CN112979427B - Process for synthesizing naphthol through sulfur trioxide indirect sulfonation reaction - Google Patents
Process for synthesizing naphthol through sulfur trioxide indirect sulfonation reaction Download PDFInfo
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—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
- C07C303/04—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
- 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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- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C07—ORGANIC CHEMISTRY
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
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Abstract
The invention discloses a process for synthesizing naphthol by indirect sulfonation reaction of sulfur trioxide, which comprises the following steps: adding excessive sulfuric acid into refined naphthalene, and generating naphthalene sulfonic acid through sulfonation reaction to completely react naphthalene; melting and crystallizing the sulfonation reaction product to obtain refined naphthalene sulfonic acid and a crystallized sulfuric acid mother solution; introducing sulfur trioxide gas into the crystallized sulfuric acid mother liquor, reacting the sulfur trioxide with water to generate sulfuric acid, and then using the sulfuric acid to carry out sulfonation reaction to realize indirect sulfonation reaction taking the sulfur trioxide as a raw material; adding molten refined naphthalene sulfonic acid into sodium sulfite mother liquor for neutralization to obtain sodium naphthalene sulfonate and sulfur dioxide, acidifying sulfur dioxide for acidification, then carrying out alkali fusion, acidification and rectification to obtain 1-naphthol and 2-naphthol, and finally recovering sodium sulfite. The content of sulfuric acid in refined naphthalene sulfonic acid obtained by melting crystallization is extremely low, so that the influence of sodium sulfate impurities on the alkali melting process and the quality of sodium sulfite byproducts is solved. The utilization rate of raw materials naphthalene and sulfur trioxide in the process is high, high-salt organic wastewater is not generated, and clean production is realized.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a process for synthesizing naphthol by indirect sulfonation reaction of sulfur trioxide.
Background
1-naphthol is commonly called alpha-naphthol, is also called alpha-naphthol, is mainly used as an intermediate of pesticide carbaryl at present, and can be used as an intermediate of some medicines and fine chemical products. The main processes for producing 1-naphthol include sulfonation method and nitration method. The sulfonation method is that naphthalene and sulfuric acid are sulfonated at low temperature, and then neutralization, alkali dissolution, acidification and rectification are carried out to obtain 1-naphthol, and the isomer produced by sulfonation needs to be removed, so that the product yield is low, about 40%, and the three wastes are discharged in large quantity. The nitration method is a process of naphthalene nitration, reduction and hydrolysis, and the nitration reaction produces about 4% of 2-nitronaphthalene, so that the general product content is about 96%, and the superior product 1-naphthol needs to be separated and purified by nitronaphthalene crystallization or product crystallization, so that the steps are long, the cost is high, and the three wastes are many.
2-naphthol is commonly called ethyl naphthol, also called beta-naphthol, is widely used as dye, pigment and medical intermediate, is sulfonated at high temperature by naphthalene and concentrated sulfuric acid, and is produced by the production methods of hydrolysis, hydrolysis and naphthalene blowing, neutralization, cooling crystallization, filtration, alkali fusion, acidification, boiling and rectification, and 1-naphthol isomer produced in the sulfonation process is removed by hydrolysis, and the production process is mature, but a large amount of high-salt organic wastewater is produced, which is difficult to treat and has large pollution.
The existing synthetic technology of naphthol mainly comprises 2 steps: melting naphthalene at about 90 ℃, reacting at high temperature in the presence of excessive sulfuric acid (about 1.5 times of the mole of naphthalene) to finish the naphthalene reaction as far as possible, blowing naphthalene, neutralizing, cooling for crystallization, filtering to remove sulfate and obtain solid sodium naphthalene sulfonate, and then carrying out alkali melting, acidification, boiling and rectification to obtain 1-naphthol and 2-naphthol; in the process 2, naphthalene and sulfuric acid react at high temperature under the condition of excessive naphthalene (about 1.25 times of the mole of sulfuric acid) to react the sulfuric acid to a lower value as much as possible, then naphthalene is blown to recover excessive naphthalene, naphthalene sulfonic acid is obtained, after neutralization, crystallization and filtration are carried out, solid sodium naphthalene sulfonate is obtained, and then alkali melting, acidification, boiling and rectification are carried out to obtain 1-naphthol and 2-naphthol.
The two production processes have larger problems, as the sulfonation reaction is carried out, the concentration of sulfuric acid is reduced by water generated by the reaction, the reaction rate is reduced, and if the molar ratio of sulfuric acid to naphthalene is equal, more naphthalene and sulfuric acid remain. In order to keep the reactivity, the most traditional process 1 promotes the reaction to proceed to the positive direction by adding a large amount of sulfuric acid, and the naphthalene reaction is completed as much as possible, and the process has the problems that a large amount of liquid alkali is needed to be added in the neutralization process to neutralize the excessive sulfuric acid, then sodium sulfite mother liquor generated in the acidification process is added, sodium naphthalene sulfonate reacts with sodium sulfite to generate sodium naphthalene sulfonate and sulfur dioxide (sulfur dioxide circulating deacidification process), solid sodium naphthalene sulfonate is obtained through cooling crystallization and filtration, and because the neutralization mother liquor contains a large amount of sodium sulfate, the filtered solid sodium naphthalene sulfonate contains more sodium sulfate, naphthalene sulfonic acid is put into an alkali melting pot to carry out alkali melting at about 300 ℃, and the solid sodium naphthalene sulfonate is brought into more sodium sulfate to rapidly corrode the alkali melting pot on one hand, and on the other hand, because the melting point of the sodium sulfate is very high, the sodium sulfate in the alkali melting pot exists in a solid form, and the operation affecting the alkali melting is obtained in the future. And the acidified mother liquor contains a large amount of mixture of sodium sulfate and sodium sulfite, and the influence of sodium sulfate on the neutralization, cooling crystallization and alkali fusion processes can be further increased when the acidified mother liquor is used in the neutralization process. And the separation of sodium sulfate and sodium sulfite is difficult, and a large amount of wastewater with high salt content and complex organic components is produced in the neutralization and acidification process, so that the wastewater is difficult to treat. Therefore, the existing naphthol production devices all require strict control of the residual amount of sulfuric acid in the sulfonation reactant, and most conventional process 1 is not adopted.
