CN112390320A - Extraction agent composition and resource utilization method of iron-containing wastewater - Google Patents
Extraction agent composition and resource utilization method of iron-containing wastewater Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000000605 extraction Methods 0.000 title claims abstract description 111
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002351 wastewater Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 title claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 16
- 239000003350 kerosene Substances 0.000 claims description 16
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910001447 ferric ion Inorganic materials 0.000 claims description 9
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000003333 secondary alcohols Chemical class 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 abstract description 8
- 239000000284 extract Substances 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 10
- 239000010881 fly ash Substances 0.000 description 8
- 238000011978 dissolution method Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GDSKPVPMABMVGJ-UHFFFAOYSA-N CCCCCCC(C)NC(=O)CCCCC Chemical compound CCCCCCC(C)NC(=O)CCCCC GDSKPVPMABMVGJ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-N sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides an extractant composition which comprises, by mass, 20-40% of a phosphate extractant shown as a formula 1 and 35-50% of C6～C10Monohydric alcohol and the balance of diluent. The invention also provides a resource utilization method of the iron-containing wastewater, which uses the extractant composition. The extractant composition of the invention does not need to use organic amine extractants, has simple extraction system and lower cost, and is not easy to generate a third phase even under high-concentration iron, thereby being applicable to the extraction treatment of various types of iron-containing wastewater. The resource utilization method can effectively extract and separate iron from the iron-containing wastewater for resource utilization, and is very suitable for resource utilizationIs suitable for large-scale application, has important economic and social values,
Description
Technical Field
The invention relates to the field of industrial wastewater treatment, in particular to an extractant composition and a resource utilization method of iron-containing wastewater by using the extractant composition.
Background
The fly ash is one of the current industrial waste residues with the largest discharge amount in China, serious social and environmental problems can be caused by unreasonable treatment, and meanwhile, the fly ash is rich in Al2O3The method is an important non-traditional alumina resource and a potential bauxite substitute, so that the comprehensive utilization of the alumina extracted from the fly ash becomes a great research hotspot. Wherein, the Shenhua group energy-quasi-resource comprehensive development company develops the process for extracting the alumina from the fly ash by the one-step acid dissolution method. In the process, fly ash is firstly subjected to a one-step acid dissolution process, aluminum, gallium, iron and some heavy metals are leached into acid leaching solution, then iron and gallium are removed through resin adsorption, almost all iron, a large amount of heavy metals and a certain amount of aluminum in the acid leaching solution are adsorbed, the adsorbed iron, heavy metals and aluminum can be eluted through acid washing, and the eluted iron, heavy metals and aluminum are elutedThe liquid is extracted with gallium by resin, and the residual liquid after extracting gallium is an aluminum-containing ferric sulfate waste liquid which needs to be treated urgently for recycling.
Iron and aluminum elements widely exist in various minerals in the nature, and are almost separated in various metallurgical processes. In the traditional hydrometallurgical industry, the precipitation method is mainly adopted to remove iron in solution, such as jarosite method, goethite method, hematite method and the like, and the methods have the problems of large aluminum loss, difficult sediment recovery, easy secondary pollution and the like. In order to further separate aluminium and iron from solution, solvent extraction methods have been studied to separate iron since the 60's of the 20 th century. Chinese patent CN102061398A adopts an extraction system of 'N503-isooctanol-sulfonated kerosene' to carry out three-stage extraction on a solution containing 2-7 g/L of iron, and then uses 2% oxalic acid and L mol/L hydrochloric acid for back extraction of iron. The invention discloses a method for extracting and separating iron and aluminum from a hydrochloric acid system, such as Limingyu, and the like, wherein an extraction system adopted is N503-TBP-N-octanol-sulfonated kerosene, the extraction system is high in selectivity, aluminum is not extracted, the iron and the aluminum are completely separated, the concentration of the ferric iron is 50-60 g/L, and the extraction and separation conditions containing the ferric iron above 60g/L are not mentioned. For the extraction separation of high-concentration iron, Chinese patent CN 110885931A adopts an extraction system of 'N, N-di (1-methylheptyl) hexanamide (N503) -tributyl phosphate-sec-octanol-sulfonated kerosene' for Fe3+The extraction is carried out on the solution of 60-120 g/L, so that the resource recycling of iron ions, aluminum ions and hydrochloric acid in the waste liquid is realized, but in an extraction system used in the technology, the proportion of N503 is up to 30%, N503 is expensive, and the extraction system is complex.
Based on the technology, the existing iron extraction system mostly uses organic amine extractants, or uses organic amine extractants and phosphate extractants cooperatively, and the organic amine extractants are expensive, so that the resource utilization cost of the wastewater is high. Therefore, a resource utilization method which is low in cost and more suitable for large-scale industrial application needs to be found.
