CN103772112B - A kind of method of n-butene skeletal isomerization preparing isobutene - Google Patents
A kind of method of n-butene skeletal isomerization preparing isobutene Download PDFInfo
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- CN103772112B CN103772112B CN201210408295.7A CN201210408295A CN103772112B CN 103772112 B CN103772112 B CN 103772112B CN 201210408295 A CN201210408295 A CN 201210408295A CN 103772112 B CN103772112 B CN 103772112B
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Abstract
The present invention discloses a kind of method of n-butene skeletal isomerization preparing isobutene, with SiO
2/ Al
2o
3mol ratio be 10 ~ 50 sodium potassium Hydrogen FER molecular sieve be catalyzer, be 300 ~ 600 DEG C containing the raw material of n-butene in temperature of reaction, reaction stagnation pressure is 0 ~ 0.25MPa, and weight space velocity is 0.5 ~ 20h
-1condition under occur skeletal isomerization reaction generate iso-butylene.In described sodium potassium Hydrogen FER molecular sieve, by weight percentage, Na
2o content is 0.1% ~ 0.5%, K
2o content is 4.0% ~ 6.3%.It is high that the method has initial selective isobutene, there is not remarkable selectivity and the advantage such as " to climb the phase ".
Description
Technical field
The present invention relates to a kind of method of n-butene skeletal isomerization preparing isobutene.
Background technology
Along with market is to the continuous growth of stop bracket gasoline demand, the demand of the methyl tertiary butyl ether as octane enhancers mixed (MTBE) is also increased thereupon.Such as China's gasoline production in 2011 8141.1 ten thousand tons, on average mixes different substances together aggregate demand than 4.5%, MTBE more than 3,500,000 tons in MTBE.The high market requirement of MTBE will certainly pull the demand to raw material iso-butylene, and the iso-butylene adopting traditional catalytic cracking and cracking of ethylene route to produce is difficult to meet the need of market.And on the other hand, the utilization ratio of the n-butene after MTBE by-product ether in carbon four is lower, is often mixed into civil liquefied gas and burns.
Normal butylenes in carbon after ether four can be iso-butylene by n-butene skeletal isomerization preparing isobutene technique, and recirculation is as MTBE raw material.This technique have raw materials cost low and be easy to get, technique is simple and invest low feature.Both can be the iso-butylene of high added value by the low value-added normal butylenes in carbon four after the ether of refinery and petrochemical plant, solve again the problem that the utilization ratio of carbon four is low after ether.
The method of existing n-butene skeletal isomerization preparing isobutene, all adopt the technical scheme contacted under isomerization conditions with catalyzer containing n-butene raw material, catalyzer is the key of this technology.Current discovery is used for catalyzer mainly FER type, TON type and the AEL type molecular sieve of n-butene skeletal isomerization preparing isobutene reaction, the wherein catalytic activity of FER type molecular sieve, selectivity and more superior (the Hou vi kaJ.andPonecV. of stability, Catal.Rev.-Sci.Eng.
1997,
39 (4), 319).
For FER type molecular sieve catalyst, lower in the selectivity of reaction starting stage iso-butylene, along with the generation of a large amount of side reaction and the formation of carbon distribution, due to the double influence of carbon distribution, there is significant selectivity " to climb the phase " (M é riaudeauP.andNaccacheC., Adv.Catal.
1999,
44, 505).As CN1068320A discloses a kind of the FER molecular sieve catalyzer and the method that normal olefine isomery are become isoolefine, on this kind of catalyzer, initial n-butene conversion is about 62%, and selective isobutene is less than 50%; And constantly little in reaction 40, n-butene conversion drops to about 48%, and selective isobutene is elevated to 85%.And for example US5,491,276 a kind of FER type molecular sieve catalyst and the methods disclosing n-butene skeletal isomerization preparing isobutene, on the catalyst, initial n-butene conversion is about 75%, and iso-butylene initial selectivity is only about 28%; Constantly little in reaction 20, n-butene conversion drops to 30%, and selective isobutene is elevated to more than 90%.For another example US6,323,384 disclose a kind of FER type molecular sieve catalyst and the method that linear alpha-olefin tautomerizes to isoolefine, and initial n-butene conversion is 50%, and selective isobutene is only 70%; Constantly little in reaction 20, n-butene conversion drops to about 32%, and selective isobutene rises to more than 90%.
Existing take FER molecular sieve as the technical scheme of catalyzer, there is starting stage selective isobutene low, and selectivity " is climbed the phase " longer deficiency.
Summary of the invention
Summary of the invention
For the deficiency that selective isobutene initial in prior art is low, the invention provides a kind of method of n-butene skeletal isomerization preparing isobutene of highly selective.It is high that the method has initial selective isobutene, there is not remarkable selectivity and the advantage such as " to climb the phase ".
