CN109987740A - The method for precipitating calcium and magnesium in industrial wastewater - Google Patents
The method for precipitating calcium and magnesium in industrial wastewater Download PDFInfo
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- CN109987740A CN109987740A CN201910088446.7A CN201910088446A CN109987740A CN 109987740 A CN109987740 A CN 109987740A CN 201910088446 A CN201910088446 A CN 201910088446A CN 109987740 A CN109987740 A CN 109987740A
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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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
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Abstract
The present invention provides a kind of methods of the calcium and magnesium in precipitating industrial wastewater, and by the alkoxyphenyl radical acetic acid that will prepare as organic precipitant, the industrial wastewater with alkali compounds and containing calcium and magnesium ion is mixed, and is precipitated；After separation of solid and liquid, the solid sediment and water phase containing calcium and magnesium are obtained；In the case where not increasing COD in water phase, remaining calcium and magnesium reaches minimum standard needed for enterprise in industrial wastewater；The solid sediment containing calcium and magnesium is eluted using acid solution, obtains the eluent and organic precipitant of enrichment calcium and magnesium.For organic precipitant provided by the invention to calcium, magnesium etc. can bring the ion of permanent hardness to have good sedimentation effect, be highly suitable for the removal of calcium and magnesium plasma in industrial wastewater, to achieve the purpose that soften waste water；And the results showed that when the industrial wastewater of magnesium is precipitated, settling velocity is fast using organic precipitant provided by the invention to calcium is contained, total rate of deposition of calcium and magnesium is greater than 95%, and organic precipitant recycling effect is good, can largely reduce production cost.
Description
Technical field
The invention belongs to a kind of methods of calcium and magnesium in field of industrial waste water treatment more particularly to precipitating industrial wastewater.
Background technique
China possesses abundant rare earth resources, and rare earth reserves and yield occupy first place in the world.However by technology and geography etc. because
The influence of element, the contaminated wastewater that rare earth generates in smelting process are not controlled effectively yet.Such as it is only in concentrated sulfuric acid roasting
In the composite ore technique for occupying stone and bastnaesite, have become the main of Yellow River in Baotou Area ammonia and nitrogen pollution in the amine wastewater of sulphuric acid of generation
One of source.Amine wastewater of sulphuric acid can recycle ammonia by reverse osmosis concentration and blow-off method, so that waste water is recycled, to realize
" zero-emission ".However, the calcium-magnesium content in amine wastewater of sulphuric acid is higher.To prevent calcium and magnesium fouling on film, it is ensured that the normal fortune of equipment
Row, there is an urgent need to efficiently remove removing calcium and magnesium and soften the technology of waste water.The Chinese invention patent Shen of Publication No. CN105461002A
A kind of method for removing removing calcium and magnesium in rare-earth industry waste water please be disclose, includes: the ammonium sulfate generated with rare earth acid system smelting process
Waste water is process object, and the sulfonated kerosene for adding 50% volume ratio using the P507 of 50% volume ratio is having as organic extractant
Machine phase and liquid volume ratio are 1~2, and saponification rate is extracted under conditions of being 45~60%, stratification after extraction；It should
Although method solves the problems, such as that ammonia steaming system line clogging is serious, but due in treated waste water can remnants have it is a certain amount of
Organic extractant and sulfonated kerosene water body is polluted to increase the COD (COD) of waste water.
Summary of the invention
In view of this, the present invention is applied to calcic, the industry of magnesium as organic precipitant for from the alkyl fibric acid of synthesis
The processing of waste water, to calcium is contained, the industrial wastewater of magnesium is precipitated, and realizes that settling velocity is fast, and total rate of deposition of calcium and magnesium is greater than
95%, it not will increase the COD of water phase, and organic precipitant can be recycled, reduce production cost.
The present invention provides a kind of method for precipitating calcium and magnesium in industrial wastewater, which comprises
Organic precipitant, alkali compounds and the industrial wastewater containing calcium and magnesium ion are mixed, preset time is precipitated, into
Row centrifuge separation, obtains the solid sediment and water phase containing calcium and magnesium；
The organic precipitant includes one of formula (I)~formula (III) structural compounds or a variety of:
Wherein, R1, R2, R3 and R, 3 independently selected from hydrogen, the straight chained alkyl, unsubstituted that substituted carbon atom number is 1~10
Carbon atom number be 1~10 straight chained alkyl, substituted carbon atom number be 3~10 branched alkyl, unsubstituted carbon atom number
For 3~10 branched alkyl, substituted aryl or unsubstituted aryl.
