CN102746139A - Method for recycling dibasic acid byproducts from adipic acid waste liquor - Google Patents
Method for recycling dibasic acid byproducts from adipic acid waste liquor Download PDFInfo
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- CN102746139A CN102746139A CN2012102469927A CN201210246992A CN102746139A CN 102746139 A CN102746139 A CN 102746139A CN 2012102469927 A CN2012102469927 A CN 2012102469927A CN 201210246992 A CN201210246992 A CN 201210246992A CN 102746139 A CN102746139 A CN 102746139A
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Abstract
The invention relates to a method for recycling dibasic acid byproducts from adipic acid waste liquor, which comprises steps as follows: dibasic acid waste liquor is preheated by a preheater and enters a climbing film evaporator; the concentrated solution from the climbing film evaporator naturally flows to a falling film evaporator; the discharged material from the bottom of the falling film evaporator is in a molten state; after a seal tank is subjected to vacuum isolation, a safe evaporating tank is operated under normal pressure; and the liquor naturally flows to the safe evaporating tank to be buffered, and enters a flaker to form flakes, thereby obtaining the dibasic acid flake byproducts. Compared with the prior art, the invention enhances the evaporization efficiency, lowers the steam consumption, implements continuous operation of evaporative concentration of adipic acid waste liquor, implements continuous discharge to avoid the possibility of explosion due to overpressure of equipment, ensures the discharge requirement for water content and the stable operation of the flaker, can adapt to great incoming material fluctuation or steam pipe network fluctuation, reasonably utilizes the energy, and lowers the comprehensive energy consumption of the products.
Description
Technical field
The present invention is to extracting the method for diprotic acid sub product in the hexane diacid preparation waste liquid.
Background technology
Hexanodioic acid is to make catalyzer with copper and vanadium, generates with the reaction of nitric acid oxidation hexalin.In hexanodioic acid is produced, contain hexanodioic acid, Succinic Acid, pentanedioic acid, water and nitric acid in the waste liquid of generation (DBA waste liquid).The method of extracting the diprotic acid sub product reclaims hexanodioic acid, Succinic Acid and pentanedioic acid exactly from mixed waste liquor.
From the hexanodioic acid waste liquid, reclaim at present the method for hexanodioic acid, Succinic Acid, pentanedioic acid, the method for intermittently evaporating pot process and two climbing-film evaporator serial operations is arranged.
But the problem that these two kinds of methods exist has:
1. the vaporization efficiency of evaporating pot is low, and steam consumption is big.
2. the evaporating pot vacuum operating needs vacuum breaker before discharge, otherwise can't blanking, and in the vacuum breaker process, because evaporating pot is still used steam heating, occurs the phenomenon of evaporating pot superpressure easily, and rupture disk need be set.
3. evaporating pot periodical operation need be established a plurality of evaporating pots, and the feed liquid concentrating degree is rule of thumb judged, occurs the underproof situation of feed liquid water cut easily, causes the flaker feed liquid of can't condensing, and the disqualification rate of product is higher.
4. evaporate the nitric acid vapor that and need use the recirculated water condensation, energy consumption is big.
5. the flow process of two climbing-film evaporator serial operations generally can not reach the evaporation requirement of diprotic acid water cut≤2%, and vaporization efficiency is low, and steam consumption is big.
Summary of the invention
The objective of the invention is to improve the treatment process of hexanodioic acid waste liquid, improve vaporization efficiency, cut down the consumption of energy, solve the problem that blanking needs vacuum breaker, make the evaporation concentration can operate continuously.
Technical scheme of the present invention is following:
A kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product; Its step is following: the diprotic acid waste liquid gets into climbing-film evaporator after the preheater preheating, and from flowing to falling-film evaporator, the falling-film evaporator bottom discharge is molten state through the liquid concentrator behind the climbing-film evaporator; After sealed can cuts off vacuum; Make security personnel's evaporating pot atmospheric operation, flow to security personnel's evaporating pot buffering certainly, get into flaker knot sheet then and obtain diprotic acid section sub product.
