CN110194501A - From the continuous process and continuous device for recycling iodide in waste water containing iodine - Google Patents
From the continuous process and continuous device for recycling iodide in waste water containing iodine Download PDFInfo
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- CN110194501A CN110194501A CN201910363801.7A CN201910363801A CN110194501A CN 110194501 A CN110194501 A CN 110194501A CN 201910363801 A CN201910363801 A CN 201910363801A CN 110194501 A CN110194501 A CN 110194501A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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Abstract
The present invention provides a kind of from waste water containing iodine extracts the continuous process and continuous device of iodide.The continuous process includes: waste water containing iodine, acid and oxidant to be continuously conveyed into continuous reacting device to carry out continuous reaction, and continuous reacting device is filled with active carbon；Lye and eluant, eluent are continuously delivered to carry out serialization desorption reaction enclosure in continuous reacting device, obtain the desorption attached liquid containing iodide ion；Processing is extracted to the desorption attached liquid containing iodide ion, obtains iodide.Enlarge-effect caused by batch charge mixes unevenly because of local material in the process can be avoided using above-mentioned continuous process, while being conducive to improve the rate of recovery of iodine, reduced process costs, and also can be reduced security risk and occur.
Description
Technical field
The present invention relates to iodide recycling fields, in particular to a kind of company for recycling iodide from waste water containing iodine
Continuousization method and continuous device.
Background technique
Iodine and iodide are common chemical raw materials, widely used, and consumption is huge, but it is expensive.After production,
Contain a large amount of iodide ion in waste water.If direct emission, the huge waste of iodine resource is not only caused, pole also is caused to environment
Big harm.
Current existing iodine recovery process includes following several:
(1) ion-exchange
If the content of iodine is lower in sample, it is insufficient to allow iodine Precipitation, it is necessary to first be enriched with to iodine.Ion exchange
Resin can play the effect of enrichment iodine well.With adsorption effect, good, desorption and regeneration is easy absorption resin, performance is stable,
The features such as scope of application is wide, practicability is good.The principle of ion exchange resin is selected to be usually that selection exchange capacity is big, be easy again
Raw, long-lived resin.Ion-exchange is to adsorb material liquid in ion exchange column, is then desorbed again, iodine analysis
Process.Common parsing agent is sodium sulfite and sodium hydroxide.Since strongly basic anionic resin has very by force more iodide ions
Exchange adsorption ability, and chemical stability is high, alkali-resistant, therefore during exchange adsorption iodide ion, general to use
Strongly basic anionic resin fills column.Ionic adsorption fado is used in the process flow that iodine is extracted from algae.
After bittern, brine or kelp-soaking liquid containing iodide are acidified with acid, add oxidizing former containing iodine
Feed liquid adsorbs iodine by ion exchange column, then parses elution iodine from resin with solvent again, and be added into the solvent containing iodine
Oxidant and sulfuric acid analyse iodine, are most separated and be refining to obtain afterwards finished product iodine.In this method, the performance of ion exchange resin determines
The pH range of process.Using 717 type anion exchange resin extract exhaust gas water in field in iodine, iodine exchange adsorption rate up to 96% with
On, total recovery is up to 85%.There are two ways to desorption: one is with sulfite solution elution iodine is precipitated with potassium chlorate again,
Centrifuge separation, thick iodine is through sulfuric acid melt refining；Another kind is eluted with sodium hydroxide solution, the iodide such as generation, in reactor
Middle sulfuric acid acidification makes the free precipitating of iodine, filtering and centrifuge separation, re-refines.This method requires raw material iodine concentration > 300mg/L.
The advantages of ion exchange adsorption, using ion exchange resin it is clear that can play the iodine of low concentration in solution
Preenrichment effect, meanwhile, the selective absorption of ion exchange resin also avoids the interference of chloride ion and bromide ion etc., improves
The purity of iodine has many advantages, such as that parsing regeneration is easy.But resin is readily dissolved in the organic solvents such as DMF or DMSO, waste water
Composition may be affected to the structure and function of resin.Its process flow chart is shown in Fig. 1.
(2) air blows out method
Air blows out method and is generally called blow-out method, this method is suitable for the relatively high material liquid (~100g/L) of amount of iodine.
Iodine mother liquor hydrochloric acid acidification (pH=1~2) will first be contained, then be passed through chlorine oxidation, while being blown into air and blowing out free-iodine.Blowout
Iodine absorbed with sulfur dioxide, then being passed through chlorine keeps iodine free, final refining and iodine.
During iodine is mentioned from brine, keep iodine free with oxidizing brine containing iodine and contacted with air, with air general
Iodine blowout, air containing iodine after blowout through absorption, crystallize, be refining to obtain new product iodine.Technical process is as follows: 1. adding in brine
Entering oxidant keeps iodine free；2. by the brine containing free-iodine from desorber top spray under, from the bottom of tower be blown into air be allowed to
Brine counter current contacting, iodine is blown out；3. air containing iodine is absorbed through absorption tower, concentration.Its process flow chart is shown in Fig. 2.
