CN103818967B - Flyash acid system produces the treatment process of acid waste liquid in alumina process - Google Patents
Flyash acid system produces the treatment process of acid waste liquid in alumina process Download PDFInfo
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- CN103818967B CN103818967B CN201310744737.XA CN201310744737A CN103818967B CN 103818967 B CN103818967 B CN 103818967B CN 201310744737 A CN201310744737 A CN 201310744737A CN 103818967 B CN103818967 B CN 103818967B
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Abstract
The invention discloses the treatment process that a kind of flyash acid system produces acid waste liquid in alumina process.The method comprises and processing acid waste liquid, obtains red iron oxide and water purification agent.Be oxidized by the spent pickle liquor produced in alumina process flyash acid system, purify and calcination processing, obtain highly purified red iron oxide and the water purification agent meeting national standard, not only solve environmental issue, achieve waste water no pollution, can " turn waste into wealth " again, achieve recycling, create profit margin.Method of the present invention solves the large and problem of polluted underground water and environment of high to acid waste liquid processing cost in prior art, energy consumption, and the process of producing spent pickle liquor in alumina process for flyash acid system provides a kind of effective and feasible approach.
Description
Technical field
The present invention relates to utilization of fly ash technical field, produce the treatment process of acid waste liquid in alumina process in particular to a kind of flyash acid system.
Background technology
Produce at flyash acid system in the process of aluminum oxide, flyash and hydrochloric acid are prepared burden by a certain percentage, to utilize in pickling equipment stripping flyash the metal oxides such as aluminium, iron, calcium, magnesium, gallium, obtain impure liquor alumini chloridi under certain temperature.Waste water---the acid waste liquid that liquor alumini chloridi produces in scavenging process and in gallium leaching process.The main moiety of acid waste liquid is: ferrous ion concentration is 80 ~ 150g/L, aluminum ion is concentration 20 ~ 30g/L, also containing a small amount of calcium, magnesium ion etc., is muriate, also has free concentration of hydrochloric acid to be 0.6-6%.
Because above-mentioned acid waste liquid acid concentration is high, the metal ion simultaneously containing higher concentration, so can not arrange directly outward, needs to process acid waste liquid.Acid waste liquid treatment process traditional at present mainly contains two kinds:
(1) select alkali neutralizing treatment, be mainly divided into two kinds of approach: 1. hydro-oxidation sodium neutralizing treatment: 500,000 tons of production line consumption costs 300,000,000 yuan/year; 2. lime (effective calcium 85%) neutralizing treatment is added: 500,000 tons of production line consumption costs 7,050 ten thousand yuan/year.Meanwhile, in above-mentioned neutralizing treatment process, also can produce a large amount of mud (Gu slag), the disposal costs of these mud about 2,000,000 yuan/year.Visible, adopt the approach appropriate litigation fees of alkali neutralizing treatment high.
(2) selecting evaporate to dryness to arrange outward, be mainly divided into two kinds of approach: 1. build ne-leakage anticorrosion dam, then there is long-term safety and the high problem of investment cost in this approach; 2. evaporate, but the solid waste of remaining after evaporation be soluble acid iron, aluminium salt be mingled with volatility hydrochloric acid, stockyard smell badly and very easily polluted underground water.
Consider and how process is optimized the variety of problems that above-mentioned two kinds of methods exist to acid waste liquid, makes acid waste liquid both can solve environmental issue, can " turn waste into wealth " again, create profit, go on the road of resource utilization, become current research tendency.
Summary of the invention
The present invention aims to provide the treatment process that a kind of flyash acid system produces acid waste liquid in alumina process, with solve in prior art to during acid waste liquid process costly or the problem of contaminate environment.
To achieve these goals, according to an aspect of the present invention, provide the treatment process that a kind of flyash acid system produces acid waste liquid in alumina process, acid waste liquid is processed, obtains red iron oxide and water purification agent.
Further, the step that acid waste liquid processes is comprised: S1, acid waste liquid is oxidized, separating-purifying, obtain Fu Tie purification liquid and rich aluminium purification liquid; And S2, rich iron purification liquid to be processed, obtain red iron oxide; Rich aluminium purification liquid is processed, obtains water purification agent.