Disclosure of Invention
In order to overcome the above-mentioned deficiencies in the prior art, an object of the present invention is to provide an extractant composition which does not require the addition of a common organic amine extractant, has a simple composition and a low cost, and can effectively extract and separate Fe3+Particularly, Fe can be effectively extracted and separated from the high-iron-content wastewater3+。
The invention also aims to provide a resource utilization method of the iron-containing wastewater.
The extractant composition provided by the invention comprises the following components in percentage by mass: 20-40% of phosphate extractant shown as formula 1 and 35-50% of C6～C10Monohydric alcohol and the balance of diluent;
in the formula 1, R represents C3～C8Straight or branched chain alkyl.
The conventional iron extraction system mostly needs to use organic amine extractants (such as N1923, N503 and the like), and the inventor of the invention finds that the phosphate extractants and C6～C10The monohydric alcohol has certain iron extraction capacity, the monohydric alcohol and the monohydric alcohol can generate a synergistic extraction effect when being combined for use, the extraction rate of iron is obviously improved, an organic amine extractant with high price is not required to be used, and the cost is greatly reduced. And, C6～C10Monohydric alcohols are also useful for eliminating the third phase formed at high iron concentrations, further increasing the extraction efficiency, in the extractant compositions of the invention, C6～C10The monohydric alcohol is both a synergist and a modifier, so the extractant composition is particularly suitable for the extraction treatment of the high-iron-content wastewater.
The amount ratio of the phosphate extractant to the monohydric alcohol in the extractant composition provided by the present invention can be adjusted within the above range by one skilled in the art. In some advantagesIn a preferred embodiment, the extractant composition comprises, in mass percent: 20-35% of phosphate extractant shown as formula 1 and 35-40% of C6～C10Monohydric alcohol and the balance of diluent.
In the extractant composition provided by the invention, the phosphate extractant can be a common type in the field. In some preferred embodiments, said R represents C3～C6Straight chain alkyl groups, including but not limited to n-propyl, n-butyl, n-pentyl, n-hexyl, and the like. In some more preferred embodiments, said R represents n-butyl, i.e. said phosphate-based extractant is selected from tributyl phosphate (TBP).
In the extractant composition provided by the invention, C6～C10The monohydric alcohol may be of a type commonly found in the art, including but not limited to primary, secondary and tertiary alcohols having a carbon number of 6-10. In some preferred embodiments, the monohydric alcohol is selected from the group consisting of secondary alcohols; in other preferred embodiments, the monohydric alcohol has a carbon number of 6 to 8. In some more preferred embodiments, the monohydric alcohols include, but are not limited to, n-octanol, iso-octanol, sec-octanol, and the like. In some most preferred embodiments, the monohydric alcohol is selected from the group consisting of sec-octanols.
In the extractant composition provided by the invention, the diluent can be a common type in the field as long as the extraction capability of the phosphate extractant and the monohydric alcohol is not influenced. In some preferred embodiments, the diluent is selected from sulfonated kerosene or kerosene.
The resource utilization method of the iron-containing wastewater provided by the invention comprises the following steps: extracting Fe in the iron-containing wastewater by using the extractant composition of any one of the preceding technical schemes as an extractant3+The obtained load extraction phase is back extracted by using a back extractant, and the Fe-containing material which can be recycled is obtained3+And (3) solution.
The resource utilization method of the invention utilizes the extractant composition of the invention as the extractant, and can extract and separate Fe from the iron-containing wastewater with high efficiency and low cost through the extraction and back extraction processes3+Thereby realizing the resource utilization of iron.The resource utilization method can be used for treating the iron-containing wastewater with various iron contents, particularly the iron-containing wastewater with higher iron content, and can also be used for treating the iron-containing wastewater containing other element components (such as Al)3+) The iron-containing wastewater has large extraction capacity and high selectivity of the extractant to iron.
In the resource utilization method provided by the invention, the stripping agent is selected from acidified water with the pH value of 1-2, and the acidified water is low in cost and easy to strip. In some preferred embodiments, the stripping agent is selected from hydrochloric acid solution with pH value of 1-2, such as 0.1mol/L hydrochloric acid solution.
In the resource utilization method provided by the invention, in the extraction process, the volume ratio of the extracting agent (namely organic phase) to the iron-containing wastewater (namely water phase) is 6: 1-1: 1, namely VExtracting agent:VIron-containing wastewater6:1 to 1:1, including but not limited to 6:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1:1, equal volume ratios; the extraction temperature is 20-30 ℃, for example, room temperature (25 ℃); the extraction time is 2-10 min.
In the resource utilization method provided by the invention, in the back extraction process, the volume ratio of the loaded extraction phase (namely organic phase) to the back extractant (namely aqueous phase) is 6: 1-1: 1, namely VLoaded extract phase:VStripping agent6:1 to 1:1, including but not limited to 6:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1:1, equal volume ratios; the back extraction temperature is 20-30 ℃, for example, room temperature (25 ℃); the back extraction time is 2-10 min.
