CN106115835A - A kind of processing method of the industrial wastewater containing oxalic acid - Google Patents
A kind of processing method of the industrial wastewater containing oxalic acid Download PDFInfo
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- CN106115835A CN106115835A CN201610584011.8A CN201610584011A CN106115835A CN 106115835 A CN106115835 A CN 106115835A CN 201610584011 A CN201610584011 A CN 201610584011A CN 106115835 A CN106115835 A CN 106115835A
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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Abstract
The method that the invention provides dialkyl alkylphosphonate industrial wastewater containing oxalic acid as the purposes of the extractant of the industrial wastewater processed containing oxalic acid and the dialkyl alkylphosphonate process of use formula I of below formula I:Wherein, R1And R2It is each independently selected from C3～C12Alkyl, R3Selected from C3～C12Alkyl, and R1、R2、R3Total carbon atom number be the integer between 10 to 30.The processing method of the present invention achieves the recycling of oxalic acid and the zero-emission of waste water, it is to avoid containing the pollution to environment of the oxalic acid discharge of wastewater, simplifies technological process simultaneously, reduces cost for wastewater treatment, and extractant used is commercially available prod, cheap and easy to get.
Description
Technical field
The present invention relates to the processing method of a kind of industrial wastewater containing oxalic acid, particularly to a kind of from the rare earth work containing oxalic acid
The method separating and recovering oxalic acid in industry waste water.
Background technology
China's rare earth resources enriches, and its reserves account for the 50% of world saving, widely distributed, great variety of goods.Rare earth due to
In the special nature of the aspect such as optical, electrical, magnetic, chemical property, it is widely used in metallurgy, glass, pottery, chemical industry, nuclear industry, electronics
All many-sides such as industrial, agriculture and medical.
In recent years, rare earth is as the raw material of new material, and international market is all with day to the demand of high purity rare earth oxides
Increase, for reaching the international market requirement to rare earth oxide purity, generally use the rare earth chloride that back extraction is got off by 10% oxalic acid
Precipitate, then with 2% oxalic acid, precipitation is washed.This technique can produce in high content acid wastewater, typically this waste water and contain
H2C2O40.5～30g/L, HCl 0.5～3mol/L, rare earth 10～200mg/L, just discharge if untreated, can be to ring
Border produces ill effect.
At present, country facilities processes this type of waste water and mainly uses Calx neutralisation or evaporation recovery oxalic acid.Calx
Although neutralisation is easy and simple to handle, with low cost, neutralize the acid in waste water, made waste water reach discharge standard, but the method is produced
Raw a large amount of waste residues pollute the environment equally, and administer difficulty；If recovering rare earth from this waste residue, recovery process is lengthy and jumbled, energy consumption
Greatly, need again to consume substantial amounts of industrial chemicals；Acid in waste water does not obtains efficient recovery, causes the wasting of resources.Though evaporation
So can reclaim oxalic acid and hydrochloric acid to a certain extent and be used back in producing, having preferable economic benefit and social benefit,
But this recovery process energy consumption is big, the corrosion resistance of equipment is required higher.
CN101503350A discloses synthetical recovery acid and the method for valuable metal in a kind of oxalic acid waste water, and the method is first used
P350 extracts oxalic acid, regulates chlorine ion concentration in raffinate with chloride or hydrochloric acid and is not less than 3.0mol/L；Use trialkylamine again
Extracting valuable metal ions from raffinate, the recovery of oxalic acid rate of the method is more than 95%, and recovery rate of valuable metals is more than
95%.The defect of the method is that P350 is expensive, and market price is about 200,000/ton, and this extractant is difficult to buying at present.
CN104610043A discloses a kind of method reclaiming oxalic acid from rare-earth industry waste water, and the method uses TBP to do
Extractant extraction oxalic acid, through 3～10 grades of extractions, 3～12 grades of back extractions, back extraction ratio is more than 95%, and technique is simple.The defect of the method
Being that the water solublity of TBP is big, during processing waste water, the loss of extractant is big, need to constantly add extractant, easily cause
The unstability of production technology.
CN104761444A discloses a kind of technique smelted from rare-earth wet method and reclaim oxalic acid the heavy waste water of grass, and this technique is led to
Cross in rare earth grass sinks waste water, add alkalescence calcium ions precipitate oxalate, then dissolve with dilute sulfuric acid, after solid-liquid separation, take liquid portion
Dividing and be cooled to 0～15 DEG C, oxalic acid crystal separates out, and the response rate reaches more than 50%, oxalic acid purity more than 95%.The defect of the method
Being when sulfuric acid dissolution calcium oxalate to be heated to 70～90 DEG C of reactions, and produce solid waste-calcium sulfate, yield is the highest.
Summary of the invention
In order to solve the problems referred to above present on oxalic acid separation and recovery technology, the invention provides a kind of industry containing oxalic acid
The processing method of waste water, it is achieved that the recycling of oxalic acid and the zero-emission of waste water, it is to avoid the discharge of wastewater containing oxalic acid is to environment
Pollute, simplify technological process simultaneously, reduce cost for wastewater treatment, and extractant used is commercially available prod, the most easily
?.
