CN104557402B - A kind of n-butene skeletal isomerization produces the method for isobutene. - Google Patents
A kind of n-butene skeletal isomerization produces the method for isobutene. Download PDFInfo
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Abstract
A kind of n-butene skeletal isomerization produces the method for isobutene., comprises the steps: a) to be loaded in reactor by the FER type molecular sieve catalyst that Si/Al mol ratio is 50～100, is warming up to 450～550 DEG C under atmosphere of inert gases；B) it is passed through at least containing the alkene that a kind of carbon number is 4～5 and the gaseous mixture A of noble gas composition；C) under atmosphere of inert gases, it is warming up to 600～700 DEG C, is preferably warming up to 600～650 DEG C；D) it is passed through at least containing the alkene that a kind of carbon number is 2～3 and the gaseous mixture B of noble gas composition, e) adjusts under atmosphere of inert gases to applicable isomerization reaction condition, be passed through containing n-butene raw material, carry out isomerization reaction.It is high that the method has initial isobutene. productivity, significantly shortens the advantage that productivity " climbs the phase ".
Description
Technical field
The present invention relates to a kind of method that n-butene skeletal isomerization produces isobutene..
Background technology
Along with the market continuous growth to high-knock rating gasoline demand, to the methyl-tert as octane enhancers mixed
The demand of butyl ether (MTBE) also increases.The total output of China MTBE in 2011 is more than 4,500,000 tons, and domestic MTBE dress
The average utilization of capacity put is only 60%, the under-supply bottleneck having become as MTBE industry development of raw material isobutene..
Along with the lighting of ethylene cracking material, and impacted, closely by ethane cracking route and methanol-to-olefins project
Nian Lai, the yield cracking carbon-4 originated as main isobutene. reduces year by year.On the other hand, methanol-to-olefins project
Fast development, its by-product carbon four provides more n-butene resource for market again.Therefore, by cheap and resourceful positive fourth
Alkene is raw material, by skeletal isomerization reaction, n-butene is tautomerized to isobutene., is re-used as the raw material of MTBE synthesis, will be to solve now
The stage MTBE most economical approach that there is lack of raw materials.
The technical scheme of existing n-butene skeletal isomerization preparing isobutene, all uses and contains n-butene raw material with catalyst at isomery
The technical scheme of contact under the conditions of change, catalyst is the key of this technology.Have now been found that for n-butene skeletal isomerization isobutyl
The catalyst of alkene reaction is mainly FER type, TON type and AEL type molecular sieve, wherein the catalysis activity of FER type molecular sieve, selectivity
And stability more superior (Hou vi ka J. and Ponec V., Catal. Rev.-Sci. Eng., 1997,39 (4),
319).
US 5,491,276 discloses a kind of method producing isobutene. for n-butene isomery, the process employs Si/
Al mol ratio be the FER type molecular sieve of 8.9 as catalyst, within the response time of first 10 hours, isobutene. productivity is by 20% liter
High to 35.7%, and after 15 hours, isobutene. productivity starts to be gradually reduced, catalyst gradually inactivates, after reacting 20 hours, and isobutyl
Alkene productivity drops to 27%.
US6,323,384 disclose a kind of linear alpha-olefin tautomerizes to FER type molecular sieve catalyst and the method for isoalkene, just
Beginning isobutene. productivity about 35%, after 20 hours reaction, isobutene. productivity drops to 28.8%.
Document (Krijn P. de Jong, et al. Stud. Surf. Sci. Catal., 1997,111,127)
Report, using FER molecular sieve that Si/Al mol ratio is 55 as catalyst, its catalyst life can reach more than 1200 hours, but
In initial 200 hours of its reaction, isobutene. productivity is then increased to 38% by 8%；Reaction 200 to 400 hours subsequently
In time, isobutene. productivity is increased to 40% by 38%；Within the response time of 400 to 1200 hours, isobutene. productivity maintains
About 40%.