This method is although at low cost, and occupation area of equipment is small, but requires content of iodine in waste water relatively high, it is desirable that dilute acid soln
Middle iodide ion content is in 50~100g/L or so, and the rate of recovery is 65%~75%, therefore, domestic at present seldom to use the method system
Iodine.
(3) active carbon adsorption
Colonial uses the method.First in acid condition, using activated carbon adsorption iodine, concentrated sodium hydroxide is then used
Solution is eluted, and being further carried out acidification can be obtained available iodine solution.Using active carbon adsorption, kelp is mentioned
The iodine in waste water after iodine carries out recycling research.Studies have shown that the iodine in waste water is under the acid condition of pH=1.5~2, through oxygen
It is enriched with after change and is eluted again with sodium hydroxide, finally acidified neutralization again, can get the solution that iodine is 300~400mg/L.It should
Technique provides a practicable new way to the recycling for mentioning iodine waste water, and active carbon can be recycled, chemistry
Drug dosage is few, at low cost, pollutes small.Its process flow chart is shown in Fig. 3.
This method is primarily adapted for use in the solution for recycling higher content of iodine (> 5%).The absorption excellent as one kind of iodine
Agent, activated carbon method absorption iodine other ions are not had an impact or influence it is small, but after active carbon is used for multiple times, mechanical damage
Greatly, the activity sufficiently used is influenced, which limits its large-scale applications.
(4) other methods
The recovery method of iodine is in conceptual phase there are also liquid membrane separating method, solvent signal suppression, electrochemical process etc. at present,
There is no large-scale application temporarily.
Therefore, these synthetic routes are all unable to satisfy wanting for iodine in economic, effective, safety recycling waste liquid containing iodine
It asks.Moreover, these methods of the prior art none can by change reactor types, be precisely controlled instead by serialization
Answer and cheap stable recycling iodine.
Summary of the invention
The main purpose of the present invention is to provide a kind of from waste water containing iodine extracts the continuous process of iodide and continuous
Makeup is set, and there is or cost recovery low to the rate of recovery of the iodine solution of low concentration to solve the recovery method of existing iodide
High problem.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of recycle iodate from waste water containing iodine
The continuous process of object, continuous process include: that waste water containing iodine, acid and oxidant are continuously conveyed into continuous reacting device
Continuous reaction is carried out, and continuous reacting device is filled with active carbon；Lye and eluant, eluent are continuously delivered to serialization
Serialization is carried out in reaction unit and desorbs reaction enclosure, obtains the desorption attached liquid containing iodide ion；To the desorption attached liquid containing iodide ion into
Row extraction process, obtains iodide.
Further, it is continuously conveyed to before continuous reacting device iodine waste water, acid and oxidant will be contained, serialization side
Method further include: iodine waste water will be contained and acid-mixed is closed, obtain the first mixed liquor；First mixed liquor and oxidant are delivered to continuously respectively
Change in reaction unit；Preferably, the ratio between iodide ion and the molal quantity of acid and oxidant are 1: in waste water containing iodine:.
Further, the temperature of continuous reaction is 0~120 DEG C, and the reaction time is 10~120min；Preferably, continuously
The temperature for changing reaction is 10~30 DEG C, and the reaction time is 20~60min.
Further, acid is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, p-methyl benzenesulfonic acid and methanesulfonic acid composition
One of group is a variety of；Preferably, iodine number >=900mg/g of active carbon, partial size are 2~5mm.
Further, oxidant is selected from hydrogen peroxide, ozone or oxygen；When oxidant is hydrogen peroxide, the concentration of hydrogen peroxide
For 30wt%.
Further, the temperature of serialization desorption reaction enclosure is 0~120 DEG C, and the reaction time is 10~120min；It is preferred that
Ground, the temperature that serialization desorbs reaction enclosure is 0~30 DEG C, and the reaction time is 20~60min.
Further, continuous process further include: in continuous reaction and/or serialization desorption reaction process, to
Solvent is continuously inputted in continuous reacting device；Preferably, solvent is selected from water, chloroform, methylene chloride, ethyl acetate, tetrahydro furan
It mutters, one of the group or a variety of of 2- methyltetrahydrofuran, 1,4- dioxane, benzene, toluene and dimethylbenzene composition.
Further, continuous reacting device is selected from continuous cylindrical reactor, tubular reactor or grating type reactor.
Further, the method for extraction process is selected from continuous concentration method, continuous crystallization method or continuous spray drying process.
Further, eluant, eluent is selected from hydrazine hydrate and/or ammonium hydroxide；Lye is aqueous alkali, and the alkali in aqueous alkali is selected from
One of group of sodium hydroxide, potassium hydroxide and lithium hydroxide composition is a variety of.
The another aspect of the application additionally provides a kind of continuous device that iodide are recycled from waste water containing iodine, serialization
Device includes: continuous reacting device and extraction element.Continuous reacting device is provided with feed inlet and eluent outlet, charging
Mouth goes out to be used to continuously be discharged eluent for continuously inputting waste water containing iodine, acid, oxidant and eluant, eluent, eluent, continuously
Change in reaction unit and is filled with active carbon；Extraction element be provided with eluent entrance and iodide outlet, eluent entrance with wash
De- liquid outlet is connected, for continuously extracting the iodide in eluent.
