CN106115835B - 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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- CN106115835B CN106115835B CN201610584011.8A CN201610584011A CN106115835B CN 106115835 B CN106115835 B CN 106115835B CN 201610584011 A CN201610584011 A CN 201610584011A CN 106115835 B CN106115835 B CN 106115835B
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- oxalic acid
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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
Abstract
The method of the present invention provides the dialkyl alkylphosphonates of following general formula the I purposes as the extractant of industrial wastewater of the processing containing oxalic acid and industrial wastewater of the dialkyl alkylphosphonate processing containing oxalic acid using general formula I:Wherein, R1And R2It is each independently selected from C3~C12Alkyl, R3Selected from C3~C12Alkyl and R1、R2、R3Total carbon atom number be 10 to 30 between integer.Processing method of the invention realizes the recycling of oxalic acid and the zero-emission of waste water, avoids pollution of the discharge of wastewater containing oxalic acid to environment, while simplifying process flow, reduces cost for wastewater treatment, and extractant used is commercial product, cheap and easy to get.
Description
Technical field
It is the present invention relates to a kind of processing method of industrial wastewater containing oxalic acid, in particular to a kind of from the rare earth work containing oxalic acid
The method of oxalic acid is separated and recovered in industry waste water.
Background technique
China's rare earth resources are abundant, and reserves account for about the 50% of world saving, widely distributed, great variety of goods.Rare earth due to
Light, electricity, magnetic, in terms of special nature, be widely used in metallurgy, glass, ceramics, chemical industry, nuclear industry, electronics
All various aspects such as industry, agricultural and medicine.
In recent years, raw material of the rare earth as new material, international market are all to the demand of high purity rare earth oxides and day
Increase, to reach requirement of the international market to rare earth oxide purity, generallys use 10% oxalic acid to the rare earth chloride being stripped
It is precipitated, then precipitating is washed with 2% oxalic acid.The technique can generate high content acid wastewater, contain in the general waste water
H2C2O40.5~3mol/L of 0.5~30g/L, HCl, 10~200mg/L of rare earth can be to rings if untreated just discharged
Border generates bad influence.
Lime neutralisation or evaporation is mainly used to recycle oxalic acid currently, country facilities handle such waste water.Lime
Neutralisation is although easy to operate, low in cost, has neutralized the acid in waste water, so that waste water has been reached discharge standard, but this method produces
Raw a large amount of waste residues equally pollute the environment, and administer difficult；If the recovering rare earth from the waste residue, recovery process is lengthy and jumbled, energy consumption
Greatly, it needs to consume a large amount of industrial chemicals again；Acid in waste water is not recycled effectively, is resulted in waste of resources.Though evaporation
So oxalic acid and hydrochloric acid can be recycled to a certain extent and use back it in production, there is preferable economic benefit and social benefit,
But energy consumption is high for the recovery process, requires the corrosion resistance of equipment relatively high.
CN101503350A discloses a kind of method of synthetical recovery acid and valuable metal in oxalic acid waste water, and this method is first used
P350 extracts oxalic acid, adjusts chlorine ion concentration in raffinate with chloride or hydrochloric acid and is not less than 3.0mol/L；Trialkylamine is used again
Valuable metal ions are extracted from raffinate, the recovery of oxalic acid rate of this method is greater than 95%, and recovery rate of valuable metals is greater than
95%.The defect of this method is that P350 is expensive, and market price is about 200,000/ton, and the extractant is not easy to purchase at present.
CN104610043A discloses a kind of method that oxalic acid is recycled from rare-earth industry waste water, and this method is done using TBP
Extractant extracts oxalic acid, extracts through 3~10 grades, and 3~12 grades of back extraction, back extraction ratio is greater than 95%, simple process.The defect of this method
It is that the water solubility of TBP is big, the loss of extractant is big during handling waste water, need to constantly add extractant, be easy to cause
The unstability of production technology.
CN104761444A discloses a kind of technique smelted from rare-earth wet method and recycle oxalic acid in the heavy waste water of grass, and the technique is logical
It crosses and alkaline calcium ions precipitate oxalate is added into the heavy waste water of rare earth grass, then dissolved with dilute sulfuric acid, after separation of solid and liquid, take liquid portion
Divide and be cooled to 0~15 DEG C, oxalic acid crystal is precipitated, and the rate of recovery reaches 50% or more, 95% or more oxalic acid purity.The defect of this method
It is that 70~90 DEG C of reactions need to be heated in sulfuric acid dissolution calcium oxalate, and generates solid waste-calcium sulfate, yield is not also high.