The existing FER molecular sieve with the high silica alumina ratio technical scheme as catalyst, the advantage with catalyst life length, but
There is initial isobutene. productivity relatively low, and productivity " climbs the phase " longer deficiency.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of method that n-butene skeletal isomerization produces isobutene..The party
It is high that method has initial isobutene. productivity, significantly shortens the advantage that productivity " climbs the phase ".
A kind of n-butene skeletal isomerization produces the method for isobutene., comprises the steps:
A) the FER type molecular sieve catalyst that Si/Al mol ratio is 50～100 is loaded in reactor, at noble gas atmosphere
It is warming up to 450～550 DEG C under enclosing, is preferably warming up to 500～550 DEG C；
B) it is passed through at least containing the alkene that a kind of carbon number is 4～5 and the gaseous mixture A of noble gas composition, at alkene body
Long-pending air speed is 200～2000h-1, under the conditions of stagnation pressure (absolute pressure) is 0.1～1MPa, contact with catalyst bed 0.5～20 hour, its
Described in gaseous mixture A in, in terms of volumn concentration, carbon number be 4～5 alkene account for 1%～20%；
C) under atmosphere of inert gases, it is warming up to 600～700 DEG C, is preferably warming up to 600～650 DEG C；
D) it is passed through at least containing the alkene that a kind of carbon number is 2～3 and the gaseous mixture B of noble gas composition, at alkene body
Long-pending air speed is 200～2000h-1, under the conditions of stagnation pressure (absolute pressure) is 0.1～1MPa, contact with catalyst bed 0.5～20 hour, its
Described in gaseous mixture B in, in terms of volumn concentration, carbon number be 2～3 alkene account for 1%～20%；
E) adjust under atmosphere of inert gases to applicable isomerization reaction condition, be passed through containing n-butene raw material, carry out different
Structureization is reacted.
In the inventive method, described FER molecular sieve is selected from ferrierite, ZSM-35, NU-23 or FU-9, preferably
Ferrierite or ZSM-35.Described FER molecular sieve can be commercial goods or prepares by existing scheme.
In the inventive method, described noble gas includes one or more in nitrogen, helium, argon, preferably nitrogen.
In the inventive method, the carbon number described in step b) be 4～5 alkene include 1-butylene, cis-2-butene,
Trans-2-butene, isobutene., 1-amylene, 2-amylene, cis-2-amylene, trans-2-amylene, 2-methyl-1-butene alkene, 3-methyl isophthalic acid-fourth
Alkene, one or more mixture of 2-methyl-2-butene, preferably 1-butylene and 1-amylene.
In the inventive method, the carbon number described in step b) is alkene and the gaseous mixture A of noble gas composition of 4～5
In, carbon number be 4～5 alkene shared by the preferred scope of volume fraction be 10～20%.
In the inventive method, the preferred scope of the volume space velocity described in step b) is 200～1000h-1, stagnation pressure (absolute pressure)
Preferably scope 0.1～0.5MPa, time of contact, preferred scope was 5～10 hours.
In the inventive method, the carbon number described in step d) be the alkene of 2～3 be ethylene and propylene.
In the inventive method, the carbon number described in step d) is alkene and the gaseous mixture of noble gas composition of 2～3
In B, carbon number be 2～3 alkene shared by volume fraction be preferably 1%～10%, more preferably 5～10%.
In the inventive method, in step d), the preferred scope of volume space velocity is 200～1000h-1, stagnation pressure (absolute pressure) preferred
Scope 0.10～0.50MPa, time of contact, preferred scope was 5～10 hours.
In the inventive method, the isomerisation conditions described in step e) includes: reaction temperature is 350～450 DEG C, reaction pressure
(absolute pressure) preferably 0.10～0.5MPa, weight space velocity is 0.5～10h-1.The described raw material containing n-butene is from refinery or petrochemical industry
Carbon four or the by-product carbon four of methanol-to-olefins device after the ether of the methyl tertiary butyl ether(MTBE) device of factory, wherein n-butene mass content is
10～95%, preferably 30～90%, more preferably 50～90%.