Further, continuous device further includes the first filling device, and the first filling device is provided with waterwater entrance containing iodine
With sour entrance and the first mixture export, the first mixture export is connected with feed inlet, mixed for continuously conveying first
Close liquid.
Further, continuous device further includes the second filling device, the second filling device be provided with oxidant inlet and
First colvent inlet and the second mixture export, the second mixture export are connected with feed inlet, for continuously conveying
Two mixed liquors.
Further, continuous device further include: eluant, eluent filling device and lye filling device, eluant, eluent filling device
It is provided with eluant, eluent entrance and the second colvent inlet and third mixture export；And lye filling device is provided with lye and goes out
Mouthful, lye export and third mixture export are connected with eluent entrance, for continuously conveying third mixed liquor and alkali
Liquid.
Further, continuous device further includes automatic feed system, and automatic feed system is for controlling the first mixed liquor
It exports, the charging rate of the second mixture export, third mixture export and lye export.
Further, continuous reacting device is selected from continuous cylindrical reactor, tubular reactor or grating type reactor.
It applies the technical scheme of the present invention, applies continuous feed technology, avoid batch charge in the process because of local object
Enlarge-effect caused by material mixing is uneven；Active carbon is seated in continuous reacting device and forms fixed adsorbent equipment
(continuous reacting device) improves the adsorption efficiency of active carbon, and only with cheap activated carbon can efficient absorption it is low dense
The iodine in waste liquid containing iodine is spent, thus to the iodine rate of recovery with higher；Eluant, eluent is continuously conveyed to above-mentioned continuous
Change after being eluted in reaction unit, above-mentioned continuous reacting device can also reuse, to effectively reduce extraction iodine
The process costs of compound.There is a large amount of heat to release in above-mentioned serialization absorption simultaneously and serialization desorption process, by even
The heat exchanger effectiveness of continuous reactor in time falls heat exchange, to be conducive to avoid the security risk of batch production.To sum up
It is described, the rate of recovery that iodide are conducive to improve iodine is extracted from waste water containing iodine using above-mentioned continuous process, reduces work
Skill cost, while also can be reduced security risk appearance.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1, which is shown, recycles the flow chart of waste stream process containing iodine using ion-exchange according to existing；
Fig. 2 shows recycle the flow chart of waste stream process containing iodine using air blowout method according to existing；
Fig. 3, which is shown, recycles the flow chart of waste stream process containing iodine using active carbon adsorption according to existing；And
Fig. 4 shows the structure of the continuous device of elemental iodine in a kind of preferred recycling waste liquid containing iodine provided by the present application
Schematic diagram.
Wherein, the above drawings include the following reference numerals:
10, continuous reacting device；20, extraction element；30, the first filling device；31, the first delivery pump；40, second dozen
Expect device；41, the second delivery pump；50, eluant, eluent filling device；51, third delivery pump；60, lye filling device；61, the 4th
Delivery pump；70, automatic feed system.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, there is the recycling to the iodine solution of low concentration in the recovery method of existing iodide
The problem that rate is low or cost recovery is high.In order to solve the above-mentioned technical problem, this application provides one kind returns from waste water containing iodine
The continuous process of iodide is received, continuous process includes: that waste water containing iodine, acid and oxidant are continuously conveyed to continuous reaction
Continuous reaction is carried out in device 10, and continuous reacting device 10 is filled with active carbon；Lye and eluant, eluent is continuously defeated
It send into continuous reacting device 10 and carries out serialization desorption reaction enclosure, obtain the desorption attached liquid containing iodide ion；To containing iodide ion
Desorption attached liquid extract processing, obtain iodide.
In the presence of acid, oxidation reaction occurs for the iodide ion in waste water containing iodine and oxidant, obtains elemental iodine, then its
The activated carbon adsorption being loaded in continuous reacting device 10；Then again under the action of eluant, eluent, above-mentioned elemental iodine and elution
Agent reacts, and elemental iodine is made to be converted into iodide ion, obtains the desorption attached liquid containing iodide ion, to realize elemental iodine from activity
The purpose eluted on charcoal；Finally iodide are extracted from the above-mentioned desorption attached liquid containing iodide ion.
Using continuous feed technology, amplification caused by batch charge mixes unevenly because of local material in the process is avoided
Effect；Active carbon is seated in continuous reacting device 10 and forms fixed adsorbent equipment (continuous reacting device 10), is mentioned
The high adsorption efficiency of active carbon, and only with cheap activated carbon can iodine in efficient absorption low concentration waste liquid containing iodine it is first
Element, thus to the iodine rate of recovery with higher；Eluant, eluent is continuously conveyed into above-mentioned continuous reacting device 10 and is carried out
After elution, above-mentioned continuous reacting device 10 can also be reused, to effectively reduce the process costs for extracting iodide.
There is a large amount of heat to release in above-mentioned serialization absorption simultaneously and serialization desorption process, by the heat exchange of flow reactor
Efficiency in time falls heat exchange, to be conducive to avoid the security risk of batch production.In conclusion using above-mentioned continuous
Change method extracts the rate of recovery that iodide are conducive to improve iodine from waste water containing iodine, reduces process costs, while can also subtract
Few security risk occurs.
