WO2020052577A1 - Procédé de production d'un h acide par recyclage de liqueur mère de fusion alcaline - Google Patents

Procédé de production d'un h acide par recyclage de liqueur mère de fusion alcaline Download PDF

Info

Publication number
WO2020052577A1
WO2020052577A1 PCT/CN2019/105277 CN2019105277W WO2020052577A1 WO 2020052577 A1 WO2020052577 A1 WO 2020052577A1 CN 2019105277 W CN2019105277 W CN 2019105277W WO 2020052577 A1 WO2020052577 A1 WO 2020052577A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
mother liquor
producing
alkali
nitro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/105277
Other languages
English (en)
Chinese (zh)
Inventor
王在军
张克宏
任帅昌
杨海军
石艳
刘吉康
代兴远
张云敬
朱德俊
刘瑞芬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Chuanglan Yaoshi Environmental Protection Technology Co Ltd
Original Assignee
Shandong Chuanglan Yaoshi Environmental Protection Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201811067656.XA external-priority patent/CN109096155B/zh
Application filed by Shandong Chuanglan Yaoshi Environmental Protection Technology Co Ltd filed Critical Shandong Chuanglan Yaoshi Environmental Protection Technology Co Ltd
Publication of WO2020052577A1 publication Critical patent/WO2020052577A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C07C303/22—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 from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification

Definitions

  • the invention relates to the technical field of preparation of H acid, in particular to a process for producing H acid by continuously recycling a mother liquor.
  • H acid (1-amino-8-naphthol-3,6-disulfonic acid monosodium) is an important intermediate for the production of reactive dyes.
  • the production of H acid uses refined naphthalene as raw material, and amino T acid is first prepared through sulfonation, nitration, denitration, neutralization, reduction, and sodium chloride salting out. The amino T acid is then subjected to alkaline melting and acidification.
  • the production of H acid however, the mother liquor produced during the production of H acid belongs to the "five high" organic wastewater with high concentration, high acidity, high salinity, high chroma, and high toxicity.
  • Chemical Oxygen Demand (COD) Up to 80-100,000, salinity up to 10-20%, chroma up to 4000-6000 times, it is difficult to effectively treat these "five high” organic wastewater with traditional biochemical and physical and chemical methods; and unconventional extraction, pyrolysis, Treatment by adsorption and other methods, the cost of pretreatment alone is high, and it cannot be completely and effectively treated.
  • COD Chemical Oxygen Demand
  • no domestic enterprise can effectively treat and treat the “five high” organic wastewater generated in the production of H acid, and make it reach the discharge standard.
  • the technical solution provided by the Chinese invention patent No. ZL201410816923.4 provides potassium hydroxide instead of traditional ammonia as a neutralizing solution to produce nitro T acid, and potassium hydroxide instead of sodium hydroxide, and alkali melting to generate potassium sulfate mother liquor through MVR Concentrated crystallization and high-temperature calcination to produce potassium sulfate have completely solved the environmental problems that plagued the enterprise, and also improved the yield of the product.
  • the disadvantage of this method is that the amount of potassium hydroxide is too large, which consumes 48% per ton of H acid product. More than 11 tons of potassium hydroxide is not conducive to controlling the production cost of the product.
  • the present invention further researches a process for producing H acid through recycling of an alkali melting mother liquor, so as to reduce the production cost of H acid on the basis of ensuring cleanliness and environmental protection.
  • the present invention aims to provide a process for producing H acid through recycling of an alkali melting mother liquor, so as to reduce the production cost of H acid on the basis of ensuring cleanness and environmental protection.
  • One of the objects of the present invention is to provide the application of sulfite in the neutralization of a denitration reaction liquid produced by the production of H acid.
  • Another object of the present invention is to provide a process for producing H acid by recycling mother liquor.
  • a third object of the present invention is to provide a method for producing H acid by complex extraction.
  • the present invention discloses an alkaline molten mother liquor for producing H acid.
  • the alkaline molten mother liquor is a solution containing sulfite.
  • the alkaline molten mother liquid is used for neutralization of the denitration reaction liquid in the H acid production process, that is, the application of the alkaline molten mother liquid in the H acid production to neutralize the denitration reaction liquid; the ratio of the alkaline molten mother liquid to the denitration reaction liquid may be Adjust according to actual needs.
  • the ratio of the denitration reaction liquid to the alkaline molten mother liquid is 1: (0.4-2), parts by weight.
  • the ratio of the denitration reaction liquid to the alkaline molten mother liquid is 1: (0.8-1.5), preferably 1: (0.9-1.2), by weight.
  • the ratio of the denitration reaction liquid to the alkaline molten mother liquid is 1: (0.4-1.0), preferably 1: (0.5-0.8), parts by weight.
  • the concentration of the sulfite solution in the alkaline molten mother liquor is 30% -50%, preferably 35% -45%, by mass.
  • the sulfite includes sodium sulfite, potassium sulfite, and the like.
  • the present invention discloses a process for producing H-acid through recycling of an alkali melting mother liquor, including the following steps:
  • step (2) Continue neutralizing the filtrate in step (1), and then reduce the temperature, crystallize, and separate to obtain sulfate and filtrate.
  • the filtrate can be further extracted and then back-extracted with dilute alkali.
  • the sulfate can be further washed, and the obtained washing liquid is used for later;
  • step (3) dissolving the nitro T acid salt in step (1) with at least one of the filtrate, back-extraction liquid, and washing liquid in step (2), and the dissolved liquid undergoes catalytic hydrogenation or reduction reaction, acidification, crystallization, Amino T acid solid and filtrate were obtained after filtration;
  • step (3) The amino T acid in step (3) is alkali-melted to obtain an alkali-melt reaction solution containing H acid.
  • the alkali-melt reaction solution is acidified with sulfur dioxide obtained in step (1), cooled and filtered. , You can separate the H acid and the sulfite-containing mother liquor.
  • step (1) the raw material for preparing the nitro T acid salt is refined naphthalene.
  • the sulfite includes sodium sulfite and potassium sulfite.
  • the ratio of the denitration reaction liquid to the alkaline molten mother liquid is 1: (0.4-2), parts by weight.
  • the ratio of the denitration reaction liquid to the alkaline molten mother liquid is 1: (0.8-1.5), preferably 1: (0.9-1.2), by weight.
  • the ratio of the denitration reaction liquid to the alkaline molten mother liquid is 1: (0.4-1.0), preferably 1: (0.5-0.8), parts by weight.
  • the concentration of the sulfite solution is 30% -50%, preferably 35% -45% by mass.
  • step (1) the temperature for removing sulfur dioxide is 80 ° C-100 ° C.
  • the substance for neutralization includes a sulfite solution, a potassium hydroxide solution, a sodium hydroxide solution, ammonia water, or lightly burned magnesium, etc., and the concentration of the substance for neutralization can be adjusted according to actual needs; further
  • the sulfite includes sodium sulfite and potassium sulfite.
  • the substance for neutralization is selected from sodium hydroxide and potassium hydroxide.
  • reaction that is, when the sulfite is used for neutralization, it is equivalent to an additional step of dissolving sulfur dioxide in the lye, but this process does not bring additional effects. Instead, it collects the generated sulfur dioxide. 2. Leakage is likely to occur during storage (this gas must be collected and processed, and cannot be directly discharged), and sulfur dioxide not only has a strong pungent odor, but also once leaked into After entering the human respiratory tract and lungs, the corrosive sulfurous acid generated will cause damage to the human respiratory system. This must be avoided in actual production.
