Treatment method of triethyl aluminum kettle residual solution

Abstract

The invention discloses a triethyl aluminum kettle residue treatment method, which comprises: 1) distilling a triethyl aluminum kettle residue solution to obtain a tri-n-butylaluminium crude product; and 2) oxidizing the tri-n-butylaluminium crude product in an oxygen-containing atmosphere to obtain aluminum oxide. According to the method, the triethylaluminium kettle residue solution is continuously distilled, the tri-n-butylaluminium in the kettle residue solution is extracted, and the tri-n-butylaluminium crude product is oxidized in the atmosphere containing a proper amount of oxygen, so that the high-purity nanoscale aluminum oxide powder is obtained, and part of the kettle residue is converted into a new product with a relatively high additional value. The waste liquid is retreated, the treatment method is simple, and the environmental pollution can be reduced while the production cost is saved.

Description

Technical Field

[0001] This invention belongs to the field of chemical catalyst technology and relates to a method for treating residual solution from a triethylaluminum reactor. Background Technology

[0002] Triethylaluminum is a metal-organic compound, a colorless liquid at room temperature and pressure, and is chemically reactive, spontaneously combusting in air and exploding upon contact with water. In the petrochemical industry, triethylaluminum is a component of Ziegler-Natta type catalysts, commonly used in the low-pressure polymerization of ethylene, propylene polymerization, and isoprene polymerization. Furthermore, triethylaluminum is a key material in the production of rocket fuel and solar-grade silicone raw materials; it also has wide applications in plastic additives, shock absorbers, and bactericides. Its pure form can be used in metal-organic chemical vapor deposition (MOCVD) processes and is an important source of aluminum for the preparation of semiconductor compound materials.

[0003] In the current synthesis process of triethylaluminum, after distillation and purification, the residue in the reactor still includes tri-n-butylaluminum, aluminum powder, alumina and other impurities. However, in existing technologies, the residue is usually directly incinerated for harmless treatment. This method not only causes environmental pollution but also wastes raw materials. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a method for treating residual triethylaluminum reactor solution, the method comprising the following steps:

[0005] 1) Distill the residual solution of triethylaluminum in the reactor to obtain crude tri-n-butylaluminum;

[0006] 2) The crude tri-n-butylaluminum product is oxidized in an oxygen-containing atmosphere to obtain aluminum oxide;

[0007] The residual solution of the triethylaluminum reactor includes tri-n-butylaluminum, aluminum powder, alumina, and other impurities.

[0008] According to an embodiment of the present invention, in step 1), the distillation temperature is 60-100°C.

[0009] According to an embodiment of the present invention, in step 1), the distillation time is 1-12 hours.

[0010] According to an embodiment of the present invention, in step 1), the triethylaluminum reactor residue solution is the solution remaining at the bottom of the reactor after the distillation and purification of triethylaluminum;

[0011] Preferably, the preparation of the triethylaluminum reactor residue solution is carried out using methods known in the art.

[0012] According to an embodiment of the present invention, step 1) may further be to first react the residual solution of triethylaluminum with ethylene to further convert the incompletely separated triethylaluminum into tri-n-butylaluminum, and then distill to obtain crude tri-n-butylaluminum.

[0013] According to an embodiment of the present invention, the temperature of the insertion reaction is 70-150°C, the time of the insertion reaction is 2-6 hours, and the pressure of the insertion reaction is 0.5-3 MPa.

[0014] According to an embodiment of the present invention, in step 1), the triethylaluminum reactor residue solution, by mass, includes 20-70 wt% tri-n-butylaluminum, 12-35 wt% aluminum powder, 5-30 wt% alumina, and 0-10 wt% other impurities.

[0015] According to an embodiment of the present invention, in step 1), the triethylaluminum reactor residue solution, by mass, includes 25-60 wt% tri-n-butylaluminum, 15-30 wt% aluminum powder, 8-25 wt% alumina, and 1-8 wt% other impurities.

[0016] According to an embodiment of the present invention, in step 2), the oxygen content in the oxygen-containing atmosphere is 1,000-500,000 ppm, preferably 2,000-100,000 ppm.

[0017] According to an embodiment of the present invention, in step 2), the oxygen-containing atmosphere further includes an inert gas, such as nitrogen or argon.

[0018] According to an embodiment of the present invention, in step 2), the oxygen-containing atmosphere is a mixture of air and nitrogen. Specifically, the ratio of air to nitrogen in the mixture is such that the oxygen content in the mixture is 1000-500000ppm (preferably 2000-100000ppm).

[0019] According to an embodiment of the present invention, in step 2), the oxidation time is 2-24 hours, preferably 4-12 hours.

