CN102649673A - Method for isomerizing butene - Google Patents
Method for isomerizing butene Download PDFInfo
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- CN102649673A CN102649673A CN2011100454867A CN201110045486A CN102649673A CN 102649673 A CN102649673 A CN 102649673A CN 2011100454867 A CN2011100454867 A CN 2011100454867A CN 201110045486 A CN201110045486 A CN 201110045486A CN 102649673 A CN102649673 A CN 102649673A
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- butylene
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Abstract
The invention relates to a method for isomerizing butane. According to the method, the technical problems of low selectivity of a reaction product and short catalyst activity period in the prior art are mainly solved. The method disclosed by the invention comprises the following step that with water as a diluting agent, raw materials containing butane and a catalyst are contacted and react to generate an effluent which containing butane-1 and butane-2 and the mol ratio of the butane-1 to the butane-2 approaches to a thermodynamic equilibrium value under the conditions that the reaction temperature is 100-450DEG C, the reaction pressure is -0.08MPa to 10MPa, the weight space velocity is 0.1-100h<-1> and the mol ratio of water to the butane is (0.1-10):1, wherein the used catalyst is a ZSM molecular sieve of which the silicon-aluminum mol ratio of SiO2 to Al2O3 is 100-2000. According to the technical scheme, the problems are better solved. The method can be used for the industrial production of the butane isomerization.
Description
Technical field
The present invention relates to a kind of method of isomerization of butene, particularly about the method for butene-2 and butene-1 double-bond isomerization.
Background technology
1-butylene is the more active terminal olefin of a kind of chemical property; High purity butene-1 is mainly used in the comonomer of production of linear new LDPE (film grade) (LLDPE); LLDPE is because of having good high-temperature creep property, higher resistance to impact shock and heat-resisting, wear resisting property; Especially suit to make hot water tubing, so become the thermoplastic macromolecule material that increases rapidly in recent years; Simultaneously; Other oligomerisation product of 1-butylene; Except that synthetic better LLDPE of alternative 1-butylene and HDPE, also can be used for automobile and oil dope, synthetic detergent in a large number, tensio-active agent and softening agent, printing and dyeing agent, emulsifying agent etc. like dimer 1-octene and tripolymer dodecylene; Its purposes is very extensive, and consumption increases year by year.The market of 1-butylene interpolymer, especially new LDPE (film grade) (LLDPE) is good, and having driven the 1-butylene demand rapidly increases.But what situation was different is, the manufacturer of 1-butylene has only minority externally to sell product, and this has more aggravated the nervous situation of 1-butylene supply and demand.
At present, global 1-butylene is produced route and is mainly contained two kinds, and a kind of is to be the oligomerization process of raw material with ethene, and another kind is to be the extraction process of raw material with the C4 hydrocarbon, and the latter accounts for 64.5% of aggregated capacity.Because the ethene imbalance between supply and demand is very outstanding, and price is higher, so the technological line that adopts ethylene dimerization to produce 1-butylene faces the higher immense pressure of production cost.And obtain the technological line of 1-butylene through extraction process for C-4-fraction; Usually will pass through divinyl extracting or hydrogenation and remove divinyl, iso-butylene etherificate, obtain the higher butene-1 product of purity after accurate the separation then, and the while by-product is rich in the hydrocarbon mixture (mainly being butene-2 and normal butane) of butene-2.If, be converted into 1-butylene through isomerization reaction with this part butene-2, and then the separation that circulates; Or the purpose of separating the high-purity butene-1 of realization raising the output separately; Its less investment income is high, and for improving carbon four hydrocarbon comprehensive utilization values, it is significant to promote the business economic benefit.In recent years, relevant both at home and abroad petro-chemical corporation produces great interest to the technology of butene-2 isomery production butene-1.
And opposite situation is; Under the certain condition; Petro-chemical corporation need turn to butene-2 with the butene-1 isomery and be used to produce methylethylketone, and raw material for alkylation or be the raw material of ethylene butene disproportionation system propylene mainly is the low-temperature hydro isomerization technique and be used for the technology that butene-1 tautomerizes to butene-2 at present; Obviously the consumption of hydrogen, there are problems in higher pressure and optionally controlling etc.
Disclose a kind of isomerization of olefins that adopts the alkaline metal oxide catalyzer among the document WO 02/096843A1 (CN1511126A),, be preferably high purity magnesium oxide, in fixed-bed reactor, realized nonterminal olefin such as 2-alkene manufacturing 1-butylene like Natural manganese dioxide.Although this method can be at high temperature about 340～500 ℃ realize that 20%～30% 2-butylene is converted into 1-butylene; But its significant disadvantages is, the raw materials pretreatment trouble is prone to poisoned by air, steam and acid, alkalization material; Catalyst life is shorter, generally only has tens hours.Document WO 02094433A1 (ABB) CN1522175A) above-mentioned activation or the renovation process that is used for the alkaline metal oxide catalyzer of isomerisation of olefin has been detailed; Promptly under active state; Make catalyst activation through contacting with the deoxidation nitrogen that contains no more than 5 volume ppm molecular oxygens; However, be very small to the improved effect of isomerization catalyst activity cycle.
