WO2019085877A1 - 一种吡唑酮系列产品生产过程中的工艺废水处理工艺 - Google Patents

一种吡唑酮系列产品生产过程中的工艺废水处理工艺 Download PDF

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WO2019085877A1
WO2019085877A1 PCT/CN2018/112590 CN2018112590W WO2019085877A1 WO 2019085877 A1 WO2019085877 A1 WO 2019085877A1 CN 2018112590 W CN2018112590 W CN 2018112590W WO 2019085877 A1 WO2019085877 A1 WO 2019085877A1
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pyrazolone series
production process
wastewater treatment
production
series product
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PCT/CN2018/112590
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English (en)
French (fr)
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庆九
俞新南
薛金全
刘芳
朱小刚
张锦凤
朱爱华
石春明
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南通醋酸化工股份有限公司
南通立洋化学有限公司
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Publication of WO2019085877A1 publication Critical patent/WO2019085877A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

Definitions

  • the invention relates to the field of wastewater treatment, in particular to a process wastewater treatment process in the production process of a pyrazolone series product.
  • C 10 H 10 N 2 O (1-phenyl-3-methyl-5-pyrazolone) as an example:
  • Appearance properties light yellow crystal or powder.
  • Solubility soluble in water, slightly soluble in alcohol and benzene, insoluble in ether, petroleum ether and cold water.
  • Boiling point 287 ° C 265 mmHg
  • This product is an important fine chemical intermediate, mainly used in the synthesis of pyrazolone antipyretic analgesics such as analgin, antipyrine, aminopyrine, pyrazolone acid dyes such as acid Medium Jujube BN, Permanent Yellow G and intermediates for color film dyes, pesticides and other fine chemicals.
  • pyrazolone antipyretic analgesics such as analgin, antipyrine, aminopyrine, pyrazolone acid dyes such as acid Medium Jujube BN, Permanent Yellow G and intermediates for color film dyes, pesticides and other fine chemicals.
  • the conventional production method in industrial production is: 30-70 ° C, aniline, hydrochloric acid, sodium nitrite solution is simultaneously added to the diazotization reactor, the diazotization reaction is cooled, and the reaction liquid is added to ammonium hydrogen sulfite.
  • the reduction reaction is carried out in the solution.
  • sulfuric acid is slowly added dropwise, and the mixture is heated to 80 to 120 ° C to carry out a hydrolysis reaction.
  • After cooling to 30 to 70 ° C it is neutralized to acidity by liquid ammonia, and acetylacetamide is added for condensation.
  • the reaction was carried out to obtain a 1-phenyl-3-methyl-5-pyrazolone reaction solution, which was filtered, washed and purified to give a product.
  • a disadvantage of this process are: the process wastewater mainly Cl - on SO4 2-, respectively, Na +, NH 4+ formed NaCl, NH 4 Cl, Na 2 SO 4, (NH 4) 2 SO 4 four salts, it is difficult to After separation and evaporation and concentration, 1 ton of product produces 4.5-7 tons of dangerous solid waste, which has a large amount of hazardous waste and low resource utilization.
  • Patent CN101429163A reports the recycling method of waste in the production of pyrazolone.
  • the process acid is added to the reaction kettle by adding process water and H 2 SO 4 , and the process acid is heated to 85 ° C to start the waste. The temperature is controlled at 90 after the end of the feed. After incubation at -95 ° C for 20 minutes, it was filtered, added to aqueous ammonia, centrifugally dehydrated and air dried to obtain a pyrazolone product.
  • the process consists mainly in the recovery of the product, without mentioning the separation of the salt components produced during the production process.
  • the technical scheme of the present invention is a process wastewater treatment process in the production process of a pyrazolone series product, wherein the pyrazolone series product production process comprises a diazo, reduction, hydrolysis, condensation step, and a process used in the diazo reaction process.
