Two-stage industrial continuous production process for condensation section of pigment yellow 139

Abstract

The invention discloses a two-stage method industrial continuous production process of a pigment yellow 139 condensation section, relates to the technical field of chemical engineering, and solves the problems that the existing production process is complicated, produced waste gas is inconvenient to recycle, the environment is easily polluted, the safety influence is relatively great, and the product supply is severely insufficient. Dropwise adding part of the phthalocyanine solution and the barbituric acid solution into the R1 reactor at the same time, starting nitrogen at the bottom of the R1 reactor, and generating ammonia gas through gas stripping discharge reaction of the nitrogen; a second reaction stage: extracting the reaction liquid 1 from the reactor R1, continuously dropwise adding the reaction liquid 1 into the reactor R2, dropwise adding a dilute sulphuric acid solution and the remaining phthalocyanine solution, and controlling the dropwise adding speed of the dilute sulphuric acid solution to keep the pH value of the system acidic; and extracting the reaction liquid 2 in the R2 reactor, and treating to obtain the pigment yellow 139. The use amount of sulfuric acid is reduced by 30-60%, and the equipment corrosion risk and the equipment investment are reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical industry, and in particular to a two-stage condensation process for industrialized continuous production of Pigment Yellow 139. Background Art

[0002] Pigment Yellow 139 is directly synthesized from 1,3-diiminoisoindoline (hereinafter referred to as phthalocyanine) and barbituric acid. The product, Pigment Yellow 139 (solid), also produces ammonia gas. As a member of the isoindoline family of pigments, Pigment Yellow 139 contains carbonyl, imino, cyano, and amide groups, which form intramolecular and intermolecular hydrogen bonds, resulting in a more planar molecular structure. Therefore, Pigment Yellow 139 is an organic pigment with excellent heat and solvent resistance.

[0003] The synthesis process for Pigment Yellow 139 disclosed in Patent CN114573998A utilizes a solid-state melting method in an intermittent, continuous, or combined manner to synthesize 1,3-diiminoisoindoline from phthalic anhydride and urea in the presence of a catalyst. The crude product, Pigment Yellow 139, is then reacted with barbituric acid to produce the crude product. It can be seen that the production of Pigment Yellow 139 in the related art is complex, costly, and highly polluting. The three wastes involved in production are substantial, and the waste gas produced is difficult to recycle, easily polluting the environment. This poses significant safety risks and results in a severe shortage of product supply, which, to a certain extent, limits its market application and promotion. Summary of the Invention

[0004] In this embodiment, a two-stage industrial continuous production process for the condensation section of Pigment Yellow 139 is provided to solve the problems in the existing technology of Pigment Yellow 139 production, such as the complex production process, large amounts of three wastes involved in the production, the difficulty in recycling the waste gas produced, the easy pollution of the environment, the great safety impact, and the serious shortage of product supply.

[0005] The present invention achieves the above-mentioned object through the following technical scheme, a two-stage industrial continuous production process of Pigment Yellow 139 condensation section, the two-stage industrial continuous production process of Pigment Yellow 139 condensation section comprising the following steps:

[0006] First reaction stage:

[0007] Under constant temperature conditions, part of the phthalocyanine solution and the barbituric acid solution were simultaneously added dropwise to the R1 reactor, and the nitrogen at the bottom of the R1 reactor was turned on to remove the ammonia generated by the reaction through nitrogen stripping;

[0008] Second reaction stage:

[0009] The reaction liquid 1 in the R1 reactor was continuously added dropwise to the R2 reactor, and the dilute sulfuric acid solution and the remaining part of the phthalocyanine solution were added dropwise, and the dropping rate of the dilute sulfuric acid solution was controlled to keep the pH value of the system acidic; the reaction liquid 2 in the R2 reactor was treated to obtain Pigment Yellow 139.

