CN102249993A - Method for treating waste water generated from production of 3-cyanopyridine and recovering nicotinic acid - Google Patents
Method for treating waste water generated from production of 3-cyanopyridine and recovering nicotinic acid Download PDFInfo
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- CN102249993A CN102249993A CN2011101226069A CN201110122606A CN102249993A CN 102249993 A CN102249993 A CN 102249993A CN 2011101226069 A CN2011101226069 A CN 2011101226069A CN 201110122606 A CN201110122606 A CN 201110122606A CN 102249993 A CN102249993 A CN 102249993A
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- nicotinic acid
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Abstract
A method for treating waste water generated from production of 3-cyanopyridine and recovering nicotinic acid. The method comprises the following steps of: taking ammonia water and waste water containing 3-cyanopyridine respectively, wherein a molar ratio of 3-cyanopyridine in waste water to ammonia water is 1:2-8; pouring the waste water and the ammonia water into a reaction vessel to react for 1-6h under heating and pressure; concentrating the reacted solution under reduced pressure to obtain a dry solid; cleaning the dry solid with water, drying, and recovering filtered aqueous solution; and sublimating the dried solid at 220-230 DEG C to obtain nicotinic acid. The invention has advantage that 3-cyanopyridine in waste water and nicotinamide are hydrolyzed to generate nicotinic acid, and a nicotinic acid mother liquor is dried and sublimated to obtain a finished product nicotinic acid with a purity higher than 99.8%, besides final washing liquid can be recovered for usage. According to the invention, not only a recovery rate of 3-cyanopyridine is increased, but also most HCN in waste water is hydrolyzed into NH3 and CO to avoid environment pollution.
Description
Technical field
The invention belongs to the chemical intermediate technical field of three-waste treatment, be specifically related to a kind of producing wastewater treatment that the 3-cyanopyridine produced and the method that reclaims nicotinic acid.
Background technology
The 3-cyanopyridine is a kind of important organic synthesis intermediate, and is of many uses, is dissolvable in water water, in particular for producing the vitamin B3-nicotinic acid of antipellagra, the raw material of niacinamide.Generally all by ammonia catalyzed oxidation 3-picoline, the product water absorbs, and extracts with organic solvent.But the ammonia in the production process is often excessive, thereby the 3-cyanopyridine that causes part continues by synthetic niacinamide of ammonia catalytic hydrolysis and nicotinic acid, and, 3-cyanopyridine in the aqueous solution can not be extracted by organic solvent fully, and whole ammonia oxidation process is mixed with a large amount of water generations, needs draining every day.So, cause in the waste water in 3-cyanopyridine workshop and contain the 3-cyanopyridine, niacinamide, nicotinic acid, and also have a large amount of HCN to generate in the entire reaction course, if do not handle i.e. discharging, then not only influence the rate of recovery of 3-cyanopyridine, and contaminate environment.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of to producing wastewater treatment that the 3-cyanopyridine produced and the method that reclaims nicotinic acid at above-mentioned prior art present situation; Present method not only can be hydrolyzed into nicotinic acid by reaction with 3-cyanopyridine, the niacinamide in the waste water, improves the rate of recovery of 3-cyanopyridine, and HCN more in the waste water can be hydrolyzed into NH simultaneously
3And CO, thereby avoid contaminate environment.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this is characterized in that: may further comprise the steps produce 3-cyanopyridine wastewater treatment that is produced and the method that reclaims nicotinic acid:
One, get ammoniacal liquor and contain the waste water of 3-cyanopyridine respectively, the consumption that contains the waste water of 3-cyanopyridine and ammoniacal liquor require for: the mol ratio of 3-cyanopyridine and ammoniacal liquor is 1: 2～8 in the waste water;
Two, the waste water of 3-cyanopyridine being poured in the reactor, added ammoniacal liquor again and stir in reactor, is 130～200 ℃, pressure the reaction kettle for reaction of 2～2.5MPa 1～6 hour in temperature;
Three, to be cooled drive still after, reacted solution is taken out, and to place temperature be that 60～80 ℃ container is evaporated to the exsiccant solid;
Four, in being equipped with the container of drying solid, add entry again and also filter, can from solid, remove by composition soluble in water, and the solid after will filtering is oven dry in 30～80 ℃ in temperature, with the aqueous solution recovery after filtering and again as the raw material for preparing nicotinic acid;
Five, the solid after will drying makes the nicotinic acid distillation in 220～230 ℃ temperature, and the nicotinic acid gas that distillation is come out from solid promptly obtains nicotinic acid after cooling.
