WO2023023883A1 - 一种3，3'，4，4'-二环己基四甲酸的制备方法、酸性废水的处理方法 - Google Patents

一种3，3'，4，4'-二环己基四甲酸的制备方法、酸性废水的处理方法 Download PDF

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WO2023023883A1
WO2023023883A1 PCT/CN2021/113953 CN2021113953W WO2023023883A1 WO 2023023883 A1 WO2023023883 A1 WO 2023023883A1 CN 2021113953 W CN2021113953 W CN 2021113953W WO 2023023883 A1 WO2023023883 A1 WO 2023023883A1
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catalyst
preparation
ruthenium
rhodium
reaction
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French (fr)
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邵帅
张云堂
李文革
张玉芬
王晶晓
王飞扬
闫琴
王晓
刘铁成
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河北海力香料股份有限公司
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Priority to US17/641,092 priority Critical patent/US20240043364A1/en
Priority to CN202180002975.6A priority patent/CN114096508B/zh
Priority to PCT/CN2021/113953 priority patent/WO2023023883A1/zh
Priority to ZA2023/01273A priority patent/ZA202301273B/en
Publication of WO2023023883A1 publication Critical patent/WO2023023883A1/zh

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    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • C02F1/02—Treatment of water, waste water, or sewage by heating
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    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/05—Nuclear magnetic resonance [NMR]
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    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
    • C07C2602/28—Hydrogenated naphthalenes

Definitions

  • the invention relates to the technical field of organic synthesis, in particular to a preparation method of 3,3',4,4'-dicyclohexyl tetracarboxylic acid and a treatment method of acidic waste water.
  • the glass transition temperature and pyrolysis onset temperature of polyimide obtained by 1,2,4,5-cyclohexyl tetracarboxylic dianhydride are higher than those obtained by aliphatic tetracarboxylic dianhydride, but it is very crisp.
  • the polyimide prepared by 3,3',4,4'-dicyclohexyltetracarboxylic acid has the advantages of excellent heat resistance, mechanical properties, flexibility, excellent solubility, etc. Therefore, for 3,3' ,4,4'-Dicyclohexyltetracarboxylic acid is in great demand.
  • 3,3',4,4'-dicyclohexyltetracarboxylic acid is based on 3,3',4,4'-biphenyl dianhydride as raw material, under the condition of catalyst palladium carbon, hydrogenation reduction It is prepared, but there are many by-products, including 3,3',4,4'-biphenyl dicarboxylic acid, 3,3',4,4'-biphenyl dicarboxylate, etc.; seriously affecting 3,3
  • the purity of ',4,4'-dicyclohexyltetracarboxylic acid makes the purity of 3,3',4,4'-dicyclohexyltetracarboxylic acid ⁇ 98.5%, which seriously restricts the industrialization of this product.
  • the object of the present invention is to provide a preparation method of 3,3',4,4'-dicyclohexyltetracarboxylic acid and a treatment method of acidic wastewater.
  • the 3',4,4'-dicyclohexyl tetracarboxylic acid prepared by the preparation method provided by the invention has high purity.
  • the invention provides a method for preparing 3,3',4,4'-dicyclohexyl tetracarboxylic acid, comprising the following steps:
  • the esterification reaction system is mixed with the ruthenium-rhodium mixed catalyst, and a hydrogenation reaction is carried out in an atmosphere of hydrogen to obtain a hydrogenation reaction system;
  • Described ruthenium-rhodium mixed catalyst is the mixed catalyst of ruthenium-containing catalyst and rhodium-containing catalyst; In the described mixed catalyst, the mass ratio of ruthenium-containing catalyst and rhodium-containing catalyst is 1:6;
  • the ruthenium-containing catalyst is a ruthenium-carbon catalyst, and the mass percentage of ruthenium in the ruthenium-carbon catalyst is 5%;
  • the rhodium-containing catalyst is a rhodium-carbon catalyst, and the mass percentage of rhodium in the rhodium-carbon catalyst is 3%.
  • the purity of the 3,3',4,4'-biphenyltetracarboxylic acid is ⁇ 99.8%.
  • the alcohol compound includes monohydric alcohol and/or dihydric alcohol; the water content of the alcohol compound is ⁇ 2%.
  • the monohydric alcohol includes one or more of methanol, ethanol and isopropanol.
  • the diol comprises 1,3-propanediol.
  • the temperature of the esterification reaction is 80-100° C.
  • the pH value is 0.5-1.0
  • the time is 3-6 hours.
  • the mass ratio of the 3,3',4,4'-biphenyltetracarboxylic acid to the ruthenium-rhodium mixed catalyst is 1:(0.02-0.05).
  • the temperature of the hydrogenation reaction is 80-90° C.
  • the pressure is 0.2-0.5 MPa.
  • the hydrolysis reaction comprises:
  • the obtained hydrogenation reaction feed liquid is subjected to solid-liquid separation to obtain a solid catalyst and a hydrogenation reaction system;
  • the temperature of the first hydrolysis is 80-90° C., and the time is 1-3 hours.
  • the second hydrolysis after the second hydrolysis, it also includes solid-liquid separation of the obtained second hydrolysis feed liquid to obtain the first acidic wastewater and crude products;
  • washing reagent includes water
  • the washing also yields a second acidic waste water.
  • the present invention also provides a kind of treatment method of acid waste water, comprises the following steps:
  • the complex reaction system is mixed with polyvinyl alcohol, and a precipitation reaction is carried out to obtain purified acidic water;
  • the acidic wastewater includes the first acidic wastewater and/or the second acidic wastewater obtained by the preparation method described in the above technical solution.
  • the mass ratio of iron to aluminum in the aluminum-iron mixed powder is 1:(1-3).
  • the mass ratio of the acidic wastewater to the mixed powder of aluminum and iron is 1: (0.001-0.02).
  • the time for the complexation reaction is 0.5-2 hours.
