CN109053423A - A kind of purification process and its recycling and processing device of ammonium adipate waste liquid - Google Patents
A kind of purification process and its recycling and processing device of ammonium adipate waste liquid Download PDFInfo
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- CN109053423A CN109053423A CN201811189344.6A CN201811189344A CN109053423A CN 109053423 A CN109053423 A CN 109053423A CN 201811189344 A CN201811189344 A CN 201811189344A CN 109053423 A CN109053423 A CN 109053423A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention discloses the purification process and its recycling and processing device of a kind of ammonium adipate waste liquid, and ammonium adipate waste liquid to be processed is divided into waste liquid A and waste liquid B two parts, and ammonium hydroxide or NH are added into waste liquid A3Gas makes its pH alkalescence, and generates Al (OH)3Precipitating；Filtering removal Al (OH)3Precipitating, obtains filtrate A；Waste liquid B is mixed with above-mentioned filtrate A, makes acquired solution pH 6.5-7.5；The solid suspension contained in the mixed solution is removed with fine filter, and using the filtrate as feeding liquid, while to be free of Cl‑Water purification as cleaning solution is received, while being passed through in diffusion dialyzer to remove Cl‑, obtain recovered liquid.Corresponding ammonium adipate devil liquor recovery processing unit is further disclosed simultaneously.The present invention, which does not introduce any additional foreign ion to electrolyte, ensure that the quality of electrolyte after purification；Entire treatment process concise in technology simultaneously, cooled down without heating and etc., energy consumption is greatly reduced；It does not consume any extra chemicals in addition to ammonia, does not generate extraneous byproducts.
Description
Technical field
The present invention relates to a kind of organic liquid waste processing method and its device, more particularly to a kind of ammonium adipate is useless
The purification process and its recycling and processing device of liquid.
Background technique
The production process of anode foil for aluminum electrolytic capacitor includes corroding and being melted into two big steps, in formation process most often
Electrolyte is ammonium adipate, and concentration is typically up to 100g/L, the ammonium adipate electrolyte of usually every chemical conversion production line
Usage amount is 4-10m3.Electrolyte is in use for some time due to being wherein mixed into more aluminium ion and some other
Impurity causes the Waste Acid From Hua Cheng Foil electrical property of production that scheduled requirement is gradually not achieved, at this moment need to just prepare new ammonium adipate solution
It could continue normally to produce to replace old electrolyte, these replaced electrolyte are ammonium adipate waste liquid.It uses at present
In electrode foil production ammonium adipate price it is very high, it is per ton to reach 15000 yuan, this make replace ammonium adipate electrolyte liquid at
This is very high, is heavy burden for electrode foil industry, has raised production cost, reduces its economic competitiveness.Separately
Outside, due to containing a large amount of organic matter (adipic acid root) and ammonium salt in these waste liquids, it is necessary to just through the appropriate harmless treatment of row
It can discharge, otherwise also will cause serious water body/soil pollution, there is very big environment hidden danger.
In the prior art, notification number is that the Chinese patent of CN101219946B discloses a kind of place of ammonium adipate waste liquid
Recovery method and its recovery system are managed, it utilizes strong inorganic acid (such as HNO3, H2SO4Or HCl) acid is carried out to ammonium adipate waste liquid
Change, using generation adipic acid at low temperature solubility (at 30 DEG C be 3.01g/100g water) far below solubility (100 under high temperature
At DEG C be 160g/100g water) characteristic decrease temperature crystalline is carried out to it, using be separated by solid-liquid separation collect obtain more pure adipic acid
Solid crystal；This method can effectively recycle the adipic acid ingredient in ammonium adipate, be circularly used for the industries such as electrode foil, economy effect
Benefit and environmental benefit are more significant.But the processing recovery method has the disadvantage in that (1) in order to avoid in the adipic acid of recycling
It is middle to carry the chemical conversion of multipair electrode foil secretly there are the SO of adverse effect4 2-And Cl-Ion, the strong inorganic acid first choice HNO for acidification3,
But HNO3The market price be much higher than H2SO4And HCl, it is less susceptible to obtain for enterprise, operability is restricted and cost
It is higher；(2) in order to make foreign ion (such as NO carried secretly in adipic acid solid3 -) less, it needs to clean using more pure water, from
And cause the wastewater flow rate generated larger, and wherein contain limiting emission object COD (adipic acid) and total nitrogen (NH4 +And NO3 -), waste water
Processing cost it is higher；(3) it needs that waste liquid is heated and cooled down in treatment process, while what is obtained contains NH4NO3Filter
Liquid needs are evaporated crystallization, can just obtain solid, energy consumption is very high.Based on the above issues, so that the processing recovery method is in electricity
Acceptance is not still high in the foil industry of pole, and practical application value is too low.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of purification process of ammonium adipate waste liquid
And its recycling and processing device, the purification process is easy to operate, and economic cost is low, and practical application value is high.
