first step: isomerization of butene reaction
Second step: 1-butylene self disproportionated reaction
The 3rd step: 3-hexene isomerization reaction
Wherein, the control of self disproportionated reaction of 1-butylene is the most key, because the 1-butylene is in self disproportionated reaction process, because under the effect of the acid of catalyst surface or basic sites, be easy to take place the reaction of 1-butylenes double-bond isomerization and generate the 2-butylene, 2-butylene and 1-butylene cross disproportionation, the amylene that the output added value is lower and a certain amount of propylene.Because the reaction speed of the reaction of 1-butylenes double-bond isomerization and 2-butylene and 1-butylene cross disproportionation is very fast, causes the hexene yield very low.
WO02059600 has reported automatic disproportionation system ethene of 1-butylene and hexene technology.The catalyst that this technology adopts is that tungsten oxide is carried on the inert carrier silica, and under 200 ℃～350 ℃ temperature, 1-butylene self disproportionation on catalyst generates ethene and 3-hexene.The 3-hexene is converted into the 1-hexene by isomerization reaction in flow process subsequently.This patent is pointed out to increase reaction velocity by reducing the pressure of reaction system, can reduce the time of contact of raw material and disproportionation catalyst, suppresses the double-bond isomerization of 1-butylene to the 2-butylene, improves the selectivity of reaction.
US6683019 has reported employing high-purity SiO
2Inert carrier 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, reduce reaction temperature, 1-butylenes double-bond isomerization reaction speed reduces greatly, so under cryogenic conditions, carry out 1-butylene self disproportionated reaction, hexene and selectivity of ethylene are improved greatly, and its key is to prepare to have highly active olefin disproportionation catalyst under cryogenic conditions.
Summary of the invention
Technical problem to be solved by this invention is to have the reaction temperature height in the conventional art, and ethene and the low problem of hexene selectivity provide a kind of new butylene disproportionation system ethene and the catalyst of hexene.Using this catalyst to be used for butylene disproportionation reaction, to have reaction temperature low, the advantage that the selectivity of ethene and hexene is high.
For solving the problems of the technologies described above, the catalyst of following a kind of butylene disproportionation system ethene of the technical solution used in the present invention and hexene 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; With carry thereon
(b) 1～20% be selected from oxide at least a among Re, Mo or the Co.
In the technique scheme, the catalyst carrier preferred version is Al
2O
3By weight percentage, preferred version is to contain 1～20% in the catalyst to be selected from oxide at least a among Re or the Mo; Being selected from oxide consumption preferable range at least a among Re, Mo or the Co by weight percentage is 6～12%.
Method for preparing catalyst can be selected co-precipitation, ion-exchange, dipping, chemisorbed, chemical deposition, physical mixed for use, and under certain atmosphere, 350～700 ℃ of roastings 0.5～20 hour.Preferred version is impregnated on the inert carrier for the transistion metal compound aqueous solution, after the drying, and under dry air atmosphere, 500～700 ℃ of roastings 4～8 hours.Catalyst need adopt spin, extruding slivering, method moulding such as compressing tablet.
Adopt the catalyst of technique scheme of the present invention can use, be catalysis 1-butylene self disproportionated reaction system hexene, ethene in embodiments of the present invention at olefin dismutation reaction.Reaction condition is that fixed bed reactors, reaction temperature are 0～200 ℃, and reaction pressure is 0～10MPa, and the liquid phase air speed is 0.1～10 hour
-1Under the condition, butene-1 carries out self disproportionated reaction.The present invention still has very high olefin dismutation reaction activity by using above-mentioned catalyst under lower reaction temperature, the reaction of 1-butylenes double-bond isomerization is inhibited, and ethene and hexene selectivity improve greatly, have obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Take by weighing 50 grams through the dried γ-Al of roasting
2O
3(specific area is 278 meters squared per gram) puts into dry glass beaker, and the concentration of accurately measuring 43 milliliters of rheniums with pipette is that 70 milligrams every milliliter the perrhenic acid aqueous solution places another beaker, adds 7 milliliters of deionized waters again, and stirs.
Above-mentioned perrhenic acid solution poured into fast γ-Al is housed
2O
3Beaker in, left standstill 120 ℃ of dryings 10 hours after stirring 4 hours.Place tube furnace to feed dry air in the above-mentioned sample that makes, gas flow rate is controlled at 1000 milligrams of per minutes, is warming up to 550 ℃ of roastings by 10 ℃ of per minute speed, and keeps 8 hours, and the content that makes rhenium is 6% Re
2O
7/ Al
2O
3Catalyst sample.