The traditional process 2 adds excessive naphthalene during sulfonation reaction, so that the utilization rate of sulfuric acid is improved, the residual amount of sulfuric acid in a sulfonation reactant can be controlled, a certain amount of alkali is needed for neutralizing the residual sulfuric acid in a neutralization process to generate a certain amount of sodium sulfate, the existence of sodium sulfate still has a certain influence on an alkali fusion process, and a large amount of excessive naphthalene is needed to blow out and recycle naphthalene under the condition of higher temperature in a naphthalene blowing process by using a large amount of direct steam, so that the consumption of the steam in the naphthalene blowing process is large, the naphthalene blowing time is long, the temperature is higher, part of naphthalene sulfonic acid in the naphthalene blowing process can be hydrolyzed to generate sulfuric acid and naphthalene, the blown naphthalene needs to be recycled by a complex system, part of naphthalene is lost in the naphthalene blowing process, a large amount of salt-containing organic wastewater is still generated, and effective treatment is difficult, and the method is the root cause of serious pollution in the naphthol industry at present.
Besides the inherent defects of the two naphthol production processes, the two naphthol production processes have the problems of complex process, long process flow, high energy consumption, large amount of waste water with high salt content and complex organic components, and difficulty in effective treatment.
Patent CN108752244a discloses a process for producing 2-naphthol by using a double sulfonation technology of waste sulfuric acid and sulfur trioxide, which is technically characterized in that waste sulfuric acid is dripped into refined naphthalene to carry out primary sulfonation reaction at 135 ℃, sulfur trioxide gas is introduced to carry out secondary sulfonation reaction at 140 ℃, sulfuric acid generated by the reaction of the sulfur trioxide and water promotes the sulfonation reaction to proceed in the forward direction, the sulfonation reaction is continued with unreacted naphthalene in a sulfonation reaction system, and then 2-naphthol products are obtained by naphthalene blowing, neutralization, crystallization filtration, alkali fusion, dilution, acidification, drying and distillation, so that the yield of 2-naphthol is improved. The biggest problem of the production process is that sulfur trioxide is directly introduced into a sulfonation reaction system through secondary sulfonation, and the theory is that the sulfur trioxide reacts with water in the sulfonation reaction system to generate sulfuric acid, and the sulfuric acid is subjected to sulfonation reaction with naphthalene, so that the reaction is promoted to be carried out in the forward direction. However, in practice, because of extremely high reaction activity of sulfur trioxide, sulfur trioxide is directly introduced into the sulfonation reaction system, and the sulfur trioxide can directly react with naphthalene in the sulfonation reaction system to generate a large amount of polysulfonic naphthalene, which is also the reason that the naphthol production process cannot directly carry out sulfonation reaction by using sulfur trioxide as a raw material.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a process for synthesizing naphthol by indirect sulfonation reaction of sulfur trioxide, which can omit naphthalene blowing process and complicated naphthalene recovery system in the traditional process, simplify the production process, improve the utilization rate of raw naphthalene and sulfuric acid, solve the influence of sodium sulfate impurities on the alkali fusion process and on the quality of recovered sodium sulfite byproducts, obtain sodium sulfite byproducts, and has high utilization rate of raw naphthalene and sulfur trioxide in the production process, does not generate high-salt organic wastewater, and can thoroughly realize clean production.
To achieve the above and other related objects, the present invention provides a process for synthesizing naphthol by indirect sulfonation of sulfur trioxide, comprising the steps of:
(1) Sulfonation: adding excessive sulfuric acid into refined naphthalene, and carrying out sulfonation reaction at 90-160 ℃ to generate naphthalene sulfonic acid, so that naphthalene is reacted completely;
(2) And (3) melting and crystallizing: melting and crystallizing the sulfonation reaction product to obtain refined naphthalene sulfonic acid and crystallized sulfuric acid mother liquor respectively;
(3) Sulfur trioxide absorption: introducing sulfur trioxide gas into the crystallized sulfuric acid mother liquor, reacting the sulfur trioxide with water to generate sulfuric acid, and recycling the sulfur trioxide absorption liquid for sulfonation reaction in the step (1);
(4) And (3) neutralization: adding molten refined naphthalene sulfonic acid into sodium sulfite mother liquor for neutralization reaction to generate sodium naphthalene sulfonate and sulfur dioxide, collecting the sulfur dioxide for recycling in a subsequent acidification process, cooling and crystallizing, and filtering to obtain sodium naphthalene sulfonate solid;
(5) Alkali fusion: adding solid sodium hydroxide into an alkali fusion kettle, heating and fusing, and then adding sodium naphthalene sulfonate solid to perform alkali fusion reaction to generate sodium naphtholate and sodium sulfite; (6) acidification: adding the alkali fusion material obtained in the step (5) into water for dilution, introducing sulfur dioxide collected in the step (4) for acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating to obtain crude naphthol and mother liquor;
(7) And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
Further, the production process also comprises the step (8) of recovering sodium sulfite: extracting mother liquor discharged in the neutralization step (4) and the acidification step (6) by using an extractant, evaporating, concentrating, crystallizing, centrifugally separating and drying to obtain sodium sulfite byproducts, circularly applying evaporation condensate in the evaporation concentration process, adding sodium hydroxide solution into extract liquor generated in the extraction process for back extraction, circularly utilizing the extractant, and applying the back extraction liquor to the neutralization step (4).
Further, in the step (1), the sulfuric acid is concentrated sulfuric acid with a content of 98%.
And (2) the sulfonation reaction in the step (1) is to throw molten refined naphthalene into a reactor, dropwise add concentrated sulfuric acid at 90-160 ℃, and keep the reaction at 90-160 ℃ for 1-3 hours after the dropwise addition.
Alternatively, the sulfonation reaction temperature is 100-140 ℃, preferably 100-130 ℃.
Further, in the step (1), the feeding molar ratio of refined naphthalene to sulfuric acid is 1:1.0-5.0, preferably 1:1.5-3.0, more preferably 1:2.0-2.5.
