CN110372547B - Method for preparing 1-amino-4-sodium naphthalene sulfonate - Google Patents
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- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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Abstract
The invention discloses a method for preparing 1-amino-4-sodium naphthalene sulfonate, which comprises the following steps: (1) reduction sulfonation reaction: sequentially adding water, an organic solvent, 1-nitronaphthalene and a reduction sulfonating agent into a reactor, heating to 108-114 ℃, carrying out reflux reaction, and reacting for 6-9h to the end point of the reaction; (2) cooling and desalting: cooling the material obtained in the step (1) to 0-10 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1; (3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, adding sulfuric acid to adjust the pH value of the filtrate to be 1-2, heating to 50-60 ℃, then carrying out suction filtration or filter pressing, and collecting a filter cake 2 and a filtrate 2; (4) adding alkali for neutralization: adding bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 20-50 ℃, adding inorganic base to adjust the pH value of the solution to 7-8, and completely dissolving the filter cake; (5) concentrating and crystallizing to obtain the target product 1-amino-4-sodium naphthalenesulfonate. The method has the characteristics of simple production process, low energy consumption, less wastewater, and higher product selectivity and purity.
Description
Technical Field
The invention relates to a production method of a chemical dye intermediate, in particular to a production method of 1-amino-4-sodium naphthalenesulfonate.
Background
Sodium 1-amino-4-naphthalenesulfonate (sodium 1,4 for short) is widely used in chemical, medical and dye fields, and its main production process is traditional solid phase sulfonation and solvent sulfonation. Both solid-phase sulfonation and solvent sulfonation generally involve hydrogenation reduction of source 1-nitronaphthalene to obtain 1-naphthylamine, and high-temperature transposition sulfonation of 1-naphthylamine to obtain sodium 1,4, and the synthetic route is complicated. Wherein, the 1-naphthylamine belongs to 3 kinds of carcinogenic substances and has certain carcinogenicity; and has potential safety hazard in the process of synthesizing 1-naphthylamine by high-pressure hydrogenation (reaction pressure is 3-4MPa) of 1-nitronaphthalene; in addition, a large amount of waste water is generated in the post-treatment process, which is not suitable for the production of the current clean process.
The reaction process of the traditional solid phase sulfonation method is as follows: ammonium salt is formed by 1-naphthylamine and equimolar sulfuric acid, and then sodium 1,4 is formed by high-temperature transposition sulfonation. The traditional solid phase method comprises baking sulfonation method, microwave heating method and the like. At present, the industrial production is also biased to the solid phase method, but the solid phase method has higher requirements on equipment, high production cost, high reaction temperature (180-.
In recent years, due to the above-mentioned disadvantages of the solid phase method, there have been many studies on the preparation of sodium 1,4 at high temperature (180 ℃ C.) by sulfonating 1-naphthylamine with a high boiling point organic solvent, such as ortho-dichlorobenzene concentrated sulfuric acid sulfonation, sulfolane concentrated sulfuric acid sulfonation, mixed solvent concentrated sulfuric acid sulfonation, and the like. The methods have the advantages of high yield, few byproducts, difficult carbonization of products and good quality, but the methods have the same high energy consumption, high solvent price and difficult recovery, and the waste of resources is caused by volatilizing part of the solvent, thereby increasing the production cost.
According to THE data, in addition to THE traditional solid phase sulfonation method and solvent sulfonation method, K.B. GOLDBLUM and so on [ A STUDY OF THE MECHANISM OF THE PIRIA REACTION ], according to THE Piria REACTION mechanism (THE REACTION OF aromatic nitrated compound and sodium bisulfite, and THE simultaneous reduction and sulfonation REACTION are called Piria REACTION), in 1947, THE reflux REACTION OF 1-nitronaphthalene and sodium bisulfite aqueous solution in a flask with a reflux device is proposed, and after THE REACTION is finished, a trace amount OF 1,4 sodium can be generated, and THE yield is not reported. Then, the inventors of the present invention conducted a repetitive experiment according to the reported experimental protocol, and found that the purity of sodium 1,4 in the reaction solution was only about 4% and the selectivity was low according to a liquid chromatography test after the reaction was completed, and in addition, a large amount of bis-sulfonate was also generated. Therefore, on the basis of the report, how to improve the selectivity and yield of the sodium 1,4 according to the Piria reaction, a new method is developed to prepare the sodium 1,4, and the method has great significance for Piria mechanism research and industrial application of the new method. According to the research direction, the invention develops a novel preparation process for obtaining products with higher purity and selectivity by utilizing the solvation effect of an organic solvent through deep synthesis research. The technical method related to the invention for preparing the dye intermediate has no related patent report.