One aspect of the present invention provides the dialkyl alkylphosphonate of below formula I as processing the Industry Waste Han oxalic acid
The purposes of the extractant of water:
Wherein, R1And R2It is each independently selected from C3～C12Alkyl, more preferably C4～C10Alkyl, most preferably C4～C9Alkane
Base；R3Selected from C3～C12Alkyl, more preferably C3～C10Alkyl, most preferably C4～C9Alkyl；And R1、R2、R3Entire carbon atom
Number is the integer between 10 to 30.
In described formula I, R1、R2、R3Identical or different, the most identical alkyl, the most identical C4～C9Alkane
Base.
R1、R2、R3Total carbon atom number include being not limited to 10,11,12,13,14,15,16,17,18,19,20,21,
22,23,24,25,26,27,28,29 and 30 carbon atoms, preferably 10～27, more preferably 12～27.
Preferably, the dialkyl alkylphosphonate of described formula I is selected from 2-ethylhexyl phosphonic acid two (2-ethylhexyl)
Ester (P503), isopropyl phosphonic acids two (2-ethylhexyl) ester (P277), dibutyl-butylphosphonate (P205), diamyl amyl phosphonate
(DAAP), octyl phosphonic acid dibutyl ester (DBOP), butyl phosphonic acids dihexyl (DHBP), DHHP dihexylhexylphosphonate (DHHP), octyl group phosphine
One or more in acid dihexyl (DHOP) and octyl phosphonic acid dioctyl ester (DOOP).
Dialkyl alkylphosphonate in described formula I can be commercially available prod, and such as can be purchased from Shanghai Lai Yashi has
Limit company.
Another aspect of the present invention relates to the processing method of a kind of industrial wastewater containing oxalic acid, and described method includes using
State the step contacting the industrial wastewater containing oxalic acid containing dialkyl alkylphosphonate of formula I.
The method of the treatment in accordance with the present invention industrial wastewater containing oxalic acid can use solvent-extracted method to carry out, such as
The dialkyl alkylphosphonate of the present invention is configured to liquid extraction systems use, it would however also be possible to employ the method for liquid-solid extraction is entered
OK, such as the dialkyl alkylphosphonate of the present invention is prepared as solid-state separation material, is such as loaded with the alkylphosphines of the present invention
The porous silicon ball of acid dialkyl ester, kieselguhr etc..
Preferably, the processing method of the industrial wastewater containing oxalic acid of the present invention, comprise the steps:
(1) by the dialkyl alkylphosphonate of above-mentioned formula I and nonessential auxiliary extraction agent, nonessential phase modifying agent
And diluent mixing, obtain organic facies；
(2) ratio of the industrial wastewater containing oxalic acid with above-mentioned prepared organic facies (0.1～10) 1 by volume is mixed
Carry out 1～20 stage countercurrent extractions, obtain loading organic facies and the raffinate aqueous phase of oxalic acid；
(3) organic facies of load oxalic acid is mixed with the ratio of back washing agent (1～10) 1 by volume carry out 1～20 grade inverse
Stream back extraction, obtain the aqueous solution containing oxalic acid or oxalates and circulation organic facies, or obtain oxalic acid metal salt precipitate, supernatant and
Circulation organic facies；Gained circulation organic facies is back to step (2) and uses,
(4) not necessarily, return in step 3 after the aqueous solution formulated one-tenth back washing agent containing oxalic acid or oxalates, with
The ratio mixing of organic facies (1～10) 1 by volume of load oxalic acid, carries out back extraction to the concentration of oxalic acid circulated in strip liquor
When reaching 65～80g/L or when the concentration of oxalates reaches 30g/L, complete the enrichment of oxalic acid, or by anti-for formulated for supernatant one-tenth
Return to after extraction agent step 3 uses.
In said method, the described industrial wastewater containing oxalic acid for example, rare-earth industry waste water, concentration of oxalic acid therein is permissible
It is 0.05～30g/L.
In said method, described in step (1), auxiliary extraction agent acts primarily as assistance extraction, can strengthen alkyl phosphonic acid two
The Arrcostab extractant extraction ability to oxalic acid.Described auxiliary extraction agent can be selected from such as straight chain trialkyl phosphine
(Cyanex 923), side chain trialkyl phosphine (Cyanex 925), trioctyl phosphine oxide (TOPO), extraction
(P350), neutral phosphor (phosphine) extractant of 2-ethylhexyl phosphonic acid two (-2-ethylhexyl) ester, tributyl phosphate (TBP)；Such as
Two (2,4,4-tri-methyl-amyl) phosphonodithioic acid (Cyanex 301), two (2,4,4-tri-methyl-amyl) phosphonothiolic acid
(Cyanex 302), di-(2-ethylhexyl)phosphoric acid (P204), 2-ethylhexyl phosphonic acid list-2-ethyl hexyl ester (P507), two
(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex 272), the acid phosphorus (phosphine) of two (2-ethylhexyl) phosphonic acids (P227 or P229)
Extractant；Neutral phosphor amide extractant as disclosed in CN201410409451.0 and CN201410040023.5, such as three is different
Octyl group phosphamide, diisooctyl-different octyloxy phosphamide, iso-octyl-two different octyloxy phosphamide, three (diisobutyl) phosphinylidyne
Amine, two (diisobutyls)-different octyloxy phosphamide, three decyl phosphamides and two base-decyloxy phosphamide etc.；With above extraction
The mixed extractant that agent mixes with arbitrary proportion.