Preferably, described R1, R2, R3 and R, 3 independently selected from hydrogen, methyl, 2,6- dimethyl heptyl, 2,4,4- trimethyls
Amyl, 2,2,4- tri-methyl-amyl, 2,3,4- tri-methyl-amyl and 1,1,3,3- tetramethyl butyl.
Preferably, the alkali compounds includes one of ammonium hydroxide, sodium hydroxide and potassium hydroxide or a variety of.
Preferably, the total moles ratio of calcium and magnesium ion is in the organic precipitant, alkali compounds and the industrial wastewater
(1~6): (0.5~6): 1.
Preferably, the method also includes:
The solid sediment containing calcium and magnesium is mixed with acid solution and is eluted, eluent and the institute of enrichment calcium and magnesium are obtained
State organic precipitant.
Preferably, in the solid sediment containing calcium and magnesium and the acid solution hydrionic molar ratio be 1:(0.3~
6)。
Preferably, the acid solution includes one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution or a variety of；The acid solution
Concentration be 5~12mol/L.
Preferably, the temperature of the elution is room temperature, and the time of the elution is 5~20min.
Preferably, the obtained step of the organic precipitant includes:
Alkylbenzene phenolic compound and halogenated acetic acids sodium are reacted in a solvent, obtain reaction solution；
The reaction solution is acidified, organic precipitant is obtained.
Preferably, the method also includes the organic precipitant is washed and is evaporated under reduced pressure, the vacuum distillation
Temperature be 130~150 DEG C.
For organic precipitant prepared by the present invention to calcium, magnesium etc. can bring the ion of permanent hardness to have precipitating well
Effect is highly suitable for the removal of calcium and magnesium plasma in industrial wastewater, the especially removal of high concentration calcium and magnesium plasma.
The beneficial effect that the present invention realizes includes at least:
Using organic precipitant provided by the invention to containing calcium, when the industrial wastewater of magnesium is precipitated, the solid of formation
Precipitate particles are big, and settling velocity is fast, and total rate of deposition of calcium and magnesium is greater than 95%, while will not increase water body new pollutant,
The COD of water body will not be promoted；And the organic precipitant stable structure, recycling 1 year or more without significantly heavy
The variation of shallow lake effect, can be recycled, and reduce production cost.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the infrared spectroscopy that the embodiment of the present invention 1 provides.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The most critical design of the present invention is: being applied to Industry Waste for alkoxyphenyl radical acetic acid obtained as organic precipitant
Calcium and magnesium etc. can bring the precipitating of the ion of permanent hardness in water.
The present invention provides a kind of method for precipitating calcium and magnesium in industrial wastewater, which comprises
Organic precipitant, alkali compounds and the industrial wastewater containing calcium and magnesium ion are mixed, preset time is precipitated, into
Row centrifuge separation, obtains the solid sediment and water phase containing calcium and magnesium；
The organic precipitant includes one of formula (I)~formula (III) structural compounds or a variety of:
Wherein, R1, R2, R3 and R, 3 independently selected from hydrogen, the straight chained alkyl, unsubstituted that substituted carbon atom number is 1~10
Carbon atom number be 1~10 straight chained alkyl, substituted carbon atom number be 3~10 branched alkyl, unsubstituted carbon atom number
For 3~10 branched alkyl, substituted aryl or unsubstituted aryl.
Preferably, described R1, R2, R3 and R, 3 independently selected from hydrogen, methyl, 2,6- dimethyl heptyl, 2,4,4- trimethyls
Amyl, 2,2,4- tri-methyl-amyl, 2,3,4- tri-methyl-amyl and 1,1,3,3- tetramethyl butyl.
Preferably, the method also includes:
The solid sediment containing calcium and magnesium is mixed with acid solution and is eluted, eluent and the institute of enrichment calcium and magnesium are obtained
State organic precipitant.