To achieve the above object, the present invention provides the following technical scheme that a kind of purification process of ammonium adipate waste liquid, packet
Include following steps:
Step 1: alkaline matter will be added in ammonium adipate waste liquid to be processed, adjusts its pH to 7.5-8.5；
Step 2: filtering removes aluminum hydroxide solid, obtains filtrate A；And the acid liquid that adjusts is added and mixes, it is mixed
Liquid, gained pH of mixed are 6.5-7.5；
Step 3: mixed liquor is diffused dialysis processing by diffusion dialyzer, to remove Cl-, finally obtain processing
Liquid；
The alkaline matter is NH3Gas or saturation ammonium hydroxide.
As a further improvement of the present invention, ammonium adipate waste liquid is first divided into waste liquid A and waste liquid B in step 1, then to
NH is added in waste liquid A3Gas or saturation ammonium hydroxide；The acid liquid that adjusts is waste liquid B.
As a further improvement of the present invention, waste liquid A accounts for the 50-95% of ammonium adipate waste liquid total volume.
As a further improvement of the present invention, Al (OH) is added into waste liquid A before step 2 filtering3Solid crystal seeds, so
Waste liquid A is filtered again afterwards.
As a further improvement of the present invention, Al of the aluminum hydroxide solid being obtained by filtration in step 2 as addition next time
(OH)3Solid crystal seeds use.
It as a further improvement of the present invention, include liquid waste tank, stirred tank, filter, mixing channel, diffusion infiltration
Parser, the pure water storage tank for placing pure water and the recycling liquid bath for purification and recovery electrolyte；The stirred tank and useless
Liquid storage tank is connected with filter；The filter is connected with mixing channel；The diffusion dialyzer and mixing channel, pure water storage tank
And recycling liquid bath is connected to；Waste liquid A in liquid waste tank passes sequentially through stirred tank, filter, mixing channel, diffusion
Dialyzer eventually arrives at recycling liquid bath；Waste liquid B positioned at liquid waste tank passes sequentially through mixing channel, diffusion dialyzer, eventually arrives at
Recycle liquid bath.
As a further improvement of the present invention, anion-exchange membrane is provided in the diffusion dialyzer.
As a further improvement of the present invention, the mixed liquor being passed through in the diffusion dialyzer is with pure water volume flow ratio
1-1.5:1-1.5 the mixed liquor traffic intensity being passed through is 1.2-21.0Lh-1·m-2。
As a further improvement of the present invention, the stirred tank and mixing channel are provided with pH detection probe.
It as a further improvement of the present invention, further include having fine filter, the fine filter and mixing channel and diffusion dialyzer
It is connected to.
Beneficial effects of the present invention:
(a) any additional foreign ion (such as NO is not introduced to electrolyte3-, Cl-, SO4 2-Deng), it ensure that purifying
The quality of electrolyte afterwards；
(b) entire treatment process concise in technology simultaneously, without heating is cooling and evaporative crystallization, energy consumption significantly under
Drop；
(c) any extra chemicals are not consumed in addition to ammonia, do not generate extraneous byproducts (such as NH4NO3Deng).
Detailed description of the invention
Fig. 1 is the structural schematic diagram of recycling and processing device in the present invention；
Appended drawing reference: 101, liquid waste tank；102, stirred tank；103, filter；104, mixing channel；105, refined filtration
Device；106, pure water storage tank；107, diffusion dialyzer；108, anion-exchange membrane；109, liquid bath is recycled；110,Cl-Ionic impurity
The low concentration wastewater storage tank of enrichment.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is described in more detail.