Further, falling-film evaporator-50 ~-the 70kPaA negative-pressure operation, preferred-70kPaA.The heating of employing MP steam, the drop temperature of control falling-film evaporator is at 145 ~ 185 ℃, and preferred 145 ~ 165 ℃, according to equilibrium partial pressure, falling-film evaporator bottom discharge moisture content is reduced to below 2%.
Further, security personnel's evaporating pot is provided with two, as security device; Under steam pipe system fluctuation or evaporation feed liquor fluctuation situation; If drop temperature does not reach 145 ~ 185 ℃, can improve the residence time of feed liquid in evaporating pot, guarantee that the feed liquid water cut of entering flaker is qualified.If the drop temperature deviation is bigger, can switch to an other evaporating pot, adopt the pattern of periodical operation, deliver to flaker knot sheet after the feed liquid water cut in the jar to be evaporated is up to standard again, guaranteed the continuous production of device.If operation is normal, evaporating pot has been realized the spissated operate continuously of hexanodioic acid waste liquid evaporation only as surge tank.Security personnel's evaporating pot has vapor pipe, enters the airing system of adipic acid plant behind the nitric acid vapor in the condenser condenses exhaust, and evaporating pot can be realized continuous pulp discharge, does not need vacuum breaker, and the superpressure explosion phenomenon can not occur.
Further, evaporate the nitric acid concentration tower recovery nitric acid that the nitric acid vapor that is delivered to adipic acid plant.Because the temperature of steam is higher, deliver to nitric acid concentration tower and can be used as thermal source, reduce the steam consumption of nitric acid concentration tower reboiler, nitric acid vapor need not use the recirculated water condensation simultaneously, reduces recirculated water consumption, has reduced the adipic acid plant energy consumption of unit product.
Further; The diprotic acid retrieving arrangement designs independently vacuum unit as subsequent use in a kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product of the present invention; Be that climbing-film evaporator and falling-film evaporator also are connected with independently vacuum unit afterwards; When adipic acid plant nitric acid concentration tower fluctuation of service, can switch to independently vacuum unit, guarantee the steady running of diprotic acid upgrading unit.Be connected with nitric acid lime set jar and nitric acid lime set pump in turn after the vacuum unit, nitric acid liquid is collected nitric acid lime set jar, get in the adipic acid plant through nitric acid lime set pump and utilize the production hexanodioic acid once more, recover materials has been carried out recycle fully again.
Advantage of the present invention:
Advantage and positively effect that compared with present technology the present invention is had are:
1. adopt climbing-film evaporator and falling-film evaporator serial operation, the vaporization efficiency that rises film and falling-film evaporator is all much higher than evaporating pot, has improved vaporization efficiency, has reduced steam consumption.
2. adopt climbing-film evaporator and falling-film evaporator serial operation, realize the spissated operate continuously of hexanodioic acid waste liquid evaporation.
3. the evaporating pot atmospheric operation of ensuring public security is realized continuous pulp discharge, avoids the possibility of equipment superpressure blast.
4. guarantee the requirement of discharging water cut through control falling-film evaporator drop temperature, guarantee the stable operation of flaker.
5. security personnel's evaporating pot is set, makes the device operator scheme flexible, can adapt to bigger supplied materials fluctuation or steam pipe system fluctuation.
6. evaporate the nitric acid vapor that and deliver to adipic acid plant nitric acid concentration tower recovery nitric acid, rationally utilize energy, reduce the product comprehensive energy consumption.
Description of drawings
Fig. 1 is a kind of process flow diagram that from the hexanodioic acid waste liquid, reclaims the method for diprotic acid sub product of the present invention.