Further, add oxygenant and be oxidized in step S1 in oxytropism waste liquid, oxygenant is O
2, Cl
2, H
2o
2, NaClO
3with one or more in HClO.
Further, as employing O
2during as oxygenant, the O passed into
2be 1.5:1 ~ 3:1 with the mass ratio of iron ion in acid waste liquid; As employing Cl
2during as oxygenant, the Cl passed into
2be 3.2:1 ~ 4.8:1 with the mass ratio of iron ion in acid waste liquid; As employing H
2o
2during as oxygenant, H
2o
2be 0.3:1 ~ 0.45:1 with the mass ratio of iron ion in acid waste liquid; When adopting NaClO as oxygenant, in NaClO and acid waste liquid, the mass ratio of iron ion is 0.67:1 ~ 1:1; As employing NaClO
3during as oxygenant, NaClO
3be 0.32:1 ~ 0.48:1 with the mass ratio of iron ion in acid waste liquid.
Further, the mode of extraction is adopted to carry out separating-purifying to the acid waste liquid after oxidation, extraction agent is selected from one or more in P204, P507, TBP, N235, and extraction agent and kerosene are mixed in proportion as organic phase, and the volume ratio of organic phase and acid waste liquid is 4:1 ~ 2.5:1.
Further, adopt the mode of counter-current extraction to carry out separating-purifying to the acid waste liquid after catalyzed oxidation, the progression of counter-current extraction is 6 ~ 9 grades.
Further, in step s 2, rich iron purification liquid is heated to 600 ~ 800 DEG C, calcines 0.5 ~ 1 hour.
Further, in step s 2, rich iron purification liquid is concentrated, then calcination processing is carried out to the rich iron purification liquid after concentrated.
Further, rich iron purification liquid is concentrated into 8 ~ more than 10wt% and carries out calcination processing.
Further, in step s 2, comprise the step that rich aluminium purification liquid processes: in rich aluminium purification liquid, add calcium aluminate, in calcium aluminate and rich aluminium purification liquid, the weight ratio of aluminum chloride is 0.28:1.
Apply technical scheme of the present invention, be oxidized by the spent pickle liquor produced in alumina process flyash acid system, purify and calcination processing, obtain highly purified red iron oxide and the water purification agent meeting national standard, not only solve environmental issue, achieve waste water no pollution, " can turn waste into wealth " again, achieve recycling, create profit margin.Method of the present invention solves the large and problem of polluted underground water and environment of high to acid waste liquid processing cost in prior art, energy consumption, and the process of producing spent pickle liquor in alumina process for flyash acid system provides a kind of effective and feasible approach.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the processing technological flow schematic diagram according to producing acid waste liquid in alumina process in a kind of exemplary embodiments of the present invention to flyash acid system.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
In order to solve at present in flyash acid system production alumina process, during spent pickle liquor process, cost is high, energy consumption large and the problem of polluted underground water and environment, the invention provides the treatment process that a kind of flyash acid system produces acid waste liquid in alumina process, the method processes acid waste liquid, obtains red iron oxide and water purification agent.
Be oxidized by the spent pickle liquor produced in alumina process flyash acid system, purify and calcination processing, obtain highly purified red iron oxide and the water purification agent meeting national standard, not only solve environmental issue, achieve waste water no pollution, can " turn waste into wealth " again, achieve recycling, create profit margin.Method of the present invention solves the large and problem of polluted underground water and environment of high to acid waste liquid processing cost in prior art, energy consumption, and the process of producing spent pickle liquor in alumina process for flyash acid system provides a kind of effective and feasible approach.
A preferred embodiment of the invention, as shown in Figure 1, comprises the step that acid waste liquid processes: S1, carry out catalyzed oxidation, separating-purifying, obtain Fu Tie purification liquid and rich aluminium purification liquid to acid waste liquid; And S2, rich iron purification liquid to be processed, obtain red iron oxide; Rich aluminium purification liquid is processed, obtains water purification agent.By being oxidized acid waste liquid, the ferrous ion in acid waste liquid is changed into ferric ion, then separating-purifying is to remove the ferric ion in acid waste liquid.