The effect of the present invention and haveing an advantage that, is directly warming up to showing of reaction temperature then haptoreaction raw material with catalyst
Technical scheme is had to compare, during using the pretreated catalyst of the inventive method to be used for n-butene isomery production isobutene.,
Its initial isobutene. productivity improves more than twice, makes reaction unit be rapidly achieved the stable and running status of high yield isobutene..
Detailed description of the invention
Effect and the effect of the inventive method is further illustrated below by embodiment and comparative example, but following example
It is not construed as limiting the invention.
Hydrogen FER type molecular sieve used in following embodiment is provided by Shanghai brilliance molecular sieve company limited.Use
Chemical reagent, as indicated without special, is analytical reagent.Binding agent used by catalyst preparation is SW-17 type aluminium hydroxide
Powder, pore volume is 0.47-0.53ml/g, than table more than 250m2/ g, average pore size is 7.5-8.5 nm, Zibo Thailand photoinitiator chemical have
Limit company provides.
N-butene isomery prepares isobutene catalyst can use customary preparation methods, if Si/Al mol ratio is 50～100
FER type molecular sieve and binding agent and water mixing, by gained mixture through molding, be dried, roasting obtains final catalyst.Binding agent
Can be binding agent conventional in the catalyst preparation of this area, such as one or more in aluminium oxide, silicon dioxide or clay.Excellent
The binding agent of choosing is aluminium oxide, such as boehmite.Described catalyst can use squeezing and pressing method, pressed disc method, drip ball or spin
Comminution granulation molding, wherein preferably squeezing and pressing method molding.Catalyst is dried 5～20 hours in 80～150 DEG C after molding, is 400
～roasting 2～15 hours, sintering temperature preferably 450～600 DEG C at 600 DEG C.
Embodiment 1～2
By the Hydrogen FER molecular sieve that Si/Al mol ratio is 52 and 94, same to aluminium hydrate powder, sesbania powder, nitric acid and deionization
By evenly mixing, the stainless steel mold pressing plate then using 1.5 mm holes is extruded for water (mass ratio is 30:20:1.5:1:50).
Gained extrudate is first dried 24 hours at room temperature, dries 24 hours then at 110 DEG C, finally in 550 DEG C of roastings 12 hours, obtains
Final catalyst, respective markers is C-1 and C-2.
Embodiment 3
With C-1 as catalyst.
Pretreatment condition: first heat up 550 DEG C in nitrogen atmosphere, then switching is passed through 1-butylene volume fraction is 10%
1-butylene/nitrogen mixture A1, the volume space velocity of gaseous mixture A1 is 250h-1, stagnation pressure (absolute pressure) 0.20MPa, in 550 DEG C of process
5 hours.Then switch to nitrogen atmosphere, be warming up to 625 DEG C, then nitrogen is switched to containing the ethylene that volume of ethylene mark is 5%/
Nitrogen mixture B1, the volume space velocity of gaseous mixture B1 is 500h-1, stagnation pressure (absolute pressure) 0.20MPa, process 5 hours in 625 DEG C.
After ether, carbon four is as raw material, and raw material composition is shown in Table 1.Product uses Agilent 7890 type gas chromatogram online
Analyze.Product uses Agilent 7890 type gas chromatogram on-line analysis.
Table 1
Appreciation condition: use the catalyst preconditioning process of the present embodiment, required pretreatment time to be achieved, switch to
Nitrogen is cooled to 375 DEG C, is passed through carbon four after above-mentioned ether, and weight space velocity is 2h-1, stagnation pressure (absolute pressure) is to carry out under the conditions of 0.20MPa
N-butene skeletal isomerization, reaction result is listed in table 2.
Table 2
Embodiment 4
With C-2 as catalyst.