The method of a kind of n-butene skeletal isomerization preparing isobutene of the present invention is as follows: with SiO
2/ Al
2o
3mol ratio be 10 ~ 50 FER molecular sieve be catalyzer, be 300 ~ 600 DEG C containing the raw material of n-butene in temperature of reaction, reaction stagnation pressure (absolute pressure) 0 ~ 0.25MPa, weight space velocity is at 0.5 ~ 20h
-1condition under occur skeletal isomerization reaction generate iso-butylene, wherein used FER molecular sieve is sodium potassium Hydrogen FER molecular sieve.
In the inventive method, by the weight percent meter of sodium potassium Hydrogen FER molecular sieve, Na
2o content is 0.1% ~ 0.5%, K
2o content is 4.0% ~ 6.3%.
The raw material containing n-butene described in aforesaid method is from the by-product carbon four of carbon four or methanol-to-olefins device after the ether of the methyl tertiary butyl ether device of refinery or petrochemical plant.Temperature of reaction preferable range is 350 ~ 450 DEG C, reaction pressure (absolute pressure) preferably 0.13 ~ 0.25MPa, and weight space velocity preferable range is 1 ~ 10h
-1.By the weight percent meter of sodium potassium Hydrogen FER molecular sieve, Na
2o content is preferably 0.1 ~ 0.4%, K
2o content is 4.5% ~ 6.3%.FER molecular sieve is selected from ferrierite, ZSM-35, NU-23 or FU-9, preferred ferrierite or ZSM-35, more preferably ferrierite.Sodium potassium Hydrogen FER molecular sieve SiO used
2/ Al
2o
3mol ratio preferable range is 10 ~ 20.
In the present invention, sodium potassium Hydrogen FER molecular sieve is that sodium potassium type FER molecular sieve exchanges through ammonium ion part, and then roasting obtains.Concrete preparation method comprises the steps: that sodium potassium type FER molecular sieve is pulled an oar with ammonium salt solution and mixes, under temperature is 20 ~ 95 DEG C of conditions preferably under 20 ~ 60 DEG C of conditions, exchange 1 ~ 2 hour, exchange disposed slurry after filtration, the thorough drip washing of filter cake deionized water, oven dry, roasting obtain sodium potassium Hydrogen FER molecular sieve.
In the preparation method of sodium potassium Hydrogen FER molecular sieve of the present invention, in ion-exchange slurries, the concentration of ammonium ion is 0.1 ~ 0.5mol/L.Ion-exchange slurries Middle molecule sieve powder is 1:10 to 1:30 with exchanging liquid mass ratio.The ammonium salt used is ammonium nitrate, one or more mixing in ammonium sulfate, ammonium chloride, ammonium acetate, ammonium phosphate, wherein preferably ammonium nitrate and ammonium chloride.The ion-exchange degree of FER molecular sieve is controlled by changing inorganic ammonium salt concentration of aqueous solution.
In the inventive method, the preparation process of sodium potassium Hydrogen FER molecular sieve is as follows: sodium potassium Hydrogen FER zeolite powder, binding agent, extrusion aid, mineral acid and water fully mix, and by gained mixture forming, drying, roasting obtain final catalyzer.Wherein sodium potassium Hydrogen FER content accounts for 10 ~ 90% by weight percentage, and all the other are binding agent.Wherein said binding agent can be binding agent conventional in the catalyst preparing of this area, as one or more mixtures in aluminum oxide, silicon-dioxide or clay.Preferred binding agent is aluminum oxide, as pseudo-boehmite.Extrusion aid is generally sesbania powder.Mineral acid is nitric acid, hydrochloric acid or sulfuric acid, shaping for making molecular sieve and binding agent be convenient to, the preferred nitric acid of wherein said mineral acid.Describedly shapingly adopt extrusion process, pressed disc method, drip ball or spin comminution granulation, wherein preferably extrusion process is shaping.Catalyzer is dried 5 ~ 20 hours in 80 ~ 150 DEG C after shaping, roasting 2 ~ 15 hours at being 400 ~ 600 DEG C, maturing temperature preferably 450 ~ 600 DEG C.
The inventive method is under the maintenance transformation efficiency of stationary phase and the condition of yield, improve the selectivity of initial iso-butylene significantly, solve selective isobutene " to climb the phase " longer problem, substantially reduce initial reaction transformation efficiency and optionally wave time, reaction unit is reached fast and carries out smooth running stationary phase.
Embodiment
Below by embodiment and comparative example, the present invention is set forth further.