In said method, phase modifying agent described in step (1) acts primarily as the effect improving extraction physical phenomenon, and it can be
Selected from C4～C10One or more in alkanol and tributyl phosphate, described C4～C10Alkanol is preferably n-octyl alcohol, isooctanol, 2-
Isoocanol and the mixed alcohol of above-mentioned three kinds of alcohol arbitrary proportions mixing；It is highly preferred that described phase modifying agent is mixed alcohol or 2-first
Base enanthol.
In said method, described in step (1), diluent is selected from: C5～C16Alkane, such as pentane, hexane, heptane, pungent
Alkane, nonane, decane, hendecane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane etc.；Aerial kerosene；Sulfonated kerosene, liquid
Paraffin body, such as 250～400 DEG C of light lubricating oil fractions etc.；C5～C16Alicyclic alkanes, such as Pentamethylene., C1～C4Alkyl takes
The Pentamethylene. in generation, hexamethylene, C1～C4The substituted hexamethylene of alkyl, decahydronaphthalene etc.；C6～C10Aromatic hydrocarbons, such as benzene, toluene, diformazan
Benzene (including o-, m-, p-xylene and mixed xylenes) etc..Preferably, diluent be selected from aerial kerosene, sulfonated kerosene,
One or more in heptane.
In said method, the dialkyl alkylphosphonate described in step (1), nonessential auxiliary extraction agent, nonessential
Phase modifying agent and the volume ratio of diluent can be: dialkyl alkylphosphonate extractant: auxiliary extraction agent: phase modifying agent:
Diluent=about 1～80: about 0～20: about 0～20: about 20～99, more preferably dialkyl alkylphosphonate: auxiliary extraction agent:
Phase modifying agent: diluent=about 25～75: about 0～15: about 0～15: about 25～75；Most preferably dialkyl alkylphosphonate:
Auxiliary extraction agent: phase modifying agent: diluent=about 30～60: about 0～10: about 0～10: about 40～70.
In said method, the concentration of oxalic acid in raffinate aqueous phase described in step (2) is less than 0.05g/L.
In said method, the back washing agent described in step (3) can be selected from: water；Oxalate precipitation can be formed with oxalate
The hydrochlorate of the metal ion of thing, nitrate, sulfate solution, described metal for example, alkaline-earth metal (such as calcium or magnesium), mistake
Cross metal (such as cobalt), rare earth element (such as lanthanum, rubidium), actinides etc.；Alkaline aqueous solution, such as NaOH aqueous solution, KOH are water-soluble
Liquid, ammonia etc..
In said method, the back extraction ratio of the oxalic acid in step 3 is more than 98%.Described back extraction ratio is calculated as below:
Wherein: St% represents: back extraction ratio；[H2C2O4](Sr): represent the concentration of oxalic acid in strip liquor；[H2C2O4](O)Represent:
Concentration of oxalic acid in organic facies；V(Sr)Represent: strip liquor volume；V(o)Represent: organic facies volume.
The method according to the invention, the yield of final oxalic acid is more than 95%.Described yield is calculated as below:
Wherein: [H2C2O4](Sr): represent the concentration of oxalic acid in strip liquor；[H2C2O4](F)Represent: the oxalic acid in feed liquid is dense
Degree；V(Sr)Represent: strip liquor volume；V(F)Represent: material liquid volume.
According in the solvent extraction method of the present invention, extraction and back extraction can use separatory as known in the art to fill
Put and carry out, preferably carry out in a series of separatory funnels, mixed settler extractor or centrifugal extractor, more preferably in mixing clarification
Extraction tank or centrifugal extractor are carried out.
According in the solvent extraction method of the present invention, above-mentioned extraction and back extraction can intermittently or serially be carried out, preferably
It is carried out continuously.
Term C used in the present invention3～C12Alkyl refers to the straight or branched alkyl containing 3 to 12 carbon atoms,
Such as there is the straight or branched alkyl of 3,4,5,6,7,8,9,10,11 or 12 carbon atoms, include without limitation n-pro-pyl,
Isopropyl, normal-butyl, the tert-butyl group, isobutyl group, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl group, nonyl, decyl, ten
One alkyl, dodecyl etc..C3～C10Alkyl, C2～C12Alkyl and C4～C9The implication of alkyl is by that analogy.
Term C used in the present invention4～C10Alkanol refers to the straight or branched alkanol containing 4 to 10 carbon atoms,
Such as there is the straight or branched alkanol of 4,5,6,7,8,9 or 10 carbon atoms, include without limitation n-butyl alcohol, the tert-butyl alcohol,
Isobutanol, n-amyl alcohol, neopentyl alcohol, isoamyl alcohol, hexanol, enanthol, capryl alcohol, nonyl alcohol, decanol etc..