The mode of movement of above-mentioned raw materials liquid can be by the way of commonly used in the art.In a kind of preferred embodiment,
Iodine waste water, acid and oxidant will be contained to be continuously conveyed to before continuous reacting device 10, continuous process further include: iodine will be contained and given up
Water and acid-mixed are closed, and the first mixed liquor is obtained；First mixed liquor and oxidant are delivered to respectively in continuous reacting device 10.It will
Waste water containing iodine and acid are first mixed, and mix the first mixed liquor in continuous reacting device 10 with oxidant,
This can make to be tightly held by activated carbon at once once generating, through oxidizing obtained elemental iodine to be conducive to further mention
The rate of recovery of iodide ion in high iodine-containing waste water.In order to further increase the conversion ratio of iodide ion, and then improve the absorption of elemental iodine
Rate, it is preferable that the ratio between waste water containing iodine and the molal quantity of acid and oxidant are 1:(0.5~4): (0.25~0.5)
In order to further increase the adsorption efficiency of elemental iodine in serialization adsorption process, in a kind of preferred embodiment,
The temperature of continuous reaction is 0~120 DEG C, and the reaction time is 10~120min；It is highly preferred that the temperature of continuous reaction is 10
~30 DEG C, the reaction time is 20~60min.
In above-mentioned serialization adsorption process, acid can be selected from type commonly used in the art.In a kind of preferred embodiment,
Acid includes but is not limited to one in the group of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, p-methyl benzenesulfonic acid and methanesulfonic acid composition
Kind is a variety of.In order to further increase the rate of recovery of iodine, it is highly preferred that iodine number >=900mg/g of active carbon, partial size 2
~5mm.
In above-mentioned serialization adsorption process, oxidant can be selected from type commonly used in the art.In a kind of preferred implementation
In example, oxidant includes but is not limited to hydrogen peroxide, ozone or oxygen.In order to improve the oxidability of oxidant, when oxidant is
When hydrogen peroxide, preferably the concentration of hydrogen peroxide is 30wt%.
The temperature of above-mentioned serialization desorption process is not particularly limited, as long as can be realized the absorption of elemental iodine solution i.e.
It can.In a kind of preferred embodiment, serialization desorb reaction enclosure temperature be 0~120 DEG C, the reaction time be 10~
120min.The temperature and time of serialization desorption process is limited to the desorption for being conducive to improve elemental iodine within the above range
Attached efficiency.It is highly preferred that the temperature of serialization desorption reaction enclosure is 0~30 DEG C, the reaction time is 20~60min.
In a kind of preferred embodiment, continuous process further include: anti-in continuous reaction and/or serialization desorption
During answering, solvent is continuously inputted into continuous reacting device 10.Solvent is added into continuous reacting device 10 to be mentioned
(reaction raw materials (waste water containing iodine, acid and oxidant) in such as adsorption process or the reaction in desorption process are former for high reaction raw materials
Expect (eluant, eluent and elemental iodine etc.) the abundant extent of reaction, while can also make reaction process in more stable environment into
Row, and then improve the safety of the rate of recovery and entire technique of iodine.
Above-mentioned solvent can select type commonly used in the art.Preferably, solvent includes but is not limited to water, chloroform, dichloro
In the group that methane, ethyl acetate, tetrahydrofuran, 2- methyltetrahydrofuran, 1,4- dioxane, benzene, toluene and dimethylbenzene form
It is one or more.Above-mentioned several solvents have excellent solvent power, thus compared to other solvents, it selects above-mentioned several molten
Agent is conducive to further increase the rate of recovery of iodine.
In a kind of preferred embodiment, continuous reacting device 10 includes but is not limited to continuous cylindrical reactor, tubulose
Reactor or grating type reactor.The preparation cost of above-mentioned several reaction units is lower, and adsorption effect is preferable, thus selects
It states several reaction units to not only contribute to save the process cost, also advantageously improves the rate of recovery of iodine.Such as when using continuous
When cylindrical reactor is as continuous reacting device 10, multilayer column plate can be set wherein, and then be conducive to further higher
Effect ground absorption elemental iodine.
Said extracted method can use extracting method commonly used in the art.In a kind of preferred embodiment, at extraction
The method of reason includes but is not limited to continuous concentration method, continuous crystallization method or continuous spray drying process.Compared to other extracting methods,
Using above-mentioned several extracting methods, not only operating procedure is simple, at low cost, but also can obtain the higher iodide of purity.
In a kind of preferred embodiment, eluant, eluent includes but is not limited to hydrazine hydrate and/or ammonium hydroxide.Compared to other elutions
Agent, is conducive to improve the eluting rate of elemental iodine using above-mentioned several eluant, eluents, and then is conducive to further increase returning for iodide
Yield.Above-mentioned lye can select alkali commonly used in the art to be configured to water solubility, and the alkali in aqueous alkali includes but is not limited to hydrogen
One of group of sodium oxide molybdena, potassium hydroxide and lithium hydroxide composition is a variety of.
The application in order to better understand is illustrated with a kind of preferred embodiment:
(1) adsorption process.
