CN113666831B - 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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- CN113666831B CN113666831B CN202110895639.0A CN202110895639A CN113666831B CN 113666831 B CN113666831 B CN 113666831B CN 202110895639 A CN202110895639 A CN 202110895639A CN 113666831 B CN113666831 B CN 113666831B
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- nitroaniline
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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 43
- 238000002425 crystallisation Methods 0.000 title claims abstract description 19
- 230000008025 crystallization Effects 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 230000035900 sweating Effects 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000010413 mother solution Substances 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 13
- 238000000746 purification Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000012043 crude product Substances 0.000 abstract description 3
- 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 5
- 239000012452 mother liquor Substances 0.000 description 5
- 210000004243 sweat Anatomy 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004519 manufacturing process 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
- 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
- 239000000975 dye Substances 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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 the material: after the temperature in the crystallizer reaches the melting temperature of the crude product, adding 85-99% of crude o-nitroaniline into a layered melting crystallizer to melt the crude o-nitroaniline. 2): cooling and crystallizing: after the raw materials are completely melted, cooling the materials in the crystallizer according to the temperature of 1-30K/h, wherein the final crystallization temperature is 30-45 ℃; 3) Heating and sweating: after the uncrystallized mother solution is discharged, the crystal is sweated, and the temperature is raised to 71-74 ℃ for 0.5-1 h. 4) And (5) material melting and discharging. The invention has the advantages that the purification process does not need solvent, 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 in particular relates to a method for purifying o-nitroaniline by using melt crystallization.
Background
O-nitroaniline is an important organic chemical raw material and is widely applied to production and preparation of veterinary medicines, medicines and dyes. At the same time, it is also a rubber antioxidant MB, an intermediate for the production of o-phenylenediamine. According to national standard GB/T4840-2016, the superior product of the o-nitroaniline should be orange red flaky solid with the purity of more than or equal to 99.5%, 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 requirement of the superior product, and related reports of the preparation of the ultra-pure o-nitroaniline are not seen.
Patent CN211170527U discloses an experimental device for purifying o-nitroaniline by using steam, which is characterized in that a primary filter screen, a middle-effect filter screen and a high-efficiency filter screen are distributed from large to small in sequence, and the foam of the purified o-nitroaniline is greatly reduced. The preparation method of the o-nitroaniline disclosed in the patent CN1693301A relates to the purification of the o-nitroaniline by distillation, and the purity of the o-nitroaniline reaches 99.8 percent. As for the high-purity (more than or equal to 99.9 percent) o-nitroaniline products, the preparation cannot be achieved in the current industry, and the purification methods such as distillation and the like are possibly 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 realization of the invention is completed by the following technical proposal:
a method for purifying o-nitroaniline by layered melt crystallization, comprising the following steps:
1) Melting: weighing a certain amount of crude o-nitroaniline, and adding the crude o-nitroaniline into a layered crystallizer to preheat materials and melt the materials.
2) Cooling and crystallizing: cooling the materials in the crystallizer according to the temperature of 1-30K/h, wherein the final crystallization temperature is 30-45 ℃;
3) Heating and sweating: after the uncrystallized mother solution is discharged, the crystal is sweated, the heating rate is 1-60K/h, the temperature is raised to 71-74 ℃, and the temperature is kept for 0.5h.
4) And (3) material melting and discharging: heating to melt the product, and discharging from the crystallizer to obtain the high-quality o-nitroaniline with the product purity more than 99.9% and the light component content less than 0.12%.
Further, the crude o-nitroaniline product used in the step 1) is 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 precipitated, the temperature is maintained for 0.5 to 1 hour, and then the temperature is reduced 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 crude products containing the o-nitroaniline, which adopts a layered melt crystallization process, is suitable for the crude products of the o-nitroaniline (the molar percentage content of the o-nitroaniline is 85-99 percent), does not add solvents, reduces the operation cost, simplifies the operation, is environment-friendly and has no three wastes, and the purity of the obtained o-nitroaniline is more than 99.9 percent.
