CN100999472A - Utilizing process of nitrobenzene distilation redsdue - Google Patents
Utilizing process of nitrobenzene distilation redsdue Download PDFInfo
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- CN100999472A CN100999472A CN 200610160044 CN200610160044A CN100999472A CN 100999472 A CN100999472 A CN 100999472A CN 200610160044 CN200610160044 CN 200610160044 CN 200610160044 A CN200610160044 A CN 200610160044A CN 100999472 A CN100999472 A CN 100999472A
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- nitrobenzene
- redsdue
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Abstract
This invention relates to a utilization method of nitrobenzene distillation residues; belong to the field of chemical technologies organic synthesis intermediate areas. It takes nitrobenzene distillation residues remaining as raw materials, and the mixture of ethyl acetate and water as solvent, to dissolve the above residues; Warming up to a certain temperature, by adding activated carbon, adsorbing and bleaching the material resin of residue, and then leaching ( spent activated carbon can be repeated use after regenerated, or discard) ; atmospheric distillation of the filtrate, to be steamed ethyl acetate, cooling and crystallization, leaching, then obtain crude meta-dinitro-benzent; then make rough meta-dinitro-benzent through re-crystallization, drying, and can be gain meta-dinitro-benzent. Steamed ethyl acetate solvent can be reused. There are many characteristics of this invention: process is simple, easy to operate, and the low cost of production, good quality products, the use of waste, and have both environmental benefits and economic benefits.
Description
Technical field
The invention belongs to the substituted arene synthesis technical field, particularly a kind of nitrobenzene distilation redsdue utilizes method.
Background technology
During industrial production oil of mirbane, oil of mirbane distills last residue and mainly contains the resinous impurities that is produced in the by product Meta-dinitrobenzene that produced in the oil of mirbane production process and the still-process.Oil of mirbane manufacturer all carries out burning disposal with these residues as waste at present, does like this and has both wasted resource, causes environmental pollution again easily.And Meta-dinitrobenzene is the intermediate of organic synthesis, be widely used in dyestuff, agricultural chemicals, medicine and other fields, it is a raw material with oil of mirbane and nitration mixture (nitric acid and sulfuric acid), make the Meta-dinitrobenzene crude product by second nitrification reaction, make the product Meta-dinitrobenzene through further operations such as separation, recrystallization.This method is suitable for large-scale commercial production, but has shortcomings such as production cost is higher, the production cycle is long, cost of equipment is high, spent acid difficult treatment.
Summary of the invention
The object of the invention is to provide a kind of method of utilizing of nitrobenzene distilation redsdue, promptly utilizes oil of mirbane to distill last residue and prepares Meta-dinitrobenzene.
For achieving the above object, the present invention adopts following technical scheme: nitrobenzene distilation redsdue utilize method, distilling last residue with oil of mirbane is raw material, by dissolving, decolouring, crystallisation step, the preparation Meta-dinitrobenzene.
Dissolving step is a solvent with ethyl acetate and water mixed liquid, and the volume ratio=85%-200% of ethyl acetate and water, solvent adding amount are the 100%-400% of nitrobenzene distilation redsdue weight; The decolouring step is discoloring agent with the gac, adds the gac of nitrobenzene distilation redsdue weight 5%-10% in the mixed solution of nitrobenzene distilation redsdue and solvent.
Decolorization is carried out soaking time 20-60min under 46-76 ℃ of stirring; Suction filtration then, filtrate steaming is removed the ethyl acetate postcooling.
The filtrate still-process is at normal pressure, liquidus temperature 71-92 ℃, add under the condition of water of nitrobenzene distilation redsdue weight 100-300% and carry out simultaneously, reclaim ethyl acetate, during to 82 ℃ of gas phase recovered temperatures, distillation finishes, in air, lower the temperature naturally earlier and be cooled to liquidus temperature 82--77 ℃, use the cold water crystallisation by cooling then instead to room temperature, suction filtration obtains the Meta-dinitrobenzene crude product.
The Meta-dinitrobenzene crude product adds its weight 3-8 water doubly, is warming up to 82-95 ℃ of insulation 20--120min, is cooled to 82--77 ℃ naturally, is cooled to room temperature with cold water again, suction filtration, and dry 30--120min under 50--80 ℃ gets the product Meta-dinitrobenzene.
Among the present invention, be raw material with nitrobenzene distilation redsdue (waste material), with ethyl acetate and water mixed liquid as solvent, with above-mentioned residue dissolving; After being warming up to certain temperature, add gac, resinous substance in the residue is carried out adsorption bleaching, suction filtration then, waste active carbon are reusable or discard through the regeneration back; Gained filtrate is distilled under normal pressure, and after waiting to steam ethyl acetate, cooling, crystallization, suction filtration promptly get the Meta-dinitrobenzene crude product; Again the Meta-dinitrobenzene crude product is carried out recrystallization, drying, can obtain the product Meta-dinitrobenzene.The solvent ethyl acetate that steams can recycle.With the Meta-dinitrobenzene of the present invention preparation, with the purity difference, for faint yellow to near-white needle crystal.The fusing point of measuring product with WRS-1 numeral fusing point instrument (Shanghai Physics Optics Instrument Factory production) meets 89.57-90.02 ℃ of bibliographical information value; Record the FT-IR spectrogram of product with U.S.'s AVATAR360 Fourier transformation infrared spectrometer, with standard infrared spectrogram basically identical.Prove that prepared product is a Meta-dinitrobenzene.