  • the acid is a sulfuric acid solution;
  • the wastewater treatment process includes:
  • Pretreatment After treating the process wastewater obtained in the production process of pyrazolone series by one or two methods of decolorization by activated carbon or continuous extraction of organic solvent, COD is reduced from 10000 to 20000 mg/L, and COD is reduced to 3000-6000 mg/ L;
  • Crystal separation 1 The separation mother liquid obtained after the pretreatment is heated to 60-100 ° C, the pressure is 0.02-0.1 MPa, 50-70% of the total water is distilled off, and the separated mother liquid is cooled to 40-80 ° C, and the crystal separation is performed. , obtaining ammonium sulfate and filtrate in line with agricultural grade standards;
  • Crystallization separation 2 adding a basic compound of sodium to the filtrate separated in the previous step, adjusting the pH to 6-8, raising the temperature to 50-100 ° C, the pressure is 0.012-0.1 MPa, evaporating water and ammonia, and concentrating The filtrate was cooled to 0 to 40 ° C and crystallized to give a by-product of sodium sulfate.
  • the temperature is raised to 50 to 100 ° C and the pressure is 0.012 to 0.1 MPa, which is the process of evaporating water and ammonia.
  • the diazotization reaction in the original process is: aromatic amine, hydrochloric acid, sodium nitrite solution is added to the diazotization reactor for reaction, and the reaction liquid of the pyrazolone series product is obtained by diazo, reduction, hydrolysis and condensation. After washing and refining, the product is obtained.
  • the diazotization reaction is carried out by adding an aromatic amine, sulfuric acid or sodium nitrite solution to the diazotization reactor, and sulfuric acid is used instead of hydrochloric acid as a diazotization strong acid medium, thereby effectively reducing the salt group in the wastewater. It is difficult to reduce the salt content in wastewater.
  • the organic solvent is one or more selected from the group consisting of benzenes, ethers, and esters.
  • the organic solvent mainly extracts the tar in the wastewater, and the principle is similar compatibility.
  • the use of activated carbon alone and extraction with an organic solvent alone is a different method for removing tar, each having advantages and disadvantages. If the two methods are combined, the tar removal is more thorough.
  • the organic solvent is an ester.
  • the aromatic nitrogen diazo sulphate is easily hydrolyzed under acidic conditions to form a by-product containing -OH, and an ester organic solvent is used to extract the hydroxy compound in the wastewater and improve the purity of the by-produced salt.
  • the benzene solvent is selected from the group consisting of benzene, toluene, ethylbenzene and the like.
  • the ether solvent may be diethyl ether or the like, and the ester solvent may be an ester such as methyl acetate or ethyl acetate.
  • the basic compound of sodium includes sodium hydroxide or sodium carbonate.
  • the generated ammonia is recycled.
  • the agricultural grade ammonium sulfate has an N content of ⁇ 20.5%.
  • the process wastewater contains 20-30% of ammonium sulfate and 2 to 3% of sodium sulfate.
  • the concentration of ammonium sulfate in the process wastewater is 20-30%, and the concentration of sodium sulfate is 2 ⁇ 3%.
  • the pretreatment method is one or more of solvent continuous extraction or activated carbon decolorization.
  • the solvent is benzene, toluene, diethyl ether and acetic acid.
  • the mother liquor after pretreatment uses the difference in solubility between different concentrations of ammonium sulfate and sodium sulfate solution at different temperatures, and the stepwise gradient cooling, crystallization, and separation, to obtain ammonium sulfate and sodium sulfate by-product.
  • the salt component in the process wastewater of the pyrazolone series product mainly aims at the problem that the salt component of the original production process is many and difficult to be separated and processed, and a new treatment method is developed.
  • the invention solves the problems that the salt content of the process wastewater is large, difficult to handle, and the amount of hazardous waste is large, and the by-product salt conforming to the standard is obtained.
  • sulfuric acid instead of hydrochloric acid as a strong acid medium for diazotization
  • process wastewater with Na 2 SO 4 and (NH 4 ) 2 SO 4 as main salts is obtained, which is pretreated by activated carbon or solvent to remove waste water.
  • By-products such as tar, a colorless clarified mother liquor is obtained, and the separated mother liquor is evaporated and concentrated.
  • the process wastewater contains sodium chloride, ammonium chloride, sodium sulfate and ammonium sulfate. After treatment, 1 ton of product produces 4.5-7 tons of salt-containing solid waste.
  • sulfuric acid is used instead of hydrochloric acid as a heavy acid medium for diazotization, which effectively reduces the salt component in the wastewater and reduces the difficulty of treating the salt in the wastewater.
  • the process wastewater contains sodium sulfate and ammonium sulfate, and after treatment, the standard is obtained. By-products, no salt solid waste is produced, and resources are rationally utilized.