[0020] According to an embodiment of the present invention, in step 2), the oxidation temperature is 300-800℃, preferably 300-600℃.

[0021] According to an embodiment of the present invention, in step 2), the particle size of the product alumina is in the nanometer range, for example, the particle size is 50-300 nm.

[0022] The beneficial effects of this invention are:

[0023] This invention extracts tri-n-butylaluminum from the residue solution of triethylaluminum by continuing distillation, and then oxidizes the crude tri-n-butylaluminum in an atmosphere containing an appropriate amount of oxygen to obtain high-purity, nano-sized alumina powder, thereby converting part of the residue into a new product with high added value.

[0024] This invention reprocesses waste liquid in a simple manner, saving production costs while reducing environmental pollution. Detailed Implementation

[0025] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0026] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0027] Example 1

[0028] (1) Distill the residual solution of triethylaluminum at 85°C for 5 h to obtain crude tri-n-butylaluminum;

[0029] (2) The crude tri-n-butylaluminum was oxidized for 5 hours in a nitrogen atmosphere containing 30,000 ppm oxygen at a temperature of 400°C to obtain aluminum oxide with a particle size of 200 nm.

[0030] The residual solution of the triethylaluminum reactor contains 60 wt% tri-n-butylaluminum, 26 wt% aluminum powder, 7 wt% alumina, and 7 wt% other impurities.

[0031] Example 2

[0032] (1) Distill the residual solution of triethylaluminum at 90°C for 4 hours to obtain crude tri-n-butylaluminum;

[0033] (2) The crude tri-n-butylaluminum was oxidized for 6 hours in a nitrogen atmosphere containing 20,000 ppm oxygen at a temperature of 550°C to obtain aluminum oxide with a particle size of 100 nm.

[0034] The residual solution of the triethylaluminum reactor contains 55 wt% tri-n-butylaluminum, 28 wt% aluminum powder, 9 wt% alumina and 8 wt% other impurities.

[0035] Example 3

[0036] (1) The residual solution of triethylaluminum in the reactor was subjected to an insertion reaction with ethylene. The temperature of the insertion reaction was 100℃, the time of the insertion reaction was 4h, and the pressure of the insertion reaction was 1MPa, so that the incompletely separated triethylaluminum was completely reacted to form tri-n-butylaluminum. After removing ethylene, the remaining solvent was distilled at 100℃ for 3h to obtain crude tri-n-butylaluminum.

[0037] (2) The crude tri-n-butylaluminum was oxidized for 10 hours in a nitrogen atmosphere containing 8000 ppm oxygen at a temperature of 600℃ to obtain aluminum oxide with a particle size of 80 nm.

[0038] The residual solution of the triethylaluminum reactor contains 50 wt% tri-n-butylaluminum, 29 wt% aluminum powder, 13 wt% alumina and 8 wt% other impurities.

[0039] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for treating triethylaluminum reactor residue, characterized in that, The method includes the following steps: 1) Distill the residual solution of triethylaluminum in the reactor to obtain crude tri-n-butylaluminum; 2) The crude tri-n-butylaluminum product is oxidized in an oxygen-containing atmosphere to obtain aluminum oxide; The residual solution of the triethylaluminum reactor includes tri-n-butylaluminum, aluminum powder, alumina, and other impurities.

2. The method according to claim 1, characterized in that, In step 1), the distillation temperature is 60-100℃.

3. The method according to claim 1, characterized in that, In step 1), the triethylaluminum reactor residue solution is the solution remaining at the bottom of the reactor after the distillation and purification of triethylaluminum.

4. The method according to claim 1, characterized in that, In step 1), the triethylaluminum reactor residue solution, by mass, includes 20-70 wt% tri-n-butylaluminum, 12-35 wt% aluminum powder, 5-30 wt% alumina, and 0-10 wt% other impurities.

5. The method according to claim 4, characterized in that, In step 1), the triethylaluminum reactor residue solution, by mass, includes 25-60 wt% tri-n-butylaluminum, 15-30 wt% aluminum powder, 8-25 wt% alumina, and 1-8 wt% other impurities.

6. The method according to claim 1, characterized in that, In step 2), the oxygen content in the oxygen-containing atmosphere is 1000-500000ppm.

7. The method according to claim 1, characterized in that, In step 2), the oxygen-containing atmosphere also includes an inert gas, which is nitrogen or argon.

8. The method according to claim 1, characterized in that, In step 2), the oxidation time is 2-24 hours.

9. The method according to claim 1, characterized in that, In step 2), the oxidation temperature is 300-800℃.

10. The method according to claim 1, characterized in that, In step 2), the particle size of the alumina in the product is in the nanometer range.