[embodiment 2]
Take by weighing 50 grams through the dried γ-Al of roasting
2O
3(specific area is 278 meters squared per gram) puts into dry glass beaker, and the concentration of accurately measuring 50 milliliters of rheniums with pipette is that 70 milligrams every milliliter the perrhenic acid aqueous solution places another beaker.Above-mentioned perrhenic acid solution poured into fast γ-Al is housed
2O
3Beaker in, left standstill 120 ℃ of dryings 10 hours after stirring 4 hours.
The concentration of accurately measuring 7 milliliters of rheniums with pipette is that the perrhenic acid aqueous solution of every milliliter of milligram places a beaker, and adding deionized water again, to make liquor capacity be 50 milliliters.Carry out second time dipping by above-mentioned steps, and in 120 ℃ of dryings 10 hours.Carry out the catalyst sample roasting by embodiment 1 described method, the content that makes rhenium is 8%Re
2O
7/ Al
2O
3Catalyst sample.
[embodiment 3～7]
The content that makes rhenium by the method for embodiment 2 respectively is 10%, 12%, 14%, 16%, 20%Re
2O
7/ Al
2O
3Catalyst sample.
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 marble fillers; With 2 gram Re
2O
7/ Al
2O
3Catalyst adds reactor, and the catalyst upper end adds 30 cubic centimetres again, and granularity is 10～20 order glass marble 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 40 ℃ of reaction temperatures.
Reactor stops to feed nitrogen, and feeds the 99.5%1-butene feedstock from reactor upper end, and raw material flow rate is the control valve control by reactor outlet of 10 milliliters/hour, reaction system pressure, and pressure is controlled at 3MPa.Product after release by the gas-chromatography on-line analysis.Reaction result such as table 1.
Table 1 Re
2O
7/ Al
2O
3The performance of 1-butylene self disproportionated reaction on the catalyst sample
| Catalyst | Re 2O 7Content (% weight) | Yield (mole %) | Conversion ratio (mole %) | Selectivity (mole %) | ||
| Ethene | Propylene | Hexene | Butylene | Ethene+hexene | ||
| Re 2O 7/Al 2O 3 | 6 | 10.11 | 0 | 12.53 | 22.86 | 99.13 |
| Re 2O 7/Al 2O 3 | 8 | 14.36 | 0 | 14.22 | 28.78 | 99.31 |
| Re 2O 7/Al 2O 3 | 10 | 15.55 | 0 | 15.97 | 31.71 | 99.37 |
| Re 2O 7/Al 2O 3 | 12 | 16.18 | 0.03 | 16.18 | 32.63 | 99.17 |
| Re 2O 7/Al 2O 3 | 14 | 16.09 | 0.47 | 20.03 | 37.00 | 97.63 |
| Re 2O 7/Al 2O 3 | 16 | 16.50 | 0.21 | 16.92 | 33.82 | 98.79 |
| Re 2O 7/Al 2O 3 | 20 | 13.67 | 0.58 | 16.13 | 30.87 | 96.53 |
[embodiment 8～11]
Take by weighing 3.68,5.52,7.36,9.20 gram ammonium molybdate sample (molecular formula (NH respectively
4)
6Mo
7O
244H
2O), place 5 glass beakers, each adds 50 milliliters of deionized waters, stirs solid sample is dissolved fully.Take by weighing 5 parts of each 50 grams through the dried γ-Al of roasting
2O
3(specific area is 278 meters squared per gram) puts into the glass beaker of 5 dryings respectively;
Pour the ammonium molybdate solution of above-mentioned variable concentrations into the different γ-Al that is equipped with respectively fast
2O
3Beaker in, left standstill 120 ℃ of dryings 10 hours after stirring 4 hours.Place tube furnace to feed dry air in the above-mentioned sample that makes, gas flow rate is controlled at 1000 ml/min, is warming up to 550 ℃ of roastings by 10 ℃ of per minute speed, and keeps 8 hours, and the content that makes molybdenum oxide is respectively 4%, 6%, 8%, 10% MoO
3/ Al
2O
3Catalyst sample.
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 marble fillers; With 2 gram MoO
3/ Al
2O
3Catalyst adds reactor, and the catalyst upper end adds 30 cubic centimetres again, and granularity is 10～20 order glass marble 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 120 ℃～150 ℃ reaction temperatures.