  • the method for treating salt in the mother liquor of the pyrazolone series product comprises the following steps:
  • the sulfuric acid is used as a heavy acid medium to produce a pyrazolone series product, and the process wastewater is separated.
  • 500 g of the process wastewater (containing 117 g of ammonium sulfate and 13 g of sodium sulfate, COD ⁇ 18500 mg / l) was added to a 1000 ml three-necked flask, and 1 g of activated carbon was added thereto, and the temperature was raised to 80 ° C, and the mixture was kept for 30 minutes, and then filtered to obtain 488.7 g of a mother liquid, which contained Ammonium sulfate 115.3 g, sodium sulfate 12.4 g, COD ⁇ 5800 mg / l.
  • the mother liquid was heated to 100 ° C, 250.5 g of water was distilled off, cooled to 80 ° C, crystallized and separated, and dried to obtain 58.7 g of ammonium sulfate.
  • the appearance was white, and the amount of N was 20.7%, which was in compliance with agricultural grade standards.
  • Sodium hydroxide was added to the separated filtrate to adjust the pH to 7.2, the negative pressure was raised to 60 ° C, 38 g of distilled water and 14.4 g of NH 3 were distilled off, and the kettle liquid was cooled to 15 ° C, separated by crystallization, and dried to obtain 53.4 g of sodium sulfate, the content was 97.2%. .
  • Example 1 The mother liquid in Example 1 was heated to 80 ° C, and 197.3 g of water was distilled off, cooled to 50 ° C, crystallized and separated, and dried to obtain 96.3 g of ammonium sulfate. The appearance was white, and the amount of N was 20.9%, which was in compliance with agricultural standards. .
  • Sodium hydroxide was added to the separated filtrate to adjust the pH to 6.9, the negative pressure was raised to 80 ° C, 104.9 g of distilled water and 4.8 g of NH 3 were distilled off, and the kettle liquid was cooled to 7 ° C, separated by crystallization, and dried to obtain 30.1 g of sodium sulfate, content 97.9. %.
  • the sulfuric acid is used as a heavy acid medium to produce a pyrazolone series product, and the process wastewater is separated.
  • 500 g of process wastewater (containing 117 g of ammonium sulfate and 13 g of sodium sulfate, COD ⁇ 18500 mg / l) was added to a 1000 ml three-necked flask, and 150 g of ethyl acetate was continuously added for extraction and separation to obtain 492.2 g of an aqueous phase containing 117 g of ammonium sulfate, sulfuric acid.
  • the mother liquid was heated to 100 ° C, 250.5 g of water was distilled off, cooled to 40 ° C, crystallized and separated, and dried to obtain 104.1 g of ammonium sulfate.
  • the appearance was white, and the amount of N was 21.1%, which was in compliance with agricultural grade standards.
  • Sodium hydroxide was added to the separated filtrate to adjust the pH to 7.6, the negative pressure was raised to 90 ° C, 78.2 g of distilled water and 3.2 g of NH 3 were distilled off, and the kettle liquid was cooled to 0 ° C, separated by crystallization, and dried to obtain 26.4 g of sodium sulfate, the content was 97.6. %.
  • Example 3 The mother liquid in Example 3 was heated to 60 ° C, and 197.3 g of water was distilled off, cooled to 40 ° C, crystallized and separated, and dried to obtain 51.5 g of ammonium sulfate. The appearance was white, and the amount of N was 21.3%, which was in compliance with agricultural standards. .
  • Sodium hydroxide was added to the separated filtrate to adjust the pH to 6.5, the negative pressure was raised to 50 ° C, 104.9 g of distilled water and 16.6 g of NH 3 were distilled off, and the kettle liquid was cooled to 40 ° C, crystallized and separated, and dried to obtain 66.8 g of sodium sulfate, the content was 97.7. %.
  • the process wastewater contains 20.56% ammonium sulfate, 1.86% ammonium chloride, 1.54% sodium chloride, 0.46% sodium sulfate, and COD ⁇ 26800 mg/l.
  • 500 g of process wastewater was added to a 1000 ml three-necked flask, and the mother liquor after pretreatment was heated to 100 ° C, 300 g of water was distilled off, cooled to 20 ° C at a constant rate, crystallized and filtered to obtain sodium chloride, ammonium chloride and sodium sulfate. And a mixed salt of ammonium sulfate.
