CN106883164A - The extraction process of 3 nitro N ethyl carbazoles in nitrification waste residue - Google Patents
The extraction process of 3 nitro N ethyl carbazoles in nitrification waste residue Download PDFInfo
- Publication number
- CN106883164A CN106883164A CN201710089208.9A CN201710089208A CN106883164A CN 106883164 A CN106883164 A CN 106883164A CN 201710089208 A CN201710089208 A CN 201710089208A CN 106883164 A CN106883164 A CN 106883164A
- Authority
- CN
- China
- Prior art keywords
- waste residue
- reaction kettle
- nitro
- steam
- ethyl carbazoles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of extraction process for nitrifying 3 nitro N ethyl carbazoles in waste residue, the step such as including distillation, purification, recycling design and crystallization, to waste residue in 3 nitro N ethyl carbazoles extracted, purified.Extraction process of the invention is simple, organic efficiency is high, the nitrocarbazole of N ethyls 3 in waste residue can be carried out effectively extracting, purified so that the yield of nitrification brings up to 97 ~ 98%, and can reduce waste residue, the yield of the permanent violet RL crude products of subsequent production is further improved, production cost is reduced.
Description
Technical field
The present invention relates to permanent violet production technical field, and in particular to 3- nitro-N- ethyl carbazoles in one kind nitrification waste residue
Extraction process.
Background technology
Permanent violet RL crude products are, with carbazole as initiation material, to be obtained with bromoethane reaction in the presence of a phase transfer catalyst
N- ethyl carbazoles, are nitrified with dust technology in chlorobenzene solvent and obtain 3- nitro-N- ethyl carbazoles, and nitro compounds are after carrying out reduction with four
Chloranil condensation, ring-closure reaction obtain permanent violet RL crude products, wherein the reaction yield for nitrifying is 90% or so.To N- ethyl carbazoles
Nitration reaction be analyzed, the reason for cause the step reaction yield not high：1st, react incomplete, there are part N- ethyl carbazoles not have
There is participation to react；2nd, reaction terminates during rear portion of product rests on reaction dissolvent.During recycling design, N- ethyl carbazoles
Nitration product with distillation waste residue mix, if can have a kind of effective method that N- ethyl -3- nitre is reclaimed from the waste residue
Base carbazole, then can not only improve the synthesis yield of permanent violet crude product, and the waste residue of synthesis permanent violet crude product can be reduced.
The content of the invention
It is high it is an object of the invention to provide a kind of process is simple, organic efficiency to solve the deficiencies in the prior art, and can
Waste residue is reduced, the extraction process of 3- nitro-N- ethyl carbazoles in the nitrification waste residue of the yield for improving nitration reaction.
In order to realize above-mentioned target, the present invention is adopted the following technical scheme that：
The extraction process of 3- nitro-N- ethyl carbazoles, comprises the following steps in nitrification waste residue：
S1, distillation：The mixed solution that N- ethyl carbazoles occur after nitration reaction is distilled, chlorobenzene is reclaimed, after distillation terminates,
Vinasse and residue enter stillpot, after cooling water dividing, collect the waste residue that precipitation is obtained；
S2, purification：To solvent is added in purified reaction kettle, it is slowly added to nitrify waste residue, closes kettle cover, opens purified reaction kettle folder
Set steam valve, is slowly warming up to 50 ~ 75 DEG C by purified reaction kettle, steam off, purified reaction kettle chuck waste heat make kettle temperature after
, progressively there is solvent evaporation phenomenon in height of continuing rising, and gasifying solvent is cooled down by condenser, reflux state occurs, and the crack steam that opens adds
Heat, keeps system to be in backflow；
S3, recycling design：After backflow certain hour, steam off stops stirring, stands 30min, then shifts supernatant liquor
To crystallization reaction kettle；Purified reaction kettle starts stirring, and opens steam, reclaims remaining solvent；
S4, crystallization：Crystallization reaction kettle opens stirring, opens the heating of crystallization reaction kettle jacket steam, reclaims out inventory 50% ~ 80%
Solvent, then material is cooled to less than 35 DEG C in kettle, the material for crystallizing out, and is put into suction filtration tank filtering, and Washing of Filter Cake drains,
3- nitro-N- the ethyl carbazoles for being extracted.
Preferably, step S0, pretreatment are provided with before abovementioned steps S1：Occur to N- ethyl carbazoles mixed after nitration reaction
Closing solution carries out centrifuge washing pretreatment.
More preferably, the solvent selected in abovementioned steps S2 is ethanol, and the mass ratio for nitrifying waste residue and ethanol is 1：（7~
10）.
It is highly preferred that the solvent selected in abovementioned steps S2 is chlorobenzene, the mass ratio of nitrification waste residue and chlorobenzene is 1：（2.8
~3.2）.
