CN113666831A - Method for preparing high-purity o-nitroaniline by layer-type melt crystallization - Google Patents
Method for preparing high-purity o-nitroaniline by layer-type 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
- crude product
- crystallizer
- purity
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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 20
- 230000008025 crystallization Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 19
- 230000035900 sweating Effects 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000012452 mother liquor Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 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
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 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
- 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
The invention belongs to the technical field of chemical separation, and discloses a method for preparing high-purity o-nitroaniline by using layered melt crystallization purification. The purification method comprises the following steps: 1) preheating and material melting: and after the temperature in the crystallizer reaches the melting temperature of the crude product, adding 85-99% of the crude product of the o-nitroaniline into a layer-type melting crystallizer to melt the crude product. 2): cooling and crystallizing: after the raw materials are completely melted, cooling the materials 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, and keeping the temperature constant for 0.5-1 h when the temperature is raised to 71-74 ℃. 4) Melting and discharging. The invention has the advantages that no solvent is needed in the purification process, the pollution of the solvent to the product is avoided, the solvent recovery process is reduced, the equipment investment is saved, and the purity of the product can reach more than 99.9 percent.
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)
1. A method for preparing o-nitroaniline by layered melt crystallization comprises the following steps:
1) preheating material, namely adding a certain amount of o-nitroaniline crude product into a preheated layer-type melt crystallizer to be heated and melted;
2) cooling and crystallizing: starting a temperature control program to cool 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 0.5-1 h;
4) material melting and discharging: the temperature is raised until the product is molten and then discharged from the crystallizer.
2. The layered melt crystallization method for preparing o-nitroaniline according to claim 1, wherein:
the o-nitroaniline crude product in the step 1) is an o-nitroaniline crude product obtained by an organic synthesis method, wherein the percentage content of the o-nitroaniline is 85-99%.
3. The layered melt crystallization method for preparing o-nitroaniline according to claim 1, wherein: the layer-type melt crystallization adopts a static or dynamic mode.
4. The layered melt crystallization method for preparing o-nitroaniline according to claim 1, wherein: and 2) when crystals are separated out, growing the crystals at constant temperature for 0.5-1 h, and then cooling according to a certain temperature program.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110895639.0A CN113666831B (en) | 2021-08-05 | 2021-08-05 | Method for preparing high-purity o-nitroaniline by layered melt crystallization |
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| CN202110895639.0A CN113666831B (en) | 2021-08-05 | 2021-08-05 | Method for preparing high-purity o-nitroaniline by layered melt crystallization |
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| CN113666831B CN113666831B (en) | 2024-02-06 |
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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 | Purification method of p-hydroxyacetophenone |
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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 | Purification method of p-hydroxyacetophenone |
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