CN116003362A - A treatment method for acetic anhydride dehydration waste liquid produced in a 3,3',4,4'-diphenyl ether dianhydride dehydration process - Google Patents
A treatment method for acetic anhydride dehydration waste liquid produced in a 3,3',4,4'-diphenyl ether dianhydride dehydration process Download PDFInfo
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 139
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 56
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 230000018044 dehydration Effects 0.000 title claims abstract description 49
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- -1 diphenyl ether tetracarboxylic acid Chemical class 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 16
- RZKIRKYGCBPVJA-UHFFFAOYSA-N 9H-fluorene-1,2,3,4-tetracarboxylic acid Chemical compound C1(=C(C(=C(C=2C3=CC=CC=C3CC12)C(=O)O)C(=O)O)C(=O)O)C(=O)O RZKIRKYGCBPVJA-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 150000007529 inorganic bases Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 44
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 41
- 235000017281 sodium acetate Nutrition 0.000 abstract description 32
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 abstract description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract description 16
- 239000001632 sodium acetate Substances 0.000 abstract description 16
- 229940087562 sodium acetate trihydrate Drugs 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- 239000001301 oxygen Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 4
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及资源回收技术领域，提供了一种3,3’,4,4’‑二苯醚二酐脱水工艺产生的醋酐脱水废液的处理方法。本发明通过第一保温反应和第一降温结晶，能够将醋酐脱水废液中的9‑氧(杂)芴二酐和3,3’,4,4’‑二苯醚二酐分别转化为9‑氧(杂)芴四甲酸和联苯醚四甲酸实现回收；同时，9‑氧(杂)芴四甲酸和联苯醚四甲酸易于再转化为9‑氧(杂)芴二酐和3,3’,4,4’‑二苯醚二酐，可用于3,3’,4,4’‑二苯醚二酐生产，且处理能耗低，具有较高的经济效益和环境效益，推广价值极高。在第一降温结晶得到的滤液中加入无机碱水溶液，将醋酐及醋酸以三水乙酸钠和乙酸钠水溶液形式进行回收，乙酸钠可用于生化提供碳源。The invention relates to the technical field of resource recovery, and provides a method for treating acetic anhydride dehydration waste liquid produced in a 3,3',4,4'-diphenyl ether dianhydride dehydration process. The present invention can convert 9-oxygen (hetero)fluorene dianhydride and 3,3',4,4'-diphenyl ether dianhydride in acetic anhydride dehydration waste liquid into 9-oxygen (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid realize recovery; Meanwhile, 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid are easy to be converted into 9-oxo (hetero) fluorene dianhydride and 3 ,3',4,4'-diphenyl ether dianhydride can be used in the production of 3,3',4,4'-diphenyl ether dianhydride, and the processing energy consumption is low, which has high economic and environmental benefits. The promotion value is extremely high. An aqueous inorganic alkali solution is added to the filtrate obtained by the first cooling crystallization, and the acetic anhydride and acetic acid are recovered in the form of sodium acetate trihydrate and an aqueous solution of sodium acetate. The sodium acetate can be used to provide carbon sources for biochemistry.
Description
技术领域technical field
本发明涉及资源回收技术领域，尤其涉及一种3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液的处理方法。The invention relates to the technical field of resource recovery, in particular to a method for treating acetic anhydride dehydration waste liquid produced in a 3,3',4,4'-diphenyl ether dianhydride dehydration process.
背景技术Background technique
3,3’,4,4’-二苯醚二酐是用于制造聚酰亚胺高分子材料(PI)的重要单体。聚酰亚胺高分子材料在航空航天、电机绕包、汽车工业、机械工业、轻工电器行业、精密机械行业、电子工业等领域有着广泛的应用。随着聚酰亚胺高分子材料种类的增多，行业需求量增大，尤其是OLED在智能手机上的大规模应用，使得聚酰亚胺高分子膜的爆发式需求，进而使得3,3’,4,4’-二苯醚二酐这些基础单体的需求也逐年变大。以往小批量生产3,3’,4,4’-二苯醚二酐中容易解决甚至忽略的一些问题在大量连续生产过程中凸显了出来，尤其是环保方面的问题。3,3',4,4'-Diphenyl ether dianhydride is an important monomer used in the manufacture of polyimide polymer materials (PI). Polyimide polymer materials are widely used in aerospace, motor wrapping, automobile industry, machinery industry, light industrial electrical industry, precision machinery industry, electronics industry and other fields. With the increase in the types of polyimide polymer materials, the industry demand increases, especially the large-scale application of OLEDs in smart phones, which makes the explosive demand for polyimide polymer films, which in turn makes 3,3' , The demand for these basic monomers, 4,4'-diphenyl ether dianhydride, is also increasing year by year. Some problems that were easy to solve or even ignored in the small batch production of 3,3',4,4'-diphenyl ether dianhydride in the past have been highlighted in the mass continuous production process, especially the environmental protection problems.
