CN115180677A - Tungsten wastewater treatment method - Google Patents
Tungsten wastewater treatment method Download PDFInfo
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- CN115180677A CN115180677A CN202210882020.0A CN202210882020A CN115180677A CN 115180677 A CN115180677 A CN 115180677A CN 202210882020 A CN202210882020 A CN 202210882020A CN 115180677 A CN115180677 A CN 115180677A
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- tungsten
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- macroporous
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention relates to a tungsten wastewater treatment method, wherein the COD content in the tungsten wastewater is 1000-1500mg/l, and the content of tungsten element is WO 3 0-20g/l, and the concentration of the sulfuric acid is 100-150g/l; the tungsten wastewater treatment method comprises the following steps: enabling the tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 1-5BV/h, and obtaining a post-crosslinking liquid 1; subjecting the post-crossing liquid 1 to coal adsorption treatment to obtain a treatment liquid; passing the treatment solution through macroporous aromatic resin, wherein the adsorption flow is 1-4BV/h, and obtaining post-hybridization solution 2; the COD content in the post-intersection liquid 2 is reduced by 90-95% compared with the COD content in the tungsten wastewater, and the change range of the concentration of the sulfuric acid in the post-intersection liquid 2 is less than or equal to 10% compared with the concentration of the sulfuric acid in the tungsten wastewater. The invention relates to a tungsten wastewater treatment methodCan obviously reduce the COD content in the wastewater, simultaneously recover tungsten, basically does not change the acid value of the wastewater, is favorable for subsequent extraction of valuable elements, and has excellent application prospect.
Description
Technical Field
The invention relates to a treatment technology of tungsten production wastewater, in particular to a tungsten wastewater treatment method.
Background
The tungsten wastewater refers to wastewater generated in a tungsten smelting process, and in an extraction-ion exchange-crystallization process, extraction and back extraction processes, operations such as sulfide precipitation, filtration, ion exchange impurity removal and the like need to be performed, and the wastewater generated in the process is acidic, high in salt content and high in COD content and is difficult to treat.
The COD in the wastewater is mainly derived from organic matters, neutral or alkaline conditions are usually required for reducing COD, the acidic wastewater cannot directly reduce COD, the chemical adding cost is increased by adding an alkaline reagent to adjust the pH value, and the added alkali cannot be recycled to generate other values, so that reagent waste is caused; meanwhile, the addition of the alkaline reagent can destroy the existing form of tungsten in the wastewater, so that the subsequent tungsten recovery is difficult.
Patent application CN105461140A discloses a tungsten smelting ion exchange method waste water integrated processing recovery system and method, the system is mainly including the crystallization mother liquor collecting vat that communicates the setting in proper order, the deamination pot, hand over back liquid collecting vat, the pH equalizing basin, hand over back liquid board frame pressure filter, hand over back liquid storage tank after the filter-pressing, D318 macroporous resin recovery column, remove heavy integrated processing pond, remove heavy board frame pressure filter, mix the collecting pit, ammonia nitrogen treatment pond, pH fine setting pond, the depositing reservoir, still including washing sodium and washing chlorine water collecting pit, it is connected with mixing the collecting pit to wash sodium and wash chlorine water collecting pit. The recovery method comprises the steps of deamination treatment of crystallization mother liquor, tungsten recovery of post-crosslinking liquor and crystallization mother liquor wastewater, de-weight comprehensive treatment of the post-crosslinking liquor and the crystallization mother liquor wastewater, recovery and treatment of sodium washing water and chlorine washing water, ammonia nitrogen and COD advanced treatment, pH fine adjustment and clarification. The process needs a plurality of equipment units, and has long flow and high cost; among them, the advanced treatment of COD must be carried out on the premise that the above steps are carried out one by one, and the application limit is large.
Disclosure of Invention
The invention aims to solve the problem of high COD content in the existing tungsten wastewater, and provides a tungsten wastewater treatment method, which greatly reduces the COD content in the wastewater after macroporous acrylic resin, coal adsorption treatment and macroporous aromatic resin are sequentially treated on the premise of keeping the original acidity of the wastewater unchanged, so that the obtained post-mixed liquid 2 has low COD content and high acidity, can directly enter separation equipment for extracting other metal elements, and is convenient for the subsequent processing operation of feed liquid.
