CN103420766A - Method for preparing 2-butene through 1-butene double bond isomerization - Google Patents
Method for preparing 2-butene through 1-butene double bond isomerization Download PDFInfo
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Abstract
The present invention relates to a method for preparing 2-butene through 1-butene double bond isomerization, wherein problems of low target product yield and poor stability in the prior art are mainly solved with the present invention. The technical scheme comprises that C4 olefin is adopted as a raw material, and the raw material passes through a catalyst bed layer at a reaction temperature of 200-450 DEG C under a reaction pressure (calculated as absolute pressure) of 0-5 MPa at a weight space velocity of 1-50 h<-1> to produce 2-butene, wherein a specific surface area of the catalyst is 200-1000 m<2>/g, a pore volume is 0.3-1.0 m<3>/g, an average pore size is 6-12 nm, and a surface alkaline site concentration is 0.3-10.0 mumol/g. With the technical scheme, the problems in the prior art are well solved, and the method can be used for industrial production of 2-butene preparation through 1-butene double bond isomerization.
Description
Technical field
The present invention relates to the method for a kind of 1-butylene double-bond isomerization 2-butylene processed.
Background technology
Double bond isomerization reaction, the namely transfer of position of double bond in olefin(e) compound, conversion of olefines that can relative importance is lower or superfluous is more valuable or relatively less isomer.
At present, market just progressively increases the demand of alhpa olefin, as 1-butylene, and 1-hexene etc.The production of business alhpa olefin usually is attended by a large amount of isomer and produces.With industrial C
4Logistics is example, and except containing 1-butylene, 2-butylene also accounts for significant proportion.By double bond isomerization reaction, 2-butylene can be converted into to 1-butylene.
On the other hand, in some technique, double bond isomerization reaction will make the boiling point of alkene change, thereby be conducive to product separation.An example, as C
4In the sepn process of hydro carbons, as 1-butylene (boiling point-6 ℃) is converted into to 2-butylene (4 ℃ of cis, trans 1 ℃), will make iso-butylene (boiling point-7 ℃) from C
4Separation in logistics becomes simple and easy to do.
In addition, double bond isomerizing catalyst usually combines to promote disproportionation reaction with disproportionation catalyst.In ethene and preparing propylene by butene disproportionation reaction, adding except 1-butylene being converted into to the required 2-butylene of reaction of isomerization catalyst, can make reactive behavior be greatly improved simultaneously.
Alkaline earth metal oxide, magnesium oxide, calcium oxide etc., be reported in the olefines double bond isomerizing reaction and have excellent catalytic performance, but under higher temperature of reaction, this class catalyst surface can be because the reasons such as coking be progressively lost its reactive behavior.The stability that how to keep this class isomerization catalyst, make its requirement that more adapts to industrial application, and the investigator has done a lot of work in this regard.
U.S. Pat 6,875,901 B2 point out by adopting the higher magnesium oxide of purity, can make the stability of butylenes double-bond isomerization reaction be extended.Sulphur content in magnesium oxide is down to 74ppm from 2335ppm, and iron level is from 692ppm is down to 330ppm, and the stability of catalyzer extended to 168 hours from 50 hours.
U.S. Pat 4,127,244 have reported a kind of renovation process of magnesium oxide isomerization catalyst.By in regeneration atmosphere, progressively increasing O
2Content, until in tail gas without CO
2Produce and pass into pure oxygen and continue roasting, can make the reactive behavior of catalyzer be improved, the catalyst surface carbon distribution reduces simultaneously, and catalyst stability is extended.
Method in above document, for the 2-butylene reaction processed of 1-butylene double-bond isomerization the time, all exists target product 2-butylene yield low, the problem of poor stability.