Preferably, the mode of extraction is adopted to carry out separating-purifying to the acid waste liquid after oxidation, wherein extraction agent is selected from one or more in P204, P507, TBP, N235, extraction agent and kerosene are mixed into organic phase by a certain percentage, by organic phase and acid waste liquid by volume 4:1 ~ 2.5:1 mix, the volume ratio of preferred organic phase and acid waste liquid is 3:1 ~ 2.5:1.The preferred above-mentioned extraction agent of the present invention, but be not limited thereto, adopt above-mentioned extraction agent can form complex compound fast with ferric ion in acid condition, from aqueous phase, enter organic phase, and then reclaim its recycle of organic mutual-assistance by back extraction.
Adopting the mode of extraction to carry out separating-purifying to the acid waste liquid after oxidation, to have extraction yield high, and the advantages such as relative resin absorption cost is low, can drop to below 0.3wt% by the concentration of iron in rich aluminium purification liquid after purification by liquid extraction.In order to reduce the internal circulating load of organic phase, reduce extraction cost, preferably, the present invention adopts the mode of reverse extraction to carry out separating-purifying to the acid waste liquid after oxidation, and the progression of counter-current extraction is 6 ~ 9 grades.Counter-current extraction contributes to the concentration improving solute.After counter-current extraction, separating-purifying, obtain the organic phase of load iron and rich iron purification liquid, adopt dilute hydrochloric acid or water washing 2 ~ 3 times to remove subsidiary foreign ion to rich iron purification liquid, then dilute hydrochloric acid solution or water is adopted to carry out 8 ~ 11 back extractions, the organic phase recycle obtained after back extraction, until when the ferric chloride Solution obtained meets the concentration requirement of calcining, enters lower road calcination procedure, if lower than the concentration requirement of calcining, then ferric chloride Solution is sent into concentration processes.Obtain red iron oxide to obtaining the process of Fu Tie purification liquid through separating-purifying, reclaim the hydrochloric acid obtained and recycle; Rich aluminium purification liquid can be returned main flow reuse, or rich aluminium purification liquid is processed, obtain water purification agent.
A preferred embodiment of the invention, adds oxygenant in oxytropism waste liquid in step S1 and is oxidized, and oxygenant is O
2, O
3, Cl
2, H
2o
2, NaClO
3with one or more in NaClO.The preferred above-mentioned oxygenant of the present invention, but be not limited thereto, as long as the ferrous ion in acid waste liquid can be converted into ferric ion effectively.Adopt above-mentioned oxidizing speed fast, and new impurity can not be introduced in oxytropism waste liquid.Preferably, when adopting O2 as oxygenant, in the oxygen passed into and acid waste liquid, the mass ratio of iron ion is 1.5:1 ~ 3:1, when adopting Cl
2during as oxygenant, the Cl passed into
2be 3.2:1 ~ 4.8:1 with the mass ratio of iron ion in acid waste liquid; As employing H
2o
2during as oxygenant, H
2o
2be 0.3:1 ~ 0.45:1 with the mass ratio of iron ion in acid waste liquid; When adopting NaClO as oxygenant, in NaClO and acid waste liquid, the mass ratio of iron ion is 0.67:1 ~ 1:1; As employing NaClO
3during as oxygenant, NaClO
3be 0.32:1 ~ 0.48:1 with the mass ratio of iron ion in acid waste liquid.
According to a kind of exemplary embodiment of the present invention, in step s 2, rich iron purification liquid is heated to 600 ~ 800 DEG C, calcines 0.5 ~ 1 hour.If calcining temperature is higher than 800 DEG C, calcination time more than 1 hour, then can cause partial oxidation iron to change into Z 250; On the contrary, if calcining temperature is lower than 600 DEG C, calcination time is less than 0.5 hour, then it is ferric oxide that partial oxidation iron can be caused unconverted.Therefore, consider, calcining temperature and calcination time control, in above-mentioned scope, both can obtain highly purified red iron oxide by the present invention, also can not cause the wasting of resources.