3,3’,4,4’-二苯醚二酐的脱水工艺中会产生大量醋酐脱水废液，醋酐脱水废液中含大量醋酐及醋酸，并含有有少量产3,3’,4,4’-二苯醚二酐及9-氧(杂)芴二酐，其中，醋酐及醋酸占比约为97wt％，9-氧(杂)芴二酐与3,3’,4,4’-二苯醚二酐占比约为3wt％。目前，国内外在生产3,3’,4,4’-二苯醚二酐过程中产生的醋酐脱水废液均直接蒸馏醋酐及醋酸，釜残作为固废处理，处理过程中不仅产生环保费用，给环保工作增加压力，同时残渣中的3,3’,4,4’-二苯醚二酐与9-氧(杂)芴二酐也作为固废处理造成物料损失。In the dehydration process of 3,3',4,4'-diphenyl ether dianhydride, a large amount of acetic anhydride dehydration waste liquid will be produced. The acetic anhydride dehydration waste liquid contains a large amount of acetic anhydride and acetic acid, and contains a small amount of 3,3 ',4,4'-diphenyl ether dianhydride and 9-oxo(hetero)fluorene dianhydride, of which acetic anhydride and acetic acid account for about 97wt%, 9-oxo(hetero)fluorene dianhydride and 3,3' , 4,4'-diphenyl ether dianhydride accounted for about 3wt%. At present, the acetic anhydride dehydration waste liquid produced in the process of producing 3,3',4,4'-diphenyl ether dianhydride at home and abroad is directly distilled with acetic anhydride and acetic acid, and the still residue is treated as solid waste. Environmental protection costs increase the pressure on environmental protection work. At the same time, 3,3',4,4'-diphenyl ether dianhydride and 9-oxo(hetero)fluorene dianhydride in the residue are also treated as solid waste, resulting in material loss.
因此，寻找一种从3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液中回收9-氧(杂)芴二酐和3,3’,4,4’-二苯醚二酐，并对废酸酐进行有效利用的方法，减少企业环保压力的方法，对提高企业的经济效益和降低环保压力具有重要意义。Therefore, looking for a method to recover 9-oxo(hetero)fluorene dianhydride and 3,3',4,4 '-Diphenyl ether dianhydride, the method of effectively utilizing waste acid anhydride, and the method of reducing the environmental protection pressure of enterprises are of great significance to improving the economic benefits of enterprises and reducing environmental protection pressure.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供一种3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液的处理方法。本发明的处理方法能够回收废液中的9-氧(杂)芴二酐和3,3’,4,4’-二苯醚二酐分别转化为9-氧(杂)芴四甲酸和联苯醚四甲酸进行回收；同时，将醋酐及醋酸以三水乙酸钠和乙酸钠水溶液形式进行回收，实现了废液中原料的有效回收，减少企业环保压力，且提高企业的经济效益。In view of this, the object of the present invention is to provide a kind of treatment method of the acetic anhydride dehydration waste liquid that 3,3',4,4'-diphenyl ether dianhydride dehydration process produces. The treatment method of the present invention can recover 9-oxo(hetero)fluorene dianhydride and 3,3',4,4'-diphenyl ether dianhydride in the waste liquid and convert them into 9-oxo(hetero)fluorene tetracarboxylic acid and diphenyl ether dianhydride respectively. At the same time, acetic anhydride and acetic acid are recovered in the form of sodium acetate trihydrate and sodium acetate aqueous solution, which realizes the effective recovery of raw materials in waste liquid, reduces the environmental protection pressure of enterprises, and improves the economic benefits of enterprises.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液的处理方法，包括以下步骤：The invention provides a treatment method for acetic anhydride dehydration waste liquid produced by a 3,3',4,4'-diphenyl ether dianhydride dehydration process, comprising the following steps:
将醋酐脱水废液和水混合，依次进行第一保温反应和第一降温析晶，得到固体和滤液；所述固体包括9-氧(杂)芴四甲酸和联苯醚四甲酸；Mixing the acetic anhydride dehydration waste liquid with water, carrying out the first heat preservation reaction and the first cooling crystallization in sequence to obtain a solid and a filtrate; the solid includes 9-oxo(hetero)fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid;
将无机碱水溶液滴加到所述滤液中，控制滴加过程的温度不超过95～105℃；待所述无机碱水溶液滴加完毕后，进行第二降温析晶，得到三水乙酸盐和乙酸盐水溶液。Add the aqueous solution of inorganic alkali dropwise to the filtrate, and control the temperature during the dropping process to not exceed 95-105°C; after the aqueous solution of inorganic alkali has been added dropwise, carry out the second cooling and crystallization to obtain acetate trihydrate and Aqueous acetate solution.