  • the mass ratio of the acidic waste water to polyvinyl alcohol is 1:(0.001-0.02).
  • the pH value of the precipitation reaction is 6-7, and the time of the precipitation reaction is 0.5-2 hours.
  • the purified acidic waste water is distilled to obtain distillate and salt solids.
  • the invention provides a preparation method of 3,3',4,4'-dicyclohexyl tetracarboxylic acid, comprising the following steps: mixing 3,3',4,4'-biphenyl tetracarboxylic acid and an alcohol compound, carrying out Esterification reaction to obtain an esterification reaction system; mixing the esterification reaction system with a ruthenium-rhodium mixed catalyst, performing a hydrogenation reaction in an atmosphere of hydrogen to obtain a hydrogenation reaction system; performing a hydrolysis reaction on the hydrogenation reaction system , to obtain the 3,3',4,4'-dicyclohexyl tetracarboxylic acid;
  • the ruthenium-rhodium mixed catalyst is a mixed catalyst containing ruthenium catalyst and rhodium-containing catalyst; the mixed catalyst contains ruthenium catalyst and rhodium-containing catalyst
  • the mass ratio of the ruthenium-containing catalyst is 1:6; the ruthenium-containing catalyst includes a ruthenium
  • the preparation method provided by the invention uses a ruthenium-rhodium mixed catalyst to catalyze the hydrogenation reduction reaction, which improves the selectivity of the reaction, reduces the generation of isomers, thereby reduces the generation of by-products, and improves the 3,3',4, The purity of 4'-dicyclohexyltetracarboxylic acid.
  • the data in the examples show that: 3,3',4,4'-dicyclohexyltetracarboxylic acid is prepared by using the method provided by the present invention, and the purity is ⁇ 99.62%.
  • the use of the above-mentioned mixed catalyst containing ruthenium catalyst and rhodium-containing catalyst makes the hydrogenation reaction condition milder, and can be carried out at a temperature of 80-90° C. and a pressure of 0.2-0.5 MPa.
  • the present invention uses 3,3',4,4'-dicyclohexyl tetracarboxylic acid with a purity ⁇ 99.8% as a raw material, which also reduces the generation of isomers and further improves the final 3,3',4,4
  • the purity of '-dicyclohexyl tetracarboxylic acid is such that the purity of 3,3',4,4'-dicyclohexyl tetracarboxylic acid is 99.94-99.96%.
  • the present invention also provides a treatment method for the acidic wastewater obtained by the preparation method described in the above technical scheme, the treatment method provided by the invention can reclaim sodium chloride from the acidic wastewater, and the TOC content in the sodium chloride is low; and the method The operation is simple, and at the same time, the COD value in the acid waste water is greatly reduced, reaching the standard of the fourth type of surface water, thereby greatly improving the energy saving and environmental protection performance of the preparation method.
  • Fig. 1 is the nuclear magnetic spectrum of embodiment 1 gained 3,3',4,4'-dicyclohexyltetracarboxylic acid;
  • Fig. 2 is the nuclear magnetic spectrum of embodiment 2 gained 3,3',4,4'-dicyclohexyltetracarboxylic acid;
  • Fig. 3 is the nuclear magnetic spectrum of embodiment 3 gained 3,3',4,4'-dicyclohexyltetracarboxylic acid;
  • Figure 4 is the NMR spectrum of 3,3',4,4'-dicyclohexyltetracarboxylic acid obtained in Comparative Example 1.
  • the invention provides a method for preparing 3,3',4,4'-dicyclohexyl tetracarboxylic acid, comprising the following steps:
  • the esterification reaction system is mixed with the ruthenium-rhodium mixed catalyst, and a hydrogenation reaction is carried out under a hydrogen atmosphere to obtain a hydrogenation reaction system;
  • the hydrogenation reaction system is hydrolyzed to obtain the 3,3',4,4'-dicyclohexyl tetracarboxylic acid.
  • the raw materials used are all preferably commercially available products.
  • the invention mixes 3,3',4,4'-biphenyltetracarboxylic acid and an alcohol compound for esterification reaction to obtain an esterification reaction system.
  • the purity of the 3,3',4,4'-biphenyltetracarboxylic acid is preferably ⁇ 98.5%, more preferably 98.5-99.8%, and more preferably 99.8%.
  • the 3,3',4,4'-biphenyltetracarboxylic acid is preferably purchased from Hebei Haili Perfume Co., Ltd.
  • the present invention uses 3,3',4,4'-biphenyltetracarboxylic acid with a purity ⁇ 98.5%, which improves the purity of 3,3',4,4'-dicyclohexyltetracarboxylic acid; further, when 3,3 The purity of ',4,4'-biphenyltetracarboxylic acid was 99.8%, and the purity of the obtained 3,3',4,4'-dicyclohexyltetracarboxylic acid was further improved.
  • the alcohol compound preferably includes monohydric alcohol and/or dihydric alcohol; the monohydric alcohol preferably includes one or more of methanol, ethanol and isopropanol; the dihydric alcohol preferably includes 1,3 - Propylene glycol; the water content of said alcohol compound is ⁇ 2%.
  • the ratio of the amount of carboxyl groups in the 3,3',4,4'-biphenyltetracarboxylic acid to the amount of hydroxyl groups in the alcohol compound is preferably 1:1.
  • the temperature of the esterification reaction is preferably 80-100°C, more preferably 85-95°C, even more preferably 90°C; the time is preferably 3-6 hours, more preferably 4-5 hours.
  • the pH value of the esterification reaction is preferably 0.5-1.0.
  • the pH value of the esterification reaction is preferably adjusted by an acid solution, and the acid solution preferably includes hydrochloric acid; the present invention does not limit the concentration and amount of the hydrochloric acid, as long as the pH value can be adjusted to 1-2 That's it.