Among the figure:
1, preheater 2, climbing-film evaporator 3, falling-film evaporator 4, cyclonic separator
5, nitric acid concentration tower 6, sealed can 7, security personnel's evaporating pot 8, flaker
9, vacuum unit 10, adipic acid plant airing system 11, adipic acid plant 12, nitric acid lime set jar
13, nitric acid lime set pump
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but does not limit protection scope of the present invention.
Embodiment 1
A kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product, hexanodioic acid DBA waste liquid is delivered to preheater 1 usefulness steam condensate through transferpump and is heated to 75 ℃, gets into climbing-film evaporator 2 evaporation concentration then.Climbing-film evaporator 2 temperature outs are controlled at 90 ℃ ,-20 ~-40kPa A negative-pressure operation.The steam that the steam that discharge at climbing-film evaporator 2 tops is discharged with falling-film evaporator 3 tops behind the drop of cyclonic separator 4 separate entrained is sent into nitric acid concentration tower 5 and is reclaimed nitric acid.Moisture content is reduced to about 40% in climbing-film evaporator 2 dischargings, flow to falling-film evaporator 3 further evaporation concentration certainly.Falling-film evaporator 3 adopts the MP steam heating in-70kPaA operation, and control bottom discharge temperature is at 160 ℃.Falling-film evaporator bottom discharge moisture content is reduced to about 2%, is molten state, after sealed can 6 cuts off vacuum, flow to a buffering in two security personnel's evaporating pots 7 certainly, gets into flaker 8 knot sheets then and obtains diprotic acid section sub product.If fluctuation appears in the discharging moisture content of falling-film evaporator 3, can not satisfy the requirement of knot sheet, can adjust the residence time of feed liquid in security personnel's evaporating pot, be no more than 2% to guarantee the discharging moisture content.Can switch to other security personnel's evaporating pot in the time of necessary, adopt andnon-continuous operation manner.Security personnel's evaporating pot 7 has vapor pipe, enters adipic acid plant airing system 10 behind the nitric acid vapor in the condenser condenses exhaust, and security personnel's evaporating pot 7 can be realized continuous pulp discharge, does not need vacuum breaker, and the superpressure explosion phenomenon can not occur.
Climbing-film evaporator 2 also is connected with independently vacuum unit 9 afterwards with falling-film evaporator 3, when adipic acid plant nitric acid concentration tower fluctuation of service, can switch to independently vacuum unit 9, guarantees the steady running of diprotic acid upgrading unit.Be connected with nitric acid lime set jar 12 and nitric acid lime set pump 13 after the vacuum unit 9 in turn; Nitric acid liquid is collected nitric acid lime set jar 12; Through utilizing the production hexanodioic acid once more in the nitric acid lime set pump 13 entering adipic acid plants 11, recover materials has been carried out recycle fully again.
A kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product of the present invention is evaporated pot process compared to general intermittence, save energy consumption and reach 40% ~ 50%; Compared to the method for two climbing-film evaporator serial operations, adopt method of the present invention, can material be evaporated to water cut below 2%, improved the quality of product, and the method ordinary material water cut of two joint climbing-film evaporator serial operations is about 20%.
Claims (7)
1. method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product, it is characterized in that: step is following:
The diprotic acid waste liquid gets into climbing-film evaporator after the preheater preheating; Certainly flow to falling-film evaporator through the liquid concentrator behind the climbing-film evaporator; The falling-film evaporator bottom discharge is molten state, after sealed can cuts off vacuum, makes security personnel's evaporating pot atmospheric operation; From flowing to security personnel's evaporating pot buffering, get into flaker knot sheet then and obtain diprotic acid section sub product.
2. a kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product according to claim 1 is characterized in that: described falling-film evaporator control pressure is-50 ~-70kPaA, the bottom discharge temperature is at 145 ~ 185 ℃.
3. a kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product according to claim 2 is characterized in that: described falling-film evaporator control bottom discharge temperature is at 145 ~ 165 ℃.
