CN110386712A - A kind of method of zinc-containing water comprehensive utilization - Google Patents
A kind of method of zinc-containing water comprehensive utilization Download PDFInfo
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- CN110386712A CN110386712A CN201910710307.3A CN201910710307A CN110386712A CN 110386712 A CN110386712 A CN 110386712A CN 201910710307 A CN201910710307 A CN 201910710307A CN 110386712 A CN110386712 A CN 110386712A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash evaporation
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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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2101/30—Organic compounds
Abstract
The present invention relates to a kind of methods of zinc-containing water comprehensive utilization, this method is for there are sodium ions in original zinc-containing water, it cannot recycle, the case where zinc salt being concentrated to get can only be as dangerous solid waste, the alkali compounds such as sodium hydroxide, sodium carbonate are replaced to carry out neutralization reaction to water containing zincic acid first with the alkali compounds containing zinc, so that zinc-containing water does not contain sodium ion；On this basis, one or more kinds of extractants are selected, the organic matter (extractant passes through recovery) in zinc-containing water is removed by multitple extraction；Aqueous solution containing zinc extracted passes through concentration purification, further recycling extractant and removing part water, the aqueous solution containing zinc (40% or more) being concentrated, major part can directly be covered for former reaction, small part aqueous solution containing zinc further removes residual organic matter by adsorbent, reach solder(ing)acid standard, is taken out as product.
Description
Technical field
The present invention relates to Fine Chemistry Wastewater processing technology fields, and in particular to a kind of side of zinc-containing water comprehensive utilization
Method.
Background technique
One zinc-containing water that zinc-containing water of the present invention generates in vitamin E production process, this stock contain zinc
Waste water is other than containing zinc ion, also containing halogen, a small amount of acetic acid, a small amount of aromatic ring type organic etc..Usually using containing soda
Compound (such as NaOH, Na2CO3Deng) zinc-containing water is neutralized.However, the zinc salt obtained after zinc-containing water concentration
As catalyst in vitamin E production process, because having larger impact, nothing for reaction efficiency and selectivity there are sodium ion
Method realization is applied, and contains aromatic ring type organic simultaneously, can only not only be added significantly to processing cost as dangerous fixed-end forces,
Also cause the waste of metallic zinc.Therefore, a kind of suitable method is found, the influence of sodium ion is eliminated, realizes the money of zinc-containing water
Sourceization utilizes, and to protection environment and realizes that resource reutilization is of great significance.
There are absorption method, electrolysis method, ion-exchange-resin process, bioanalysis, chemistry heavy the processing method of zinc-containing water at present
Shallow lake method, extraction etc.:
1, absorption method: as patent CN106423045A provides a kind of adsorbent Treatment of Zinc-containing Wastewater with modified montmorillonoid
Method, based on montmorillonite, adsorbent passes through modification twice, modified montmorillonoid adsorbent is obtained, to solution of zinc sulfate
(zinc ion content 465.14mgL-1) in zinc ion removal rate 88.0% or more.The montmorillonite conduct that this method is selected
Adsorbent can remove most zinc ion in solution, but still have residual, while the montmorillonite after absorption is further desorbed
There are still difficulties, do not achieve the effect that recycling, and are only suitable for the removal of low concentration zinc ion, for Treatment with High Concentration Zinc ion
Removal has difficulties.
2, electrolysis method: if patent CN101717134A is put into electrolytic cell using Zinc-containing electroplating waste water as electrolyte, in electricity
Weak caustic solution is added in solution preocess in the electrolytic solution, the pH value of electrolyte is adjusted between 6.0~7.9, is electrolysed by metering
The charge accumulation amount of liquid, the zinc that cathode plate is precipitated are recycled.This method institute's power consumption and zinc ion concentration are directly proportional,
It needs to add weak base simultaneously, is relatively suitble to the recycling of low concentration zinc ion.
3, ion-exchange: as patent CN107902855A is reacted and to be formed by the way that pulverized limestone is added in viscose fiber wastewater
Sludge, the metal ion being added in sulfuric acid dissolution sludge, filtering, filtrate adjust pH and sulfuric acid tune pH are added for alkalinity, filtering, filtrate
For acid, macropore chelating type divinyl benzene polymer ion exchange resin absorption, sulfuric acid solution elution, collecting eluent, this is special
The technological operation for determining sequence realizes effective recycling of discarded zinc ion, it is demonstrated experimentally that can be in sediment using the technique
Zinc ion content is reduced to 1g/kg hereinafter, sludge is made to reach discharge standard.This method primarily directed to the zinc ion in sludge,
Using ion exchange resin treatment, relatively it is suitble to the removal of low concentration zinc ion, technics comparing is complicated, and due to the presence of sludge,
Treatment effect is unsatisfactory.
