CN103420766B - 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 PDF

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CN103420766B
CN103420766B CN201210150473.0A CN201210150473A CN103420766B CN 103420766 B CN103420766 B CN 103420766B CN 201210150473 A CN201210150473 A CN 201210150473A CN 103420766 B CN103420766 B CN 103420766B
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butylene
reaction
bond isomerization
temperature
butene
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CN103420766A (en
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董静
刘苏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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

The method of 1-butylene double-bond isomerization 2-butylene
Technical field
The present invention relates to a kind of method of 1-butylene double-bond isomerization 2-butylene.
Background technology
Double bond isomerization reaction, conversion of olefines lower or superfluous for relative importance can be more valuable or relatively less isomer by the namely transfer of position of double bond in olefin(e) compound.
At present, the demand of market to alhpa olefin just progressively increases, as 1-butylene, and 1-hexene etc.The production of business alhpa olefin is usually 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 1-butylene.
On the other hand, in some technique, double bond isomerization reaction changes making the boiling point of alkene, thus is conducive to product separation.An example, as C 4in the sepn process of hydro carbons, as 1-butylene (boiling point-6 DEG C) being converted into 2-butylene (cis 4 DEG C, trans 1 DEG C), iso-butylene (boiling point-7 DEG C) will be made 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, the 2-butylene added except being converted into by 1-butylene needed for reaction of isomerization catalyst, can make reactive behavior be greatly improved simultaneously.
Alkaline earth metal oxide, magnesium oxide, calcium oxide etc., be reported in olefines double bond isomerizing reaction and have excellent catalytic performance, but in high reaction temperatures, this kind of catalyst surface can because the reasons such as coking progressively lose its reactive behavior.How to keep the stability of this kind of isomerization catalyst, make it more adapt to the requirement of industrial application, investigator has done a lot of work in this regard.
US Patent No. 6,875,901 B2 point out that the stability that butylenes double-bond isomerization can be made to react is extended by adopting the magnesium oxide that purity is higher.When the sulphur content in magnesium oxide is down to 74ppm from 2335ppm, after iron level is down to 330ppm from 692ppm, the stability of catalyzer extended to 168 hours from 50 hours.
US Patent No. 4,127,244 renovation process reporting a kind of magnesium oxide isomerization catalyst.By progressively increasing O in regeneration atmosphere 2content, until without CO in tail gas 2produce and pass into pure oxygen and continue roasting, the reactive behavior of catalyzer can be made to be improved, and catalyst surface carbon distribution reduces simultaneously, and catalyst stability is extended.
When reacting for 1-butylene double-bond isomerization 2-butylene, all there is target product 2-butylene yield low, the problem of poor stability in the method in above document.
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, the problem of poor stability, provides a kind of method of new 1-butylene double-bond isomerization 2-butylene.When the method is used for isomerization reaction, there is the advantage that 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, and taking 1-butylene as raw material, is 200 ~ 450 DEG C in temperature of reaction, reaction pressure counts 0 ~ 5MPa with absolute pressure, and weight space velocity is 1 ~ 50 hour -1under condition, raw material and catalyst exposure react and generate 2-butylene, and wherein catalyst comprises following component:
A) 80 ~ 100% at least one oxide compound in alkaline-earth metal is selected from;
B) 0 ~ 20% at least one in neutrality or meta-alkalescence carrier is selected from;
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, and 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 DEG C, and more preferably scope is 250 ~ 350 DEG C; Reaction pressure is in absolute pressure preferable range for 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 for being selected from calcium, magnesium, barium, strontium, at least one in radium oxide compound; Described neutrality or meta-alkalescence carrier preferred version are for being selected from SiO 2or at least one in gac.Preferred technical scheme alkaline earth metal oxide is selected from magnesium oxide.Isomerization catalyst needs in the reactor through calcination process, and maturing temperature preferable range is 500 ~ 650 DEG C, and roasting time preferable range is 4 ~ 12 hours.
The preparation method of olefines double bond isomerizing catalyst, comprises the following steps: the alkaline earth metal oxide of aequum fully mixes with the acid solution of aequum by (a), stirs 1 ~ 20h, obtain reaction product A at 20 ~ 120 DEG C of temperature; B () reaction product A is through suction filtration at 40 ~ 120 DEG C of temperature, dry 3 ~ 20h obtains the precursor B of catalyzer; On c neutrality that the precursor B of catalyzer is supported on aequum by () or meta-alkalescence carrier, be that under the condition of 300 ~ 850 DEG C, roasting 2 ~ 12h obtains required catalyzer in temperature after drying; 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 at 40 ~ 100 DEG C; After preferred technical scheme reaction product A suction filtration at 60 ~ 100 DEG C of temperature dry 6 ~ 16h; Maturing temperature preferable range is 400 ~ 600 DEG C, and 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, also may be the Sauerstoffatom from former alkaline earth metal oxide plane of crystal.Therefore, dehydration will cause the surface imperfection of alkaline earth metal oxide, make to there is the positively charged ion of exposure and the negative oxygen ion center of different ligancy on the 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.Be 200 ~ 450 DEG C in temperature of reaction, reaction pressure counts 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, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Take 50 grams of commodity MgO, add containing 112.5 grams of oxalic acid, mass concentration is the acid solution of 5%, obtain mixing solutions after 50 DEG C of heating in water bath stir 5 hours, moisture in suction filtration solution, product is dried 6 hours at 120 DEG C, products therefrom 400 DEG C of roastings 5 hours, the product obtained is designated as JT-1.