Term C used in the present invention5～C16Alkane refers to the straight or branched alkane containing 5 to 16 carbon atoms,
Such as there is the straight or branched alkane of 5,6,7,8,9,10,11,12,13,14,15 or 16 carbon atoms, such as pentane, oneself
Alkane, heptane, octane, nonane, decane, hendecane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane etc..
Term C used in the present invention5～C16Alicyclic alkanes refers to the carbon number including substituent group and is being contained within 5
To the saturated cyclic alkane of 16 carbon atoms, described saturated cyclic alkane can be monocycle or dicyclo, for example, Pentamethylene., hexamethylene
Alkane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decahydronaphthalene etc., described substituent group can be selected from C1～C4One or many of alkyl
Individual substituent group.
Term C used in the present invention6～C10Aromatic hydrocarbons refers to the carbon number including substituent group and is being contained within 6 to 10
The aromatic hydrocarbons of carbon atom, such as benzene and with selected from C1～C4The substituted benzene of one or more substituent groups of alkyl, such as benzene, toluene, two
Toluene etc..
The description " about " used in this application has and well known to a person skilled in the art implication, and it represents corresponding numerical value
Can change within the specific limits, but the degree of this change is limited with the realization not affecting the object of the invention.Such as, the model of change
Enclosing can be in the range of ± 20%, in the range of ± 15%, in the range of ± 10%, or in the range of ± 5%.
Except as otherwise noted, listed in the present invention numerical range includes between endpoint value therein and endpoint value
With all point values of the least unit increasing or decreasing of endpoint value and all subranges of being made up of these point values.
Beneficial effect
Dialkyl alkylphosphonate extractant of the present invention such as P503 water solublity is little, thus damages when recycling
Consumption is little；Additionally, extractant is while the extract and separate industrial wastewater mesoxalic acid containing oxalic acid, to other slaines in waste water and
Acid is almost without extracting power.Therefore by selection use water, alkali liquor or alkaline-earth metal, transition metal, rare earth element, actinides
It is back washing agent etc. the aqueous solution of corresponding slaine, can directly prepare oxalic acid, oxalates.Both the grass in industrial wastewater had been reclaimed
Acid, achieves again the recycling of raffinate aqueous phase, it is to avoid the interference of oxalic acid, it is achieved that the zero-emission of waste water.This technique can realize
Automated condtrol, easy and simple to handle, with low cost, it is the work of the oxalic acid processed in industrial wastewater of a kind of economy, green, environmental protection
Skill.
Detailed description of the invention
Embodiment
In order to the solution of the present invention is expanded on further, it is provided that the specific embodiment of the present invention is to contribute to people in the art
Member understands and implements the present invention, but the invention is not restricted to these embodiments.
Reagent and source
2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (P503), isopropyl phosphonic acids two (2-ethylhexyl) ester
(P277), dibutyl-butylphosphonate (P205), diamyl amyl phosphonate (DAAP), octyl phosphonic acid dibutyl ester (DBOP), butyl phosphine
Acid dihexyl (DHBP), DHHP dihexylhexylphosphonate (DHHP), octyl phosphonic acid dihexyl (DHOP) and octyl phosphonic acid dioctyl ester
(DOOP), P507, aerial kerosene and TBP are purchased from Shanghai Lai Yashi Chemical Co., Ltd.；Sulfonated kerosene reaches chemical industry purchased from Luoyang Austria
Company limited；Cyanex 923, Cyanex 272 and first enanthol are purchased from Shanghai Qing Te Chemical Co., Ltd..
Embodiment 1
1,6L P503 is mixed to prepare organic facies with 4L sulfonated kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 3g/L, and the concentration of hydrochloric acid is 0.5mol/L, metal La3+Dense
Degree 0.01g/L；
Back washing agent is 0.5mol/L LaCl3, pH=1.
2, by organic facies and rare-earth industry waste water by volume 13 ratio mix and carry out 6 stage countercurrent extractions, loaded
The organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of rare earth chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.05g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 51 ratio mix and carry out 2 stage countercurrent back extractions, obtain
Oxalic rare earth precipitates, supernatant and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is
99.9%.
4, by the LaCl in supernatant3Allotment returns in step 3 to 0.5mol/L, presses with the organic facies of load oxalic acid
Volume ratio 51 mixing carries out 2 stage countercurrent back extractions, and carries out stripping section by this step cycle.
The yield of final oxalic acid is 96%.
Embodiment 2
1,5L P277,1L Cyanex 272 are mixed to prepare organic facies with 4L aerial kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 5g/L, and the concentration of hydrochloric acid is 1.5mol/L, metal Nd3+Dense
Degree 1g/L；
Back washing agent is 0.5mol/L NdCl3, pH=2.
2, by organic facies and rare-earth industry waste water by volume 32 ratio mix and carry out 20 stage countercurrent extractions, born
Carrying the organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of Neodymium chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.03g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 1 10 ratio mix and carry out 3 stage countercurrent back extractions, must
To oxalic rare earth precipitates, supernatant and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is more than
99%.
4, by the NdCl in supernatant3Allotment returns in step 3 to 0.5mol/L, presses with the organic facies of load oxalic acid
Volume ratio 1 10 mixing carries out 3 stage countercurrent back extractions, and carries out stripping section by this step cycle.
