CN102381955A - Method for recycling acetic acid from industrial wastewater - Google Patents
Method for recycling acetic acid from industrial wastewater Download PDFInfo
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- CN102381955A CN102381955A CN2010102696851A CN201010269685A CN102381955A CN 102381955 A CN102381955 A CN 102381955A CN 2010102696851 A CN2010102696851 A CN 2010102696851A CN 201010269685 A CN201010269685 A CN 201010269685A CN 102381955 A CN102381955 A CN 102381955A
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Abstract
The invention discloses a method for separating and recycling acetic acid from industrial wastewater by combined operation of absorption and heat regeneration step by step. The method comprises the steps of: absorbing and separating acetic acid from wastewater by solid absorbents such as active carbon, a molecular screen and zeolite and the like, then performing heating and regeneration for the absorption column step by step; heating to remove residual water in the column to condense absorbed acetic acid and then heating to desorb and recycle the absorbed acetic acid so as to regenerate the absorbents. An acetic acid solution which is greater than or equal to 30% in concentration can be recycled and obtained from wastewater with acetic acid which is smaller than or equal to 5% in concentration by the method. The method is mainly based on physical process without chemical separators, environmental-friendly without secondary pollution and has a simple device, is convenient to operate and control and has higher utilization rate of available energy. The acetic acid recycled can return back directly to the industrial normal acetic acid separator for further concentration so as to obtain high purity acetic acid products. The invention is a method with wastewater treatment and resource recycling integrally.
Description
Technical field
The invention belongs to the separation engineering technical field, relate to a kind of treatment process, particularly from the waste water that contains low-concentration acetic acid, reclaim the method for acetic acid low-concentration acetic acid wastewater.
Background technology
In FM, acetic acid alkyl esters, ketene, glycerine, epoxyalkane acid; In the production process of Chemicals such as vinylformic acid and propenoate; And send out at metal treatment process and acetic acid and all to produce the trade effluent that contains low-concentration acetic acid in a large number in the process, these waste water not only pollute the environment if do not handle; And can cause the loss of acetic acid resource, therefore from acetic acid containing waste water, separate and reclaim the benefit that acetic acid has economic and social two aspects.At present, the method for separation and recovery dilute acetic acid mainly contains extraction process, membrane separation process and absorption method from industrial acetic acid waste water.
Utilizing organic solvent from waste water, to extract and reclaiming dilute acetic acid is a kind of method commonly used, and like U.S. Pat, 4100189. utilize the butanols and the mixture of N-BUTYL ACETATE composition to make extraction agent reclaims acetic acid from acetate concentration is 0.5～3% the aqueous solution.Chinese patent CN1141302 with trialkylamine as extraction agent Separation and Recovery acetic acid separated from waste water.It is extraction agent that Chinese patent CN101172941A adopts the tertiary amine of 12-16 carbon atom and the mixture of alphanol and kerosene, Separation and Recovery acetic acid from trade effluent, and yield reaches 75%～98%.Though the dilute acetic acid of extraction process in can efficient recovery waste water, for acetic acid, the partition ratio of most of organic extractants is all smaller, and therefore, the large usage quantity of extraction agent increases the energy consumption of later separation workshop section, and causes secondary pollution easily.
Membrane separation process reclaims the technology of dilute acetic acid in the waste water and is also probed into and pay close attention in recent years.Like [J] .Desalination.2000,129 (3): 283-288 adopts the bipolar membrane electrodialysis method to reclaim the acetic acid in the waste water (containing acetic acid 0.2%), and the result shows that this method has feasibility technically, and can handle acetic acid content up to the waste water that reaches 70%.[J] .2004 AIChE Annual Meeting, 2004.11,687-692 has studied the effect of utilizing anion-exchange membrane separating acetic acid from the DI aqueous solution and acid hydrolysis of hemicellulose product, finds that this exchange membrane shows good performance.Membrane separation process is a kind of method of safety and environmental protection, but its technological feasibility depends on the performance and the life-span, particularly trade effluent of the film hazardness to the film pollution, the further investigation of still needing to a great extent.