  • the present invention mixes the esterification reaction system with a ruthenium-rhodium mixed catalyst, and performs a hydrogenation reaction under a hydrogen atmosphere to obtain a hydrogenation reaction system.
  • the ruthenium-rhodium mixed catalyst is a mixed catalyst containing ruthenium catalyst and rhodium-containing catalyst; the mass ratio of ruthenium-containing catalyst and rhodium-containing catalyst in the mixed catalyst is 1:6; the ruthenium-containing catalyst is ruthenium A carbon catalyst, the mass percent of ruthenium in the ruthenium-carbon catalyst is 5%; the rhodium-containing catalyst is a rhodium-carbon catalyst, and the mass percent of rhodium in the rhodium-carbon catalyst is 3%.
  • both the ruthenium carbon catalyst and the rhodium carbon catalyst are preferably purchased from Xi'an Kaili New Materials Co., Ltd.
  • the mass ratio of the 3,3',4,4'-biphenyltetracarboxylic acid to the ruthenium-rhodium mixed catalyst is preferably 1:(0.02-0.05).
  • the temperature of the hydrogenation reaction is preferably 80-90° C., more preferably 85° C.; the pressure is preferably 0.2-0.5 MPa, more preferably 0.3-0.4 MPa.
  • the present invention does not specifically limit the time of the hydrogenation reaction, as long as the hydrogenation reaction system no longer absorbs hydrogen.
  • the present invention preferably further includes solid-liquid separation of the obtained hydrogenation reaction feed liquid to obtain a solid catalyst and a hydrogenation reaction system.
  • the method of solid-liquid separation is preferably filtration.
  • the present invention performs a hydrolysis reaction on the hydrogenation reaction system to obtain the 3,3',4,4'-dicyclohexyltetracarboxylic acid.
  • the step of the hydrolysis reaction preferably includes: adjusting the pH value of the hydrogenation reaction system to 9-11 to perform the first hydrolysis to obtain the first hydrolysis system;
  • the present invention adjusts the pH value of the hydrogenation reaction system to 9-11 to perform the first hydrolysis to obtain the first hydrolysis system.
  • the reagent for adjusting the pH value of the hydrogenation reaction system to 9-11 preferably includes caustic soda.
  • the temperature of the first hydrolysis is preferably 80-90° C.
  • the time is preferably 1-3 hours, more preferably 2 hours.
  • the present invention preferably further includes cooling the obtained first hydrolysis feed liquid and then filtering to obtain the first hydrolysis system and alkaline wastewater.
  • the alkaline waste water is preferably refluxed to the esterification reaction stage for mechanical application.
  • the present invention adjusts the pH value of the first hydrolysis system to 1-2, and performs the second hydrolysis.
  • the second hydrolysis preferably includes the following steps: after dissolving the first hydrolysis system with water, adjusting the pH value to 1-2.
  • the ratio of the water to the first hydrolysis system is not specifically limited, as long as the first hydrolysis system can be completely solvent.
  • the reagent for adjusting the pH value to 1-2 is preferably hydrochloric acid.
  • the present invention does not specifically limit the concentration and addition amount of the hydrochloric acid, as long as the pH value can be adjusted to 1-2.
  • the present invention preferably further includes solid-liquid separation of the obtained second hydrolysis feed liquid to obtain the first acidic wastewater and crude products.
  • the present invention preferably further includes purifying the crude product, and the purification process preferably includes the following steps: washing and drying the crude product to obtain the 3,3', 4,4' - dicyclohexyltetracarboxylic acid.
  • the washing reagent is preferably water, and the water is preferably deionized water.
  • the present invention does not specifically limit the washing reagent, as long as it can be cleaned.
  • the present invention does not specifically limit the drying parameters, as long as the product can be dried to a constant weight.
  • the second acidic wastewater is preferably obtained by washing the crude product.
  • the present invention also provides a treatment method for acidic wastewater, comprising:
  • the complexation reaction system is adjusted and mixed with polyvinyl alcohol to carry out precipitation reaction to obtain purified acidic water.
  • the invention mixes acid waste water and aluminum-iron mixed powder to carry out complexation reaction to obtain complexation reaction system.
  • the mass ratio of iron to aluminum in the aluminum-iron mixed powder is preferably 1:(1-3), more preferably 1:2.
  • the acidic wastewater is the first acidic wastewater and/or the second acidic wastewater obtained by the preparation method described in the above technical solution.
  • the mass ratio of the acid waste water to the aluminum-iron mixed powder is preferably 1:(0.001-0.02).
  • the temperature of the complexation reaction is preferably room temperature, that is, neither additional heating nor cooling is required; the time of the complexation reaction is preferably 0.5-2 hours.
  • the complexation reaction can remove organic matter in acidic wastewater.
  • the present invention mixes the complexation reaction system with polyvinyl alcohol for precipitation reaction to obtain purified acidic water.
  • the polyvinyl alcohol is preferably polyvinyl alcohol 2499.
  • the mass ratio of the acidic wastewater to polyvinyl alcohol is preferably 1:(0.001-0.02).
  • the pH value of the precipitation reaction is preferably 6-7, and the reagent for adjusting the pH value of the precipitation reaction is preferably sodium hydroxide.
  • the time of the precipitation reaction is preferably 0.5-2 hours.
  • the precipitation reaction is preferably carried out under stirring conditions.
  • the precipitation reaction After the precipitation reaction, it also includes solid-liquid separation of the obtained precipitation reaction feed liquid to obtain the purified acid wastewater.
  • the method of solid-liquid separation is preferably filtration.
  • COD in the described purified acid waste water, COD is 50 ⁇ 150mg/L.
  • the precipitation reaction can remove organic matter in acidic wastewater.
  • the present invention preferably further includes distilling the purified acidic wastewater to obtain distillate and salt solids.
  • the operation of the distillation is specifically limited, and the distillation parameters well known to those skilled in the art can be used.