[0010] Preferably, the first reaction stage comprises:

[0011] S1. Establish an R1 reactor with a bottom nitrogen blowing system and a top open structure;

[0012] S2, dissolving phthalocyanine and barbituric acid in a molar ratio of 1:2 in a solvent;

[0013] S3. Under constant temperature conditions, 10-90% of the total amount of phthalocyanine solution and barbituric acid solution are simultaneously added dropwise to the R1 reactor, and nitrogen is turned on at the bottom of the R1 reactor to remove ammonia generated by the reaction through nitrogen stripping;

[0014] S4, after the predetermined time of dropwise addition, while continuing the dropwise addition, the reaction solution 1 in the R1 reactor is continuously withdrawn, and the liquid level of the R1 reactor is controlled to remain unchanged;

[0015] Preferably, the second reaction stage comprises:

[0016] S5, continuously adding the reaction solution 1 extracted from the R1 reactor to the R2 reactor, and adding a 10-30 wt% dilute sulfuric acid solution and the remaining amount of the phthalocyanine solution, controlling the dripping rate of the dilute sulfuric acid to keep the pH value of the system at 1.5-2.5;

[0017] S6, after the predetermined time of dropwise addition, while continuing the dropwise addition, the reaction liquid 2 in the R2 reactor is continuously withdrawn, and the liquid level of the R2 reactor is controlled to remain unchanged;

[0018] S7. Treat the reaction solution 2 to obtain Pigment Yellow 139.

[0019] Preferably, the phthalocyanine solution in step S2 is a solution formed by dissolving phthalocyanine in methanol, and the barbituric acid solution is a solution formed by dissolving barbituric acid in deionized water.

[0020] Preferably, in step S1, the nitrogen blowing system provides a stable gas source through a nitrogen generator or a high-pressure nitrogen cylinder, and uses a precise airflow control system to adjust the nitrogen flow rate and pressure. The nitrogen is evenly sprayed into the interior of the R1 reactor through a nozzle to form a high-speed airflow layer.

[0021] Preferably, the phthalocyanine solution in step S2 is prepared into a solution with a mass ratio concentration of 40-70%, and the insoluble matter is removed by filtration to ensure that the solution is clear.

[0022] Preferably, the barbituric acid solution in step S2 is prepared into a solution with a mass concentration of 40-70%, and is stirred at a temperature above 60°C until it is completely dissolved.

[0023] Preferably, the temperature of the constant temperature condition in step S3 is 65±2°C; and the reaction temperature of the R2 reactor in step S5 is 65±2°C.

[0024] Preferably, the reaction solution 2 in step S6 includes a solid solution of the product Pigment Yellow 139 and the by-product ammonium sulfate.

[0025] Preferably, the predetermined time in step S4 and step S6 is 30±5 minutes.

[0026] The beneficial effects of the present invention are as follows: the two-stage industrial continuous production process of Pigment Yellow 139 adopts a staged reaction design, reduces sulfuric acid usage by 30-60%, reduces equipment corrosion risk and equipment investment, reduces three wastes by 30%, generates recyclable ammonium sulfate and ammonia, and the product purity can reach more than 95%. Excessive barbituric acid is used to maintain the acidity of the reaction system to ensure smooth reaction; in the second reaction stage, dilute sulfuric acid is used to convert the generated small amount of barbituric acid ammonia into barbituric acid and ammonium sulfate, thereby reducing the overall sulfuric acid usage; sulfuric acid is not involved in the first reaction stage, the reactor material selection is simple, and the overall equipment investment is reduced; the nitrogen gas in the first stage is used to achieve selective removal of ammonia, thereby reducing sulfuric acid usage and also reducing the output of three wastes; and the removed ammonia can also be applied to the previous production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a production flow chart of the present invention.