The yield of final oxalic acid is 97%.
Embodiment 3
1,0.1L P205,0.5L P507 are mixed to prepare organic facies with 9.4L aerial kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 0.05g/L, and the concentration of hydrochloric acid is 1.0mol/L, metal Y3+'s
Concentration 0.1g/L；
Back washing agent is water.
2, by organic facies and rare-earth industry waste water by volume 10 1 ratio mix and carry out 20 stage countercurrent extractions, born
Carrying the organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of rare earth chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.002g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 10 1 ratio mix and carry out 20 stage countercurrent back extractions, must
To containing grass aqueous acid and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is 99.5%.
4, grass aqueous acid will be contained and return in step 3,10 1 be mixed into by volume with the organic facies of load oxalic acid
Row 20 stage countercurrent back extraction, when the strip liquor mesoxalic acid concentration containing oxalic acid obtained reaches 65g/L, completes enrichment.
The yield of final oxalic acid is 95%.
Embodiment 4
1,5L DAAP, 1L Cyanex 923 are mixed to prepare organic facies with 4L sulfonated kerosene；
The concentration of industrial wastewater mesoxalic acid is 1.2g/L, and the concentration of hydrochloric acid is 2.0mol/L, metal Fe3+Concentration 0.2g/
L；
Back washing agent is 0.5mol/L NaOH aqueous solution.
2, by organic facies and industrial wastewater by volume 1 10 ratio mix and carry out 8 stage countercurrent extractions, obtain load grass
The organic facies of acid and hydrochloric, the raffinate aqueous phase of iron chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.04g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 11 ratio mix and carry out 5 stage countercurrent back extractions, obtain
Aqueous solution containing Disodium oxalate. and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is 99.9%.
4, aqueous solution containing Disodium oxalate. adds NaOH allocate to [OH]-Return to after=0.5mol/L in step 3, with load
1 10 mixing by volume of the organic facies of oxalic acid carry out 8 stage countercurrent back extractions, when the Disodium oxalate. concentration obtained in strip liquor reaches
During 30g/L, low-temperature reduced-pressure distills, crystallization Disodium oxalate..Back washing agent is continued to serve as after crystalline mother solution allotment.
The yield of final oxalic acid is 95.5%.
Embodiment 5
1,5L DBOP, 1L Cyanex 923 are mixed to prepare organic facies with 4L sulfonated kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 15g/L, and the concentration of hydrochloric acid is 2.0mol/L, metal Lu3+'s
Concentration 0.5g/L；
Back washing agent is water.
2, by organic facies and rare-earth industry waste water by volume 11 ratio mix and carry out 8 stage countercurrent extractions, loaded
The organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of rare earth chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.05g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 81 ratio mix and carry out 5 stage countercurrent back extractions, obtain
Containing grass aqueous acid and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is 99.9%.
4, grass aqueous acid will be contained and return in step 3, and by volume with the organic facies of load oxalic acid 81 mix and carry out
5 stage countercurrent back extractions, when the strip liquor mesoxalic acid concentration containing oxalic acid obtained reaches 70g/L, complete enrichment.
The yield of final oxalic acid is 99%.
Embodiment 6
1,6L DHBP, 1L TBP are mixed to prepare organic facies with 3L sulfonated kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 20g/L, and the concentration of hydrochloric acid is 2.5mol/L, metal Gd3+'s
Concentration 0.8g/L；
Back washing agent is 0.1mol/L NaOH.
2, by organic facies and rare-earth industry waste water by volume 18 ratio mix and carry out 9 stage countercurrent extractions, loaded
The organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of rare earth chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.1g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 10 1 ratio mix and carry out 4 stage countercurrent back extractions, must
To containing grass aqueous acid and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is 98%.
4, grass aqueous acid will be contained and return in step 3,10 1 be mixed into by volume with the organic facies of load oxalic acid
Row 4 stage countercurrent back extraction, when the strip liquor mesoxalic acid concentration containing oxalic acid obtained reaches 75g/L, completes enrichment.
The yield of final oxalic acid is 98%.
Embodiment 7
1,6L DHHP, 0.5L 2-isoocanol are mixed to prepare organic facies with 3.5L aerial kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 30g/L, and the concentration of hydrochloric acid is 3.0mol/L, metal Yb3+'s
Concentration 0.05g/L；
Back washing agent is 0.5mol/L ammonia.
2, by organic facies and rare-earth industry waste water by volume 16 ratio mix and carry out 10 stage countercurrent extractions, born
Carrying the organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of rare earth chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.03g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 10 1 ratio mix and carry out 5 stage countercurrent back extractions, must
To containing grass aqueous acid and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is 98%.
4, grass aqueous acid will be contained and return in step 3,10 1 be mixed into by volume with the organic facies of load oxalic acid
Row 5 stage countercurrent back extraction, when the strip liquor mesoxalic acid concentration containing oxalic acid obtained reaches 80g/L, completes enrichment.
The yield of final oxalic acid is 98.5%.
Embodiment 8
1,6L DHOP, 0.5L Cyanex 272 are mixed to prepare organic facies with 3.5L aerial kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 25g/L, and the concentration of hydrochloric acid is 3.0mol/L, Ni metal2+'s
Concentration 0.4g/L；
Back washing agent is 0.5mol/L ammonia.