It is further preferred that the steam pressure of purified reaction kettle is 0.2~0.25Mpa in abovementioned steps S2.
The present invention is advantageous in that：Extraction process of the invention is simple, organic efficiency is high, can be to the N- second in waste residue
Base -3- nitrocarbazoles effectively extract, purified so that the yield of nitrification brings up to 97 ~ 98%, and can reduce waste residue, further
The yield of the permanent violet RL crude products of subsequent production is improved, production cost is reduced.
Specific embodiment
Make specific introduction to the present invention below in conjunction with specific embodiment.
Embodiment 1
The extraction process of 3- nitro-N- ethyl carbazoles, comprises the following steps that in nitrification waste residue：
1st, after N- ethyl carbazoles are nitrified, material enters collection settling tank, removal by centrifuge washing, mother liquor and early stage mother liquor
After moisture, mother liquor is transferred to distillation still, and Distillation recovery goes out the solvent of nitrification, and then bottoms and raffinate enter stillpot, through cold
But after dividing water, the waste residue that precipitation is obtained is collected；
2nd, the ethanol 2400kg of concentration more than 92% is added in purified reaction kettle, then slow input nitrification waste residue 300kg, throws
After good, closing kettle cover opens purified reaction kettle jacket steam, and 0.2 ~ 0.25MPa of steam pressure in control kettle will slowly be purified anti-
Temperature in the kettle is answered to rise to 60 ~ 62 DEG C；
3rd, the stirring of purified reaction kettle is opened, block nitrification waste residue is progressively stirred, after stirring, continuously open stirring, work as temperature
When degree is warmed up to 64 ~ 66 DEG C, steam off valve；
4th, in the presence of waste heat, purified reaction kettle temperature is stepped up, ethanol evaporating in kettle, and boil-off flows back by heat exchanger
It is crack to open steam to purified reaction kettle, keep 2 ~ 3h of purification kettle backflow；
5th, backflow terminates, and steam off closes stirring, stands 30min；
6th, crystallization reaction kettle vacuum is opened, the supernatant liquor in purified reaction kettle is transferred in crystallization reaction kettle, transfer terminates,
Purified reaction kettle opens stirring and steam, and ethanol distillation remaining in kettle is reclaimed, and can directly be applied mechanically；
7th, stirring and steam heating are opened in crystallization reaction kettle, 1100 ~ 1200kg ethanol is reclaimed, steam, opening clamp is then shut off
Jacket water, 30 ~ 35 DEG C are cooled to by kettle temperature, and now 3- nitros-N- ethyl carbazoles are crystallized out in ethanol, keep temperature
Degree continues to stir 30min；
8 and then material is put into suction filtration tank, after draining, ethanol mother liquor is transferred to purified reaction kettle and applies mechanically, after typically applying mechanically 3 times
Distillation still need to be entered and reclaim purification；
9th, filter cake is washed with water, and then draining detection level after blending, solid content is used for the production in rear road.
Embodiment 2：
1st, after N- ethyl carbazoles are nitrified, material enters collection settling tank, removal by centrifuge washing, mother liquor and early stage mother liquor
After moisture, mother liquor is transferred to distillation still, and Distillation recovery goes out the solvent of nitrification, and then bottoms and raffinate enter stillpot, through cold
But after dividing water, the waste residue that precipitation is obtained is collected;
2nd, the chlorobenzene 900kg of concentration more than 96% is added in purified reaction kettle, then slow input nitrification waste residue 300kg, throws
Afterwards, kettle cover is closed, purified reaction kettle jacket steam, 0.2 ~ 0.25MPa of steam pressure in control kettle, slowly by purification kettle is opened
Temperature rises to 60 ~ 62 DEG C；
3rd, the stirring of purified reaction kettle is opened, block nitrification waste residue is progressively stirred, after stirring, continuously open stirring, work as temperature
When degree is warmed up to 80 ~ 82 DEG C, steam off valve；
4th, in the presence of waste heat, purified reaction kettle temperature is stepped up, chlorobenzene and the waste residue vaporization of band water azeotropic, vaporization in itself in kettle
Steam is back in purification kettle by heat exchanger, crack to open steam, keeps 1 ~ 1.5h of purification kettle backflow；
5th, backflow terminates, and steam off closes stirring, stands 30min, and kettle temperature is reduced to 80 ~ 82 by crack chuck cooling water
℃；
6th, crystallization reaction kettle vacuum is opened, the supernatant liquor in purified reaction kettle is transferred in crystallization reaction kettle, transfer terminates,
Purified reaction kettle opens stirring and steam, and chlorobenzene Distillation recovery remaining in kettle can be applied mechanically directly after point water；
7th, stirring and steam heating are opened in crystallization reaction kettle, 650 ~ 750kg chlorobenzenes are reclaimed, steam is then shut off, chuck is opened
Cooling water, 20 ~ 25 DEG C are cooled to by kettle temperature, and now 3- nitros-N- ethyl carbazoles are crystallized out in chlorobenzene, close stirring
Keeping temperature maintains 60 min；
8 and then material is put into suction filtration tank, after draining, chlorobenzene mother liquor is transferred to purification kettle and applies mechanically, need to be with after typically applying mechanically 1 time
Purification kettle waste residue reclaims chlorobenzene together；
9th, filter cake is transferred to centrifuge pull open powder solution, water washing, after then detection level, solid content are used for after drying blending
The production in road.