As improvement, in the described step 1, the mol ratio of 3-cyanopyridine and ammoniacal liquor is 1: 3～5 in the described waste water.
Improve, in the described step 2, the temperature in the described reactor is 150～180 ℃ again.
Improve, pressure is 2.1～2.3MPa in the described reactor again.
Improve, the described reaction kettle for reaction time is 3～5 hours again.
Improve again, get and contain the 3-cyanopyridine: 3.76～3.88%, nicotinic acid: 2.52～2.75%, niacinamide: 4.93～5.13%, waste water 1000～1200 grams of HCN:0.25～0.27%, pour volume into and be in 2 liters the reactor, add 25% ammoniacal liquor, 74～110 grams again, in reactor, be heated with stirring to 170～180 ℃, and 170～180 ℃ temperature, pressure was the reaction kettle for reaction of 2.1～2.3MPa 3.5～4 hours, to be cooled drive still after, reacted solution is taken out, and to place temperature be that 60～80 ℃ container is evaporated to the exsiccant solid, in being equipped with the container of drying solid, add 180～250 ml waters and filtration again, can from solid, remove by composition soluble in water, and the solid after will filtering is 40～70 ℃ of oven dry in temperature, with the aqueous solution recovery after filtering and again as the raw material for preparing nicotinic acid, solid after then will drying makes the nicotinic acid distillation in 220～230 ℃ temperature, the nicotinic acid gas cooling that will from solid, distil and, promptly obtain purity and be 99.87～99.89% nicotinic acid, above-mentioned is mass percent.
Compared with prior art, the invention has the advantages that present method is under the ammonia existence condition, 3-cyanopyridine in the waste water and niacinamide hydrolysis are generated nicotinic acid, the nicotinic acid mother liquor of producing concentrates after-filtration earlier, filter cake is dried distillation after water washing can obtain finished product nicotinic acid, its purity reaches more than 99.8%, last washings (filtered water) again can recovery set with (referring to utilize again); Present method has not only improved the rate of recovery of 3-cyanopyridine, and HCN more in the waste water can be hydrolyzed into NH simultaneously
3And CO, thereby avoid contaminate environment.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The present invention may further comprise the steps produce 3-cyanopyridine wastewater treatment that is produced and the method that reclaims nicotinic acid:
One, get ammoniacal liquor and contain the waste water of 3-cyanopyridine respectively, the consumption that contains the waste water of 3-cyanopyridine and ammoniacal liquor require for: the mol ratio of 3-cyanopyridine and ammoniacal liquor is 1: 2～8 in the waste water;
Two, the waste water of 3-cyanopyridine being poured in the reactor, added ammoniacal liquor again and stir in reactor, is 130～200 ℃, pressure the reaction kettle for reaction of 2～2.5MPa 1～6 hour in temperature;
Three, to be cooled drive still after, reacted solution is taken out, and to place temperature be that 60～80 ℃ container is evaporated to the exsiccant solid;
Four, in being equipped with the container of drying solid, add entry again and also filter, can from solid, remove by composition soluble in water, and the solid after will filtering is oven dry in 30～80 ℃ in temperature, with the aqueous solution recovery after filtering and again as the raw material for preparing nicotinic acid;
Five, the solid after will drying makes the nicotinic acid distillation in 220～230 ℃ temperature, and the nicotinic acid gas that distillation is come out from solid promptly obtains nicotinic acid after cooling.
Below in conjunction with embodiment the present invention is described in further detail.