优选地，所述醋酐脱水废液和水的质量比为100：40～50。Preferably, the mass ratio of the acetic anhydride dehydration waste liquid to water is 100:40-50.
优选地，所述将醋酐脱水废液和水混合的方式包括：在所述醋酐脱水废液中滴加水，所述水的滴加温度为95～105℃；所述水在1h内滴加完成。Preferably, the method of mixing the acetic anhydride dehydration waste liquid and water includes: adding water dropwise to the acetic anhydride dehydration waste liquid, the temperature of adding the water is 95-105°C; the water is dripped within 1 hour Plus done.
优选地，所述第一保温反应的温度为95～105℃，时间6～10h。Preferably, the temperature of the first heat preservation reaction is 95-105° C., and the time is 6-10 hours.
优选地，所述第一降温析晶的温度为20～30℃，时间为1～2h。Preferably, the temperature of the first cooling crystallization is 20-30° C., and the time is 1-2 hours.
优选地，所述无机碱水溶液中的无机碱包括氢氧化钠和/或氢氧化钾。Preferably, the inorganic base in the aqueous inorganic base solution includes sodium hydroxide and/or potassium hydroxide.
优选地，所述无机碱水溶液的质量浓度为30～50％。Preferably, the mass concentration of the aqueous inorganic alkali solution is 30-50%.
优选地，所述滤液和无机碱水溶液中无机碱的质量比为100：72～76。Preferably, the mass ratio of the filtrate to the inorganic base in the aqueous solution of the inorganic base is 100:72-76.
优选地，所述无机碱水溶液在1～2h滴加完毕。Preferably, the aqueous inorganic alkali solution is added dropwise within 1-2 hours.
优选地，所述第二降温结晶的温度为5～15℃，时间为1～2h。Preferably, the temperature of the second temperature-lowering crystallization is 5-15° C., and the time is 1-2 hours.