Summary of the invention
In order to solve the above problem present on oxalic acid separation and recovery technology, the present invention provides a kind of industry containing oxalic acid
The processing method of waste water realizes the recycling of oxalic acid and the zero-emission of waste water, avoids discharge of wastewater containing oxalic acid to environment
Pollution, while process flow is simplified, cost for wastewater treatment is reduced, and extractant used is commercial product, it is cheap easy
?.
One aspect of the present invention provides the dialkyl alkylphosphonate of following general formula I as processing Industry Waste containing oxalic acid
The purposes of the extractant of water:
Wherein, R1And R2It is each independently selected from C3~C12Alkyl, more preferable C4~C10Alkyl, most preferably C4~C9Alkane
Base；R3Selected from C3~C12Alkyl, more preferable C3~C10Alkyl, most preferably C4~C9Alkyl；And R1、R2、R3Entire carbon atom
Number is the integer between 10 to 30.
In the general formula I, R1、R2、R3It is identical or different, preferably identical alkyl, more preferably identical C4~C9Alkane
Base.
R1、R2、R3Total carbon atom number include be 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 the general formula I is selected from 2- ethylhexyl phosphonic acids 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 phosphine
One of sour dihexyl (DHOP) and octyl phosphonic acid dioctyl ester (DOOP) are a variety of.
Dialkyl alkylphosphonate in the general formula I can be commercial product, such as can be purchased from Shanghai Lai Yashi and have
Limit company.
Another aspect of the present invention relates to a kind of processing methods of industrial wastewater containing oxalic acid, on using
State the step of contacting the industrial wastewater containing oxalic acid containing dialkyl alkylphosphonate of general formula I.
The method of industrial wastewater of the processing containing oxalic acid according to the present invention can be carried out using solvent-extracted method, such as
By dialkyl alkylphosphonate of the invention be configured to liquid extraction systems use, can also using liquid-solid extraction method into
Row, such as dialkyl alkylphosphonate of the invention is prepared into solid-state separation material, for example load has alkylphosphines of the invention
Porous silicon ball, diatomite of acid dialkyl ester etc..
Preferably, the processing method of the industrial wastewater of the invention containing oxalic acid, includes the following steps:
(1) by the dialkyl alkylphosphonate of above-mentioned general formula I and nonessential auxiliary extraction agent, nonessential phase modifying agent
And diluent mixing, obtain organic phase；
(2) by containing oxalic acid industrial wastewater and organic phase obtained above (ratio of 0.1~10) ︰ 1 mixes by volume
The extraction of 1~20 stage countercurrent is carried out, the organic phase and raffinate water phase of load oxalic acid are obtained；
(3) by load oxalic acid organic phase and stripping agent by volume (1~10) ︰ 1 ratio mix carry out 1~20 grade it is inverse
Stream back extraction obtains aqueous solution containing oxalic acid or oxalates and circulation organic phase, or obtain oxalic acid metal salt precipitate, supernatant and
Recycle organic phase；Gained circulation organic phase is back to step (2) use,
(4) not necessarily, by the aqueous solution containing oxalic acid or oxalates it is formulated at after stripping agent return to step 3 in, with
(ratio of 1~10) ︰ 1 mixes the organic phase of load oxalic acid, the concentration of oxalic acid being stripped into circulation strip liquor by volume
When reaching 65~80g/L or when the concentration of oxalates reaches 30g/L, the enrichment of oxalic acid is completed, or supernatant is formulated at anti-
It returns in step 3 and uses after extraction agent.
In the above method, the industrial wastewater containing oxalic acid is, for example, rare-earth industry waste water, and concentration of oxalic acid therein can be with
For 0.05~30g/L.
In the above method, auxiliary extraction agent described in step (1) mainly plays assistance extraction, can enhance alkyl phosphonic acid two
Extraction ability of the alkyl ester extractant to oxalic acid.The auxiliary extraction agent can be selected from such as straight chain trialkyl phosphine
(Cyanex 923), branch trialkyl phosphine (Cyanex 925), trioctyl phosphine oxide (TOPO), extraction
(P350), neutral phosphor (phosphine) extractant of 2- ethylhexyl phosphonic acids two (- 2- ethylhexyl) ester, tributyl phosphate (TBP)；Such as
Two (2,4,4- tri-methyl-amyl) phosphonodithioic acids (Cyanex 301), two (2,4,4- tri-methyl-amyl) phosphonothiolic acids
(Cyanex 302), di-(2-ethylhexyl)phosphoric acid (P204), 2- ethylhexyl phosphonic acid mono -2- ethylhexyl (P507), two
The acid phosphorus (phosphine) of (2,4,4- tri-methyl-amyl) phosphonic acids (Cyanex 272), two (2- ethylhexyl) phosphonic acids (P227 or P229)
Extractant；The neutrality phosphamide extractant as disclosed in CN201410409451.0 and CN201410040023.5, such as three is different
The different octyloxy phosphamide of octyl phosphamide, diisooctyl-, the different octyloxy phosphamide of iso-octyl-two, three (diisobutyl) phosphinylidynes
Base-decyloxy the phosphamide etc. of amine, two (diisobutyls)-different octyloxy phosphamide, three decyl phosphamides and two；With the above extraction
The mixed extractant that agent is mixed with arbitrary proportion.