  • the salt solid is preferably sodium chloride; TOC in the sodium chloride is 10-50 mg/L.
  • the distilled liquid obtained in the present invention reaches the standard of four types of surface water, thereby greatly improving the energy saving and environmental protection performance of the preparation method.
  • Figure 1 is the NMR spectrum of the obtained 3,3',4,4'-dicyclohexyltetracarboxylic acid. It can be seen from Figure 1 that the structure of the substance is correct, and the impurity content is basically free.
  • the purified acidic waste water was distilled, 85% of the solution was distilled and filtered to obtain solid sodium chloride 25.17g, TOC in sodium chloride: 45.7mg/kg; COD in distilled water was 26.4mg/L; COD in distilled water reached The four types of surface water standards.
  • Figure 2 is the NMR spectrum of the obtained 3,3',4,4'-dicyclohexyltetracarboxylic acid. It can be seen from Figure 2 that the structure of the substance is correct, and the impurity content is basically free.
  • the purified acidic waste water is distilled, 85% of the solution is distilled and filtered to obtain solid sodium chloride 23.1g, TOC in sodium chloride: 35.7mg/kg; COD in distilled water is 21.4mg/L; COD in distilled water reaches The four types of surface water standards.
  • Figure 3 is the NMR spectrum of the obtained 3,3',4,4'-dicyclohexyltetracarboxylic acid. It can be seen from Figure 3 that the structure of the substance is correct, but the impurity content is relatively high.
  • the purified acidic waste water is distilled, 85% of the solution is distilled and filtered to obtain solid sodium chloride 23.4g, TOC in sodium chloride: 42.8mg/kg; COD in distilled water is 22.4mg/L; COD in distilled water reaches The four types of surface water standards.
  • Figure 4 is the NMR spectrum of the obtained 3,3',4,4'-dicyclohexyltetracarboxylic acid, and it can be seen from Figure 4 that the structure of the substance is correct.
  • the purified acidic waste water was distilled, 85% of the solution was distilled off, and then cooled and filtered to obtain 22.9 g of solid sodium chloride.
  • TOC in sodium chloride 67.9 mg/kg; COD in distilled water was 143.2 mg/L.

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Abstract

本发明属于有机合成技术领域，提供了一种3,3',4,4'-二环己基四甲酸的制备方法、酸性废水的处理方法。本发明提供的制备方法，以钌铑混合催化剂催化加氢还原反应，提高了反应的选择性，减少了异构体的产生，从而减少了副产物的生成，提高了3,3',4,4'-二环己基四甲酸的纯度。实施例的数据表明：利用本发明提供的方法制备3,3',4,4'-二环己基四甲酸，纯度≥99.62％。

Description

一种3，3’，4，4’-二环己基四甲酸的制备方法、酸性废水的处理方法 技术领域