本发明提供了一种3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液的处理方法，包括以下步骤：将醋酐脱水废液和水混合，依次进行第一保温反应和第一降温析晶，得到固体和滤液；所述固体包括9-氧(杂)芴四甲酸和联苯醚四甲酸；将无机碱水溶液滴加到所述滤液中，控制滴加过程的温度不超过95～105℃；待所述无机碱水溶液滴加完毕后，进行第二降温析晶，得到三水乙酸钠和乙酸钠水溶液。本发明通过第一保温反应和第一降温结晶，能够将醋酐脱水废液中的9-氧(杂)芴二酐和3,3’,4,4’-二苯醚二酐分别转化为9-氧(杂)芴四甲酸和联苯醚四甲酸实现回收；同时，9-氧(杂)芴四甲酸和联苯醚四甲酸易于再转化为9-氧(杂)芴二酐和3,3’,4,4’-二苯醚二酐，可用于3,3’,4,4’-二苯醚二酐生产，且处理能耗低，具有较高的经济效益和环境效益，推广价值极高。在滤液中加入无机碱水溶液，将醋酐及醋酸以三水乙酸钠和乙酸钠水溶液形式进行回收，乙酸钠可用于生化提供碳源。本发明提供的处理方法实现了废液中原料的有效回收，减少企业环保压力，且提高企业的经济效益。The invention provides a treatment method for the acetic anhydride dehydration waste liquid produced in the 3,3',4,4'-diphenyl ether dianhydride dehydration process, comprising the following steps: mixing the acetic anhydride dehydration waste liquid and water, and sequentially carrying out The first heat preservation reaction and the first cooling and crystallization obtain a solid and a filtrate; the solid includes 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid; an aqueous solution of an inorganic alkali is added dropwise to the filtrate, and the dropwise The temperature in the addition process does not exceed 95-105° C.; after the addition of the inorganic alkali aqueous solution is completed, a second cooling and crystallization is performed to obtain sodium acetate trihydrate and an aqueous solution of sodium acetate. The present invention can convert 9-oxo(hetero)fluorene dianhydride and 3,3',4,4'-diphenyl ether dianhydride in acetic anhydride dehydration waste liquid into 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid realize reclaiming; Simultaneously, 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid are easy to be converted into 9-oxo (hetero) fluorene dianhydride and 3 ,3',4,4'-Diphenyl ether dianhydride can be used in the production of 3,3',4,4'-diphenyl ether dianhydride, and the processing energy consumption is low, which has high economic and environmental benefits. The promotion value is extremely high. An inorganic alkali aqueous solution is added to the filtrate, and the acetic anhydride and acetic acid are recovered in the form of sodium acetate trihydrate and an aqueous solution of sodium acetate, and the sodium acetate can be used for biochemically providing carbon sources. The treatment method provided by the invention realizes the effective recovery of raw materials in the waste liquid, reduces the environmental protection pressure of the enterprise, and improves the economic benefit of the enterprise.
具体实施方式Detailed ways
本发明提供了一种3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液的处理方法，包括以下步骤：The invention provides a treatment method for acetic anhydride dehydration waste liquid produced by a 3,3',4,4'-diphenyl ether dianhydride dehydration process, comprising the following steps:
将醋酐脱水废液和水混合，依次进行第一保温反应和第一降温析晶，得到固体和滤液；所述固体包括9-氧(杂)芴四甲酸和联苯醚四甲酸；Mixing the acetic anhydride dehydration waste liquid with water, carrying out the first heat preservation reaction and the first cooling crystallization in sequence to obtain a solid and a filtrate; the solid includes 9-oxo(hetero)fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid;
将无机碱水溶液滴加到所述滤液中，控制滴加过程的温度不超过95～105℃；待所述无机碱水溶液滴加完毕后，进行第二降温析晶，得到三水乙酸盐和乙酸盐水溶液。Add the aqueous solution of inorganic alkali dropwise to the filtrate, and control the temperature during the dropping process to not exceed 95-105°C; after the aqueous solution of inorganic alkali has been added dropwise, carry out the second cooling and crystallization to obtain acetate trihydrate and Aqueous acetate solution.
在本发明中，如无特殊说明，本发明所用原料均优选为市售产品。In the present invention, unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.
本发明将醋酐脱水废液和水混合，依次进行第一保温反应和第一降温析晶，得到固体和滤液；所述固体包括9-氧(杂)芴四甲酸和联苯醚四甲酸。The invention mixes the acetic anhydride dehydration waste liquid with water, carries out the first heat preservation reaction and the first cooling crystallization successively, and obtains a solid and a filtrate; the solid includes 9-oxo(hetero)fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid.
在本发明中，所述醋酐脱水废液中包括醋酐、醋酸、3,3’,4,4’-二苯醚二酐和9-氧(杂)芴二酐；所述酐脱水废液中醋酐的质量百分含量为40～80％，醋酸的质量百分含量为20～50％，3,3’,4,4’-二苯醚二酐的质量百分含量为0～10％，9-氧(杂)芴二酐的质量百分含量为0～10％。In the present invention, the acetic anhydride dehydration waste liquid includes acetic anhydride, acetic acid, 3,3',4,4'-diphenyl ether dianhydride and 9-oxo (hetero)fluorene dianhydride; the anhydride dehydration waste The mass percentage of acetic anhydride in the liquid is 40-80%, the mass percentage of acetic acid is 20-50%, and the mass percentage of 3,3',4,4'-diphenyl ether dianhydride is 0-80%. 10%, the mass percent content of 9-oxo(hetero)fluorene dianhydride is 0-10%.