[0028] Figure 2 Flow chart of the method of the present invention. DETAILED DESCRIPTION

[0029] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0030] like Figure 1-2 As shown, the embodiment of the present invention provides a two-stage industrial continuous production process of Pigment Yellow 139 condensation section, the following steps:

[0031] First reaction stage:

[0032] Under constant temperature conditions, part of the phthalocyanine solution and the barbituric acid solution were simultaneously added dropwise to the R1 reactor, and the nitrogen at the bottom of the R1 reactor was turned on to remove the ammonia generated by the reaction through nitrogen stripping;

[0033] Second reaction stage:

[0034] The reaction liquid 1 in the R1 reactor was continuously added dropwise to the R2 reactor, and the dilute sulfuric acid solution and the remaining part of the phthalocyanine solution were added dropwise, and the dropping rate of the dilute sulfuric acid solution was controlled to keep the pH value of the system acidic; the reaction liquid 2 in the R2 reactor was treated to obtain Pigment Yellow 139.

[0035] In an embodiment of the present invention, the one-stage reaction design of the prior art is improved to a two-stage reaction design. In the first reaction stage, excess barbituric acid is used to maintain the acidity of the reaction system, ensuring smooth reaction. In the second reaction stage, dilute sulfuric acid is used to convert the small amount of barbituric acid ammonia generated into barbituric acid and ammonium sulfate. This reduces the overall sulfuric acid usage, and since sulfuric acid is not involved in the first reaction stage, the reactor material selection is simple and the overall equipment investment is reduced. The staged reaction design uses nitrogen gas in the first stage to achieve selective removal of ammonia, reducing sulfuric acid usage and also reducing the output of three wastes. The removed ammonia can also be applied to the previous production process.

[0036] Example 1:

[0037] A two-stage industrial continuous production process for a condensation section of Pigment Yellow 139, comprising the following steps:

[0038] First reaction stage:

[0039] S1. Establish an R1 reactor with a bottom nitrogen blowing system and a top open structure;

[0040] S2, dissolving phthalocyanine and barbituric acid in a molar ratio of 1:2 in a solvent;

[0041] S3. Under constant temperature conditions, 10-90% of the total amount of phthalocyanine solution and barbituric acid solution are simultaneously added dropwise to the R1 reactor, and nitrogen is turned on at the bottom of the R1 reactor to remove ammonia generated by the reaction through nitrogen stripping;

[0042] S4, after the predetermined time of dropwise addition, while continuing the dropwise addition, the reaction solution 1 in the R1 reactor is continuously withdrawn, and the liquid level of the R1 reactor is controlled to remain unchanged;

[0043] Second reaction stage:

[0044] S5, continuously adding the reaction solution 1 extracted from the R1 reactor to the R2 reactor, and adding a 10-30 wt% dilute sulfuric acid solution and the remaining amount of the phthalocyanine solution, controlling the dripping rate of the dilute sulfuric acid to keep the pH value of the system at 1.5-2.5;

[0045] S6, after the predetermined time of dropwise addition, while continuing the dropwise addition, the reaction liquid 2 in the R2 reactor is continuously withdrawn, and the liquid level of the R2 reactor is controlled to remain unchanged;

[0046] S7. Treat the reaction solution 2 to obtain Pigment Yellow 139.

[0047] Preferably, in step (S2), the phthalocyanine solution is a solution formed by dissolving phthalocyanine in methanol, and the barbituric acid solution is a solution formed by dissolving barbituric acid in deionized water.

[0048] Preferably, in the step (S1), the nitrogen blowing system provides a stable gas source through a nitrogen generator or a high-pressure nitrogen bottle, and uses a precise airflow control system to adjust the nitrogen flow rate and pressure. The nitrogen is evenly sprayed into the interior of the R1 reactor through a nozzle to form a high-speed airflow layer.

[0049] Preferably, the phthalocyanine solution in step (S2) is prepared into a solution with a mass concentration of 40-70%, and the insoluble matter is removed by filtration to ensure that the solution is clear.

[0050] Preferably, the barbituric acid solution in step (S2) is prepared into a solution with a mass concentration of 40-70%, and stirred at a temperature above 60° until it is completely dissolved.

