CN113666831A - Method for preparing high-purity o-nitroaniline by layered melt crystallization - Google Patents
Method for preparing high-purity o-nitroaniline by layered melt crystallization Download PDFInfo
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- CN113666831A CN113666831A CN202110895639.0A CN202110895639A CN113666831A CN 113666831 A CN113666831 A CN 113666831A CN 202110895639 A CN202110895639 A CN 202110895639A CN 113666831 A CN113666831 A CN 113666831A
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- Prior art keywords
- nitroaniline
- temperature
- crystallization
- crystallizer
- product
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- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002425 crystallisation Methods 0.000 title claims abstract description 22
- 230000008025 crystallization Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 15
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000012452 mother liquor Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 210000004243 sweat Anatomy 0.000 claims abstract 4
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000035900 sweating Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于化工分离技术领域，公开了一种利用层式熔融结晶提纯制备高纯邻硝基苯胺的方法。该提纯方法包括以下步骤：1)预热化料：待结晶器内温度达到粗品的熔化温度后，将85～99％的邻硝基苯胺粗品加到层式熔融结晶器中使其熔化。2)：降温结晶：待原料全部熔化后，使结晶器内物料按照1～30K/h进行降温，结晶终温为30‑45℃；3)升温发汗：待排出未结晶母液后，对晶体进行发汗，升温至71‑74℃时，恒温0.5～1h。4)化料排料。本发明的优点是，提纯过程无需溶剂，避免了溶剂对产品的污染，又减少了溶剂回收过程，节省了设备投资，产品的纯度可达到99.9％以上。The invention belongs to the technical field of chemical separation, and discloses a method for preparing high-purity o-nitroaniline by utilizing layered melting crystallization purification. The purification method includes the following steps: 1) Preheating the material: after the temperature in the crystallizer reaches the melting temperature of the crude product, 85-99% of the crude o-nitroaniline is added to the layered melting crystallizer to melt it. 2): cooling and crystallization: after all the raw materials are melted, the materials in the crystallizer are cooled according to 1～30K/h, and the final temperature of crystallization is 30-45°C; 3) the temperature rises and sweats: after the uncrystallized mother liquor is discharged, the crystals are subjected to Sweat, when the temperature rises to 71-74°C, the constant temperature is 0.5-1h. 4) Chemical discharge. The advantages of the invention are that the purification process does not need solvent, avoids the pollution of the solvent to the product, reduces the solvent recovery process, saves equipment investment, and the purity of the product can reach more than 99.9%.
Description
Technical Field
The invention belongs to the technical field of chemical separation, relates to a purification technology of o-nitroaniline, and particularly relates to a method for purifying the o-nitroaniline by utilizing melt crystallization.
Background
The o-nitroaniline is an important organic chemical raw material and is widely applied to the production and preparation of veterinary drugs, medicines and dyes. Meanwhile, the rubber antioxidant is also an intermediate for producing rubber antioxidant MB and o-phenylenediamine. According to the national standard GB/T4840-2016, the excellent o-nitroaniline product is orange-red flaky solid with the purity of more than or equal to 99.5 percent, however, the o-nitroaniline synthesized by the common industrial route contains light components such as benzofuran, o-chloroaniline, o-nitrophenol, o-nitrochlorobenzene and the like, the purity of the o-nitroaniline cannot meet the requirements of the excellent product, and no relevant report on the preparation of the ultra-pure o-nitroaniline is found.
Patent CN211170527U discloses an experimental apparatus that relates to and utilizes steam purification o-nitroaniline, its characterized in that primary filter screen, well effect filter screen and high-efficient filter screen distribute in proper order from big to little, very big reduction the foam of the o-nitroaniline after the purification. The preparation method of o-nitroaniline disclosed in patent CN1693301A relates to the purification of o-nitroaniline by distillation, and the purity reaches 99.8%. As for the o-nitroaniline products with high purity (more than or equal to 99.9 percent), the o-nitroaniline products cannot be prepared in the industry at present, and the purification method such as distillation and the like is possible to be realized only when the boiling point (250-300 ℃) of the o-nitroaniline is reached, so that the energy consumption is high, the equipment investment is large, and the operation cost is high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing high-purity o-nitroaniline by layered melt crystallization, wherein the purity of the obtained o-nitroaniline is more than 99.9%.
The purpose of the invention is realized by the following technical scheme:
a method for purifying o-nitroaniline by layered melt crystallization, which comprises the following steps:
1) material melting: weighing a certain amount of o-nitroaniline crude product, adding into a layer type crystallizer, and preheating the material to melt.
2) Cooling and crystallizing: cooling the material in the crystallizer according to 1-30K/h, wherein the final crystallization temperature is 30-45 ℃;
3) warming and sweating: after discharging the non-crystallized mother liquor, sweating the crystals, wherein the heating rate is 1-60K/h, heating to 71-74 ℃, and keeping the temperature for 0.5 h.