  • sodium hydroxide or potassium hydroxide When using sodium hydroxide or potassium hydroxide for direct neutralization, It can avoid the additional production of sulfur dioxide when sulfite neutralization is used, and neutralization with sodium hydroxide or potassium hydroxide can achieve the same neutralization effect as sulfite neutralization.
  • the substance for neutralization is selected from light-burned magnesium powder.
  • Light-burned magnesium is obtained from magnesite, brucite and other ore through high-temperature calcination. During the high-temperature calcination process, the ore is decomposed and the components such as CO 2 and H 2 O are discharged. This makes the light-burned magnesium powder loose. It contains a large number of micropores and has a high chemical reaction activity.
  • the lightly burned magnesium is used as the neutralizer of the filtrate in step (1), the lightly burned magnesium can not only neutralize the acid solution in the filtrate, In the neutralization process, the acid solution can modify the lightly burned magnesium particles, create richer micropores and cracks in the lightly burned magnesium particles, and produce rich Mg- on the surface of the lightly burned magnesium particles.
  • the acid liquid achieves the modification of lightly burned magnesium, and the lightly burned magnesium that is more reactive after being modified also achieves the acid liquid Neutralization, the two promote each other, can quickly and efficiently complete the neutralization of the filtrate, and will not produce other additional toxic and harmful waste;
  • the cost of light burning magnesium is low, which is more conducive to reducing the production of H acid Cost and sulfuric acid produced during neutralization After purification may also be sold as a by-product, the production cost can be further offset the H acid.
  • step (2) the filtrate in step (1) may be neutralized to a liquid acidity of 2% -10%, and the specific amount of the neutralization solution may be added according to actual needs.
  • the extraction agent used is N235 and 200 # solvent oil, and preferably, the extraction agent is a complex extraction agent formed by N235 and 200 # solvent oil with a mass ratio of 1: 3.
  • the dilute alkali is potassium hydroxide or sodium hydroxide, and preferably, the mass concentration of potassium hydroxide or sodium hydroxide is 5% -10%.
  • step (2) the sulfate is washed with water and the same quality as the sulfate.
  • the catalyst used in the catalytic hydrogenation reaction is a nickel catalyst.
  • step (3) the temperature of the catalytic hydrogenation reaction is 80 ° C-120 ° C.
  • the reducing agent used in the reduction reaction includes iron powder, zinc powder, and the like.
  • the alkaline solution for the alkali melting includes potassium hydroxide or sodium hydroxide solution.
  • step (4) the alkali melting reaction is performed between 160 ° C. and 195 ° C. for a time of 0.5 h to 5 h, preferably 0.5 h to 2 h.
  • the main reason for collecting sulfur dioxide produced by sulfite in step (1) is that it can be used for the neutralization of the alkali melting reaction solution in step (4), so that it can be used instead of the alkali melting in the acidification step (4).
  • the acid of the mother liquor reduces the production cost of the H acid.
  • the sulfur dioxide can be converted into sulfite through the reaction with the alkali molten mother liquor to obtain an alkali molten mother liquor containing sulfite; using the sulfite-containing solution obtained in step (4)
  • the alkaline molten mother liquid neutralizes the reaction solution after denitration in step (1), so that not only the recycling of the alkaline molten mother liquid containing sulfite, but also the elimination of the sulfite containing liquid in step (4)
  • the treatment of the "five high" organic waste water of the alkaline molten mother liquor, while greatly reducing the production cost of H acid makes the production process of H acid cleaner and more environmentally friendly; in this way, the alkaline mother liquor can be recycled to save potassium hydroxide Or the consumption of sodium hydroxide solution, the purpose of reducing product production costs.
  • the concentration of the sulfite-containing alkali molten mother liquor obtained in step (4) is insufficient, it can also be solved by adding sulfite or
  • the reason why the alkaline melt mother liquor is used to neutralize the filtrate in step (1) again is that the filtrate contains a part of the denitrated product. After the neutralization, a part of the nitro T acid can be obtained, and the nitro T acid Salt is an important intermediate product for the preparation of H acid in subsequent steps, which can improve the utilization of raw materials.
  • step (2) after the separation, the obtained filtrate still contains a part of the nitro T salt product. Therefore, this part of the nitro T salt product can be extracted again from the filtrate by extraction.
  • the oil After extraction oil phase
  • the nitro T acid salt enters the oil phase
  • potassium hydroxide or sodium hydroxide water phase
  • the concentration of nitro T acid in the stripping solution is increased, which is more conducive to subsequent reactions.
  • step 2 Since a part of the nitro T acid salt product is still attached to the surface of the sulfate obtained in step (2), you can choose to wash the part of sulfate, and then use a washing solution containing nitro T acid salt after washing, step (2
  • the back extraction solution containing the nitro T acid salt obtained in step) dissolves the nitro T acid salt in step (1), and a mixed solution containing the nitro T acid salt can be obtained, and the mixed liquid will be used in the next step of the amino T acid.
  • the preparation of acid can realize the maximum utilization of nitro T acid salt, washing liquid and back extraction liquid.
  • the process for producing H-acid by recycling the mother liquor of the alkali melt further includes a step of preparing sulfate, as follows:
  • step S2 The sulfate solid obtained in step S1 and the sulfate obtained in step (2) are calcined at a high temperature to remove impurities such as organic matter therein, and a sulfate in accordance with national standards can be obtained.
  • the calcination temperature is 800 ° C-1000 ° C, and the calcination time can be adjusted according to the amount of sulfate, preferably 0.5h-1h.
  • the step of preparing the sulfate salt further includes: a treatment step of the tail gas generated in the calcination process, preferably, the calcined tail gas is discharged after being processed by the RTO regenerative incinerator and meeting the standard.