  • sulfuric acid is used as the diazotization strong acid medium, and the salt component in the produced process wastewater can be separated and the by-products meeting the quality standards can be obtained.
  • hydrochloric acid is used as a heavy acid medium for diazotization, and there are many salt components in the process wastewater. It is difficult to separate and obtain qualified by-products, and it can only be treated as dangerous solid waste.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

一种吡唑酮系列产品生产过程中的工艺废水处理工艺，吡唑酮系列产品生产过程包括重氮、还原、水解、缩合步骤，重氮反应过程中采用的酸为硫酸溶液；该工艺包括：将吡唑酮系列产品生产过程中得到的工艺废水经活性炭脱色或有机溶剂连续萃取中的一种或两种方法预处理后，COD下降；将预处理后得到的分离母液升温，蒸发，釜液冷却至40～80℃，结晶分离，得到符合农用级标准的硫酸铵和滤液；在上一步分离后的滤液中加入钠的碱性化合物，调节pH值，升温，釜液冷却至0～40℃，结晶分离，得到硫酸钠副产。该方法采用硫酸代替盐酸做重氮化强酸介质，工艺废水中含硫酸钠、硫酸铵盐，经处理后得到符合标准的副产，不产生含盐固废，资源得到合理利用。

Description

一种吡唑酮系列产品生产过程中的工艺废水处理工艺 技术领域
本发明涉及废水处理领域，具体涉及一种吡唑酮系列产品生产过程中的工艺废水处理工艺。
背景技术
以吡唑酮系列产品为C nH mN pO qCl rS t，n＝10～11，m＝9～12，p＝2，q＝1～4，r＝0～2，t＝0～1。下面以C 10H 10N 2O(1-苯基-3-甲基-5-吡唑酮)为例：
外观性质：浅黄色结晶或粉末。
溶解性：溶于水、微溶于醇和苯，不溶于醚、石油醚及冷水。
分子量：174.20
熔点：127-131℃
沸点：287℃ 265mmHg
密度：1.26
闪点：191℃
相对密度:1.17
水溶解性：3g/L(20℃)
用途：
本品为是一种重要的精细化学品中间体，主要用于合成吡唑酮类解热镇痛药如安乃近、安替比林、氨基比林，也是吡唑酮类酸性染料如酸性媒介枣红BN、永固黄G以及彩色胶片染料、农药及及其他一些精细化学品的中间体。
现有技术合成工艺：
目前工业生产上的常规生产方法为：30-70℃，苯胺、盐酸、亚硝酸钠溶液同时加到重氮化反应器中反应，重氮化反应结束后冷却，反应液加入到亚硫酸氢铵溶液中进行还原反应， 还原反应结束后，缓慢滴加硫酸，升温至80～120℃进行水解反应，冷却至30～70℃后，通入液氨中和至酸性,加入乙酰基乙酰胺进行缩合反应，得到1-苯基-3-甲基-5-吡唑酮反应液，过滤后经洗涤、精制得到产品。
该工艺的缺点是：工艺废水中主要存在Cl —和SO4 2—，分别于Na +、NH 4+形成NaCl、NH 4Cl、Na 2SO 4、(NH 4) 2SO 4四种盐，难以分离，蒸发浓缩后，1吨产品产生4.5～7吨的危险固废，危废量大，资源利用率低。
专利CN101429163A报道了吡唑酮生产中废料的回收处理方法，向反应釜中加入工艺用水和H 2SO 4制得工艺酸，将工艺酸加热至85℃开始投废料，投料结束后温度控制在90～95℃保温20分钟后过滤，加入氨水中和，离心脱水和气流干燥得到吡唑酮产品。该工艺主要在于回收产品，未提及生产过程中产生的盐组分分离。
发明内容
因此，为了解决工艺废水中含盐组分多、难处理、危废量大等问题，提供一种分级处理吡唑酮系列产品生产过程中的工艺废水的方法。
本发明的技术方案是，一种吡唑酮系列产品生产过程中的工艺废水处理工艺，所述吡唑酮系列产品生产过程包括重氮、还原、水解、缩合步骤，重氮反应过程中采用的酸为硫酸溶液；该废水处理工艺包括：