Pretreatment condition: first heat up 500 DEG C in nitrogen atmosphere, then switching is passed through 1-amylene volume fraction is 20%
1-amylene/nitrogen mixture A2, the volume space velocity of gaseous mixture A2 is 200h-1, stagnation pressure (absolute pressure) 0.30MPa, in 500 DEG C of process
5 hours.Then switch to nitrogen atmosphere, be warming up to 650 DEG C, then nitrogen is switched to containing the ethylene that volume of ethylene mark is 10%/
Nitrogen mixture B2, the volume space velocity of gaseous mixture B2 is 450h-1, stagnation pressure (absolute pressure) 0.30MPa, process 10 hours in 650 DEG C.
Appreciation condition: use the catalyst preconditioning process of the present embodiment, required pretreatment time to be achieved, switch to
Nitrogen is cooled to 450 DEG C, is passed through carbon four after ether described in embodiment 3, and weight space velocity is 3.5h-1, stagnation pressure (absolute pressure) is 0.50MPa bar
Carrying out n-butene skeletal isomerization under part, reaction result is listed in table 3.
Table 3
Embodiment 4
With C-2 as catalyst.
Pretreatment condition: first heat up 525 DEG C in nitrogen atmosphere, then switching is passed through 1-amylene volume fraction is 10%
1-amylene/nitrogen mixture A3, the volume space velocity of gaseous mixture A3 is 300h-1, stagnation pressure (absolute pressure) 0.13MPa, in 525 DEG C of process
10 hours.Then switch to nitrogen atmosphere, be warming up to 650 DEG C, then switch to nitrogen containing volume of ethylene mark be the third of 10%
Alkene/nitrogen mixture B3, the volume space velocity of gaseous mixture B3 is 300h-1, stagnation pressure (absolute pressure) 0.13MPa, process 5 hours in 650 DEG C.
Appreciation condition: use the catalyst preconditioning process of the present embodiment, required pretreatment time to be achieved, switch to
Nitrogen is cooled to 400 DEG C, is passed through carbon four after ether described in embodiment 3, and weight space velocity is 2.5h-1, stagnation pressure (absolute pressure) is 0.13MPa bar
Carrying out n-butene skeletal isomerization under part, reaction result is listed in table 4.
Table 4
Comparative example 1
With C-2 as catalyst, do not carry out pre-carbon distribution process, nitrogen atmosphere is directly warming up to 375 DEG C, is passed through embodiment
Carbon four after ether described in 3, weight space velocity is 2.0h-1, stagnation pressure (absolute pressure) is that to carry out n-butene skeletal isomerization under the conditions of 0.20MPa anti-
Should, reaction result is listed in table 5.
Table 5
Claims (13)
1. the method that a n-butene skeletal isomerization produces isobutene., it is characterised in that: comprise the steps:
A) the FER type molecular sieve catalyst that Si/Al mol ratio is 50～100 is loaded in reactor, under atmosphere of inert gases
It is warming up to 450～550 DEG C；
B) it is passed through at least containing the alkene that a kind of carbon number is 4～5 and the gaseous mixture A of noble gas composition, empty at alkene volume
Speed is 200～2000h-1, under the conditions of stagnation pressure is 0.1～1MPa in terms of absolute pressure, contact 0.5～20 hour with catalyst bed, wherein
In described gaseous mixture A, in terms of volumn concentration, carbon number be 4～5 alkene account for 1%～20%；
C) under atmosphere of inert gases, 600～700 DEG C it are warming up to；
D) it is passed through at least containing the alkene that a kind of carbon number is 2～3 and the gaseous mixture B of noble gas composition, empty at alkene volume
Speed is 200～2000h-1, under the conditions of stagnation pressure is 0.1～1MPa in terms of absolute pressure, contact 0.5～20 hour with catalyst bed, wherein
In described gaseous mixture B, in terms of volumn concentration, carbon number be 2～3 alkene account for 1%～20%；
E) adjust under atmosphere of inert gases to applicable isomerization reaction condition, be passed through containing n-butene raw material, carry out isomerization
Reaction.