Embodiment 1: the ammonium adipate waste liquid group of collection becomes ammonium adipate 100g/L, pH 5.8, Cl-Impurity concentration is
100mg/L, Al3+Impurity concentration is 0.54mg/L.Devil liquor recovery processing unit is as shown in Figure 1, wherein set stirred tank
102pH setting value is 7.5, and mixing channel 104pH setting value is 7.2.Operation result shows that the flow-rate ratio of waste liquid A and waste liquid B is about
9.5:1, filtering resulting solution composition by fine filter 105 is ammonium adipate 100g/L, pH 7.2, Cl-Impurity concentration is
100mg/L, Al3+Impurity concentration is 0.11mg/L.In diffusion dialyzer 107, anion-exchange membrane 108 selects Shandong day dimension film
The volume flow ratio of the TWDDA model anionic membrane of Technology Co., Ltd., import feed liquid and pure water is 1:1, traffic intensity control
System is 6Lh-1·m-2.The recycling electrolyte group obtained at this time becomes ammonium adipate 98g/L, pH 7.2, Cl-Impurity concentration is
59mg/L, Al3+Impurity concentration is 0.11mg/L.After reclaiming clean is handled, the pH of original solution restores from 5.8 to 7.2,
Al3+Impurity has been removed 79%, Cl-Impurity has been removed 41%, and the loss late of adipic acid radical ion is only 7.02%.
Embodiment 2: being 8.5 by pH setting value in stirred tank 102, and pH setting value is 6.5 in mixing channel 104, other
Condition is same as Example 1.Operation result shows that the flow-rate ratio of waste liquid A and waste liquid B is about 1.9:1 in this case.By returning
After receiving purified treatment, the pH of original solution restores from 5.8 to 6.5, Al3+Impurity has been removed 54%, Cl-Impurity is removed
41%, and the loss late of adipic acid radical ion is 7%.
Embodiment 3-7: being that 1:1 adjusts import in diffusion dialyzer 107 by the volume flow ratio of import feed liquid and pure water
Feed liquid flow intensity value size, other all conditions keep consistent with embodiment 1.In this case, gained recycles electrolyte pH
It is 7.2, Al3+Removal of impurity is 79%.Cl-The removal rate of impurity and the loss late of adipic acid radical ion become with traffic intensity
Change and changes.
Embodiment 8: the volume flow ratio of 107 import feed liquid of diffusion dialyzer and water receiving liquid is adjusted to 1.5:1, feed liquid
Inlet flow rate intensity is 6.0Lh-1·m-2, water receiving liquid inlet flow rate intensity is 4.0Lh-1·m-2, other conditions and implement
Example 1 is consistent.After reclaiming clean is handled, Cl-Impurity has been removed 35%, and the loss late of adipic acid radical ion is only
6.4%.
Embodiment 9: the volume flow ratio of 107 import feed liquid of diffusion dialyzer and water receiving liquid is adjusted to 1:1.5, feed liquid
Inlet flow rate intensity is 4.0Lh-1·m-2, water receiving liquid inlet flow rate intensity is 6.0Lh-1·m-2, other conditions and implement
Example 1 is consistent.After reclaiming clean is handled, Cl-Impurity has been removed 49%, and the loss late of adipic acid radical ion is only
8.5%.
Embodiment 10: anion-exchange membrane used in diffusion dialyzer 107 is changed to Japanese ASTOM company
Neosepta AFN anion-exchange membrane, other conditions are consistent with embodiment 1.It is original useless after reclaiming clean is handled
The pH of liquid restores from 5.8 to 7.2, Al3+Impurity has been removed 79%, Cl-Impurity has been removed 56%, and adipic acid radical ion
Loss late is only 4.35%.
