Production method for 1-butylene

Abstract

The present invention relates to a preparation method for butylene-1; the method is to overcome the shortcoming in the prior technology that: the selectivity of the produced butylene-1 is lower; the benefit ratio is lower; the regeneration period for the catalyzer is much shorter; and the energy consumption is much higher. The steps in turn include: (1) the raw material including butylenes is contacted with a molecule screen catalyzer to produce the first reaction flow with the molar ratio between butylene-2 and butylene-1 closing to the thermodynamics balance value; (b) the first reaction flow enters a separated tower for separating to obtain butylene-1 in the tower top and the second reaction flow including butylene-2 is obtained in the tower bottom; (c) the second reaction flow used as butylene-2 directly or turned back to the difference reaction device to be reacted continually; the method can solve the problem greatly, which can be uses in the industrial production of butylene-1.

Description

Technical field

[0001] The invention relates to a method for producing butene-1, in particular to a method for isomerizing butene-1 with butene-2 ​​double bond. Background technique

[0002] 1-Butene is a chemically active α-olefin. High-purity 1-butene is mainly used to produce linear low-density polyethylene (LLDPE) comonomers. LLDPE has good high-temperature creep properties, High impact strength, heat resistance and wear resistance, especially suitable for hot water pipes, so it has become a rapidly growing thermoplastic polymer material in recent years; at the same time, other oligomerization products of 1-butene, such as dimer 1 -Octene and trimer dodecene can not only replace 1-butene to synthesize better LLDPE and HDPE, but also can be used in a large number of automotive and lubricant additives, synthetic detergents, surfactants and plasticizers, Printing and dyeing agents, emulsifiers, etc., have a wide range of uses, and their dosage is increasing year by year. The mar...

Examples

Embodiment 1

[0016] According to the molar ratio of silicon to aluminum SiO 2 / Al 2 O 3 Prepare a slurry containing silicon, aluminum, template agent (n-butylamine) and water at a ratio of 200, and the molar ratio of raw materials is 150 SiO 2 : Al 2 O 3 : 50 n-butylamine: 17OH-: 200NaCl: 6300H 2 O was stirred at room temperature for 15 hours. Then, it is crystallized at a temperature of 140°C for 50 hours, and then the crystallization solution is washed, dried, and calcined to obtain ZSM-5 molecular sieve. After adding 50 grams of ZSM-5 molecular sieve into 87 grams of 40% (weight) silica gel, the mixture is extruded, dried at 130°C, and calcined at 430°C to prepare a ZSM-5 catalyst.

[0017] Load the above-mentioned ZSM-5 molecular sieve catalyst into a fixed-bed isomerization reactor, using pure butene-2 ​​as raw material, and the space velocity of the isomerization reactor is 0.5 hours -1 , The pressure (gauge pressure) is 1MPa, the reaction temperature is 320°C, the theoretical plate numb...

Embodiment 2

[0019] Refer to the various steps of Example 1 to obtain the molar ratio of silicon to aluminum SiO 2 / Al 2 O 3 It is a 450 ZSM-5 molecular sieve catalyst, using pure butene-2 ​​as the raw material, and the space velocity of the isomerization reactor is 25 hours -1 , The pressure (gauge pressure) is 0.2MPa, the reaction temperature is 200°C, the theoretical plate number of the separation tower is 100, the operating pressure is 0.8MPa, the reflux ratio is 45, and the reaction result when the bottom butene-2 ​​is fully circulated is: butene The single-pass conversion rate of -2 and the yield of butene-1 are 12%, and the total conversion rate of butene-2 ​​and the yield of butene-1 based on the butene-2 ​​raw material are greater than 94%.