After carrying out nitration reaction under the same conditions as example 1, waste residue is not extracted, the 3- nitros for obtaining-
N- ethyl carbazoles are designated as comparative example 1.3- nitro-N- the ethyl carbazoles obtained in calculating embodiment 1, embodiment 2 and comparative example 1
Yield and purity, as a result such as following table：
| Embodiment 1 | Embodiment 2 | Comparative example 1 | |
| Yield | 98% | 97.5% | 78.6% |
| Purity | 97.4% | 97.3% | 96.1% |
By experimental result, extraction process of the invention is extracted to waste residue, purified on the basis of original yield,
May be such that the yield of nitrification brings up to 97 ~ 98%, and the purity of 3- nitro N- ethyl carbazoles can reach more than 97%, be above into
The comparative example 1 of row waste residue purification, after the 3- nitro N- ethyl carbazoles for obtaining can be through reduction reaction, condensation, closed loop for rear road
Reaction, and obtain permanent violet RL crude products.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Necessarily refer to identical embodiment or example.And, the specific features of description, structure, material or feature can be any
One or more embodiments or example in combine in an appropriate manner.
The basic principles, principal features and advantages of the present invention have been shown and described above.The technical staff of the industry should
Understand, the invention is not limited in any way for above-described embodiment, it is all to be obtained by the way of equivalent or equivalent transformation
Technical scheme, all falls within protection scope of the present invention.
Claims (5)
1. the extraction process of 3- nitro-N- ethyl carbazoles in waste residue is nitrified, it is characterised in that comprised the following steps：
S1, distillation：The mixed solution that N- ethyl carbazoles occur after nitration reaction is distilled, chlorobenzene is reclaimed, after distillation terminates,
Vinasse and residue enter stillpot, after cooling water dividing, collect the waste residue that precipitation is obtained；
S2, purification：To solvent is added in purified reaction kettle, it is slowly added to nitrify waste residue, closes kettle cover, opens purified reaction kettle folder
Set steam valve, is slowly warming up to 50 ~ 75 DEG C by purified reaction kettle, steam off, purified reaction kettle chuck waste heat make kettle temperature after
, progressively there is solvent evaporation phenomenon in height of continuing rising, and gasifying solvent is cooled down by condenser, reflux state occurs, and the crack steam that opens adds
Heat, keeps system to be in backflow；
S3, recycling design：After backflow certain hour, steam off stops stirring, stands 30min, then shifts supernatant liquor
To crystallization reaction kettle；Purified reaction kettle starts stirring, and opens steam, reclaims remaining solvent；
S4, crystallization：Crystallization reaction kettle opens stirring, opens the heating of crystallization reaction kettle jacket steam, reclaims out inventory 50% ~ 80%
Solvent, then material is cooled to less than 35 DEG C in kettle, the material for crystallizing out, and is put into suction filtration tank filtering, and Washing of Filter Cake drains,
3- nitro-N- the ethyl carbazoles for being extracted.
2. it is according to claim 1 nitrification waste residue in 3- nitro-N- ethyl carbazoles extraction process, it is characterised in that institute
Step S0, pretreatment are provided with before stating step S1：Centrifugation is carried out to the mixed solution that N- ethyl carbazoles occur after nitration reaction to wash
Wash pretreatment.
3. it is according to claim 1 nitrification waste residue in 3- nitro-N- ethyl carbazoles extraction process, it is characterised in that institute
It is ethanol to state the solvent selected in step S2, and the mass ratio for nitrifying waste residue and ethanol is 1：（7~10）.
4. it is according to claim 1 nitrification waste residue in 3- nitro-N- ethyl carbazoles extraction process, it is characterised in that institute
It is chlorobenzene to state the solvent selected in step S2, and the mass ratio for nitrifying waste residue and chlorobenzene is 1：（2.8~3.2）.