Preferably, in the solid sediment containing calcium and magnesium and the acid solution hydrionic molar ratio be 1:(0.3~
6)。
In the method for the calcium and magnesium in precipitating industrial wastewater provided by the invention, first by the organic precipitant, alkalinity
Compound and the industrial wastewater mixing to be processed containing calcium and magnesium ion.Wherein, the industrial wastewater containing calcium and magnesium ion
The total concentration of middle calcium and magnesium is preferably 0.01~15g/L, more preferably 0.1~5g/L；The alkali compounds includes ammonium hydroxide, hydrogen-oxygen
Change one of sodium and potassium hydroxide or a variety of.Calcium in the organic precipitant, alkali compounds and the industrial wastewater, magnesium from
The total moles of son are than being preferably (1~6): (0.5~6): 1.Solid sediment is generated after mixing.Wherein, the temperature of the reaction
Preferably room temperature, the time-consuming of the reaction are preferably 2~10min, concretely 5min.After being separated by solid-liquid separation later, wherein described
Mode after separation of solid and liquid is preferably centrifugated, and the revolving speed of the centrifuge separation is preferably 2500~5000rpm, the centrifugation
The isolated time is preferably 5~15min.
After obtaining the solid sediment containing calcium and magnesium, the solid sediment containing calcium and magnesium is washed using acid solution
It is de-.Wherein, the acid solution includes but is not limited to hydrochloric acid solution, sulfuric acid solution or nitric acid solution；The concentration of the acid solution is preferably 5
~12mol/L, more preferably 6~10mol/L, concretely 8mol/L；The solid sediment containing calcium and magnesium and the acid
In liquid hydrionic mole preferably than for 1:(0.3~6), more preferably 1:(2~4)；The temperature of the elution is preferably room temperature；
The time of the elution is preferably 5~20min, more preferably 10~15min.After elution, the elution of enrichment calcium and magnesium is obtained
The liquid organic precipitant as before with recovery.
Preferably, the obtained step of the organic precipitant includes:
Alkylbenzene phenolic compound and halogenated acetic acids sodium are reacted in a solvent, obtain reaction solution；
The reaction solution is acidified, organic precipitant is obtained.
In above-mentioned organic precipitant preparation method provided by the invention, first by the alkylbenzene phenolic compound and halogen
It is mixed in a solvent for sodium acetate.Wherein, ' 3 R1, R2, R3 and R in the alkylbenzene phenolic compound independently selected from hydrogen,
Straight chained alkyl that substituted carbon atom number is 1~10, the straight chained alkyl that unsubstituted carbon atom number is 1~10, substituted carbon are former
Branched alkyl that subnumber is 3~10, the branched alkyl that unsubstituted carbon atom number is 3~10, substituted aryl or unsubstituted
Aryl preferably is selected from the straight chained alkyl, substitution that hydrogen, the straight chained alkyl that substituted carbon atom number is 1, substituted carbon atom number are 2
The straight chain alkane that straight chained alkyl that carbon atom number is 3, the straight chained alkyl that substituted carbon atom number is 4, substituted carbon atom number are 5
Base, the straight chained alkyl that substituted carbon atom number is 6, the straight chained alkyl that substituted carbon atom number is 7, substituted carbon atom number are 8
Straight chained alkyl, the straight chained alkyl that substituted carbon atom number is 9, substituted carbon atom number be 10 straight chained alkyl, unsubstituted
The straight chain that straight chained alkyl that straight chained alkyl that carbon atom number is 1, unsubstituted carbon atom number are 2, unsubstituted carbon atom number are 3
Straight chained alkyl that straight chained alkyl that alkyl, unsubstituted carbon atom number are 4, unsubstituted carbon atom number are 5, unsubstituted carbon are former
The straight chain alkane that straight chained alkyl that straight chained alkyl that subnumber is 6, unsubstituted carbon atom number are 7, unsubstituted carbon atom number are 8
Straight chained alkyl that base, unsubstituted carbon atom number are 9, the straight chained alkyl that unsubstituted carbon atom number is 10, substituted carbon atom
Count the branched alkyl, substitution that the branched alkyl, the branched alkyl that substituted carbon atom number is 2, substituted carbon atom number that are 1 are 3
Carbon atom number be 4 branched alkyl, the branched alkyl that substituted carbon atom number is 5, substituted carbon atom number be 6 branched alkane
Base, the branched alkyl that substituted carbon atom number is 7, the branched alkyl that substituted carbon atom number is 8, substituted carbon atom number are 9
Branched alkyl, substituted carbon atom number be 10 branched alkyl, unsubstituted carbon atom number be 1 branched alkyl, unsubstituted
Carbon atom number be 2 branched alkyl, unsubstituted carbon atom number be 3 branched alkyl, unsubstituted carbon atom number be 4 branch
Branched alkyl that branched alkyl that alkyl group, unsubstituted carbon atom number are 5, unsubstituted carbon atom number are 6, unsubstituted carbon
The branched alkane that branched alkyl that branched alkyl that atomicity is 7, unsubstituted carbon atom number are 8, unsubstituted carbon atom number are 9
Base or unsubstituted carbon atom number are 10 branched alkyl, concretely hydrogen, methyl, 2,6- dimethyl heptyl, 2,4,4- front threes
Base amyl, 2,2,4- tri-methyl-amyl, 2,3,4- tri-methyl-amyl and 1,1,3,3- tetramethyl butyl.Provided by the invention one
In a embodiment, the alkylbenzene phenolic compound concretely 2,6- dimethyl heptyl sodium phenate, 2,4,4- tri-methyl-amyls
Sodium phenate, 2,2,4- tri-methyl-amyl sodium phenate, 2,3,4- tri-methyl-amyl sodium phenate and 1,1,3,3- tetramethyl butyl phenol
One of sodium is a variety of.
