CN102649674A - Method for double bond isomerization of n-butene - Google Patents
Method for double bond isomerization of n-butene Download PDFInfo
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- CN102649674A CN102649674A CN2011100454871A CN201110045487A CN102649674A CN 102649674 A CN102649674 A CN 102649674A CN 2011100454871 A CN2011100454871 A CN 2011100454871A CN 201110045487 A CN201110045487 A CN 201110045487A CN 102649674 A CN102649674 A CN 102649674A
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Abstract
The invention relates to a method for double bond isomerization of n-butene, and mainly solves the technical problem in the prior art that the reaction product selectivity is low, and the active period of a catalyst is short. Through the adoption of the technical scheme that under the conditions that the reaction temperature is 100 to 450 DEG C, the reaction pressure is -0.08 to 10 MPa, the weight space velocity is 0.1 to 100 hours<-1>, a n-butene raw material is in contact reaction with a catalyst to generate an effluent containing the butene-1 and butene-2 mol ratio close to a thermodynamic equilibrium value, wherein the catalyst comprises the following components in part by weight: (a) 90 to 100 parts of ZSM molecular sieve with silicon aluminum mole ratio being 40 to 1,000, (b) 0.001 to 10 parts of alkali metal element oxide, solonetz metal element oxide or other oxides on the ZSM molecular sieves, wherein the ZSM molecular sieve is a binderless molecular sieve, and the crushing strength of the catalyst is larger than 20 N/cm, and the invention solves the problems well, and can be used in the industrial production of double bond isomerization of n-butene.
Description
Technical field
The present invention relates to the method that a kind of n-butene carries out double-bond isomerization, particularly carry out the method for double-bond isomerization about butene-2 and butene-1.
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 simultaneously.
In sum, mainly there is the catalyst activity short or lower problem of selectivity in sexual cycle in prior art, and 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 new n-butene to carry out the method for double-bond isomerization.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 n-butene carries out the method for double-bond isomerization, and the raw material that contains n-butene contacts with catalyzer, is 100～450 ℃ in temperature of reaction; Reaction pressure is-0.08～10MPa, and weight space velocity is 0.1～100 hour
-1Condition under, reaction generates and to contain butene-1 and the butene-2 mol ratio elute near thermodynamic equilibrium value, wherein used catalyzer comprises following component in parts by weight:
A) 90～100 parts silica alumina ratio SiO
2/ Al
2O
3It is 40～1000 ZSM molecular sieve; With carry on it
B) 0.001～10 part basic metal, alkali earth metal or its oxide compound;
Wherein, the ZSM molecular sieve is the molecular sieve of binder free, and the crushing strength of catalyzer is greater than 20N/cm.
Reaction conditions is preferably in the technique scheme: temperature of reaction is 150～380 ℃, and reaction pressure is 0～2MPa, and weight space velocity is 1～60 hour
-1More preferably reaction conditions is: temperature of reaction is 180～350 ℃, and reaction pressure is 0～1.5MPa, and weight space velocity is 2～50 hours
-1The ZSM molecular sieve is at least a in ZSM-5, ZSM-11, ZSM-22, ZSM-48 or ZSM-35 preferably; More preferably at least a in ZSM-5 or ZSM-35 molecular sieve; In parts by weight, its consumption preferable range is greater than 92 parts, and more preferably scope is greater than 95 parts; Silica alumina ratio SiO
2/ Al
2O
3Preferable range is 60～800; Silica alumina ratio SiO
2/ Al
2O
3More preferably scope is 60～600.The crushing strength of catalyzer is preferably greater than 30N/cm.
Basic metal, alkali earth metal are preferably selected from least a in potassium, rubidium, caesium, magnesium, calcium, strontium or the barium.Basic metal, alkali earth metal more preferably are selected from least a in potassium, rubidium, magnesium, the calcium.The consumption preferable range of basic metal, alkali earth metal or its oxide compound is 0.01～8%, and more preferably scope is 0.01～6%.N-butene is preferably butene-1, butene-2 or does not meet the mixture that contains butene-1 and butene-2 of thermodynamic equilibrium value.
Catalyzer of the present invention prepares according to following method:
1, ZSM-type molecular sieve without binding agent preparation: with silica alumina ratio SiO
2/ Al
2O
3Be that 40～1000 ZSM type molecular sieve powder mixes with the amorphous silica sticker; After the moulding; 120 ℃ of dryings 12～24 hours, in the aqueous solution that contains halogenation organic amine and alkyl diamine or steam, be converted into ZSM-type molecular sieve without binding agent then through hydrothermal treatment consists; Wherein treatment temp is 120～250 ℃, and the treatment time is 10～240 hours.
