Device for producing electronic grade ethanol and its application

Abstract

The present application discloses a device and application for producing electronic-grade ethanol, the device comprising a synthesis reaction distillation tower and a cracking reaction distillation tower; the synthesis reaction distillation tower is connected to the cracking reaction distillation tower; the synthesis reaction distillation tower comprises a distillation section I, a reaction section I, and a stripping section I; the cracking reaction distillation tower comprises a distillation section II, a reaction section II, and a stripping section II; the stripping section I is provided with a raw material inlet connected to the cracking reaction distillation tower; the upper end of the cracking reaction distillation tower is provided with a recyclable raw material inlet; the lower end of the cracking reaction distillation tower is provided with an electronic-grade ethanol outlet. The present application uses high-purity ethanol after metal ion removal to react with isobutylene to generate ethyl tert-butyl ether, and then generates isobutylene and ethanol by catalytic cracking of ethyl tert-butyl ether, wherein ethanol is separated and purified to obtain electronic-grade ethanol to achieve effective removal of fusel alcohols in ethanol, thereby improving resource utilization efficiency.

Description

Technical Field

[0001] The present application relates to a device for producing electronic-grade ethanol and its application, belonging to the field of chemical engineering. Background Art

[0002] Electronic-grade ethanol is widely used in the production of semiconductor manufacturing, optoelectronic devices, and other high-precision electronic devices. In order to ensure product quality and performance, electronic-grade ethanol must have extremely high purity, and it is usually necessary to remove the fusel alcohols. Traditional ethanol purification methods mostly rely on multi-stage distillation or membrane separation technology, but these methods often have certain limitations in the efficiency and economy of removing fusel alcohols. Therefore, it is of great practical significance to develop an efficient and economical method for producing electronic-grade ethanol. Summary of the invention

[0003] The present invention provides a device for producing electronic-grade ethanol and its application, which realizes the effective removal of fusel alcohols in ethanol through a series of catalytic reactions and separation and purification steps. The method comprises the following steps: using high-purity ethanol after metal ions are removed to react with isobutylene to generate ethyl tert-butyl ether, and then catalytically cracking ethyl tert-butyl ether to generate isobutylene and ethanol, wherein the ethanol is separated and purified to obtain electronic-grade ethanol. Isobutylene can be recycled, which improves the utilization efficiency of resources.

[0004] According to one aspect of the present application, there is provided a device for producing electronic-grade ethanol, the device comprising a synthesis reaction distillation tower and a cracking reaction distillation tower;

[0005] The synthesis reaction distillation tower is connected to the cracking reaction distillation tower;

[0006] The synthetic reaction distillation tower comprises a distillation section I, a reaction section I, and a stripping section I;

[0007] The cracking reaction distillation tower comprises a distillation section II, a reaction section II, and a stripping section II;

[0008] The stripping section I is provided with a raw material inlet connected to the cracking reaction distillation tower;

[0009] The upper end of the cracking reaction distillation tower is provided with a recyclable raw material inlet;

[0010] An electronic grade ethanol outlet is provided at the lower end of the cracking reaction distillation tower.

[0011] Optionally, a light component outlet is provided at the upper end of the synthesis reaction distillation tower;

[0012] The lower end of the synthetic reaction distillation tower is provided with a heavy component outlet;

[0013] The upper end of the reaction section I is provided with an inlet for raw material I;

[0014] The lower end of the reaction section I is provided with an inlet for raw material II.

[0015] According to another aspect of the present application, there is provided a use of a device in producing electronic grade ethanol, comprising at least the following steps:

[0016] Step I: mixing ethanol and isobutylene in a synthetic reaction distillation tower of the device, reacting under the action of catalyst I to obtain ethyl tert-butyl ether;

[0017] Step II: contacting the ethyl tert-butyl ether obtained in step I with catalyst II in a cracking reaction distillation tower of the device to undergo cracking reaction to obtain a product containing isobutylene and ethanol.

[0018] Optionally, the molar ratio of ethanol to isobutylene is 1.0:1.0 to 5.0:1.0.

[0019] Optionally, the molar ratio of ethanol to isobutylene is independently selected from any value of 1.0:1.0, 1.5:1.0, 2.0:1.0, 2.5:1.0, 3.0:1.0, 3.5:1.0, 4.0:1.0, 4.5:1.0, 5.0:1.0 or a range between any two of the above points.

[0020] Optionally, the volume space velocity of isobutylene is 0.5 to 5 h -1 .