在本发明中，所述水优选为纯水。In the present invention, the water is preferably pure water.
在本发明中，所述醋酐脱水废液和水的质量比优选为100：40～50，进一步优选为100：42～48，更优选为100：44～46。In the present invention, the mass ratio of the acetic anhydride dehydration waste liquid to water is preferably 100:40-50, more preferably 100:42-48, more preferably 100:44-46.
在本发明中，所述将醋酐脱水废液和水混合的方式优选包括：在所述醋酐脱水废液中滴加水。在本发明中，所述水的滴加温度优选为95～105℃，进一步优选为97～98℃。在本发明中，所述水优选在1h内滴加完成。In the present invention, the method of mixing the acetic anhydride dehydration waste liquid and water preferably includes: adding water dropwise to the acetic anhydride dehydration waste liquid. In the present invention, the dropping temperature of the water is preferably 95-105°C, more preferably 97-98°C. In the present invention, the water is preferably added dropwise within 1 h.
在本发明中，所述第一保温反应的温度优选为95～105℃；时间优选为6～10h，进一步优选为8h。In the present invention, the temperature of the first heat preservation reaction is preferably 95-105°C; the time is preferably 6-10 hours, more preferably 8 hours.
在本发明中，所述第一降温析晶的温度优选为20～30℃，时间优选为1～2h。在本发明中，由所述第一保温反应的温度降至第一降温析晶的温度的速率优选为1～2℃/min。In the present invention, the temperature of the first cooling crystallization is preferably 20-30° C., and the time is preferably 1-2 hours. In the present invention, the rate of decreasing from the temperature of the first heat preservation reaction to the temperature of the first cooling crystallization is preferably 1-2° C./min.
所述第一降温析晶后，本发明优选还包括离心，得到固体和滤液。在本发明中，所述离心的温度优选与所述第一降温析晶的温度一致，在此不再赘述。After the first cooling and crystallization, the present invention preferably further includes centrifugation to obtain a solid and a filtrate. In the present invention, the temperature of the centrifugation is preferably consistent with the temperature of the first cooling and crystallization, which will not be repeated here.
得到滤液后，本发明将无机碱水溶液滴加到所述滤液中，控制滴加过程的温度不超过95～105℃；待无机碱水溶液滴加完毕后，进行第二降温析晶，得到三水乙酸盐和乙酸盐水溶液。After the filtrate is obtained, the present invention adds the inorganic alkali aqueous solution dropwise to the filtrate, and controls the temperature in the dropping process to not exceed 95-105°C; Acetate and Acetate Aqueous Solution.
在本发明中，所述无机碱水溶液中的无机碱优选包括氢氧化钠和/或氢氧化钾，进一步优选为氢氧化钠。在本发明中，所述无机碱水溶液的质量浓度优选为30～50％，进一步优选为40％。在本发明中，所述滤液和无机碱水溶液中无机碱的质量比优选为100：72～76。在本发明中，所述无机碱水溶液全部加入到所述滤液中，所得体系的pH值优选为9.2～9.7。In the present invention, the inorganic base in the aqueous inorganic base solution preferably includes sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide. In the present invention, the mass concentration of the aqueous inorganic alkali solution is preferably 30-50%, more preferably 40%. In the present invention, the mass ratio of the filtrate to the inorganic base in the aqueous solution of the inorganic base is preferably 100:72-76. In the present invention, all of the aqueous inorganic alkali solution is added to the filtrate, and the pH value of the obtained system is preferably 9.2-9.7.
在本发明中，所述无机碱水溶液优选在1～2h滴加完毕，进一步优选为1.8h滴加完毕。In the present invention, the aqueous inorganic alkali solution is preferably added dropwise within 1-2 hours, more preferably within 1.8 hours.
在本发明中，所述滤液中的醋酸和醋酐与无机碱的反应为放热反应；随着无机碱水溶液的加入，滤液的温度逐步升高；优选当随着无机碱水溶液的加入，体系的温度升温至98℃，开始降温，控制体系的温度为95～105℃。In the present invention, the reaction of acetic acid and acetic anhydride in the filtrate with the inorganic base is an exothermic reaction; with the addition of the aqueous solution of the inorganic base, the temperature of the filtrate gradually increases; preferably when the aqueous solution of the inorganic base is added, the system The temperature of the system was raised to 98°C, and then started to cool down, and the temperature of the control system was 95-105°C.