本发明涉及有机合成技术领域，尤其涉及一种3,3',4,4'-二环己基四甲酸的制备方法、酸性废水的处理方法。
背景技术
1,2,4,5-环己基四甲酸二酐所得到的聚酰亚胺的玻璃化温度和热解开始温度比用脂肪族四甲酸二酐所得到的聚酰亚胺高些，但是很脆。3,3',4,4'-二环己基四甲酸制备的聚酰亚胺有极好的抗热性、机械性能、柔韧性、极好的溶解性等优点，因此，对3,3',4,4'-二环己基四甲酸的需求量很大。
目前，3,3',4,4'-二环己基四甲酸的制备是以3,3',4,4'-联苯二酐为原料，在催化剂钯碳的条件下，经加氢还原制备得到，但是副产物较多，副产物包括3,3',4,4'-联苯二甲酸、3,3',4,4'-联苯二甲酸盐等；严重影响3,3',4,4'-二环己基四甲酸的纯度，使得3,3',4,4'-二环己基四甲酸的纯度<98.5％，严重制约该产品的工业化。
发明内容
有鉴于此，本发明的目的在于提供一种3,3',4,4'-二环己基四甲酸的制备方法、酸性废水的处理方法。本发明提供的制备方法制备的,3',4,4'-二环己基四甲酸具有高纯度。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种3,3',4,4'-二环己基四甲酸的制备方法，包括以下步骤：
将3,3',4,4'-联苯四甲酸和醇化合物混合，进行酯化反应，得到酯化反应体系；
将所述酯化反应体系和钌铑混合催化剂混合，在氢气的氛围中进行加氢反应，得到加氢反应体系；
对所述加氢反应体系进行水解反应，得到所述3,3',4,4'-二环己基四甲酸；
所述钌铑混合催化剂为含钌催化剂和含铑催化剂的混合催化剂；所述 混合催化剂中含钌催化剂和含铑催化剂的质量比为1：6；
所述含钌催化剂为钌碳催化剂，所述钌碳催化剂中钌的质量百分含量为5％；
所述含铑催化剂为铑碳催化剂，所述铑碳催化剂中铑的质量百分含量为3％。
优选地，所述3,3',4,4'-联苯四甲酸的纯度≥99.8％。
优选地，所述醇化合物包括一元醇和/或二元醇；所述醇化合物的含水量≤2％。
优选地，所述一元醇包括甲醇、乙醇和异丙醇中的一种或多种。
优选地，所述二元醇包括1,3-丙二醇。
优选地，所述酯化反应的温度为80～100℃，pH值为0.5～1.0，时间为3～6h。
优选地，所述3,3',4,4'-联苯四甲酸和钌铑混合催化剂的质量比为1：(0.02～0.05)。
优选地，所述加氢反应的温度为80～90℃，压力为0.2～0.5MPa。
优选地，所述水解反应包括：
所述加氢反应后，将所得加氢反应料液进行固液分离，得到固体催化剂和加氢反应体系；
调节所述加氢反应体系的pH值为9～11进行第一水解，得到第一水解体系；
调节所述第一水解体系的pH值为1～2，进行第二水解。
优选地，所述第一水解的温度为80～90℃，时间为1～3h。
优选地，所述第二水解后，还包括将所得第二水解料液进行固液分离，得到第一酸性废水和粗产品；
将所述粗产品进行洗涤和干燥，得到3,3',4,4'-二环己基四甲酸纯品；所述洗涤的试剂包括水；
所述洗涤还得到第二酸性废水。
本发明还提供了一种酸性废水的处理方法，包括以下步骤：
将酸性废水与铝铁混合粉体混合，进行络合反应，得到络合反应体系；
将所述络合反应体系与聚乙烯醇混合，进行沉淀反应，得到净化酸性 水；
所述酸性废水包括上述技术方案所述的制备方法得到的第一酸性废水和/或第二酸性废水。
优选地，所述铝铁混合粉体中铁和铝的质量比为1：(1～3)。
优选地，所述酸性废水和铝铁混合粉体的质量比为1：(0.001～0.02)。
优选地，所述络合反应的时间为0.5～2h。
优选地，所述酸性废水和聚乙烯醇的质量比为1：(0.001～0.02)。
优选地，所述沉淀反应的pH值为6～7，所述沉淀反应的时间为0.5～2h。
优选地，所述沉淀反应后，还包括将所得沉淀反应料液进行固液分离，得到所述净化酸性废水；
所述净化酸性废水进行蒸馏，得到馏出液和盐类固体。
本发明提供了一种3,3',4,4'-二环己基四甲酸的制备方法，包括以下步骤：将3,3',4,4'-联苯四甲酸和醇化合物混合，进行酯化反应，得到酯化反应体系；将所述酯化反应体系和钌铑混合催化剂混合，在氢气的氛围中进行加氢反应，得到加氢反应体系；对所述加氢反应体系进行水解反应，得到所述3,3',4,4'-二环己基四甲酸；所述钌铑混合催化剂为含钌催化剂和含铑催化剂的混合催化剂；所述混合催化剂中含钌催化剂和含铑催化剂的质量比为1：6；所述含钌催化剂包括钌碳催化剂，所述钌碳催化剂中钌的质量百分含量为5％；所述含铑催化剂包括铑碳催化剂，所述铑碳催化剂中铑的质量百分含量为3％。本发明提供的制备方法，以钌铑混合催化剂催化加氢还原反应，提高了反应的选择性，减少了异构体的产生，从而减少了副产物的生成，提高了3,3',4,4'-二环己基四甲酸的纯度。实施例的数据表明：利用本发明提供的方法制备3,3',4,4'-二环己基四甲酸，纯度≥99.62％。
同时，上述含钌催化剂和含铑催化剂的混合催化剂的使用，使加氢反应反应条件变得温和，在温度为80～90℃，压力为0.2～0.5MPa的条件下即可进行。
进一步地，本发明使用纯度≥99.8％的3,3',4,4'-二环己基四甲酸为原料，也减少了异构体的产生，进一步提高了最终3,3',4,4'-二环己基四甲酸 的纯度，使3,3',4,4'-二环己基四甲酸的纯度为99.94～99.96％。
本发明还提供了一种上述技术方案所述的制备方法得到的酸性废水的处理方法，本发明提供的处理方法能够从酸性废水中回收得到氯化钠，氯化钠中TOC含量低；且方法操作简单，同时大大降低了酸性废水中COD值，达到地表四类水标准，从而大大提高了制备方法的节能环保性。
附图说明
图1为实施例1所得3,3',4,4'-二环己基四甲酸的核磁谱图；
图2为实施例2所得3,3',4,4'-二环己基四甲酸的核磁谱图；