The concentration of the iron ion of the rich iron purification liquid after separating-purifying is lower than 7wt%, if the too low direct high-temperature calcination of concentration of rich iron purification liquid, then calcining cost can be caused higher.A preferred embodiment of the invention, in step s 2, concentrates rich iron purification liquid, then carries out calcination processing to the rich iron purification liquid after concentrated.After concentrated, richer iron purification liquid is carried out high-temperature calcination process contribute to reduction and burn till cost.Preferably, the iron concentration in rich iron purification liquid is concentrated into 8 ~ more than 10wt% and carries out calcination processing, be easy to the red iron oxide obtaining high purity 99.3%.Red iron oxide (Fe
2o
3) red also referred to as rust, be red oxidization iron powder, have fast light, high-temperature stability, the present invention preferably adopts Spray calcination stove dinectly bruning to produce iron oxide red, the uniform particles of the red iron oxide powder obtained after Spray calcination and purity is high.
The method of carrying out concentration to rich iron purification liquid is more, preferably, the present invention adopts acidproof nanofiltration membrane treatment system, first ferric chloride Solution is filtered, remove oarse-grained impurity, be sent to afterwards in nanofiltration membrane treatment system and carry out recycle to extinction, holding temperature stable (40 ~ 50 DEG C) in working cycle, calcine to sending in calcining furnace when meeting the concentration of calcining when rich iron purification liquid iron concentration reaches 10wt%, the permeate obtained through nanofiltration membrane treatment system is recycled as the reverse-extraction agent of extraction process.
According to a kind of exemplary embodiment of the present invention, in step s 2, comprise the step that rich aluminium purification liquid processes: in rich aluminium purification liquid, add calcium aluminate, in calcium aluminate and rich aluminium purification liquid, the weight ratio of aluminum chloride is 0.28:1.The concentration of the iron ion in rich aluminium purification liquid, generally lower than 0.3%, just can obtain meeting the aluminium iron polychloride of water purification agent industry standard after adding calcium aluminate allotment.In rich aluminium purification liquid, adding calcium aluminate, to prepare water purification agent be a kind of utilization ways, when rich aluminium purification liquid also can be returned the reuse of host system acid recovery operation when water purification agent market is bad by rich aluminium purification liquid.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment and comparative example:
Embodiment 1
Get flyash acid system and produce the acid waste liquid (being provided by Zhun Zi company of Shenhua) obtained in alumina process, the concentration of this acid waste liquid ferrous ions is 80 ~ 150g/L, aluminum ions concentration is 20 ~ 30g/L.
1) by acid waste liquid with 0.6m
3/ h flow pump is squeezed in oxidation trough, adds oxygenant NaClO in oxidation trough
3, stop 0.5 hour, make the ferrous iron Quick Oxidation in acid waste liquid be ferric iron, deliver to extracting and separating purification process afterwards.Wherein oxygenant NaClO
3be 0.32:1 with the mass ratio of iron ion in acid waste liquid.
2) 60% organic extractant P204+40% kerosene is adopted to carry out 6 stage countercurrent extractions, separating-purifying as organic phase to the acid waste liquid after oxidation in step 1).Wherein the volume ratio of organic phase and acid waste liquid is 4:1, extracts and reaches balance in 3 minutes.Be separated, obtain Fu Tie purification liquid (organic phase of load iron) and rich aluminium purification liquid.The percentage extraction of iron reaches 98.5%, and in raffinate, the mass percent concentration of iron is lower than 1%.
3) dilute hydrochloric acid (PH=1.5) is adopted to carry out 3 grades of washings to the organic phase of load iron, dilute hydrochloric acid (PH=1.5) is adopted to carry out 11 grades of back extractions to the organic phase after washing, the volume ratio of organic phase and reverse-extraction agent dilute hydrochloric acid is 3:1, and in the rich iron purification liquid after back extraction, the mass percent concentration of iron ion is more than 7%.
4) the rich iron purification liquid obtained in step 3) is filtered, remove oarse-grained impurity, send into nanofiltration membrane treatment system afterwards and carry out recycle to extinction, in working cycle, holding temperature is 50 DEG C, after iron concentration reaches 10wt%, just can send into red iron oxide production line as the raw material of production red iron oxide, the permeate obtained is as the reverse-extraction agent reuse of extraction process.
5) be that the rich iron purification liquid of 10wt% sends into Spray calcination stove by the iron concentration obtained in step 4), calcine 0.5 hour at 800 DEG C, obtain the red iron oxide that purity reaches more than 99.0%.The method can produce the red iron oxide of 0.03t/h, produces the hydrochloric acid that 0.12t/h and concentration reach more than 18%, and wherein red iron oxide can direct marketing, and hydrochloric acid is got back to main flow and utilized.