Further, in the step (1), the residual amount of naphthalene in the sulfonation reaction product is detected as not detected to 1.0%, preferably not detected to 0.2%.
Further, the melt crystallization step in the step (2) is to add the sulfonation reaction product into a melt crystallizer for melt crystallization, wherein the melt crystallizer is a falling film crystallizer or a static crystallizer, or the falling film crystallizer and the static crystallizer are combined for crystallization. The two crystallizers are combined for crystallization, so that the yield of refined naphthalene sulfonic acid can be further improved.
Further, in the step (2), the melt crystallization process includes three processes of crystallization, sweating, and melting.
Optionally, the crystallization temperature of the melting crystallizer is 20-150 ℃, and the cooling rate is 0.1-10 ℃/min; preferably, the crystallization temperature of the melting crystallizer is 40-120 ℃, and the cooling rate is 0.3-5 ℃/min; more preferably, the crystallization temperature of the melting crystallizer is 60-100 ℃, and the cooling rate is 0.5-3 ℃/min.
Optionally, the sweating temperature of the melting crystallizer is 20-130 ℃, and the heating rate is 0.1-10 ℃/min; preferably, the sweat temperature of the melting crystallizer is 40-110 ℃, and the heating rate is 0.3-5 ℃/min; more preferably, the sweat temperature of the melt crystallizer is 60-90 ℃, and the heating rate is 0.3-3 ℃/min.
Optionally, the melting temperature of the melting crystallizer is 60-150 ℃, and the heating rate is 1-10 ℃/min; preferably, the melting temperature of the melting crystallizer is 90-120 ℃, and the heating rate is 3-5 ℃/min.
Further, in the step (2), the content of refined naphthalene sulfonic acid obtained by melting and crystallizing is 98-99.9%, and the content of sulfuric acid is less than 2%; preferably, the content of refined naphthalene sulfonic acid obtained by melt crystallization is 99.5-99.8%, and the content of sulfuric acid is less than 0.2%.
In the step (3), the absorption equipment of the sulfur trioxide is a packed tower or a falling film absorption tower, or the packed tower and the falling film absorption tower are combined for absorption.
Further, in the step (3), the sulfuric acid content in the sulfur trioxide absorbent is 96 to 105%, preferably 98 to 102%.
Further, in the step (5), solid sodium hydroxide is added into a soda melting kettle, and the temperature is raised to 200-300 ℃ for melting.
The technological reaction chemical formula of the naphthol synthesis process is as follows:
1. sulfonation:
2. sulfur trioxide absorption:
SO 3 +H 2 O→H 2 SO 4
3. and (3) neutralization:
4. alkali fusion:
5. acidifying:
as described above, the process for synthesizing naphthol by the indirect sulfonation reaction of sulfur trioxide has the following beneficial effects:
the invention provides a process for synthesizing naphthol by taking sulfur trioxide as a raw material and adopting indirect sulfonation reaction of the sulfur trioxide, wherein excessive sulfuric acid is adopted to completely react naphthalene in the sulfonation reaction of step (1), and then the sulfuric acid is separated by melting crystallization of step (2) to respectively obtain refined naphthalene sulfonic acid and crystallized sulfuric acid mother liquor; in the step (3), sulfur trioxide gas is introduced into the crystallized sulfuric acid mother liquor, the sulfur trioxide reacts with water to generate sulfuric acid, and the sulfur trioxide absorption liquid is recycled and used for sulfonation reaction, so that indirect sulfonation reaction taking sulfur trioxide as a raw material is realized; the content of sulfuric acid in refined naphthalene sulfonic acid obtained through melt crystallization is extremely low, so that the influence of sodium sulfate impurities on the alkali melting process is solved, the influence of sodium sulfate impurities on the quality of recovered sodium sulfite byproducts is more thoroughly solved, and high-quality sodium sulfite byproducts are obtained. In addition, the utilization rate of raw materials naphthalene and sulfur trioxide in the production process is high, high-salt organic wastewater is not generated, and clean production can be thoroughly realized.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The invention provides a process for synthesizing naphthol by indirect sulfonation reaction of sulfur trioxide, which comprises the following steps:
(1) Sulfonation: adding excessive sulfuric acid into refined naphthalene, and carrying out sulfonation reaction at 90-160 ℃ to generate naphthalene sulfonic acid, so that naphthalene is reacted completely;
(2) And (3) melting and crystallizing: melting and crystallizing the sulfonation reaction product to obtain refined naphthalene sulfonic acid and crystallized sulfuric acid mother liquor respectively;
(3) Sulfur trioxide absorption: introducing sulfur trioxide gas into the crystallized sulfuric acid mother liquor, reacting the sulfur trioxide with water to generate sulfuric acid, and recycling the sulfur trioxide absorption liquid for sulfonation reaction in the step (1);
(4) And (3) neutralization: adding molten refined naphthalene sulfonic acid into sodium sulfite mother liquor for neutralization reaction to generate sodium naphthalene sulfonate and sulfur dioxide, collecting the sulfur dioxide for recycling in a subsequent acidification process, cooling and crystallizing, and filtering to obtain sodium naphthalene sulfonate solid;
(5) Alkali fusion: adding solid sodium hydroxide into an alkali fusion kettle, heating to 200-300 ℃ for fusion, slowly adding sodium naphthalene sulfonate solid for alkali fusion reaction, and generating sodium naphtholate and sodium sulfite;
(6) Acidifying: adding the alkali fusion material obtained in the step (5) into water for dilution, introducing sulfur dioxide collected in the step (4) for acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating to obtain crude naphthol and mother liquor;
(7) And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
Further, the production process also comprises the step (8) of recovering sodium sulfite: extracting mother liquor discharged in the neutralization step (4) and the acidification step (6) by using an extractant, evaporating, concentrating, crystallizing, centrifugally separating and drying to obtain sodium sulfite byproducts, circularly applying evaporation condensate in the evaporation concentration process, adding sodium hydroxide solution into extract liquor generated in the extraction process for back extraction, circularly utilizing the extractant, and applying the back extraction liquor to the neutralization step (4).