A, by waste liquid containing iodine to be recycled and sulfuric acid wiring solution-forming, as the first dnockout bottle；
B, by 30% hydrogen peroxide as the second dnockout bottle；
C, with automatic feed system, system in the first dnockout bottle, B is squeezed into column holding reactor, reactor heat preservation 20~30
Degree, retention time 30min, column outlet obtains de- iodine waste liquid, wait scrap.
Principle are as follows:
(2) elution process.
A, by KOH solution as eluant, eluent dnockout bottle；
B, by 80% hydrazine hydrate as (lye dnockout bottle)；
C, with automatic feed system, system in eluant, eluent dnockout bottle, D is squeezed into column holding reactor, reactor heat preservation 20~
30 degree, retention time 30min.
Principle are as follows:
(3) extraction process.
React the KI system completed and exported from continuous reaction device and flowed out, subsequently into continuous concentration or continuous crystalizer into
Row crystallization；Or the KI system that reaction is completed be spray-dried in spray drying system, and it is high-purity finally to collect drying
KI。
On the other hand the application additionally provides a kind of continuous device that iodide are extracted from waste water containing iodine, such as Fig. 4 institute
Show, which includes: continuous reacting device 10 and extraction element 20.Continuous reacting device 10 is provided with feed inlet
It is exported with eluent, feed inlet goes out to be used for continuous for continuously inputting waste water containing iodine, acid, oxidant and eluant, eluent, eluent
Eluent is discharged in ground, is filled with active carbon in continuous reacting device 10；Extraction element 20 is provided with eluent entrance and iodate
Object outlet, eluent entrance is connected with eluent outlet, for continuously extracting the iodide in eluent.
Active carbon is seated in continuous reacting device 10 and forms fixed adsorbent equipment continuous reacting device 10, this
So that only with cheap activated carbon can iodine in efficient absorption low concentration waste liquid containing iodine, thus to iodine have compared with
The high rate of recovery；Eluant, eluent is continuously conveyed into above-mentioned continuous reacting device 10 after being eluted, above-mentioned continuous reaction
Device 10 can also reuse, to effectively reduce the process costs for extracting iodide.The absorption of above-mentioned serialization simultaneously with
There is a large amount of heat to release in serialization desorption process, this can be improved the absorption of the iodine in continuous reacting device 10
And desorption efficiency, to be conducive to avoid the security risk of batch production.In conclusion using above-mentioned continuous process from
The rate of recovery that iodide are conducive to improve iodine is extracted in waste water containing iodine, reduces process costs, while it is hidden also to can be reduced safety
Suffer from and occurring.
In a kind of preferred embodiment, as shown in figure 4, continuous device further includes the first filling device 30, first dozen
Material device 30 is provided with waterwater entrance containing iodine and sour entrance and the first mixture export, the first mixture export and feed inlet phase
Connection, for continuously conveying the first mixed liquor.Iodine waste water will be contained and acid first mixes in the first filling device 30, this energy
Enough make to be tightly held by activated carbon once generating, contain at once to be conducive to further increase through oxidizing obtained elemental iodine
The rate of recovery of iodide ion in iodine waste water.
In a kind of preferred embodiment, as shown in figure 4, continuous device further includes the second filling device 40, second dozen
Material device 40 is provided with oxidant inlet and the first colvent inlet and the second mixture export, the second mixture export and charging
Mouth is connected, for continuously conveying the second mixed liquor.Oxidant and the first solvent are mixed into energy in the second filling device 40
The abundant extent of reaction of reaction raw materials (reaction raw materials waste water containing iodine, acid and oxidant in such as adsorption process) is enough improved, simultaneously
Reaction process can also be made to carry out in more stable environment, and then improve the rate of recovery of iodine and the safety of entire technique
Property.
In a kind of preferred embodiment, as shown in figure 4, continuous device further includes eluant, eluent filling device 50 and lye
Filling device 60, eluant, eluent filling device 50 are provided with eluant, eluent entrance and the second colvent inlet and third mixture export；
And lye filling device 60 is provided with lye export, lye export and third mixture export are connected with eluent entrance,
For continuously conveying third mixed liquor and lye.Eluant, eluent and the second solvent are mixed in third filling device, Neng Gouti
The abundant extent of reaction of high reaction raw materials (reaction raw materials eluant, eluent, elemental iodine in such as elution process), while can also make anti-
It answers process to carry out in more stable environment, and then improves the safety of the rate of recovery and entire technique of iodine.Wherein
One solvent and the second solvent are separately selected from water, chloroform, methylene chloride, ethyl acetate, tetrahydrofuran, 2- methyl tetrahydro furan
It mutters, one of the group or a variety of of 1,4- dioxane, benzene, toluene and dimethylbenzene composition.
In order to further enhance feed rate, it is preferable that above-mentioned continuous device further includes that the first delivery pump 31, second is defeated
Send pump 41, third delivery pump 51 and the 4th delivery pump 61.
In order to reduce the labor intensity of technique, while the charging rate of eluant, eluent and lye is preferably controlled, a kind of excellent
In the embodiment of choosing, as shown in figure 4, continuous device further includes automatic feed system 70, automatic feed system 70 is for controlling
The charging rate of first mixture export, the second mixture export, third mixture export and lye export.