In the present invention, halogen concretely one of fluorine, chlorine, bromine and iodine or a variety of in the halogenated acetic acids sodium；Institute
Stating solvent includes but is not limited to ethyl alcohol.
In the present invention, the molar ratio of the alkylbenzene phenolic compound and halogenated acetic acids sodium is preferably 1:(1~4), more
Preferably 1:(1.2~2.4), further preferably 1:(1.6~2.4).In the present invention, it is preferred to first by alkylbenzene phenols chemical combination
Halogenated acetic acids sodium, is added in mixed system again reacts later by object and solvent mixing.In the present invention, the reaction
Temperature is preferably 100~120 DEG C, and more preferably 110 DEG C；The time of the reaction is preferably 0.5~3.5h, more preferably
1.5h.After reaction, reaction solution is obtained.After obtaining reaction solution, the reaction solution is acidified.In the present invention, it is preferred to
The solvent in the reaction solution is removed before being acidified, except the mode of solvent is preferably evaporated under reduced pressure.In the present invention, described
The reagent of acidification is preferably hydrochloric acid solution, and the concentration of the hydrochloric acid solution is preferably 5~7mol/L, more preferably 6mol/L.?
In the present invention, the amount ratio of the hydrochloric acid solution and the alkylbenzene phenolic compound preferably (40~90) mL:(0.15~
0.3) mol, more preferably (50~80) mL:(0.2~0.21) mol.In the present invention, the temperature of the acidification be preferably 20~
40 DEG C, concretely 30 DEG C；The time of the acidification is preferably 2~10min, concretely 5min.After acidification, to acidification
Product is post-processed, and the alkyl phenoxy acetic acid is obtained.In the present invention the mode of the post-processing preferably include successively into
Row washing and vacuum distillation, wherein the number of the washing is preferably 2~5 times, and more preferably 3 times；The temperature of the vacuum distillation
Degree is 130~190 DEG C, preferably 130~150 DEG C, more preferably 130~140 DEG C.
Preparation method synthetic route provided by the invention is simple, and raw material sources are extensive, the organic precipitant of synthesis to calcium,
Magnesium etc. can bring the ion of permanent hardness to have good sedimentation effect, be highly suitable for calcium and magnesium plasma in industrial wastewater
Removal.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1
1) preparation of 1,1,3,3- tetramethyl butyl phenoxy acetic acid:
100 grams of dehydrated alcohol are added in reaction vessel, 1,1,3,3- 48.4 grams of tetramethyl butyl sodium phenate (0.21mol).
Stirring and heating are opened, 110 DEG C is warming up to, 37.8 grams of sodium chloroacetate (0.32mol) is slowly added into reaction vessel.Instead
It is cooled to room temperature after answering 1.5 hours, obtained reaction product is evaporated under reduced pressure solvent, the hydrochloric acid of 50mL 6mol/L is then added
Solution is acidified, and the temperature of acidification is 30 DEG C, and the time of acidification is 5min, after the product after acidification is washed 3 times, 160 DEG C
Vacuum distillation, obtains 1,1,3,3- tetramethyl butyl phenoxy acetic acid.