Disclosure of Invention
The invention provides a method for preparing 1-amino-4-sodium naphthalene sulfonate by using 1-nitronaphthalene and a reductive sulfonating agent through a reductive sulfonation reaction by utilizing a solvation effect, which is simple in production process, low in energy consumption, less in waste water, higher in product selectivity and purity and solves the problems that a process route is complicated, potential safety hazards exist when an intermediate product is prepared, a large amount of waste water is generated in a production process, the intermediate product has strong carcinogenicity, the sulfonation reaction temperature is high, the energy consumption is high, products are easy to carbonize, and a solvent is easy to damage and difficult to recover.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing sodium 1-amino-4-naphthalenesulfonate, comprising the steps of:
(1) reduction sulfonation reaction: sequentially adding water, an organic solvent, 1-nitronaphthalene and a reduction sulfonating agent into a reactor, heating to 108-114 ℃, carrying out reflux reaction, and reacting for 6-9h to the end point of the reaction; the organic solvent is one or a mixture of any more of N-N dimethylacetamide, N-N dimethylformamide, 1-methyl-2-pyrrolidone, sulfolane, ethylene glycol, ethanol and the like; the reduction sulfonating agent is one or the mixture of sodium bisulfite and sodium metabisulfite; the mass ratio of the 1-nitronaphthalene to the reduction sulfonating agent to the water to the organic solvent is 1 (2.1-2.7) to (3.0-3.8) to (3.0-7.0);
(2) cooling and desalting: cooling the material obtained in the step (1) to 0-10 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, adding sulfuric acid (preferably 98% sulfuric acid) to adjust the pH value of the filtrate to be 1-2, heating to 50-60 ℃, then carrying out suction filtration or pressure filtration, and collecting a filter cake 2 and the filtrate 2;
(4) adding alkali for neutralization: adding bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 20-50 ℃ (preferably 20-40 ℃), and adding inorganic base to adjust the pH value of the solution to 7-8 so as to completely dissolve the filter cake;
(5) concentration and crystallization: evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution; cooling and crystallizing the obtained concentrated solution, then carrying out suction filtration or filter pressing, and collecting a filter cake to obtain the target product 1-amino-4-sodium naphthalenesulfonate.
Further, the reductive sulfonating agent in the step (1) is preferably added in batches, namely, water, an organic solvent, 1-nitronaphthalene and a part of the reductive sulfonating agent are sequentially added into a reactor, the temperature is raised to 108-114 ℃ for reflux reaction, the rest reductive sulfonating agent is added in batches, and then the reaction is continued to the end point of the reaction. In the invention, the yield, purity and content of the product can be obviously improved by adding the reductive sulfonating agent in batches, and the interval time and the batches of the reductive sulfonating agent in batches can be selected by a person skilled in the art according to actual conditions (such as adding the reductive sulfonating agent in 3-6 times at intervals of 30-60 min) so as to obtain balance between reaction effect and production efficiency.
Furthermore, the part of the reducing sulfonating agent added in the first batch accounts for 35 to 45 percent of the total mass of the reducing sulfonating agent.
Further, the organic solvent is preferably a mixture of two or more of N-N dimethylacetamide, N-N dimethylformamide, 1-methyl-2-pyrrolidone, sulfolane, ethylene glycol, ethanol, and the like.
Further, the organic solvent is preferably a mixture of 1-methyl-2-pyrrolidone and ethylene glycol. More preferably, the volume ratio of 1-methyl-2-pyrrolidone to ethylene glycol in the mixture is from 0.5 to 2:1, most preferably 1: 1.
Further, the mass ratio of the 1-nitronaphthalene, the reductive sulfonating agent, the water and the organic solvent in the step (1) is preferably 1 (2.2-2.6): 3.2-3.5): 3.2-7.0, more preferably 1 (2.28-2.53):3.47: (3.47-6.94), and most preferably 1 (2.28-2.53):3.47: 3.47.