In the above method, phase modifying agent described in step (1) mainly plays a part of to improve extraction physical phenomenon, can be
Selected from C4~C10One of alkanol and tributyl phosphate are a variety of, the 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 the phase modifying agent is mixed alcohol or 2- first
Base enanthol.
In the above method, diluent described in step (1) is selected from: C5~C16Alkane, for example, it is pentane, hexane, heptane, pungent
Alkane, nonane, decane, hendecane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane etc.；Aviation kerosine；Sulfonated kerosene, liquid
Body paraffin, such as 250~400 DEG C of light lubricating oil fractions etc.；C5~C16Alicyclic alkanes, such as pentamethylene, C1~C4Alkyl takes
Pentamethylene, hexamethylene, the C in generation1~C4Alkyl-substituted hexamethylene, 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 aviation kerosine, sulfonated kerosene,
One of heptane is a variety of.
It is dialkyl alkylphosphonate described in step (1), nonessential auxiliary extraction agent, nonessential in the above method
Phase modifying agent and the volume ratio of diluent can be with are as follows: 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 the above method, the concentration of oxalic acid in raffinate water phase described in step (2) is lower than 0.05g/L.
In the above method, stripping agent described in step (3) can be selected from: water；Oxalate precipitation can be formed with oxalate
Hydrochloride, nitrate, the sulfate solution of the metal ion of object, the metal are, for example, alkaline-earth metal (such as calcium or magnesium), mistake
Cross metal (such as cobalt), rare earth element (such as lanthanum, rubidium), actinides；Alkaline aqueous solution, such as NaOH aqueous solution, KOH are water-soluble
Liquid, ammonium hydroxide etc..
In the above method, the back extraction ratio of the oxalic acid in step 3 is greater than 98%.The back extraction ratio calculates as follows:
Wherein: St% is indicated: back extraction ratio；[H2C2O4](Sr): indicate the concentration of oxalic acid in strip liquor；[H2C2O4](O)It indicates:
Concentration of oxalic acid in organic phase；V(Sr)It indicates: strip liquor volume；V(o)It indicates: organic phase volume.
According to the method for the present invention, the yield of final oxalic acid is greater than 95%.The yield calculates as follows:
Wherein: [H2C2O4](Sr): indicate the concentration of oxalic acid in strip liquor；[H2C2O4](F)Indicate: the oxalic acid in feed liquid is dense
Degree；V(Sr)It indicates: strip liquor volume；V(F)It indicates: material liquid volume.
In solvent extraction method according to the present invention, extraction and back extraction can be filled using liquid separation as known in the art
Progress is set, is preferably carried out in a series of separatory funnels, mixed settler extractor or centrifugal extractor, is more preferably clarified in mixing
It is carried out in extraction tank or centrifugal extractor.
In solvent extraction method according to the present invention, above-mentioned extraction and back extraction can be carried out intermittently or serially, preferably
It is carried out continuously.
Term C used in the present invention3~C12Alkyl refers to the linear or branched alkyl group containing 3 to 12 carbon atoms,
Such as the linear or branched alkyl group with 3,4,5,6,7,8,9,10,11 or 12 carbon atoms, without limitation include n-propyl,
Isopropyl, normal-butyl, tert-butyl, isobutyl group, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, ten
One alkyl, dodecyl etc..C3~C10Alkyl, C2~C12Alkyl and C4~C9Meaning of alkyl and so on.
Term C used in the present invention4~C10Alkanol refers to the linear chain or branched chain alkanol containing 4 to 10 carbon atoms,
Such as the linear chain or branched chain alkanol with 4,5,6,7,8,9 or 10 carbon atoms, without limitation include n-butanol, the tert-butyl alcohol,
Isobutanol, n-amyl alcohol, neopentyl alcohol, isoamyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol etc..
Term C used in the present invention5~C16Alkane refers to the linear chain or branched chain alkane containing 5 to 16 carbon atoms,
Such as the linear chain or branched chain alkane with 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 refer to containing 5 including the carbon atom number of substituent group
To the saturated cyclic alkane of 16 carbon atoms, the saturated cyclic alkane can be monocycle or bicyclic, for example, pentamethylene, hexamethylene
Alkane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decahydronaphthalene etc., the substituent group can be selected from C1~C4One or more of alkyl
A substituent group.