The specific scheme is as follows:
a tungsten wastewater treatment method, wherein the COD content in the tungsten wastewater is 1000-1500mg/l, and the content of tungsten element is WO 3 The concentration is 0-20g/l, and the concentration of the sulfuric acid is 100-150g/l;
the tungsten wastewater treatment method comprises the following steps: enabling the tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 1-5BV/h, and obtaining a post-crosslinking liquid 1; adsorbing the post-crossing liquid 1 by coal to obtain a treatment liquid; passing the treatment solution through macroporous aromatic resin, wherein the adsorption flow is 1-4BV/h, and obtaining post-hybridization solution 2;
the COD content in the post-intersection liquid 2 is reduced by 90-95% compared with the COD content in the tungsten wastewater, and the change amplitude of the concentration of the sulfuric acid in the post-intersection liquid 2 compared with the concentration of the sulfuric acid in the tungsten wastewater is less than or equal to 10%.
Further, the COD content in the tungsten wastewater is 1100-1350mg/l, and the content of tungsten element is WO 3 9-17g/l, and the concentration of sulfuric acid is 100-120g/l.
Further, the macroporous acrylic resin is one or two of D318 and D314 macroporous resin.
Further, the particle size of the coal is 1-10mm, and the flow of the post-crossing liquid 1 through the coal is 1-3BV/h, so as to obtain the treatment liquid.
Further, the macroporous aromatic resin is one or two of SD201 and SD300 aromatic macroporous adsorption resins.
Further, the concentration of tungsten element in the post-crosslinking liquid 2 is calculated according to WO 3 The tungsten content is less than 0.06g/l, and the recovery rate of tungsten is more than 99 percent.
Has the beneficial effects that:
according to the invention, the macroporous acrylic resin is adopted to adsorb tungsten, and due to the special pore structure and performance of the macroporous acrylic resin, the macroporous acrylic resin has a good effect on the adsorption and purification of tungstate and ammonium paramolybdate, can preferentially adsorb tungstate and molybdate under the condition of high concentrations of chloride and sulfate radicals, and ensures the recovery effect of tungsten.
Furthermore, the invention can adsorb organic solute from water through van der Waals attraction by using coal adsorption treatment and macroporous aromatic resin, thereby realizing the enrichment and separation of organic matters in the aqueous solution, being suitable for the adsorption of lipophilic large molecular weight organic matters in the aqueous solution and the separation of some specific substances, and the combination of the two has excellent adsorption property on hydrophobic organic matters in the aqueous solution. The water solution containing organic matters passes through the coal and the macroporous aromatic adsorption resin adsorption column at a certain flow rate, the organic matters are adsorbed by the resin, the water solution is purified, the concentration of the organic matters in the water solution is reduced, and the easiness in removing the organic matters in the water solution is improved.
In a word, the tungsten wastewater treatment method can obviously reduce the COD content in the wastewater, simultaneously recovers tungsten, basically does not change the acid value of the wastewater, is favorable for subsequent extraction of valuable elements, and has excellent application prospect.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The tungsten wastewater used in the following is derived from wastewater obtained by an extraction-ion exchange process, and the content of main components in the wastewater fluctuates due to the difference of raw materials of different batches, which is shown in each example in detail.
The macroporous acrylic resin adopted in the embodiment is one or two of D318 and D314 macroporous resin; the macroporous aromatic resin is one or two of SD201 and SD300 aromatic macroporous adsorption resins. The grain sizes of the coal and the active carbon are both 0.5-1mm.
Example 1
A tungsten wastewater treatment method comprises the steps of enabling tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 3BV/h, and obtaining a post-crosslinking liquid 1; subjecting the post-crossing liquid 1 to coal adsorption treatment with an adsorption flow of 2BV/h to obtain a treatment liquid; the treated liquid is passed through macroporous aromatic resin with an adsorption flow of 2BV/h to obtain a post-crosslinking liquid 2, and the contents of the main components of each liquid are shown in Table 1. Wherein, the macroporous acrylic resin is D318, and the macroporous aromatic resin is SD201.
Table 1 example 1 content of feed liquid
Compared with tungsten wastewater, COD content of the post-hybridization solution 2 is reduced by 92.4%, and the concentration change range of sulfuric acid is 9.8%.
Example 2
A tungsten wastewater treatment method comprises the steps of enabling tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 3BV/h, and obtaining a post-crosslinking liquid 1; subjecting the post-crossing liquid 1 to coal adsorption treatment with the adsorption flow of 3BV/h to obtain a treatment liquid; the treated liquid is passed through macroporous aromatic resin, the adsorption flow is 3BV/h, and a post-crosslinking liquid 2 is obtained, and the contents of the main components of each liquid are shown in Table 2. Wherein, the macroporous acrylic resin is D314, and the macroporous aromatic resin is SD300.
