CN112225750A - Permanent violet preparation method with low wastewater discharge - Google Patents
Permanent violet preparation method with low wastewater discharge Download PDFInfo
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- CN112225750A CN112225750A CN202011184459.3A CN202011184459A CN112225750A CN 112225750 A CN112225750 A CN 112225750A CN 202011184459 A CN202011184459 A CN 202011184459A CN 112225750 A CN112225750 A CN 112225750A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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Abstract
The invention discloses a preparation method of permanent violet with low wastewater discharge, relating to the technical field of organic chemistry and specifically comprising four steps of alkylation, nitration, reduction and condensation ring closure. The invention has the technical effects that: the method takes carbazole as a raw material and obtains a permanent violet crude product through alkylation, nitration, reduction and condensation ring closure. In the purification process of the crude nitration product, the use of nekal and a large amount of water washing are avoided, and the solvent for washing can be recycled, so that the discharge of three wastes is reduced; in the purification process of the permanent violet wet crude product, washing by pulling powder water, a large amount of hot water and water is not needed; the wastewater amount is reduced fundamentally from more than 50 tons of wastewater amount per ton of the permanent violet crude product to about 15 tons, the environmental protection cost is reduced, and the market competitiveness is improved.
Description
The technical field is as follows:
the invention relates to the technical field of organic chemistry, in particular to a preparation method of permanent violet with low wastewater discharge.
Background art:
the permanent violet RL is a stable dioxazine high-grade organic pigment with excellent dispersibility, has bright color, high tinting strength, strong migration resistance, excellent sun-proof, acid-proof, alkali-proof and heat-resistant properties, and has wide application fields: can be applied to paint, printing ink, plastics, synthetic and natural rubber, is suitable for coloring the primary pulp of PE, TPP and PE viscose fiber, and is applied to textile coating printing and the like.
Yangpeng, Zhenggang, etc. (environmental science and technology, 2017, 30(6), 33-36) and patent CN110591408A, etc. all report that a large amount of wastewater (50-100 tons of wastewater per ton of crude product of the permanent violet) is generated in the production process of the permanent violet, and mainly concentrate on the washing process of a nitration intermediate and the washing process of the crude product. With the increasing strictness of environmental protection requirements, the reduction of the discharge of three wastes has become a trend.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a preparation method of permanent violet with low wastewater discharge.
The invention relates to a method for preparing permanent violet with low wastewater discharge, wherein the synthetic route of the permanent violet (V) is shown as the following figure:
as a further improvement of the invention, the preparation method of the permanent violet with low wastewater discharge comprises the following steps:
1) alkylation: adding carbazole (I), chlorobenzene, caustic soda flakes and tetrabutylammonium bromide into a reaction kettle, dropwise adding ethyl bromide for reaction, judging that the reaction is finished through HPLC, and washing with a small amount of water to obtain a chlorobenzene solution containing N-ethyl carbazole (II), wherein the molar ratio of carbazole to ethyl bromide to caustic soda flakes to tetrabutylammonium bromide is 1: 1-1.5: 1: 0.05-0.1, and the dosage of chlorobenzene is 2-5 ml/g based on the mass of carbazole;
2) nitration: nitrifying the chlorobenzene solution containing the N-ethyl carbazole (II) obtained in the step 1) by using dilute nitric acid, wherein the molar ratio of the N-ethyl carbazole to the nitric acid is 1: 1-2, the concentration of the dilute nitric acid is 30% -40%, after the HPLC judgment reaction is finished, cooling to 5-10 ℃, naturally crystallizing, centrifugally separating, transferring the obtained solid crude product into a purification kettle, refluxing for 2-8 hours by using a solvent water solution with the weight ratio of 2-6 times, cooling to 5-10 ℃, centrifuging, and leaching by using water to obtain a nitrification intermediate 3-nitro-N-ethyl carbazole (III);
3) reduction: dissolving the nitration intermediate 3-nitro-N-ethyl carbazole (III) obtained in the step 2) with 2-5 g/g of o-dichlorobenzene, then carrying out hydrogenation reduction by using raney nickel as a catalyst, wherein the dosage of the catalyst is 0.05% -0.1%, judging the reaction to be finished by HPLC, and carrying out centrifugal separation to obtain a recovered catalyst and a solution containing 3-amino-N-ethyl carbazole (IV) o-dichlorobenzene;
4) condensation and ring closure: adding tetrachlorobenzoquinone with a molar ratio of 2: 1-2.5 into the 3-amino-N-ethylcarbazole (IV) o-dichlorobenzene solution obtained in the step 3), reacting for 3 hours, adding benzene sulfonyl chloride with a molar ratio of 1: 0.2-0.5 for reaction, judging the reaction completion through HPLC, cooling to 5-10 ℃, centrifuging to obtain a wet filter cake, refluxing the wet filter cake with a solution of solvent water with a weight ratio of 2-6 times for 2-8 hours, cooling to 5-10 ℃, centrifuging, and drying to obtain a permanent violet crude product (V).