Term C used in the present invention6~C10Aromatic hydrocarbons refers to containing 6 to 10 including the carbon atom number of substituent group
The aromatic hydrocarbons of carbon atom, for example, benzene and be selected from C1~C4The benzene that one or more substituent groups of alkyl replace, such as benzene, toluene, two
Toluene etc..
The description " about " used in this application has well known to a person skilled in the art meaning, indicates corresponding numerical value
It can change in a certain range, but the degree of the variation is limited with the realization for not influencing the object of the invention.For example, the model of variation
Enclosing can be in ± 20% range, in ± 15% range, in ± 10% range, or in ± 5% range.
Unless otherwise indicated, numberical range listed in the present invention includes between endpoint value and endpoint value therein
With all point values of the minimum unit increasing or decreasing of endpoint value and all subranges being made of these point values.
Beneficial effect
Dialkyl alkylphosphonate extractant such as P503 water solubility of the present invention is small, thus damages when being recycled
Consumption is small；In addition, extractant is while industrial wastewater mesoxalic acid of the extraction and separation containing oxalic acid, to other metal salts in waste water and
Acid is almost without extracting power.Therefore pass through selection water, lye or alkaline-earth metal, transition metal, rare earth element, actinides
Aqueous solution etc. corresponding metal salt is stripping agent, and oxalic acid, oxalates can directly be made.Both the grass in industrial wastewater had been recycled
Acid, and the recycling of raffinate water phase is realized, the interference of oxalic acid is avoided, the zero-emission of waste water is realized.The technique can be realized
Automation control, it is easy to operate, it is low in cost, it is a kind of economic, green, environmental protection work for handling the oxalic acid in industrial wastewater
Skill.
Specific embodiment
Embodiment
For the scheme that the present invention is further explained, specific embodiments of the present invention are provided to facilitate those skilled in the art
Member understands and implements the present invention, but the present invention is not limited to these Examples.
Reagent and source
2- ethylhexyl phosphonic acids 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
Sour dihexyl (DHBP), DHHP dihexylhexylphosphonate (DHHP), octyl phosphonic acid dihexyl (DHOP) and octyl phosphonic acid dioctyl ester
(DOOP), P507, aviation kerosine and TBP are purchased from Shanghai Lai Yashi Chemical Co., Ltd.；Sulfonated kerosene reaches chemical industry purchased from Luoyang Austria
Co., Ltd；Cyanex 923, Cyanex 272 and first enanthol are purchased from Shanghai Qing Te Chemical Co., Ltd..
Embodiment 1
1,6L P503 and 4L sulfonated kerosene is mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 3g/L, the concentration of hydrochloric acid is 0.5mol/L, metal La3+It is dense
Spend 0.01g/L；
Stripping agent is 0.5mol/L LaCl3, pH=1.
2, by organic phase and rare-earth industry waste water by volume 1 ︰ 3 ratio mix carry out 6 stage countercurrent extractions, loaded
The organic phase of oxalic acid and hydrochloric, rare earth chloride raffinate water phase, the concentration of raffinate water phase mesoxalic acid are 0.05g/L.
3, by load oxalic acid organic phase and stripping agent by volume 5 ︰ 1 ratio mix carry out 2 stage countercurrent back extraction, obtain
Oxalic rare earth precipitates, supernatant and circulation organic phase, circulation organic phase are back to step 2 use, and the back extraction ratio of oxalic acid is
99.9%.
4, by the LaCl in supernatant3It returns in step 3 after allotment to 0.5mol/L, is pressed with the organic phase of load oxalic acid
5 ︰ 1 of volume ratio mixing carries out 2 stage countercurrent back extraction, 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 and 4L aviation kerosine are mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 5g/L, the concentration of hydrochloric acid is 1.5mol/L, metal Nd3+It is dense
Spend 1g/L；
Stripping agent is 0.5mol/L NdCl3, pH=2.
2, by organic phase and rare-earth industry waste water by volume 3 ︰ 2 ratio mix carry out 20 stage countercurrent extractions, born
The organic phase and hydrochloric, neodymium chloride raffinate water phase of oxalic acid are carried, the concentration of raffinate water phase mesoxalic acid is 0.03g/L.
3, by load oxalic acid organic phase and stripping agent by volume 1 ︰ 10 ratio mix carry out 3 stage countercurrent back extraction, obtain
To oxalic rare earth precipitates, supernatant and circulation organic phase, circulation organic phase is back to step 2 use, and the back extraction ratio of oxalic acid is greater than
99%.
4, by the NdCl in supernatant3It returns in step 3 after allotment to 0.5mol/L, is pressed with the organic phase of load oxalic acid
1 ︰ 10 of volume ratio mixing carries out 3 stage countercurrent back extraction, 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 and 9.4L aviation kerosine are mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 0.05g/L, the concentration of hydrochloric acid is 1.0mol/L, metal Y3+'s
Concentration 0.1g/L；
Stripping agent is water.