在本发明中，所述第二降温结晶的温度优选为5～15℃，时间优选为1～2h。In the present invention, the temperature of the second temperature-lowering crystallization is preferably 5-15° C., and the time is preferably 1-2 hours.
在本发明中，由95～105℃降温至第二降温结晶的温度的速率优选为0.5～2℃/min。In the present invention, the cooling rate from 95-105°C to the temperature of the second cooling crystallization is preferably 0.5-2°C/min.
下面结合实施例对本发明提供的3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液的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。The treatment method of the acetic anhydride dehydration waste liquid produced by the 3,3',4,4'-diphenyl ether dianhydride dehydration process provided by the present invention will be described in detail below in conjunction with the examples, but they cannot be understood as protecting the scope of the present invention limit.
实施例1Example 1
取3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液(其中，醋酐的含量为65wt％，醋酸的含量为32wt％，9-氧(杂)芴二酐的含量为0.7wt％，3,3’,4,4’-二苯醚二酐的含量为2.3wt％)100g升温至97℃，滴加纯水50g，用时1小时，滴加完毕后，于105℃保温6h，然后以1℃/min降温至20℃，保温1h，离心，得9-氧(杂)芴四甲酸与联苯醚四甲酸3.55g，烘干后得到9-氧(杂)芴四甲酸与联苯醚四甲酸3.33g。Get the acetic anhydride dehydration waste liquid (wherein, the content of acetic anhydride is 65wt%, the content of acetic acid is 32wt% that 3,3 ', 4,4'-diphenyl ether dianhydride dehydration process produces, 9-oxo (hetero) fluorene The content of dianhydride is 0.7wt%, the content of 3,3',4,4'-diphenyl ether dianhydride is 2.3wt%) 100g is heated up to 97°C, and 50g of pure water is added dropwise for 1 hour, and the dropwise addition is completed Afterwards, keep warm at 105°C for 6h, then cool down to 20°C at 1°C/min, keep warm for 1h, and centrifuge to obtain 3.55g of 9-oxo(hetero)fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid, and obtain 9-oxo (Hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid 3.33g.
在滤液31℃滴加40wt％氢氧化钠水溶液，当温度达到98℃开始降温，维持温度95～105℃，180.9g氢氧化钠水溶液1.8小时滴加完毕，滴加完毕后体系pH为9.25，开始降温，以1℃/min降温至10℃，保温1h，离心得到三水乙酸钠160.27g，乙酸钠水溶液166.28g。Add 40wt% sodium hydroxide aqueous solution dropwise at 31°C of the filtrate, start cooling when the temperature reaches 98°C, maintain the temperature at 95-105°C, and finish adding 180.9g of sodium hydroxide aqueous solution in 1.8 hours. After the dropwise addition, the pH of the system is 9.25, start Cool down to 10°C at 1°C/min, keep warm for 1h, and centrifuge to obtain 160.27g of sodium acetate trihydrate and 166.28g of sodium acetate aqueous solution.
经检测：三水乙酸钠中三水乙酸钠的质量含量为99.4％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐未检出；乙酸钠水溶液中乙酸钠的质量含量为31.37％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐的质量含量为120ppm。After testing: the mass content of sodium acetate trihydrate in sodium acetate trihydrate is 99.4%, 9-oxo (hetero) fluorene tetracarboxylic acid tetrasodium salt and biphenyl ether tetracarboxylic acid tetrasodium salt are not detected; sodium acetate in sodium acetate aqueous solution The mass content is 31.37%, and the mass content of 9-oxo(hetero)fluorene tetracarboxylic acid tetrasodium salt and diphenyl ether tetracarboxylic acid tetrasodium salt is 120ppm.