图3为实施例3所得3,3',4,4'-二环己基四甲酸的核磁谱图；
图4为对比例1所得3,3',4,4'-二环己基四甲酸的核磁谱图。
具体实施方式
本发明提供了一种3,3',4,4'-二环己基四甲酸的制备方法，包括以下步骤：
将3,3',4,4'-联苯四甲酸和醇化合物混合，进行酯化反应，得到酯化反应体系；
将所述酯化反应体系和钌铑混合催化剂混合，在氢气的氛围下进行加氢反应，得到加氢反应体系；
对所述加氢反应体系进行水解反应，得到所述3,3',4,4'-二环己基四甲酸。
在本发明中，如无特殊说明，所用原料均优选为市售产品。
本发明将3,3',4,4'-联苯四甲酸和醇化合物混合，进行酯化反应，得到酯化反应体系。
在本发明中，所述3,3',4,4'-联苯四甲酸的纯度优选≥98.5％，进一步优选为98.5～99.8％，更优选99.8％。在本发明中，所述3,3',4,4'-联苯四甲酸优选购自河北海力香料股份有限公司。本发明使用纯度≥98.5％的3,3',4,4'-联苯四甲酸，提高了3,3',4,4'-二环己基四甲酸的纯度；进一步地，当3,3',4,4'-联苯四甲酸的纯度为99.8是，所得3,3',4,4'-二环己基四甲酸的纯度也进一步提高。
在本发明中，所述醇化合物优选包括一元醇和/或二元醇；所述一元醇优选包括甲醇、乙醇和异丙醇中的一种或多种；所述二元醇优选包括 1,3-丙二醇；所述醇化合物的含水量≤2％。
在本发明中，所述3,3',4,4'-联苯四甲酸中的羧基的物质的量和醇化合物中羟基的物质的量的比优选为1：1。
在本发明中，所述酯化反应的温度优选为80～100℃，进一步优选为85～95℃，进一步优选为90℃；时间优选为3～6h，进一步优选为4～5h。在本发明中，所述酯化反应的pH值优选为0.5～1.0。在本发明中，所述酯化反应的pH值优选采用酸液调整，所述酸液优选包括盐酸；本发明对所述盐酸的浓度和用量不做限定，只要能够使pH值为1～2即可。
得到酯化反应体系后，本发明将所述酯化反应体系和钌铑混合催化剂混合，在氢气的氛围下进行加氢反应，得到加氢反应体系。
在本发明中，所述钌铑混合催化剂为含钌催化剂和含铑催化剂的混合催化剂；所述混合催化剂中含钌催化剂和含铑催化剂的质量比为1：6；所述含钌催化剂为钌碳催化剂，所述钌碳催化剂中钌的质量百分含量为5％；所述含铑催化剂为铑碳催化剂，所述铑碳催化剂中铑的质量百分含量为3％。在本发明的具体实施例中，所述钌碳催化剂和铑碳催化剂均优选购自西安凯立新材料股份有限公司。
在本发明中，所述3,3',4,4'-联苯四甲酸和钌铑混合催化剂的质量比优选为1：(0.02～0.05)。
在本发明中，所述加氢反应的温度优选为80～90℃，进一步优选为85℃；压力优选为0.2～0.5MPa，进一步优选为0.3～0.4MPa。本发明对所述加氢反应的时间不做具体限定，至加氢反应体系不再吸氢即可。
所述加氢反应后，本发明优选还包括将所得加氢反应料液进行固液分离，得到固体催化剂和加氢反应体系。在本发明中，所述固液分离的方式优选为过滤。
得到加氢反应体系后，本发明对所述加氢反应体系进行水解反应，得到所述3,3',4,4'-二环己基四甲酸。
在本发明中，所述水解反应的步骤优选包括：调节所述加氢反应体系的pH值为9～11进行第一水解，得到第一水解体系；
调节所述第一水解体系的pH值为1～2，进行第二水解。
本发明调节所述加氢反应体系的pH值为9～11进行第一水解，得到 第一水解体系。
在本发明中，所述调节加氢反应体系的pH值为9～11的试剂优选包括片碱。
在本发明中，所述第一水解的温度优选为80～90℃，时间优选为1～3h，进一步优选为2h。
所述第一水解后，本发明优选还包括将所得第一水解料液降温后过滤，得到第一水解体系和碱性废水。在本发明中，所述碱性废水优选回流至酯化反应阶段进行套用。
得到第一水解体系后，本发明调节所述第一水解体系的pH值为1～2，进行第二水解。
在本发明中，所述第二水解的优选包括以下步骤：将所述第一水解体系用水溶解后，调节pH值为1～2。在本发明中，所述水和第一水解体系的用量比不做具体限定，只要能够将第一水解体系完全溶剂即可。
在本发明中，调节pH值为1～2的试剂优选为盐酸。本发明对所述盐酸的浓度和加入量不做具体限定，只要能够调节pH值为1～2即可。
所述第二水解后，本发明优选还包括将所得第二水解料液进行固液分离，得到第一酸性废水和粗产品。
得到粗产品后，本发明优选还包括将所述粗产品进行纯化处理，所述纯化处理优选包括以下步骤：对所述粗产品进行洗涤和干燥，得到所述3,3',4,4'-二环己基四甲酸。
在本发明中，所述洗涤的试剂优选为水，所述水优选为去离子水，本发明对所述洗涤的试剂不做具体限定，只要能够洗涤干净即可。本发明对所述干燥的参数不做具体限定，只要能够将产品干燥至恒重即可。
在本发明中，对所述粗产品进行洗涤优选还得到第二酸性废水。
本发明还提供了一种酸性废水的处理方法，包括：
将酸性废水与铝铁混合粉体混合，进行络合反应，得到络合反应体系；
调节所述络合反应体系与聚乙烯醇混合，进行沉淀反应，得到净化酸性水。
本发明将酸性废水与铝铁混合粉体混合，进行络合反应，得到络合反应体系。
在本发明中，所述铝铁混合粉体中铁和铝的质量比优选为1：(1～3)，进一步优选为1：2。
在本发明中，所述酸性废水为上述技术方案所述的制备方法得到的第一酸性废水和/或第二酸性废水。在本发明中，所述酸性废水和铝铁混合粉体的质量比优选为1：(0.001～0.02)。
在本发明中，所述络合反应的温度优选为室温，即既不需要额外加热也不需要额外降温；所述络合反应的时间优选为0.5～2h。
本发明中，所述络合反应能够除去酸性废水中的有机物。
得到络合反应体系后，本发明将所述络合反应体系与聚乙烯醇混合，进行沉淀反应，得到净化酸性水。
在本发明中，所述聚乙烯醇优选为聚乙烯醇2499。
在本发明中，所述酸性废水和聚乙烯醇的质量比优选为1：(0.001～0.02)。