4. a kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product according to claim 1, it is characterized in that: said falling-film evaporator bottom discharge moisture content is reduced to below 2%.
5. a kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product according to claim 1, it is characterized in that: described security personnel's evaporating pot is provided with two.
6. a kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product according to claim 1 is characterized in that: evaporate the nitric acid concentration tower recovery nitric acid that the nitric acid vapor that is delivered to adipic acid plant from climbing-film evaporator.
7. a kind of method that from the hexanodioic acid waste liquid, reclaims the diprotic acid sub product according to claim 1 is characterized in that: also be connected with independently vacuum unit after described climbing-film evaporator and the falling-film evaporator.
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| CN201210246992.7A CN102746139B (en) | 2012-07-17 | 2012-07-17 | Method for recycling dibasic acid byproducts from adipic acid waste liquor |
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| CN201210246992.7A CN102746139B (en) | 2012-07-17 | 2012-07-17 | Method for recycling dibasic acid byproducts from adipic acid waste liquor |
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| CN102746139B CN102746139B (en) | 2014-11-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906122A (en) * | 2016-05-23 | 2016-08-31 | 江苏瑞升华能源科技有限公司 | Treatment technology of high-organic matter high-salt wastewater and treatment device thereof |
| CN105923673A (en) * | 2016-05-23 | 2016-09-07 | 江苏瑞升华能源科技有限公司 | Adipic acid waste water evaporation and concentration process and device thereof |
| CN112439216A (en) * | 2020-12-14 | 2021-03-05 | 河南久圣化工有限公司 | Tertiary evaporation system for recovering dicarboxylic acid from adipic acid waste liquid |
| CN112457186A (en) * | 2020-11-25 | 2021-03-09 | 重庆华峰化工有限公司 | Device and method for separating and recovering dibasic acid and catalyst in adipic acid production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010001649A1 (en) * | 1997-12-08 | 2001-05-24 | Decoster David C. | Methods and devices for separating catalyst from oxidation mixtures containing dibasic acids |
| CN101362607A (en) * | 2008-08-12 | 2009-02-11 | 山东洪业化工集团有限公司 | Process for treating waste water from hexane diacid production system |
| CN102211992A (en) * | 2011-04-18 | 2011-10-12 | 湖南百利工程科技有限公司 | Process for reclaiming dibasic acid from adipic acid production waste solution |
-
2012
- 2012-07-17 CN CN201210246992.7A patent/CN102746139B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010001649A1 (en) * | 1997-12-08 | 2001-05-24 | Decoster David C. | Methods and devices for separating catalyst from oxidation mixtures containing dibasic acids |
| CN101362607A (en) * | 2008-08-12 | 2009-02-11 | 山东洪业化工集团有限公司 | Process for treating waste water from hexane diacid production system |
| CN102211992A (en) * | 2011-04-18 | 2011-10-12 | 湖南百利工程科技有限公司 | Process for reclaiming dibasic acid from adipic acid production waste solution |
Non-Patent Citations (1)
| Title |
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| 方鸿元: "双效升降膜蒸发器的设计使用", 《医药设计》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906122A (en) * | 2016-05-23 | 2016-08-31 | 江苏瑞升华能源科技有限公司 | Treatment technology of high-organic matter high-salt wastewater and treatment device thereof |
| CN105923673A (en) * | 2016-05-23 | 2016-09-07 | 江苏瑞升华能源科技有限公司 | Adipic acid waste water evaporation and concentration process and device thereof |
| CN112457186A (en) * | 2020-11-25 | 2021-03-09 | 重庆华峰化工有限公司 | Device and method for separating and recovering dibasic acid and catalyst in adipic acid production |
| CN112439216A (en) * | 2020-12-14 | 2021-03-05 | 河南久圣化工有限公司 | Tertiary evaporation system for recovering dicarboxylic acid from adipic acid waste liquid |
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| CN102746139B (en) | 2014-11-05 |
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