2, by organic facies and rare-earth industry waste water by volume 16 ratio mix and carry out 10 stage countercurrent extractions, born
Carrying the organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of rare earth chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.03g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 10 1 ratio mix and carry out 5 stage countercurrent back extractions, must
To containing grass aqueous acid and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is 98%.
4, grass aqueous acid will be contained and return in step 3,10 1 be mixed into by volume with the organic facies of load oxalic acid
Row 5 stage countercurrent back extraction, when the strip liquor mesoxalic acid concentration containing oxalic acid obtained reaches 70g/L, completes enrichment.
The yield of final oxalic acid is 98.5%.
Embodiment 9
1,6L DOOP, 0.5LTBP are mixed to prepare organic facies with 3.5L sulfonated kerosene；
The concentration of the rare-earth industry waste water mesoxalic acid used is 18g/L, and the concentration of hydrochloric acid is 2.5mol/L, metal Co2+'s
Concentration 0.6g/L；
Back washing agent is 0.5mol/L CoCl2, pH=1.
2, by organic facies and rare-earth industry waste water by volume 15 ratio mix and carry out 10 stage countercurrent extractions, born
Carrying the organic facies of oxalic acid and hydrochloric, the raffinate aqueous phase of cobaltous chloride, the concentration of raffinate aqueous phase mesoxalic acid is 0.05g/L.
3, by organic facies and the back washing agent of load oxalic acid by volume 81 ratio mix and carry out 2 stage countercurrent back extractions, obtain
Cobalt oxalate precipitation, supernatant and circulation organic facies, circulation organic facies is back to step 2 and uses, and the back extraction ratio of oxalic acid is 99.9%.
4, by the CoCl in supernatant2Allotment returns in step 3 to 0.5mol/L, presses with the organic facies of load oxalic acid
Volume ratio 81 mixing carries out 2 stage countercurrent back extractions, and carries out stripping section by this step cycle.
The yield of final oxalic acid is 98%.
Comparative example 1:
According to method disclosed in Chinese patent application CN200910042961.8, from oxalic acid waste water, synthetical recovery is sour and has
Valency metal.
Taking 1000ml oxalic acid waste water, its composition is: oxalic acid content 30g/l, content of hydrochloric acid 2.0mol/l, metal Co2+Concentration
1.0g/l。
(1) extraction and recovery oxalic acid:
(1) by acidity oxalic acid waste water secondary filter, clear liquor is obtained:
(2) from clear liquor, oxalic acid is extracted with extraction+sulfonated kerosene (volume ratio is 1:1), extraction
Incorporation time is 5 minutes, and organic facies is 0.5 with the volume ratio of aqueous phase, and progression is 5 grades.
(3) being washed with deionized the organic facies of load oxalic acid, organic facies is 6 with the volume ratio of deionized water, and progression is 2
Level；
(4) volume ratio of oxalic acid, organic facies and deionized water is taken out with deionized water back extraction from washed organic facies
Being 0.8, progression is 10 grades.
(5) dilute oxalic acid solution condensing crystallizing that (4th) step obtains is obtained oxalic acid crystal；
(2) from raffinate, mineral acid and valuable metal are reclaimed:
(1) (one) (2) step is extracted the acid solution after oxalic acid, adds 115 grams of sodium chloride regulation Chlorine in Solution ions
Concentration is 4.0mol/l；
(2) from solution, metal ion is extracted, during extraction mixing with trialkylamine+sulfonated kerosene (volume ratio is 1:1)
Between be 5 minutes, the volume ratio of organic facies and aqueous phase is 0.2, and progression is 5 grades；
(3) by the organic facies of the dilute hydrochloric acid wash load metallic cobalt ion that pH is 4.5, organic facies and the volume ratio of dilute hydrochloric acid
Being 6, progression is 3 grades；
(4) metallic cobalt, organic facies and dilute hydrochloric acid are taken out with the dilute hydrochloric acid that pH is 0.5 back extraction from washed organic facies
Volume ratio is 3, and progression is 5 grades；
Finally obtain oxalic acid solid 29.5 grams, be 99.6% through analyzing the content of oxalic acid；Obtain cobalt chloride solution 72ml, cobalt
Content is 13.5g/l；Obtaining dilute hydrochloric acid solution 1120ml, content of hydrochloric acid is 1.75mol/l, and the content of oxalic acid is 0.15g/l, cobalt
Concentration is 0.03g/l.
Compared with the method for CN200910042961.8, the advantage of the application method is:
1, extractant is cheap, be easy to get；The market price of extraction is about 200,000 yuan/ton at present, and at present
Manufacturer production without extractant, needs to order.And extractant used in this application such as P503 all can directly purchase, procurement price is
30000/ton.
2, in comparative example, strip liquor used is deionized water, and through calculating, gained strip liquor mesoxalic acid concentration is less than
48g/l, in order to prepare oxalic acid crystal, needs evaporating, concentrating and crystallizing, need to consume the substantial amounts of energy；And the back extraction that the application recommends
Agent contains the metal ion in corresponding system, forms metal oxalate precipitation.Extra foreign ion will not be brought.