Ammonium adipate thin stillage recycling processing unit, as shown in Figure 1.First extremely by the unified collection of the ammonium adipate waste liquid of factory
In liquid waste tank 101, then using pump divide two-way from liquid waste tank 101 outward distribution conveying waste liquid, be denoted as respectively waste liquid A and
Waste liquid B.Waste liquid A is delivered to stirred tank 102, enters NH3 gas or saturation ammonium hydroxide together thereto；In stirred tank 102
It is additionally provided with pH monitoring probe, NH is added3Amount controlled by pH value, terminal pH is set as between 7.5-8.5；In order to increase this mistake
Al (OH) in journey3The precipitation rate of solid, while increasing its filtrability, Al (OH) can be added into stirred tank 1023Solid
Crystal seed.The solidliquid mixture reacted in stirred tank 102 is transported in filter 103 and is separated by solid-liquid separation；Gained
To solid filter cake mainly organize as Al (OH)3Solid can be handled directly as solid waste, part Al (OH) therein3Solid
It is also used as crystal seed and obtains reuse；Cleaner liquid obtained in this process is sent in mixing channel 104, and the waste liquid with subacidity
The direct hybrid reaction of B；PH detection probe also is provided in mixing channel 104, and the flow of waste liquid B is popped one's head in by pH and automatically controlled, so that
PH in mixing channel 104 is controlled between 6.5 to 7.5.The mixed solution exported in mixing channel 104 is using 105 mistake of fine filter
Filter is to completely remove any solid suspended particles that may wherein contain, since liquid solid content is minimum at this time, fine filter 105
It lasts a long time.It is achromaticity and clarification clear solution through the filtered solution of fine filter 105, pH is accurately adjusted, and wherein
Part Al3+Precipitated removal comes out, wherein Al3+Removal ratio by waste liquid A and waste liquid B ratio and filter
Set pH control terminal is determined that total removal rate is up to 40-85% in 103.Uniquely exceed permissible value in solution at this time
Only Cl-Impurity.The clear solution that fine filter 105 is exported as feed liquid, while in pure water storage tank 106 be free of Cl-Impurity
Water purification be passed into the form of reverse flow in diffusion dialyzer 107 as acceptable solution；It is handed in diffusion dialyzer 107 containing anion
Film 108 is changed, the Cl during handling herein in ammonium adipate waste liquid-Impurity is (with NH4Cl form) preferential cross-film diffusion transport is to connecing
It receives in liquid liquid stream.The Cl- in waste liquid is removed by partial selective in the process, obtain can direct reuse purifying electrolysis liquid simultaneously
It is delivered to recycling liquid bath 109；Acceptable solution liquid stream has received most Cl in waste liquid at the same time-Impurity and a small amount of adipic acid
Ammonium leakage, has obtained Cl-The low concentration wastewater of impurity enriched.
Formation process generally carries out at high temperature, and ammonium adipate electrolytic bath temperature is up to 60-95 DEG C.Since ammonium salt is weak
Alkali salt can have following chemical balance NH in aqueous solution4 ++H2O→NH3·H2O+H+, NH at high temperature3Readily volatilized loss,
Ammonium adipate bath acidity is caused to increase.Apparent ammonia smell can be usually smelt in electrode foil industry formation workshop, it can be with
Above-mentioned principle is supported from side.The Life cycle chemical constituent monitoring result of ammonium adipate forming liquid is further displayed, newly
The ammonium adipate electrolyte pH of preparation is 6.5-7.5, and however as the progress of chemical conversion production, tank liquor pH is gradually reduced；When the slot
Liquid by it is discarded when (after about 25 days) its pH drop to 5.8.Therefore, first chemical group of electrolyte and depleted electrolytes is newly prepared
It is the significant changes of its acidity at difference.
The production of electrode foil is currently to be carried out in a manner of automatic assembly line, and the light foil breadth used is generally 0.50m,
Operation linear velocity is 2-5m/min.(generally 25 days), the aluminium foil area of processing in the life cycle of ammonium adipate electrolyte
Up to 90000m2.Since the aluminium foil area of processing is very big, the trace impurity accumulation carried secretly in filtering also just be can not be ignored
?.For low-voltage foil production, need to carry out to corrode hair engaging aperture processing before formation process using high concentration HCl, treated
Aluminium foil needs to wash off Cl using high purity water-Impurity.Electrode foil industry is usually required the remaining Cl of aluminium foil surface-Impurity is clear
It is washed till 1mg/m2Below to reach quality control requirement, however much etched foil Cl of producers in practical operation China-Content is still more
Up to 10-16mg/m2(electronic component and material, 20 (2001) 12-13).In subsequent formation process, these Cl being adsorbed-
Impurity can partially be got off by the adipic acid root anion exchange of high concentration, stay in electrolyte, cause Cl in electrolyte-It is dense
Degree rises.The purity of chemicals that electrode foil industry uses requires capacitor stage ammonium adipate that is very high, such as producing for electrode foil
It requires to be practically free of any Cl in solid-Impurity (< 0.8mg/kg).Our Life cycle to ammonium adipate forming liquid
It learns component monitoring result to show, any Cl is practically free of in the forming liquid newly prepared-Impurity (< 1mg/L), however its Cl-It is miscellaneous
Matter concentration with chemical conversion production can gradually increase, and this tired in the prime electrolytic bath in multistage chemical conversion production line
Product is more significant, and concentration increases to 200-300mg/L.Therefore, second chemical composition of new electrolyte and waste electrolyte is poor
Different is wherein Cl-The accumulation of impurity.In previous work (Chinese patent application CN106868544A), we have proposed a kind of benefits
With diffusion dialysis technology from sulfuric acid system electrolyte selective removal univalent anion impurity (such as Cl-) method.We
It is found for the first time in neutral high concentration ZnSO4In solution system, Cl-It is biggish relative to hydration radius since hydration radius is smaller
SO4 2-Can Cl preferentially be realized through anion-exchange membrane-Selective removal.In ammonium adipate electrolyte system, situation
Also very similar, since adipic acid root is dicarboxylic acids, for-divalent anion, hydration radius can be noticeably greater than the Cl of -1 valence-
Ion.Therefore, also with the ion selectivity separation process based on diffusion dialysis, we can be from the waste liquid selectively
Remove substantial portion of Cl-Ionic impurity.