As a further improvement of the present invention, the solvent in the aqueous solvent solution in step 2) is one or a combination of more than one of methanol, ethanol and propanol in any proportion.
As a further improvement of the invention, the mass percentage of the solvent content in the solvent water solution in the step 2) is 20-80%.
In a further improvement of the present invention, the solvent in the aqueous solvent solution in step 4) is one or a combination of more than one of methanol, ethanol, propanol, acetonitrile and tetrahydrofuran in any proportion.
As a further improvement of the invention, the mass percentage of the solvent content in the solvent water solution in the step 4) is 20-60%.
The invention has the following technical effects:
in the purification process of the nitration crude product, the use of nekal and a large amount of water washing are avoided, and the solvent for washing can be recycled, so that the discharge of three wastes is reduced;
in the purification process of the permanent violet wet crude product, washing by pulling powder water, a large amount of hot water and water is not needed; the wastewater amount is reduced fundamentally from more than 50 tons of wastewater amount per ton of the permanent violet crude product to about 15 tons, the environmental protection cost is reduced, and the market competitiveness is improved.
Description of the drawings:
FIG. 1 is a HPLC check chart of the content of N-ethylcarbazole (II);
FIG. 2 is a HPLC check chart of the content of 3-nitro-N-ethylcarbazole (III);
FIG. 3 is a HPLC check chart of the 3-amino-N-ethylcarbazole (IV) content;
FIG. 4 is a HPLC detection chart of the content of crude product (V) of permanent violet.
The specific implementation mode is as follows:
example 1
The synthetic route of the permanent violet (V) is shown as the following figure:
the preparation method of the permanent violet with low wastewater discharge comprises the following steps:
1) alkylation: adding carbazole (I), chlorobenzene, caustic soda flakes and tetrabutylammonium bromide into a reaction kettle, dropwise adding ethyl bromide for reaction, judging that the reaction is finished by HPLC, and washing with a small amount of water to obtain a chlorobenzene solution containing N-ethyl carbazole (II), wherein the molar ratio of carbazole to ethyl bromide to caustic soda flakes to tetrabutylammonium bromide is 1:1:1:0.05, and the dosage of chlorobenzene is 2ml/g based on the mass of carbazole;
2) nitration: nitrifying the chlorobenzene solution containing the N-ethyl carbazole (II) obtained in the step 1) by using dilute nitric acid, wherein the molar ratio of the N-ethyl carbazole to the nitric acid is 1: 1-2, the concentration of the dilute nitric acid is 30%, after HPLC (high performance liquid chromatography) judgment reaction is finished, cooling to 5 ℃, naturally crystallizing, centrifugally separating, transferring the obtained solid crude product into a purification kettle, adding a solvent water solution with 2 times of weight ratio (20 mass percent of the solvent) into the purification kettle, refluxing for 2 hours, cooling to 5 ℃, centrifuging, and leaching by using water to obtain a nitrification intermediate 3-nitro-N-ethyl carbazole (III); wherein, the solvent in the solvent water solution is one or the combination of more than one of methanol, ethanol and propanol in any proportion;
3) reduction: dissolving the nitration intermediate 3-nitro-N-ethyl carbazole (III) obtained in the step 2) with 2g/g of o-dichlorobenzene, then carrying out hydrogenation reduction by using raney nickel as a catalyst, wherein the dosage of the catalyst is 0.05%, judging the reaction completion by HPLC, and carrying out centrifugal separation to obtain a recovered catalyst and a solution containing 3-amino-N-ethyl carbazole (IV) o-dichlorobenzene;
4) condensation and ring closure: adding tetrachlorobenzoquinone with the molar ratio of 2:1 into the 3-amino-N-ethylcarbazole (IV) o-dichlorobenzene solution obtained in the step 3), reacting for 3 hours, adding benzene sulfonyl chloride with the molar ratio of 1:0.2 for reaction, judging the reaction completion through HPLC, cooling to 5 ℃, and centrifuging to obtain a wet filter cake; adding a solvent water solution with the weight of 2 times (the mass percentage of the solvent is 20%) into the wet filter cake, refluxing for 2 hours, cooling to 5 ℃, centrifuging and drying to obtain a permanent violet crude product (V); wherein the solvent in the solvent water solution is a mixture of propanol, acetonitrile and tetrahydrofuran, and the mass ratio of the propanol, the acetonitrile and the tetrahydrofuran is 1:2: 3.
