METHOD FOR REPLACEMENT OF PHOSGENE SYNTHESIS COLUMN CATALYST

Abstract

The present invention discloses a method of quickly desorbing phosgene from a catalyst in a phosgene synthesizing tower when the catalyst in the phosgene synthesizing tower is replaced. The method is carried out by first purging out easily-desorbed phosgene from the catalyst activated carbon in the phosgene synthesizing tower with nitrogen gas, then purging with ammonia gas, and the ammonia gas is reacted with the hardly-desorbed phosgene in the catalyst of the phosgene synthesizing tower. Then the phosgene synthesizing tower is rinsed with a water gun and then dried with hot gas. The phosgene content at an outlet of the phosgene synthesizing tower after purging is below 0.5 ppm, which can significantly save the time of the phosgene synthesizing tower for purging the phosgene, greatly reduce the amount of nitrogen gas consumed, and improve the safety of the process operation.

Claims

1. A method of quickly desorbing phosgene from a catalyst in a phosgene synthesizing tower having a bottom inlet and an outlet before the catalyst in the phosgene synthesizing tower is replaced, comprising: (A) purging with nitrogen gas: after feeding of carbon monoxide and chlorine to the phosgene synthesizing tower is discontinued, nitrogen gas is introduced into the bottom of the phosgene synthesizing tower for purging, the phosgene in the phosgene synthesizing tower is purged to a phosgene decomposition tower until the phosgene concentration at the outlet of the phosgene synthesizing tower is measure as 0.05-0.5% (v/v), preferably 0.1-0.45% (v/v) relative to the overall volume of gas; and (C) purging with ammonia gas: ammonia gas is continuously introduced into the bottom of the phosgene synthesizing tower for purging.

2. The method of claim 1, further comprising: (D) replacing catalyst: the catalyst is taken out from the phosgene synthesizing tower, and the fresh catalyst is loaded therein; or when a tubular phosgene synthesizing tower is used, the catalyst is taken out from tubes of the phosgene synthesizing tower, and then the tubes of the phosgene synthesizing tower were rinsed with a water gun, and then dried with hot gas, and finally the fresh catalyst is filled into the tubes of the phosgene synthesizing tower.

3. The method of claim 1, wherein, in step (A), the temperature of the nitrogen gas for purging is from 80 to 160° C., preferably from 100 to 150° C., and/or the content of moisture in the nitrogen gas is below 500 ppm, preferably from 30 to 500 ppm, more preferably from 50 to 300 ppm.

4. The method of claim 1, wherein, in step (A), the flow of the nitrogen gas for purging is from 50 to 500 Nm3/h, preferably from 100 to 400 Nm3/h, and the time for purging with nitrogen gas is from 1 to 10 days, preferably from 2 to 6 days, and the pressure for purging with nitrogen gas is from 0.05 to 1.0 MPa, preferably from 0.102 to 0.3 MPa, more preferably from 0.15 to 0.25 MPa.

5. The method of claim 1, wherein, in step (C), purging with ammonia gas is conducted until the phosgene concentration at the outlet of the phosgene synthesizing tower is below 1 ppm, preferably from 0.1 to 1 ppm, more preferably from 0.2 to 0.5 ppm.

6. The method of claim 15, wherein, in step (B), ammonia gas is introduced into the phosgene synthesizing tower for building up the pressure, such that the pressure in the phosgene synthesizing tower reaches from 0.11 to 5 MPa, preferably from 0.2 to 4 MPa, more preferably from 0.5 to 3 MPa, more preferably from 0.7 to 2 MPa, e.g. 1 MPa, or reaches from 0.5 to 5 MPa, preferably from 1 to 3 MPa; and/or, two operations including building up the pressure and opening the outlet of the phosgene synthesizing tower are repeated 3 to 10 times, preferably 4 to 8 times, preferably, each time for building up the pressure is from 1 to 10 h, preferably from 2 to 8 h.