  • water vapor or distilled water generated in the processes of distillation, evaporation, and concentration can be recovered and used for production, so as to achieve the purpose of saving water.
  • an alkali melting mother liquor is used to neutralize the denitration solution, which reduces the amount of alkali.
  • lightly burned magnesium, lime, etc. can be used instead of ammonia to further neutralize the denitration solution, reduce the amount of wastewater generated, and greatly reduce the cost.
  • magnesium sulfate or calcium sulfate is produced during the production process, and the amount of waste salt is relatively large, and these waste salts need to be disposed of.
  • the invention provides a method for producing H acid by complex extraction.
  • the complex extraction method can be combined with the above-mentioned process for producing H acid through recycling of an alkali molten mother liquor to solve the above technical problems.
  • the method for producing H acid by complex extraction is to produce H acid by using combined complex extraction through recycling of an alkali melting mother liquor, comprising the following steps:
  • step 5 Add alkali and methanol to the amino T acid to perform alkali melting. After the end of the alkali melting, the sulfur dioxide collected in step 2) is used to acidify the alkali molten solution. After filtering the obtained solid, it is added with water to beat and then used in step 3). The water washing solution was acidified and filtered, and the filter cake was washed with water, filtered, and dried to obtain a product.
  • the filtered nitro T acid solids and the back-extracted liquid after extraction of the nitro T acid are produced by hydrogenation or iron powder reduction to produce amino T acid.
  • the acid used for acidification of amino T acid can be extracted with complexed nitro T acid.
  • the remaining filtrate replaced the sulfuric acid.
  • the extract is first washed with water, and the sulfuric acid part extracted into the extract is washed into water. Control the amount of washing water, the sulfuric acid content in the washing water can reach about 20%. This part of dilute sulfuric acid is colorless and transparent, and the organic matter is very small. It can be used for acidification of H acid without affecting the product quality of H acid.
  • the method can not only reduce the alkali for neutralizing the denitration solution, the amount of sulfuric acid used in the acidification of the amino T acid, the amount of sulfuric acid used in the acidification of the H acid, but also use only one base in the entire production process, and only one salt in the mother liquor. Salt and concentrated water are used in production, and no waste gas, waste water and waste residue are produced during production.
  • the production process is environmentally friendly, and the comprehensive cost is reduced by more than 25% compared with the traditional process.
  • step 1) the nitro T acid reaction solution is cooled to -5 ° C to 10 ° C.
  • step 2) the content of sodium sulfite in the H acid-base molten mother liquor is 35% -45%.
  • step 2) after the nitro T acid solid is slurried with water, it is neutralized with the H acid-base molten mother liquor until the pH value of the nitro T acid slurry is 4-6. .
  • the complex extractant is a mixture of N 235 and a solvent oil and a phenalkyl ether, and the mass percentage of N 235 in the complex extractant is 20% -50%, which can be 20%, 25%, 30%, 35%, 40%, 45%, or 50%.
  • the solvent oil is 200 # solvent oil or kerosene.
  • phenyl alkyl ether compounds include anisole, phenyl ether, butyl ether, phenyloctyl ether and the like.
  • step 3 the sulfuric acid content in the remaining filtrate after the extraction is 35% -45% (mass percentage).
  • the content of nitro T acid can be reduced to less than 0.5%, and the sulfuric acid content is about 40%, which can be used for the acidification of amino T acid.
  • the catalyst is a nickel catalyst, and the temperature of catalytic hydrogenation is 80 ° C-120 ° C.
  • the base is sodium hydroxide or potassium hydroxide.
  • the mass fraction of the base is 40% -50%.
  • step 5 the temperature of the alkali melting is 160 ° C-195 ° C, and the time of the alkali melting is 1-3 hours.
  • the process for producing H acid by recycling the mother molten liquor provided by the present invention By replacing potassium hydroxide or sodium hydroxide with a sulfite as a neutralizing solution for the denitration reaction, the content of Sulfite mother liquor can be continuously recycled, which not only greatly reduces the consumption of potassium hydroxide or sodium hydroxide, but also reduces the amount of alkali molten mother liquor treatment, which effectively reduces the production cost of the product.
  • the present invention circulates in the process of preparing H acid by replacing the potassium hydroxide neutralization denitration reaction solution with a sulfite-containing H acid-base molten mother liquor. Utilization, the reductions reached 54.5% and 56.25% respectively, greatly reducing the consumption of potassium hydroxide or sodium hydroxide, effectively reducing the production cost of the product.
  • the process for producing H-acid by recycling the molten mother liquor provided by the present invention can use light-burned magnesium and ammonia water as further neutralizing substances.
  • the acid liquid realizes the modification of light-burned magnesium and is modified.
  • the more reactive light-burned magnesium after neutralization has realized the neutralization of the acid solution.
  • the two promote each other and can quickly complete the neutralization of the filtrate.
  • the light-burned magnesium has low cost and is more conducive to reducing the production of H acid. Cost, and the magnesium sulfate produced in the neutralization process can be sold as a by-product after purification treatment, which can further offset the production cost of H acid.
  • the method for producing H acid by complex extraction is to reduce the temperature of the denitrified crystals and filter out the nitro T acid.
  • the nitro T acid is neutralized with an alkaline molten mother liquor and further reduced to produce amino T acid.
  • the mother liquor after the nitro T acid was filtered, the filtrate was extracted with N 235 and solvent oil, and then back-extracted with an alkaline solution, and the back-extracted liquid was reduced to produce amino T acid.
  • the filtrate after the extraction of nitro T acid, the content of nitro T acid can be reduced to less than 0.5%, and the sulfuric acid content is about 40%, which can be used as an acid for the acidification of amino T acid.