Absorption method is to handle the effective ways of low-concentration acetic acid wastewater; Be characterized at first utilizing solid adsorbent with dilute acetic acid from waste water or in the unclassified stores fractionation by adsorption come out; Make acetic acid desorption and recovery through diverse ways then, different adsorption agent or desorption method have constituted the different techniques characteristics.[J] .Separation Science and Technology.2001,36 (12): 2623-2646
]Adopt Zeo-karb as sorbent material, adsorbing and removing is as the acetic acid of impurity from vinyl acetic monomer, and absorption back resin carries out desorb with vinyl acetic monomer and alcohol mixture, then through rectifying Separation and Recovery in addition.The clear 53-135920 of Japanese Patent adopts gac fractionation by adsorption acetic acid from waste water; Take in adsorption column to feed gas then or sorbent material taken out the method for centrifuge dehydration; After removing the remaining water of part in adsorbent bed; Again with the method desorption of thermal regeneration and reclaim acetic acid, to improve the concentration that reclaims acetic acid.Chinese patent CN01125273 adopts gac fractionation by adsorption acetic acid from waste water, washs adsorption column with methanol aqueous solution then, makes the acetic acid desorption, adsorbent reactivation.The desorption liquid that contains methyl alcohol and acetic acid continues to contact with cation exchange resin catalyst, generates the methyl acetate product, reclaims through rectifying.
Summary of the invention
The sorbent material of at first selecting a kind of Dichlorodiphenyl Acetate to have good adsorption properties comes out acetic acid fractionation by adsorption from waste water, utilizes the method for substep heating to make acetic acid desorption and the recovery that is adsorbed then, makes adsorbent reactivation simultaneously.
Usually, owing to the capillary action in adsorbent bed, the remaining large quantity of moisture of common meeting in the bed before the regeneration; Make that the acetate concentration add behind the thermal desorption is diluted, do not reach the requirement of recycle or cause the follow-up dense difficulty of putting forward, therefore; The present invention imagines the method that adopts substep to heat and addresses this problem, and promptly substep is controlled Heating temperature, and the first step is warming up to the vaporization temperature of moisture; To remove adsorbent bed part residual water-content; Second step continued to be warming up to the desorption temperature of acetic acid, and desorption also reclaims acetic acid, and the decreasing ratio of residual water was regulated when the concentration of recovery acetic acid can heat up through the first step.
The invention provides a kind of from low-concentration acetic acid wastewater separation, carry dense and reclaim the simple and easy effective ways of acetic acid.Adopt this method, both can be through the selection of sorbent material, separating acetic acid; Purify liquid waste, can improve the concentration that reclaims acetic acid effectively through the selection and the control of the hot regeneration temperature of substep again; Equipment is simple, and control is convenient, and turndown ratio is big; Reclaiming acetic acid and can directly turn back to and further carry densely in the industrial conventional acetic acid separated device, obtain the high purity acetate products, is a kind of method that wastewater treatment and resource are recovered as one that collects.
The said method key step of the present invention is following:
(1) acetic acid content≤4% waste water is fed filled in the adsorption column of solid adsorbent, until the absorption outflow point that reaches capacity, the waste water flow velocity is 0.5～3.0BV/h, is good with flow velocity 1.0BV/h.Said sorbent material is solid adsorbent such as gac, molecular sieve, zeolite, MOX, and preferred sorbent material is a coconut husk class gac.
Effusive waste water before the adsorption column breakthrough point, directly discharging; Effusive waste water returns the waste water storage tank between breakthrough point and the saturation point.
(2) adsorption column that absorption is reached capacity carries out heat temperature raising; Controlled temperature is at 105～150 ℃, and preferably 130 ℃, to remove the residual water in the adsorption column; The recovery ratio of control residual water (distillates the remaining liquid measure of liquid measure/adsorption column; Volume ratio) be 30%～60%, be preferably 35%～40%, the residual water of extraction returns the waste water storage tank.
(3) adsorption column after the dehydration is continued heat temperature raising; Controlled temperature is at 300～350 ℃, and preferably 320～330 ℃, so that acetic acid desorption from the adsorption column; Adopt the ordinary method condensation and collect desorption liquid, can obtain the concentrated vinegar acid solution of concentration >=30% (weight percent).
(4) sorbent material behind the substep thermal regeneration can be reused, and continues to handle acetic acid containing waste water, realizes systemic circulation.
Method of the present invention is handled acetic acid containing waste water and is based on sorbent material to organic selective adsorption performance; Therefore; There is stronger flexibility in the source of Dichlorodiphenyl Acetate waste water, can remove through the combination of different sorbent materials to disturb or detrimental impurity, guarantees the treatment effect of waste water and the efficient that acetic acid reclaims.