2, by organic phase and rare-earth industry waste water by volume 10 ︰ 1 ratio mix carry out 20 stage countercurrent extractions, born
The organic phase and hydrochloric, rare earth chloride raffinate water phase of oxalic acid are carried, the concentration of raffinate water phase mesoxalic acid is 0.002g/L.
3, by load oxalic acid organic phase and stripping agent by volume 10 ︰ 1 ratio mix carry out 20 stage countercurrent back extraction, obtain
To aqueous solution and circulation organic phase containing oxalic acid, circulation organic phase is back to step 2 use, and the back extraction ratio of oxalic acid is 99.5%.
4, the aqueous solution containing oxalic acid is returned in step 3,10 ︰ 1 are mixed by volume with the organic phase of load oxalic acid
The back extraction of 20 stage countercurrent of row completes enrichment when the strip liquor medium-height grass acid concentration containing oxalic acid of acquisition reaches 65g/L.
The yield of final oxalic acid is 95%.
Embodiment 4
1,5L DAAP, 1L Cyanex 923 and 4L sulfonated kerosene are mixed to prepare organic phase；
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；
Stripping agent is 0.5mol/L NaOH aqueous solution.
2, by organic phase and industrial wastewater by volume 1 ︰ 10 ratio mix carry out 8 stage countercurrent extractions, obtain load grass
The organic phase and hydrochloric, iron chloride raffinate water phase of acid, the concentration of raffinate water phase mesoxalic acid are 0.04g/L.
3, by load oxalic acid organic phase and stripping agent by volume 1 ︰ 1 ratio mix carry out 5 stage countercurrent back extraction, obtain
Aqueous solution and circulation organic phase containing sodium oxalate, circulation organic phase are back to step 2 use, and the back extraction ratio of oxalic acid is 99.9%.
4, NaOH is added to deploy to [OH] aqueous solution containing sodium oxalate-It is returned in step 3 after=0.5mol/L, with load
1 ︰ 10 mixing by volume of the organic phase of oxalic acid carries out 8 stage countercurrent back extraction, when the oxalic acid na concn obtained in strip liquor reaches
When 30g/L, sodium oxalate is precipitated in low-temperature reduced-pressure distillation, crystallization.Stripping 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 and 4L sulfonated kerosene are mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 15g/L, the concentration of hydrochloric acid is 2.0mol/L, metal Lu3+'s
Concentration 0.5g/L；
Stripping agent is water.
2, by organic phase and rare-earth industry waste water by volume 1 ︰ 1 ratio mix carry out 8 stage countercurrent extractions, loaded
The organic phase of oxalic acid and hydrochloric, rare earth chloride raffinate water phase, the concentration of raffinate water phase mesoxalic acid are 0.05g/L.
3, by load oxalic acid organic phase and stripping agent by volume 8 ︰ 1 ratio mix carry out 5 stage countercurrent back extraction, obtain
Aqueous solution and circulation organic phase containing oxalic acid, circulation organic phase are back to step 2 use, and the back extraction ratio of oxalic acid is 99.9%.
4, the aqueous solution containing oxalic acid is returned in step 3,8 ︰ 1 mix progress by volume with the organic phase of load oxalic acid
The back extraction of 5 stage countercurrents completes enrichment when the strip liquor medium-height grass acid concentration containing oxalic acid of acquisition reaches 70g/L.
The yield of final oxalic acid is 99%.
Embodiment 6
1,6L DHBP, 1L TBP and 3L sulfonated kerosene are mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 20g/L, the concentration of hydrochloric acid is 2.5mol/L, metal Gd3+'s
Concentration 0.8g/L；
Stripping agent is 0.1mol/L NaOH.
2, by organic phase and rare-earth industry waste water by volume 1 ︰ 8 ratio mix carry out 9 stage countercurrent extractions, loaded
The organic phase of oxalic acid and hydrochloric, rare earth chloride raffinate water phase, the concentration of raffinate water phase mesoxalic acid are 0.1g/L.
3, by load oxalic acid organic phase and stripping agent by volume 10 ︰ 1 ratio mix carry out 4 stage countercurrent back extraction, obtain
To aqueous solution and circulation organic phase containing oxalic acid, circulation organic phase is back to step 2 use, and the back extraction ratio of oxalic acid is 98%.
4, the aqueous solution containing oxalic acid is returned in step 3,10 ︰ 1 are mixed by volume with the organic phase of load oxalic acid
The back extraction of 4 stage countercurrent of row completes enrichment when the strip liquor medium-height grass acid concentration containing oxalic acid of acquisition reaches 75g/L.
The yield of final oxalic acid is 98%.