1 that the present embodiment is prepared, 1,3,3- tetramethyl butyl phenoxy acetic acid are detected by acid base titration and nuclear-magnetism,
Purity is greater than 99%, has formula (I) structure.
2) calcium ions and magnesium ions in industrial wastewater are removed:
Organic precipitant and industrial wastewater are mixed at room temperature and precipitated.The composition of industrial wastewater are as follows: calcium and magnesium is always dense
Spend 3.45 grams per liters, pH=7.5, specific ingredient is as shown in table 1.Organic precipitant, in sodium hydroxide and low-concentration industrial waste water
The total moles ratio of calcium and magnesium ion is 2.1:1.68:1.After precipitating carries out 5min, (revolving speed 5000rpm, centrifugation are centrifuged
Time 5min), obtain the solid sediment and water phase containing calcium and magnesium.Total rate of deposition of calcium and magnesium reaches 95.5%.Remaining Ca2+With
Mg2+Concentration be respectively 0.09 and 0.08g/L, reached the requirement (Ca of enterprise2+<0.1g/L,Mg2+<0.5g/L)。
Low concentration used in 1 embodiment of the present invention 1 of table contains the ingredient of the industrial wastewater of calcium and magnesium ion
| Ingredient | Ca2+ | Mg2+ | NH4+ | Na+ | SO4 2- |
| Concentration, grams per liter | 0.451 | 3.00 | 11.8 | 0.18 | 32.5 |
The solid sediment containing calcium and magnesium and the mixed in hydrochloric acid of 8.0 mol/Ls are eluted at room temperature, contain calcium and magnesium
Solid sediment and the molar ratio of hydrochloric acid be 1:2.1, elute time-consuming 10min, after elution, obtain being enriched with calcium and magnesium and wash
The de- liquid organic precipitant as before with recovery.Constituent analysis is carried out to the de- solid sediment containing calcium and magnesium, as the result is shown:
Ingredient is 1,1,3,3- tetramethyl butyl phenoxy acetic acid.
After being recycled 1 year, Assignment of Infrared Spectrum is carried out to organic precipitant, as a result as shown in Figure 1.By comparing may be used
Know, organic precipitant (b) of the circulation after 1 year is consistent with the Assignment of Infrared Spectrum result of fresh organic precipitant (a).It can be seen that
The stable structure of 1,1,3,3- tetramethyl butyl phenoxy acetic acid is recycled 1 year molecular structure and has no significant change.
Comparative example 1
The calcium ions and magnesium ions in industrial wastewater are removed with oxalic acid:
Oxalic acid and industrial wastewater are mixed at room temperature and precipitated.The composition of industrial wastewater is the same as embodiment 1；Oxalic acid, hydrogen
The total moles ratio of calcium and magnesium ion is 1.05:1:1 in sodium oxide molybdena and low-concentration industrial waste water.After precipitating carries out 5min, it is centrifuged
It separates (revolving speed 5000rpm, centrifugation time 5min), obtains oxalic acid precipitation object and the water phase containing calcium and magnesium.Total rate of deposition of calcium and magnesium
Reach 24.0%.Remaining Ca2+And Mg2+Concentration be respectively 0.10 and 2.4g/L, Mg is not up to the requirement (Ca of enterprise2+<
0.1g/L,Mg2+<0.5g/L)。
At room temperature by the mixed in hydrochloric acid of the oxalic acid precipitation object containing calcium and magnesium and 8.0 mol/Ls, effect is not eluted.Grass
Acid can not be recycled.
Embodiment 2
1) preparation of 2,6- dimethyl heptyl phenoxy acetic acid:
100 grams of dehydrated alcohol are added in reaction vessel, 2,6- dimethyl heptyl sodium phenate 0.21mol.It opens stirring and adds
Heat is warming up to 110 DEG C, and bromoacetic acid sodium 0.32mol is slowly added into reaction vessel.Reaction was cooled to room after 1.5 hours
Obtained reaction product is evaporated under reduced pressure solvent by temperature, and the hydrochloric acid solution 50mL that 6mol/L is then added is acidified, the temperature of acidification
Degree is 30 DEG C, and the time of acidification is 5min, and after the product after acidification is washed 3 times, 140 DEG C of vacuum distillations obtain 2,6- diformazan
Base heptyl phenoxy acetic acid.