预处理：将吡唑酮系列产品生产过程中得到的工艺废水经活性炭脱色或有机溶剂连续萃取中的一种或两种方法处理后，COD从10000～20000mg/L，COD降至3000～6000mg/L；
结晶分离1：将预处理后得到的分离母液升温至60～100℃，压力为0.02～0.1MPa，蒸出总水量的50～70％，浓缩后的分离母液冷却至40～80℃，结晶分离，得到符合农用级标准的硫酸铵和滤液；
结晶分离2：在上一步分离后的滤液中加入钠的碱性化合物，调节pH值至6～8，升温至50～100℃，压力为0.012～0.1MPa，蒸发水和氨，浓缩后得到的滤液冷却至0～40℃，结晶分离，得到硫酸钠副产。
升温至50～100℃，压力为0.012～0.1MPa，就是蒸发水和氨的过程。
原有工艺中的重氮化反应是：芳香胺、盐酸、亚硝酸钠溶液加到重氮化反应器中反应，经重氮、还原、水解、缩合得到吡唑酮系列产品的反应液，过滤后经洗涤、精制得到产品。而本发明在生产过程中，重氮化反应采用芳香胺、硫酸、亚硝酸钠溶液加到重氮化反应器中反应，采用硫酸代替盐酸做重氮化强酸介质，有效减少废水中的盐组分，降低废水中盐分的处理难度。
根据本发明的吡唑酮系列产品生产过程中的工艺废水处理工艺，优选的是，所述有机溶剂选自苯类，醚类，酯类中的一种或几种。有机溶剂主要萃取废水中的焦油，原理是相似相溶。单独用活性炭，单独用有机溶剂萃取，是脱除焦油的不同方法，各有优缺点。两种方法合用的话，脱除焦油更加彻底。
更优选的是，有机溶剂为酯类。芳香胺的重氮硫酸氢盐易在酸性条件下水解，生成含-OH的副产，用酯类有机溶剂，更有助于萃取出废水中的羟基化合物，提高副产盐的纯度。
苯类溶剂选自苯、甲苯、乙苯等。醚类溶剂可以选用乙醚等，酯类溶剂可以选用乙酸甲酯、乙酸乙酯等酯类。
优选的是，m(有机溶剂)：m(工艺废水)＝0.1～1:1。
根据本发明的吡唑酮系列产品生产过程中的工艺废水处理工艺，优选的是，所述钠的碱性化合物包括氢氧化钠、碳酸钠。
根据本发明的吡唑酮系列产品生产过程中的工艺废水处理工艺，优选的是，所述结晶分离1步骤中得到馏出液部分或全部套用至生产系统中。
根据本发明的吡唑酮系列产品生产过程中的工艺废水处理工艺，优选的是，所述结晶分离2中，生成的氨回收套用。
根据本发明的吡唑酮系列产品生产过程中的工艺废水处理工艺，优选的是，所述农用级硫酸铵的含N量≥20.5％。
根据本发明的吡唑酮系列产品生产过程中的工艺废水处理工艺，优选的是，所述工艺废水中含硫酸铵20～30％，硫酸钠2～3％。
工艺废水中硫酸铵浓度为20～30％，硫酸钠浓度为2～3％，预处理方法为溶剂连续萃取法或活性炭脱色法中的一种或几种，溶剂为苯、甲苯、乙醚、乙酸甲酯、乙酸乙酯等有机 溶剂中的一种或几种，m(溶剂)：m(工艺废水)＝0.1～1:1，主要除去其中焦油等有机物。预处理后的母液，利用不同温度下的不同浓度的硫酸铵、硫酸钠溶液之间的溶解度差异，分段梯度冷却、结晶、分离，得到硫酸铵和硫酸钠副产。
吡唑酮系列产品工艺废水中含盐组分，本发明主要针对原有生产工艺的盐组分多且不易分离处理的问题，研制了新的处理方法。
本发明的解决了工艺废水中含盐组分多、难处理、危废量大等问题，并得到符合标准的副产盐。以硫酸代替盐酸作重氮化反应的强酸介质，在产品生产过程中，得到以Na 2SO 4、(NH 4) 2SO 4为主要盐分的工艺废水，经活性炭或溶剂预处理，除去废水中的焦油等副产物，得到无色澄清母液，分离母液蒸发浓缩，利用不同温度下的不同浓度的硫酸铵、硫酸钠溶液之间的溶解度差异，采用分段梯度结晶的方法，得到硫酸铵、硫酸钠副产，实现清洁生产的目的。
有益效果
采用盐酸作重氮化强酸介质的工艺，工艺废水中含氯化钠、氯化铵、硫酸钠、硫酸铵盐，经处理后，1吨产品生产4.5～7吨的含盐固废。本发明中，采用硫酸代替盐酸做重氮化强酸介质，有效减少废水中的盐组分，减低废水中盐分的处理难度，工艺废水中含硫酸钠、硫酸铵盐，经处理后得到符合标准的副产，不产生含盐固废，资源得到合理利用。
具体实施方式
实施例1：
吡唑酮系列产品母液中盐分的处理方法，包括下列步骤：
以硫酸做重氮化强酸介质，生产吡唑酮系列产品，分离出工艺废水。在1000ml三口烧瓶中加入该工艺废水500g(含117g硫酸铵和13g硫酸钠，COD≈18500mg/l)，加入1g活性炭，升温至80℃，保温30分钟后过滤，得到488.7g的母液，其中含硫酸铵115.3g，硫酸钠12.4g，COD≈5800mg/l。母液升温至100℃，蒸馏出250.5g的水，冷却至80℃，结晶分离，烘干得到58.7g硫酸铵，外观为白色，含N量20.7％，符合农用级标准。分离滤液中加入氢氧化钠，调节pH至7.2，负压升温至60℃，蒸馏出水38g和NH 314.4g，釜液冷却至15℃， 结晶分离，烘干得到53.4g硫酸钠，含量97.2％。