Being arranged in the fixed-bed reactor of Φ 25mm by catalyzer 10 grams, is that the 1-butylene of 99.9% is for raw material was weight space velocity 1 hour with weight content -1, check and rate catalyst performance under 250 DEG C and 1MPa condition, the results are shown in list 2.
[embodiment 2]
Take 50 grams of commodity MgO, add containing 120.09 grams of citric acids, mass concentration is the solution of 1%, and obtain mixing solutions and leave standstill 3 hours again, moisture in suction filtration solution after 80 DEG C of heating in water bath stir 4 hours, product is dried 3 hours at 80 DEG C, and products therefrom is supported on SiO 2(mass content 5%), 500 DEG C of roastings 8 hours, the product obtained is designated as JT-2.
Being arranged in the fixed-bed reactor of Φ 25mm by catalyzer 10 grams, is that the 1-butylene of 99.9% is for raw material was weight space velocity 10 hours with weight content -1, check and rate catalyst performance under 300 DEG C and 0.5MPa condition, the results are shown in list 2.
[embodiment 3]
Take 50 grams of commodity CaO, add containing 5.54 grams of carbonic acid, mass concentration is the solution of 10%, obtain mixing solutions and leave standstill 3 hours again after 90 DEG C of heating in water bath stir 1 hour, moisture in suction filtration solution, product is dried 10 hours at 100 DEG C, and products therefrom is supported on gac (mass content 10%), 300 DEG C of roastings 12 hours, the product obtained is designated as JT-3.
Being arranged in the fixed-bed reactor of Φ 25mm by catalyzer 10 grams, is that the 1-butylene of 99.9% is for raw material was weight space velocity 20 hours with weight content -1, check and rate catalyst performance under 400 DEG C and 2MPa condition, the results are shown in list 2.
[embodiment 4]
Take 50 grams of commodity BaO, add containing 148.5 grams of oxalic acid, mass concentration is the solution of 15%, obtains mixing solutions after stirring 10 hours in 30 DEG C of heating in water bath, moisture in suction filtration solution, and product is dried 18 hours at 60 DEG C, and products therefrom is supported on activated carbon and SiO 2mixture on (mass content 15% of the two), 700 DEG C of roastings 3 hours, the product obtained is designated as JT-4.
Being arranged in the fixed-bed reactor of Φ 25mm by catalyzer 10 grams, is that the 1-butylene of 99.9% is for raw material was weight space velocity 30 hours with weight content -1, check and rate catalyst performance under 450 DEG C and 3MPa condition, the results are shown in list 2.
[embodiment 5]
Take 50 grams of commodity MgO, add containing 120.09 grams of citric acids, mass concentration is the solution of 1%, and adds containing 112.5 grams of oxalic acid, and mass concentration is the acid solution of 5%, obtain mixing solutions and leave standstill 3 hours again after 80 DEG C of heating in water bath stir 4 hours, moisture in suction filtration solution, product is dried 3 hours at 80 DEG C, and products therefrom is supported on gac (mass content 20%), 800 DEG C of roastings 2 hours, the product obtained is designated as JT-5.
Being arranged in the fixed-bed reactor of Φ 25mm by catalyzer 10 grams, is that the 1-butylene of 99.9% is for raw material was weight space velocity 40 hours with weight content -1, check and rate catalyst performance under 500 DEG C and 4MPa condition, the results are shown in list 2.
[embodiment 6]
Take 50 grams of commodity MgO, 50 grams of commodity BaO, add containing 240 grams of citric acids, mass concentration is the solution of 3%, obtains mixing solutions and leave standstill 3 hours again, moisture in suction filtration solution after 80 DEG C of heating in water bath stir 4 hours, product is dried 3 hours at 80 DEG C, and products therefrom is supported on SiO 2(mass content 5%), 850 DEG C of roastings 2 hours, the product obtained is designated as JT-6.
Being arranged in the fixed-bed reactor of Φ 25mm by catalyzer 10 grams, is that the 1-butylene of 99.9% is for raw material was weight space velocity 50 hours with weight content -1, check and rate catalyst performance under 200 DEG C and 5MPa condition, the results are shown in list 2.
[embodiment 7]
The sign of catalyzer.The specific surface of sample, pore volume, aperture measures on MicromeriticsASAP2000 physical adsorption appearance, and adsorbate is N 2, adsorption temp is liquid nitrogen temperature.The basic sites concentration on surface is at CO 2the temperature programmed desorption(TPD) device of-TPD carries out.The results are shown in Table 1.
Table 1
[comparative example 1]
Being arranged in the fixed-bed reactor of Φ 25mm by commodity MgO 10 grams, is that the 1-butylene of 99.9% is for raw material was weight space velocity 1 hour with weight content -1, check and rate catalyst performance under 250 DEG C and 1MPa condition, the results are shown in list 2.
[comparative example 2]
By 10 grams of loads at SiO 2commodity CaO on (mass content is 10%), is arranged in the fixed-bed reactor of Φ 25mm, is that the 1-butylene of 99.9% is for raw material was weight space velocity 10 hours with weight content -1, check and rate catalyst performance under 300 DEG C 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, and 2-butylene yield is high by about 20%, and stability is also significantly improved, and can reach 850 hours.