4, bioanalysis: if bacterial strain selected in patent CN103642702A is fungal bacterial strain LP-16, which has life
The strong advantage of long fast, the long-pending big, large amount of adsorption of hyphal surface, adsorption capacity, can effectively remove or recycle the zinc in zinc-containing water
Ion.For another example patent CN105585136A describes a kind of side precipitated using microorganism and to form granule sludge Treatment of Zinc-containing Wastewater
Living body filamentous fungi or dead volume filamentous fungi are directly added in zinc-containing water by method, and living body filamentous fungi method and dead volume are Filamentous
The rate of settling for the chemical precipitation granule sludge that fungi method obtains reaches 3.2cm/s and 3.0cm/s respectively, is much higher than cotton-shaped dirt
Mud.Using bioanalysis, by the way of absorption and sedimentation, adsorption efficiency is obviously improved, but how zinc is recycled not
There is method, while being difficult to ensure that zinc ion removal is clean using this method.
It is analyzed by above-mentioned patent, it is mainly suitable using the methods of absorption method, electrolysis method, ion-exchange-resin process, bioanalysis
Processing low concentration zinc-containing water is closed, mainly for the separation and removal of zinc ion micro in waste water system, this is for low concentration
Zinc-containing water treatment effect is preferable, but they are the problem is that processing cost is high, and energy consumption is high, treated COD value of waste water compared with
Greatly.On the other hand, from the point of view of final process effect, zinc ion removal is not clean, causes the waste of useful metal zinc, outlet is still deposited
It is polluting.Meanwhile treated how zinc recycles no suitable scheme.
5, chemical precipitation method: as used NaOH as pH adjusting agent in patent CN109881011A, first by zincky waste liquor
PH is adjusted to 3.0~6.0, separates non-zinc metal with metallic zinc；The pH value for adjusting waste liquid again is 7.0~9.0, makes the zinc in waste liquid
It is constantly precipitated in the form of zinc hydroxide, finally meets emission request.This method utilizes precipitation method separation zinc ion and non-
Zinc ion can be separated most zinc in the form of zinc hydroxide, but zinc hydroxide still has centainly in aqueous solution
Dissolubility is difficult processing completely, and on the other hand, zinc hydroxide precipitation exists with slurry form, is separated by filtration that there are larger difficulty.
6, extraction: the sulfonated kerosene and P pretreated with NaOH such as patent CN107779598A2O4Mixing organic phase is
Extractant is added in lime progress and filtering in zinc-containing water；It carries out 3 grades to filtrate using extractant to extract, in raffinate
The content of zinc is 0.4~0.6g/L.The extraction yield of this method zinc is about 95%, and the extractant used is more complicated, after further
Processing has difficulties.
Chemical precipitation method and extraction are mainly for the treatment of high concentration zinc-containing water, although can be effectively reduced zinc-containing water
In zinc ion content, but clean (removal rate of 90%-95%) can not be handled, still have zinc ion residual, can equally make
At the waste of useful metal zinc.In addition, other cations are introduced in obtained zinc salt, it can not benefit for certain specific zinc salts
With.
7, method of reutilization is adsorbed: if the waste water filtering containing zinc ion is obtained filtrate by patent CN108794105A, then
Filtrate adsorbs zinc ion by ion exchange resin, elution ionic exchanger resin obtains zinc ion concentrate, by zinc
Ion concentration liquid is mixed with industrial or agricultural by-product, is obtained ecological zinc fertilizer through microbial fermentation, drying and granulation, is realized zinc-containing water
Resource utilization.This method provides the new approaches that a kind of absorption and regeneration combine, and can not only remove zinc ion, may be used also
To be recycled as ecological zinc fertilizer.But this method is needed by the complexity such as filtering, absorption, concentration, fermentation, dry, granulation
Technical process, while all having higher requirements to waste water stock blend and final products (ecological zinc fertilizer), it is difficult to it promotes and applies.