2, catalyst modification: with the basic metal or the alkaline earth salt solution impregnation of ZSM-type molecular sieve without binding agent and requirement, oven dry, roasting then gets the ZSM type sieve catalyst of the modification of various basic metal or alkaline earth content.
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; The present inventor is surprised to find at research process, adopts ZSM-type molecular sieve without binding agent, and passes through the modification of basic metal or earth alkali metal; The strongly-acid position of neutralization part molecular sieve; Reduced the catalyzer that makes after the strength of acid of molecular sieve when carrying out the isomerization of butene reaction, the reaction product selectivity is high, and the activity of such catalysts cycle is long.In addition, the Adhesive-free Molecular Sieve for preparing for adopting mechanically mixing, generally its crushing strength is lower, and catalyzer is easy to crushing and can't normal reaction in reaction process.Adopt in-situ transesterification crystals growth preparation method to guarantee the binder free catalyzer that makes among the present invention, crushing strength is high, and activity stability is good.
The present invention adopts and comprises following component by weight percentage: (a) 90～100 parts silica alumina ratio SiO
2/ Al
2O
3It is 40～1000 ZSM molecular sieve; With the basic metal, alkali earth metal or its oxide compound that carry on it (b) 0.001～10 part; Wherein, the ZSM molecular sieve is the molecular sieve of binder free, and the crushing strength of catalyzer is greater than 20N/cm, by fixed-bed reactor; Raw material to contain n-butene contacts with catalyzer, is 100～450 ℃ in temperature of reaction, and reaction pressure is-0.08～10MPa; Weight space velocity is that when butylene was carried out double bond isomerization reaction, its purpose selectivity of product can be greater than 99% under 0.1～100 hour-1 the condition; 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]
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 60 ZSM-5 molecular sieve, add after 40 gram 40% (weight) silicon sol mix that extrusion moulding through 120 ℃ of oven dry, obtains sample A.
The tetrapropyl amine bromide, 10 grams 1 that add 5 grams in the reaction kettle in advance, the mixture of 6-hexanediamine and 30 gram zero(ppm) water places sealing back, the online side of reaction kettle Porous Stainless Steel under 180 ℃, to carry out gas-solid 10 gram sample A and handled (changeing brilliant process) mutually 100 hours.Product takes out the back and use distilled water wash, dry back in air atmosphere in 600 ℃ of roastings 2 hours.
Above-mentioned molecular sieve 50 grams are joined in 80 milliliters of aqueous solution that contain MgO 2.0 grams, under agitation be heated to driedly, 110 ℃ of oven dry are 8 hours then, 580 ℃ of roastings 4 hours.In parts by weight, getting catalyzer MgO is 3.8 parts, and molecular sieve is 96.2 parts a catalyzer, and its crushing strength is 35N/cm.
In temperature of reaction is 320 ℃, and reaction pressure is 0.2MPa, and weight space velocity is 8 hours
-1Condition under, be that raw material (by weight percentage, normal butane 17.8%, suitable-2-butylene 22.2%, anti--2-butylene 60%) carries out double bond isomerization reaction to adopting the refinery to take out surplus II, the transformation efficiency of its butene-2 is 21.5%, butene-1 selectivity 98.4%.After catalyst activity was carried out 3000 hours sexual cycle, it is stable that activity still keeps.
[embodiment 2～15]
With the identical preparation process of embodiment 1, change the SiO of molecular sieve
2/ Al
2O
3Mole is basic metal, alkaline earth content when, gets catalyzer, and adopt raw material appraisal result under the differential responses operating mode of enforcement 1 to see tabulation 1.
Table 1
Annotate: alkaline earth content is that benchmark calculates with its oxide content all in the foregoing description.
[embodiment 16]
Adopt the catalyzer of embodiment 6, under corresponding reaction conditions, carry out the catalyst life test, its result such as following table 2
Table 2
[comparative example 1]
Adopt preparation technology and the process of embodiment 1, just do not change brilliant process, and in total catalyst weight; MgO is 3.8 parts, and molecular sieve is 90.0 parts, and the sticker silicon oxide is 6.2 parts; Its crushing strength is 30N/cm; Also adopt raw material and the reaction conditions of embodiment 1, its reaction result is: the transformation efficiency of its butene-2 is 19.8%, butene-1 selectivity 96.1%.
[comparative example 2]
Adopt preparation technology and the process of embodiment 1, just take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 60 the laggard row metal load of ZSM-5 molecular screen primary powder direct mechanical moulding, in total catalyst weight, MgO is 3.8 parts; Molecular sieve is 96.2 parts, and sticker is 0 part, and its crushing strength is 5N/cm; Also adopt raw material and the reaction conditions of embodiment 1, its reaction result is: the transformation efficiency of its butene-2 is 21.6%, butene-1 selectivity 98.1%; But because intensity is low, after catalyst activity is carried out 400 hours sexual cycle, break-up of catalyst; Reactor drum pressure is excessive, and reaction can't normally be carried out and interrupt.