Aluminium foil is anode in electrode foil formation process, and graphite or Ti electrode are cathode.Aluminium foil surface can shape in the process
At one layer of fine and close Al2O3Passivation layer, but at the same time inevitable that micro Al can be with Al3+Form is dissolved into chemical conversion
In electrolyte.Due to Al3+Minimum (the Al (OH) of solubility in the electrolyte close to pH neutrality3Solubility product Ksp=3 ×
10-34), therefore these Al for being dissolved out3+Ion may reach Al (OH)3Oversaturated state, to cause Al (OH)3
It is not that inner roller surface is precipitated that solid pastes in electrolytic bath, scratches aluminium foil surface.Our full life to ammonium adipate forming liquid
Period chemical constituent monitoring result shows, the Al in formation process in forming liquid3+Ion concentration quickly (~1 day) just from can not examine
(< 0.1mg/L) is increased to saturation state (~0.250mg/L) out, and is gradually increased in chemical conversion production process (the 2nd -25 day)
Add to about 0.40mg/L.According to this data, we judge, the Al in entire formation process3+Ion is nearly always at saturation shape
State, later period Al3+Ion concentration it is slightly increased the reason is that due to electrolyte ph slightly decline.In conclusion new electrolyte
Third chemical composition difference with waste electrolyte is wherein Al3+The accumulation of impurity and Al (OH)3Saturation state it is different.
In previous ammonium adipate waste liquor recovery process, people only generally recognize to be mixed into electrolyte harmful miscellaneous
Matter needs to remove, but recognizes the specific inefficacy mechanism of ammonium adipate electrolyte is specific not yet.Condition is recognized herein
Under, it is merely able to the selective adipic acid root by waste liquid and separates (such as Chinese patent in the form of adipic acid crystals
CN101219946B) to achieve the purpose that purifying and reuse.In the present invention, by certain electrode foil producer low pressure foil production line
The detailed chemical constituent analysis of the Life cycle of ammonium adipate forming liquid, we recognize that ammonium adipate electrolyte is caused to lose
The basic reason of effect is: (1) NH during high temperature chemical conversion3Gas evolution, electrolyte pH decline, acidity increase；(2) low pressure is rotten
The Cl that aluminium foil surface adsorbs during erosion-Ion is released in electrolytic bath, causes Cl in tank liquor-Content is exceeded；(3) electrolyte
In the Al that has been mixed into3+Impurity, so that Al (OH) in electrolyte3Reach saturation, inner roller surface is especially in electrolytic bath and is precipitated
Al(OH)3Solid makes finished product foil surface mechanical defect occur.Therefore, we have proposed a kind of completely different in the present invention
Ammonium adipate waste liquid purifying and reuse thinking: by chemical constituent adjustment and selective membrane separation method, selective removal oneself
Cl in diacid waste liquor of ammonium-And Al3+, while its acidity is adjusted to initial value, so that it is reached an agreement again with brand-new electrolyte, from
And direct reuse is melted into production line in original.Its concrete processing procedure is as follows:
1, ammonium adipate waste liquid to be processed is divided into waste liquid A and waste liquid B two parts in proportion；
2, appropriate concentrated ammonia liquor is added into waste liquid A or is passed through NH3Gas, make its pH alkalescence (pH from~5.8 improve to
> 7.5), Al (OH) in the solution at this time3Solubility can be greatly reduced, and generate Al (OH)3Precipitating.In order to accelerate Al (OH)3It is heavy
The generation in shallow lake simultaneously increases its filterability, and a small amount of Al (OH) is added thereto3Solid crystal seeds simultaneously stir；
3, the Al (OH) in filtering removal solution A3Precipitating, obtains clear filtrate A and Al (OH)3Filter cake.Part filter cake can
Continue to reuse as crystal seed；
4, waste liquid B is mixed with above-mentioned filtrate A, acquired solution pH is made to restore (to prepare adipic acid with new between 6.5-7.5
Ammonium electrolyte is consistent).Simultaneously as having had been removed most Al in waste liquid A3+Impurity, the at this time Al in solution3+It is miscellaneous
Matter concentration is greatly reduced to acceptable level；
5, any solid suspension that may contain in the mixed solution is removed using fine filter (accurate filter), and will
The filtrate as feeding liquid, while be free of Cl-Water purification as cleaning solution is received, while being passed through in a diffusion dialyzer.