7. The method of claim 1, wherein, in step (C) of purging with ammonia gas, the flow of the ammonia gas for purging the phosgene synthesizing tower is from 50 to 200 Nm3/h, preferably from 80 to 150 Nm3/h, and/or the pressure of the ammonia gas is from 0.05 to 1.0 MPa, preferably from 0.10 to 0.3 MPa, more preferably from 0.15 to 0.25 MPa, and/or the temperature of the ammonia gas is from 30 to 100° C., preferably from 40 to 80° C.; it is preferred that the ammonia gas used for purging is free of moisture or contains trace amounts of moisture, such as from 20 to 500 ppm, preferably from 50 to 300 ppm of moisture.

8. The method of claim 1, wherein, in the step (C) of purging with ammonia gas, the time for purging with ammonia gas is from 1 to 10 days, preferably from 2 to 5 days.

9. The method of claim 1, wherein, the phosgene purged out by the phosgene synthesizing tower and excess ammonia gas are transferred to a phosgene decomposition tower and are decomposed by inorganic acids with the catalysis of the activated carbon.

10. The method of claim 8, wherein the inorganic acids are hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, preferably hydrochloric acid or sulfuric acid, more preferably hydrochloric acid.

11. The method of claim 9, wherein the concentration of the inorganic acids is from 0.5 to 10% by mass, preferably from 1 to 5% by mass.

12. The method of claim 2, wherein the hot gas used in step (D) is one of air, nitrogen gas, and CO2, preferably air, and/or the temperature of the hot gas is from 100 to 200° C., preferably from 120 to 180° C., and/or, the pressure of the hot gas is from 0.05 to 1.0 MPa, preferably from 0.102 to 0.3 MPa, preferably from 0.15 to 0.25 MPa, and/or the flow of the hot gas is from 200 to 1000 Nm3/h, preferably from 300 to 800 Nm3/h.

13. The method of claim 2, wherein, after the phosgene synthesizing tower is dried with the hot gas, the dew point measured therein is below −30° C., preferably below −40° C.

14. The method of claim 1, wherein the catalyst in the phosgene synthesizing tower or the catalyst filled into the tubes of the phosgene synthesizing tower is activated carbon, preferably coke, coal-based charcoal, coconut charcoal, more preferably coconut charcoal.

15. The method of claim 1, further comprising: (B) building the pressure: the outlet of the phosgene synthesizing tower is closed, ammonia gas is introduced into the bottom of the phosgene synthesizing tower to build up pressure in the phosgene synthesizing tower, and then the outlet of the phosgene synthesizing tower is opened to discharge gas from the phosgene synthesizing tower, wherein two operations including building up pressure and opening the outlet of the phosgene synthesizing tower are carried out once or several times repeatedly, wherein step (B) is performed after step (A) and prior to step (C).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 is a schematic view of a phosgene synthesizing tower apparatus used in Examples 1 to 4, wherein numerical reference 1 represents a phosgene synthesizing tower.

DETAILED DESCRIPTION OF THE INVENTION

[0038] The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. The experimental methods not specified for the specific conditions in the following examples are generally in accordance with conventional conditions.

[0039] The phosgene concentration at the outlet of the phosgene synthesizing tower can be measured by an iodometric method known to those skilled in the art.

Example 1

[0040] After feeding to the phosgene synthesizing tower was stopped, 100 Nm.sup.3/h of nitrogen gas was introduced from the bottom of the synthesizing tower, wherein the temperature of the nitrogen gas was 100° C., the moisture content in the nitrogen gas was 100 ppm, and the pressure of the nitrogen gas was 0.15 MPa. The nitrogen gas was continuously introduced for 2 days, and the phosgene concentration at the outlet of the phosgene synthesizing tower was measured as 0.45% (v/v) after purging. Ammonia gas was then introduced for purging. The ammonia gas was first introduced to build up the pressure, the phosgene synthesizing tower was built up pressure to 1 MPa and maintained at this pressure for 2 h, and then the outlet of the phosgene synthesizing tower was opened, and the process of building up pressure was repeated for 8 times as such. And then ammonia gas was continuously introduced, the flow of the ammonia gas was 80 Nm.sup.3/h, the temperature of the ammonia gas was 40° C., and the moisture content in the ammonia gas was 50 ppm. Purging with the ammonia gas was continued for 5 days, and the phosgene concentration at the outlet of the phosgene synthesizing tower was measured as 0.5 ppm. After purging, the phosgene was transferred to in a phosgene decomposition tower for decomposition, wherein the concentration of the inorganic acid was 1%, and the inorganic acid was hydrochloric acid. After purging with the ammonia gas, the tubes of the phosgene synthesizing tower were cleaned with a water gun, and the tubes were purged with hot air of 120° C. The hot air pressure was 0.15 MPa and the flow of the hot air was 300 Nm.sup.3/h, and the dew point of the synthesizing tower was measured as −40° C. The phosgene concentration at the outlet of the phosgene synthesizing tower and total purge time were shown in Table 1.