在本发明中，所述沉淀反应的pH值优选为6～7，调节沉淀反应的pH值的试剂优选为氢氧化钠。在本发明中，所述沉淀反应的时间优选为0.5～2h。在本发明中，所述沉淀反应优选在搅拌的条件下进行。
所述沉淀反应后，还包括将所得沉淀反应料液进行固液分离，得到所述净化酸性废水。
在本发明中，所述固液分离的方式优选为过滤。
在本发明中，所述净化酸性废水中，COD 50～150mg/L。
在本发明中，所述沉淀反应能够除去酸性废水中的有机物。
得到净化酸性废水后，本发明优选还包括将所述净化酸性废水进行蒸馏，得到蒸出液和盐类固体。
本发明对所述蒸馏的操作具体限定，采用本领域技术人员熟知的蒸馏参数即可。
在本发明中，所述蒸出液中：COD 20～120mg/L。
在本发明中，所述盐类固体优选为氯化钠；所述氯化钠中TOC 10～50mg/L。
本发明所得蒸出液达到地表四类水标准，从而大大提高了制备方法的节能环保性。
下面结合实施例对本发明提供的3,3',4,4'-二环己基四甲酸的制备方法、酸性废水处理方法进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
室温下在四口瓶中加入高纯度3,3',4,4'-联苯四甲酸(纯度为99.8％)200g、工业盐酸20g(质量百分含量31.5％)、1,3-丙二醇1200g，升温至85℃保温5h至完全溶解，溶解后降至室温加入至反应釜中，投入混合催化剂(混合催化剂中钌碳催化剂和铑碳催化剂的质量比为1：6；钌碳催化剂中钌的质量百分含量为5％，铑碳催化剂中铑的质量百分含量为3％)湿品3.3g，干基1.48g，关闭投料口进行氮气置换3次，置换完毕泄压至常压后开升温至85℃反应，开始连续通氢，釜内压力控制在0.4MPa，至吸氢结束，过滤回收催化剂套用，第一滤液加入35g片碱于80～90℃保温2h，保温结束降温过滤，第二滤液进行套用，第二固体烘干后加入至450g水中溶解，溶解后加入盐酸调pH至1.5过滤，得到第三滤液和第三固体；所述第三固体使用200g纯水淋洗得到3,3',4,4'-二环己基四甲酸湿品和酸性废水，3,3',4,4'-二环己基四甲酸湿品进行烘干得到产品204.2g，摩尔收率98.52％，纯度99.94％。
图1为所得3,3',4,4'-二环己基四甲酸的核磁谱图，从图1可以看出：该物质结构正确，杂质含量基本没有。
在酸性废水634g加入铁粉2g、铝粉3g进行络合反应0.5h后，加入片碱调pH至7搅拌30min后，加入聚乙烯醇24995g搅拌1h后过滤，得到净化酸性废水和残渣；所述净化酸性废水中：COD 98mg/L；
对所述净化酸性废水进行蒸馏，蒸馏出85％溶液后降温过滤得到固体氯化钠25.17g，氯化钠中TOC：45.7mg/kg；蒸出水中COD为26.4mg/L；蒸出水COD达到地表四类水标准。
实施例2
室温下在四口瓶中加入高纯度3,3',4,4'-联苯四甲酸(纯度为99.8％)200g、工业盐酸25g(质量百分含量31.5％)、1,3-丙二醇1200g，升温至90～100℃保温3.5h至完全溶解，溶解后降至室温加入至反应釜中，投入混合催化剂(混合催化剂中钌碳催化剂和铑碳催化剂的质量比为1：6； 钌碳催化剂中钌的质量百分含量为5％，铑碳催化剂中铑的质量百分含量为3％)湿品3.1g，干基1.48g，关闭投料口进行氮气置换3次，置换完毕泄压至常压后开升温至85℃反应，开始连续通氢，釜内压力控制在0.4MPa，至吸氢结束，过滤回收催化剂套用，第一滤液加入40g片碱于85℃保温2h，保温结束降温过滤，第二滤液进行套用，第二固体烘干后加入至550g水中溶解，溶解后加入盐酸调pH至1～2过滤，得到第三滤液和第三固体；使用100g纯水淋洗第三固体得到产品3,3',4,4'-二环己基四甲酸湿品和酸性废水，3,3',4,4'-二环己基四甲酸湿品进行烘干得到产品205.2g，摩尔收率99.0％，纯度99.96％。
图2为所得3,3',4,4'-二环己基四甲酸的核磁谱图，从图2可以看出：该物质结构正确，杂质含量基本没有。
酸性废水628g加入铁粉4g，铝粉6g进行络合反应0.5h后，加入片碱调pH至7.5搅拌30min后加入聚乙烯醇24997g搅拌1h后过滤，得到净化酸性废水和残渣；所述净化酸性废水中：COD：76mg/L；
对所述净化酸性废水进行蒸馏，蒸馏出85％溶液后降温过滤得到固体氯化钠23.1g，氯化钠中TOC：35.7mg/kg；蒸出水中COD为21.4mg/L；蒸出水COD达到地表四类水标准。
实施例3
室温下在四口瓶中加入高纯度3,3',4,4'-联苯四甲酸(纯度为98.5％)200g、工业盐酸25g(质量百分含量31.5％)、1,3-丙二醇1200g，升温至90～100℃保温3.5h至完全溶解，溶解后降至室温加入至反应釜中，投入混合催化剂(混合催化剂中钌碳催化剂和铑碳催化剂的质量比为1：6；所述钌碳催化剂中钌的质量百分含量为5％，铑碳催化剂中铑的质量百分含量为3％)湿品3.1g，干基1.48g，关闭投料口进行氮气置换3次，置换完毕泄压至常压后开升温至85℃反应，开始连续通氢，釜内压力控制在0.4MPa，至吸氢结束，过滤回收催化剂套用，第一滤液加入40g片碱于85℃保温2h，保温结束降温过滤，第二滤液进行套用，第二固体烘干后加入至550g水中溶解，溶解后加入盐酸调pH至1～2过滤，得到第三滤液和第三固体；使用100g纯水淋洗第三固体得到产品3,3',4,4'-二环己基四甲酸湿品和酸性废水，3,3',4,4'-二环己基四甲酸湿品进行烘干得到产 品198.2g，摩尔收率为97.0％，纯度99.62％。
图3为所得3,3',4,4'-二环己基四甲酸的核磁谱图，从图3可以看出：该物质结构正确，但杂质含量较高。
酸性废水634g加入铁粉4g，铝粉6g进行络合反应0.5h后，加入片碱调pH至7.5搅拌30min后加入聚乙烯醇24997g搅拌1h后过滤，得到净化酸性废水和残渣；所述净化酸性废水中：COD：186mg/L；