Table 2 example 2 feed liquid content scale
Compared with tungsten wastewater, the COD content of the treatment liquid is reduced by 92.2%, and the concentration change range of the sulfuric acid is 4.2%.
Example 3
A tungsten wastewater treatment method comprises the steps of enabling tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 3BV/h, and obtaining a post-crosslinking liquid 1; subjecting the post-crossing liquid 1 to coal adsorption treatment with an adsorption flow of 4BV/h to obtain a treatment liquid; the treated liquid is passed through macroporous aromatic resin with an adsorption flow of 4BV/h to obtain a post-crosslinking liquid 2, and the contents of the main components of each liquid are shown in Table 3. Wherein, the macroporous acrylic resin is D314, and the macroporous aromatic resin is SD201.
Table 3 example 3 feed liquid content scale
Compared with tungsten wastewater, the COD content of the post-crosslinking liquid 2 is reduced by 90.6%, and the concentration change range of the sulfuric acid is 7.0%.
Comparative example 1
A tungsten wastewater treatment method comprises the steps of enabling tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 3BV/h, and obtaining a post-crosslinking liquid 1; and (3) passing the post-crosslinking liquid 1 through macroporous aromatic resin, wherein the adsorption flow is 2BV/h, so as to obtain a post-crosslinking liquid 2, and the main component content of each feed liquid is shown in Table 4. Wherein, the macroporous acrylic resin is D318, and the macroporous aromatic resin is SD201.
Table 4 feed solution content of comparative example 1
Compared with tungsten wastewater, COD content of the post-hybridization solution 2 is reduced by 78.6%, and the concentration change range of sulfuric acid is 9.8%.
Comparative example 2
A tungsten wastewater treatment method comprises the steps of enabling tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 3BV/h, and obtaining a post-crosslinking liquid 1; and (3) subjecting the post-crossing liquid 1 to coal adsorption treatment with the adsorption flow of 2BV/h to obtain a treatment liquid, wherein the main component content of each feed liquid is shown in Table 5. Wherein the macroporous acrylic resin is D314.
Table 5 feed liquid content of comparative example 2
Compared with tungsten waste water, the COD content of the treatment liquid is reduced by 72.4 percent, and the concentration change range of the sulfuric acid is 4.2 percent.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (6)
1. A tungsten wastewater treatment method is characterized by comprising the following steps: the COD content in the tungsten wastewater is 1000-1500mg/l, and the content of tungsten element is WO 3 0-20g/l, and the concentration of the sulfuric acid is 100-150g/l;
the tungsten wastewater treatment method comprises the following steps: enabling the tungsten wastewater to pass through macroporous acrylic resin, wherein the adsorption flow is 1-5BV/h, and obtaining a post-crosslinking liquid 1; subjecting the post-crossing liquid 1 to coal adsorption treatment to obtain a treatment liquid; passing the treatment solution through macroporous aromatic resin with the adsorption flow of 1-4BV/h to obtain post-hybridization solution 2;
the COD content in the post-intersection liquid 2 is reduced by 90-95% compared with the COD content in the tungsten wastewater, and the change range of the concentration of the sulfuric acid in the post-intersection liquid 2 is less than or equal to 10% compared with the concentration of the sulfuric acid in the tungsten wastewater.
2. The tungsten wastewater treatment method according to claim 1, characterized in that: the COD content in the tungsten wastewater is 1100-1350mg/l, and the content of tungsten element is WO 3 9-17g/l, and the concentration of sulfuric acid is 100-120g/l.
3. The tungsten wastewater treatment method according to claim 1, characterized in that: the macroporous acrylic resin is one or two of D318 and D314 macroporous resin.
4. The tungsten wastewater treatment method according to claim 1, characterized in that: the particle size of the coal is 1-10mm, and the flow of the post-crossing liquid 1 through the coal is 1-3BV/h, so as to obtain the treating liquid.
5. The tungsten wastewater treatment method according to claim 4, characterized in that: the macroporous aromatic resin is one or two of SD201 and SD300 aromatic macroporous adsorption resins.
6. The tungsten wastewater treatment method according to any one of claims 1 to 5, characterized in that: the concentration of tungsten element in the post-crosslinking liquid 2 is calculated by WO 3 The tungsten content is less than 0.06g/l, and the recovery rate of tungsten is more than 99 percent.
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| CN202210882020.0A CN115180677A (en) | 2022-07-26 | 2022-07-26 | Tungsten wastewater treatment method |
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| CN101985692A (en) * | 2010-12-02 | 2011-03-16 | 江西修水湘赣有色金属有限公司 | Method for removing arsenic and recycling tungsten from tungsten smelting wastewater |
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