According to above-mentioned patented method, using the removal of low concentration zinc ion and Treatment with High Concentration Zinc ion remaval method, for this system
In zinc-containing water, be all difficult to remove zinc ion clean, not only Zn content is difficult to up to standard waste water outlet, while will also result in zinc
Resource loss.
The Chinese patent application of 103820644 A of Publication No. CN discloses one kind and extracts from vitamin E pharmaceutical waste liquor
The step of method of zinc chloride, this method, is as follows: (1) under room temperature state, with extractant n-butyl acetate extraction vitamin E pharmacy
High boiling point organic compound in waste liquid, and separate its zinc chloride；(2) raffinate is concentrated by evaporation, to obtain Containing Zinc Chloride crude product
Concentrate；(3) hydrogen peroxide is added in the concentrate of Containing Zinc Chloride crude product, and carries out heating stirring at 80 DEG C, must turn
Become the concentrate of Containing Zinc Chloride；(4) concentrate of Containing Zinc Chloride is flowed back at 130 DEG C with chlorobenzene, to obtain anhydrous zinc chloride.It should
The method rate of recovery can achieve 95%, and obtained product is anhydrous zinc chloride solid, however in order to obtain anhydrous zinc chloride solid,
It needs all to remove all moisture, energy consumption is higher, and chlorination Zn content is higher in the waste water vitamin E pharmaceutical waste liquor used
(about 700~800g/L), hence it is evident that have already been through certain pre-treatment step.Anhydrous zinc chloride purity obtained in this way
Only 94%, containing more impurity, can not directly cover in preparation or other application for vitamin E.
Summary of the invention
Technical problem to be solved by the present invention lies in providing a kind of method of zinc-containing water comprehensive utilization, this method can be with
The rate of recovery of zinc chloride is improved, and recycle obtained solder(ing)acid to cover in the production for using vitamin E, realized
The recycling of zinc resource.
Technical scheme is as follows:
A kind of method of zinc-containing water comprehensive utilization, comprising the following steps:
(1) alkali compounds containing zinc is added into zinc-containing water and carries out neutralization reaction, waste water after being neutralized；
The waste water that the zinc-containing water generates in vitamin E production process, the waste water is in addition to containing zinc ion
Outside, also containing halogen, a small amount of acetic acid, a small amount of aromatic ring type organic etc..
(2) it uses extractant to carry out extracting operation to waste water after the neutralization to remove organic matter, gives up after being extracted
Water；
(3) concentration purification is carried out to waste water after extraction, obtains aqueous solution containing zinc.
It is generated in the zinc-containing water vitamin E production process, and in particular to trimethylhydroquinone is anti-with different vegetable alcohol
The production process of vitamin E should be prepared.
This method replaces the alkali compounds such as sodium hydroxide, sodium carbonate to water containing zincic acid first with alkali compounds containing zinc
Neutralization reaction is carried out, so that zinc-containing water does not contain sodium ion；On this basis, one or more kinds of extractants are selected, are passed through
Multitple extraction removes the organic matter in zinc-containing water (extractant passes through recovery)；Aqueous solution containing zinc extracted passes through concentration
Purification further recycles extractant and removes part water, and the aqueous solution containing zinc being concentrated (40% or more) can directly be covered and is used for
Trimethylhydroquinone is reacted with different vegetable alcohol in the production process for preparing vitamin E.The aqueous solution containing zinc of the concentration can also lead to
Cross adsorbent and further remove residual organic matter, reach solder(ing)acid standard (Zn content >=40%, content of organics≤
0.5%, pH value 2~5), taken out as product.
Using this method, by cation type in control waste water, while passing through removal organic matter, the hands such as concentration water removal
Section enables aqueous solution containing zinc to re-apply as new catalyst system and reacts in original；Or further adsorption treatment, it reaches
Not only solve the wasting of resources to realize comprehensive utilization to the commercially available professional standard of aqueous solution containing zinc, but solve as waste water or
The useless solid higher problem of processing cost of person.
Preferably, in step (1), the alkali compounds containing zinc is zinc oxide, zinc carbonate, one in zinc hydroxide
Kind or two kinds.