4) Material melting and discharging: heating to melt the product, and discharging from the crystallizer to obtain high-quality o-nitroaniline with the product purity of more than 99.9 percent and the light component content of less than 0.12 percent.
Further, the o-nitroaniline crude product used in the step 1) is an o-nitroaniline crude product obtained by an organic synthesis method, wherein the molar percentage content of the o-nitroaniline is 85-99%.
Further, in the step 2), when crystals are separated out, growing the crystals at constant temperature for 0.5 to 1 hour, and then cooling according to a certain temperature program.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for separating pure o-nitroaniline from an o-nitroaniline-containing crude product, which adopts a layered melt crystallization process, is suitable for an o-nitroaniline crude product (the molar percentage of the o-nitroaniline is 85-99 percent), does not add any solvent, reduces the operation cost, simplifies the operation, is environment-friendly, does not generate three wastes, and obtains the o-nitroaniline with the purity of more than 99.9 percent.
Detailed description of the invention
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be described in detail with reference to the best embodiments
Example 1
257.42g of crude o-nitroaniline with the content of 88 percent is put into a 300mL layered melt crystallizer, the temperature is increased to 72 ℃ until the material is completely melted into liquid, and the temperature is reduced at the rate of 15K/h until the final crystallization temperature is 36 ℃; after which the mother liquor is discharged. Then the temperature is increased to the final sweating temperature of 74 ℃ at the temperature increase rate of 30K/h. Then, the sweating liquid is discharged, and the temperature is raised to melt and discharge the materials.
The product purity obtained by the operations is 99.91%, the light component content is 0.02%, and the one-way yield is 40.04%.
Example 2
259.44g of o-nitroaniline crude product with the content of 90 percent is put into a 300mL layered melt crystallizer, the temperature is raised to 72 ℃ until the material is completely melted into liquid, and the temperature is lowered to the final crystallization temperature of 37 ℃ at the cooling rate of 12K/h; after which the mother liquor is discharged. Then rapidly increasing the temperature to the sweating final temperature of 73 ℃ at the temperature increasing rate of 12K/h. Then, the sweating liquid is discharged, and the temperature is raised to melt and discharge the materials.
The product purity obtained by the operations is 99.95%, the light component content is 0.03%, and the one-way yield is 43.90%.
Example 3
250.51g of o-nitroaniline crude product with the content of 95 percent is put into a 300mL layered melt crystallizer, the temperature is raised to 72 ℃ until the material is completely melted into liquid, and the temperature is lowered to 36 ℃ at the crystallization final temperature at the cooling rate of 18K/h; after which the mother liquor is discharged. Then the temperature is rapidly increased to the final sweating temperature of 74 ℃ at the temperature increase rate of 15K/h. Then, the sweating liquid is discharged, and the temperature is raised to melt and discharge the materials.
The product purity obtained by the operations is 99.84%, the light component content is 0.04%, and the one-way yield is 46.78%.
Example 4
244.57g of an o-nitroaniline crude product with the content of 97 percent is put into a 300mL layered melt crystallizer, the temperature is raised to 72 ℃ until the material is completely melted into liquid, and the temperature is lowered to 36 ℃ at the final crystallization temperature at the cooling rate of 10K/h; after which the mother liquor is discharged. Then rapidly increasing the temperature to 72 ℃ of the final sweating temperature at the temperature increasing rate of 10K/h. Then, the sweating liquid is discharged, and the temperature is raised to melt and discharge the materials.
The product purity obtained by the operations is 99.95%, the light component content is 0.03%, and the one-way yield is 50.49%.
Example 5
236.37g of o-nitroaniline crude product with the content of 97.5 percent is put into a 300mL layered melt crystallizer, the temperature is raised to 72 ℃ until the material is completely melted into liquid, and the temperature is lowered to the final crystallization temperature of 41 ℃ at the cooling rate of 16K/h; after which the mother liquor is discharged. Then the temperature is rapidly increased to the final sweating temperature of 71 ℃ at the temperature increase rate of 16K/h. Then, the sweating liquid is discharged, and the temperature is raised to melt and discharge the materials.