  • Extract the extract of nitro T acid wash the sulfuric acid extracted into the extract with water before back extraction, adjust the amount of washing water, the sulfuric acid concentration can reach about 20%, colorless and transparent, can be used for the acid of H acid Without affecting the quality, through this cycle, not only the alkali used for neutralizing the denitration solution, but also the sulfuric acid used for the acidification of amino T acid and H acid, and only one base is used in the entire production process, and only one salt is used in the mother liquor , The mother liquor is concentrated and crystallized to recover the sulfate, and the concentrated water is applied to the production, and no waste gas, waste water and waste residue are produced during the production process.
  • the production process is green and environmentally friendly, which effectively solves the environmental protection problem of H-acid enterprises, and the comprehensive production cost is reduced by more than 25% compared with the traditional process.
  • Example 1 the sulphite-containing alkali molten mother liquor described in step (1) was generated in step (4) when the H acid was produced using the process of the present invention.
  • a newly prepared sulfate solution is added as a neutralization solution of the reaction solution obtained by denitration.
  • the sulfur dioxide generated in the neutralization process is used to acidify the alkali melting reaction solution in step (4), a sulfite-containing solution is finally obtained.
  • the alkaline molten mother liquor can be used for neutralization of the reaction solution obtained in step (1) of Example 1 by denitration.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same below) obtained from refined naphthalene through traditional process sulfonation, nitration and denitrification, and take 560 parts of alkaline molten mother liquor containing 45% potassium sulfite and nitro T
  • the acid reaction solution was neutralized, and sulfur dioxide generated during the neutralization reaction was removed at 80-100 ° C for 1 hour. Then, the reaction solution was cooled to room temperature, crystallized, and filtered to obtain a nitro T acid salt solid and a filtrate, which are reserved for use. ; Centralized collection of sulfur dioxide, standby;
  • step (3) Dissolve the nitro T acid salt in step (1) with the washing solution and back-extract solution in step (2), add 32 parts of nickel catalyst, and catalyze hydrogenation to the end point at 80 ° C, reduce to room temperature, and filter , Acidified with 50% sulfuric acid, filtered to obtain 227 parts of amino T acid, amino T acid content 38%;
  • step (3) Take 200 parts of amino T acid in step (3), add 120 parts of 48% potassium hydroxide to alkali melting, control the reaction temperature between 160-170 ° C for 3 hours, discharge and dilute with 1 times water
  • the sulfur dioxide obtained in steps (1) and (2) is used for acidification, filtration, water washing, and then filtration and flash drying to obtain H acid and an alkali molten mother liquor containing potassium sulfite, wherein H acid is 72.3 parts , Content 82.56%, purity 98.89%;
  • step (3) The filtrate obtained after the amino T acid solid is separated in step (3) is reacted with potassium hydroxide, the pH of the reaction solution is adjusted to neutral, and potassium sulfate solid is obtained after evaporation, concentration and crystallization.
  • the potassium sulfate solid and the potassium sulfate produced in step (2) are calcined at 1000 ° C for 0.5 h, and impurities such as organic matter are removed to obtain sulfates in accordance with national standards;
  • a process for producing H acid by recycling mother liquor including the following steps:
  • step (3) Dissolve the nitro T acid salt in step (1) with the washing solution and back-extracting solution in step (2), add 60 parts of nickel catalyst, and catalyze hydrogenation to the end point at 80 ° C, reduce to room temperature, and filter , Acidified with 50% sulfuric acid, filtered to obtain 530 parts of amino T acid, amino T acid content 39.56%, mass;
  • step (3) Take 500 parts of amino T acid in step (3), add 400 parts of 48% sodium hydroxide alkali melt, 100 parts of methanol, control the reaction temperature between 190-195 ° C, time is 5h, discharge, use Diluted 1.5 times with water, acidified with sulfur dioxide obtained in steps (1) and (2), filtered, and flash-dried to obtain H acid and an alkaline molten mother liquor containing sodium sulfite, of which 192.1 parts of H acid, the content of 86.15%, Chromatographic purity 99.05%;
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same below) obtained from refined naphthalene through traditional process sulfonation, nitration and denitrification, and take 560 parts of alkaline molten mother liquor containing 45% potassium sulfite and nitro T
  • the acid reaction solution was neutralized, and sulfur dioxide generated during the neutralization reaction was removed at 80-100 ° C for 1 hour. Then, the reaction solution was cooled to room temperature, crystallized, and filtered to obtain a nitro T acid salt solid and a filtrate, which are reserved for use. ; Centralized collection of sulfur dioxide, standby;
  • step (3) Dissolve the nitro T acid salt in step (1) with the washing solution and back-extract solution in step (2), add 32 parts of nickel catalyst, and catalyze hydrogenation to the end point at 80 ° C, reduce to room temperature, and filter , Acidified with 50% sulfuric acid, filtered to obtain 148 parts of amino T acid, amino T acid content 40.34%, mass;
  • step (3) Take 135 parts of amino T acid in step (3), add 120 parts of 48% potassium hydroxide to alkali melting, control the reaction temperature between 160-170 ° C for 3 hours, discharge and dilute with 1 times water , Acidify, filter, wash with sulfur dioxide obtained in step (1), and then filter and flash dry to obtain H acid and an alkali molten mother liquor containing potassium sulfite, wherein the H acid is 52.1 parts, the content is 81.21%, Purity was 99.16%.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same hereinafter) obtained from refined naphthalene through traditional process sulfonation, nitration and denitrification, and take 1000 parts of alkaline molten mother liquor containing 35% potassium sulfite and nitro T
  • the acid reaction solution was neutralized, and sulfur dioxide generated during the neutralization reaction was removed at 80-100 ° C for 1 hour. Then, the reaction solution was cooled to room temperature, crystallized, and filtered to obtain a nitro T acid salt solid and a filtrate, which are reserved for use. ; Centralized collection of sulfur dioxide, standby;