In the resource utilization method provided by the invention, the extraction can also adopt multi-stage countercurrent extraction, and the extraction stages are 4-8 stages, including but not limited to 4, 5, 6, 7 and 8 stages; optionally, the stripping can also adopt multi-stage counter-current stripping, and the number of stripping stages is 4-8, including but not limited to 4, 5, 6, 7, and 8 stages.
In the resource utilization method provided by the invention, the iron-containing wastewater can be gallium extraction wastewater generated in the process of one-step acid dissolution method, and Fe in the gallium extraction wastewater is Fe3+High content, easy formation of three phases in the extraction process and influence on extraction efficiency, and the methodThe extracting agent composition is particularly suitable for extraction treatment of gallium extracting wastewater, so that the gallium extracting wastewater is easier to recycle. The resource utilization method is suitable for gallium extraction wastewater generated by different gallium extraction processes (such as resin adsorption) in the process of the one-step acid dissolution method. In some preferred embodiments, the gallium extraction wastewater contains Fe3+Has an Al content of 60-140 g/L3+The content of (b) is 10-50 g/L, and the concentration of hydrochloric acid is 1.5-4.5 mol/L. In some more preferred embodiments, the gallium-extracting wastewater contains Al3+The content of (b) is 10-20 g/L, and the concentration of hydrochloric acid is 3-4 mol/L.
The resource utilization method provided by the invention also comprises the step of utilizing the Fe-containing3+Fe in solution3+And preparing iron oxide. The process for preparing iron oxide can use the prior art, such as the technology described in Chinese patent CN 110885931A, and can recover hydrochloric acid. In addition, when the iron-containing wastewater is gallium extraction wastewater generated in the process of the one-step acid dissolution method, the iron extraction raffinate also contains a certain amount of Al3+And can be returned to the fly ash acid leaching process for recycling.
The technical scheme provided by the invention has the following advantages:
the extractant composition disclosed by the invention does not need to use an organic amine extractant, has a simple extraction system, is low in cost, has high extraction selectivity on ferric ions and large saturation capacity, is not easy to generate a third phase even under high-concentration iron, is high in extraction efficiency and easy to back extract, and is suitable for extraction treatment of various types of iron-containing wastewater, particularly high-iron-containing wastewater.
The resource utilization method can effectively extract and separate iron from the iron-containing wastewater for resource utilization by using the extractant composition, has high separation efficiency and good separation effect, greatly reduces the treatment cost, is very suitable for large-scale application, and has important economic and social values.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
The extraction stock solution used in the embodiment of the invention is gallium extraction wastewater generated in the process of the one-step acid dissolution method of the comprehensive development company Limited of quasi-energy resources.
The percentages used in the examples of the present invention are all percentages by mass, unless otherwise specified.
Example 1
The extraction stock solution contains Fe3+102.61g/L、Al3+12.81g/L and 3.7mol/L hydrochloric acid, and the extraction system is shown in Table 1. The extraction process conditions are as follows: o/a-2/1, extraction time 5min, extraction temperature 25 ℃.
TABLE 1 extraction results of different extraction systems
The results in Table 1 show that the iron distribution ratio is 0.98 when the extraction system is "25% TBP + 35% sec-octanol + sulfonated kerosene", and is greater than the sum of the iron distribution ratios of the extraction system when the extraction system is "25% TBP + sulfonated kerosene" and "35% sec-octanol + sulfonated kerosene" by 0.59, which indicates that TBP and sec-octanol have a synergistic extraction effect, and that sec-octanol is also beneficial to eliminating three phases formed. Therefore, in the extraction system of '25% TBP + 35% secondary octanol + sulfonated kerosene', the secondary octanol is not only a synergist, but also a modifier.
Example 2
The extraction stock solution contains Fe3+76.24g/L、Al3+13.56g/L and 3.3mol/L hydrochloric acid, wherein the used extraction system comprises phosphate TBP: secondary octanol: 6:7:7 (namely 30% TBP + 35% secondary octanol + 35% sulfonated kerosene), 3/1 compared with O/A (organic phase/aqueous phase), the extraction temperature is room temperature, the extraction time is 4min, and six-stage countercurrent extraction is carried out.
TABLE 2 data sheet for six-stage countercurrent cascade extraction
The raffinate is returned to fly ash hydrochloric acid for aluminum leaching.
And (3) carrying out back extraction on the extracted loaded organic phase, wherein the back extraction phase ratio is 3.5/1, the back extraction agent is acidified water (0.1mol/L hydrochloric acid solution) with the pH value of 1, the back extraction is carried out at room temperature, the back extraction time is 5min, and six-stage counter-current back extraction is carried out.