实施例2：
实施例1中的母液负压升温至80℃，蒸馏出197.3g的水，冷却至50℃，结晶分离，烘干得到96.3g硫酸铵，外观为白色，含N量20.9％，符合农用级标准。分离滤液中加入氢氧化钠，调节pH至6.9，负压升温至80℃，蒸馏出水104.9g和NH 34.8g，釜液冷却至7℃，结晶分离，烘干得到30.1g硫酸钠，含量97.9％。
实施例3：
以硫酸做重氮化强酸介质，生产吡唑酮系列产品，分离出工艺废水。在1000ml三口烧瓶中加入工艺废水500g(含117g硫酸铵和13g硫酸钠，COD≈18500mg/l)，连续加入150g乙酸乙酯进行萃取分离，得到492.2g的水相，其中含硫酸铵117g，硫酸钠13g，COD≈3000mg/l。母液升温至100℃，蒸馏出250.5g的水，冷却至40℃，结晶分离，烘干得到104.1g硫酸铵，外观为白色，含N量21.1％，符合农用级标准。分离滤液中加入氢氧化钠，调节pH至7.6，负压升温至90℃，蒸馏出水78.2g和NH 33.2g，釜液冷却至0℃，结晶分离，烘干得到26.4g硫酸钠，含量97.6％。
实施例4：
实施例3中的母液负压升温至60℃，蒸馏出197.3g的水，冷却至40℃，结晶分离，烘干得到51.5g硫酸铵，外观为白色，含N量21.3％，符合农用级标准。分离滤液中加入氢氧化钠，调节pH至6.5，负压升温至50℃，蒸馏出水104.9g和NH 316.6g，釜液冷却至40℃，结晶分离，烘干得到66.8g硫酸钠，含量97.7％。
对比实施例1：
采用盐酸作重氮化强酸介质的生产工艺，工艺废水中含20.56％硫酸铵、1.86％氯化铵、1.54％氯化钠、0.46％硫酸钠，COD≈26800mg/l。在1000ml三口烧瓶中加入生产的工艺废 水500g，预处理后的母液，升温至100℃，蒸出300g水，匀速冷却至20℃，结晶、过滤，得到含有氯化钠、氯化铵、硫酸钠、硫酸铵的混合盐。
实施例中，采用硫酸做重氮化强酸介质，产生的工艺废水中的含盐组分可以分离出，并得到符合质量标准的副产。而对比例，采用盐酸做重氮化强酸介质，工艺废水中的含盐组分多，难以分离得到合格的副产，只能作为危险固废处理。
以上已以较佳实施例公开了本发明，然其并非用以限制本发明，凡采用等同替换或者等效变换方式所获得的技术方案，均落在本发明的保护范围之内。

Claims (9)

  1. 一种吡唑酮系列产品生产过程中的工艺废水处理工艺，所述吡唑酮系列产品生产过程包括重氮、还原、水解、缩合步骤，其特征在于：重氮反应过程中采用的酸为硫酸溶液；该废水处理工艺包括：
    预处理：将吡唑酮系列产品生产过程中得到的工艺废水经活性炭脱色或有机溶剂连续萃取中的一种或两种方法处理后，COD从10000～20000mg/L，COD降至3000～6000mg/L；
    结晶分离1：将预处理后得到的分离母液升温至60～100℃，压力为0.02～0.1MPa，蒸出总水量的50～70％，浓缩后的分离母液冷却至40～80℃，结晶分离，得到符合农用级标准的硫酸铵和滤液；
    结晶分离2：在上一步分离后的滤液中加入钠的碱性化合物，调节pH值至6～8，升温至50～100℃，压力为0.012～0.1MPa，蒸发水和氨，浓缩后得到的滤液冷却至0～40℃，结晶分离，得到硫酸钠副产。
  2. 根据权利要求1所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：所述有机溶剂选自苯类，醚类，酯类中的一种或几种。
  3. 根据权利要求2所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：有机溶剂为酯类。
  4. 根据权利要求1所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：m(有机溶剂)：m(工艺废水)＝0.1～1:1。
  5. 根据权利要求1所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：所述钠的碱性化合物包括氢氧化钠、碳酸钠。