  • step (3) Use the filtrate in step (2) to dissolve the nitro T acid salt in step (1), add 30 parts of nickel catalyst, catalyze hydrogenation to the end point at 120 ° C, drop to room temperature, filter, and use 50% Acidified with sulfuric acid and filtered to obtain 153 parts of amino T acid, with an amino T acid content of 45.34%, mass;
  • step (3) Take 145 parts of amino T acid in step (3), add 115 parts of 50% sodium hydroxide to alkali melt, control the reaction temperature between 160-170 ° C, time is 2.5h, discharge, use 1 times water Dilute, acidify with sulfur dioxide obtained in step (1), filter, wash with water, and then filter and flash dry to obtain H acid and an alkaline molten mother liquor containing potassium sulfite.
  • H acid is 58.2 parts, and the content is 83.19%. , Purity 99.28%.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • step (2) Take 300 parts of 30% sodium hydroxide by mass, continue to neutralize with the filtrate generated in step (1), and then cool, crystallize, and filter to obtain sodium sulfate solids and filtrates. Wash sodium sulfate with water and wash solution for later use;
  • step (3) Dissolve the nitro T acid salt in step (1) with the filtrate and washing solution in step (2), add 35 parts of nickel catalyst, and catalyze hydrogenation to the end point at 80 ° C, reduce to room temperature, filter, and use 50% sulfuric acid was acidified and filtered to obtain 272 parts of amino T acid, the content of amino T acid was 45.51%, mass;
  • step (3) Take 250 parts of amino T acid in step (3), add 200 parts of 45% sodium hydroxide to alkali melt, control the reaction temperature between 160-170 ° C, time is 0.5h, discharge, use 1 times water Diluted, acidified with sulfur dioxide obtained in step (1), filtered, washed with water, and then filtered and flash-dried to obtain H acid and an alkaline molten mother liquor containing sodium sulfite.
  • H acid is 113.96 parts, content is 80.33%, purity 98.83%.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same hereinafter) obtained from refined naphthalene through traditional process sulfonation, nitration, and denitration, and take the sodium sulfite-containing alkaline molten mother liquid 800 produced in step (4) of Example 5 It is formulated into a neutralization solution with a mass concentration of 45% sodium sulfite, and a neutralization reaction with a nitro T acid reaction solution, and the sulfur dioxide generated during the neutralization reaction is removed at 80-100 ° C for 1 hour, and then The reaction solution was cooled to room temperature, crystallized, and filtered to obtain a solid salt of the nitro T salt and the filtrate, which were reserved; the sulfur dioxide was collected centrally, and was reserved;
  • step (3) Dissolve the nitro T acid salt in step (1) with the extract in step (2), add 40 parts of iron powder to perform the reduction reaction at 100 ° C, reduce to room temperature, filter, and acidify with 50% sulfuric acid , Filtered to obtain 433 parts of amino T acid, amino T acid content 46.47%, mass;
  • step (3) Take 370 parts of amino T acid in step (3), add 300 parts of 50% potassium hydroxide to alkali melt, and control the reaction temperature between 170-180 ° C for 2 hours, discharge and dilute with 1 times water , Acidify, filter, wash with sulfur dioxide obtained in step (1), and then filter and flash dry to obtain H acid and an alkali molten mother liquor containing potassium sulfite, wherein H acid is 94.2 parts, and the content is 83.22%, Purity was 99.19%.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same hereinafter) obtained from refined naphthalene through sulfonation, nitration, and denitration in the traditional process, and take 240 parts of an alkaline molten mother liquid containing 50% by weight of sodium sulfite.
  • the nitro T acid reaction solution is neutralized, and sulfur dioxide generated during the neutralization reaction is removed at 80-100 ° C for 2 hours. Then the reaction solution is cooled to room temperature, crystallized, and filtered to obtain a nitro T acid salt solid and Filtrate, reserve; Sulfur dioxide is collected centrally, reserve;
  • step (3) Dissolve the nitro T acid salt in step (1) with the extract in step (2), add 40 parts of zinc powder to carry out the reduction reaction at 110 ° C, reduce to room temperature, filter, and acidify with 50% sulfuric acid , Filtered to obtain 112 parts of amino T acid, amino T acid content 44.45%, mass;
  • step (3) Take 200 parts of amino T acid in step (3), add 170 parts of 45% sodium hydroxide to alkali melt, control the reaction temperature between 180-195 ° C for 1 hour, discharge, and dilute with 1 times water
  • the sulfuric acid obtained in step (1) is used for acidification, filtration, water washing, and then filtration and flash evaporation to obtain H acid and an alkali molten mother liquor containing sodium sulfite.
  • the H acid is 82.4 parts
  • the content is 85.22%
  • the purity is 99.01. %.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same hereinafter) obtained from refined naphthalene through the traditional process sulfonation, nitration, and denitrification, and take 600 parts of an alkaline molten mother liquor containing 35% by weight of sodium sulfite, and The nitro T acid reaction solution was neutralized, and sulfur dioxide generated during the neutralization reaction was removed at 80-100 ° C for 3 hours. Then the reaction solution was cooled to room temperature, crystallized, and filtered to obtain a nitro T acid salt solid and Filtrate, reserve; Sulfur dioxide is collected centrally, reserve;
  • step (3) dissolving the nitro T acid salt in step (1) with the filtrate in step (2), adding 80 parts of iron powder to perform a reduction reaction at 100 ° C, lowering to room temperature, filtering, and acidifying with 50% sulfuric acid, Filtration yielded 293 parts of amino T acid with an amino T acid content of 43.88%;
  • step (3) Take 400 parts of amino T acid in step (3), add 65 parts of 45% sodium hydroxide to alkali melt, and control the reaction temperature between 180-190 ° C for 2 hours, discharge and dilute with 1 times water , Acidify, filter, wash with sulfur dioxide obtained in step (1), and then filter and flash dry to obtain H acid and an alkaline molten mother liquor containing sodium sulfite, wherein H acid is 161.4 parts, the content is 82.41%, and the purity is 99.2 %.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same hereinafter) obtained from refined naphthalene through traditional process sulfonation, nitration, and denitrification, and take 540 parts of 50% alkaline molten mother liquor containing potassium sulfite Neutralize reaction with nitro T acid reaction solution, and remove sulfur dioxide generated during neutralization reaction at 80-100 ° C for 3 h, then reduce the reaction solution to room temperature, crystallize, and filter to obtain nitro T acid salt Solids and filtrates, reserve; Sulfur dioxide is collected centrally, reserve;