TABLE 3 data sheet for counter-current cascade counter-extraction of six stages
The back extraction solution refers to Chinese patent CN 110885931A, and adopts a spray burning process to produce iron oxide red and recover hydrochloric acid.
The results in tables 2 and 3 show that when the extraction system of 30% TBP + 35% sec-octanol + 35% sulfonated kerosene is used for extracting iron, the extraction efficiency of iron is high, the saturation capacity is large, the selectivity is high (aluminum is hardly extracted), and back extraction is easy. Therefore, the iron and the aluminum in the gallium extraction wastewater can be effectively separated and respectively recycled.
Example 3
The extraction stock solution contains Fe3+127.98g/L、Al3+11.36g/L and 3.5mol/L hydrochloric acid, wherein the used extraction system comprises phosphate TBP: secondary octanol: and (3) extracting sulfonated kerosene at the ratio of 1:2:2 (namely 20 percent of TBP, 40 percent of secondary octanol and 40 percent of sulfonated kerosene) at room temperature for 4min compared with O/A of 3.5/1 by five-stage countercurrent extraction.
TABLE 4 five-stage countercurrent cascade extraction data sheet
The raffinate is returned to fly ash hydrochloric acid for aluminum leaching.
And (3) carrying out back extraction on the extracted loaded organic phase, wherein the back extraction phase ratio is 3/1, the back extraction agent is acidified water with the pH value of 1, the back extraction is carried out at room temperature, the back extraction time is 5min, and six-stage counter-current back extraction is carried out.
TABLE 5 data sheet for counter-current cascade counter-extraction of six stages
The back extraction solution refers to Chinese patent CN 110885931A, and adopts a spray burning process to produce iron oxide red and recover hydrochloric acid.
The results in tables 4 and 5 show that when the extraction system of 20% TBP + 40% secondary octanol + 40% sulfonated kerosene is used for extracting iron, the extraction efficiency of iron is high, the saturation capacity is large, the selectivity is high, and back extraction is easy. Therefore, the iron and the aluminum in the gallium extraction wastewater can be effectively separated and respectively recycled.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (10)
1. An extractant composition is characterized by comprising the following components in percentage by mass: 20-40% of phosphate extractant shown as formula 1 and 35-50% of C6～C10Monohydric alcohol and the balance of diluent;
in the formula 1, R represents C3～C8Straight or branched chain alkyl.
2. The extractant composition according to claim 1, characterized by comprising, in mass percent: 20-35% of phosphate extractant shown as formula 1 and 35-40% of C6～C10Monohydric alcohol and the balance of diluent.
3. The extractant composition according to claim 1 or 2, characterized in that said R represents C3～C6Linear alkyl, preferably, the phosphate extractant is selected from tributyl phosphate; and/or
Said C is6～C10The monohydric alcohol is selected from secondary alcohols, preferably from C6～C8More preferably one or more selected from n-octanol, iso-octanol, and sec-octanol; and/or
The diluent is selected from sulfonated kerosene or kerosene.
4. A resource utilization method of iron-containing wastewater, characterized in that the extractant composition of any one of claims 1 to 3 is used as an extractant to extract Fe in the iron-containing wastewater3+The obtained load extraction phase is back extracted by using a back extractant, and the Fe-containing material which can be recycled is obtained3+And (3) solution.
5. The resource utilization method according to claim 4, wherein the stripping agent is selected from acidified water having a pH of 1-2, preferably from hydrochloric acid solution having a pH of 1-2.
6. A resource utilization method according to claim 4 or 5, wherein in the extraction process, the volume ratio of the extracting agent to the iron-containing wastewater is 6: 1-1: 1, the extraction temperature is 20-30 ℃, and the extraction time is 2-10 min.
7. The resource utilization method according to claim 4 or 5, wherein in the stripping process, the volume ratio of the loaded extraction phase to the stripping agent is 6: 1-1: 1, the stripping temperature is 20-30 ℃, and the stripping time is 2-10 min.
8. A resource utilization method according to any one of claims 4 to 7, wherein the extraction is performed by multistage countercurrent extraction, and the number of extraction stages is 4-8; and/or
And the back extraction adopts multi-stage counter-current back extraction, and the number of the back extraction stages is 4-8.
9. The resource utilization method according to any one of claims 4 to 8, wherein the iron-containing wastewater is gallium-extracting wastewater generated in a one-step acid dissolution process; preferably, in the gallium extraction wastewater, Fe3+Has an Al content of 60-140 g/L3+The content of (b) is 10-50 g/L, and the concentration of hydrochloric acid is 1.5-4.5 mol/L.
10. The resource utilization method according to claim 9, further comprising utilizing the Fe-containing component3+Fe in solution3+And preparing iron oxide.
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