6) in the rich aluminium purification liquid after extraction, add calcium aluminate to allocate, produce the aluminium iron polychloride of 0.02t/h, produce according to existing method, aluminum chloride quality proportioning wherein in calcium aluminate and rich aluminium purification liquid is 0.28:1, and the aluminum chlorate of polymerized silicic acid quality product obtained meets the requirement of rower water purification agent.
7), when water purification agent market is bad, rich aluminium purification liquid directly returns the reuse of host system acid recovery operation.
Embodiment 2
Its raw material adopted is identical with embodiment 1 with operation steps, and difference is the oxygenant NaClO added in oxidation trough in step 1)
3be 0.48:1 with the mass ratio of iron ion in acid waste liquid.
Embodiment 3
Its raw material adopted is identical with embodiment 1 with operation steps, and difference is that the mass ratio of iron ion in the oxygenant NaClO that adds in oxidation trough in step 1) and acid waste liquid is 0.28:1.
Embodiment 4 ~ 6
The raw material adopted in embodiment 4 to 6 is identical with embodiment 1 with operation steps, and difference is the mass ratio of iron ion in the oxygenant that adopts in step 1) and oxygenant and acid waste liquid, and proportioning, transformation efficiency and red iron oxide purity are specifically in table 1.
Embodiment 7 to 12
The raw material adopted in embodiment 7 to 12 is identical with embodiment 1 with operation steps, and difference is: adopt H in embodiment 7 and embodiment 8
2o
2as oxygenant, in embodiment 9 and embodiment 10, adopt O
2as oxygenant, in embodiment 11 and embodiment 12, adopt Cl
2as oxygenant, proportioning, transformation efficiency and red iron oxide purity are specifically in table 1.
Wherein, adopt the purity of sulfate by ion chromatography red iron oxide product, adopt dichromate titration to calculate transformation efficiency, specifically in table 1 and table 2.
Table 1
As can be seen from Table 1, as employing oxygenant NaClO of the present invention
3, NaClO, H
2o
2, O
2or Cl
2when acid waste liquid is oxidized, all can obtain high conversion and high-purity mangesium oxide iron oxide red product.As employing NaClO
3as oxygenant and by NaClO
3relative to the ratio outside scope, there is better effect when controlling in the scope for 0.32:1 ~ 0.48:1 with the mass ratio of iron ion in acid waste liquid.Equally, when adopting NaClO as oxygenant, and when being controlled by the mass ratio of iron ion in NaClO and acid waste liquid in the scope for 0.67:1 ~ 1:1, relative to the ratio outside scope, there is better effect.As employing O
2during as oxygenant, when the mass ratio of iron ion in passed into oxygen and acid waste liquid controls as 1.5:1 ~ 3:1, as employing Cl
2during as oxygenant, by the Cl passed into
2control as 3.2:1 ~ 4.8:1 with the mass ratio of iron ion in acid waste liquid, as employing H
2o
2during as oxygenant, by oxygenant H
2o
2control, for 0.3:1 ~ 0.45:1, there is better effect with the mass ratio of iron ion in acid waste liquid.
Embodiment 13
Get flyash acid system and produce the acid waste liquid (being provided by Zhun Zi company of Shenhua) obtained in alumina process, the concentration of this acid waste liquid ferrous ions is 80 ~ 150g/L, aluminum ions concentration is 20 ~ 30g/L.
1) by acid waste liquid with 0.6m
3/ h flow pump is squeezed in oxidation trough, adds oxygenant NaClO in oxidation trough
3, stop 1 hour, make the ferrous iron Quick Oxidation in acid waste liquid be ferric iron, deliver to extracting and separating purification process afterwards.Wherein oxygenant NaClO
3be 4.8:1 with the mass ratio of iron ion in acid waste liquid.
2) 60%P507+40% kerosene is adopted to carry out 9 stage countercurrent extractions, separating-purifying as organic phase to the acid waste liquid after oxidation in step 1).Wherein the volume ratio of organic phase and acid waste liquid is 2.5:1, extracts and reaches balance in 3 minutes.Be separated, obtain Fu Tie purification liquid (organic phase of load iron) and rich aluminium purification liquid.The percentage extraction of iron reaches 98.8%, and in raffinate, the mass percent concentration of iron is lower than 1%.