The purity of the product obtained by the operations is 99.94%, the content of light components is 0.03%, and the one-way yield is 53.53%.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (4)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114671768A (en) * | 2022-04-22 | 2022-06-28 | 上海东庚化工技术有限公司 | Industrial purification method of hexamethylene diamine |
| CN115504872A (en) * | 2022-09-19 | 2022-12-23 | 北京天弘天达科技股份有限公司 | A kind of purification method of p-hydroxyacetophenone |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03227943A (en) * | 1990-01-30 | 1991-10-08 | Honsyu Kagaku Kogyo Kk | Transformation of crystal form of solid organic compound |
| RU2006115007A (en) * | 2006-05-04 | 2007-11-10 | Институт нефтехимического синтеза им. А.В. Топчиева РАН (ИНХС РАН) (RU) | METHOD FOR SEPARATING COMPOUNDS BY THIN-LAYER CHROMATOGRAPHY METHOD AND DEVICE FOR ITS IMPLEMENTATION |
| CN102134198A (en) * | 2010-12-29 | 2011-07-27 | 安徽八一化工股份有限公司 | Method for separating nitrochlorobenzene meta-position oil |
| CN102701997A (en) * | 2012-07-09 | 2012-10-03 | 江苏飞亚化学工业有限责任公司 | Process for purifying dialkyl diphenylamine |
| CN108047054A (en) * | 2018-01-23 | 2018-05-18 | 贵州大学 | A kind of method of fusion-crystallization separating-purifying neighbour's Iodoaniline |
| CN109134310A (en) * | 2018-10-19 | 2019-01-04 | 天津科技大学 | The method that layer-based melt crystallization prepares high-purity aniline-acetonitrile |
| CN211170527U (en) * | 2019-12-05 | 2020-08-04 | 湖北进创博生物科技有限公司 | Purification device for o-nitroaniline |
-
2021
- 2021-08-05 CN CN202110895639.0A patent/CN113666831B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03227943A (en) * | 1990-01-30 | 1991-10-08 | Honsyu Kagaku Kogyo Kk | Transformation of crystal form of solid organic compound |
| RU2006115007A (en) * | 2006-05-04 | 2007-11-10 | Институт нефтехимического синтеза им. А.В. Топчиева РАН (ИНХС РАН) (RU) | METHOD FOR SEPARATING COMPOUNDS BY THIN-LAYER CHROMATOGRAPHY METHOD AND DEVICE FOR ITS IMPLEMENTATION |
| CN102134198A (en) * | 2010-12-29 | 2011-07-27 | 安徽八一化工股份有限公司 | Method for separating nitrochlorobenzene meta-position oil |
| CN102701997A (en) * | 2012-07-09 | 2012-10-03 | 江苏飞亚化学工业有限责任公司 | Process for purifying dialkyl diphenylamine |
| CN108047054A (en) * | 2018-01-23 | 2018-05-18 | 贵州大学 | A kind of method of fusion-crystallization separating-purifying neighbour's Iodoaniline |
| CN109134310A (en) * | 2018-10-19 | 2019-01-04 | 天津科技大学 | The method that layer-based melt crystallization prepares high-purity aniline-acetonitrile |
| CN211170527U (en) * | 2019-12-05 | 2020-08-04 | 湖北进创博生物科技有限公司 | Purification device for o-nitroaniline |
Non-Patent Citations (4)
| Title |
|---|
| SHENGZHE JIA等: "Purification of 2,4-dinitrochlorobenzene using layer melt crystallization: Model and experiment", SEPARATION AND PURIFICATION TECHNOLOGY, vol. 270, pages 1 - 10 * |
| 丁雪峰;李天祥;朱静;: "熔融结晶工艺研究及应用", 应用化工, vol. 41, no. 08, pages 1430 - 1433 * |
| 汪斌,王车礼,云志: "基于直接冷却固化与发汗提纯的熔融结晶研究", 江苏工业学院学报, vol. 16, no. 02, pages 33 - 36 * |
| 王雅珍;庄苍伟;周源;刘琦琦;: "邻硝基苯胺的合成研究", 江苏理工学院学报, vol. 22, no. 04, pages 29 - 35 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114671768A (en) * | 2022-04-22 | 2022-06-28 | 上海东庚化工技术有限公司 | Industrial purification method of hexamethylene diamine |
| CN114671768B (en) * | 2022-04-22 | 2023-09-12 | 上海东庚化工技术有限公司 | Industrial purifying method for hexamethylenediamine |
| CN115504872A (en) * | 2022-09-19 | 2022-12-23 | 北京天弘天达科技股份有限公司 | A kind of purification method of p-hydroxyacetophenone |
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| CN113666831B (en) | 2024-02-06 |
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Effective date of registration: 20240428 Address after: 300457 Tianjin Binhai New Area Economic and Technological Development Zone Binhai Zhongguancun Science and Technology Park Rongchuang Rongsheng Square Building 4 North Tower 604 Patentee after: Tianjin Zhongfu Chemical Technology Co.,Ltd. Country or region after: China Address before: No.9, 13th Street, economic and Technological Development Zone, Binhai New Area, Tianjin Patentee before: TIANJIN University OF SCIENCE AND TECHNOLOGY Country or region before: China |