Detailed description of the preferred embodiments
In order to make the technical scheme of the present invention better understood by those skilled in the art, the present invention will be described in further detail with reference to the best mode
Example 1
Adding 257.42g of crude o-nitroaniline with 88% content into a 300mL layer type melt crystallizer, heating to 72 ℃ until the materials are completely melted into liquid state, and cooling at a cooling rate of 15K/h to a crystallization final temperature of 36 ℃; after which the mother liquor is discharged. Then the temperature is raised to the final sweating temperature of 74 ℃ at the temperature rising rate of 30K/h. And then discharging the sweat, and heating to melt and discharge the material.
The product purity is 99.91%, the light component content is 0.02%, and the single pass yield is 40.04%.
Example 2
Adding 259.44g of crude o-nitroaniline with the content of 90% into a 300mL layer type melt crystallizer, heating to 72 ℃ until the materials are completely melted into a liquid state, and cooling to the final crystallization temperature of 37 ℃ at a cooling rate of 12K/h; after which the mother liquor is discharged. Then the temperature is quickly increased to 73 ℃ at the temperature rising rate of 12K/h. And then discharging the sweat, and heating to melt and discharge the material.
The product purity is 99.95%, the light component content is 0.03%, and the single pass yield is 43.90%.
Example 3
Adding 250.51g of crude o-nitroaniline with the content of 95% into a 300mL layer type melt crystallizer, heating to 72 ℃ until the materials are completely melted into a liquid state, and cooling to the final crystallization temperature of 36 ℃ at a cooling rate of 18K/h; after which the mother liquor is discharged. Then the temperature is quickly increased to 74 ℃ at the temperature rising rate of 15K/h. And then discharging the sweat, and heating to melt and discharge the material.
The product purity is 99.84%, the light component content is 0.04%, and the single pass yield is 46.78%.
Example 4
Adding 244.57g of crude o-nitroaniline with 97% content into a 300mL layer type melt crystallizer, heating to 72 ℃ until the materials are completely melted into a liquid state, and cooling to the final crystallization temperature of 36 ℃ at a cooling rate of 10K/h; after which the mother liquor is discharged. Then the temperature is quickly increased to 72 ℃ at the temperature rising rate of 10K/h. And then discharging the sweat, and heating to melt and discharge the material.
The product purity is 99.95%, the light component content is 0.03%, and the single pass yield is 50.49%.
Example 5
Adding 236.37g of crude o-nitroaniline with 97.5% content into a 300mL layer type melt crystallizer, heating to 72 ℃ until the materials are completely melted into a liquid state, and cooling to the final crystallization temperature of 41 ℃ at a cooling rate of 16K/h; after which the mother liquor is discharged. Then the temperature is quickly increased to 71 ℃ of final sweating temperature at the temperature increasing rate of 16K/h. And then discharging the sweat, and heating to melt and discharge the material.
The purity of the product obtained by the operation is 99.94%, the content of light components is 0.03%, and the single pass yield is 53.53%.
The foregoing is merely exemplary of the present invention, and those skilled in the art should not be considered as limiting the invention, since modifications may be made in the specific embodiments and application scope of the invention in light of the teachings of the present invention.
Claims (3)
1. A method for preparing o-nitroaniline by layered melt crystallization, comprising the following steps:
1) Preheating the material: adding a certain amount of crude o-nitroaniline into a preheated layered melting crystallizer to be heated and melted, wherein the crude o-nitroaniline is obtained by an organic synthesis method, and the molar percentage of the crude o-nitroaniline is 85-99%;
2) Cooling and crystallizing: starting a temperature control program to cool the materials in the crystallizer according to 10-18K/h, wherein the final crystallization temperature is 36-41 ℃;
3) Heating and sweating: after the uncrystallized mother solution is discharged, sweating the crystals, wherein the heating rate is 10-30K/h, the temperature is raised to 71-74 ℃, and after the temperature is kept constant for 0.5-1 h, the sweating solution is discharged;
4) And (3) material melting and discharging: the temperature is raised until the product melts and is then withdrawn from the crystallizer.
2. The method for preparing o-nitroaniline by layered melt crystallization according to claim 1, wherein: layered melt crystallization is either static or dynamic.
3. The method for preparing o-nitroaniline by layered melt crystallization according to claim 1, wherein: and 2) when crystals are separated out, growing the crystals at a constant temperature for 0.5-1 h, and then cooling according to a certain temperature program.
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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 true CN113666831B (en) | 2024-02-06 |
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| 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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