[0051] Preferably, the temperature of the constant temperature condition in the step (S3) is 65±2°C; and the reaction temperature of the R2 reactor in the step (S5) is 65±2°C.

[0052] Preferably, the reaction solution 2 in step (S6) includes a solid solution of the product Pigment Yellow 139 and the by-product ammonium sulfate.

[0053] Preferably, the predetermined time in step (S4) and step (S6) is 30±5 minutes.

[0054] The two-stage industrial continuous production process of the Pigment Yellow 139 condensation section adopts a staged reaction design, which reduces the amount of concentrated sulfuric acid by 30-60%, reduces the risk of equipment corrosion and equipment investment, reduces the three wastes by 30%, generates recyclable ammonium sulfate and ammonia, and the product purity can reach more than 95%. Excess barbituric acid is used to maintain the acidity of the reaction system to ensure smooth reaction. In the second reaction stage, dilute sulfuric acid is used to convert the small amount of barbituric acid ammonia generated into barbituric acid and ammonium sulfate, reducing the overall sulfuric acid usage. In addition, no sulfuric acid is involved in the first reaction stage, the reactor material selection is simple, and the overall equipment investment is reduced. The nitrogen gas in the first stage is used to achieve selective removal of ammonia, reducing the amount of sulfuric acid used and also reducing the output of the three wastes. The removed ammonia can also be applied to the previous production.

[0055] Example 2:

[0056] A two-stage industrial continuous production process for a condensation section of Pigment Yellow 139, comprising the following steps:

[0057] First reaction stage:

[0058] S11, establishing an R1 reactor with a bottom nitrogen blowing system and a top open structure;

[0059] S12, dissolving phthalocyanine and barbituric acid in a molar ratio of 1:2 in a solvent;

[0060] S13. At a constant temperature of 65±2°C, 10-90% of the total amount of the phthalocyanine solution and the barbituric acid solution are simultaneously added dropwise to the R1 reactor. The nitrogen gas at the bottom of the R1 reactor is turned on to remove the ammonia generated by the reaction by nitrogen stripping.

[0061] S14, after 30±5 minutes of dropwise addition, while continuing the dropwise addition, continuously withdraw the reaction solution 1 from the R1 reactor and control the liquid level of the R1 reactor to remain constant;

[0062] Second reaction stage:

[0063] S15, continuously adding the reaction solution 1 extracted from the R1 reactor to the R2 reactor, and adding a 10-30 wt% dilute sulfuric acid solution and the remaining 90-10% of the total amount of the phthalocyanine solution, controlling the dripping rate of the dilute sulfuric acid to maintain the system pH value at 1.5-2.5;

[0064] S16, after 30±5 minutes of dropwise addition, while continuing the dropwise addition, continuously withdraw the reaction solution 2 from the R2 reactor, and control the liquid level of the R2 reactor to remain unchanged;

[0065] S17, treating the reaction solution 2 to obtain Pigment Yellow 139.

[0066] Preferably, in the step (S12), the phthalocyanine solution is a solution formed by dissolving phthalocyanine in methanol, and the barbituric acid solution is a solution formed by dissolving barbituric acid in deionized water.

[0067] Preferably, in the step (S11), the nitrogen blowing system provides a stable gas source through a nitrogen generator or a high-pressure nitrogen bottle, and uses a precise airflow control system to adjust the nitrogen flow rate and pressure. The nitrogen is evenly sprayed into the interior of the R1 reactor through a nozzle to form a high-speed airflow layer.

[0068] Preferably, in the step (S12), the phthalocyanine solution is prepared by dissolving phthalocyanine in methanol to prepare a solution with a concentration of 40-70% (w / w), and filtering to remove insoluble matter to ensure that the solution is clear.

[0069] Preferably, the barbituric acid solution in step (S12) is prepared by dissolving barbituric acid in deionized water to prepare a solution of appropriate concentration, and stirring the solution at a temperature above 60° until it is completely dissolved.