Method the most according to claim 1, it is characterised in that: step a) is warming up to 500～550 under atmosphere of inert gases
℃；Step c) is warming up to 600～650 DEG C under atmosphere of inert gases.
Method the most according to claim 1, it is characterised in that: described FER molecular sieve is selected from ferrierite, ZSM-
35, NU-23 or FU-9.
Method the most according to claim 1, it is characterised in that: described noble gas includes in nitrogen, helium, argon
Plant or several.
Method the most according to claim 1, it is characterised in that: the carbon number described in step b) is the alkene bag of 4～5
Include 1-butylene, cis-2-butene, Trans-2-butene, isobutene., 1-amylene, cis-2-amylene, trans-2-amylene, 2-methyl-1-butene alkene,
3-methyl-1-butene, one or more mixture of 2-methyl-2-butene.
Method the most according to claim 5, it is characterised in that: the carbon number described in step b) is that the alkene of 4～5 is
1-butylene and 1-amylene.
Method the most according to claim 1, it is characterised in that: the carbon number described in step b) is the alkene of 4～5 and lazy
Property gas composition gaseous mixture A in, carbon number be 4～5 alkene shared by the preferred scope of volume fraction be 10～20%.
Method the most according to claim 1, it is characterised in that: the volume space velocity scope described in step b) is 200～1000h-1, in terms of absolute pressure, stagnation pressure scope is 0.1～0.5MPa, and time of contact is 5～10 hours.
Method the most according to claim 1, it is characterised in that: the carbon number described in step d) is that the alkene of 2～3 is
Ethylene and propylene.
Method the most according to claim 1, it is characterised in that: the carbon number described in step d) is the alkene of 2～3
With noble gas composition gaseous mixture B in, carbon number be 2～3 alkene shared by volume fraction be 1%～10%.
11. methods according to claim 1, it is characterised in that: in step d), volume space velocity scope is 200～1000h-1,
In terms of absolute pressure, stagnation pressure scope is 0.10～0.50MPa, and time of contact, scope was 5～10 hours.
12. methods according to claim 1, it is characterised in that: the isomerisation conditions described in step e) includes: reaction temperature
Being 350～450 DEG C, in terms of absolute pressure, reaction pressure is 0.10～0.5MPa, and weight space velocity is 0.5～10h-1。
13. methods according to claim 12, it is characterised in that: the described raw material containing n-butene is from refinery or petrochemical industry
Carbon four or the by-product carbon four of methanol-to-olefins device after the ether of the methyl tertiary butyl ether(MTBE) device of factory, wherein n-butene mass content is
10～95%.
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Citations (4)
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|---|---|---|---|---|
| US5321194A (en) * | 1992-05-11 | 1994-06-14 | Mobil Oil Corporation | N-olefin skeletal isomerization process using dicarboxylic acid treated zeolites |
| US5382743A (en) * | 1993-04-26 | 1995-01-17 | Mobil Oil Corporation | Skeletal isomerization of n-pentenes using ZSM-35 in the presence of hydrogen |
| US5491276A (en) * | 1992-12-12 | 1996-02-13 | Texaco Inc. | Skeletal isomerization of n-butylenes to isobutylene on zeolites |
| CN101475432A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for improving butene double bond isomerization reaction |
-
2013
- 2013-10-23 CN CN201310499283.4A patent/CN104557402B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5321194A (en) * | 1992-05-11 | 1994-06-14 | Mobil Oil Corporation | N-olefin skeletal isomerization process using dicarboxylic acid treated zeolites |
| US5491276A (en) * | 1992-12-12 | 1996-02-13 | Texaco Inc. | Skeletal isomerization of n-butylenes to isobutylene on zeolites |
| US5382743A (en) * | 1993-04-26 | 1995-01-17 | Mobil Oil Corporation | Skeletal isomerization of n-pentenes using ZSM-35 in the presence of hydrogen |
| CN101475432A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for improving butene double bond isomerization reaction |
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