In the present invention, the bottom water is the bottom water, which is a chemical reaction usually carried out in water in industrial production and a certain amount of water is added to the bottom of the reaction equipment.
The method can realize the recycling of water in the reaction process, for example, the filtrate 2 collected in the step (3) can be used for the next batch of reduction sulfonation bottom water; collecting the water generated by evaporation and concentration in the step (5) and using the water for the next batch of neutralization reaction; and collecting the crystallization mother liquor to be used for the bottom water of the next batch of neutralization reaction or applied to a water reducing agent.
Compared with the prior art, the invention has the innovation that:
(1) the invention provides a novel method for preparing 1-amino-4-naphthalene sulfonic acid by using a solvation effect to realize direct reduction sulfonation reaction of 1-nitronaphthalene, which avoids a hydrogenation reduction process in the traditional method, shortens a preparation process route, reduces potential safety hazards in the preparation process, removes waste water in the process of preparing 1-naphthylamine by hydrogenation reduction of 1-nitronaphthalene, and has higher product selectivity and product purity.
(2) Compared with the traditional process, the invention has the advantages of low reaction temperature and low energy consumption, and also avoids the defects of product carbonization, unqualified product quality and the like caused by overhigh sulfonation temperature in the traditional process.
(3) The invention obviously improves the product yield by adding the reductive sulfonating agent in batches.
Drawings
FIG. 1 is a process flow diagram of one embodiment of the process of the present invention for preparing 1-amino-4-naphthalenesulfonic acid.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The methods used in the following examples are conventional unless otherwise specified, and the materials and reagents used are commercially available.
Example 1
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 60g of bottom water into a reactor, sequentially adding 60g of N-N dimethylacetamide, 60g of ethylene glycol, 17.3g of 1-nitronaphthalene and 16.42g of sodium bisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 4.47g of sodium bisulfite every 1h for 5 times, and reacting for 1h to the end point of the reaction after the sodium bisulfite is completely added;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 3.3g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reductive sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 80g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 3.5g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 15.8g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.2% and the content of 99.1%.
Example 2
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 240g of bottom water into a reactor, then sequentially adding 120g of 1-methyl-2-pyrrolidone, 120g of ethylene glycol, 69.2g of 1-nitronaphthalene and 59.38g of sodium metabisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 19.8g of sodium metabisulfite every 1 hour, adding for 5 times in total, and reacting for 1 hour to the end of the reaction after the feeding of the sodium metabisulfite is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 13.4g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reductive sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 320g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 35 ℃, adding 14.1g of sodium carbonate to adjust the pH value of the solution to 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 63.9g of 1-amino-4-sodium naphthalenesulfonate with the purity of 98.9% and the content of 98.8%.
Example 3
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, sequentially adding 150g of N-N dimethylformamide, 150g of ethylene glycol, 86.5g of 1-nitronaphthalene and 82.1g of sodium bisulfite, heating to 108-phase reaction at 114 ℃, carrying out reflux reaction, adding 27.3g of sodium bisulfite every 1h for 5 times, and reacting for 1h to the end point of the reaction after the sodium bisulfite is completely added;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.5g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reductive sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 79.5g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.4% and the content of 99.0%.
Example 4
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 240g of bottom water into a reactor, then sequentially adding 120g of N-N dimethylacetamide, 120g of ethylene glycol, 69.2g of 1-nitronaphthalene and 65.68g of sodium bisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 21.9g of sodium bisulfite every 1h for 5 times, and reacting for 1h to the end point of the reaction after the sodium bisulfite is completely added;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 13.5g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 14.3g of sodium carbonate to adjust the pH value of the solution to 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 63.5g of 1-amino-4-sodium naphthalenesulfonate, wherein the purity of a filter cake is 99.2%, and the content of the filter cake is 98.9%.
Example 5
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, then sequentially adding 150g of 1-methyl-2-pyrrolidone, 150g of ethylene glycol, 86.5g of 1-nitronaphthalene and 74.2g of sodium metabisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 24.7g of sodium metabisulfite every 1 hour, feeding for 5 times in total, and reacting for 1 hour to the end of the reaction after the feeding is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 80g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.1% and the content of 98.9%.