[0070] Preferably, the reaction temperature of the R2 reactor in the step (S15) is 65±2°C.

[0071] Preferably, the reaction solution 2 in step (S16) is mainly a solid solution of the product Pigment Yellow 139 and the by-product ammonium sulfate.

[0072] The two-stage industrial continuous production process for the condensation section of Pigment Yellow 139 adopts a staged reaction design, which reduces the use of concentrated sulfuric acid by 30-60%, reduces the risk of equipment corrosion and equipment investment, reduces the three wastes by 30%, generates recyclable ammonium sulfate and ammonia, and achieves a product purity of over 95%. Excess barbituric acid is used to maintain the acidity of the reaction system to ensure smooth reaction. In the second reaction stage, dilute sulfuric acid is used to convert the generated small amount of barbituric acid ammonia into barbituric acid and ammonium sulfate, thereby reducing the overall sulfuric acid usage. In addition, no sulfuric acid is involved in the first reaction stage, the selection of reactor materials is simple, and the overall equipment investment is reduced.

[0073] Example 3:

[0074] A two-stage industrial continuous production process for a condensation section of Pigment Yellow 139, comprising the following steps:

[0075] First reaction stage:

[0076] S21, establishing an R1 reactor with a bottom nitrogen blowing system and a top open structure;

[0077] S22, dissolving phthalocyanine and barbituric acid in a molar ratio of 1:2 in a solvent;

[0078] S23. At a constant temperature of 65±2°C, 40-70% of the total amount of the phthalocyanine solution and the barbituric acid solution are simultaneously added dropwise to the R1 reactor. The nitrogen gas at the bottom of the R1 reactor is turned on to remove the ammonia generated by the reaction by nitrogen stripping.

[0079] S24, after 30±5 minutes of dropwise addition, while continuing the dropwise addition, continuously withdraw the reaction solution 1 from the R1 reactor and control the liquid level of the R1 reactor to remain constant;

[0080] Second reaction stage:

[0081] S25, continuously adding the reaction solution 1 extracted from the R1 reactor to the R2 reactor, and adding a 10-30 wt% dilute sulfuric acid solution and the remaining 60-30% of the total amount of the phthalocyanine methanol solution, controlling the dripping rate of the dilute sulfuric acid to keep the pH value of the system at 1.5-2.5;

[0082] S26, after 30±5 minutes of dropwise addition, while continuing the dropwise addition, continuously withdraw the reaction solution 2 from the R2 reactor, and control the liquid level of the R2 reactor to remain unchanged;

[0083] S27. Treat the reaction solution 2 to obtain Pigment Yellow 139.

[0084] Preferably, in the step (S22), the phthalocyanine solution is a solution formed by dissolving phthalocyanine in methanol, and the barbituric acid solution is a solution formed by dissolving barbituric acid in deionized water.

[0085] Preferably, in the step (S21), the nitrogen blowing system provides a stable gas source through a nitrogen generator or a high-pressure nitrogen bottle, and uses a precise airflow control system to adjust the nitrogen flow rate and pressure. The nitrogen is evenly sprayed into the interior of the R1 reactor through a nozzle to form a high-speed airflow layer.

[0086] Preferably, in the step (S22), the phthalocyanine solution is prepared by dissolving phthalocyanine in methanol to prepare a solution with a concentration of 40-70% (w / w), and filtering to remove insoluble matter to ensure that the solution is clear.

[0087] Preferably, the barbituric acid solution in step (S22) is prepared by dissolving barbituric acid in deionized water to prepare a solution of appropriate concentration, and stirring the solution at a temperature above 60° until it is completely dissolved.

[0088] Preferably, the reaction temperature of the R2 reactor in the step (S25) is 65±2°C.

[0089] Preferably, the reaction solution 2 in the step (S26) is mainly a solid solution of the product Pigment Yellow 139 and the by-product ammonium sulfate.