实施例2Example 2
取3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液(其中，醋酐的含量为65wt％，醋酸的含量为32wt％，9-氧(杂)芴二酐的含量为0.7wt％，3,3’,4,4’-二苯醚二酐的含量为2.3wt％)100g升温至98℃，滴加纯水40g，用时1小时，滴加完毕后，于105℃保温10h，然后以20℃/15min降温至20℃，保温1h，离心，得9-氧(杂)芴四甲酸与联苯醚四甲酸3.6g，烘干后得到9-氧(杂)芴四甲酸与联苯醚四甲酸3.32g。Get the acetic anhydride dehydration waste liquid (wherein, the content of acetic anhydride is 65wt%, the content of acetic acid is 32wt% that 3,3 ', 4,4'-diphenyl ether dianhydride dehydration process produces, 9-oxo (hetero) fluorene The content of dianhydride is 0.7wt%, and the content of 3,3',4,4'-diphenyl ether dianhydride is 2.3wt%) 100g is heated up to 98°C, and 40g of pure water is added dropwise for 1 hour, and the dropwise addition is completed Afterwards, keep warm at 105°C for 10h, then cool down to 20°C at 20°C/15min, keep warm for 1h, and centrifuge to get 3.6g of 9-oxo(hetero)fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid. After drying, 9-oxo (Hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid 3.32g.
滤液31℃滴加质量浓度为40％的氢氧化钠水溶液，当温度达到98℃开始降温，维持温度95～105℃，185g氢氧化钠水溶液在1.8小时滴加完毕，滴加完毕后体系的pH为9.7，开始降温，以1℃/min降温至10℃，保温1h，离心得到三水乙酸钠176.31g，乙酸钠水溶液144.33g。The filtrate was added dropwise with an aqueous sodium hydroxide solution with a mass concentration of 40% at 31°C. When the temperature reached 98°C, the temperature began to drop, and the temperature was maintained at 95 to 105°C. 185g of aqueous sodium hydroxide solution was added dropwise in 1.8 hours. After the dropwise addition, the pH of the system When the temperature was 9.7, the temperature was lowered to 10°C at 1°C/min, kept for 1h, and centrifuged to obtain 176.31g of sodium acetate trihydrate and 144.33g of sodium acetate aqueous solution.
经检测：三水乙酸钠中三水乙酸钠的质量含量为99.3％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐未检出；乙酸钠水溶液中，乙酸钠的质量含量为29.58％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐的质量含量为198ppm。After testing: the mass content of sodium acetate trihydrate in sodium acetate trihydrate is 99.3%, 9-oxo (hetero) fluorene tetracarboxylic acid tetrasodium salt and biphenyl ether tetracarboxylic acid tetrasodium salt are not detected; in sodium acetate aqueous solution, acetic acid The mass content of sodium is 29.58%, and the mass content of 9-oxo(hetero)fluorene tetracarboxylic acid tetrasodium salt and diphenyl ether tetracarboxylic acid tetrasodium salt is 198ppm.
实施例3Example 3
取3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液(其中，醋酐的含量为65wt％，醋酸的含量为32wt％，9-氧(杂)芴二酐的含量为0.7wt％，3,3’,4,4’-二苯醚二酐的含量为2.3wt％)100g升温至95℃，滴加纯水50g，用时1小时，滴加完毕后，于105℃保温8h，然后以25℃/15min降温至20℃，保温1h，离心，得9-氧(杂)芴四甲酸与联苯醚四甲酸3.54g，烘干后得到9-氧(杂)芴四甲酸与联苯醚四甲酸3.34g。Get the acetic anhydride dehydration waste liquid (wherein, the content of acetic anhydride is 65wt%, the content of acetic acid is 32wt% that 3,3 ', 4,4'-diphenyl ether dianhydride dehydration process produces, 9-oxo (hetero) fluorene The content of dianhydride is 0.7wt%, and the content of 3,3',4,4'-diphenyl ether dianhydride is 2.3wt%) 100g is heated up to 95°C, and 50g of pure water is added dropwise for 1 hour, and the dropwise addition is completed Afterwards, keep warm at 105°C for 8h, then cool down to 20°C at 25°C/15min, keep warm for 1h, and centrifuge to obtain 3.54g of 9-oxo(hetero)fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid, and obtain 9-oxo (Hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid 3.34g.