Claims (6)
1. a n-butene carries out the method for double-bond isomerization, and the raw material that contains n-butene 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
-1Condition under, reaction generates and to contain butene-1 and the butene-2 mol ratio elute near thermodynamic equilibrium value, wherein used catalyzer comprises following component in parts by weight:
A) 90～100 parts silica alumina ratio SiO
2/ Al
2O
3It is 40～1000 ZSM molecular sieve; With carry on it
B) 0.001～10 part basic metal, alkali earth metal or its oxide compound;
Wherein, the ZSM molecular sieve is the molecular sieve of binder free, and the crushing strength of catalyzer is greater than 20N/cm.
2. carry out the method for double-bond isomerization according to the said n-butene of claim 1, it is characterized in that temperature of reaction is 150～380 ℃, reaction pressure is 0～2MPa, and weight space velocity is 1～60 hour
-1At least a in ZSM-5, ZSM-11, ZSM-22, ZSM-48 or ZSM-35 of ZSM molecular screening, in parts by weight, its consumption is 92～100 parts, silica alumina ratio SiO
2/ Al
2O
3Be 60～800, the crushing strength of catalyzer is greater than 30N/cm.
3. carry out the method for double-bond isomerization according to the said n-butene of claim 2, it is characterized in that temperature of reaction is 180～350 ℃, reaction pressure is 0～1.5MPa, and weight space velocity is 2～50 hours
-1At least a in ZSM-5 or ZSM-35 molecular sieve of ZSM molecular screening; In parts by weight, its consumption is 93～100 parts, silica alumina ratio SiO
2/ Al
2O
3Be 60～600.
4. carry out the method for double-bond isomerization according to the said n-butene of claim 1, it is characterized in that basic metal, alkali earth metal are selected from least a in potassium, rubidium, caesium, magnesium, calcium, strontium or the barium; Consumption in parts by weight basic metal, alkali earth metal or its oxide compound is 0.01～8 part.
5. carry out the method for double-bond isomerization according to the said n-butene of claim 4, it is characterized in that basic metal, alkali earth metal are selected from least a in potassium, rubidium, magnesium, the calcium; Consumption in parts by weight basic metal, alkali earth metal or its oxide compound is 0.01～6 part.
6. carry out the method for double-bond isomerization according to the said n-butene of claim 1, it is characterized in that n-butene 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769204A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst used for production of isobutene via isomerization of n-butene skeleton, and preparation method and applications thereof |
| CN111013640A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Isomerization catalyst, preparation method and application thereof |
| CN111018649A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Method for producing 1-butene by isomerization |
| CN113773166A (en) * | 2021-08-31 | 2021-12-10 | 国药集团威奇达药业有限公司 | Olefin isomerization method |
| US11261141B2 (en) | 2017-12-14 | 2022-03-01 | Exxonmobil Chemical Patents Inc. | Processes for isomerizing alpha olefins |
| US11332420B2 (en) | 2017-12-14 | 2022-05-17 | Exxonmobil Chemical Patents Inc. | Processes for isomerizing alpha olefins |
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| US3475511A (en) * | 1967-10-02 | 1969-10-28 | Petro Tex Chem Corp | Butene-2 isomerization |
| 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
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Patent Citations (3)
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|---|---|---|---|---|
| US3475511A (en) * | 1967-10-02 | 1969-10-28 | Petro Tex Chem Corp | Butene-2 isomerization |
| 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 |
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Non-Patent Citations (1)
| Title |
|---|
| 程晓维等: "无粘结剂ZSM-5沸石催化剂骨架脱铝改性的研究", 《化学学报》, vol. 66, no. 19, 31 December 2008 (2008-12-31), pages 2099 - 2106 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769204A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst used for production of isobutene via isomerization of n-butene skeleton, and preparation method and applications thereof |
| US11261141B2 (en) | 2017-12-14 | 2022-03-01 | Exxonmobil Chemical Patents Inc. | Processes for isomerizing alpha olefins |
| US11332420B2 (en) | 2017-12-14 | 2022-05-17 | Exxonmobil Chemical Patents Inc. | Processes for isomerizing alpha olefins |
| CN111013640A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Isomerization catalyst, preparation method and application thereof |
| CN111018649A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Method for producing 1-butene by isomerization |
| CN113773166A (en) * | 2021-08-31 | 2021-12-10 | 国药集团威奇达药业有限公司 | Olefin isomerization method |
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Application publication date: 20120829 |