3, comparative example finally obtains dilute hydrochloric acid (1.75mol/l) solution of large volume, but is not given such as where
Manage these acid.And all of aqueous phase of the application all forms closed cycle, without efflux wastewater.
Claims (10)
1. the dialkyl alkylphosphonate of below formula I is as the purposes of the extractant of the industrial wastewater processed containing oxalic acid:
Wherein, R1And R2It is each independently selected from C3～C12Alkyl, more preferably C4～C10Alkyl, most preferably C4～C9Alkyl；R3
Selected from C3～C12Alkyl, more preferably C3～C10Alkyl, most preferably C4～C9Alkyl；And R1、R2、R3Total carbon atom number be 10
Integer between 30.
2. the purposes described in claim 1, wherein, in formula I, R1、R2、R3For identical alkyl, the most identical C4～C9
Alkyl.
3. the purposes described in claim 1, wherein, R1、R2、R3Total carbon atom number be 10～27, preferably 12～27.
4. the purposes described in claim 1, wherein, the dialkyl alkylphosphonate of described formula I is selected from 2-ethylhexyl phosphine
Acid two (2-ethylhexyl) ester, isopropyl phosphonic acids two (2-ethylhexyl) ester, dibutyl-butylphosphonate, diamyl amyl phosphonate,
In octyl phosphonic acid dibutyl ester, butyl phosphonic acids dihexyl, DHHP dihexylhexylphosphonate, octyl phosphonic acid dihexyl and octyl phosphonic acid dioctyl ester
One or more.
5. the method processing the industrial wastewater containing oxalic acid, described method includes using according to any one of claim 1-4
The step of industrial wastewater containing oxalic acid of the contact containing dialkyl alkylphosphonate of formula I.
6. the method described in claim 5, it comprises the steps:
(1) by the dialkyl alkylphosphonate of described formula I and nonessential auxiliary extraction agent, nonessential phase modifying agent and
Diluent mixes, and obtains organic facies；
(2) industrial wastewater containing oxalic acid is mixed with the above-mentioned prepared organic facies ratio of (0.1～10) 1 by volume carry out 1
～20 stage countercurrent extractions, obtain loading the organic facies of oxalic acid and raffinate aqueous phase；
(3) organic facies of load oxalic acid is mixed that to carry out 1～20 stage countercurrents anti-with the ratio of back washing agent (1～10) 1 by volume
Extraction, obtains the aqueous solution containing oxalic acid or oxalates and circulation organic facies, or obtains oxalic acid metal salt precipitate, supernatant and circulation
Organic facies；Gained circulation organic facies is back to step (2) and uses,
(4) not necessarily, by returning to after the aqueous solution formulated one-tenth back washing agent containing oxalic acid or oxalates, step 3 uses, enter
When row back extraction to the concentration of oxalic acid in circulation strip liquor reaches 65～80g/L or when the concentration of oxalates reaches 30g/L, complete grass
The enrichment of acid, or by returning to after formulated for supernatant one-tenth back washing agent, step 3 uses.
7. the method described in claim 5 or 6, wherein, the described industrial wastewater containing oxalic acid is rare-earth industry waste water, grass therein
Acid concentration can be 0.05～30g/L.
8. the method described in claim 5 or 6, wherein,
Auxiliary extraction agent described in step (1) is selected from neutral phosphor (phosphine) extractant, acid phosphorus (phosphine) extractant, neutral phosphor amide extraction
Take agent and mixed extractant that above extractant mixes with arbitrary proportion；
Preferably, described neutral phosphor (phosphine) extractant is selected from straight chain trialkyl phosphine, side chain trialkyl phosphine, trioctylphosphine oxygen
Change phosphine, extraction, 2-ethylhexyl phosphonic acid two (-2-ethylhexyl) ester and tributyl phosphate；Described acid phosphorus
(phosphine) extractant selected from two (2,4,4-tri-methyl-amyl) phosphonodithioic acid, two (2,4,4-tri-methyl-amyl) phosphonothiolic acid, two
(2-ethylhexyl) phosphoric acid, 2-ethylhexyl phosphonic acid list-2-ethyl hexyl ester, two (2,4,4-tri-methyl-amyl) phosphonic acids, two (2-
Ethylhexyl) phosphonic acids；Described neutral phosphor amide extractant selected from three iso-octyl phosphamides, diisooctyl-different octyloxy phosphamide,
Iso-octyl-two different octyloxy phosphamide, three (diisobutyl) phosphamide, two (diisobutyls)-different octyloxy phosphamide, three decyls
Phosphamide and two base-decyloxy phosphamide；And/or
Described in step (1), phase modifying agent is selected from C4～C10One or more in alkanol and tributyl phosphate, described C4~
C10Alkanol is preferably n-octyl alcohol, isooctanol, 2-isoocanol and the mixed alcohol of above-mentioned three kinds of alcohol arbitrary proportions mixing；More preferably
Ground, described phase modifying agent is mixed alcohol or 2-isoocanol；
Diluent described in step (1) is selected from C5～C16Alkane；Aerial kerosene；Sulfonated kerosene, liquid paraffin；C5～C16Alicyclic