Embodiment 7
1,6L DHHP, 0.5L 2- isoocanol and 3.5L aviation kerosine are mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 30g/L, the concentration of hydrochloric acid is 3.0mol/L, metal Yb3+'s
Concentration 0.05g/L；
Stripping agent is 0.5mol/L ammonium hydroxide.
2, by organic phase and rare-earth industry waste water by volume 1 ︰ 6 ratio mix carry out 10 stage countercurrent extractions, born
The organic phase and hydrochloric, rare earth chloride raffinate water phase of oxalic acid are carried, the concentration of raffinate water phase mesoxalic acid is 0.03g/L.
3, by load oxalic acid organic phase and stripping agent by volume 10 ︰ 1 ratio mix carry out 5 stage countercurrent back extraction, obtain
To aqueous solution and circulation organic phase containing oxalic acid, circulation organic phase is back to step 2 use, and the back extraction ratio of oxalic acid is 98%.
4, the aqueous solution containing oxalic acid is returned in step 3,10 ︰ 1 are mixed by volume with the organic phase of load oxalic acid
The back extraction of 5 stage countercurrent of row completes enrichment when the strip liquor medium-height grass acid concentration containing oxalic acid of acquisition reaches 80g/L.
The yield of final oxalic acid is 98.5%.
Embodiment 8
1,6L DHOP, 0.5L Cyanex 272 and 3.5L aviation kerosine are mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 25g/L, the concentration of hydrochloric acid is 3.0mol/L, Ni metal2+'s
Concentration 0.4g/L；
Stripping agent is 0.5mol/L ammonium hydroxide.
2, by organic phase and rare-earth industry waste water by volume 1 ︰ 6 ratio mix carry out 10 stage countercurrent extractions, born
The organic phase and hydrochloric, rare earth chloride raffinate water phase of oxalic acid are carried, the concentration of raffinate water phase mesoxalic acid is 0.03g/L.
3, by load oxalic acid organic phase and stripping agent by volume 10 ︰ 1 ratio mix carry out 5 stage countercurrent back extraction, obtain
To aqueous solution and circulation organic phase containing oxalic acid, circulation organic phase is back to step 2 use, and the back extraction ratio of oxalic acid is 98%.
4, the aqueous solution containing oxalic acid is returned in step 3,10 ︰ 1 are mixed by volume with the organic phase of load oxalic acid
The back extraction of 5 stage countercurrent of row completes enrichment when the strip liquor medium-height grass acid concentration containing oxalic acid of acquisition reaches 70g/L.
The yield of final oxalic acid is 98.5%.
Embodiment 9
1,6L DOOP, 0.5LTBP and 3.5L sulfonated kerosene are mixed to prepare organic phase；
For the concentration of the rare-earth industry waste water mesoxalic acid used for 18g/L, the concentration of hydrochloric acid is 2.5mol/L, metal Co2+'s
Concentration 0.6g/L；
Stripping agent is 0.5mol/L CoCl2, pH=1.
2, by organic phase and rare-earth industry waste water by volume 1 ︰ 5 ratio mix carry out 10 stage countercurrent extractions, born
The organic phase and hydrochloric, cobalt chloride raffinate water phase of oxalic acid are carried, the concentration of raffinate water phase mesoxalic acid is 0.05g/L.
3, by load oxalic acid organic phase and stripping agent by volume 8 ︰ 1 ratio mix carry out 2 stage countercurrent back extraction, obtain
Cobalt oxalate precipitation, supernatant and circulation organic phase, circulation organic phase are back to step 2 use, and the back extraction ratio of oxalic acid is 99.9%.
4, by the CoCl in supernatant2It returns in step 3 after allotment to 0.5mol/L, is pressed with the organic phase of load oxalic acid
8 ︰ 1 of volume ratio mixing carries out 2 stage countercurrent back extraction, 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, synthetical recovery is sour from oxalic acid waste water and has
Valence metal.
Take 1000ml oxalic acid waste water, ingredient are as follows: 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 acid oxalic acid waste water secondary filter, clarified solution is obtained:
(2) oxalic acid is extracted from clarified solution with extraction+sulfonated kerosene (volume ratio 1:1), extract
Incorporation time is 5 minutes, and the volume ratio of organic phase and water phase is 0.5, and series is 5 grades.
(3) organic phase of load oxalic acid is washed with deionized, the volume ratio of organic phase and deionized water is 6, series 2
Grade；
(4) it is stripped from washed organic phase with deionized water and takes out oxalic acid, the volume ratio of organic phase and deionized water
It is 0.8, series is 10 grades.