Example 2
The synthetic route of the permanent violet (V) is shown as the following figure:
the preparation method of the permanent violet with low wastewater discharge comprises the following steps:
1) alkylation: adding carbazole (I), chlorobenzene, caustic soda flakes and tetrabutylammonium bromide into a reaction kettle, dropwise adding ethyl bromide for reaction, judging that the reaction is finished by HPLC, and washing with a small amount of water to obtain a chlorobenzene solution containing N-ethyl carbazole (II), wherein the molar ratio of carbazole to ethyl bromide to caustic soda flakes to tetrabutylammonium bromide is 1:1.5:1:0.1, and the dosage of chlorobenzene is 5ml/g based on the mass of carbazole;
2) nitration: nitrifying the chlorobenzene solution containing the N-ethyl carbazole (II) obtained in the step 1) by using dilute nitric acid, wherein the molar ratio of the N-ethyl carbazole to the nitric acid is 1:2, the concentration of the dilute nitric acid is 40%, after HPLC (high performance liquid chromatography) judgment reaction is finished, cooling to 10 ℃, naturally crystallizing, centrifugally separating, transferring the obtained solid crude product into a purification kettle, adding a solvent water solution with 6 times of weight ratio (80 mass percent of the solvent) into the purification kettle, refluxing for 8 hours, cooling to 10 ℃, centrifuging, and leaching by using water to obtain a nitrification intermediate 3-nitro-N-ethyl carbazole (III); wherein, the solvent in the solvent water solution is one or the combination of more than one of methanol, ethanol and propanol in any proportion;
3) reduction: dissolving the nitration intermediate 3-nitro-N-ethyl carbazole (III) obtained in the step 2) by using 5g/g of o-dichlorobenzene, then using raney nickel as a catalyst for hydrogenation reduction, wherein the dosage of the catalyst is 0.1%, judging the reaction completion by HPLC, and performing centrifugal separation to obtain a recovered catalyst and a solution containing 3-amino-N-ethyl carbazole (IV) o-dichlorobenzene;
4) condensation and ring closure: adding tetrachlorobenzoquinone with a molar ratio of 2:2.5 into the 3-amino-N-ethylcarbazole (IV) o-dichlorobenzene solution obtained in the step 3), reacting for 3 hours, adding benzene sulfonyl chloride with a molar ratio of 1:0.5 for reaction, judging the reaction completion through HPLC, cooling to 10 ℃, centrifuging to obtain a wet filter cake, adding a solvent water solution with a weight ratio of 6 times (the mass percentage of the solvent is 60%) into the wet filter cake, refluxing for 8 hours, cooling to 10 ℃, centrifuging, and drying to obtain a permanent violet crude product (V); wherein the solvent in the solvent aqueous solution is a mixture of ethanol and propanol, and the mass ratio of the ethanol to the propanol is 5: 2.