Example 6
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 240g of bottom water, 120g of 1-methyl-2-pyrrolidone, 120g of ethylene glycol, 69.2g of 1-nitronaphthalene and 172.18g of sodium bisulfite into a reactor in sequence, and then heating to 108-;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 6.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 6.9g of sodium carbonate to adjust the pH value of the solution to 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling and crystallizing the concentrated solution, and then carrying out suction filtration or pressure filtration to obtain 29.4g of 1-amino-4-sodium naphthalenesulfonate, wherein the purity of a filter cake is 98.3%, and the content of the filter cake is 98.1%.
Example 7
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, then sequentially adding 150g of 1-methyl-2-pyrrolidone, 150g of ethylene glycol, 86.5g of 1-nitronaphthalene and 74.2g of sodium metabisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 30.9g of sodium metabisulfite every 45min, feeding for 4 times in total, and reacting for 3 hours to the end of the reaction after the feeding is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 30 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 73g of 1-amino-4-sodium naphthalenesulfonate with the purity of 98.1% and the content of 98.0%.
Example 8
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, then sequentially adding 300g of 1-methyl-2-pyrrolidone, 86.5g of 1-nitronaphthalene and 74.2g of sodium metabisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 24.7g of sodium metabisulfite every 1h, feeding for 5 times in total, and reacting for 1h to the end of the reaction after the feeding is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 25 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or filter pressing to obtain 71g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.3 percent and the content of 97.9 percent.
Example 9
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, then sequentially adding 300g of ethylene glycol, 86.5g of 1-nitronaphthalene and 74.2g of sodium metabisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 24.7g of sodium metabisulfite every 1h, feeding for 5 times in total, and reacting for 1h to the end of the reaction after the feeding is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 76g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.5 percent and the content of 97.6 percent.
Example 10
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, then sequentially adding 100g of ethylene glycol, 200g of 1-methyl-2-pyrrolidone, 86.5g of 1-nitronaphthalene and 74.2g of sodium metabisulfite, heating to 108-114 ℃ for reflux reaction, then adding 24.7g of sodium metabisulfite every 1h, feeding for 5 times in total, and reacting for 1h to the end of the reaction after the feeding is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 78g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.2% and the content of 99.4%.
Example 11
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, then sequentially adding 200g of ethylene glycol, 100g of 1-methyl-2-pyrrolidone, 86.5g of 1-nitronaphthalene and 74.2g of sodium metabisulfite, heating to 108-114 ℃ for reflux reaction, then adding 24.7g of sodium metabisulfite every 1h, feeding for 5 times in total, and reacting for 1h to the end of the reaction after the feeding is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 75g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.2 percent and the content of 98.7 percent.
Example 12
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 240g of bottom water into a reactor, then sequentially adding 120g of 1-methyl-2-pyrrolidone, 120g of ethylene glycol, 69.2g of 1-nitronaphthalene and 59.38g of sodium metabisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 33.0g of sodium metabisulfite every 30min for 3 times, and reacting for 4 hours to the end of the reaction after the sodium metabisulfite is fed;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 13.4g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 320g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 40 ℃, adding 14.1g of sodium carbonate to adjust the pH value of the solution to 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or pressure filtration to obtain 63.9g of 1-amino-4-sodium naphthalenesulfonate with the purity of 98.0% and the content of 98.5%.
Example 13
A method for preparing 1-amino-4-sodium naphthalene sulfonate is implemented according to the following steps:
(1) reduction sulfonation reaction: adding 300g of bottom water into a reactor, then sequentially adding 150g of 1-methyl-2-pyrrolidone, 150g of ethylene glycol, 86.5g of 1-nitronaphthalene and 74.2g of sodium metabisulfite, heating to 108 ℃ and 114 ℃ for reflux reaction, then adding 24.7g of sodium metabisulfite every 1 hour, feeding for 5 times in total, and reacting for 1 hour to the end of the reaction after the feeding is finished;
(2) desalting: cooling the material obtained in the step (1) to 5 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1, wherein the filtrate 1 is used for acidification;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, heating to 50-60 ℃, adding 16.6g of 98% sulfuric acid to adjust the pH value of the filtrate to 1-2, then carrying out suction filtration or filter pressing, collecting a filter cake 2 and a filtrate 2, using the collected filtrate 2 for the next batch of reduction sulfonation bottom water, and using the collected filter cake 2 for neutralization reaction;
(4) and (3) neutralization reaction: adding 400g of bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 20 ℃, adding 17.8g of sodium carbonate to adjust the pH value of the solution to be 7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: and (3) evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution, cooling the concentrated solution to 10 ℃ for crystallization, and then carrying out suction filtration or filter pressing to obtain 79g of 1-amino-4-sodium naphthalenesulfonate with the purity of 99.0% and the content of 98.9%.
