CN1142107C - Process for treating waste liquid of furaldehyde and recovering butyl acetate, ammonium sulfate, ammonium acetate, acetamide and acetonitrile - Google Patents
Process for treating waste liquid of furaldehyde and recovering butyl acetate, ammonium sulfate, ammonium acetate, acetamide and acetonitrile Download PDFInfo
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- CN1142107C CN1142107C CNB011140380A CN01114038A CN1142107C CN 1142107 C CN1142107 C CN 1142107C CN B011140380 A CNB011140380 A CN B011140380A CN 01114038 A CN01114038 A CN 01114038A CN 1142107 C CN1142107 C CN 1142107C
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- furfural
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Abstract
The present invention relates to a technology for treating furfural wastewater. Firstly, wastewater is cooled to room temperature, filtrate is placed in a phase transfer separating device containing multifunctional polymer adsorbing agents after filtration, treatment is carried out under the action of adsorbing agents in the device, neutral purified water with the pH value of 7 to 8 is continuously discharged by the device, and furfural mother liquid and ammonium acetate mother liquid are separated by ammonia separating liquid in the separating device. The furfural mother liquid is evaporated and concentrated, condensate returns to be used as ammonia separating liquid, and residues at the bottom of a still are crude furfural and sent to a furfural primary distillation tower for recovering furfural. The ammonium acetate mother liquid respectively separates ammonium acetate from wastewater by correspondingly treating, butyl acetate, ammonium sulfate, acetamide and acetonitrile are produced further, treated purified water can be directly used for being supplied for boilers, and the operation cost of wastewater treatment is obviously reduced.
Description
Technical field
The present invention relates to a kind of sewage disposal novel method, N-BUTYL ACETATE, ammonium sulfate, ammonium acetate, ethanamide and acetonitrile method are administered and reclaimed to particularly a kind of furfural waste-water.
Background technology
As everyone knows, furfural is an important chemical material.China's furfurol industry is raw material mostly with the corn cob, ton surplus the annual production about 50,000.Because of its technology imperfection, resource is not only wasted in the discharging of furfural waste-water, and causes the severe contamination of environment, and waste water institute is withered through the part farm crop, and fishes and shrimps disappear, even jeopardizes the water source of domestic water.Confirm through environmental monitoring results, contain acetic acid 1.0%-2.5% in the furfural waste-water, furfural 0.2%-0.5% and multiple organic compound are yellow acid, PH＜2, and the about 15000mg/1 of COD value is above 150 times of the wastewater discharge standards of stipulating.At present, factory does not all have ideal waste water treatment technology mostly, and for this reason, scientific and technical personnel once proposed many resolutions, but did not still have the practical application precedent so far.
Furfural waste-water commonly used is administered technology and is summarized as follows:
One, sodium-acetate method: adopt in the sodium hydroxide and the acetic acid in the furfural waste-water to sodium-acetate, then it is supplied water as low pressure boiler, make its concentration be evaporated to 15%-25%, at last its concentrated salt is changed into acetic acid.
The drawback of this method is that furfural do not separate, and the sodium-acetate of recovery is with low quality, and sodium hydroxide costs an arm and a leg, and is uneconomical.Therefore, this method is eliminated.
Two, extraction process: adopt the trialkylamine kind of extractants with the acetic acid in the extraction process recovery waste water, when carrying out production test, find,, cause extraction agent to be poisoned, so waste water is difficult to administer because of furfural disturbs.
Three, electroosmose process: adopt emerging membrane separation technique from furfural waste-water, to reclaim acetic acid.Reclaim the water quality of acetic acid through pretreated furfural waste-water with electrodialysis (ED), concentrate acetic acid with ED again, make by product acetic acid through extraction, rectifying with the control discharge water.In process of the test, find, the easily contaminated or obstruction of film, the deposition fouling of suspended substance easily makes the current skewness, and resistance increases, and causes polarization, is forced to stop trial production.Its reason is in advance furfural waste-water character to be understood not enough, the changeable easy oxypolymerization of furfural chemical property, and electroosmose process is difficult to adapt to.
Four, anaerobic process: the anaerobic treatment technology is a kind of biological process, and it can effectively be removed organic pollutant and make it pass through microbial process, changes organic compound into methane and carbonic acid gas.This method investment is big, working cost is high, and process control condition is strict.
Five, intermittent activated sludge process (SBR): the SBR method is more noticeable a kind of waste water treatment process in the active sludge processing system in recent ten years.But the automatic control technology of this treatment process is had relatively high expectations, the engineering operation operational administrative is comparatively complicated, invests greatlyyer, influences it and applies.