[0021] Optionally, the volume space velocity of isobutylene is independently selected from 0.5h -1 , 1.0h -1 , 1.5h -1 , 2.0h -1 , 2.5h -1 , 3.0h -1 , 3.5h -1 , 4.0h -1 , 4.5h -1 , 5.0h -1 Any value in or a range of values ​​between any two of the above points.

[0022] Optionally, the catalyst I is selected from at least one of a heteropoly acid / titanium-based composite oxide catalyst, a heteropoly acid / aluminum-based composite oxide catalyst, a solid acid catalyst, and a cation exchange resin.

[0023] Optionally, in step I, the conversion rate of ethanol is <95%.

[0024] Optionally, in step I, the reaction conditions are as follows:

[0025] The reaction temperature is 80-150°C;

[0026] The reaction pressure is 0.5-5.0 MPa.

[0027] Optionally, the catalyst II is selected from at least one of metal element modified silica and alumina-silicon dioxide catalyst;

[0028] Optionally, the space velocity of the ethyl tert-butyl ether is 1 to 2 h -1 .

[0029] Optionally, the space velocity of the ethyl tert-butyl ether is independently selected from 1.0h -1 , 1.1h -1 , 1.2h -1 , 1.3h -1 , 1.4h -1 , 1.5h -1 , 1.6h -1 , 1.7h -1 , 1.8h -1 , 1.9h -1 , 2.0h -1 Any value in or a range of values ​​between any two of the above points.

[0030] Optionally, the reaction conditions of the cleavage reaction are as follows:

[0031] The reaction temperature of the cracking reaction is 170-250°C;

[0032] The reaction pressure of the cracking reaction is 0.7-2Mpa.

[0033] Optionally, the purity of ethanol in the product is 99.99% to 99.999%.

[0034] The beneficial effects of this application include:

[0035] 1) The method provided in the present application can prepare high-purity electronic-grade ethanol. By controlling the reaction conditions and selecting an appropriate catalyst, the method can effectively remove the fusel alcohols in ethanol to obtain high-purity electronic-grade ethanol.

[0036] 2) The method provided in the present application is economical and efficient. The recycling of isobutylene in the method reduces the raw material cost and improves the production efficiency.

[0037] 3) The method provided in the present application is environmentally friendly, and the operating conditions of the method are relatively mild, which reduces the impact on the environment and has more environmental advantages than the traditional high-energy consumption distillation method. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a diagram of the device used in Examples 1 to 4 of the present application and the comparative example. DETAILED DESCRIPTION

[0039] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0040] Unless otherwise specified, the raw materials and reagents in the examples of this application were purchased through commercial channels.

[0041] Example 1

[0042] Using high-purity ethanol (purity 99.5%) after metal ion removal as raw material, isobutylene and heteropoly acid / titanium-based composite oxide catalyst (mass ratio of heteropoly acid to composite oxide is 0.9:1), reaction temperature is controlled at 80°C, reaction pressure is 1.0MPa, and alcohol conversion rate is controlled at 92%. After the reaction, ethyl tert-butyl ether is separated by a synthetic reaction distillation tower and analyzed by gas chromatography. Ethyl tert-butyl ether is then heated to 150°C together with an alumina-silicon dioxide catalyst for cracking. The isobutylene and ethanol in the obtained product are separated by a cracking reaction distillation tower to obtain electronic grade ethanol, the purity of which reaches 99.99%. The specific test results are shown in Table 1.

[0043] Example 2

[0044] The ethanol (purity 99.5%) after metal ion removal was used as raw material, and was reacted with isobutylene under the catalysis of a solid acid catalyst. The reaction temperature was set at 75°C, the pressure was maintained at 0.8MPa, and the alcohol conversion rate was maintained at 93%. The ethyl tert-butyl ether separated by the synthesis reaction distillation tower was then cracked by a cracking reaction distillation tower, the temperature was set at 160°C, and an alumina-silicon dioxide catalyst was used. The purity of the ethanol in the final product reached 99.999%, which met the electronic grade standard. The specific test results are shown in Table 1.

[0045] Example 3

[0046] High-purity ethanol (purity 99.5%) after metal ion removal is used as raw material, isobutylene and cation exchange resin catalyst are introduced, the reaction temperature is controlled at 80°C, the reaction pressure is 1.5MPa, and the alcohol conversion rate is controlled at 92%. After the reaction is completed, ethyl tert-butyl ether is separated by a synthetic reaction distillation tower and analyzed by gas chromatography. Ethyl tert-butyl ether is then heated to 140°C together with an alumina-silicon dioxide catalyst for cracking. The isobutylene and ethanol in the obtained product are separated and purified by a cracking reaction distillation tower to obtain electronic grade ethanol, and its purity reaches 98%. The specific test results are shown in Table 1.