Embodiment
Embodiment 1
With 95 grams is 28mm at the YK-15 of the 130 times drying and dewaterings coconut carbon diameter of packing in advance, and in the stainless steel adsorption column that height 600mm is, admission space is 222cm
3, controlled temperature is 20 ℃.Then, being 3% waste water with acetic acid content feeds adsorption column with the flow velocity of 1.0BV/h, and the sampling in the adsorption column exit, uses the gas chromatographic detection acetate concentration.With acetate concentration≤30ppm in the effluent is breakthrough point, and recording wastewater treatment capacity is 446ml, is saturation point with acetate concentration in the effluent 2.9%, and recording waste water accumulative total treatment capacity is 750ml, and when reaching saturation point, the loading capacity of gac is 182.2mg/g
(gac)
After adsorption column is saturated, stop charging, ponding in the emptying post is warming up to 130 ℃ with adsorption column, condensation and intercepting distillate 35ml, and wherein acetate concentration is 4.23%, incorporates in the liquid stock.Then, continue to be warming up to 320 ℃, keep this temperature, till no lime set flows out, be total to intercepting distillate 47ml, the lime set acetate concentration is 33.6%, and the total desorption rate of acetic acid is 96.7%, and the recovery is 91.2%.
Embodiment 2
With 95 grams is 28mm at the YK-15 of the 130 times drying and dewaterings coconut carbon diameter of packing in advance, and in the stainless steel adsorption column that height 600mm is, admission space is 222cm
3, controlled temperature is 20 ℃.Then, being 3% waste water with acetic acid content feeds adsorption column with the flow velocity of 3.0BV/h, and the sampling in the adsorption column exit, uses the gas chromatographic detection acetate concentration.With acetate concentration≤30ppm in the effluent is breakthrough point, and the wastewater treatment capacity that records is 251ml; With acetate concentration in the effluent 2.9% is saturation point, and the waste water accumulative total treatment capacity that records is 1010ml, and when reaching saturation point, the loading capacity of gac is 183.8mg/g
(gac)
After adsorption column is saturated, stop charging, ponding in the emptying post is warming up to 110 ℃ with adsorption column, condensation and intercepting distillate 37ml, and wherein acetate concentration is 4.25%, incorporates in the liquid stock.Then, continue to be warming up to 280 ℃, keep this temperature, till no lime set flows out, be total to intercepting distillate 48ml, the lime set acetate concentration is 31.7%, and the total desorption rate of acetic acid is 96.1%, and the recovery is 87.1%.
Embodiment 3
With 95 grams is 28mm at the YK-15 of the 130 times drying and dewaterings coconut carbon diameter of packing in advance, and in the stainless steel adsorption column that height 600mm is, admission space is 222cm
3, controlled temperature is 30 ℃.Then, being 1% waste water with acetic acid content feeds adsorption column with the flow velocity of 3.0BV/h, and the sampling in the adsorption column exit, uses the gas chromatographic detection acetate concentration.With acetate concentration≤30ppm in the effluent is breakthrough point, and the wastewater treatment capacity that records is 620ml; With acetate concentration in the effluent 2.9% is saturation point, and the waste water accumulative total treatment capacity that records is 1889ml, and when reaching saturation point, the loading capacity of gac is 121.5mg/g
(gac)
After adsorption column is saturated, stop charging, ponding in the emptying post is warming up to 130 ℃ with adsorption column, condensation and intercepting distillate 46ml, and wherein acetate concentration is 1.05%, incorporates in the liquid stock.Then, continue to be warming up to 320 ℃, keep this temperature, till no lime set flows out, be total to intercepting distillate 35ml, the lime set acetate concentration is 29.9%, and the total desorption rate of acetic acid is 96.1%, and the recovery is 90.7%.
Embodiment 4
With 95 grams is 28mm at the YK-15 of the 130 times drying and dewaterings coconut carbon diameter of packing in advance, and in the stainless steel adsorption column that height 600mm is, admission space is 222cm
3, controlled temperature is 30 ℃.Then, being 3% waste water with acetic acid content feeds adsorption column with the flow velocity of 0.6BV/h, and the sampling in the adsorption column exit, uses the gas chromatographic detection acetate concentration.With acetate concentration≤30ppm in the effluent is breakthrough point, and recording wastewater treatment capacity is 351ml, and when reaching breakthrough point, the loading capacity of gac is 112.6mg/g
(gac)
After adsorption column reaches breakthrough point, stop charging, ponding in the emptying post is warming up to 130 ℃ with adsorption column, condensation and intercepting distillate 46ml, and wherein acetate concentration is 0.936%, incorporates in the liquid stock.Then, continue to be warming up to 320 ℃, keep this temperature, till no lime set flows out, be total to intercepting distillate 35.5ml, the lime set acetate concentration is 26.9%, and the total desorption rate of acetic acid is 92.0%, and the recovery is 88%.