The preferred proportion of the mol ratio of 3-cyanopyridine is 1: 3～5 in ammonia vol that the present invention adds and the waste water, reaction process is to be that 2～2.5MPa, temperature are preferably under 150-180 ℃ and carry out at pressure, reacting the preferred time is 3-5 hour, in addition, the purification of nicotinic acid can be by distillation realizes that its purity reaches more than 99.8% to nicotinic acid.
Relevant reaction equation is as follows:
T in the reaction equation refers to temperature, P finger pressure power.
Embodiment one
Get and wherein contain 3-cyanopyridine 3.88%, nicotinic acid 2.52%, niacinamide 4.93%, waste water 1200 grams of HCN0.25% are poured in the 2L highly compressed reactor, ammoniacal liquor 110 grams of adding 25%, heating, stir, the solution of reaction is warming up to 170 ℃, reaction is 4 hours under this temperature, pressure is 2.3MPa, after question response is finished, cooling is driven still and is obtained 1300 gram mother liquors, record and contain 3-cyanopyridine 0.034% in the mother liquor, nicotinic acid 11.54%, niacinamide 0.06%, HCN0.005%, mother liquor is concentrated into dried in decompression or vacuum decompression, add the 200ml water filtration again, with filter cake again with drying after the 50ml water washing, 220-230 ℃ distil 138 gram nicotinic acid, content is 99.87%, fusing point 238-240 ℃.Washings (referring to that filtered water adds the 50ml washing water that clean filter cake, down together) recovery set is used.3-cyanopyridine transformation efficiency is 99.05%, and the niacinamide transformation efficiency is 98.68%, HCN clearance 97.83%.
Embodiment two
Getting waste water 1000 grams that contain 3-cyanopyridine 3.76%, nicotinic acid 2.75%, niacinamide 5.13%, HCN0.27% pours in the 2L highly compressed reactor, add 25% ammoniacal liquor, 74 grams, heated and stirred, the solution of reaction is warming up to 180 ℃, reacted 3.5 hours down at 180 ℃, pressure is 2.1MPa, and cooling is driven still and obtained 1070 gram mother liquors, contains 3-cyanopyridine 0.038%, nicotinic acid 11.43%, niacinamide 0.08%, HCN0.006% in the mother liquor.Mother liquor is concentrated into driedly in decompression or vacuum decompression, adds the 200ml water filtration again, filter cake is dried after with the 50ml water washing again, distils to such an extent that 110 restrain the nicotinic acid finished products at 215-220 ℃, and content is 99.89%, fusing point 238-240 ℃.The washings recovery set is used.3-cyanopyridine transformation efficiency is 98.92%, and the niacinamide transformation efficiency is 98.33%, HCN clearance 97.62%.
Above-mentioned per-cent is mass percent.
Claims (6)
1. one kind to producing wastewater treatment that the 3-cyanopyridine produced and the method that reclaims nicotinic acid, it is characterized in that: may further comprise the steps:
One, get ammoniacal liquor and contain the waste water of 3-cyanopyridine respectively, the consumption that contains the waste water of 3-cyanopyridine and ammoniacal liquor require for: the mol ratio of 3-cyanopyridine and ammoniacal liquor is 1: 2～8 in the waste water;
Two, the waste water of 3-cyanopyridine being poured in the reactor, added ammoniacal liquor again and stir in reactor, is 130～200 ℃, pressure the reaction kettle for reaction of 2～2.5MPa 1～6 hour in temperature;
Three, to be cooled drive still after, reacted solution is taken out, and to place temperature be that 60～80 ℃ container is evaporated to the exsiccant solid;
Four, in being equipped with the container of drying solid, add entry again and also filter, can from solid, remove by composition soluble in water, and the solid after will filtering is oven dry in 30～80 ℃ in temperature, with the aqueous solution recovery after filtering and again as the raw material for preparing nicotinic acid;
Five, the solid after will drying makes the nicotinic acid distillation in 220～230 ℃ temperature, and the nicotinic acid gas that distillation is come out from solid promptly obtains nicotinic acid after cooling.