Ferrerite Molecular sieve raw material used in the following example and comparative example, is provided by eastern Cao Da (Shanghai) trade Co., Ltd, content meter by weight, Na
2o content is 0.9%, K
2o content is 6.32%.The chemical reagent used, as indicated without special, is analytical reagent.Catalyst preparing binding agent used is SW-17 type aluminium hydrate powder, and pore volume is 0.47-0.53ml/g, is greater than 250m than table
2/ g, mean pore size is 7.5-8.5nm, and by Zibo, safe photoinitiator chemical company limited provides.
Embodiment 1 ~ 3
The preparation of sodium potassium Hydrogen FER molecular sieve.
By the NH of the concentration of ferrerite molecular sieve and different ammonium ion
4cl aqueous solution is evenly pulled an oar, change ferrerite molecular sieve solid and exchange liquid mass ratio, stir 2 hours under differing temps, filter, gained filter cake 30 times of deionized water cleaning downs to ferrerite molecular sieve butt weight, dry and 550 DEG C of roastings through 110 DEG C, obtain sodium potassium Hydrogen FER molecular sieve, be labeled as NaKH-1, NaKH-2 and NaKH-3 respectively.By weight percentage, the Na of the sodium potassium Hydrogen FER molecular sieve adopting x-ray fluorescence spectrometry to obtain
2o and K
2o content.Preparation condition and the Na recording sodium potassium Hydrogen FER molecular sieve
2o and K
2o content is in table 1.
Table 1
| Title | NH 4 +Concentration (mol/L) | Sieve/liquor ratio * (g/g) | Exchange temperature ( oC） | Na 2O content | K 2O content |
| NaKH-1 | 0.01 | 1/30 | 60 | 0.38 | 6.23 |
| NaKH-2 | 0.02 | 1/20 | 40 | 0.23 | 5.68 |
| NaKH-3 | 0.05 | 1/10 | 25 | 0.18 | 4.74 |
* ferrerite molecular sieve solid and exchange liquid mass ratio
By NaKH-1, mediate the dense thick paste body of formation with SW-17 aluminium hydrate powder, sesbania powder, nitric acid and deionized water (mass ratio is 42.5:7.5:1.5:1:50) at CD4X1TS type polyfunctional catalyst forming machine, adopt the stainless steel moulded board extrusion molding in 1.5mm hole.Gained extrudate prior to drying under room temperature 24 hours, then is dried 8 hours in 110 DEG C, and finally in 550 DEG C of roastings 12 hours, obtain final catalyzer, respective markers is C-1.Adopt identical forming method, NaKH-1 is replaced with NaKH-2 and NaKH-2 respectively, obtained final catalyzer C-2 and C-3.
Embodiment 4
Adopt the performance of n-butene skeletal isomerization reaction evaluating catalyzer.Before each evaluating catalyst, by catalyzer first pre-treatment 2 hours in the High Purity Nitrogen atmosphere of 500 DEG C, then temperature of reaction need be cooled to.With carbon after ether four for raw material, raw material composition is in table 1.Reaction product adopts the on-line analysis of Agilent7890 type gas-chromatography.Reaction product adopts the on-line analysis of Agilent7890 type gas-chromatography.
Table 1
| Component | Raw material composition (% by weight) |
| Carbon three | 0.12 |
| Trimethylmethane | 48.44 |
| Iso-butylene | 1.93 |
| 1-butylene | 14.41 |
| Cis-2-butene | 10.33 |
| Trans-2-butene | 15.15 |
| Normal butane | 9.52 |
| Carbon five | 0.09 |
Take C-1 as catalyzer, with carbon after ether four for raw material, at 450 DEG C, weight space velocity is 1h
-1, stagnation pressure is carry out n-butene skeletal isomerization under 0.5MPa condition, and reaction result lists in table 2.
Table 2
| Reaction times (h) | N-butene conversion (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 52.1 | 77.9 | 40.6 |
| 1 | 48.9 | 86.8 | 42.4 |
| 3.5 | 47.9 | 94.3 | 45.1 |
| 10 | 45.0 | 93.1 | 41.9 |
| 20 | 43.5 | 90.9 | 39.6 |
Embodiment 5
Take C-2 as catalyzer, with carbon four after the ether described in embodiment 4 for raw material, at 420 DEG C, weight space velocity is 4h
-1, stagnation pressure is carry out n-butene skeletal isomerization under 0.15MPa condition, and reaction result lists in table 3.
Table 3
| Reaction times (h) | N-butene conversion (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 60.5 | 56.2 | 34.0 |
| 3.5 | 55.2 | 70.2 | 38.8 |
| 10 | 49.7 | 78.5 | 39.0 |
| 20 | 45.6 | 88.6 | 40.4 |
Embodiment 6
Take C-3 as catalyzer, with carbon four after the ether described in embodiment 4 for raw material, at 350 DEG C, weight space velocity is 10h
-1, stagnation pressure is carry out n-butene skeletal isomerization under 0.25MPa condition, and reaction result lists in table 4..