在滤液31℃中滴加质量百分含量为40％的氢氧化钠水溶液，当温度达到98℃开始降温，维持温度95～105℃，183.8g氢氧化钠水溶液1.8小时滴加完毕，滴加完毕后体系的pH为9.51，开始降温，以2℃/min降温至9℃，保温1h，离心得到三水乙酸钠166.32g，乙酸钠水溶液162.28g。In the filtrate 31 ℃, dropwise add a sodium hydroxide aqueous solution with a mass percentage of 40%, when the temperature reaches 98 ℃, start to cool down, maintain the temperature at 95-105 ℃, 183.8g of sodium hydroxide aqueous solution is added dropwise in 1.8 hours, and the dropwise addition is completed After the pH of the system was 9.51, the temperature was lowered to 9°C at 2°C/min, kept for 1 hour, and centrifuged to obtain 166.32g of sodium acetate trihydrate and 162.28g of sodium acetate aqueous solution.
经检测：三水乙酸钠中三水乙酸钠的质量含量未99.4％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐未检出；乙酸钠水溶液中乙酸钠的质量百分含量为29.92％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐的质量百分含量为65ppm。After testing: the mass content of sodium acetate trihydrate in sodium acetate trihydrate was not 99.4%, 9-oxo(hetero)fluorene tetracarboxylic acid tetrasodium salt and biphenyl ether tetracarboxylic acid tetrasodium salt were not detected; sodium acetate in sodium acetate aqueous solution The mass percent content of 9-oxo (hetero) fluorene tetracarboxylic acid tetrasodium salt and diphenyl ether tetracarboxylic acid tetrasodium salt is 65ppm.
对比例1Comparative example 1
本对比例提供一种3,3’,4,4’-二苯醚二酐脱水废酸酐处理方法，包括如下步骤：This comparative example provides a kind of 3,3 ',4,4'-diphenyl ether dianhydride dehydration waste acid anhydride treatment method, comprises the following steps:
取3,3’,4,4’-二苯醚二酐脱水工艺产生的醋酐脱水废液(其中，醋酐的含量为65wt％，醋酸的含量为32wt％，9-氧(杂)芴二酐的含量为0.7wt％，3,3’,4,4’-二苯醚二酐的含量为2.3wt％)100g在25℃的条件下滴加质量百分含量为40％的氢氧化钠水溶液与50g纯水，当温度达到98℃开始降温，维持温度95～105℃，184.9g氢氧化钠水溶液1.8小时滴加完毕，滴加完毕后体系的pH为9.45，开始降温，以15℃/15min降温至10℃，保温1h，离心得到三水乙酸钠163.54g，乙酸钠水溶液170.26g。Get the acetic anhydride dehydration waste liquid (wherein, the content of acetic anhydride is 65wt%, the content of acetic acid is 32wt% that 3,3 ', 4,4'-diphenyl ether dianhydride dehydration process produces, 9-oxo (hetero) fluorene The content of dianhydride is 0.7wt%, and the content of 3,3',4,4'-diphenyl ether dianhydride is 2.3wt%) 100g is added dropwise at 25°C with a mass percentage of 40% hydrogen Sodium aqueous solution and 50g pure water, when the temperature reaches 98°C, start to cool down, maintain the temperature at 95-105°C, 184.9g sodium hydroxide aqueous solution is added dropwise in 1.8 hours. Cool down to 10°C per 15 min, keep warm for 1 h, and centrifuge to obtain 163.54 g of sodium acetate trihydrate and 170.26 g of sodium acetate aqueous solution.
经检测：三水乙酸钠中三水乙酸钠的质量含量97.4％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐的质量含量0.46％；乙酸钠水溶液中乙酸钠的质量含量为30.65％，9-氧(杂)芴四甲酸四钠盐与联苯醚四甲酸四钠盐的质量含量为2.03％。After testing: the mass content of sodium acetate trihydrate in sodium acetate trihydrate is 97.4%, the mass content of 9-oxo (hetero) fluorene tetracarboxylic acid tetrasodium salt and biphenyl ether tetracarboxylic acid tetrasodium salt is 0.46%; acetic acid in sodium acetate aqueous solution The mass content of sodium is 30.65%, and the mass content of 9-oxo(hetero)fluorene tetracarboxylic acid tetrasodium salt and diphenyl ether tetracarboxylic acid tetrasodium salt is 2.03%.
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。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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Application publication date: 20230425 |