2. method according to claim 1 is characterized in that: in the described step 1, the mol ratio of 3-cyanopyridine and ammoniacal liquor is 1: 3～5 in the described waste water.
3. method according to claim 2 is characterized in that: in the described step 2, the temperature in the described reactor is 150～180 ℃.
4. method according to claim 3 is characterized in that: pressure is 2.1～2.3MPa in the described reactor.
5. method according to claim 4 is characterized in that: the described reaction kettle for reaction time is 3～5 hours.
6. method according to claim 1, it is characterized in that: get and contain the 3-cyanopyridine: 3.76～3.88%, nicotinic acid: 2.52～2.75%, niacinamide: 4.93～5.13%, waste water 1000～1200 grams of HCN:0.25～0.27%, pour volume into and be in 2 liters the reactor, add 25% ammoniacal liquor, 74～110 grams again, in reactor, be heated with stirring to 170～180 ℃, and 170～180 ℃ temperature, pressure was the reaction kettle for reaction of 2.1～2.3MPa 3.5～4 hours, to be cooled drive still after, reacted solution is taken out, and to place temperature be that 60～80 ℃ container is evaporated to the exsiccant solid, in being equipped with the container of drying solid, add 180～250 ml waters and filtration again, can from solid, remove by composition soluble in water, and the solid after will filtering is 40～70 ℃ of oven dry in temperature, with the aqueous solution recovery after filtering and again as the raw material for preparing nicotinic acid, solid after then will drying makes the nicotinic acid distillation in 220～230 ℃ temperature, the nicotinic acid gas cooling that will from solid, distil and, promptly obtain purity and be 99.87～99.89% nicotinic acid, above-mentioned is mass percent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133467A (en) * | 2018-09-19 | 2019-01-04 | 安徽瑞邦生物科技有限公司 | A method of niacin and ammonium chloride in the washing water of recycling acidization production niacin |
| CN111170931A (en) * | 2019-12-31 | 2020-05-19 | 南通醋酸化工股份有限公司 | Method for recovering 3-methylpyridine in 3-cyanopyridine preparation process |
| CN113562912A (en) * | 2021-06-28 | 2021-10-29 | 佳尔科生物科技南通有限公司 | Method for treating spironolactone intermediate production wastewater |
| CN114456106A (en) * | 2020-11-10 | 2022-05-10 | 安徽瑞邦生物科技有限公司 | Method for recovering nicotinic acid in industrial wastewater |
-
2011
- 2011-05-10 CN CN2011101226069A patent/CN102249993A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133467A (en) * | 2018-09-19 | 2019-01-04 | 安徽瑞邦生物科技有限公司 | A method of niacin and ammonium chloride in the washing water of recycling acidization production niacin |
| CN109133467B (en) * | 2018-09-19 | 2021-08-03 | 安徽瑞邦生物科技有限公司 | Method for recovering nicotinic acid and ammonium chloride in washing water for producing nicotinic acid by acidification method |
| CN111170931A (en) * | 2019-12-31 | 2020-05-19 | 南通醋酸化工股份有限公司 | Method for recovering 3-methylpyridine in 3-cyanopyridine preparation process |
| CN111170931B (en) * | 2019-12-31 | 2023-05-23 | 南通醋酸化工股份有限公司 | Recovery method of 3-picoline in preparation process of 3-cyanopyridine |
| CN114456106A (en) * | 2020-11-10 | 2022-05-10 | 安徽瑞邦生物科技有限公司 | Method for recovering nicotinic acid in industrial wastewater |
| CN114456106B (en) * | 2020-11-10 | 2024-01-16 | 安徽瑞邦生物科技有限公司 | Method for recycling nicotinic acid in industrial wastewater |
| CN113562912A (en) * | 2021-06-28 | 2021-10-29 | 佳尔科生物科技南通有限公司 | Method for treating spironolactone intermediate production wastewater |
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Application publication date: 20111123 |