Technical process of the present invention is simple, easy handling, and the Meta-dinitrobenzene production cost is low, and good product quality not only produces good benefits in environment but also bring good economic benefit.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the FT-IR spectrogram of embodiment 2 gained samples.
Embodiment
Embodiment 1: under the room temperature in the four-necked bottle that electric mixer, reflux exchanger, thermometer and dropping funnel are installed, add ethyl acetate 200ml, water 100ml, start agitator, the back adding 110g oil of mirbane that stirs distills last residue, 6g powdered carbon, be warming up to 64-66 ℃, behind the insulation 30min, when being cooled to 30 ℃, suction filtration discards waste active carbon (or reusing after treatment).Above-mentioned filtrate is added in the four neck flasks, open to stir heat up, during to 71 ℃ of 76 ℃ of liquidus temperatures, gas phase temperature, beginning has overhead product; Open the dropping funnel valve slowly add water (about 150ml) this moment in flask, stops to distill when continuing to be distilled to 82 ℃ of 92 ℃ of liquidus temperatures, gas phase recovered temperature, steams ethyl acetate 178ml altogether; The interior material of flask is lowered the temperature naturally, when liquidus temperature is reduced to 82 ℃, begin to occur the Meta-dinitrobenzene crystallization; Use cold water instead and be cooled to 25 ℃, suction filtration obtains faint yellow Meta-dinitrobenzene crude product 59.5g.Above-mentioned Meta-dinitrobenzene crude product is added in the four clean neck flasks, add water 300ml, open and stir and heating unit, be warming up to 90 ℃, behind the insulation 10min, be cooled to 82 ℃ naturally; Use cold water instead and be cooled to 25 ℃, suction filtration at 75 ℃ of dry 1h, obtains near-white Meta-dinitrobenzene needle crystal 54.7g, and total recovery is 49.7%; Porphyrize promptly gets to measure and uses the Meta-dinitrobenzene product.The fusing point of measuring product with WRS-1 numeral fusing point instrument (Shanghai Physics Optics Instrument Factory production) is 89.8 ℃, meets 89.57-90.02 ℃ of bibliographical information value; Record the FT-IR spectrogram of product with U.S.'s AVATAR360 Fourier transformation infrared spectrometer, with standard infrared spectrogram basically identical.
Embodiment 2: under the room temperature in the four neck flasks that electric mixer, reflux exchanger, thermometer and dropping funnel are installed, add ethyl acetate 200ml, water 150ml, start agitator, the back adding 120g oil of mirbane that stirs distills last residue, 6g powdered carbon, be warming up to 74-76 ℃, behind the insulation 30min, when being cooled to 25 ℃, suction filtration.Filtrate is added in the four neck flasks, open and stir the distillation that heats up, during to 71 ℃ of 76 ℃ of liquidus temperatures, gas phase temperature, open the dropping funnel valve and slowly in flask, add the about 100ml of water, stop distillation when continuing to be distilled to 82 ℃ of 92 ℃ of liquidus temperatures, gas phase recovered temperature, steam ethyl acetate 155ml altogether; Make the interior material of flask lower the temperature, be cooled to 25 ℃ naturally then, suction filtration obtains yellowish brown Meta-dinitrobenzene crude product 89.8g.Above-mentioned Meta-dinitrobenzene crude product is added in the four clean neck flasks, add water 300ml, be warming up to 90 ℃, behind the insulation 10min, cooling, cold water are cooled to 25 ℃, suction filtration naturally, at 75 ℃ of dry 50min, obtain yellow-white Meta-dinitrobenzene needle crystal 81.7g, total recovery is 60.1%.The fusing point of measuring product with WRS-1 numeral fusing point instrument (Shanghai Physics Optics Instrument Factory production) is 90.0 ℃, records the FT-IR spectrogram of product with U.S.'s AVATAR360 Fourier transformation infrared spectrometer, with standard infrared spectrogram basically identical.