Table 4
| Reaction times (h) | N-butene conversion (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 75.2 | 40.8 | 30.7 |
| 5 | 63.4 | 51.6 | 32.7 |
| 10 | 58.4 | 64.8 | 37.8 |
| 20 | 51.3 | 75.8 | 38.9 |
Comparative example 1
With embodiment 1 ~ 3, just sodium potassium Hydrogen FER molecular sieve is replaced with Hydrogen HFER, the preparation process of HFER molecular sieve is as follows: by the ferrerite molecular sieve of 200g, the NH of 214g
4cl and 4000g deionized water mixes making beating, stirs 2 hours at 75 DEG C, filters, repeat above-mentioned exchange process at least 5 times, through filtering after exchange, the 30 times of thorough drip washing of deionized water to NaK-FER zeolite butt weight of gained filter cake, dry and 550 DEG C of roastings through 110 DEG C, obtain HFER.The SiO of the HFER adopting x-ray fluorescence spectrometry to obtain
2/ Al
2o
3mol ratio 16.5.Adopt the method described in embodiment 1 ~ 3 shaping, the final catalyzer made is labeled as C-4.
Take C-4 as catalyzer, with carbon four after the ether described in embodiment 4 for raw material, at 450 DEG C, weight space velocity is 1h
-1, stagnation pressure is carry out n-butene skeletal isomerization under the condition of 0.15MPa, and reaction result lists in table 5.
Table 5
| Reaction times (h) | N-butene conversion (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 67.0 | 35.0 | 23.5 |
| 5 | 51.0 | 48.9 | 24.9 |
| 10 | 44.8 | 60.1 | 26.9 |
| 20 | 44.6 | 66.2 | 29.5 |
Claims (7)
1. a method for n-butene skeletal isomerization preparing isobutene, is characterized in that: with SiO
2/ Al
2o
3mol ratio be 10 ~ 50 sodium potassium Hydrogen FER molecular sieve be catalyzer, be 300 ~ 600 DEG C containing the raw material of n-butene in temperature of reaction, reaction stagnation pressure is 0 ~ 0.25MPa, and weight space velocity is 0.5 ~ 20h
-1condition under occur skeletal isomerization reaction generate iso-butylene, the described raw material containing n-butene is from the by-product carbon four of carbon four or methanol-to-olefins device after the ether of the methyl tertiary butyl ether device of refinery or petrochemical plant, in sodium potassium Hydrogen FER molecular sieve, by weight percentage, Na
2o content is 0.1% ~ 0.5%, K
2o content is 4.0% ~ 6.3%.
2. method according to claim 1, is characterized in that: temperature of reaction is 350 ~ 450 DEG C, and reaction stagnation pressure is 0.13 ~ 0.25MPa, and weight space velocity is 1 ~ 10h
-1.
3. method according to claim 1, is characterized in that: Na
2o content is 0.1 ~ 0.4%, K
2o content is 5.5% ~ 6.3%.
4. method according to claim 1, is characterized in that: FER molecular sieve is selected from ferrierite, ZSM-35, NU-23 or FU-9.
5. method according to claim 1, it is characterized in that: the preparation process of described catalyzer is as follows: sodium potassium Hydrogen FER zeolite powder, binding agent, extrusion aid, mineral acid and water fully mix, by gained mixture forming, drying, roasting obtain final catalyzer.
6. method according to claim 5, is characterized in that: described shaping employing extrusion process, pressed disc method, droplet ball or spin comminution granulation.
7. method according to claim 6, is characterized in that: catalyzer is dried 5 ~ 20 hours in 80 ~ 150 DEG C after shaping, roasting 2 ~ 15 hours at being 400 ~ 600 DEG C.
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| CN106675639B (en) * | 2015-11-09 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method that isobutene and high-knock rating gasoline are produced using n-butene as raw material |
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2012
- 2012-10-24 CN CN201210408295.7A patent/CN103772112B/en active Active
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| US4942027A (en) * | 1986-08-05 | 1990-07-17 | Shell Oil Company | Method for preparing ferrierite |
| US5510560A (en) * | 1993-08-30 | 1996-04-23 | Texaco Inc. | Skeletal isomerization of n-olefins to iso-olefins on binded ferrierite zeolites |
| CN101928011A (en) * | 2009-06-18 | 2010-12-29 | 中国石油化工股份有限公司 | Method for preparing ZSM-35 molecular sieve |
| CN103043682A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Sodium-potassium-hydrogen type ferrierite and method for preparing same |
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| Title |
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