Embodiment 3

[0021] According to the steps and operating conditions of Example 1, only change: the molar ratio of silicon to aluminum SiO of the ZSM-5 molecular sieve catalyst 2 / Al 2 O3 Is 30, the reaction temperature is 420℃, and the reaction weight space velocity is 45 hours -1 , The reaction pressure (gauge pressure) is 0.5MPa, the raw material is pure butene-2, the theoretical plate number of the separation tower is 60, the operating pressure is 1.3MPa, the reflux ratio is 40, and the reaction result is when the bottom butene-2 ​​is fully circulated : The single-pass conversion rate of butene-2 ​​and butene-1 yield is 25%, and the total butene-2 ​​conversion rate and butene-1 yield based on butene-2 ​​raw materials are greater than 97%.

Technical field

[0001] The invention relates to a method for producing butene-1, in particular to a method for isomerizing butene-1 with butene-2 ​​double bond. Background technique

[0002] 1-Butene is a chemically active α-olefin. High-purity 1-butene is mainly used to produce linear low-density polyethylene (LLDPE) comonomers. LLDPE has good high-temperature creep properties, High impact strength, heat resistance and wear resistance, especially suitable for hot water pipes, so it has become a rapidly growing thermoplastic polymer material in recent years; at the same time, other oligomerization products of 1-butene, such as dimer 1 -Octene and trimer dodecene can not only replace 1-butene to synthesize better LLDPE and HDPE, but also can be used in a large number of automotive and lubricant additives, synthetic detergents, surfactants and plasticizers, Printing and dyeing agents, emulsifiers, etc., have a wide range of uses, and their dosage is increasing year by year. The mar...

Examples

Embodiment 1

[0016] According to the molar ratio of silicon to aluminum SiO 2 / Al 2 O 3 Prepare a slurry containing silicon, aluminum, template agent (n-butylamine) and water at a ratio of 200, and the molar ratio of raw materials is 150 SiO 2 : Al 2 O 3 : 50 n-butylamine: 17OH-: 200NaCl: 6300H 2 O was stirred at room temperature for 15 hours. Then, it is crystallized at a temperature of 140°C for 50 hours, and then the crystallization solution is washed, dried, and calcined to obtain ZSM-5 molecular sieve. After adding 50 grams of ZSM-5 molecular sieve into 87 grams of 40% (weight) silica gel, the mixture is extruded, dried at 130°C, and calcined at 430°C to prepare a ZSM-5 catalyst.

[0017] Load the above-mentioned ZSM-5 molecular sieve catalyst into a fixed-bed isomerization reactor, using pure butene-2 ​​as raw material, and the space velocity of the isomerization reactor is 0.5 hours -1 , The pressure (gauge pressure) is 1MPa, the reaction temperature is 320°C, the theoretical plate numb...

Embodiment 2

[0019] Refer to the various steps of Example 1 to obtain the molar ratio of silicon to aluminum SiO 2 / Al 2 O 3 It is a 450 ZSM-5 molecular sieve catalyst, using pure butene-2 ​​as the raw material, and the space velocity of the isomerization reactor is 25 hours -1 , The pressure (gauge pressure) is 0.2MPa, the reaction temperature is 200°C, the theoretical plate number of the separation tower is 100, the operating pressure is 0.8MPa, the reflux ratio is 45, and the reaction result when the bottom butene-2 ​​is fully circulated is: butene The single-pass conversion rate of -2 and the yield of butene-1 are 12%, and the total conversion rate of butene-2 ​​and the yield of butene-1 based on the butene-2 ​​raw material are greater than 94%.

Embodiment 3

[0021] According to the steps and operating conditions of Example 1, only change: the molar ratio of silicon to aluminum SiO of the ZSM-5 molecular sieve catalyst 2 / Al 2 O3 Is 30, the reaction temperature is 420℃, and the reaction weight space velocity is 45 hours -1 , The reaction pressure (gauge pressure) is 0.5MPa, the raw material is pure butene-2, the theoretical plate number of the separation tower is 60, the operating pressure is 1.3MPa, the reflux ratio is 40, and the reaction result is when the bottom butene-2 ​​is fully circulated : The single-pass conversion rate of butene-2 ​​and butene-1 yield is 25%, and the total butene-2 ​​conversion rate and butene-1 yield based on butene-2 ​​raw materials are greater than 97%.