(5) the dilute oxalic acid solution condensing crystallizing for obtaining (4) step obtains oxalic acid crystal；
(2) inorganic acid and valuable metal are recycled from raffinate:
(1) (one) (2) step is extracted to the acid solution after oxalic acid, 115 grams of sodium chloride are added and adjust Chlorine in Solution ion
Concentration is 4.0mol/l；
(2) metal ion is extracted from solution with trialkylamine+sulfonated kerosene (volume ratio 1:1), when extraction mixes
Between be 5 minutes, the volume ratio of organic phase and water phase is 0.2, and series is 5 grades；
(3) with the organic phase of the pH dilute hydrochloric acid wash load metal cobalt ions for being 4.5, the volume ratio of organic phase and dilute hydrochloric acid
It is 6, series is 3 grades；
(4) be stripped taking-up metallic cobalt from washed organic phase with the dilute hydrochloric acid that pH is 0.5, organic phase and dilute hydrochloric acid
Volume ratio is 3, and series is 5 grades；
29.5 grams of oxalic acid solid are finally obtained, the content for being analyzed oxalic acid is 99.6%；Obtain cobalt chloride solution 72ml, cobalt
Content is 13.5g/l；Dilute hydrochloric acid solution 1120ml, content of hydrochloric acid 1.75mol/l are obtained, the content of oxalic acid is 0.15g/l, cobalt
Concentration is 0.03g/l.
Compared with the method for CN200910042961.8, the advantages of the application method are as follows:
1, extractant is cheap, is easy to get；The market price of extraction is about 200,000 yuan/ton at present, and at present
No extractant producer production, needs to order.And extractant used in this application such as P503 can be purchased directly, procurement price is
30000/ton.
2, in comparative example, strip liquor used is deionized water, and through calculating, gained strip liquor medium-height grass acid concentration is lower than
48g/l needs evaporating, concentrating and crystallizing in order to which oxalic acid crystal is made, and need to consume a large amount of energy；And the back extraction that the application is recommended to use
Agent contains the metal ion in corresponding system, forms metal oxalate precipitating.Additional foreign ion will not be brought.
3, comparative example finally obtains dilute hydrochloric acid (1.75mol/l) solution of large volume, but does not provide such as where
Manage these acid.And all water phase of the application all forms closed cycle, no efflux wastewater.
Claims (32)
1. purposes of the dialkyl alkylphosphonate of following general formula I as the extractant of industrial wastewater of the processing containing oxalic acid:
Wherein, R1And R2It is each independently selected from C3~C12Alkyl；R3Selected from C3~C12Alkyl；And R1、R2、R3Entire carbon atom
Number is the integer between 10 to 30.
2. purposes described in claim 1, wherein R1And R2It is each independently selected from C4~C10Alkyl.
3. purposes as claimed in claim 2, wherein R1And R2It is each independently selected from C4~C9Alkyl.
4. purposes described in claim 1, wherein R3Selected from C3~C10Alkyl.
5. purposes as claimed in claim 4, wherein R3Selected from C4~C9Alkyl.
6. purposes described in claim 1, wherein in general formula I, R1、R2、R3For identical alkyl.
7. purposes as claimed in claim 6, wherein R1、R2、R3For identical C4~C9Alkyl.
8. purposes described in claim 1, wherein R1、R2、R3Total carbon atom number be 10~27.
9. purposes according to any one of claims 8, wherein R1、R2、R3Total carbon atom number be 12~27.
10. purposes described in claim 1, wherein the dialkyl alkylphosphonate of the general formula I is selected from 2- ethylhexyl phosphine
Sour two (2- ethylhexyl) esters, 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
It is one or more.
11. a kind of method for handling the industrial wastewater containing oxalic acid, the method includes using any one of claim 1-10 institute
The dialkyl alkylphosphonate of the general formula I stated contacts the step of industrial wastewater containing oxalic acid.
12. method described in claim 11 comprising following steps:
(1) by the dialkyl alkylphosphonate of the general formula I and nonessential auxiliary extraction agent, nonessential phase modifying agent and
Diluent mixing, obtains organic phase；
(2) by containing oxalic acid industrial wastewater and organic phase obtained above by volume (0.1~10) ︰ 1 ratio mix carry out 1
The extraction of~20 stage countercurrents, obtains the organic phase and raffinate water phase of load oxalic acid；
(3) by load oxalic acid organic phase and stripping agent by volume (1~10) ︰ 1 ratio mix carry out 1~20 stage countercurrent it is anti-
Extraction obtains the aqueous solution and circulation organic phase containing oxalic acid or oxalates, or obtains oxalic acid metal salt precipitate, supernatant and circulation
Organic phase；Gained circulation organic phase is back to step (2) use,
(4) not necessarily, by the aqueous solution containing oxalic acid or oxalates it is formulated at after stripping agent return to step (3) in use,
When the concentration of oxalic acid being stripped into circulation strip liquor reaches 65~80g/L or when the concentration of oxalates reaches 30g/L, complete
The enrichment of oxalic acid, or by supernatant it is formulated at after stripping agent return to step (3) in use.