Specifically, the sulfonation reaction in the step (1) is to throw molten refined naphthalene into a reactor, dropwise add concentrated sulfuric acid at 90-160 ℃, and keep the reaction for 1-3 hours at 90-160 ℃ after the dropwise addition; the sulfuric acid is concentrated sulfuric acid with 98 percent of content.
Specifically, in the step (1), the feeding molar ratio of refined naphthalene to sulfuric acid is 1:1.0-5.0, preferably 1:1.5-3.0, and more preferably 1:2.0-2.5.
Specifically, in the step (1), the residual amount of naphthalene in the sulfonation reaction product is detected as not detected to 1.0%, preferably not detected to 0.1%.
The melt crystallization process is to add the sulfonation reaction product into a falling film crystallizer or a static crystallizer for melt crystallization, and the melt crystallization process comprises three processes of crystallization, sweating and melting. Through melting crystallization, naphthalene sulfonic acid and sulfuric acid are separated to obtain refined naphthalene sulfonic acid and crystallized sulfuric acid mother liquor with high purity.
Specifically, in the step (2), the melt crystallization step is to add the sulfonation reaction product into a melt crystallizer for melt crystallization. Through melting crystallization, naphthalene sulfonic acid and sulfuric acid are separated to obtain refined naphthalene sulfonic acid and crystallized sulfuric acid mother liquor with high purity. The melting crystallizer adopts a falling film crystallizer or a static crystallizer, or adopts the falling film crystallizer and the static crystallizer to carry out combined crystallization, and the two crystallizers carry out combined crystallization, so that the yield of refined naphthalene sulfonic acid can be further improved.
Specifically, in step (2), the melt crystallization process includes three processes of crystallization, sweating, and melting. Wherein, the crystallization temperature of the melting crystallizer is 20-150 ℃, and the cooling rate is 0.1-10 ℃/min; preferably, the crystallization temperature of the melting crystallizer is 40-120 ℃, and the cooling rate is 0.3-5 ℃/min; more preferably, the crystallization temperature of the melting crystallizer is 60-100 ℃, and the cooling rate is 0.5-3 ℃/min. The sweating temperature of the melting crystallizer is 20-130 ℃, and the heating rate is 0.1-10 ℃/min; preferably, the sweat temperature of the melting crystallizer is 40-110 ℃, and the heating rate is 0.3-5 ℃/min; more preferably, the sweat temperature of the melt crystallizer is 60-90 ℃, and the heating rate is 0.3-3 ℃/min. The melting temperature of the melting crystallizer is 60-150 ℃, and the heating rate is 1-10 ℃/min; preferably, the melting temperature of the melting crystallizer is 90-120 ℃, and the heating rate is 3-5 ℃/min.
Specifically, in the step (2), the content of refined naphthalene sulfonic acid obtained by melting and crystallizing is 98-99.9%, and the content of sulfuric acid is less than 2%; preferably, the content of refined naphthalene sulfonic acid obtained by melt crystallization is 99.5-99.8%, and the content of sulfuric acid is less than 0.2%.
Specifically, in the step (3), the absorption equipment of sulfur trioxide is a packed tower or a falling film absorption tower, or the packed tower and the falling film absorption tower are combined for absorption.
Specifically, in the step (3), the sulfuric acid content in the sulfur trioxide absorption solution is 96 to 105%, preferably 98 to 102%.
The invention is further illustrated by the following specific examples.
Example 1
The naphthol is synthesized by indirect sulfonation reaction, and the steps are as follows:
1. sulfonation: 258.6kg of naphthalene (99%, 2 kmol) is added into a 2000L enamel reaction kettle, the temperature is raised to 100 ℃, 240L (4.4 kmol) of concentrated sulfuric acid with 98% content is slowly dripped into the reaction kettle for 120 minutes, the temperature of reaction materials in the dripping process is increased, the reaction temperature is controlled to 120 ℃, the temperature is raised to 130 ℃ after the dripping is finished, and the temperature is kept for 2 hours, so that naphthalene sulfonic acid is generated. The sulphonation reaction product was sampled and analysed, and the naphthalene content was detected to be 0.13%.
2. And (3) melting and crystallizing: the sulfonation reaction product was fed into a falling film crystallizer at a crystallization onset temperature of 120 ℃. Starting a circulating pump for pumping circulation, starting cooling and crystallizing, setting the crystallization cooling rate to 0.5 ℃/min, cooling to 60 ℃ after 120 minutes, stopping crystallizing, and putting the crystallization mother liquor into a mother liquor tank. Heating to sweat, wherein the heating rate of the sweat is set to 0.5 ℃/min, the temperature is increased to 90 ℃ after 60 min, the sweat is stopped, the sweat enters a sweat tank, and the circulating sleeve is used for the crystallization process of the next batch. Continuously heating to melt, wherein the temperature rising speed is 3 ℃/min, the temperature is raised to 120 ℃ after 10 min, the temperature is kept at 120 ℃ for 1 hour, the naphthalene sulfonic acid is completely melted, the melted naphthalene sulfonic acid enters a refined naphthalene sulfonic acid tank, and the naphthalene sulfonic acid content in the refined naphthalene sulfonic acid is 99.71% and the sulfuric acid content is 0.19% through sampling analysis.
3. Sulfur trioxide absorption: transferring the crystallized sulfuric acid mother liquor in the mother liquor tank into a sulfur trioxide absorption tower, starting a circulating pump for pumping circulation, slowly introducing sulfur trioxide, reacting the sulfur trioxide with water in the crystallized sulfuric acid mother liquor to generate sulfuric acid, introducing 170kg of sulfur trioxide after 4 hours, stopping introducing sulfur trioxide, sampling and analyzing, wherein the content of the sulfuric acid is 98.51%, and the sulfur trioxide absorption liquid circulating sleeve is used for the sulfonation reaction of the next batch.