对所述净化酸性废水进行蒸馏，蒸馏出85％溶液后降温过滤得到固体氯化钠23.4g，氯化钠中TOC：42.8mg/kg；蒸出水中COD为22.4mg/L；蒸出水COD达到地表四类水标准。
对比例1
室温下在四口瓶中加入高纯度3,3',4,4'-联苯四甲酸(纯度为98.5％)200g、工业盐酸25g(质量百分含量31.5％)、1,3-丙二醇1200g，升温至90～100℃保温3.5h至完全溶解，溶解后降至室温加入至反应釜中，投入混合催化剂(混合催化剂中钌碳催化剂和铑碳催化剂的质量比为1：6；所述钌碳催化剂中钌的质量百分含量为5％，铑碳催化剂中铑的质量百分含量为3％)湿品3.1g，干基1.48g，关闭投料口进行氮气置换3次，置换完毕泄压至常压后开升温至95℃反应，开始连续通氢，釜内压力控制在0.4MPa，至吸氢结束，过滤回收催化剂套用，第一滤液加入40g片碱于85℃保温2h，保温结束降温过滤，第二滤液进行套用，第二固体烘干后加入至550g水中溶解，溶解后加入盐酸调pH至1～2过滤，得到第三滤液和第三固体；使用100g纯水淋洗第三固体得到产品3,3',4,4'-二环己基四甲酸湿品和酸性废水，3,3',4,4'-二环己基四甲酸湿品进行烘干得到产品182g，摩尔收率87.81％，纯度98.3％。
图4为所得3,3',4,4'-二环己基四甲酸的核磁谱图，从图4可以看出：该物质结构正确。
酸性废水628g加入铁粉4g，铝粉6g进行络合反应0.5h后，加入片碱调pH至7.5搅拌30min后加入聚乙烯醇24997g搅拌1h后过滤，得到净化酸性废水和残渣；所述净化酸性废水中：COD：352mg/L；
对所述净化酸性废水进行蒸馏，蒸馏出85％溶液后降温过滤得到固体氯化钠22.9g，氯化钠中TOC：67.9mg/kg；蒸出水中COD为143.2mg/L。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (18)

  1. 一种3,3',4,4'-二环己基四甲酸的制备方法，其特征在于，包括以下步骤：
    将3,3',4,4'-联苯四甲酸和醇化合物混合，进行酯化反应，得到酯化反应体系；
    将所述酯化反应体系和钌铑混合催化剂混合，在氢气的氛围中进行加氢反应，得到加氢反应体系；
    对所述加氢反应体系进行水解反应，得到所述3,3',4,4'-二环己基四甲酸；
    所述钌铑混合催化剂为含钌催化剂和含铑催化剂的混合催化剂；所述混合催化剂中含钌催化剂和含铑催化剂的质量比为1：6；
    所述含钌催化剂为钌碳催化剂，所述钌碳催化剂中钌的质量百分含量为5％；
    所述含铑催化剂为铑碳催化剂，所述铑碳催化剂中铑的质量百分含量为3％。
  2. 根据权利要求1所述的制备方法，其特征在于，所述3,3',4,4'-联苯四甲酸的纯度≥99.8％。
  3. 根据权利要求1所述的制备方法，其特征在于，所述醇化合物包括一元醇和/或二元醇；所述醇化合物的含水量≤2％。
  4. 根据权利要求3所述的制备方法，其特征在于，所述一元醇包括甲醇、乙醇和异丙醇中的一种或多种。
  5. 根据权利要求3所述的制备方法，其特征在于，所述二元醇包括1,3-丙二醇。
  6. 根据权利要求1所述的制备方法，其特征在于，所述酯化反应的温度为80～100℃，pH值为0.5～1.0，时间为3～6h。
  7. 根据权利要求1所述的制备方法，其特征在于，所述3,3',4,4'-联苯四甲酸和钌铑混合催化剂的质量比为1：(0.02～0.05)。
  8. 根据权利要求1或7所述的制备方法，其特征在于，所述加氢反应的温度为80～90℃，压力为0.2～0.5MPa。
  9. 根据权利要求1所述的制备方法，其特征在于，所述水解反应包 括：
    所述加氢反应后，将所得加氢反应料液进行固液分离，得到固体催化剂和加氢反应体系；
    调节所述加氢反应体系的pH值为9～11进行第一水解，得到第一水解体系；
    调节所述第一水解体系的pH值为1～2，进行第二水解。
  10. 根据权利要求9所述的制备方法，其特征在于，所述第一水解的温度为80～90℃，时间为1～3h。
  11. 根据权利要求9所述的制备方法，其特征在于，所述第二水解后，还包括将所得第二水解料液进行固液分离，得到第一酸性废水和粗产品；
    将所述粗产品进行洗涤和干燥，得到3,3',4,4'-二环己基四甲酸纯品；所述洗涤的试剂包括水；
    所述洗涤还得到第二酸性废水。
  12. 一种酸性废水的处理方法，其特征在于，包括以下步骤：
    将酸性废水与铝铁混合粉体混合，进行络合反应，得到络合反应体系；
    将所述络合反应体系与聚乙烯醇混合，进行沉淀反应，得到净化酸性水；
    所述酸性废水包括权利要求11所述的制备方法得到的第一酸性废水和/或第二酸性废水。
  13. 根据权利要求12所述的处理方法，其特征在于，所述铝铁混合粉体中铁和铝的质量比为1：(1～3)。
  14. 根据权利要求12所述的处理方法，其特征在于，所述酸性废水和铝铁混合粉体的质量比为1：(0.001～0.02)。
  15. 根据权利要求12或13或14所述的处理方法，其特征在于，所述络合反应的时间为0.5～2h。
  16. 根据权利要求12所述的处理方法，其特征在于，所述酸性废水和聚乙烯醇的质量比为1：(0.001～0.02)。
  17. 根据权利要求12或16所述的处理方法，其特征在于，所述沉淀反应的pH值为6～7，所述沉淀反应的时间为0.5～2h。
  18. 根据权利要求12所述的处理方法，其特征在于，所述沉淀反应 后，还包括将所得沉淀反应料液进行固液分离，得到所述净化酸性废水；
    所述净化酸性废水进行蒸馏，得到馏出液和盐类固体。
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