Summary of the invention
The purpose of this invention is to provide a kind of furfural waste-water and administer and reclaim N-BUTYL ACETATE, ammonium sulfate, ammonium acetate, ethanamide and acetonitrile method, this technical process is controlled easily, operate steadily, compare with other existing treatment process, can not only effectively ammonium acetate be separated from waste water, and further produce N-BUTYL ACETATE, ammonium sulfate, ethanamide and acetonitrile, and purifying waste water after handling can be directly used in oiler feed, obviously reduces the working cost of wastewater treatment.
The object of the present invention is achieved like this: earlier waste water is cooled to room temperature, after the filtration, filtrate putting into is equipped with the phase transition tripping device of multifunctional macromolecule polymer absorbant, handle under the sorbent material effect in device, making it to discharge continuously pH value purifies waste water for 7-8 neutrality, in tripping device, isolate furfural mother liquor and ammonium acetate mother liquor then with alkaline parting liquid, carry out evaporation concentration more respectively, further make with extra care and promptly obtain furfural and ammonium acetate, the consumption of alkaline parting liquid is 1/10th of a furfural waste-water amount.
Above-mentioned isolated furfural mother liquor concentrates with the furfural steam raising, and the distillation phlegma returns as alkaline parting liquid, and residue is chaff aldehyde at the bottom of the still, delivers to the furfural primary tower and reclaims furfural.
Above-mentioned isolated ammonium acetate mother liquor is 40% o'clock through further evaporation concentration to concentration, is the consumption acidifying of the vitriol oil excessive 2% of 93-98% with concentration, separates out ammonium sulfate crystallization, through centrifuging, promptly gets ammonium sulfate product.
After the acidifying of above-mentioned ammonium acetate mother liquor, the centrifuging, filtrate places synthesis reactor, adds butanols, its weight is 2: 1 with the ratio of filtrate weight, under 116 ℃ of conditions, reacted 4-6 hour, carry out rectifying at 89-92 ℃, phlegma divides water-yielding stratum, ester layer in water trap, 30% of ester layer is turned back in the rectifying tower, and all the other are collected as thick ester, carry out rectifying then according to a conventional method, collect 124-126 ℃ of fraction, be the N-BUTYL ACETATE finished product.
Above-mentioned isolated ammonium acetate mother liquor is 40% o'clock through further evaporation concentration to concentration, to the saturated solution state, has the ammonium acetate crystallization to separate out 105-112 ℃ of evaporation concentration, suction filtration after the cooling of ammonium acetate saturated solution, is separated out the ammonium acetate crystallization while hot, through centrifuging, promptly get the ammonium acetate product.
Above-mentioned solid ammonium acetate is placed the dehydration still, and heating makes ammonium acetate dehydration, generates ethanamide, under negative pressure, distillates in 120-150 ℃, or under normal pressure, makes in 210-216 ℃ of distillation, through cold analysis, promptly gets solid ethanamide product.
Above-mentioned solid ethanamide is placed still kettle, and the ratio that adds its weight of liquid acetic anhydride is 1: 1-2, stir, slowly dehydration reaction promptly takes place in heating, generates acetonitrile, collect 77-80 ℃ of fraction, promptly get and contain water-acetonitrile liquid, extract with 42% sodium hydroxide solution, tell organic layer, promptly get water content, be placed in the still kettle less than 3% acetonitrile liquid, add Vanadium Pentoxide in FLAKES, its weight ratio is 1: 0.05, again distillation, collect 77-82 ℃ of fraction, promptly get the acetonitrile product.
Used alkaline parting liquid is the ammoniacal liquor of concentration 5-7%, and it is directly prepared by strong aqua or is prepared by the distillation phlegma of strong aqua and furfural mother liquor.
Used multifunctional macromolecule polymer absorbant adopts the 506 type polystyrene pyridine resins of being produced by Beijing chemical industry Zhi Jin research institute, the II type porous negative resin that Nanjing resin processing plant produces, the LDX-602 type sorbent material that Zhang Dian chemical plant, Zibo produces, the GDX-103 type sorbent material that the chemical plant, Shenyang produces.
Because the present invention adopts phase transfer of technology that furfural waste-water is carried out the comprehensive regulation, this technical process is controlled easily, easy to operate, operate steadily, it has fundamentally changed existing improvement technology, not only furfural and ammonium acetate can be separated from furfural waste-water effectively, and be reclaimed, further produce N-BUTYL ACETATE, ammonium sulfate,, ethanamide and acetonitrile, and the waste water after handling becomes and purifies waste water, and can be directly used in oiler feed, thereby realize the zero release that furfural is produced.Owing to do not use expensive equipment and raw material, so obviously reduce the working cost of wastewater treatment.Therefore, the present invention very easily applies.