Contain anion-exchange membrane in diffusion dialyzer, feed liquid and acceptable solution are located at the two sides of film.In the driving of ion concentration difference
Under, the Cl in feed liquid-(with NH4Cl form) and adipic acid radical ion (in the form of ammonium adipate) can be from high concentration side (feed liquid
Side) to low concentration side (receiving liquid side) cross-film diffusion transport；But in the process due to Cl-Be hydrated radius it is small, relative to oneself two
Acid ion can show good preferential selective penetrated property, so that obtaining under lesser ammonium adipate loss late higher
Cl-Removal rate realizes Cl in feed liquid-Selective removal；
6, Cl is removed-Solution after impurity can direct reuse to original be melted into production line.
The present invention further discloses a kind of corresponding ammonium adipate devil liquor recovery processing unit simultaneously, under which successively includes
Column component: ammonium adipate liquid waste tank 101, stirred tank 102, filter 103, mixing channel 104, fine filter 105 and diffusion
Dialyzer 107, pure water storage tank 106 and recovered liquid storage tank 109.The entry/exit material mouth of above-mentioned each component is directly or indirectly through pump
It is connected with each other with pipeline.Recycling and processing equipment of the invention can to chemical conversion waste liquid component be adjusted make its again with brand-new
Electrolyte is reached an agreement, so that direct reuse is melted into production line in original.It is tested by the actual production of electrode foil producer, recycling electrolysis
The Waste Acid From Hua Cheng Foil quality that liquid produces is consistent with new electrolyte.
The advantages of this patent recovery and treatment method and device, is: not introducing to electrolyte (a) any additional miscellaneous
Matter ion (such as NO3 -, Cl-, SO4 2-Deng), it ensure that the quality of electrolyte after purification；(b) entire treatment process technique letter simultaneously
Clean, without heating is cooling and evaporative crystallization, energy consumption is greatly reduced；(c) any extra chemicals are not consumed in addition to ammonia, no
Generate extraneous byproducts (such as NH4NO3Deng).
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of purification process of ammonium adipate waste liquid, it is characterised in that: the following steps are included:
Step 1: alkaline matter will be added in ammonium adipate waste liquid to be processed, adjusts its pH to 7.5-8.5；
Step 2: filtering removes aluminum hydroxide solid, obtains filtrate A；And the acid liquid that adjusts is added and mixes, mixed liquor is obtained, institute
Obtaining pH of mixed is 6.5-7.5；
Step 3: mixed liquor is diffused dialysis processing by diffusion dialyzer (107), to remove Cl-, finally obtain processing
Liquid；
The alkaline matter is NH3Gas or saturation ammonium hydroxide.
2. a kind of purification process of ammonium adipate waste liquid according to claim 1, it is characterised in that: first by oneself in step 1
Diacid waste liquor of ammonium is divided into waste liquid A and waste liquid B, then adds NH into waste liquid A3Gas or saturation ammonium hydroxide；The acidity adjusts liquid
Waste liquid B.