Claims (8)
1. A method for preparing sodium 1-amino-4-naphthalenesulfonate, comprising the steps of:
(1) reduction sulfonation reaction: sequentially adding water, an organic solvent, 1-nitronaphthalene and a reduction sulfonating agent into a reactor, heating to 108-114 ℃, carrying out reflux reaction, and reacting for 6-9h to the end point of the reaction; the reduction sulfonating agent is one or the mixture of sodium bisulfite and sodium metabisulfite; the mass ratio of the 1-nitronaphthalene to the reduction sulfonating agent to the water to the organic solvent is 1 (2.1-2.7) to (3.0-3.8) to (3.0-7.0); adding a reducing sulfonating agent in batches, namely sequentially adding water, an organic solvent, 1-nitronaphthalene and a part of reducing sulfonating agent into a reactor, heating to 108-; the step of adding the reducing sulfonating agent in batches is to add the reducing sulfonating agent in 3-6 times at intervals of 30-60min, wherein the part of the reducing sulfonating agent added in the first batch accounts for 35-45% of the total mass of the reducing sulfonating agent; the organic solvent is a mixture of more than two of N, N-dimethylacetamide, N-dimethylformamide, 1-methyl-2-pyrrolidone and ethylene glycol;
(2) cooling and desalting: cooling the material obtained in the step (1) to 0-10 ℃, precipitating inorganic salt, then carrying out suction filtration or filter pressing, and collecting filtrate 1;
(3) material acidification: adding the filtrate 1 collected in the step (2) into a reactor, adding sulfuric acid to adjust the pH =1-2 of the filtrate, heating to 50-60 ℃, then carrying out suction filtration or filter pressing, and collecting a filter cake 2 and a filtrate 2;
(4) adding alkali for neutralization: adding bottom water into a reactor, adding the filter cake 2 collected in the step (3), heating to 20-50 ℃, adding inorganic base to adjust the pH =7-8, and completely dissolving the filter cake;
(5) concentration and crystallization: evaporating and concentrating the solution obtained in the step (4) to obtain a concentrated solution; cooling and crystallizing the obtained concentrated solution, then carrying out suction filtration or filter pressing, and collecting a filter cake to obtain the target product 1-amino-4-sodium naphthalenesulfonate.
2. The method of claim 1, wherein: the organic solvent is a mixture of 1-methyl-2-pyrrolidone and ethylene glycol.
3. The method of claim 2, wherein: in the mixture of the 1-methyl-2-pyrrolidone and the ethylene glycol, the volume ratio of the 1-methyl-2-pyrrolidone to the ethylene glycol is 0.5-2: 1.
4. The method of claim 2, wherein: in the mixture of the 1-methyl-2-pyrrolidone and the ethylene glycol, the volume ratio of the 1-methyl-2-pyrrolidone to the ethylene glycol is 1: 1.
5. The method of any of claims 1 to 4, wherein: in the step (1), the mass ratio of the 1-nitronaphthalene, the reducing sulfonating agent, the water and the organic solvent is 1 (2.2-2.6) to (3.2-3.5) to (3.2-7.0).
6. The method of claim 5, wherein: in the step (1), the mass ratio of the 1-nitronaphthalene, the reducing sulfonating agent, the water and the organic solvent is 1 (2.28-2.53) to 3.47 (3.47-6.94).
7. The method of claim 6, wherein: in the step (1), the mass ratio of the 1-nitronaphthalene, the reducing sulfonating agent, the water and the organic solvent is 1 (2.28-2.53) to 3.47.
8. The method of claim 1, wherein: using the filtrate 2 collected in the step (3) for the next batch of reduction sulfonation bottom water; and (5) collecting water generated by evaporation concentration in the step (5) for bottom water of the next batch of neutralization reaction, and collecting crystallization mother liquor for bottom water of the next batch of neutralization reaction or for water reducing agent.
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