[0047] Example 4

[0048] High-purity ethanol (purity 99.5%) after metal ion removal is used as raw material, isobutylene and cation exchange resin catalyst are introduced, the reaction temperature is controlled at 80°C, the reaction pressure is 2.0MPa, and the alcohol conversion rate is controlled at 94%. After the reaction is completed, ethyl tert-butyl ether is separated by a synthetic reaction distillation tower and analyzed by gas chromatography. Ethyl tert-butyl ether is then heated to 160°C together with an alumina-silicon dioxide catalyst for cracking. The isobutylene and ethanol in the obtained product are separated and purified by a cracking reaction distillation tower to obtain electronic grade ethanol, and its purity reaches 99%. The specific test results are shown in Table 1.

[0049] Comparative Example

[0050] High-purity ethanol (purity 99.5%) after metal ion removal is used as raw material, isobutylene and cation exchange resin catalyst are introduced, the reaction temperature is controlled at 80°C, the reaction pressure is 2.0MPa, and after the reaction is completed, ethyl tert-butyl ether is separated by a synthetic reaction distillation tower and analyzed by gas chromatography. Ethyl tert-butyl ether and cation exchange resin are then heated to 160°C for cracking, and the isobutylene and ethanol in the obtained product are separated and purified by a cracking reaction distillation tower to obtain electronic grade ethanol, the purity of which reaches 65%. The specific test results are shown in Table 1.

[0051] Table 1 Experimental results of examples and comparative examples

[0052]

[0053] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A device for producing electronic grade ethanol, characterized in that: The device comprises a synthesis reaction distillation tower and a cracking reaction distillation tower; The synthesis reaction distillation tower is connected to the cracking reaction distillation tower; The synthetic reaction distillation tower comprises a distillation section I, a reaction section I, and a stripping section I; The cracking reaction distillation tower comprises a distillation section II, a reaction section II, and a stripping section II; The stripping section I is provided with a raw material inlet connected to the cracking reaction distillation tower; The upper end of the cracking reaction distillation tower is provided with a recyclable raw material inlet; An electronic grade ethanol outlet is provided at the lower end of the cracking reaction distillation tower.

2. The device according to claim 1, characterized in that The upper end of the synthetic reaction distillation tower is provided with a light component outlet; The lower end of the synthetic reaction distillation tower is provided with a heavy component outlet; The upper end of the reaction section I is provided with an inlet for raw material I; The lower end of the reaction section I is provided with an inlet for raw material II.

3. Use of the device according to any one of claims 1 to 2 in the production of electronic grade ethanol, characterized in that: At least the following steps are included: Step I: mixing ethanol and isobutylene in a synthetic reaction distillation tower of the device, reacting under the action of catalyst I to obtain ethyl tert-butyl ether; Step II: contacting the ethyl tert-butyl ether obtained in step I with catalyst II in a cracking reaction distillation tower of the device to undergo cracking reaction to obtain a product containing isobutylene and ethanol.

4. The use according to claim 3, characterized in that: The molar ratio of ethanol to isobutylene is 1.0:1.0 to 5.0:1.0; Preferably, the volume space velocity of isobutylene is 0.5 to 5 h -1 .

5. The use according to claim 3, characterized in that: The catalyst I is selected from at least one of a heteropolyacid / titanium-based composite oxide catalyst, a heteropolyacid / aluminum-based composite oxide catalyst, a solid acid catalyst, and a cation exchange resin; Preferably, the conversion rate of ethanol is <95%.

6. The use according to claim 3, characterized in that: The reaction conditions are as follows: The reaction temperature is 80-150°C; The reaction pressure is 0.5-5.0 MPa.

7. The use according to claim 1, characterized in that: The catalyst II is selected from at least one of silica modified by metal elements and alumina-silica catalysts.

8. The method according to claim 1, characterized in that The space velocity of the ethyl tert-butyl ether is 1 to 2 h -1 .

9. The method according to claim 1, characterized in that: The reaction conditions of the cleavage reaction are as follows: The reaction temperature of the cracking reaction is 170-250°C; The reaction pressure of the cracking reaction is 0.7-2Mpa.

10. The method according to claim 1, characterized in that The purity of ethanol in the product is 99.99% to 99.999%.

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