4. And (3) neutralization: 1000kg of sodium sulfite aqueous solution with the content of 25% is added into a neutralization kettle, molten refined naphthalene sulfonic acid is slowly added, generated sulfur dioxide gas is collected for a subsequent naphthol acidification procedure, then cooling crystallization is carried out, and sodium naphthalene sulfonate solid is obtained through filtration.
5. Alkali fusion: adding solid NaOH into an alkali fusion kettle, heating to 250 ℃ for fusion, and slowly adding sodium naphthalene sulfonate solid for alkali fusion reaction to generate sodium naphtholate and sodium sulfite.
6. Acidifying: adding alkali melt materials into water for dilution, introducing sulfur dioxide collected in the step 4, performing acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating crude naphthol and mother liquor.
7. And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
8. And (3) recovering sodium sulfite: and (3) decoloring the mother liquor discharged from the neutralization step and the acidification step by adding active carbon, extracting by adding an extracting agent, and concentrating the extracted mother liquor by triple-effect evaporation to obtain a sodium sulfite byproduct, wherein the sodium sulfite content is 95.45% by sampling analysis. And (3) adding sodium hydroxide solution into the extract to carry out back extraction, recycling the extractant, and applying the back extraction solution to a neutralization process.
Example 2
The naphthol is synthesized by indirect sulfonation reaction, and the steps are as follows:
1. sulfonation: 258.6kg of naphthalene (99%, 2 kmol) is added into a 2000L enamel reaction kettle, the temperature is raised to 100 ℃, 240L (4.4 kmol) of sulfur trioxide absorption liquid with the sulfuric acid content of 98.51% in the embodiment 1 is slowly dripped into the reaction kettle, the dripping time is 120 minutes, the temperature of reaction materials rises in the dripping process, the reaction temperature is controlled to 130 ℃, the temperature is raised to 140 ℃ after the dripping is finished, and the temperature is kept for 2 hours, so that naphthalene sulfonic acid is generated. The sulphonation reaction product was sampled and analysed, and the naphthalene content was found to be 0.08%.
2. And (3) melting and crystallizing: the sulphonation reaction product and the perspiration from example 1 were fed into a falling film crystallizer at a crystallization onset temperature of 125 ℃. Starting a circulating pump for pumping circulation, starting cooling and crystallizing, setting the crystallization cooling rate to 0.5 ℃/min, cooling to 60 ℃ after 130 minutes, stopping crystallizing, and putting the crystallization mother liquor into a mother liquor tank. Heating to sweat, wherein the heating rate of the sweat is set to 0.5 ℃/min, the temperature is increased to 90 ℃ after 60 min, the sweat is stopped, the sweat enters a sweat tank, and the circulating sleeve is used for the crystallization process of the next batch. Continuously heating to melt, wherein the temperature rising speed is 3 ℃/min, the temperature is raised to 120 ℃ after 10 min, the temperature is kept at 120 ℃ for 1 hour, the naphthalene sulfonic acid is completely melted, the melted naphthalene sulfonic acid enters a refined naphthalene sulfonic acid tank, the sample analysis is carried out, the naphthalene sulfonic acid content in the refined naphthalene sulfonic acid is 99.48%, and the sulfuric acid content is 0.16%.
3. Sulfur trioxide absorption: transferring the crystallized sulfuric acid mother liquor in the mother liquor tank into a sulfur trioxide absorption tower, starting a circulating pump for pumping circulation, slowly introducing sulfur trioxide, reacting the sulfur trioxide with water in the crystallized mother liquor to generate sulfuric acid, introducing 180kg of sulfur trioxide after 4 hours, stopping introducing sulfur trioxide, sampling and analyzing, wherein the content of the sulfuric acid is 98.89%, and the sulfur trioxide absorption liquid circulating sleeve is used for the sulfonation reaction of the next batch.
4. And (3) neutralization: 1000kg of sodium sulfite aqueous solution with the content of 25% is added into a neutralization kettle, molten refined naphthalene sulfonic acid is slowly added, generated sulfur dioxide gas is collected for a subsequent naphthol acidification procedure, then cooling crystallization is carried out, and sodium naphthalene sulfonate solid is obtained through filtration.
5. Alkali fusion: adding solid NaOH into an alkali fusion kettle, heating to 200 ℃ for fusion, and slowly adding sodium naphthalene sulfonate solid for alkali fusion reaction to generate sodium naphtholate and sodium sulfite.
6. Acidifying: adding alkali melt materials into water for dilution, introducing sulfur dioxide collected in the step 4, performing acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating crude naphthol and mother liquor.
7. And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
8. And (3) recovering sodium sulfite: and (3) decoloring the mother liquor discharged from the neutralization step and the acidification step by adding active carbon, extracting by adding an extracting agent, and concentrating the extracted mother liquor by triple-effect evaporation to obtain a sodium sulfite byproduct, wherein the sodium sulfite content is 95.03% by sampling analysis. And (3) adding sodium hydroxide solution into the extract to carry out back extraction, recycling the extractant, and applying the back extraction solution to a neutralization process.
Example 3
The naphthol is synthesized by indirect sulfonation reaction, and the steps are as follows:
1. sulfonation: 258.6kg of naphthalene (99%, 2 kmol) is added into a 2000L enamel reaction kettle, the temperature is raised to 100 ℃, 240L (4.5 kmol) of sulfur trioxide absorption liquid with the sulfuric acid content of 98.89% in the embodiment 2 is slowly added into the reaction kettle in a dropwise manner for 120 minutes, the temperature of reaction materials in the dropwise manner is raised, the reaction temperature is controlled to 140 ℃, the dropwise addition temperature is raised to 140 ℃ after the completion of the dropwise addition, and the temperature is kept for 3 hours, so that naphthalene sulfonic acid is generated. The sulphonation reaction product was sampled and analysed, and the naphthalene content was detected to be 0.05%.