Al introduced in research one literary composition of document (petrochemical complex, 18 (2), 1989:75～80) 2-butylene isomerization catalyst
2O
3Catalyzer (specific surface 85.8 meters squared per gram); With a small amount of transition metal oxide modification; Can realize isomerization reaction, but this catalyzer temperature in isomerization reaction is very high, by product is more in the reaction process; Through this catalyzer of verification experimental verification decay of activity after 500 hours reaction times, the selectivity of butene-1 is lower than 98% simultaneously.
In sum, mainly have the catalyst activity short or lower problem of selectivity in sexual cycle in the prior art, this uses industry practice and brings big difficulty.
Summary of the invention
Technical problem to be solved by this invention is that the reaction product selectivity that in the past exists in the technical literature is low, and catalyst activity short problem in sexual cycle provides a kind of method of new isomerization of butene.It is high that this method has the reaction product selectivity, catalyst activity long advantage in sexual cycle.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method of isomerization of butene is a thinner with water; The raw material that contains butylene contacts with catalyzer; In temperature of reaction is 100～450 ℃, and reaction pressure is-0.08～10MPa, and weight space velocity is 0.1～100 hour
-1, the mol ratio of water and butylene is under 0.1～10: 1 the condition, and reaction generates and contains butene-1 and the butene-2 mol ratio elute near thermodynamic equilibrium value, and wherein used catalyzer is silica alumina ratio SiO
2/ Al
2O
3It is 100～2000 ZSM molecular sieve.
Reaction conditions is preferably in the technique scheme: temperature of reaction is 150～380 ℃, and pressure is 0～2MPa, and weight space velocity is 1～60 hour
-1, the mol ratio of water and butylene is 0.2～8: 1; Reaction conditions is more preferably: temperature of reaction is 180～350 ℃, and pressure is 0～1.5MPa, and weight space velocity is 2～50 hours
-1, the mol ratio of water and butylene is 0.2～6: 1.The silica alumina ratio SiO of catalyzer
2/ Al
2O
3Preferable range is 150～1000, and more preferably scope is 150～800; The ZSM molecular sieve is preferably from ZSM-5 molecular sieve, ZSM-35 molecular sieve or ZSM-11 molecular sieve, more preferably from the ZSM-5 molecular sieve.
Butene feedstock is butene-1, butene-2 or the mixture that contains butene-1 and butene-2 that does not meet thermodynamic equilibrium value in the technique scheme.
As everyone knows, the character of butylene is more active, and the required activation energy of butylenes double-bond isomerization reaction is very low; If the active sites acidity that catalyzer provided is on the low side, difficult guarantee of activity of such catalysts cycle is if the activity of such catalysts position is too strong; When the butylenes double-bond isomerization reaction took place, butylene skeletal isomerization and cracking and polyreaction all can take place, thereby cause purpose product selectivity variation; And the water stronger oxide compound that is polarity, under the condition that multiple oxide compound exists, because the existence of competitive adsorption; Make generally; Water is preferentially adsorbed on the active sites, and this can play the effect that catalyzer is modified to a certain extent, and then improves catalytic perfomance.For the isomerization of butene reaction, the present inventor is surprised to find at research process, the introducing of diluent water, and when catalyzer carried out the isomerization of butene reaction, the reaction product selectivity improved, and there is bigger improvement in the activity of such catalysts cycle.
The present invention adopts silica alumina ratio SiO
2/ Al
2O
3Being that 100～2000 ZSM molecular sieve is a catalyzer, by fixed-bed reactor, is thinner with water, and the raw material that contains butylene contacts with catalyzer, is 100～450 ℃ in temperature of reaction, and reaction pressure is-0.08～10MPa, and weight space velocity is 0.1～100 hour
-1, the mol ratio of water and butylene is under 0.1～10: 1 the condition butylene to be carried out isomerization reaction, and its purpose selectivity of product can be greater than 99%, and catalyzer is after reaction 3000 hours, and activity remains unchanged, and has obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1～9]
Reference literature CN200310108177.5 is according to silica alumina ratio (SiO
2/ Al
2O
3) be respectively the slurry that contains silicon, aluminium, template and water of 200 ratio preparation, at 130 ℃, under 70 hours conditions; Synthetic 150 gram ZSM-5 molecular sieves; After adding 18 gram 40% (weight) silicon sol mixing then, extrusion moulding is through 120 ℃ of oven dry; In 550 ℃ of roastings 4 hours, make required catalyzer.