2, the 6- dimethyl heptyl phenoxy acetic acid that the present embodiment is prepared is detected by acid base titration and nuclear-magnetism, purity
Greater than 99%, there is formula (I) structure.
2) calcium ions and magnesium ions in industrial wastewater are removed:
Organic precipitant and industrial wastewater are mixed at room temperature and precipitated.The group of industrial wastewater becomes with embodiment 1.
The total moles ratio of calcium and magnesium ion is 3.0:2.7:1 in organic precipitant, ammonium hydroxide and low-concentration industrial waste water.Precipitating carries out 5min
Afterwards, plate compression is carried out, the solid sediment and water phase containing calcium and magnesium are obtained.Total rate of deposition of calcium and magnesium reaches 96.5%.
The solid sediment containing calcium and magnesium and the mixed in hydrochloric acid of 6.0 mol/Ls are eluted at room temperature, contain calcium and magnesium
Solid sediment and the molar ratio of hydrochloric acid be 1:2.1, elute time-consuming 8min, after elution, obtain being enriched with calcium and magnesium and wash
The de- liquid organic precipitant as before with recovery.Constituent analysis is carried out to the de- solid sediment containing calcium and magnesium, as the result is shown:
Ingredient is 2,6- dimethyl heptyl phenoxy acetic acid.
Embodiment 3
1) preparation of the double phenoxy acetic acids of 4,4'- isopropylidene:
100 grams of dehydrated alcohol are added in reaction vessel, 2,2- bis- 45.7 grams of propane of (4- hydroxy phenyl) (0.20mol).It opens
Stirring and heating are opened, is warming up to 110 DEG C, 58.3 grams of sodium chloroacetate (0.5mol) are slowly added into reaction vessel.Reaction
It is cooled to room temperature after 1.5 hours, obtained reaction product is evaporated under reduced pressure solvent, the hydrochloric acid that 80mL 6mol/L is then added is molten
Liquid is acidified, and the temperature of acidification is 30 DEG C, and the time of acidification is 5min, and after the product after acidification is washed 3 times, 160 DEG C subtract
Pressure distillation obtains the double phenoxy acetic acids of 4,4'- isopropylidene.
The double phenoxy acetic acids of 4,4'- isopropylidene that the present embodiment is prepared are detected by acid base titration and nuclear-magnetism, it is pure
Degree is greater than 99%, has formula (III) structure, and in formula (III), R3 and R'3 take methyl.
2) calcium ions and magnesium ions in industrial wastewater are removed:
Organic precipitant and industrial wastewater are mixed at room temperature and precipitated.The composition of industrial wastewater are as follows: calcium and magnesium is always dense
Spend 1.73 grams per liters, pH=7.0.The total moles ratio of calcium and magnesium ion is in organic precipitant, ammonium hydroxide and low-concentration industrial waste water
1.1:1.1:1.After precipitating carries out 5min, plate compression is carried out, the solid sediment and water phase containing calcium and magnesium are obtained.Calcium and magnesium it is total
Rate of deposition reaches 97.1%.
The mixed in hydrochloric acid of the solid sediment containing calcium and magnesium and 6.0mol/L is eluted at room temperature, contains calcium and magnesium
Solid sediment and hydrochloric acid molar ratio be 1:1.1, elute time-consuming 8min, after elution, obtain be enriched with calcium and magnesium elution
The liquid organic precipitant as before with recovery.Constituent analysis is carried out to the de- solid sediment containing calcium and magnesium, as the result is shown: at
It is divided into the double phenoxy acetic acids of 4,4'- isopropylidene.
Embodiment 4
1) preparation of p- phenylenedioxydiacetic acid:
100 grams of dehydrated alcohol, 22.0 grams of hydroquinone (0.20mol) are added in reaction vessel.Stirring and heating are opened, is risen
Temperature is slowly added into 58.3 grams of sodium chloroacetate (0.5mol) in reaction vessel to 110 DEG C.Reaction was cooled to room after 1.5 hours
Obtained reaction product is evaporated under reduced pressure solvent by temperature, and the hydrochloric acid solution that 60mL 6mol/L is then added is acidified, acidification
Temperature is 30 DEG C, and the time of acidification is 5min, and after the product after acidification is washed 3 times, 150 DEG C of vacuum distillations obtain p- benzene oxygen
Oxalic acid.