2. And (3) melting and crystallizing: the sulphonation reaction product and the perspiration from example 2 were fed into a falling film crystallizer with a crystallization onset temperature of 130 ℃. Starting a circulating pump for pumping circulation, starting cooling and crystallizing, setting the crystallization cooling rate to 0.5 ℃/min, cooling to 60 ℃ after 140 minutes, stopping crystallizing, and putting the crystallization mother liquor into a mother liquor tank. Heating to sweat, wherein the heating rate of the sweat is set to 0.5 ℃/min, the temperature is increased to 90 ℃ after 60 min, the sweat is stopped, the sweat enters a sweat tank, and the circulating sleeve is used for the crystallization process of the next batch. Continuously heating to melt, wherein the temperature rising speed is set to be 3 ℃/min, the temperature is increased to 120 ℃ after 10 min, and the temperature is kept at 120 ℃ for 1 hour, so that the naphthalene sulfonic acid is completely melted, the melted naphthalene sulfonic acid enters a refined naphthalene sulfonic acid tank, and the naphthalene sulfonic acid content in the refined naphthalene sulfonic acid is 99.63% and the sulfuric acid content is 0.12% through sampling analysis.
3. Sulfur trioxide absorption: transferring the crystallized sulfuric acid mother liquor in the mother liquor tank into a sulfur trioxide absorption tower, starting a circulating pump for pumping circulation, slowly introducing sulfur trioxide, reacting the sulfur trioxide with water in the crystallized mother liquor to generate sulfuric acid, introducing 180kg of sulfur trioxide after 4 hours, stopping introducing sulfur trioxide, sampling and analyzing, wherein the content of the sulfuric acid is 99.08%, and the sulfur trioxide absorption liquid circulating sleeve is used for the sulfonation reaction of the next batch.
4. And (3) neutralization: 1000kg of sodium sulfite aqueous solution with the content of 25% is added into a neutralization kettle, molten refined naphthalene sulfonic acid is slowly added, generated sulfur dioxide gas is collected for a subsequent naphthol acidification procedure, then cooling crystallization is carried out, and sodium naphthalene sulfonate solid is obtained through filtration.
5. Alkali fusion: adding solid NaOH into an alkali fusion kettle, heating to 300 ℃ for fusion, and slowly adding sodium naphthalene sulfonate solid for alkali fusion reaction to generate sodium naphtholate and sodium sulfite.
6. Acidifying: adding alkali melt materials into water for dilution, introducing sulfur dioxide collected in the step 4, performing acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating crude naphthol and mother liquor.
7. And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
8. And (3) recovering sodium sulfite: and (3) decoloring the mother liquor discharged from the neutralization step and the acidification step by adding active carbon, extracting by adding an extracting agent, and concentrating the extracted mother liquor by triple-effect evaporation to obtain a sodium sulfite byproduct, wherein the sodium sulfite content is 94.88% by sampling analysis. And (3) adding sodium hydroxide solution into the extract to carry out back extraction, recycling the extractant, and applying the back extraction solution to a neutralization process.
Example 4
The naphthol is synthesized by indirect sulfonation reaction, and the steps are as follows:
1. sulfonation: 258.6kg of naphthalene (99%, 2 kmol) is added into a 2000L enamel reaction kettle, the temperature is raised to 90 ℃, 430L (7.9 kmol) of concentrated sulfuric acid with 98% content is slowly dripped into the reaction kettle for 120 minutes, the temperature of reaction materials in the dripping process is increased, the reaction temperature is controlled to 100 ℃, the temperature is raised to 110 ℃ after the dripping is finished, and the temperature is kept for 1.5 hours, so that naphthalene sulfonic acid is generated. The sulphonation reaction product was sampled and analysed, and the naphthalene content was detected to be 0.15%.
2. And (3) melting and crystallizing: the sulphonation reaction product and the perspiration from example 3 were fed into a falling film crystallizer at a crystallization onset temperature of 110 ℃. Starting a circulating pump for pumping circulation, starting cooling and crystallizing, setting the crystallization cooling rate to be 1.0 ℃/min, cooling to 40 ℃ after 70 minutes, stopping crystallizing, and putting the crystallization mother liquor into a mother liquor tank. Heating to sweat, wherein the heating rate of the sweat is set to be 1.0 ℃/min, the temperature is raised to 80 ℃ after 40 min, the sweat is stopped, the sweat enters a sweat tank, and the circulating sleeve is used for the crystallization process of the next batch. Continuously heating to melt, wherein the temperature rising speed is 5 ℃/min, the temperature is raised to 150 ℃ after 14 min, the temperature is kept at 150 ℃ for 1 hour, the naphthalene sulfonic acid is completely melted, the melted naphthalene sulfonic acid enters a refined naphthalene sulfonic acid tank, and the naphthalene sulfonic acid content in the refined naphthalene sulfonic acid is 99.50% and the sulfuric acid content is 0.19% through sampling analysis.
3. Sulfur trioxide absorption: transferring the crystallized sulfuric acid mother liquor in the mother liquor tank into a sulfur trioxide absorption tower, starting a circulating pump for pumping circulation, slowly introducing sulfur trioxide, reacting the sulfur trioxide with water in the crystallized sulfuric acid mother liquor to generate sulfuric acid, introducing 200kg of sulfur trioxide after 4 hours, stopping introducing sulfur trioxide, sampling and analyzing, wherein the content of sulfuric acid is 99.17%, and the sulfur trioxide absorption liquid circulating sleeve is used for the sulfonation reaction of the next batch.
4. And (3) neutralization: 1000kg of sodium sulfite aqueous solution with the content of 25% is added into a neutralization kettle, molten refined naphthalene sulfonic acid is slowly added, generated sulfur dioxide gas is collected for a subsequent naphthol acidification procedure, then cooling crystallization is carried out, and sodium naphthalene sulfonate solid is obtained through filtration.
5. Alkali fusion: adding solid NaOH into an alkali fusion kettle, heating to 250 ℃ for fusion, and slowly adding sodium naphthalene sulfonate solid for alkali fusion reaction to generate sodium naphtholate and sodium sulfite.
6. Acidifying: adding alkali melt materials into water for dilution, introducing sulfur dioxide collected in the step 4, performing acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating crude naphthol and mother liquor.