Reactor stops to feed nitrogen, and feeds the 99.5%1-butene feedstock from reactor upper end, and raw material flow rate is the control valve control by reactor outlet of 10 milliliters/hour, reaction system pressure, and pressure is controlled at 3MPa.Product after release by the gas-chromatography on-line analysis.Reaction result such as table 2.
Table 2 MoO
3/ Al
2O
3The 1-butylene of catalyst self disproportionated reaction performance
| MoO 3Content (% weight) | Weight space velocity (hour -1) | Reaction temperature | Yield (mole %) | Butene conversion (mole %) | Ethene+hexene selectivity (mole %) | ||
| Ethene | Propylene | Hexene | |||||
| 4 | 0.6 | 120 | 2.50 | 1.59 | 2.84 | 8.43 | 63.3 |
| 6 | 2.4 | 150 | 2.46 | 2.32 | 3.81 | 10.82 | 57.9 |
| 8 | 0.6 | 120 | 5.05 | 15.67 | 8.48 | 37.24 | 36.3 |
| 10 | 2.4 | 150 | 6.7 | 19.4 | 8.4 | 59.8 | 25.3 |
Claims (4)
1, the catalyst of a kind of butylene disproportionation system ethene and hexene 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; With carry thereon
(b) 1～20% be selected from oxide at least a among Re, Mo or the Co.
2,, it is characterized in that catalyst carrier is Al according to the catalyst of described butylene disproportionation system ethene of claim 1 and hexene
2O
3
3, according to the catalyst of described butylene disproportionation system ethene of claim 1 and hexene, it is characterized in that by weight percentage, contain 1～20% in the catalyst and be selected from oxide at least a among Re or the Mo.
4, according to the catalyst of described butylene disproportionation system ethene of claim 1 and hexene, it is characterized in that being selected from by weight percentage oxide consumption at least a among Re, Mo or the Co is 6～12%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100287939A CN100408165C (en) | 2005-08-15 | 2005-08-15 | Catalyst for preparing ethane and hexane through butene disproportionation |
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|---|---|---|---|
| CNB2005100287939A CN100408165C (en) | 2005-08-15 | 2005-08-15 | Catalyst for preparing ethane and hexane through butene disproportionation |
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| Publication Number | Publication Date |
|---|---|
| CN1915492A true CN1915492A (en) | 2007-02-21 |
| CN100408165C CN100408165C (en) | 2008-08-06 |
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ID=37736642
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030512A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for production of hexene by butene disproportionation |
| CN107737595A (en) * | 2017-10-23 | 2018-02-27 | 王卓 | A kind of preparation method of olefin isomerization catalyst |
| CN108080021A (en) * | 2017-12-18 | 2018-05-29 | 陕西省石油化工研究设计院 | It is a kind of to be used for oligomeric catalyst for preparing 1- hexenes of butylene disproportionation and its preparation method and application |
| CN109833915A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | Molybdenum loaded catalyst and preparation method thereof for 1- butylene self disproportionation reaction |
| CN113385208A (en) * | 2020-03-12 | 2021-09-14 | 中国科学院大连化学物理研究所 | Molybdenum-based catalyst and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6683019B2 (en) * | 2001-06-13 | 2004-01-27 | Abb Lummus Global Inc. | Catalyst for the metathesis of olefin(s) |
| CN1201862C (en) * | 2002-06-21 | 2005-05-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof |
-
2005
- 2005-08-15 CN CNB2005100287939A patent/CN100408165C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030512A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for production of hexene by butene disproportionation |
| CN103030512B (en) * | 2011-09-30 | 2015-10-21 | 中国石油化工股份有限公司 | The method of production of hexene by butene disproportionation |
| CN107737595A (en) * | 2017-10-23 | 2018-02-27 | 王卓 | A kind of preparation method of olefin isomerization catalyst |
| CN109833915A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | Molybdenum loaded catalyst and preparation method thereof for 1- butylene self disproportionation reaction |
| CN108080021A (en) * | 2017-12-18 | 2018-05-29 | 陕西省石油化工研究设计院 | It is a kind of to be used for oligomeric catalyst for preparing 1- hexenes of butylene disproportionation and its preparation method and application |
| CN108080021B (en) * | 2017-12-18 | 2020-11-17 | 陕西省石油化工研究设计院 | Catalyst for preparing 1-hexene through butene disproportionation and oligomerization, and preparation method and application thereof |
| CN113385208A (en) * | 2020-03-12 | 2021-09-14 | 中国科学院大连化学物理研究所 | Molybdenum-based catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100408165C (en) | 2008-08-06 |
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