3. a kind of purification process of ammonium adipate waste liquid according to claim 2, it is characterised in that: waste liquid A accounts for adipic acid
The 50-95% of waste liquor of ammonium total volume.
4. a kind of purification process of ammonium adipate waste liquid according to claim 3, it is characterised in that: before step 2 filtering
Al (OH) is added into waste liquid A3Then solid crystal seeds are again filtered waste liquid A.
5. a kind of purification process of ammonium adipate waste liquid according to claim 4, it is characterised in that: filtered in step 2
Al (OH) of the aluminum hydroxide solid arrived as addition next time3Solid crystal seeds use.
6. according to claim 1 to a kind of recycling and processing device of ammonium adipate waste liquid described in 5 any one, feature exists
In: it include liquid waste tank (101), stirred tank (102), filter (103), mixing channel (104), diffusion dialyzer
(107), for placing the pure water storage tank (106) of pure water and for the recycling liquid bath (109) of purification and recovery electrolyte；The stirring
Reactor tank (102) is connected with liquid waste tank (101) and filter (103)；The filter (103) and mixing channel (104) phase
Connection；The diffusion dialyzer (107) is connected to mixing channel (104), pure water storage tank (106) and recycling liquid bath (109)；Position
Waste liquid A in liquid waste tank (101) passes sequentially through stirred tank (102), filter (103), mixing channel (104), diffusion
Dialyzer (107) eventually arrives at recycling liquid bath (109)；Waste liquid B positioned at liquid waste tank (101) passes sequentially through mixing channel
(104), diffusion dialyzer (107) eventually arrive at recycling liquid bath (109).
7. a kind of recycling and processing device of ammonium adipate waste liquid according to claim 6, it is characterised in that: the diffusion is seeped
Anion-exchange membrane (108) are provided in parser (107).
8. a kind of recycling and processing device of ammonium adipate waste liquid according to claim 7, it is characterised in that: the diffusion is seeped
The mixed liquor and pure water volume flow ratio being passed through in parser (107) are 1-1.5:1-1.5, and the mixed liquor traffic intensity being passed through is
1.2-21.0L·h-1·m-2。
9. a kind of recycling and processing device of ammonium adipate waste liquid according to claim 6, it is characterised in that: the stirring is anti-
Tank (102) and mixing channel (104) is answered to be provided with pH detection probe.
10. a kind of recycling and processing device of ammonium adipate waste liquid according to claim 6, it is characterised in that: further include having
Fine filter (105), the fine filter (105) are connected to mixing channel (104) and diffusion dialyzer (107).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219946A (en) * | 2007-12-25 | 2008-07-16 | 乳源瑶族自治县东阳光化成箔有限公司 | Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof |
| CN103508596A (en) * | 2012-06-29 | 2014-01-15 | 温州大学 | Treatment system and recycling method of ammonium adipate cleansing wastewater |
| CN106868544A (en) * | 2017-03-06 | 2017-06-20 | 温州大学 | A kind of method of selective removal univalent anion impurity in electrolyte from sulfuric acid system |
| CN107200304A (en) * | 2017-06-21 | 2017-09-26 | 周口师范学院 | A kind of electrode foil corrodes waste liquor recovery process |
-
2018
- 2018-10-12 CN CN201811189344.6A patent/CN109053423B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219946A (en) * | 2007-12-25 | 2008-07-16 | 乳源瑶族自治县东阳光化成箔有限公司 | Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof |
| CN103508596A (en) * | 2012-06-29 | 2014-01-15 | 温州大学 | Treatment system and recycling method of ammonium adipate cleansing wastewater |
| CN106868544A (en) * | 2017-03-06 | 2017-06-20 | 温州大学 | A kind of method of selective removal univalent anion impurity in electrolyte from sulfuric acid system |
| CN107200304A (en) * | 2017-06-21 | 2017-09-26 | 周口师范学院 | A kind of electrode foil corrodes waste liquor recovery process |
Non-Patent Citations (2)
| Title |
|---|
| 杜明桂 等: "扩散渗析法回收铝箔腐蚀废酸中HCl", 《辽宁化工》 * |
| 陈庆 等: "基于膜分离的电极箔行业减排降耗过程研究", 《水处理技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746291A (en) * | 2019-09-18 | 2020-02-04 | 山东凯米科环保科技有限公司 | Purification method of ammonium adipate waste liquid and recovery processing device thereof |
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