  • step (3) dissolving the nitro T acid salt in step (1) with the filtrate in step (2), adding 80 parts of iron powder to perform a reduction reaction at 100 ° C, lowering to room temperature, filtering, and acidifying with 50% sulfuric acid, Filtration yielded 293 parts of amino T acid with an amino T acid content of 43.88%;
  • step (3) Take 400 parts of amino T acid in step (3), add 65 parts of 48% potassium hydroxide to alkali melt, control the reaction temperature between 165-175 ° C, time is 1 hour, discharge and dilute with 1 times water , Acidify, filter, wash with sulfur dioxide obtained in step (1), and then filter and flash dry to obtain H acid and an alkali molten mother liquor containing potassium sulfite, in which H acid is 119.46 parts and the content is 82.41%, Purity 99.2%.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same hereinafter) obtained from refined naphthalene through sulfonation, nitration, and denitration in the traditional process.
  • the nitro T acid reaction solution is neutralized, and sulfur dioxide generated during the neutralization reaction is removed at 80-100 ° C for 2 hours. Then the reaction solution is cooled to room temperature, crystallized, and filtered to obtain a nitro T acid salt solid and Filtrate, reserve; Sulfur dioxide is collected centrally, reserve;
  • step (3) Dissolve the nitro T acid salt in step (1) with the filtrate in step (2), add 25 parts of nickel catalyst, and catalyze hydrogenation at 100 ° C to the end point, reduce to room temperature, filter, and use 50% Acidified with sulfuric acid and filtered to obtain 124 parts of amino T acid, with an amino T acid content of 41.31%, mass;
  • step (3) Take 100 parts of amino T acid in step (3), add 80 parts of 45% sodium hydroxide to alkali melt, control the reaction temperature between 180-190 ° C for 2 hours, discharge and dilute with 1 times water
  • the sulfuric acid obtained in step (1) is used for acidification, filtration, water washing, and then filtration and flash evaporation to obtain H acid and an alkali molten mother liquor containing sodium sulfite.
  • the H acid is 39.7 parts, the content is 83.97%, and the purity is 99.23. %.
  • a process for producing H acid by recycling mother liquor including the following steps:
  • nitro T acid reaction solution (parts by weight, the same hereinafter) obtained from refined naphthalene through traditional process sulfonation, nitration, and denitrification, and take 720 parts of alkali molten mother liquor containing 30% potassium sulfite.
  • step (3) Dissolve the nitro T acid salt in step (1) with the filtrate in step (2), add 50 parts of nickel catalyst, catalyze hydrogenation to the end point at 90 ° C, reduce to room temperature, filter, and use 50% Acidified by sulfuric acid and filtered to obtain 418 parts of amino T acid, with an amino T acid content of 42.07%, mass;
  • step (3) Take 300 parts of amino T acid in step (3), add 320 parts of 48% potassium hydroxide to alkali melt, and control the reaction temperature between 165-170 ° C, the time is 1.5h, discharge and use 1 time water Diluted, acidified with sulfur dioxide obtained in step (1), filtered, washed with water, and then filtered and flash-dried to obtain H acid and an alkali molten mother liquor containing sodium sulfite, wherein H acid is 121.75 parts, content is 81.22%, purity 99.17%.
  • a method for producing H acid by H acid-base molten mother liquor and complex extraction including the following steps;
  • step (2) Add 15 parts of nickel catalyst obtained in step (2) to the nickel nitrate solution, hydrogenate at 120 ° C to the end point, filter off the catalyst, acidify with dilute sulfuric acid generated after extraction in (3), and obtain amino group by filtration T acid was 298 parts, and amino T acid was 38.5%.
  • step (3) Add 5 parts of nickel catalyst to the stripping solution in step (3), and add hydrogen to the end point at 120 ° C.
  • the catalyst was filtered off, and then acidified and filtered to obtain 89 parts of amino T acid with a content of 32.8%.
  • a method for producing H acid by H acid-base molten mother liquor and complex extraction method comprising the following steps:
  • step 2) Combine step 2) and the potassium nitrate solution obtained in step 2 and add 20 parts of nickel catalyst, hydrogenate to the end point at 80 ° C, filter off the catalyst, and generate dilute sulfuric acid (content 39.8%) after extraction in (3) ) Neutralization and filtration to obtain 370 parts of amino T acid, the content of amino T acid is 41.3%.
  • Example 5 6 parts of nickel catalyst was added to the back-extraction liquid in Example 3, and hydrogen was added to the end point at 120 ° C. The catalyst was filtered off, and then acidified and filtered to obtain 108 parts of amino T acid with a content of 34.6%.
  • a method for producing H acid by H acid-base molten mother liquor and complex extraction including the following steps;
  • step (2) Combine the sodium nitro T sodium solution obtained in step (2), add 50 parts of nickel catalyst, hydrogenate at 100 ° C to the end point, filter off the catalyst, acidify with dilute sulfuric acid generated after extraction in (3), and filter to obtain 290 parts of amino T acid, the content of amino T acid was 40.5%.
  • step 5 Add 4 parts of the nickel catalyst to the stripping solution in step 3, hydrogenate at 100-120 ° C to the end point, filter off the catalyst, and then acidify and filter to obtain 86 parts of amino T acid with a content of 35.3%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'un H acide par recyclage d'une liqueur mère de fusion alcaline. La liqueur mère de fusion alcaline est utilisée comme liqueur de neutralisation pour une liqueur de réaction de dénitration, ou une liqueur de neutralisation pour une liqueur de dénitration après refroidissement, cristallisation et filtration d'un gâteau de filtration. La liqueur de réaction de dénitration neutralisée est ensuite réduite pour produire un acide aminé T. Le filtrat obtenu après refroidissement et filtration de la liqueur de dénitration est soumis à une extraction de coordination pour obtenir l'acide aminé T, puis soumis à une extraction et une réduction inverses pour produire de l'acide aminé T. L'acide dilué restant après extraction de l'acide nitro T dans le filtrat de liqueur de dénitrification est utilisé pour l'acidification de l'acide aminé T, réduisant ainsi la quantité d'acide et d'alcali et le coût de production dans le procédé de production du H acide.
PCT/CN2019/105277 2018-09-13 2019-09-11 Procédé de production d'un h acide par recyclage de liqueur mère de fusion alcaline Ceased WO2020052577A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201811067656.XA CN109096155B (zh) 2018-07-09 2018-09-13 一种通过碱熔母液循环利用生产h酸的工艺
CN201811067656.X 2018-09-13
CN201910570207.5A CN110256302B (zh) 2019-06-27 2019-06-27 一种络合萃取生产h酸的方法
CN201910570207.5 2019-06-27