Summary of the invention
Technical problem to be solved by this invention is that the product 2-butylene yield existed in prior art is low, and the problem of poor stability provides a kind of method of new 1-butylene double-bond isomerization 2-butylene processed.When the method is used for isomerization reaction, have advantages of that the 2-butylene yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of 1-butylene double bond isomerization reaction generates the method for 2-butylene, take 1-butylene as raw material, in temperature of reaction, is 200 ~ 450 ℃, reaction pressure is counted 0 ~ 5MPa with absolute pressure, and weight space velocity is 1 ~ 50 hour
-1Under condition, raw material and catalyzer contact reacts generate 2-butylene, and wherein used catalyst by weight percentage, comprises following component:
A) 80 ~ 100% at least one oxide compound be selected from alkaline-earth metal;
B) 0 ~ 20% at least one being selected from neutrality or meta-alkalescence carrier;
Described specific surface area of catalyst is 200～1000m
2/ g, pore volume is 0.3 ~ 1.0m
3/ g, mean pore size is 6 ~ 12nm, the basic sites concentration on surface is 0.3 ~ 10.0umol/g.
In technique scheme, the preferable range of temperature of reaction is 200 ~ 400 ℃, and more preferably scope is 250 ~ 350 ℃; Reaction pressure be take the absolute pressure preferable range as 0.2 ~ 3MPa, and more preferably scope is 0.5 ~ 1MPa; Liquid phase air speed preferable range is 2 ~ 25 hours
-1, more preferably scope is 4 ~ 10 hours
-1.
Selected alkaline earth metal oxide preferred version is for being selected from calcium, magnesium, barium, strontium, at least one in the radium oxide compound; Described neutrality or meta-alkalescence carrier preferred version are for being selected from SiO
2Perhaps at least one in gac.Preferred technical scheme alkaline earth metal oxide is selected from magnesium oxide.Isomerization catalyst needs through calcination process in reactor, and the maturing temperature preferable range is 500～650 ℃, and the roasting time preferable range is 4～12 hours.
The preparation method of olefines double bond isomerizing catalyst comprises the following steps: (a) alkaline earth metal oxide of aequum is fully mixed with the acid solution of aequum, at 20 ~ 120 ℃ of temperature, stir 1 ~ 20h, obtain reaction product A; (b) through suction filtration, at 40 ~ 120 ℃ of temperature, dry 3 ~ 20h obtains the precursor B of catalyzer to reaction product A; (c) the precursor B of catalyzer is supported on the neutrality or meta-alkalescence carrier of aequum, under the condition that is 300 ~ 850 ℃ in temperature after drying, roasting 2 ~ 12h obtains required catalyzer; Wherein, the mass concentration of acid solution used is 1 ~ 15%, and acid is 0.1～5:1 with the mol ratio of oxide compound.
In technique scheme, preferred technical scheme mixing solutions stirs 5 ~ 15h under 40 ~ 100 ℃; After preferred technical scheme reaction product A suction filtration at 60 ~ 100 ℃ of temperature dry 6 ~ 16h; The maturing temperature preferable range is 400 ~ 600 ℃, and the roasting time preferable range is 3 ~ 10 hours; The mass concentration preferable range of acid solution is 3 ~ 10%; Acid is 0.5 ~ 3:1 with the mol ratio preferable range of oxide compound.
Alkaline earth metal oxide can be had an effect with acid solution, generates water-fast alkaline earth salt.High temperature sintering can make alkaline earth salt again dehydration obtain oxide compound.In said process, the Sauerstoffatom of dehydration may be from the Sauerstoffatom in solvent, may be also the Sauerstoffatom from former alkaline earth metal oxide plane of crystal.Therefore, dehydration will cause the surface imperfection of alkaline earth metal oxide, make the upper positively charged ion of exposure and the negative oxygen ion center of different ligancies of existing, surface, on limit, angle, cationic omission can form more negative oxygen ion group, alkalescence is improved, specific surface area also can increase simultaneously, is conducive to the raising of catalyzer isomerization performance.In temperature of reaction, be 200 ~ 450 ℃, reaction pressure is counted 0 ~ 5MPa with absolute pressure, 1-butylene weight space velocity be 1 ~ 50 hour
-1Under condition, by catalyzer and 1-butylene contact reacts, the weight yield of its 2-butylene can reach more than 80%, and catalyst life can reach 850 hours, has obtained technique effect preferably.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Take 50 gram commodity MgO, add containing 112.5 gram oxalic acid the acid solution that mass concentration is 5%, obtain mixing solutions after 50 ℃ of heating in water bath stir 5 hours, moisture in suction filtration solution, product is dried 6 hours at 120 ℃, 400 ℃ of roastings of products therefrom 5 hours, the product obtained is designated as JT-1.