In a kind of preferred embodiment, continuous reacting device 10 be selected from continuous cylindrical reactor, tubular reactor or
Grating type reactor.The preparation cost of above-mentioned several reaction units is lower, and adsorption effect is preferable, thus selects above-mentioned several anti-
It answers device to not only contribute to save the process cost, also advantageously improves the rate of recovery of iodine.
Said extracted device can use extraction element commonly used in the art.Preferably, said extracted system 20 include but
It is not limited to continuous crystallisation device, continuous concentration device or spray-drying installation.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
The active carbon used in embodiment 1 to 6 is Jiangxi elementary force Huaiyu Shan Mountain particle charcoal type active carbon.
Embodiment 1 to 6 and comparative example are using the elemental iodine in continuous device shown in Fig. 4 recycling waste liquid containing iodine.
Embodiment 1
Equipment prepares: the continuous reacting device 10 (continuous cylindrical reactor) of 600mL dried and clean is filled particle wood
Then charcoal type active carbon 100g empties bubble with tap water.
Mixed solution is made in the waste liquid and 40g (0.40mol) sulfuric acid for taking 2000g 5% (0.79mol) amount of iodine, is placed in
In one dnockout bottle 30.It takes 30% hydrogen peroxide of 45.5g (0.40mol) and 200g distilled water that mixed solution is made, is placed in the second dnockout
In bottle 40.Start dnockout, 31 (waste liquid containing iodine) charging rate of the first delivery pump setting: 15.01g/ by automatic feed system
Min, 41 (hydrogen peroxide solution) charging rate of the second delivery pump setting: 1.66g/min.Conversion zone retention time 30min, reactor
20~25 degree of temperature, internal pressure is controlled in 0.1~0.5MPa.Discharge port is directly connected to plastics temporary storage barrel, receives waste liquid system and waits reporting
It is useless.Dnockout finishes, and with 500mL distilled water liftout, washes column, completes absorbing unit.
It takes 44.2g (0.79mol) KOH and 400g distilled water that mixed solution is made, is placed in eluant, eluent filling device 50.It takes
Mixed solution is made in 80% hydrazine hydrate of 12.3g (0.20mol) and 100g distilled water, is placed in lye filling device eluant, eluent dnockout dress
It sets in 50.Start dnockout by automatic feed system, the setting of 61 (KOH solution) charging rate of the 4th delivery pump: 13.34g/min,
(hydrazine hydrate solution) charging rate of third delivery pump 51 setting: 3.33g/min.Conversion zone retention time 30min, temperature of reactor
20~30 degree, internal pressure is controlled in 0.1~0.5MPa.Discharge port is directly connected to the (thin film concentrator being sequentially communicated of extraction element 10
And continuous crystallization-filtration system, and continuous crystallization-filtration system is squeezed into through the heavy constituent that thin film concentrator obtains), what is obtained mentions
Product is taken, cooling crystallization at 10~20 DEG C, retention time 30min, crystallization system carries out solid-liquid point through continuous filtration system later
From.The filter cake isolated is collected, and 40~50 DEG C drying to constant weight, obtains 149.0g product, purity 99%, yield 90.2%.
Embodiment 2
Equipment prepares: the continuous reacting device 10 (continuous cylindrical reactor) of 600mL dried and clean is filled particle wood
Then charcoal type active carbon 100g empties bubble with tap water.
Mixed solution is made in the waste liquid and 40g (0.40mol) sulfuric acid for taking 10Kg 1% (0.79mol) amount of iodine, is placed in
In one dnockout bottle 30.It takes 30% hydrogen peroxide of 45.5g (0.40mol) and 200g distilled water that mixed solution is made, is placed in the second dnockout
In bottle 40.Start dnockout, 31 (waste liquid containing iodine) charging rate of the first delivery pump setting: 16.26g/ by automatic feed system 70
Min, 41 (hydrogen peroxide solution) charging rate of the second delivery pump setting: 0.40g/min.Conversion zone retention time 30min, reactor
20~25 degree of temperature, internal pressure is controlled in 0.1~0.5MPa.Discharge port is directly connected to plastics temporary storage barrel, receives waste liquid system and waits reporting
It is useless.Dnockout finishes, and with 500mL distilled water liftout, washes column, completes absorbing unit.
It takes 44.2g (0.79mol) KOH and 400g distilled water that mixed solution is made, is placed in eluant, eluent filling device 50.It takes
Mixed solution is made in 80% hydrazine hydrate of 12.3g (0.20mol) and 100g distilled water, is placed in the 4th delivery pump 61 (KOH solution).
Start dnockout, 61 (KOH solution) charging rate of the 4th delivery pump setting: 13.34g/min, third by automatic feed system 70
(hydrazine hydrate solution) charging rate of delivery pump 51 setting: 3.33g/min.Conversion zone retention time 30min, temperature of reactor 20~
30 degree, internal pressure is controlled in 0.1~0.5MPa.Discharge port is directly connected to thin film concentrator, and heavy constituent squeezes into continuous crystallization-filtering system
It unites, cooling crystallization at 10~20 DEG C, retention time 30min, crystallization system is separated by solid-liquid separation through continuous filtration system later.