The additional amount and mixing time of the alkali compounds containing zinc and the ingredient in waste water are closely related, especially
On the one hand the amount of hydrogen chloride and acetic acid needs to convert zinc chloride as far as possible for the hydrogen chloride in waste water, to avoid to subsequent processing
It on the other hand to reduce generation zinc acetate to the greatest extent with the influence for applying step, influence the purity of liquor zinci chloridi.Therefore, adding
Before entering the alkali compounds containing zinc, the content to hydrogen chloride in waste water is needed to detect, to determine the alkaline chemical combination containing zinc
The dosage of object.In general, after neutralization reaction terminates, the pH value of waste water can reach preferable and neutralize effect between 2~3
Fruit.
In step (2), the effect of the extractant is the high boiling point organic compound removed in waste water, preferably, described
Extractant is one or both of toluene, ethyl acetate, pentane, chloroform, selects these types of extractant, and extraction efficiency is high,
And cost is relatively low.
Preferably, the extraction series is 3~10 grades, preferably 5~8 grades.
In step (2), extractant can be carried out recovery by distilling by obtained extraction phase.
Preferably, in step (3), the mode of the concentration purification is vacuum distillation, pressure range be -0.03MPa~-
0.10MPa, temperature range are 110 DEG C~180 DEG C；It is preferred that pressure range -0.05MPa~-0.08MPa, temperature range is 120 DEG C
~160 DEG C.When carrying out concentration purification, steams group and be divided into remaining extractant and part water, extractant can be carried out by liquid separation
Further recycling.
The aqueous solution containing zinc that step (3) obtains can directly be applied back in the preparation section of vitamin E, can also be using suction
Attached dose of progress adsorption treatment obtains solder(ing)acid product.
The adsorbent is one of macroporous absorbent resin XDA-1, XDA-1G, XDA-11, XDA-200.
The granularity of the macroporous absorbent resin is 0.1~10mm, 1000~2000m of specific surface area21~20m of/g, Kong Rong3/
mL。
The mass ratio of macroporous absorbent resin and zinc-containing water is 1:1~20, adsorbs preferably 1~10 grade of series, preferred mass
Than 1:1~10,1~5 grade of series is preferably adsorbed.
Preferably, the resin filling device be resin tower, Diameter Range of Tower-type Equipment 300mm~2000mm, tower height 2000~
10000mm；It is preferred that Diameter Range of Tower-type Equipment 500mm~1500mm, 3000~8000mm of tower height.
Preferably, the zinc-containing water input and output material mode is to feed from resin tower bottom, top discharge.
In the present invention, macroporous absorbent resin can be handled by desorbing agent, then be reused, preferably,
The desorbing agent is one or both of ethyl acetate, methanol, ethyl alcohol, acetone.
Preferably, the input and output material mode of the desorbing agent is from resin tower top feed, from bottom discharge.
Preferably, the liquor zinci chloridi standard is Zn content >=30%~70%, content of organics≤1%, pH value 1
~7, preferably Zn content >=40%~60%, content of organics≤0.5%, pH value 2~5.
Using zinc-containing water treatment process of the invention, has the advantages that and sodium ion is not introduced by this method,
So that being reduced into catalyst system after zinc-containing water is by processing, can directly cover for being catalyzed reaction, so that zinc-containing water is comprehensive
Utilization rate is closed to increase substantially；Simultaneously by carrying out removing organic matter processing to remaining zinc-containing water, reach solder(ing)acid
Professional standard；Organic matter is concentrated furthermore with extractant, prepares steam for liquid waste incineration.Prevented using this technique
The introducing of interfering ion, so that the zinc of zinc-containing water, organic matter and water etc. realize the purpose of comprehensive utilization substantially.
Detailed description of the invention
Fig. 1 is zinc-containing water comprehensive utilization treatment process flow chart of the present invention.
Specific embodiment
Below in conjunction with specification drawings and specific embodiments, the present invention is described in detail.
Zinc-containing water used in embodiment first uses EDTA titration, measures the content of zinc in zinc-containing water.Step 3 is dense
The content of zinc in the liquor zinci chloridi that the content and step 4 of zinc obtain after resin adsorption in the liquor zinci chloridi that contracting obtains
Using EDTA titration measuring, the rate of recovery of zinc is then calculated.