Catalyzer 10 grams are arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 1 hour
-1, check and rate catalyst performance under 250 ℃ and 1MPa condition, the results are shown in list 2.
[embodiment 2]
Take 50 gram commodity MgO, add containing 120.09 gram citric acids, the solution that mass concentration is 1%, obtain mixing solutions after 80 ℃ of heating in water bath stir 4 hours standing 3 hours again, moisture in suction filtration solution, and product is dried 3 hours at 80 ℃, and products therefrom is supported on SiO
2(mass content 5%), 500 ℃ of roastings 8 hours, the product obtained is designated as JT-2.
Catalyzer 10 grams are arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 10 hours
-1, check and rate catalyst performance under 300 ℃ and 0.5MPa condition, the results are shown in list 2.
[embodiment 3]
Take 50 gram commodity CaO, add containing 5.54 gram carbonic acid, the solution that mass concentration is 10%, obtain mixing solutions after 90 ℃ of heating in water bath stir 1 hour standing 3 hours again, moisture in suction filtration solution, product is dried 10 hours at 100 ℃, and products therefrom is supported on gac (mass content 10%), 300 ℃ of roastings 12 hours, the product obtained is designated as JT-3.
Catalyzer 10 grams are arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 20 hours
-1, check and rate catalyst performance under 400 ℃ and 2MPa condition, the results are shown in list 2.
[embodiment 4]
Take 50 gram commodity BaO, add containing 148.5 gram oxalic acid, the solution that mass concentration is 15%, obtain mixing solutions after in 30 ℃ of heating in water bath, stirring 10 hours, moisture in suction filtration solution, and product is dried 18 hours at 60 ℃, and products therefrom is supported on activated carbon and SiO
2Mixture on (mass content 15% of the two), 700 ℃ of roastings 3 hours, the product obtained is designated as JT-4.
Catalyzer 10 grams are arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 30 hours
-1, check and rate catalyst performance under 450 ℃ and 3MPa condition, the results are shown in list 2.
[embodiment 5]
Take 50 gram commodity MgO, add containing 120.09 gram citric acids, the solution that mass concentration is 1%, and add containing 112.5 gram oxalic acid the acid solution that mass concentration is 5%, obtain mixing solutions after 80 ℃ of heating in water bath stir 4 hours standing 3 hours again, moisture in suction filtration solution, product is dried 3 hours at 80 ℃, and products therefrom is supported on gac (mass content 20%), 800 ℃ of roastings 2 hours, the product obtained is designated as JT-5.
Catalyzer 10 grams are arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 40 hours
-1, check and rate catalyst performance under 500 ℃ and 4MPa condition, the results are shown in list 2.
[embodiment 6]
Take 50 gram commodity MgO, 50 gram commodity BaO, add containing 240 gram citric acids, the solution that mass concentration is 3%, obtain mixing solutions after 80 ℃ of heating in water bath stir 4 hours standing 3 hours again, moisture in suction filtration solution, product is dried 3 hours at 80 ℃, and products therefrom is supported on SiO
2(mass content 5%), 850 ℃ of roastings 2 hours, the product obtained is designated as JT-6.
Catalyzer 10 grams are arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 50 hours
-1, check and rate catalyst performance under 200 ℃ and 5MPa condition, the results are shown in list 2.
[embodiment 7]
The sign of catalyzer.The specific surface of sample, pore volume, aperture is measured on the MicromeriticsASAP2000 physical adsorption appearance, and adsorbate is N
2, adsorption temp is liquid nitrogen temperature.The basic sites concentration on surface is at CO
2On the temperature programmed desorption(TPD) device of-TPD, carry out.The results are shown in Table 1.
Table 1
[comparative example 1]
Commodity MgO 10 grams are arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 1 hour
-1, check and rate catalyst performance under 250 ℃ and 1MPa condition, the results are shown in list 2.