The filter cake isolated is collected, and 40~50 DEG C drying to constant weight, obtains 140.0g product, purity 99%, yield 84.3%.
Embodiment 3
Equipment prepares: the continuous cylindrical reactor of 600mL dried and clean being filled particle charcoal type active carbon 100g, so
Afterwards, bubble is emptied with tap water.
Mixed solution is made in the waste liquid and 40g (0.40mol) sulfuric acid for taking 2000g 5% (0.79mol) amount of iodine, is placed in
In one dnockout bottle 30.It takes 30% hydrogen peroxide of 45.5g (0.40mol) and 200g distilled water that mixed solution is made, is placed in the second dnockout
In bottle 40.Start dnockout, 31 (waste liquid containing iodine) charging rate of the first delivery pump setting: 15.01g/ by automatic feed system 70
Min, 41 (hydrogen peroxide solution) charging rate of the second delivery pump setting: 1.66g/min.Conversion zone retention time 30min, reactor
20~25 degree of temperature, internal pressure is controlled in 0.1~0.5MPa.Discharge port is directly connected to plastics temporary storage barrel, receives waste liquid system and waits reporting
It is useless.Dnockout finishes, and with 500mL distilled water liftout, washes column, completes absorbing unit.
It takes 44.2g (0.79mol) KOH and 400g distilled water that mixed solution is made, is placed in eluant, eluent filling device 50.It takes
Mixed solution is made in 80% hydrazine hydrate of 12.3g (0.20mol) and 100g distilled water, is placed in the 4th delivery pump 61 (KOH solution).
Start dnockout, 61 (KOH solution) charging rate of the 4th delivery pump setting: 13.34g/min, third by automatic feed system 70
(hydrazine hydrate solution) charging rate of delivery pump 51 setting: 3.33g/min.Conversion zone retention time 30min, temperature of reactor 20~
30 degree, internal pressure is controlled in 0.1~0.5MPa.Discharge port is directly connected to be spray-dried, and obtains 154.3g product, purity 98%, yield
93.3%.
Embodiment 4
Difference from example 1 is that: using ozone as oxidant.
After above-mentioned processing, the purity of the product of acquisition is 97%, yield 90%.
Embodiment 5
Difference from example 1 is that: the ratio between waste water containing iodine and the molal quantity of acid and oxidant are 1:0.1:0.1.
After above-mentioned processing, the purity of the product of acquisition is 90%, yield 10%.
Embodiment 6
Difference from example 1 is that: the iodine number 200mg/g of active carbon, partial size are 5~10mm.
After above-mentioned processing, the purity of the product of acquisition is 95%, yield 15%.
Comparative example 1
Difference from example 1 is that: take the waste liquid and 40g of 2000g 5% (0.79mol) amount of iodine
Mixed solution is made in (0.40mol) sulfuric acid, is placed in the first dnockout bottle 30.Take 30% hydrogen peroxide of 45.5g (0.40mol) and 200g
Mixed solution is made in distilled water, is placed in the second dnockout bottle 40.Start dnockout, the first delivery pump 31 by automatic feed system 70
(waste liquid containing iodine) charging rate setting: 15.01g/min, 41 (hydrogen peroxide solution) charging rate of the second delivery pump setting: 1.66g/
min.Then by the material liquid in the material liquid and the second dnockout bottle 40 in the first dnockout bottle 30 directly with 100g granular activated carbon
Mixing.
After above-mentioned processing, the purity of the product of acquisition is 95%, yield 80%.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Using continuous feed technology, batch charge is avoided in the process because amplifying effect caused by the mixing unevenly of local material
It answers；Active carbon is seated in continuous reacting device and forms fixed adsorbent equipment (continuous reacting device), improves work
The adsorption efficiency of property charcoal, this make only with cheap activated carbon can iodine in efficient absorption low concentration waste liquid containing iodine,
To the iodine rate of recovery with higher；Eluant, eluent is continuously conveyed into above-mentioned continuous reacting device and is eluted
Afterwards, above-mentioned continuous reacting device can also reuse, to effectively reduce the process costs for extracting iodide.On simultaneously
Stating has a large amount of heat to release in serialization absorption and serialization desorption process, by flow reactor heat exchanger effectiveness and
When heat exchange is fallen, to be conducive to avoid the security risk of batch production.In conclusion using above-mentioned continuous process
Be conducive to improve the rate of recovery of iodine from extraction iodide in waste water containing iodine, reduce process costs, while also can be reduced safety
Hidden danger occurs.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (16)
1. a kind of continuous process for recycling iodide from waste water containing iodine, which is characterized in that the continuous process includes:
The waste water containing iodine, acid and oxidant are continuously conveyed into continuous reacting device (10) and carry out continuous reaction, and
The continuous reacting device (10) is filled with active carbon；
Lye and eluant, eluent are continuously delivered to carry out serialization desorption reaction enclosure in the continuous reacting device (10), obtained
To the desorption attached liquid containing iodide ion；
Processing is extracted to the desorption attached liquid containing iodide ion, obtains the iodide.