3) dilute hydrochloric acid (PH=1.5) is adopted to carry out 3 grades of washings to the organic phase of load iron, dilute hydrochloric acid (PH=1.5) is adopted to carry out 11 grades of back extractions to the organic phase after washing, the volume ratio of organic phase and reverse-extraction agent dilute hydrochloric acid is 3:1, and in the rich iron purification liquid after back extraction, the mass percent concentration of iron ion is more than 7%.
4) the rich iron purification liquid obtained in step 3) is filtered, remove oarse-grained impurity, send into nanofiltration membrane treatment system afterwards and carry out recycle to extinction, in working cycle, holding temperature is 60 DEG C, after iron concentration reaches 10wt%, just can send into red iron oxide production line as the raw material of production red iron oxide, the permeate obtained is as the reverse-extraction agent reuse of extraction process.
5) be that the rich iron purification liquid of 10wt% sends into Spray calcination stove by the iron concentration obtained in step 4), calcine 1 hour at 650 DEG C, obtain the red iron oxide that purity reaches more than 99.3%.The method can produce the red iron oxide of 0.03t/h, produces the hydrochloric acid that 0.12t/h and concentration reach more than 18%, and wherein red iron oxide can direct marketing, and hydrochloric acid is got back to main flow and utilized.
6) in the rich aluminium purification liquid after extraction, add calcium aluminate to allocate, produce the aluminium iron polychloride of 0.02t/h, produce according to existing method, aluminum chloride quality proportioning wherein in calcium aluminate and rich aluminium purification liquid is 0.28:1, and the aluminum chlorate of polymerized silicic acid quality product obtained meets the requirement of rower water purification agent.
Embodiment 14 to 16
Its raw material is identical with embodiment 13 with operation, and difference is step 2) volume ratio of middle organic phase and acid waste liquid.Specifically in table 2.
Table 2
As can be seen from Table 2, when other condition is identical, when the volume ratio of organic phase and acid waste liquid is in the scope of 2.5:1 ~ 4:1, higher iron ion percentage extraction and the ferric oxide rate of recovery can be obtained.When the volume ratio of organic phase and acid waste liquid is 2:1, the percentage extraction of iron ion and the rate of recovery of ferric oxide all lower; When the volume ratio of organic phase and acid waste liquid is 6:1, although organic phase improves the percentage extraction of iron ion after increasing, but the rate of recovery of simultaneous oxidation iron also reduces, this is because organic phase is more, reverse-extraction agent and organic phase fluid, than after reduction, can affect the effect of back extraction, increase stream ratio, whole system internal circulating load is large, and production cost is high.Therefore, through considering, the volume ratio of organic phase and acid waste liquid controls, in the scope of 2.5:1 ~ 4:1, can obtain higher percentage extraction and the rate of recovery by the present invention.
Embodiment 17
Get flyash acid system and produce the acid waste liquid (being provided by Zhun Zi company of Shenhua) obtained in alumina process, the concentration of this acid waste liquid ferrous ions is 80 ~ 150g/L, aluminum ions concentration is 20 ~ 30g/L.
1) by acid waste liquid with 0.6m
3/ h flow pump is squeezed in oxidation trough, adds oxygenant NaClO in oxidation trough, stops 1 hour, makes the ferrous iron Quick Oxidation in acid waste liquid be ferric iron, delivers to extracting and separating purification process afterwards.Wherein in oxygenant NaClO and acid waste liquid, the mass ratio of iron ion is 1:1.
2) 50% organic extractant BTP+10% organic extractant N235+40% kerosene is adopted to carry out 6 stage countercurrent extractions, separating-purifying as organic phase to the acid waste liquid after oxidation in step 1).Wherein the volume ratio of organic phase and acid waste liquid is 2.5:1, extracts and reaches balance in 3 minutes.Be separated, obtain Fu Tie purification liquid (organic phase of load iron) and rich aluminium purification liquid.The percentage extraction of iron reaches more than 99.5%, and in raffinate, the mass percent concentration of iron is lower than 0.3%.