With the above-mentioned catalyzer that makes, in the fixed-bed reactor of packing into, adopting the refinery to take out surplus II is raw material (by weight percentage, normal butane 17.8%, suitable-2-butylene 22.2%, anti--2-butylene 60%), is 8 hours at weight space velocity
-1, pressure is normal pressure, the mol ratio of water and butylene is that the butene-2 of differential responses temperature tautomerizes to the reaction result such as the following table 1 of butene-1 under 0.5: 1 the condition:
Table 1
| Sequence number | Temperature (℃) | The butene-2 transformation efficiency, % | The butene-1 selectivity, % |
| 1 | 150 | 9.32 | 99.52 |
| 2 | 200 | 13.25 | 99.43 |
| 3 | 250 | 16.01 | 99.35 |
| 4 | 300 | 19.62 | 99.28 |
| 5 | 320 | 20.06 | 98.85 |
| 6 | 340 | 22.10 | 98.93 |
| 7 | 360 | 23.24 | 97.01 |
| 8 | 380 | 25.34 | 96.46 |
| 9 | 400 | 27.94 | 92.13 |
[embodiment 10～19]
Each step according to embodiment 1 makes the isomerization of butene catalyzer, just silica alumina ratio (the SiO of ZSM-5 molecular sieve
2/ Al
2O
3) 300, adopting the refinery to take out surplus II is raw material (by weight percentage, normal butane 17.8%, suitable-2-butylene 22.2%, anti--2-butylene 60%), is 320 hours in temperature
-1, pressure is 0.1MPa, the mol ratio of water and butylene is that butene-2 tautomerizes to the reaction result such as the following table 2 of butene-1 under the differential responses weight space velocity condition under 0.3: 1 the condition:
Table 2
| Sequence number | Weight space velocity | The butene-2 transformation efficiency, % | The butene-1 selectivity, % |
| 10 | 0.48 | 21.66 | 94.68 |
| 11 | 2.15 | 21.25 | 96.84 |
| 12 | 8.43 | 30.63 | 97.71 |
| 13 | 13.11 | 20.38 | 98.47 |
| 14 | 16.98 | 20.24 | 99.02 |
| 15 | 20.36 | 20.05 | 99.24 |
| 16 | 35.77 | 20.05 | 97.62 |
| 17 | 40.89 | 19.51 | 99.52 |
| 18 | 50.38 | 17.06 | 98.02 |
| 19 | 90.68 | 14.43 | 98.93 |
[embodiment 20]
Each step according to embodiment 1 makes the isomerization of butene catalyzer, just silica alumina ratio (the SiO of ZSM-5 molecular sieve
2/ Al
2O
3) be 400, the employing butene-2 is a raw material, is 250 ℃ in temperature, weight space velocity 2 hours
-1, pressure is 0.5MPa, the mol ratio of water and butylene is under 0.8: 1 the condition; Butene-2 tautomerizes to the reaction result of butene-1: the butene-2 transformation efficiency is 16.8%; The butene-1 selectivity is 98.11%, and after the catalyst activity test was carried out 3000 hours, it is stable that activity still keeps.
[embodiment 21]
Each step according to embodiment 1 makes the isomerization of butene catalyzer, just silica alumina ratio (the SiO of ZSM-5 molecular sieve
2/ Al
2O
3) be 800, adopting pure butene-1 is raw material, is 150 ℃ in temperature, weight space velocity 3 hours
-1, pressure is 0.2MPa, the mol ratio of water and butylene is under 1: 1 the condition; Butene-1 tautomerizes to the reaction result of butene-2: the butene-1 transformation efficiency is 86.6%; The butene-2 selectivity is 98.8%, and after the catalyst activity test was carried out 5000 hours, it is stable that activity still keeps.
[embodiment 22]
Each step according to embodiment 1 makes the isomerization of butene catalyzer, and just molecular sieve adopts the ZSM-35 molecular sieve, and the silica alumina ratio (SiO of ZSM-35 molecular sieve
2/ Al
2O
3) be 150, adopting pure butene-1 is raw material, is 280 ℃ in temperature, weight space velocity 10 hours
-1, pressure is-0.06MPa, the mol ratio of water and butylene is under 5: 1 conditions; Butene-1 tautomerizes to the reaction result of butene-2: the butene-1 transformation efficiency is 82.03%; The butene-2 selectivity is 98.55%, and after the catalyst activity test was carried out 3000 hours, it is stable that activity still keeps.