Example 3
The synthetic route of the permanent violet (V) is shown as the following figure:
the preparation method of the permanent violet with low wastewater discharge comprises the following steps:
1) alkylation: adding carbazole (I), chlorobenzene, caustic soda flakes and tetrabutylammonium bromide into a reaction kettle, dropwise adding ethyl bromide for reaction, judging that the reaction is finished by HPLC, and washing with a small amount of water to obtain a chlorobenzene phase containing N-ethyl carbazole (II), wherein the molar ratio of carbazole to ethyl bromide to caustic soda flakes to tetrabutylammonium bromide is 1:1.2:1:0.08, and the dosage of chlorobenzene is 3ml/g based on the mass of carbazole;
2) nitration: nitrifying the chlorobenzene solution containing the N-ethyl carbazole (II) obtained in the step 1) by using dilute nitric acid, wherein the molar ratio of the N-ethyl carbazole to the nitric acid is 1:1.5, the concentration of the dilute nitric acid is 35%, after HPLC (high performance liquid chromatography) judgment reaction is finished, cooling to 8 ℃, naturally crystallizing, centrifugally separating, transferring the obtained solid crude product into a purification kettle, adding 4 times of solvent aqueous solution in weight ratio (the mass percentage of the solvent is 50%) into the purification kettle, refluxing for 5 hours, cooling to 8 ℃, centrifuging, and leaching by using water to obtain a nitrification intermediate 3-nitro-N-ethyl carbazole (III); wherein, the solvent in the solvent water solution is one or the combination of more than one of methanol, ethanol and propanol in any proportion;
3) reduction: dissolving the nitration intermediate 3-nitro-N-ethyl carbazole (III) obtained in the step 2) by using 3g/g of o-dichlorobenzene, then using raney nickel as a catalyst for hydrogenation reduction, wherein the dosage of the catalyst is 0.08%, judging the reaction completion by HPLC, and performing centrifugal separation to obtain a recovered catalyst and a solution containing 3-amino-N-ethyl carbazole (IV) o-dichlorobenzene;
4) condensation and ring closure: adding tetrachlorobenzoquinone with a molar ratio of 2:2 into the 3-amino-N-ethylcarbazole (IV) o-dichlorobenzene solution obtained in the step 3), reacting for 3 hours, adding benzenesulfonyl chloride with a molar ratio of 1:0.3 for reaction, judging the reaction completion through HPLC, cooling to 8 ℃, centrifuging to obtain a wet filter cake, adding a solvent water solution with a weight ratio of 4 times (the mass percentage of the solvent is 40%) into the wet filter cake, refluxing for 5 hours, cooling to 8 ℃, centrifuging, and drying to obtain a permanent violet crude product (V), wherein the content: 97.6 percent; wherein the solvent in the aqueous solvent solution is methanol.
In the above method, HPLC (high performance liquid chromatography) detection selects liquid chromatograph LC5090 of seiku analysis instruments ltd, and detects the intermediates N-ethylcarbazole (ii), 3-nitro-N-ethylcarbazole (iii), 3-amino-N-ethylcarbazole (iv) and permanent violet crude product (v) prepared by the method of example 3, under the following detection conditions: a chromatographic column; c18, 4.6X 250 mm; column temperature: 30 ℃; detection wavelength: 240 nm; flow rate: 1.0 ml/min; mobile phase: acetonitrile: keeping the temperature for 30 minutes when the water is 80:20, and detecting the results as shown in figures 1-4.
The following compares the wastewater usage of the conventional permanent violet technology and the process method of the embodiment 3 of the invention, and the comparison results are shown in table 1, when the usage is converted into the usage of crude products per ton:
TABLE 1 comparison table of waste water consumption of current permanent violet technology and technology of the present invention
In the existing permanent violet technology, the water consumption of the nitration part and the crude product washing part is large, wherein the nitration intermediate is washed by 2 percent de-powdering solution for completely washing the residual solvent, and then the residual de-powdering solution is washed by clean water; the purpose of washing the crude product of the permanent violet by using a 3% nekal solution is to completely wash the residual solvent, and then, the nekal residue and the salt residue are rinsed by using hot water, so that the generated wastewater is high in quantity. In table 1, the water usage in the steps of nitration and crude product washing in the permanent violet production process in the prior art is listed, and if the water usage is converted to the crude product usage of each ton as a reference, the water usage of the 2% nekal water solution is 5 tons when the nitration intermediate is produced, and the water usage of the clean water washing is 10 tons; when the permanent violet crude product is produced, if the water consumption of the 3.0% nekal aqueous solution is 10 tons, the water consumption for hot water rinsing is 25 tons. The method of the invention is used for purification, and the water consumption of the nitration part is 5 tons; the water consumption of the crude product portion is 10 tons.