2. continuous process according to claim 1, which is characterized in that will the waste water containing iodine, described sour and described
Oxidant is continuously conveyed to before continuous reacting device (10), the continuous process further include:
The waste water containing iodine and the acid-mixed are closed, the first mixed liquor is obtained；
First mixed liquor and the oxidant are delivered to respectively in the continuous reacting device (10)；
Preferably, iodide ion and the ratio between the acid and the molal quantity of the oxidant are 1:(0.5~4 in the waste water containing iodine):
(0.25~0.5).
3. continuous process according to claim 1 or 2, which is characterized in that the temperature of the continuous reaction be 0~
120 DEG C, the reaction time is 10~120min；Preferably, the temperature of the continuous reaction is 10~30 DEG C, the reaction time 20
~60min.
4. continuous process according to any one of claim 1 to 3, which is characterized in that the acid is selected from hydrochloric acid, sulphur
One of group of acid, nitric acid, phosphoric acid, formic acid, acetic acid, p-methyl benzenesulfonic acid and methanesulfonic acid composition is a variety of；Preferably, the work
Property charcoal iodine number >=900mg/g, partial size be 2~5mm.
5. continuous process according to claim 1, which is characterized in that the oxidant is selected from hydrogen peroxide, ozone or oxygen
Gas；
When the oxidant is hydrogen peroxide, the concentration of the hydrogen peroxide is 30wt%.
6. continuous process according to claim 1, which is characterized in that the temperature of the serialization desorption reaction enclosure is 0
~120 DEG C, the reaction time is 10~120min；Preferably, the temperature of the serialization desorption reaction enclosure is 0~30 DEG C, reaction
Time is 20~60min.
7. continuous process according to claim 1, which is characterized in that the continuous process further include: in the company
In continuousization reaction and/or the serialization desorption reaction process, continuously inputted in Xiang Suoshu continuous reacting device (10) molten
Agent；
Preferably, the solvent is selected from water, chloroform, methylene chloride, ethyl acetate, tetrahydrofuran, 2- methyltetrahydrofuran, Isosorbide-5-Nitrae-
One of group of dioxane, benzene, toluene and dimethylbenzene composition is a variety of.
8. continuous process according to claim 1, which is characterized in that the continuous reacting device (10) is selected from continuous
Cylindrical reactor, tubular reactor or grating type reactor.
9. continuous process according to claim 1, which is characterized in that the method for the extraction process is selected from continuous concentration
Method, continuous crystallization method or continuous spray drying process.
10. continuous process according to claim 1, which is characterized in that the eluant, eluent is selected from hydrazine hydrate and/or ammonia
Water；The lye is aqueous alkali, and the alkali in the aqueous alkali is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide composition
One of group is a variety of.
11. a kind of continuous device for recycling iodide from waste water containing iodine, which is characterized in that the continuous device includes:
Continuous reacting device (10), the continuous reacting device (10) be provided with feed inlet and eluent outlet, it is described into
For continuously inputting the waste water containing iodine, acid, oxidant and eluant, eluent, the eluent goes out to be used to continuously be discharged to be washed material mouth
Liquid is taken off, is filled with active carbon in the continuous reacting device (10)；
Extraction element (20), the extraction element (20) are provided with eluent entrance and iodide outlet, the eluent entrance
It is connected with eluent outlet, for continuously extracting the iodide in eluent.
12. continuous device according to claim 11, which is characterized in that the continuous device further includes the first dnockout
Device (30), first filling device (30) are provided with waterwater entrance containing iodine and sour entrance and the first mixture export, institute
It states the first mixture export to be connected with the feed inlet, for continuously conveying the first mixed liquor.
13. continuous device according to claim 12, which is characterized in that the continuous device further includes the second dnockout
Device (40), second filling device (40) is provided with oxidant inlet and the first colvent inlet and the second mixed liquor goes out
Mouthful, second mixture export is connected with the feed inlet, for continuously conveying the second mixed liquor.
14. continuous device according to claim 13, which is characterized in that the continuous device further include:
Eluant, eluent filling device (50), the eluant, eluent filling device (50) be provided with eluant, eluent entrance and the second colvent inlet with
And third mixture export；And
Lye filling device (60), the lye filling device (60) are provided with lye export, the lye export and described
Three mixture exports are connected with the eluent entrance, for continuously conveying third mixed liquor and lye.
15. continuous device according to claim 14, which is characterized in that the continuous device further includes automatic feed
System (70), the automatic feed system (70) is for controlling first mixture export, second mixture export, institute
State the charging rate of third mixture export and the lye export.
16. continuous device described in any one of 1 to 15 according to claim 1, which is characterized in that the continuous reaction dress
It sets (10) and is selected from continuous cylindrical reactor, tubular reactor or grating type reactor.
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| CN112551733A (en) * | 2020-11-03 | 2021-03-26 | 浙江海拓环境技术有限公司 | Device and method for treating hypophosphite in chemical nickel plating waste liquid |
| CN112919678A (en) * | 2021-01-29 | 2021-06-08 | 江苏集萃托普索清洁能源研发有限公司 | Acetic acid production wastewater treatment process |
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