[embodiment 23]
Each step according to embodiment 1 makes the isomerization of butene catalyzer, and just molecular sieve adopts the ZSM-11 molecular sieve, and the ZSM-11 molecular sieve silica alumina ratio (SiO
2/ Al
2O
3) be 170, adopting pure butene-1 is raw material, is 300 ℃ in temperature, weight space velocity 18 hours
-1, pressure is 0.8MPa, the mol ratio of water and butylene is under 8: 1 conditions; Butene-1 tautomerizes to the reaction result of butene-2: the butene-1 transformation efficiency is 80.28%; The butene-2 selectivity is 98.15%, and after the catalyst activity test was carried out 3000 hours, it is stable that activity still keeps.
[comparative example 1]
Each step and operational condition according to embodiment 21; Just do not add diluent water in the reaction process, its reaction result is: the butene-1 transformation efficiency is 87.1%, and the butene-2 selectivity is 95.7%; When activity rating of catalyst was 2500 hours, activity began decay.
[comparative example 2]
Each step and operational condition according to embodiment 23; Just do not add diluent water in the reaction process, its reaction result is: the butene-2 transformation efficiency is 20.06%, and the butene-1 selectivity is 94.31%; When activity rating of catalyst was 1800 hours, activity began decay.
Claims (4)
1. the method for an isomerization of butene is a thinner with water, and the raw material that contains butylene contacts with catalyzer, is 100～450 ℃ in temperature of reaction, and reaction pressure is-0.08～10MPa, and weight space velocity is 0.1～100 hour
-1, the mol ratio of water and butylene is under 0.1～10: 1 the condition, and reaction generates and contains butene-1 and the butene-2 mol ratio elute near thermodynamic equilibrium value, and wherein used catalyzer is silica alumina ratio SiO
2/ Al
2O
3It is 100～2000 ZSM molecular sieve.
2. according to the method for the said isomerization of butene of claim 1, it is characterized in that temperature of reaction is 150～380 ℃, pressure is 0～2MPa, and weight space velocity is 1～60 hour
-1, the mol ratio of water and butylene is 0.2～8: 1; The silica alumina ratio SiO of catalyzer
2/ Al
2O
3Be 150～1000, the ZSM molecular screening is from ZSM-5 molecular sieve, ZSM-35 molecular sieve or ZSM-11 molecular sieve.
3. according to the method for the said isomerization of butene of claim 2, it is characterized in that temperature of reaction is 180～350 ℃, pressure is 0～1.5MPa, and weight space velocity is 2～50 hours
-1, the mol ratio of water and butylene is 0.2～6: 1; The silica alumina ratio SiO of catalyzer
2/ Al
2O
3Be 150～800, the ZSM molecular screening is from the ZSM-5 molecular sieve.
4. according to the method for the said isomerization of butene of claim 1, it is characterized in that butene feedstock is butene-1, butene-2 or the mixture that contains butene-1 and butene-2 that does not meet thermodynamic equilibrium value.
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| CN2011100454867A CN102649673A (en) | 2011-02-25 | 2011-02-25 | Method for isomerizing butene |
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|---|---|---|---|
| CN2011100454867A CN102649673A (en) | 2011-02-25 | 2011-02-25 | Method for isomerizing butene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272800A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Method for isomerizing butene-2 into butene-1 |
| CN112794783A (en) * | 2019-11-14 | 2021-05-14 | 赢创运营有限公司 | Process for isomerization of olefins |
Citations (2)
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|---|---|---|---|---|
| CN1662478A (en) * | 2002-06-18 | 2005-08-31 | 埃克森美孚化学专利公司 | Method for isomerizing a mixed olefin feedstock to 1-olefin |
| CN1902149A (en) * | 2003-12-30 | 2007-01-24 | 巴斯福股份公司 | Method for the production of butadiene and 1-butene |
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2011
- 2011-02-25 CN CN2011100454867A patent/CN102649673A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1662478A (en) * | 2002-06-18 | 2005-08-31 | 埃克森美孚化学专利公司 | Method for isomerizing a mixed olefin feedstock to 1-olefin |
| CN1902149A (en) * | 2003-12-30 | 2007-01-24 | 巴斯福股份公司 | Method for the production of butadiene and 1-butene |
Non-Patent Citations (1)
| Title |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272800A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Method for isomerizing butene-2 into butene-1 |
| CN105272800B (en) * | 2014-07-24 | 2018-07-17 | 中国石油化工股份有限公司 | The method that butene-2 is isomerized to butene-1 |
| CN112794783A (en) * | 2019-11-14 | 2021-05-14 | 赢创运营有限公司 | Process for isomerization of olefins |
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Application publication date: 20120829 |