Embodiment
Below in conjunction with embodiment the present invention is further described, but the recovery of Dichlorodiphenyl Acetate butyl ester, ammonium sulfate, ammonium acetate, ethanamide and acetonitrile is not subjected to the restriction of embodiment in this technical process.
Embodiment one:
Get furfural mill waste water 10L, use filter paper filtering, filtrate entering is equipped with in the phase transition tripping device of high molecular polymer GDX-103 type sorbent material, and the control flow velocity is the 50ml/ branch, and discharge neutrality continuously and purify waste water, pH value 7-8, the COD clearance reaches more than 95%.In tripping device, use the alkaline parting liquid 1L that directly prepares by strong aqua then, furfural and acetic acid are separated.The further evaporation concentration of furfural mother liquor obtains the about 2.5.ml of chaff aldehyde.The further evaporation concentration of ammonium acetate mother liquor, concentration is about 40%.With concentration is the consumption acidifying of the vitriol oil excessive 2% of 93-98%, separates out ammonium sulfate crystallization, through centrifuging, promptly gets ammonium sulfate product.
After the acidifying of ammonium acetate mother liquor, the centrifuging, filtrate places synthesis reactor, adds butanols, its weight is 2: 1 with the ratio of filtrate weight, under 116 ℃ of conditions, reacted 4-6 hour, carry out rectifying at 89-92 ℃, phlegma divides water-yielding stratum, ester layer in water trap, 30% of ester layer is turned back in the rectifying tower, and all the other are collected as thick ester, carry out rectifying then according to a conventional method, collect 124-126 ℃ of fraction, be the N-BUTYL ACETATE finished product.
Embodiment two:
After the cooling of furfural mill waste water, filter through sand-bed filter, filtrate entering is equipped with in the tripping device of multifunctional macromolecule polymkeric substance 506 type polystyrene pyridine resin sorbents, the control flow velocity is 5m3/ hour, discharges neutrality continuously and purifies waste water, pH value 7-8, the COD clearance is done boiler water supply below 95%.The alkaline parting liquid of preparing with the phlegma by strong aqua and furfural mother liquor of wastewater flow rate 1/10th consumptions in tripping device is isolated furfural mother liquor and ammonium acetate mother liquor then.The furfural mother liquor returns as alkaline parting liquid with the further evaporation concentration of furfural steam, distillation phlegma, and residue is chaff aldehyde at the bottom of the still, and purity is 85%, send the furfural primary tower to reclaim furfural.The further evaporation concentration of ammonium acetate mother liquor, concentration is about 40%, 105-112 ℃ of evaporation concentration to the saturated solution state, have the ammonium acetate crystallization to separate out, suction filtration while hot is after the cooling of ammonium acetate saturated solution, separate out the ammonium acetate crystallization,, promptly get the ammonium acetate product through centrifuging.About 1.5 tons of day output.
Embodiment three:
The solid ammonium acetate that obtains among the embodiment two is placed the dehydration still, and heating makes the ammonium acetate dehydration, generates ethanamide, under negative pressure (1.3-13Kpa), distillate in 120-150 ℃, or under normal pressure, make in 210-216 ℃ of distillation, through cold analysis, promptly get solid ethanamide product, purity reaches 95% approximately.
Embodiment four:
The solid ethanamide that obtains among the embodiment three is placed still kettle, the ratio that adds its weight of liquid acetic anhydride is 1: 1-2, stir, slowly dehydration reaction promptly takes place in heating, generates acetonitrile, collect 77-80 ℃ of fraction, promptly get and contain water-acetonitrile liquid,, tell organic layer with the extraction of 42% sodium hydroxide solution, promptly get water content less than 3% acetonitrile liquid, be placed in the still kettle, add Vanadium Pentoxide in FLAKES, its weight ratio is 1: 0.05, again distillation, collect 77-82 ℃ of fraction, promptly get the acetonitrile product, purity reaches 99% approximately.
Claims (8)
1, a kind of furfural waste-water improvement method, it is characterized in that earlier waste water being cooled to room temperature: after the filtration, filtrate putting into is equipped with multifunctional macromolecule polymer absorbant 506 type polystyrene pyridine resins, II type porous negative resin, LDX-602 type sorbent material, in the phase transition tripping device of GDX-103 type sorbent material, under device internal adsorption agent effect, handle, making it to discharge continuously pH value purifies waste water for 7-8 neutrality, the alkaline parting liquid that with concentration is the ammoniacal liquor of 5-7% then in tripping device is isolated furfural mother liquor and ammonium acetate mother liquor, carry out evaporation concentration more respectively, further make with extra care and promptly obtain furfural and ammonium acetate, the consumption of alkaline parting liquid is 1/10th of a furfural waste-water amount.