Claims (7)
1. the method for acetic acid is separated and reclaimed to an absorption and the hot regenerative combination of substep from waste water, it is characterized in that in turn including the following steps:
(1) acetic acid content≤5% waste water is fed filled in the adsorption column of solid adsorbent, until the absorption outflow point that reaches capacity, the waste water flow velocity is 0.5～3.0BV/h.Said sorbent material is solid adsorbent such as gac, molecular sieve, zeolite, MOX.
(2) adsorption column that absorption is reached capacity carries out thermal regeneration, and controlled temperature is at 105～150 ℃, and removing the residual water in the adsorption column, and the recovery ratio of control residual water (distillating the remaining liquid measure of liquid measure/adsorption column, volume ratio) is 30%～60%.The residual water of extraction returns the waste water storage tank.
(3) adsorption column after the dehydration is continued heat temperature raising, controlled temperature is at 280～350 ℃, so that acetic acid desorption from the adsorption column adopts the ordinary method condensation also to collect desorption liquid, obtains spissated acetum.
(4) sorbent material behind the substep thermal regeneration can be reused, and accomplishes systemic circulation.
2. method according to claim 1 is characterized in that, the sorbent material of use in waste water treatment is solid adsorbent such as gac, molecular sieve, zeolite.
3. according to claim 1 and 2 described methods, it is characterized in that, in absorption phase; Waste water is through the effluent separated into two parts behind the adsorption column; A part is that absorption reaches breakthrough point effluent before, and its acetic acid is removed fully, can directly discharge; Another part be the adsorption penetration point to the effluent between the saturation point, this part solution returns the waste water storage tank.
4. according to claim 1 and 2 described methods, it is characterized in that preferred sorbent material is a coconut husk class gac.
5. method according to claim 1 is characterized in that, the preferred temperature of step (2) is 130 ℃, and recovery ratio is controlled at 35%～40%, and acetate concentration is 3.5%-4% (weight percent) in the extraction liquid, can directly return the waste water storage tank.
6. method according to claim 1 is characterized in that, step (3) preferred temperature be 320～330 ℃, the acetate concentration that distillates liquid can reach more than 30% (wt), acetic acid yield is more than 85%.
7. according to claim 1,2,3,4,5,6 described methods, it is characterized in that the decreasing ratio of acetic acid is 100% in the waste water, total desorption rate of acetic acid is that sorbent material is reusable more than 95% behind the stepwise regeneration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102696851A CN102381955A (en) | 2010-08-31 | 2010-08-31 | Method for recycling acetic acid from industrial wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102696851A CN102381955A (en) | 2010-08-31 | 2010-08-31 | Method for recycling acetic acid from industrial wastewater |
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| CN102381955A true CN102381955A (en) | 2012-03-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675407A (en) * | 2020-05-18 | 2020-09-18 | 南京工业大学 | Treatment method of low-concentration acetic acid wastewater |
| CN115279724A (en) * | 2020-03-26 | 2022-11-01 | 株式会社大赛璐 | Preparation method of purified acetic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5035056A (en) * | 1973-07-17 | 1975-04-03 | ||
| CN1133833A (en) * | 1994-04-07 | 1996-10-23 | 戈里特斯奇公司 | Method and apparatus for recovering carboxylic acids from aqueous solutions |
-
2010
- 2010-08-31 CN CN2010102696851A patent/CN102381955A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5035056A (en) * | 1973-07-17 | 1975-04-03 | ||
| CN1133833A (en) * | 1994-04-07 | 1996-10-23 | 戈里特斯奇公司 | Method and apparatus for recovering carboxylic acids from aqueous solutions |
Non-Patent Citations (1)
| Title |
|---|
| 侯宝军等: "吸附-热再生法回收废水中醋酸的研究", 《高校化学工程学报》, vol. 22, no. 4, 15 August 2008 (2008-08-15), pages 580 - 584 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115279724A (en) * | 2020-03-26 | 2022-11-01 | 株式会社大赛璐 | Preparation method of purified acetic acid |
| CN111675407A (en) * | 2020-05-18 | 2020-09-18 | 南京工业大学 | Treatment method of low-concentration acetic acid wastewater |
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Application publication date: 20120321 |