13. method described in claim 11 or 12, wherein the industrial wastewater containing oxalic acid is rare-earth industry waste water.
14. method described in claim 13, wherein the concentration of oxalic acid in the industrial wastewater containing oxalic acid is 0.05~30g/
L。
15. method described in claim 12, wherein auxiliary extraction agent described in step (1) be selected from neutral phosphor or phosphine extractant,
The mixed extractant that acid phosphorus or phosphine extractant, neutral phosphamide extractant and the above extractant are mixed with arbitrary proportion.
16. method of claim 15, wherein
The neutral phosphor or phosphine extractant are selected from straight chain trialkyl phosphine, branch trialkyl phosphine, trioctyl phosphine oxide, first
Base phosphonic acids diformazan heptyl ester, the (- 2- ethylhexyl) ester of 2- ethylhexyl phosphonic acids two and tributyl phosphate；
The acid phosphorus or phosphine extractant are selected from two (2,4,4- tri-methyl-amyl) phosphonodithioic acids, two (2,4,4- trimethyls penta
Base) phosphonothiolic acid, di-(2-ethylhexyl)phosphoric acid, 2- ethylhexyl phosphonic acid mono -2- ethylhexyl, two (2,4,4- trimethyls
Amyl) phosphonic acids and two (2- ethylhexyl) phosphonic acids；
The neutrality phosphamide extractant is selected from three iso-octyl phosphamides, the different octyloxy phosphamide of diisooctyl-, iso-octyl-two
Different octyloxy phosphamide, three (diisobutyl) phosphamides, two (diisobutyls)-different octyloxy phosphamide, three decyl phosphamides and
Two base-decyloxy phosphamides.
17. method described in claim 12, wherein phase modifying agent described in step (1) is selected from C4~C10Alkanol and phosphoric acid
One of tributyl is a variety of.
18. method described in claim 17, wherein the C4~C10Alkanol be n-octyl alcohol, isooctanol, 2- isoocanol or
The mixed alcohol of above-mentioned three kinds of alcohol arbitrary proportions mixing.
19. method of claim 18, wherein the phase modifying agent is to appoint n-octyl alcohol, isooctanol and 2- isoocanol
The mixed alcohol or 2- isoocanol of meaning ratio mixing.
20. method described in claim 12, wherein diluent described in step (1) is selected from C5~C16Alkane, aviation kerosine,
Sulfonated kerosene, atoleine, C5~C16Alicyclic alkanes and C6~C10Aromatic hydrocarbons.
21. method of claim 20, wherein the diluent is one in aviation kerosine, sulfonated kerosene, heptane
Kind is a variety of.
22. method described in claim 12, wherein dialkyl alkylphosphonate described in step (1), nonessential auxiliary
The volume ratio of extractant, nonessential phase modifying agent and diluent is dialkyl alkylphosphonate extractant: auxiliary extraction agent: phase
Modifying agent: diluent=1~80:0~20:0~20:20~99.
23. method described in claim 22, wherein the dialkyl alkylphosphonate, nonessential auxiliary extraction agent, non-
The volume ratio of required phase modifying agent and diluent is dialkyl alkylphosphonate: auxiliary extraction agent: phase modifying agent: diluent=
25~75:0~15:0~15:25~75.
24. method described in claim 23, wherein the dialkyl alkylphosphonate, nonessential auxiliary extraction agent, non-
The volume ratio of required phase modifying agent and diluent are as follows: dialkyl alkylphosphonate: auxiliary extraction agent: phase modifying agent: diluent
=30~60:0~10:0~10:40~70.
25. method described in claim 12, wherein the concentration of oxalic acid in raffinate water phase described in step (2) is lower than 0.05g/
L。
26. method described in claim 12, wherein stripping agent described in step (3) is selected from: water；It can be formed with oxalate
Hydrochloride, nitrate, the sulfate solution of the metal ion of oxalate precipitation object；And alkaline aqueous solution.
27. method described in claim 26, wherein the metal is selected from alkaline-earth metal, transition metal, rare earth element and actinium series
Element.
28. method described in claim 27, wherein the alkaline-earth metal is selected from calcium and magnesium, and the transition metal is cobalt, described
Rare earth element is lanthanum.
29. method described in claim 26, wherein the alkaline aqueous solution is selected from NaOH aqueous solution, KOH aqueous solution and ammonia
Water.
30. method described in claim 12, wherein extraction and be stripped a series of separatory funnels, mixed settler extractor or
It is carried out in centrifugal extractor.
31. method described in claim 30, wherein extraction and be stripped in mixed settler extractor or centrifugal extractor into
Row.
32. method described in claim 12, wherein extraction and back extraction intermittently or serially carry out.
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