7. And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
8. And (3) recovering sodium sulfite: and (3) decoloring the mother liquor discharged from the neutralization step and the acidification step by adding active carbon, extracting by adding an extracting agent, and concentrating the extracted mother liquor by triple-effect evaporation to obtain a sodium sulfite byproduct, wherein the sodium sulfite content is 95.56% by sampling analysis. And (3) adding sodium hydroxide solution into the extract to carry out back extraction, recycling the extractant, and applying the back extraction solution to a neutralization process.
Example 5
The naphthol is synthesized by indirect sulfonation reaction, and the steps are as follows:
1. sulfonation: 258.6kg of naphthalene (99%, 2 kmol) is added into a 2000L enamel reaction kettle, the temperature is raised to 140 ℃, 545L (10.0 kmol) of concentrated sulfuric acid with 98% content is slowly dripped into the reaction kettle for 120 minutes, the temperature of reaction materials in the dripping process is increased, the reaction temperature is controlled to 150 ℃, the temperature is raised to 160 ℃ after the dripping is finished, and the temperature is kept for 1 hour, so that naphthalene sulfonic acid is generated. The sulphonation reaction product was sampled and analysed, and the naphthalene content was detected to be 0.09%.
2. And (3) melting and crystallizing: the sulphonation reaction product and the perspiration from example 4 were fed into a falling film crystallizer with a crystallization onset temperature of 150 ℃. Starting a circulating pump for pumping circulation, starting cooling and crystallizing, setting the crystallization cooling rate to 3 ℃/min, cooling to 40 ℃ after 40 minutes, stopping crystallizing, and placing the crystallization mother liquor into a mother liquor tank. Heating to induce sweat, setting the heating rate of the sweat to 3 ℃/min, heating to 100 ℃ after 20 min, stopping inducing sweat, and enabling the sweat to enter a sweat tank, wherein the circulating sleeve is used for the crystallization process of the next batch. Continuously heating to melt, wherein the temperature rising speed is 5 ℃/min, the temperature is raised to 150 ℃ after 10 min, the temperature is kept at 150 ℃ for 1 hour, the naphthalene sulfonic acid is completely melted, the melted naphthalene sulfonic acid enters a refined naphthalene sulfonic acid tank, and the naphthalene sulfonic acid content in the refined naphthalene sulfonic acid is 99.65% and the sulfuric acid content is 0.13% through sampling analysis.
3. Sulfur trioxide absorption: transferring the crystallized sulfuric acid mother liquor in the mother liquor tank into a sulfur trioxide absorption tower, starting a circulating pump for pumping circulation, slowly introducing sulfur trioxide, reacting the sulfur trioxide with water in the crystallized sulfuric acid mother liquor to generate sulfuric acid, introducing 200kg of sulfur trioxide after 4 hours, stopping introducing sulfur trioxide, sampling and analyzing, wherein the content of the sulfuric acid is 98.93%, and the sulfur trioxide absorption liquid circulating sleeve is used for the sulfonation reaction of the next batch.
4. And (3) neutralization: 1000kg of sodium sulfite aqueous solution with the content of 25% is added into a neutralization kettle, molten refined naphthalene sulfonic acid is slowly added, generated sulfur dioxide gas is collected for a subsequent naphthol acidification procedure, then cooling crystallization is carried out, and sodium naphthalene sulfonate solid is obtained through filtration.
5. Alkali fusion: adding solid NaOH into an alkali fusion kettle, heating to 250 ℃ for fusion, and slowly adding sodium naphthalene sulfonate solid for alkali fusion reaction to generate sodium naphtholate and sodium sulfite.
6. Acidifying: adding alkali melt materials into water for dilution, introducing sulfur dioxide collected in the step 4, performing acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating crude naphthol and mother liquor.
7. And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
8. And (3) recovering sodium sulfite: and (3) decoloring the mother liquor discharged from the neutralization step and the acidification step by adding active carbon, extracting by adding an extracting agent, and concentrating the extracted mother liquor by triple-effect evaporation to obtain a sodium sulfite byproduct, wherein the sodium sulfite content is 95.35% by sampling analysis. And (3) adding sodium hydroxide solution into the extract to carry out back extraction, recycling the extractant, and applying the back extraction solution to a neutralization process.
Example 6
The naphthol is synthesized by indirect sulfonation reaction, and the steps are as follows:
1. sulfonation: 258.6kg of naphthalene (99%, 2 kmol) is added into a 2000L enamel reaction kettle, the temperature is raised to 120 ℃, 330L (6.05 kmol) of concentrated sulfuric acid with 98% content is slowly dripped into the reaction kettle for 120 minutes, the temperature of reaction materials in the dripping process is raised, the reaction temperature is controlled to 140 ℃, the temperature is raised to 150 ℃ after the dripping is finished, and the temperature is kept for 1 hour, so that naphthalene sulfonic acid is generated. The sulphonation reaction product was sampled and analysed, and the naphthalene content was detected to be 0.11%.
2. And (3) melting and crystallizing: the sulphonation reaction product was hit with the perspiration from example 5 and put into a falling film crystalliser with a crystallisation onset temperature of 140 ℃. Starting a circulating pump for pumping circulation, starting cooling and crystallizing, setting the crystallization cooling rate to be 2 ℃/min, cooling to 40 ℃ after 50 minutes, stopping crystallizing, and putting the crystallization mother liquor into a mother liquor tank. Heating to induce sweat, setting the heating rate of the sweat to 2 ℃/min, heating to 110 ℃ after 35 min, stopping inducing sweat, and enabling the sweat to enter a sweat tank, wherein the circulating sleeve is used for the crystallization process of the next batch. Continuously heating to melt, wherein the temperature rising speed is set to be 4 ℃/min, the temperature is increased to 150 ℃ after 10 min, the temperature is kept at 150 ℃ for 1 hour, the naphthalene sulfonic acid is completely melted, the melted naphthalene sulfonic acid enters a refined naphthalene sulfonic acid tank, and the naphthalene sulfonic acid content in the refined naphthalene sulfonic acid is 99.57% and the sulfuric acid content is 0.14% through sampling analysis.