[0090] The two-stage industrial continuous production process for the condensation section of Pigment Yellow 139 adopts a staged reaction design, which reduces the use of concentrated sulfuric acid by 30-60%, reduces the risk of equipment corrosion and equipment investment, reduces the three wastes by 30%, generates recyclable ammonium sulfate and ammonia, and achieves a product purity of over 95%. Excess barbituric acid is used to maintain the acidity of the reaction system, ensuring smooth reaction.

[0091] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

[0092] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A two-stage industrial continuous production process for the condensation section of Pigment Yellow 139, characterized by: The two-stage industrial continuous production process of the Pigment Yellow 139 condensation section comprises the following steps: First reaction stage: S1. Establish an R1 reactor with a bottom nitrogen blowing system and a top open structure; S2, dissolving phthalocyanine and barbituric acid in a molar ratio of 1:2 in a solvent; S3. Under constant temperature conditions, 10-90% of the total amount of phthalocyanine solution and barbituric acid solution are simultaneously added dropwise to the R1 reactor, and nitrogen is turned on at the bottom of the R1 reactor to remove ammonia generated by the reaction through nitrogen stripping; S4, after the predetermined time of dropwise addition, while continuing the dropwise addition, the reaction solution 1 in the R1 reactor is continuously withdrawn, and the liquid level of the R1 reactor is controlled to remain unchanged; Second reaction stage: S5, continuously adding the reaction solution 1 extracted from the R1 reactor to the R2 reactor, and adding a 10-30 wt% dilute sulfuric acid solution and the remaining amount of the phthalocyanine solution, controlling the dripping rate of the dilute sulfuric acid to keep the pH value of the system at 1.5-2.5; S6, after the predetermined time of dropwise addition, while continuing the dropwise addition, the reaction liquid 2 in the R2 reactor is continuously withdrawn, and the liquid level of the R2 reactor is controlled to remain unchanged; S7. Treat the reaction solution 2 to obtain Pigment Yellow 139.

2. The two-stage industrial continuous production process of Pigment Yellow 139 condensation section according to claim 1 is characterized in that: In step S2, the phthalocyanine solution is a solution formed by dissolving phthalocyanine in methanol, and the barbituric acid solution is a solution formed by dissolving barbituric acid in deionized water.

3. The two-stage industrial continuous production process of Pigment Yellow 139 condensation section according to claim 1 is characterized in that: In step S1, the nitrogen blowing system provides a stable gas source through a nitrogen generator or a high-pressure nitrogen cylinder, and uses a precise airflow control system to adjust the nitrogen flow rate and pressure. Nitrogen is evenly sprayed into the interior of the R1 reactor through a nozzle to form a high-speed airflow layer.

4. The two-stage industrial continuous production process of Pigment Yellow 139 condensation section according to claim 1 is characterized in that: In step S2, the phthalocyanine solution is prepared into a solution with a mass concentration of 40-70%, and the insoluble matter is removed by filtration to ensure that the solution is clear.

5. The two-stage industrial continuous production process of Pigment Yellow 139 condensation section according to claim 1 is characterized in that: In step S2, the barbituric acid solution is prepared into a solution with a mass concentration of 40-70%, and stirred at a temperature above 60°C until it is completely dissolved.

6. The two-stage industrial continuous production process of Pigment Yellow 139 condensation section according to claim 1 is characterized in that: The temperature of the constant temperature condition in step S3 is 65±2°C; the reaction temperature of the R2 reactor in step S5 is 65±2°C.

7. The two-stage industrial continuous production process of Pigment Yellow 139 condensation section according to claim 1 is characterized in that: In step S6, the reaction solution 2 includes a solid solution of the product Pigment Yellow 139 and the by-product ammonium sulfate.

8. The two-stage industrial continuous production process of Pigment Yellow 139 condensation section according to claim 1 is characterized in that: The predetermined time in step S4 and step S6 is 30±5 minutes.

Images