Claims (6)

1. a method for 1-butylene double-bond isomerization 2-butylene, take 1-butylene as raw material, be 200 ~ 500 DEG C in temperature of reaction, reaction pressure counts 0 ~ 5MPa with absolute pressure, and weight space velocity is 1 ~ 50 hour -1under condition, raw material and catalyst exposure react and generate 2-butylene, and wherein catalyst comprises following component:
A) 80 ~ 100% at least one oxide compound in alkaline-earth metal is selected from;
B) 0 ~ 20% at least one in neutrality or meta-alkalescence carrier is selected from;
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, and the basic sites concentration on surface is 0.3 ~ 10.0umol/g; The preparation method of described catalyzer, comprises the following steps: the alkaline earth metal oxide of aequum fully mixes with the acid solution of aequum by (a), stirs 1 ~ 20h, obtain reaction product A at 20 ~ 120 DEG C of temperature; B () reaction product A is through suction filtration at 40 ~ 120 DEG C of temperature, dry 3 ~ 20h obtains the precursor B of catalyzer; On c neutrality that the precursor B of catalyzer is supported on aequum by () or meta-alkalescence carrier, be that under the condition of 300 ~ 850 DEG C, roasting 2 ~ 12h obtains required catalyzer in temperature after drying; 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.
2. the method for 1-butylene double-bond isomerization 2-butylene according to claim 1, it is characterized in that temperature of reaction is 200 ~ 400 DEG C, reaction pressure counts 0.2 ~ 3MPa with absolute pressure, and weight space velocity is 2 ~ 25 hours -1.
3. the method for 1-butylene double-bond isomerization 2-butylene according to claim 2, it is characterized in that temperature of reaction is 250 ~ 350 DEG C, reaction pressure counts 0.5 ~ 1MPa with absolute pressure, and weight space velocity is 4 ~ 10 hours -1.
4. the method for 1-butylene double-bond isomerization 2-butylene according to claim 1, is characterized in that selected alkaline earth metal oxide is preferably from calcium, magnesium, barium, strontium, at least one in radium oxide compound; Described neutrality or meta-alkalescence carrier are selected from SiO 2or at least one in gac.
5. the method for 1-butylene double-bond isomerization 2-butylene according to claim 1, is characterized in that selected alkaline earth metal oxide preferential oxidation magnesium.
6. the method for 1-butylene double-bond isomerization 2-butylene according to claim 1, is characterized in that isomerization catalyst needs in the reactor through calcination process, and maturing temperature is 500 ~ 650 DEG C, and roasting time is 4 ~ 12 hours.
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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
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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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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

Patent Citations (2)

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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

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