3. Sulfur trioxide absorption: transferring the crystallized sulfuric acid mother liquor in the mother liquor tank into a sulfur trioxide absorption tower, starting a circulating pump for pumping circulation, slowly introducing sulfur trioxide, reacting the sulfur trioxide with water in the crystallized sulfuric acid mother liquor to generate sulfuric acid, introducing 200kg of sulfur trioxide after 4 hours, stopping introducing sulfur trioxide, sampling and analyzing, wherein the content of the sulfuric acid is 99.51%, and the sulfur trioxide absorption liquid circulating sleeve is used for the sulfonation reaction of the next batch.
4. And (3) neutralization: 1000kg of sodium sulfite aqueous solution with the content of 25% is added into a neutralization kettle, molten refined naphthalene sulfonic acid is slowly added, generated sulfur dioxide gas is collected for a subsequent naphthol acidification procedure, then cooling crystallization is carried out, and sodium naphthalene sulfonate solid is obtained through filtration.
5. Alkali fusion: adding solid NaOH into an alkali fusion kettle, heating to 250 ℃ for fusion, and slowly adding sodium naphthalene sulfonate solid for alkali fusion reaction to generate sodium naphtholate and sodium sulfite.
6. Acidifying: adding alkali melt materials into water for dilution, introducing sulfur dioxide collected in the step 4, performing acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating crude naphthol and mother liquor.
7. And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products.
8. And (3) recovering sodium sulfite: and (3) decoloring the mother liquor discharged from the neutralization step and the acidification step by adding active carbon, extracting by adding an extracting agent, and concentrating the extracted mother liquor by triple-effect evaporation to obtain a sodium sulfite byproduct, wherein the sodium sulfite content is 94.85% by sampling analysis. And (3) adding sodium hydroxide solution into the extract to carry out back extraction, recycling the extractant, and applying the back extraction solution to a neutralization process.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The process for synthesizing naphthol by using sulfur trioxide indirect sulfonation reaction is characterized by comprising the following steps:
(1) Sulfonation: adding excessive sulfuric acid into refined naphthalene, and carrying out sulfonation reaction at 90-160 ℃ to generate naphthalene sulfonic acid, so that naphthalene is reacted completely;
(2) And (3) melting and crystallizing: melting and crystallizing the sulfonation reaction product to obtain refined naphthalene sulfonic acid and crystallized sulfuric acid mother liquor respectively; the melting crystallization process is to add the sulfonation reaction product into a melting crystallizer for melting crystallization, and the melting crystallization process comprises three processes of crystallization, sweating and melting; the crystallization temperature of the melting crystallizer is 20-150 ℃, and the cooling rate is 0.1-10 ℃/min; the sweating temperature of the melting crystallizer is 20-130 ℃, and the heating rate is 0.1-10 ℃/min; the melting temperature of the melting crystallizer is 60-150 ℃, and the heating rate is 1-10 ℃/min;
(3) Sulfur trioxide absorption: introducing sulfur trioxide gas into the crystallized sulfuric acid mother liquor, reacting the sulfur trioxide with water to generate sulfuric acid, and recycling the sulfur trioxide absorption liquid for sulfonation reaction in the step (1);
(4) And (3) neutralization: adding molten refined naphthalene sulfonic acid into sodium sulfite mother liquor for neutralization reaction to generate sodium naphthalene sulfonate and sulfur dioxide, collecting the sulfur dioxide for recycling in a subsequent acidification process, cooling and crystallizing, and filtering to obtain sodium naphthalene sulfonate solid;
(5) Alkali fusion: adding solid sodium hydroxide into an alkali fusion kettle, heating and fusing, and then adding sodium naphthalene sulfonate solid to perform alkali fusion reaction to generate sodium naphtholate and sodium sulfite;
(6) Acidifying: adding the alkali fusion material obtained in the step (5) into water for dilution, introducing sulfur dioxide collected in the step (4) for acidification reaction to generate naphthol and sodium sulfite, standing for layering, and separating to obtain crude naphthol and mother liquor;
(7) And (3) rectifying: rectifying the crude naphthol to obtain 1-naphthol and 2-naphthol products;
(8) And (3) recovering sodium sulfite: and (3) extracting the sodium sulfite mother liquor discharged in the neutralization step of the step (4) and the acidification step of the step (6) by using an extracting agent, evaporating, concentrating, crystallizing, centrifugally separating and drying to obtain sodium sulfite byproducts, circularly applying the evaporating condensate in the evaporating and concentrating process, adding sodium hydroxide solution into the extract liquor generated in the extraction process for back extraction, circularly utilizing the extracting agent, and applying the back extraction liquor to the neutralization step of the step (4).
2. The process according to claim 1, characterized in that: in the step (1), the sulfuric acid is concentrated sulfuric acid with the content of 98 percent.
3. The process according to claim 1, characterized in that: the sulfonation reaction in the step (1) is to throw molten refined naphthalene into a reactor, dropwise add concentrated sulfuric acid at 90-160 ℃, and keep the reaction for 1-3 hours at 90-160 ℃ after the dropwise addition.
4. The process according to claim 1, characterized in that: in the step (1), the feeding mole ratio of refined naphthalene to sulfuric acid is 1:1.0 to 5.0;
and/or, in the step (1), the residual content of naphthalene in the sulfonation reaction product is detected as undetected to 1.0%.
5. The process according to claim 1, characterized in that: in the step (2), the melting crystallizer is a falling film crystallizer or a static crystallizer, or the falling film crystallizer and the static crystallizer are combined for crystallization.
6. The process according to claim 1, characterized in that: in the step (2), the content of refined naphthalene sulfonic acid obtained by melting and crystallizing is 98-99.9%, and the content of sulfuric acid is less than 2%.
7. The process according to claim 1, characterized in that: in the step (3), the absorption equipment of sulfur trioxide is a packed tower or a falling film absorption tower, or the packed tower and the falling film absorption tower are combined for absorption;
and/or, in the step (3), the sulfuric acid content in the sulfur trioxide absorption liquid is 96-105%.
8. The process according to claim 1, characterized in that: in the step (5), solid sodium hydroxide is added into a alkali fusion kettle, and the temperature is raised to 200-300 ℃ for fusion.
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