Alkane and C6～C10Aromatic hydrocarbons；Preferably, diluent is one or more in aerial kerosene, sulfonated kerosene, heptane；With/
Or
Dialkyl alkylphosphonate described in step (1), nonessential auxiliary extraction agent, nonessential phase modifying agent and dilution
The volume ratio of agent is: dialkyl alkylphosphonate extractant: auxiliary extraction agent: phase modifying agent: diluent=about 1～80: about 0～
20: about 0～20: about 20～99, more preferably dialkyl alkylphosphonate: auxiliary extraction agent: phase modifying agent: diluent=about 25
～75: about 0～15: about 0～15: about 25～75；Most preferably dialkyl alkylphosphonate: auxiliary extraction agent: phase modifying agent: dilute
Release agent=about 30～60: about 0～10: about 0～10: about 40～70；And/or
Concentration of oxalic acid in raffinate aqueous phase described in step (2) is less than 0.05g/L；And/or
Back washing agent described in step (3) is selected from: water；The hydrochloric acid of the metal ion of oxalate precipitation thing can be formed with oxalate
Salt, nitrate, sulfate solution and alkaline aqueous solution；Preferably, described metal is selected from alkaline-earth metal, transition metal, rare earth
Element and actinides；It is highly preferred that described alkaline aqueous solution is selected from NaOH aqueous solution, KOH aqueous solution and ammonia；Described alkaline earth
Metal is selected from calcium and magnesium, and described transition metal is cobalt, and described rare earth element is selected from lanthanum and rubidium.
9. the method described in claim 5 or 6, wherein, extraction and back extraction a series of separatory funnels, mixed settler extractor or
Centrifugal extractor is carried out, preferably carries out in mixed settler extractor or centrifugal extractor.
10. the method described in claim 5 or 6, wherein, extraction and back extraction are intermittently or serially carried out, and are preferably carried out continuously.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109295307A (en) * | 2018-09-30 | 2019-02-01 | 中铝广西有色金源稀土有限公司 | A method of remaining oxalic acid in removal P350 extractant |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
| CN109626532A (en) * | 2019-01-22 | 2019-04-16 | 四川高绿平环境科技有限公司 | A kind of oxalic acid scavenger and preparation method thereof and application method |
| CN110228867A (en) * | 2019-06-25 | 2019-09-13 | 北京惠宇乐邦环保科技有限公司 | A kind of preprocess method of time acid producing waste water |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU956432A1 (en) * | 1980-12-12 | 1982-09-07 | Предприятие П/Я А-7587 | Process for recovering oxalic acid from liquids |
| GB2191490A (en) * | 1986-06-10 | 1987-12-16 | East China Inst Of Chemical Te | Trialkyl phosphine oxides and their use in a process for recovery of organic acids from aqueous solutions |
| CN101503350A (en) * | 2009-03-25 | 2009-08-12 | 中南大学 | Method for recycling acid and valuable metal from oxalic acid wastewater |
| CN104610043A (en) * | 2015-01-09 | 2015-05-13 | 东北大学 | Method for recycling oxalic acid from rear-earth industrial wastewater |
-
2016
- 2016-07-22 CN CN201610584011.8A patent/CN106115835B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU956432A1 (en) * | 1980-12-12 | 1982-09-07 | Предприятие П/Я А-7587 | Process for recovering oxalic acid from liquids |
| GB2191490A (en) * | 1986-06-10 | 1987-12-16 | East China Inst Of Chemical Te | Trialkyl phosphine oxides and their use in a process for recovery of organic acids from aqueous solutions |
| CN101503350A (en) * | 2009-03-25 | 2009-08-12 | 中南大学 | Method for recycling acid and valuable metal from oxalic acid wastewater |
| CN104610043A (en) * | 2015-01-09 | 2015-05-13 | 东北大学 | Method for recycling oxalic acid from rear-earth industrial wastewater |
Non-Patent Citations (2)
| Title |
|---|
| TIAN QING-HUA ET AL: "Recovery of oxalic acid from mother-liquor containing hydrochloric acid and cobalt by solvent extraction with P350", 《TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA》 * |
| 邱廷省等: "络合萃取法处理稀土冶炼废水", 《稀土》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109295307A (en) * | 2018-09-30 | 2019-02-01 | 中铝广西有色金源稀土有限公司 | A method of remaining oxalic acid in removal P350 extractant |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
| CN109516623B (en) * | 2018-11-16 | 2021-06-01 | 浙江万盛股份有限公司 | Comprehensive utilization method of tributoxyethyl phosphate wastewater |
| CN109626532A (en) * | 2019-01-22 | 2019-04-16 | 四川高绿平环境科技有限公司 | A kind of oxalic acid scavenger and preparation method thereof and application method |
| CN110228867A (en) * | 2019-06-25 | 2019-09-13 | 北京惠宇乐邦环保科技有限公司 | A kind of preprocess method of time acid producing waste water |
| CN110228867B (en) * | 2019-06-25 | 2021-09-14 | 北京惠宇乐邦环保科技有限公司 | Pretreatment method of waste water from production of kungfu acid |
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