Example 2

[0041] After feeding to the phosgene synthesizing tower was stopped, 200 Nm.sup.3/h of nitrogen gas was introduced from the bottom of the synthesizing tower, wherein the temperature of the nitrogen gas was 120° C., the moisture content in the nitrogen gas was 300 ppm, and the pressure of the nitrogen gas was 0.2 MPa. The nitrogen gas was continuously introduced for 3 days, and the phosgene concentration at the outlet of the phosgene synthesizing tower was measured as 0.3% (v/v) after purging. Ammonia gas was first introduced to build up the pressure, the phosgene synthesizing tower was built up pressure to 2 MPa and maintained at this pressure for 4 h, and then the outlet of the phosgene synthesizing tower was opened, and the process of building up pressure was repeated for 4 times as such. And then ammonia gas was continuously introduced, the flow of ammonia gas was 100 Nm.sup.3/h, and the temperature of the ammonia gas was 60° C. Purging with the ammonia gas was continued for 3 days, and the phosgene concentration at the out let of the phosgene synthesizing tower was measured as 0.4 ppm. After purging, the phosgene was decomposed in a phosgene decomposition tower, wherein the concentration of the inorganic acid was 2%, and the inorganic acid was hydrochloric acid. After purging with the ammonia gas, the tubes of the phosgene synthesizing tower were cleaned with a water gun, and the tubes were purged with hot nitrogen gas of 150° C. The pressure of the nitrogen gas was 0.25 MPa and the flow of the nitrogen gas was 500 Nm.sup.3/h, and the dew point of the synthesizing tower was measured as −40° C. The phosgene concentration at the outlet of the phosgene synthesizing tower and total purge time were shown in Table 1.

Example 3

[0042] After feeding to the phosgene synthesizing tower was stopped, 400 Nm.sup.3/h of nitrogen gas was introduced from the bottom of the synthesizing tower, wherein the temperature of the nitrogen gas was 150° C., the moisture content in the nitrogen gas was 200 ppm, and the pressure of the nitrogen gas was 0.25 MPa. The nitrogen gas was continuously introduced for 6 days, and the phosgene concentration at the outlet of the phosgene synthesizing tower was measured as 0.1% (v/v) after purging. And then Ammonia gas was introduced for purging, the ammonia gas was first introduced to build up the pressure, the phosgene synthesizing tower was built up pressure to 3 MPa and maintained at this pressure for 5 h, and then the outlet of the phosgene synthesizing tower was opened, and the process of building up pressure was repeated for 5 times as such. And then ammonia gas was continuously introduced for purging, the flow of the ammonia gas is 150 Nm.sup.3/h, and the temperature of the ammonia gas was 80° C. Purging with the ammonia gas was conducted for 1 day, and the phosgene concentration at the out let of the phosgene synthesizing tower was measured as 0.2 ppm. After purging, the phosgene was decomposed in a phosgene decomposition tower, wherein the concentration of the inorganic acid was 5%, and the inorganic acid was hydrochloric acid. After purging with the ammonia gas, the tubes of the phosgene synthesizing tower were cleaned with a water gun, and the tubes were purged with hot air of 150° C. The pressure of the hot air was 0.2 MPa and the flow of the hot air was 800 Nm.sup.3/h, and the dew point of the synthesizing tower was measured as −40° C. The phosgene concentration at the outlet of the phosgene synthesizing tower and total purge time were shown in Table 1.