Embodiment 3: under the room temperature in the four neck flasks that electric mixer, reflux exchanger, thermometer and dropping funnel are installed, add ethyl acetate 300ml, water 100ml, start agitator, the back adding 110g oil of mirbane that stirs distills last residue, 8g powdered carbon, be warming up to 54-56 ℃, behind the insulation 30min, when being cooled to 25 ℃, suction filtration.Filtrate is added unlatching stirring intensification distillation in the four neck flasks, during to 71 ℃ of 76 ℃ of liquidus temperatures, gas phase temperature, open the dropping funnel valve and slowly in flask, add the about 100ml of water, stop distillation when continuing to be distilled to 82 ℃ of 92 ℃ of liquidus temperatures, gas phase recovered temperature, steam ethyl acetate 255ml altogether; Make the interior material of flask lower the temperature, be cooled to 25 ℃ naturally then, suction filtration obtains yellow Meta-dinitrobenzene crude product 93.6g.Above-mentioned Meta-dinitrobenzene crude product is added in the four clean neck flasks, add water 300ml, be warming up to 90 ℃, behind the insulation 10min, cooling, cold water are cooled to 25 ℃, suction filtration naturally, at 65 ℃ of dry 1.5h, obtain yellow Meta-dinitrobenzene needle crystal 85.2g, total recovery is 77.4%.The fusing point of measuring product with WRS-1 numeral fusing point instrument (Shanghai Physics Optics Instrument Factory production) is 90.1 ℃, records the FT-IR spectrogram of product with U.S.'s AVATAR360 Fourier transformation infrared spectrometer, with standard infrared spectrogram basically identical.
Claims (5)
1, nitrobenzene distilation redsdue utilize method, it is characterized in that distilling last residue with oil of mirbane is raw material, by dissolving, decolouring, crystallisation step, the preparation Meta-dinitrobenzene.
2, nitrobenzene distilation redsdue as claimed in claim 1 utilizes method, it is characterized in that, dissolving step is a solvent with ethyl acetate and water mixed liquid, and the volume ratio=85%-200% of ethyl acetate and water, solvent adding amount are the 100%-400% of nitrobenzene distilation redsdue weight; The decolouring step is discoloring agent with the gac, adds the gac of nitrobenzene distilation redsdue weight 5%-10% in the mixed solution of nitrobenzene distilation redsdue and solvent.
3, nitrobenzene distilation redsdue as claimed in claim 2 utilize method, it is characterized in that decolorization is carried out soaking time 20-60min under 46-76 ℃ of stirring; Suction filtration then, filtrate steaming is removed the ethyl acetate postcooling.
4, nitrobenzene distilation redsdue as claimed in claim 3 utilizes method, it is characterized in that, the filtrate still-process is at normal pressure, liquidus temperature 71-92 ℃, add under the condition of water of nitrobenzene distilation redsdue weight 100-300% and carry out simultaneously, reclaim ethyl acetate, during to 82 ℃ of gas phase recovered temperatures, distillation finishes, in air, lower the temperature naturally earlier and be cooled to liquidus temperature 82-77 ℃, use the cold water crystallisation by cooling then instead to room temperature, suction filtration obtains the Meta-dinitrobenzene crude product.
5, nitrobenzene distilation redsdue as claimed in claim 4 utilizes method, it is characterized in that, the Meta-dinitrobenzene crude product adds its weight 3-8 water doubly, be warming up to 82-95 ℃ of insulation 20-120min, naturally be cooled to 82-77 ℃, be cooled to room temperature with cold water again, suction filtration, dry 30-120min under 50-80 ℃ gets the product Meta-dinitrobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101600446A CN100434414C (en) | 2006-12-31 | 2006-12-31 | Utilizing process of nitrobenzene distilation redsdue |
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| CNB2006101600446A CN100434414C (en) | 2006-12-31 | 2006-12-31 | Utilizing process of nitrobenzene distilation redsdue |
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| CN100999472A true CN100999472A (en) | 2007-07-18 |
| CN100434414C CN100434414C (en) | 2008-11-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012013678A2 (en) | 2010-07-30 | 2012-02-02 | Bayer Materialscience Ag | Method for continuously producing nitrobenzene |
| CN105859561A (en) * | 2016-04-28 | 2016-08-17 | 刘更力 | Crystallization process of needle-like 2,4-dinitrotoluene crystals |
| CN107986250A (en) * | 2017-10-31 | 2018-05-04 | 湖北东方化工有限公司 | A kind of concentration unit of nitrotoleune sulfur waste acid treatment low concentration dust technology |
-
2006
- 2006-12-31 CN CNB2006101600446A patent/CN100434414C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012013678A2 (en) | 2010-07-30 | 2012-02-02 | Bayer Materialscience Ag | Method for continuously producing nitrobenzene |
| CN105859561A (en) * | 2016-04-28 | 2016-08-17 | 刘更力 | Crystallization process of needle-like 2,4-dinitrotoluene crystals |
| CN107986250A (en) * | 2017-10-31 | 2018-05-04 | 湖北东方化工有限公司 | A kind of concentration unit of nitrotoleune sulfur waste acid treatment low concentration dust technology |
| CN107986250B (en) * | 2017-10-31 | 2020-08-04 | 湖北东方化工有限公司 | Concentration device for treating low-concentration dilute nitric acid by nitrotoluene waste sulfuric acid |
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| Publication number | Publication date |
|---|---|
| CN100434414C (en) | 2008-11-19 |
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