Publications (1)

Publication Number Publication Date
WO2020052577A1 true WO2020052577A1 (fr) 2020-03-19

Family

ID=67922615

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/105277 Ceased WO2020052577A1 (fr) 2018-09-13 2019-09-11 Procédé de production d'un h acide par recyclage de liqueur mère de fusion alcaline

Country Status (2)

Country Link
CN (1) CN110256302B (fr)
WO (1) WO2020052577A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118439978B (zh) * 2024-06-28 2024-09-06 山东创蓝垚石环保技术有限公司 一种t酸母液循环利用生产h酸的工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4534905A (en) * 1980-05-29 1985-08-13 Bayer Aktiengesellschaft Process for the preparation of nitronaphthalene-sulphonic acids
CN104592063A (zh) * 2014-12-24 2015-05-06 青岛奥盖克化工股份有限公司 一种h酸的环保生产工艺
CN105669500A (zh) * 2016-02-29 2016-06-15 江苏吉华化工有限公司 一种采用清洁工艺制备h-酸的方法
CN109096155A (zh) * 2018-07-09 2018-12-28 山东垚石化工科技有限公司 一种通过碱熔母液循环利用生产h酸的工艺

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54163563A (en) * 1978-06-15 1979-12-26 Sugai Chemical Ind Co Ltd Method of isolating naphthalenedisulfonic acids
JPS5951253A (ja) * 1982-09-14 1984-03-24 Sugai Kagaku Kogyo Kk １・８―ジニトロナフタレン―３・６―ジスルホン酸の製造法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4534905A (en) * 1980-05-29 1985-08-13 Bayer Aktiengesellschaft Process for the preparation of nitronaphthalene-sulphonic acids
CN104592063A (zh) * 2014-12-24 2015-05-06 青岛奥盖克化工股份有限公司 一种h酸的环保生产工艺
CN105669500A (zh) * 2016-02-29 2016-06-15 江苏吉华化工有限公司 一种采用清洁工艺制备h-酸的方法
CN109096155A (zh) * 2018-07-09 2018-12-28 山东垚石化工科技有限公司 一种通过碱熔母液循环利用生产h酸的工艺

Also Published As

Publication number Publication date
CN110256302B (zh) 2020-07-17
CN110256302A (zh) 2019-09-20

Similar Documents

Publication Publication Date Title
CN104944400B (zh) 水解法制备磷酸铁的工艺
CN109516479B (zh) 电池级氢氧化锂的制备方法
CN109592699B (zh) 电池级氢氧化锂的制备方法
CN114655969A (zh) 高杂磷酸铁锂正极废料回收制备碳酸锂和磷酸铁的方法
CN109911909B (zh) 一种钴酸锂正极材料制备过程中废弃匣钵的回收处理方法
WO2014194790A1 (fr) Procédé d'extraction de deux sels secondaires à partir d'un déchet liquide désulfurisé contenant du sel de gaz de four à coke
CN105060599A (zh) 一种不锈钢酸洗废水资源化回收方法
WO2024174341A1 (fr) Procédé de traitement des eaux usées de synthèse de précurseur de matériau d'électrode positive de batterie
CN108358221A (zh) 一种用硫酸镁亚型盐湖卤水制取氯化锂的工艺
CN109096155B (zh) 一种通过碱熔母液循环利用生产h酸的工艺
CN106884090A (zh) 一种废弃脱硝催化剂中钒钨钛全回收的亚熔盐方法
CN106315930A (zh) 一种乙烯废碱液再生回用的方法
CN114835611A (zh) 一种降低磺化产品重烷基苯磺酸中硫酸含量的工艺及设备
CN101195594B (zh) 一种从生产吐氏酸的废水中提取有效成分的制备方法
CN102992469B (zh) 一种处理硫化碱废水的方法
CN118851226A (zh) 一种处理加压碱溶铂氧化铝催化剂废水副产铝酸钠的绿色工艺
CN118439978A (zh) 一种t酸母液循环利用生产h酸的工艺
CN101402461B (zh) 一种从焦炉煤气脱硫脱氰废水中回收无机盐的工艺
CN115818605A (zh) 二水磷酸铁及其制备方法、磷酸铁锂正极材料的制备方法
CN110294677A (zh) 一种提高邻硝基氯苯纯度的生产方法
CN106495190B (zh) 一种含锂废盐煅烧回收方法
CN110256302A (zh) 一种络合萃取生产h酸的方法
CN112811647B (zh) 一种生产dl-蛋氨酸的废液处理方法
CN103754828A (zh) 一种重铬酸钠闭路循环制备氯酸钠的清洁生产方法
CN1206165C (zh) 一种铬酸酐的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19859194

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19859194

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19859194

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 04/11/2021)