5. it is according to claim 1 nitrification waste residue in 3- nitro-N- ethyl carbazoles extraction process, it is characterised in that institute
The steam pressure for stating purified reaction kettle in step S2 is 0.2~0.25Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710089208.9A CN106883164A (en) | 2017-02-20 | 2017-02-20 | The extraction process of 3 nitro N ethyl carbazoles in nitrification waste residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710089208.9A CN106883164A (en) | 2017-02-20 | 2017-02-20 | The extraction process of 3 nitro N ethyl carbazoles in nitrification waste residue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106883164A true CN106883164A (en) | 2017-06-23 |
Family
ID=59178901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710089208.9A Pending CN106883164A (en) | 2017-02-20 | 2017-02-20 | The extraction process of 3 nitro N ethyl carbazoles in nitrification waste residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106883164A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225750A (en) * | 2020-10-30 | 2021-01-15 | 安达市多森新材料科技有限公司 | Permanent violet preparation method with low wastewater discharge |
| CN115232061A (en) * | 2021-09-18 | 2022-10-25 | 山西紫罗蓝新材料科技有限公司 | Extraction process of 3-nitro-9-ethyl carbazole crude product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254117A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Method for extracting nitration product from N-ethyl carbazole nitration solvent distillation residue |
| CN103254116A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Preparation method of 3-nitro-N-ethyl carbazole |
| CN103497107A (en) * | 2013-09-23 | 2014-01-08 | 杨洪永 | Dinitro substance prepared by using industrial waste and processing and producing method thereof |
-
2017
- 2017-02-20 CN CN201710089208.9A patent/CN106883164A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254117A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Method for extracting nitration product from N-ethyl carbazole nitration solvent distillation residue |
| CN103254116A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Preparation method of 3-nitro-N-ethyl carbazole |
| CN103497107A (en) * | 2013-09-23 | 2014-01-08 | 杨洪永 | Dinitro substance prepared by using industrial waste and processing and producing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王璇，等: "提高颜料永固紫粗品合成收率的一种方法", 《上海染料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225750A (en) * | 2020-10-30 | 2021-01-15 | 安达市多森新材料科技有限公司 | Permanent violet preparation method with low wastewater discharge |
| CN115232061A (en) * | 2021-09-18 | 2022-10-25 | 山西紫罗蓝新材料科技有限公司 | Extraction process of 3-nitro-9-ethyl carbazole crude product |
| CN115232061B (en) * | 2021-09-18 | 2024-01-30 | 山西紫罗蓝新材料科技有限公司 | Extraction process of 3-nitro-9-ethylcarbazole crude product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022156623A1 (en) | Comprehensive utilization process of pta oxidation residue | |
| CN101693701A (en) | Purification process for vulcanization accelerator 2-mercaptobenzothiazole | |
| CN109776482A (en) | The method of the continuous preparation high-purity lactide of industrialization | |
| CN102781913A (en) | Method of manufacturing epsilon-caprolactam | |
| CN106883164A (en) | The extraction process of 3 nitro N ethyl carbazoles in nitrification waste residue | |
| CN111718391B (en) | Residual oil treatment method for recovering sterol | |
| CN103396413A (en) | Preparation method of nifuratel | |
| CN109867607B (en) | Method for continuously recovering product from pendimethalin residue | |
| WO2022233040A1 (en) | Method for purifying sucralose-6-ethyl ester | |
| CN108675919A (en) | A kind of method that double trimethylolpropane is extracted in trimethylolpropane heavy constituent | |
| CN103787820B (en) | A kind of method reclaiming toluene from the mother liquor producing polypropylene nucleater | |
| CN210826005U (en) | 1, 2-benzisothiazole-3-ketone production system | |
| CN108409536B (en) | Method for recovering pentaerythritol from alcohol hydrolysis liquid filter residue of antioxidant 1010 mother liquor | |
| WO1994019303A1 (en) | A dephenolization process for obtaining ultrapure polycarbonate grade bisphenol a | |
| CN112266329A (en) | Efficient production method of bromhexine hydrochloride | |
| CN101580509B (en) | Method for producing electronic-grade pyromellitic dianhydride from secondary trapped coarse anhydride | |
| CN106316875A (en) | Method for recycling N,N-dimethylformamide from alprazolam intermediate refined mother liquor | |
| CN204996158U (en) | System for recovering solvent in trimethylolpropane light component | |
| CN109503332B (en) | Method for decomposing and recycling sodium phenolate by using salicylic acid residues | |
| CN114591178B (en) | ODA production process and production system | |
| CN115301173B (en) | Preparation device and method of sodium tert-butoxide | |
| CN111995586B (en) | Synthetic method of agricultural herbicide | |
| CN105152875A (en) | Method for recovering ditrimethylolpropane from trimethylolpropane raffinate | |
| CN115141160A (en) | Preparation method of 2-thiazolidinone | |
| CN116003353A (en) | Method for recovering andrographolide from crystallization mother liquor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170623 |
|
| RJ01 | Rejection of invention patent application after publication |