  6. 根据权利要求1所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：所述结晶分离1步骤中得到馏出液部分或全部套用至生产系 统中。
  7. 根据权利要求1所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：所述结晶分离2中，生成的氨回收套用。
  8. 根据权利要求1所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：所述农用级硫酸铵的含N量≥20.5％。
  9. 根据权利要求1所述的吡唑酮系列产品生产过程中的工艺废水处理工艺，其特征在于：所述工艺废水中含硫酸铵20～30％，硫酸钠2～3％。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292043A (en) * 1979-02-15 1981-09-29 Bayer Antwerpen Process for working up effluent containing ammonium sulphate
KR100216278B1 (ko) * 1992-09-18 1999-08-16 전원중 카프로락탐 폐액 처리방법 및 그 장치
CN102531221A (zh) * 2010-12-09 2012-07-04 攀钢集团钢铁钒钛股份有限公司 沉钒废水的处理方法
CN103922532A (zh) * 2014-04-29 2014-07-16 宁夏东吴农化有限公司 咪唑烷尾液处理工艺
CN105130079A (zh) * 2015-09-09 2015-12-09 江西玛德精细化学工业有限公司 一种兼具h酸母液和t酸母液的处理工艺
CN107188199A (zh) * 2017-07-14 2017-09-22 深圳市瑞升华科技股份有限公司 一种从废水中回收硫酸铵、硫酸钠的工艺及设备
CN107915343A (zh) * 2017-10-31 2018-04-17 南通醋酸化工股份有限公司 一种吡唑酮系列产品生产过程中的工艺废水处理工艺

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429163B (zh) * 2008-12-17 2010-09-01 安徽富博医药化工股份有限公司 吡唑酮生产中废料的回收处理方法
CN103332821B (zh) * 2013-06-21 2016-03-30 浙江吉华集团股份有限公司 一种染料及中间体生产过程中含硫酸的废水处理方法
CN106632047A (zh) * 2015-11-14 2017-05-10 宁夏际华环境安全科技有限公司 一种吡唑酮生产工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292043A (en) * 1979-02-15 1981-09-29 Bayer Antwerpen Process for working up effluent containing ammonium sulphate
KR100216278B1 (ko) * 1992-09-18 1999-08-16 전원중 카프로락탐 폐액 처리방법 및 그 장치
CN102531221A (zh) * 2010-12-09 2012-07-04 攀钢集团钢铁钒钛股份有限公司 沉钒废水的处理方法
CN103922532A (zh) * 2014-04-29 2014-07-16 宁夏东吴农化有限公司 咪唑烷尾液处理工艺
CN105130079A (zh) * 2015-09-09 2015-12-09 江西玛德精细化学工业有限公司 一种兼具h酸母液和t酸母液的处理工艺
CN107188199A (zh) * 2017-07-14 2017-09-22 深圳市瑞升华科技股份有限公司 一种从废水中回收硫酸铵、硫酸钠的工艺及设备
CN107915343A (zh) * 2017-10-31 2018-04-17 南通醋酸化工股份有限公司 一种吡唑酮系列产品生产过程中的工艺废水处理工艺

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