Embodiment 1
The present embodiment is a kind of new method of zinc-containing water comprehensive utilization, and this method comprises the following steps:
Weighing 500g zinc-containing water, (zinc oxide concentration 27.84%, hydrogen cloride concentration 2.10%, TOC value are
12175.3ppm, pH < 1) in 1000mL beaker, 20g zinc oxide is added, stirs 10min, is filtered to remove not molten zinc oxide
8.20g, filtrate pH=2~3.Filtrate is poured into 1000ml separatory funnel, using ethyl acetate as extractant, extraction 5 times, every time
30mL ethyl acetate is added, after extraction, water phase presents faint yellow.Water phase is evaporated under reduced pressure, pressure -0.05MPa, temperature
130 DEG C of degree, removes ethyl acetate therein and part water, obtains the aqueous solution containing zinc that zinc oxide concentration is 45.30%
349.87g。
At room temperature, into 500mL three-necked flask, be added 51.10g trimethylhydroquinone and 112.80g aqueous solution containing zinc and
4.70mL concentrated hydrochloric acid is mixed with 150mL ethyl acetate, is heated to 40 DEG C, and 100g different vegetable alcohol is added dropwise in 2h, and reaction is mixed
Object keeps the temperature 1.5h at 40 DEG C, is then warming up to 60~65 DEG C, keeps the temperature 2h, ethyl acetate is recovered under reduced pressure in reaction solution, is obtained
Crude product and aceticanhydride are esterified, and then rectifying obtains vitamin E, yield 98.70%.Resulting zinc-containing water uses same procedure
It repeats to apply after processing, as a result as shown in the table.
1 zinc-containing water of table applies influence of the number to content of vitamin E
| Apply number | 1 | 2 | 3 | 10 | 15 |
| Vitamin E yield | 98.70% | 97.43% | 97.32% | 95.32% | 90.82% |
Comparative example 1
Weighing 500g zinc-containing water, (zinc oxide concentration 27.84%, hydrogen cloride concentration 2.10%, TOC value are
12175.3ppm, pH < 1) it pours into 1000ml separatory funnel, using ethyl acetate as extractant, extracts 5 times, 30mL is added every time
Ethyl acetate, after extraction, rufous, pH < 1 is presented in water phase.Water phase is evaporated under reduced pressure, pressure -0.08MPa, temperature
150 DEG C, ethyl acetate therein and part water are removed, obtains the 316.65g of aqueous solution containing zinc that zinc oxide concentration is 43.58%.
At room temperature, into 500mL three-necked flask, be added 51.10g trimethylhydroquinone and 117.26g aqueous solution containing zinc and
4.70mL concentrated hydrochloric acid is mixed with 150mL ethyl acetate, is heated to 40 DEG C, and 100g different vegetable alcohol is added dropwise in 2h, and reaction is mixed
Object keeps the temperature 1.5h at 40 DEG C, is then warming up to 60~65 DEG C, keeps the temperature 2h, ethyl acetate is recovered under reduced pressure in reaction solution, is obtained
Crude product and aceticanhydride are esterified, and then rectifying obtains vitamin E, yield 89.30%.
Comparative example 1 the result shows that, be added without alkali compounds neutralizing to reaction system, directly extracted,
There can be large effect to extraction efficiency, not only reduce the rate of recovery of zinc chloride, but also organic substance residues is caused to increase, it is final to influence
To applying for solder(ing)acid.
Comparative example 2
Weighing 500g zinc-containing water, (zinc oxide concentration 27.84%, hydrogen cloride concentration 2.10%, TOC value are
12175.3ppm, pH < 1) in 1000mL beaker, 20g sodium carbonate is added, stirs 10min, pH value of solution=2~3.After neutralizing
Zinc-containing water pour into 1000ml separatory funnel, using ethyl acetate as extractant, extract 5 times, every time be added 30mL acetic acid second
Ester, after extraction, water phase presents faint yellow.Water phase is evaporated under reduced pressure, pressure -0.05MPa, 130 DEG C of temperature, removes it
In ethyl acetate and part water, obtain zinc oxide concentration be 44.52% the 309.97g of aqueous solution containing zinc.
At room temperature, into 500mL three-necked flask, be added 51.10g trimethylhydroquinone and 114.78g aqueous solution containing zinc and
4.70mL concentrated hydrochloric acid is mixed with 150mL ethyl acetate, is heated to 40 DEG C, and 100g different vegetable alcohol is added dropwise in 2h, and reaction is mixed
Object keeps the temperature 1.5h at 40 DEG C, is then warming up to 60~65 DEG C, keeps the temperature 2h, ethyl acetate is recovered under reduced pressure in reaction solution, is obtained
Crude product and aceticanhydride are esterified, and then rectifying obtains vitamin E, yield 85.70%.