The p- phenylenedioxydiacetic acid that the present embodiment is prepared is detected by acid base titration and nuclear-magnetism, and purity is greater than
98.5%, there is formula (II) structure, in formula (II), R2 takes hydrogen.
2) calcium ions and magnesium ions in industrial wastewater are removed:
Organic precipitant and industrial wastewater are mixed at room temperature and precipitated.The composition of industrial wastewater are as follows: calcium and magnesium is always dense
Spend 1.73 grams per liters, pH=7.0.The total moles ratio of calcium and magnesium ion in organic precipitant, potassium hydroxide and low-concentration industrial waste water
For 6:2:1.After precipitating carries out 5min, plate compression is carried out, the solid sediment and water phase containing calcium and magnesium are obtained.The total of calcium and magnesium sinks
Shallow lake rate reaches 98%.
The solid sediment containing calcium and magnesium is mixed with the sulfuric acid of 3.0mol/L at room temperature and is eluted, calcium and magnesium is contained
Solid sediment and sulfuric acid molar ratio be 1:3, elute time-consuming 8min, after elution, obtain be enriched with calcium and magnesium eluent
The organic precipitant as before with recovery.Constituent analysis is carried out to the de- solid sediment containing calcium and magnesium, as the result is shown: ingredient
For p- phenylenedioxydiacetic acid.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method of calcium and magnesium in precipitating industrial wastewater, which is characterized in that the described method includes:
Organic precipitant, alkali compounds and industrial wastewater containing calcium and magnesium ion are mixed, preset time is precipitated, carry out from
Heart separation, obtains the solid sediment and water phase containing calcium and magnesium；
The organic precipitant includes one of formula (I)~formula (III) structural compounds or a variety of:
Wherein, ' 3 R1, R2, R3 and R are independently selected from hydrogen, the straight chained alkyl that substituted carbon atom number is 1~10, unsubstituted carbon
Branched alkyl that straight chained alkyl that atomicity is 1~10, substituted carbon atom number are 3~10, unsubstituted carbon atom number be 3~
10 branched alkyl, substituted aryl or unsubstituted aryl.
2. the method according to claim 1, wherein ' 3 described R1, R2, R3 and R independently selected from hydrogen, methyl,
2,6- dimethyl heptyl, 2,4,4- tri-methyl-amyl, 2,2,4- tri-methyl-amyl, 2,3,4- tri-methyl-amyl and 1,1,3,3- tetra-
Methyl butyl.
3. the method according to claim 1, wherein the alkali compounds includes ammonium hydroxide, sodium hydroxide and hydrogen
One of potassium oxide is a variety of.
4. the method according to claim 1, wherein the organic precipitant, alkali compounds and the industry
The total moles ratio of calcium and magnesium ion is (1~6): (0.5~6): 1 in waste water.
5. method according to any of claims 1-4, which is characterized in that the method also includes:
The solid sediment containing calcium and magnesium is mixed with acid solution and is eluted, the eluent of enrichment calcium and magnesium is obtained and described is had
Machine precipitating reagent.
6. according to the method described in claim 5, it is characterized in that, in the solid sediment containing calcium and magnesium and the acid solution
Hydrionic molar ratio is 1:(0.3~6).
7. according to the method described in claim 5, it is characterized in that, the acid solution includes that hydrochloric acid solution, sulfuric acid solution, nitric acid are molten
One of liquid is a variety of；The concentration of the acid solution is 5~12mol/L.
8. according to the method described in claim 5, it is characterized in that, the temperature of the elution is room temperature, the time of the elution
For 5~20min.
9. the method according to claim 1, wherein the obtained step of the organic precipitant includes:
Alkylbenzene phenolic compound and halogenated acetic acids sodium are reacted in a solvent, obtain reaction solution；
The reaction solution is acidified, organic precipitant is obtained.
10. according to the method described in claim 9, it is characterized in that, the method also includes carrying out to the organic precipitant
Washing and vacuum distillation, the temperature of the vacuum distillation are 130~150 DEG C.
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| CN111453861A (en) * | 2020-05-19 | 2020-07-28 | 新疆维吾尔自治区环境保护科学研究院 | Agent and method for removing calcium and magnesium ions in high-salinity wastewater |
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