2, method according to claim 1 is characterized in that isolated furfural mother liquor concentrates with the furfural steam raising, and the distillation phlegma returns as alkaline parting liquid, and residue is chaff aldehyde at the bottom of the still, delivers to the furfural primary tower and reclaims furfural.
3, method according to claim 1, it is characterized in that isolated ammonium acetate mother liquor is through further evaporation concentration to concentration at 40% o'clock, is the consumption acidifying of the vitriol oil excessive 2% of 93-98% with concentration, separates out ammonium sulfate crystallization, through centrifuging, promptly get ammonium sulfate product.
4, method according to claim 3, it is characterized in that the acidifying of ammonium acetate mother liquor, centrifuging after, filtrate places synthesis reactor, add butanols, its weight is 2: 1 with the ratio of filtrate weight, under 116 ℃ of conditions, reacted 4-6 hour, carry out rectifying at 89-92 ℃, phlegma divides water-yielding stratum, ester layer in water trap, and 30% of ester layer is turned back in the rectifying tower, all the other are collected as thick ester, carry out rectifying then according to a conventional method, collect 124-126 ℃ of fraction, be the N-BUTYL ACETATE finished product.
5, method according to claim 1, it is characterized in that isolated ammonium acetate mother liquor is through further evaporation concentration to concentration at 40% o'clock, 105-112 ℃ of evaporation concentration to the saturated solution state, there is the ammonium acetate crystallization to separate out, suction filtration after the cooling of ammonium acetate saturated solution, is separated out the ammonium acetate crystallization while hot, through centrifuging, promptly get the ammonium acetate product.
6, method according to claim 5 is characterized in that the solid ammonium acetate is placed the dehydration still, and heating makes the ammonium acetate dehydration, generates ethanamide, under negative pressure, distillate in 120-150 ℃, or under normal pressure, make in 210-216 ℃ of distillation,, promptly get solid ethanamide product through cold analysis.
7, method according to claim 6, it is characterized in that the solid ethanamide is placed still kettle, the ratio that adds its weight of liquid acetic anhydride is 1: 1-2, stir, slowly dehydration reaction promptly takes place in heating, generate acetonitrile, collect 77-80 ℃ of fraction, promptly get and contain water-acetonitrile liquid, extract with 42% sodium hydroxide solution, tell organic layer, promptly get water content less than 3% acetonitrile liquid, be placed in the still kettle, add Vanadium Pentoxide in FLAKES, its weight ratio is 1: 0.05, again 77-82 ℃ of fraction collected in distillation, promptly gets the acetonitrile product.
8, method according to claim 1 is characterized in that used concentration is the alkaline parting liquid of the ammoniacal liquor of 5-7%, and it is directly prepared by strong aqua or is prepared by strong aqua and furfural mother liquor distillation phlegma.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011140380A CN1142107C (en) | 2001-06-06 | 2001-06-06 | Process for treating waste liquid of furaldehyde and recovering butyl acetate, ammonium sulfate, ammonium acetate, acetamide and acetonitrile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011140380A CN1142107C (en) | 2001-06-06 | 2001-06-06 | Process for treating waste liquid of furaldehyde and recovering butyl acetate, ammonium sulfate, ammonium acetate, acetamide and acetonitrile |
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| Publication Number | Publication Date |
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| CN1327953A CN1327953A (en) | 2001-12-26 |
| CN1142107C true CN1142107C (en) | 2004-03-17 |
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| CNB011140380A Expired - Fee Related CN1142107C (en) | 2001-06-06 | 2001-06-06 | Process for treating waste liquid of furaldehyde and recovering butyl acetate, ammonium sulfate, ammonium acetate, acetamide and acetonitrile |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1250672C (en) * | 2004-12-24 | 2006-04-12 | 长春市佳辰环保设备有限公司 | Process for preparing calcium acetate snow thawing agent |
| CN1872726A (en) | 2006-06-07 | 2006-12-06 | 济南圣泉集团股份有限公司 | Method for treating wastewater from furfural production |
| CN101215063B (en) * | 2007-12-27 | 2010-06-09 | 沙隆达集团公司 | Integral treatment method for waste water of acephate producing process |
| CN103214439B (en) * | 2013-04-09 | 2016-03-02 | 江苏清泉化学股份有限公司 | A kind of method of separating-purifying furfural |
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