Example 4

[0043] After feeding to the phosgene synthesizing tower was stopped, 100 Nm.sup.3/h of nitrogen gas was introduced from the bottom of the synthesizing tower, wherein the temperature of the nitrogen gas was 100° C., the moisture content in the nitrogen gas was 100 ppm, the pressure of the nitrogen gas was 0.15 MPa. The nitrogen gas was continuously introduced for 2 days, and the phosgene concentration at the outlet of the phosgene synthesizing tower was measured as 0.45% (v/v) after purging. Ammonia gas was then continuously introduced, the flow of the ammonia gas was 80 Nm.sup.3/h, the temperature of the ammonia gas was 40° C., and the moisture content in the ammonia gas was 50 ppm. Purging with the ammonia gas was conducted for 7 days, and the phosgene concentration at the out let of the phosgene synthesizing tower was measured as 0.5 ppm. After purging, the phosgene was decomposed in a phosgene decomposition tower, wherein the concentration of the inorganic acid was 1%, and the inorganic acid was hydrochloric acid. After purging with the ammonia gas, the tubes of phosgene synthesizing tower were cleaned with a water gun, and the tubes were purged with hot air of 120° C. The pressure of the hot air was 0.15 MPa and the flow of the hot air was 300 Nm.sup.3/h, and the dew point of the synthesizing tower was measured as −40° C. The phosgene concentration at the outlet of the phosgene synthesizing tower and total purge time were shown in Table 1.

Comparative Example 1

[0044] After feeding to the phosgene synthesizing tower was stopped, 500 Nm.sup.3/h of nitrogen gas was introduced from the bottom of the synthesizing tower, the temperature of the nitrogen gas was 120° C., the moisture content in the nitrogen gas was 100 ppm, and the pressure of the nitrogen gas was 0.5 MPa. The nitrogen gas was continuously introduced for 35 days, and the phosgene concentration at the outlet of the phosgene synthesizing tower was measured as 8.1 ppm after purging. The phosgene was decomposed in a phosgene decomposition tower after purging, wherein the concentration of the inorganic acid was 2%, and the inorganic acid was hydrochloric acid. After purging with the nitrogen gas, the tubes of the phosgene synthesizing tower tube were cleaned with a water gun, and the tubes were purged with hot nitrogen gas of 150° C. The dew point of the synthesizing tower was measured as −40° C., and the phosgene concentration at the outlet of the phosgene synthesizing tower and total purge time were shown in Table 1.

Comparative Example 2

[0045] After feeding to the phosgene synthesizing tower was stopped, 500 Nm.sup.3/h of nitrogen gas was introduced from the bottom of the synthesizing tower, the temperature of the nitrogen gas was 150° C., the moisture content in the nitrogen gas was 100 ppm, the pressure of the nitrogen gas was 0.2 MPa. The nitrogen gas was continuously introduced for 30 days, and the phosgene concentration at the outlet of the phosgene synthesizing tower was measured as 10.2 ppm after purging. The phosgene was decomposed in a phosgene decomposition tower after purging, the concentration of the inorganic acid was 1%, and the inorganic acid was hydrochloric acid. After purging with the nitrogen gas, the tubes of the phosgene synthesizing tower were cleaned with a water gun, and the tubes were purged with hot nitrogen gas of 150° C. The dew point of the synthesizing tower was measured as −40° C., and the phosgene concentration at the outlet of the phosgene synthesizing tower and total purge time were shown in Table 1.

TABLE-US-00001 TABLE 1 Analysis results Phosgene concentration Ammonia after Nitrogen gas gas purging consumption consumption Purging time (ppm) (Nm.sup.3) (Nm.sup.3) (Days) Example 1 0.5 4800 9600 7 Example 2 0.4 14400 7200 6 Example 3 0.2 57600 3600 7 Comparative 8.1 420000 0 35 example 1 Comparative 10.2 360000 0 30 example 2 Example 4 0.5 4800 13440 10