[comparative example 2]
10 grams are loaded on to SiO
2Commodity CaO on (mass content is 10%), be arranged in the fixed-bed reactor of Φ 25mm, the 1-butylene that the weight content of take is 99.9% as raw material weight space velocity 10 hours
-1, check and rate catalyst performance under 300 ℃ and 0.5MPa condition, the results are shown in list 2.
Table 2
As can be seen from Table 2, under identical reaction conditions, the isomerization activity of JT-1 and JT-2 catalyzer is higher than the activity of comparative example 1 and 2, high 20% left and right of 2-butylene yield, and stability also is significantly improved, and can reach about 850 hours.
Claims (6)
1. the method for a 1-butylene double-bond isomerization 2-butylene processed, take 1-butylene as raw material, in temperature of reaction, is 200 ~ 500 ℃, and reaction pressure is counted 0 ~ 5MPa with absolute pressure, and weight space velocity is 1 ~ 50 hour
-1Under condition, raw material and catalyzer contact reacts generate 2-butylene, and wherein used catalyst by weight percentage, comprises following component:
A) 80 ~ 100% at least one oxide compound be selected from alkaline-earth metal;
B) 0 ~ 20% at least one being selected from neutrality or meta-alkalescence carrier;
Described specific surface area of catalyst is 200～1000m
2/ g, pore volume is 0.3 ~ 1.0m
3/ g, mean pore size is 6 ~ 12nm, the basic sites concentration on surface is 0.3 ~ 10.0umol/g.
2. the method for 1-butylene double-bond isomerization according to claim 1 2-butylene processed, is characterized in that temperature of reaction is 200 ~ 400 ℃, and reaction pressure is counted 0.2 ~ 3MPa with absolute pressure, and weight space velocity is 2 ~ 25 hours
-1.
3. the method for 1-butylene double-bond isomerization according to claim 2 2-butylene processed, is characterized in that temperature of reaction is 250 ~ 350 ℃, and reaction pressure is counted 0.5 ~ 1MPa with absolute pressure, and weight space velocity is 4 ~ 10 hours
-1.
4. the method for 1-butylene double-bond isomerization according to claim 1 2-butylene processed, is characterized in that selected alkaline earth metal oxide is preferably from calcium, magnesium, barium, strontium, at least one in the radium oxide compound; Described neutrality or meta-alkalescence carrier are selected from SiO
2Perhaps at least one in gac.
5. the method for 1-butylene double-bond isomerization according to claim 1 2-butylene processed, is characterized in that selected alkaline earth metal oxide preferential oxidation magnesium.
6. the method for 1-butylene double-bond isomerization according to claim 1 2-butylene processed, is characterized in that isomerization catalyst needs through calcination process in reactor, and maturing temperature is 500～650 ℃, and roasting time is 4～12 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923200A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Composite magnesium-based oxide catalyst and method for synthesis of hydroxypivalaldehyde |
| CN105037068A (en) * | 2015-06-26 | 2015-11-11 | 中石化炼化工程（集团）股份有限公司 | Preparation method of propylene and equipment |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120894A (en) * | 1988-09-19 | 1992-06-09 | Lyondell Petrochemical Company | Olefin conversion process |
| CN101121121A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Olefines double bond isomerizing catalyst and its preparation method |
-
2012
- 2012-05-16 CN CN201210150473.0A patent/CN103420766B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120894A (en) * | 1988-09-19 | 1992-06-09 | Lyondell Petrochemical Company | Olefin conversion process |
| CN101121121A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Olefines double bond isomerizing catalyst and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 王华军等: "正丁烯双键位置异构催化剂研究进展", 《化工进展》, vol. 26, no. 10, 2007 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923200A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Composite magnesium-based oxide catalyst and method for synthesis of hydroxypivalaldehyde |
| CN105037068A (en) * | 2015-06-26 | 2015-11-11 | 中石化炼化工程（集团）股份有限公司 | Preparation method of propylene and equipment |
| CN105037068B (en) * | 2015-06-26 | 2017-03-08 | 中石化炼化工程（集团）股份有限公司 | A kind of preparation method of propylene and equipment |
| 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 |
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