Comparative example 2 the result shows that, be added the neutralizing to reaction system of alkali compounds containing sodium, extracted,
The rate of recovery of zinc chloride can be improved, reduce organic substance residues, but the presence due to remaining sodium ion, lead to solder(ing)acid
When applying, reaction yield is not high.
Embodiment 2
Weighing 500g zinc-containing water, (zinc oxide concentration 27.84%, hydrogen cloride concentration 2.10%, TOC value are
12175.3ppm, pH < 1) in 1000mL beaker, 35g zinc carbonate is added, stirs 10min, is filtered to remove not molten zinc carbonate
16.82g, filtrate pH=2~3.Filtrate is poured into 1000ml separatory funnel, using toluene as extractant, extracts 7 times, adds every time
Enter 30mL toluene, after extraction, water phase presents light yellow.Water phase is evaporated under reduced pressure, pressure -0.08MPa, temperature 150
DEG C, toluene therein and part water are removed, the 334.97g of aqueous solution containing zinc that zinc oxide concentration is 47.22% is obtained.
111.66g XDA-1G macroporous absorbent resin (dosage is the 1/3 of the quality of aqueous solution containing zinc) is taken, deionized water is first used
Then cleaning 5~10 times is transferred in resin filling column, adds water there be not 2~3 centimetres of resin, empty bubble.Contain zinc for after cooling
Aqueous solution flows through XDA-1G macroporous absorbent resin filling column and further purifies, and finally obtaining zinc oxide concentration is 43.69% to contain
Zinc aqueous solution 354.83g, the rate of recovery for being computed zinc is 97.52%.TOC measurement, TOC are carried out to the aqueous solution containing zinc after absorption
Value is 36ppm, meets solder(ing)acid and recycles standard.
Embodiment 3
Weighing 500g zinc-containing water, (zinc oxide concentration 27.84%, hydrogen cloride concentration 2.10%, TOC value are
12175.3ppm, pH < 1) in 1000mL beaker, 30g zinc hydroxide is added, stirs 10min, is filtered to remove not molten hydrogen-oxygen
Change zinc 15.59g, filtrate pH=2~3.Filtrate is poured into 1000ml separatory funnel, using pentane as extractant, is extracted 6 times,
30mL pentane is added every time, after extraction, water phase presents faint yellow.Water phase is evaporated under reduced pressure, pressure -0.10MPa,
160 DEG C of temperature, pentane therein and part water are removed, obtains the aqueous solution containing zinc that zinc oxide concentration is 48.37%
326.02g。
108.67g XDA-11 macroporous absorbent resin (dosage is the 1/3 of the quality of aqueous solution containing zinc) is taken, deionized water is first used
Then cleaning 5~10 times is transferred in resin filling column, adds water there be not 2~3 centimetres of resin, empty bubble.Contain zinc for after cooling
Aqueous solution flows through XDA-11 macroporous absorbent resin filling column and further purifies, and finally obtaining zinc oxide concentration is 46.24% to contain
Zinc aqueous solution 333.03g, the rate of recovery for being computed zinc is 96.87%.TOC measurement, TOC are carried out to the aqueous solution containing zinc after absorption
Value is 98ppm, meets solder(ing)acid and recycles standard.
Claims (10)
1. a kind of method of zinc-containing water comprehensive utilization, which comprises the following steps:
(1) alkali compounds containing zinc is added into zinc-containing water and carries out neutralization reaction, waste water after being neutralized；
(2) extracting operation, waste water after being extracted are carried out to waste water after neutralization using extractant；
(3) concentration purification is carried out to waste water after extraction, obtains aqueous solution containing zinc.
2. the method as described in claim 1, which is characterized in that in step (1), the alkali compounds containing zinc be zinc oxide,
One of zinc carbonate, zinc hydroxide are a variety of.
3. the method as described in claim 1, which is characterized in that in step (2), the extractant is toluene, ethyl acetate, just
One of pentane, chloroform are a variety of.
4. the method as described in claim 1, which is characterized in that in step (2), the mode of extraction is multitple extraction, extracts grade
Number is 3~10 grades, preferably 5~8 grades.