Claims (6)
1. The preparation method of the permanent violet with low wastewater discharge is characterized in that the synthetic route of the permanent violet (V) is shown as the following figure:
2. the method for preparing permanent violet with low wastewater discharge according to claim 1, which is characterized by comprising the following steps:
1) alkylation: adding carbazole (I), chlorobenzene, caustic soda flakes and tetrabutylammonium bromide into a reaction kettle, dropwise adding ethyl bromide for reaction, judging that the reaction is finished through HPLC, and washing with a small amount of water to obtain a chlorobenzene solution containing N-ethyl carbazole (II), wherein the molar ratio of carbazole to ethyl bromide to caustic soda flakes to tetrabutylammonium bromide is 1: 1-1.5: 1: 0.05-0.1, and the dosage of chlorobenzene is 2-5 ml/g based on the mass of carbazole;
2) nitration: nitrifying the chlorobenzene solution containing the N-ethyl carbazole (II) obtained in the step 1) by using dilute nitric acid, wherein the molar ratio of the N-ethyl carbazole to the nitric acid is 1: 1-2, the concentration of the dilute nitric acid is 30% -40%, after the HPLC judgment reaction is finished, cooling to 5-10 ℃, naturally crystallizing, centrifugally separating, transferring the obtained solid crude product into a purification kettle, refluxing for 2-8 hours by using a solvent water solution with the weight ratio of 2-6 times, cooling to 5-10 ℃, centrifuging, and leaching by using water to obtain a nitrification intermediate 3-nitro-N-ethyl carbazole (III);
3) reduction: dissolving the nitration intermediate 3-nitro-N-ethyl carbazole (III) obtained in the step 2) with 2-5 g/g of o-dichlorobenzene, then carrying out hydrogenation reduction by using raney nickel as a catalyst, wherein the dosage of the catalyst is 0.05% -0.1%, judging the reaction to be finished by HPLC, and carrying out centrifugal separation to obtain a recovered catalyst and a solution containing 3-amino-N-ethyl carbazole (IV) o-dichlorobenzene;
4) condensation and ring closure: adding tetrachlorobenzoquinone with a molar ratio of 2: 1-2.5 into the 3-amino-N-ethylcarbazole (IV) o-dichlorobenzene solution obtained in the step 3), reacting for 3 hours, adding benzene sulfonyl chloride with a molar ratio of 1: 0.2-0.5 for reaction, judging the reaction completion through HPLC, cooling to 5-10 ℃, centrifuging to obtain a wet filter cake, refluxing the wet filter cake with a solution of solvent water with a weight ratio of 2-6 times for 2-8 hours, cooling to 5-10 ℃, centrifuging, and drying to obtain a permanent violet crude product (V).
3. The method for preparing permanent violet with low wastewater discharge according to claim 1, wherein the solvent in the aqueous solvent solution in the step 2) is one or more of methanol, ethanol and propanol.
4. The method for preparing permanent violet with low wastewater discharge according to claim 1, wherein the solvent content of the solvent aqueous solution in the step 2) is 20-80% by mass.
5. The method for preparing low wastewater discharge permanent violet according to claim 1, wherein the solvent in the aqueous solvent solution in the step 4) is one or more of methanol, ethanol, propanol, acetonitrile and tetrahydrofuran.
6. The method for preparing permanent violet with low wastewater discharge according to claim 1, wherein the solvent content of the solvent aqueous solution in the step 4) is 20-60% by mass.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724700A (en) * | 2021-01-22 | 2021-04-30 | 内蒙古彩晶新材料科技有限公司 | Process for synthesizing permanent violet RL by one-pot method |
| CN116715975A (en) * | 2023-05-05 | 2023-09-08 | 中钞油墨有限公司 | Preparation method and application of permanent violet |
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| CN116715975A (en) * | 2023-05-05 | 2023-09-08 | 中钞油墨有限公司 | Preparation method and application of permanent violet |
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Application publication date: 20210115 |