5. the method as described in claim 1, which is characterized in that in step (3), the mode of the concentration purification is that decompression is steamed
It evaporates, pressure range is -0.03MPa~-0.10MPa, and temperature range is 110 DEG C~180 DEG C；It is preferred that pressure range is -0.05MPa
~-0.08MPa, temperature range are 120 DEG C~160 DEG C.
6. the method as described in claim 1, which is characterized in that can directly apply the aqueous solution containing zinc that step (3) obtain
It is reacted in the production process for preparing vitamin E in trimethylhydroquinone with different vegetable alcohol.
7. the method as described in claim 1, which is characterized in that can be obtained using adsorbent to step (3) water-soluble containing zinc
Liquid carries out adsorption treatment, obtains solder(ing)acid product.
8. the method for claim 7, which is characterized in that the adsorbent be macroporous absorbent resin XDA-1, XDA-1G,
One of XDA-11, XDA-200.
9. method according to claim 8, which is characterized in that the granularity of the macroporous absorbent resin is 0.1~10mm, compares table
Area is 1000~2000m21~20m of/g, Kong Rongwei3/mL；
The mass ratio of the macroporous absorbent resin and the aqueous solution containing zinc is 1:1~20, and absorption series is 1~10 grade；Preferred mass
It is 1~5 grade than for 1:1~10, adsorbing series.
10. method as claimed in claim 9, which is characterized in that after adsorption treatment, carried out using desorbing agent to adsorbent
Regeneration treatment；
The desorbing agent is one of ethyl acetate, methanol, ethyl alcohol, acetone or a variety of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112611749A (en) * | 2020-10-30 | 2021-04-06 | 重庆金美新材料科技有限公司 | Method for detecting content of ammonium citrate in liquid |
| CN113501607A (en) * | 2021-07-05 | 2021-10-15 | 山东新和成维生素有限公司 | Recycling method of zinc-containing wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084180A (en) * | 1990-10-25 | 1992-01-28 | Cominco Ltd. | Method for treating zinc-containing sulfate solution |
| CN1189495A (en) * | 1996-12-23 | 1998-08-05 | 巴斯福股份公司 | Process for preparing Alpha-tocopherol or Alpha-tocopheryl acetate |
| CN103820644A (en) * | 2014-03-20 | 2014-05-28 | 重庆大学 | Method for extracting zinc chloride from pharmaceutical waste liquid of vitamin E |
| CN107902855A (en) * | 2017-11-07 | 2018-04-13 | 宜宾海丝特纤维有限责任公司 | The recovery process of zinc ion is discarded in a kind of viscose rayon production |
| CN108193052A (en) * | 2017-12-28 | 2018-06-22 | 江苏永葆环保科技有限公司 | Resource utilization prepares the method without ammonium fluxing agent using low acid waste water containing zinc |
-
2019
- 2019-08-02 CN CN201910710307.3A patent/CN110386712B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084180A (en) * | 1990-10-25 | 1992-01-28 | Cominco Ltd. | Method for treating zinc-containing sulfate solution |
| CN1189495A (en) * | 1996-12-23 | 1998-08-05 | 巴斯福股份公司 | Process for preparing Alpha-tocopherol or Alpha-tocopheryl acetate |
| CN103820644A (en) * | 2014-03-20 | 2014-05-28 | 重庆大学 | Method for extracting zinc chloride from pharmaceutical waste liquid of vitamin E |
| CN107902855A (en) * | 2017-11-07 | 2018-04-13 | 宜宾海丝特纤维有限责任公司 | The recovery process of zinc ion is discarded in a kind of viscose rayon production |
| CN108193052A (en) * | 2017-12-28 | 2018-06-22 | 江苏永葆环保科技有限公司 | Resource utilization prepares the method without ammonium fluxing agent using low acid waste water containing zinc |
Non-Patent Citations (2)
| Title |
|---|
| 傅强: "《现代药物分离与分析技术》", 30 November 2017, 西安交通大学出版社 * |
| 缪应祺: "《水污染控制工程》", 31 December 2002, 东南大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112611749A (en) * | 2020-10-30 | 2021-04-06 | 重庆金美新材料科技有限公司 | Method for detecting content of ammonium citrate in liquid |
| CN113501607A (en) * | 2021-07-05 | 2021-10-15 | 山东新和成维生素有限公司 | Recycling method of zinc-containing wastewater |
| CN113501607B (en) * | 2021-07-05 | 2023-02-03 | 山东新和成维生素有限公司 | Recycling method of zinc-containing wastewater |
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