3) dilute hydrochloric acid (PH=1.5) is adopted to carry out 3 grades of washings to the organic phase of load iron, dilute hydrochloric acid (PH=1.5) is adopted to carry out 10 grades of back extractions to the organic phase after washing, the volume ratio of organic phase and reverse-extraction agent dilute hydrochloric acid is 3:1, and in the rich iron purification liquid after back extraction, the mass percent concentration of iron ion is more than 8%.
4) the rich iron purification liquid obtained in step 3) just can be sent into red iron oxide production line as the raw material of production red iron oxide.
5) be that the rich iron purification liquid of 8wt% sends into Spray calcination stove by the iron concentration obtained in step 4), calcine 1 hour at 650 DEG C, obtain the red iron oxide that purity reaches more than 99.3%.The method can produce the red iron oxide of 0.03t/h, produces the hydrochloric acid that 0.12t/h and concentration reach more than 18%, and wherein red iron oxide can direct marketing, and hydrochloric acid is got back to main flow and utilized.
6) in the rich aluminium purification liquid after extraction, add calcium aluminate to allocate, produce the aluminium iron polychloride of 0.02t/h, produce according to existing method, aluminum chloride quality proportioning wherein in calcium aluminate and rich aluminium purification liquid is 0.28:1, and the aluminum chlorate of polymerized silicic acid quality product obtained meets the requirement of rower water purification agent.
Embodiment 18
Its raw material is identical with embodiment 17 with operation, and difference is step 2) volume ratio of middle organic phase and acid waste liquid.Specifically in table 3.
Table 3
As can be seen from Table 3, when adopting the mixed extractant synergistic extraction of 50%TBP+10%N235+40% kerosene, relative to adopting single 60%P507+40% kerosene in table 2, there is better effect of extracting, and extraction progression can be reduced to 6 grades, and percentage extraction is up to 99.9%, the red iron oxide product of high purity 99.3% can be obtained equally.
The water purification agent of preparation in embodiment 1 to 18 is detected, the method of aluminum oxide in GB GB14592-09 is adopted to detect the content of the aluminum oxide in polymerize aluminum chloride iron product, adopt the method for ferric oxide in GBl5891-09 to detect the content of the ferric oxide in polymerize aluminum chloride iron product, indices is specifically in table 4.
Table 4
As can be seen from Table 4, the quality of the aluminum chlorate of polymerized silicic acid product adopting method of the present invention to prepare all meets the requirement of rower water purification agent.
As fully visible, be oxidized by the spent pickle liquor produced in alumina process flyash acid system, purify and calcination processing, obtain highly purified red iron oxide and the water purification agent meeting industry standard, not only solve environmental issue, achieve waste water no pollution, " can turn waste into wealth " again, achieve recycling, create profit margin.Method of the present invention solves the large and problem of polluted underground water and environment of high to acid waste liquid processing cost in prior art, energy consumption, and the process of producing spent pickle liquor in alumina process for flyash acid system provides a kind of effective and feasible approach.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. flyash acid system produces a treatment process for acid waste liquid in alumina process, it is characterized in that, processes described acid waste liquid, obtain red iron oxide and water purification agent, comprise the step that described acid waste liquid processes:
S1, described acid waste liquid is oxidized, separating-purifying, obtain Fu Tie purification liquid and rich aluminium purification liquid, the mode of extraction is wherein adopted to carry out separating-purifying to the described acid waste liquid after oxidation, extraction agent is selected from one or more in P204, P507, TBP, N235, described extraction agent and kerosene are mixed in proportion as organic phase, and the volume ratio of described organic phase and described acid waste liquid is 4:1 ~ 2.5:1; And
S2, described rich iron purification liquid to be processed, obtain red iron oxide; Described rich aluminium purification liquid is processed, obtains water purification agent; Wherein, the step that described rich iron purification liquid processes is comprised: described rich iron purification liquid is concentrated, then calcination processing is carried out to the described rich iron purification liquid after concentrated; Comprise the step that described rich aluminium purification liquid processes: in described rich aluminium purification liquid, add calcium aluminate, in described calcium aluminate and described rich aluminium purification liquid, the weight ratio of aluminum chloride is 0.28:1.
2. method according to claim 1, is characterized in that, adds oxygenant and be oxidized in described step S1 in described acid waste liquid, and described oxygenant is O
2, Cl
2, H
2o
2, NaClO
3with one or more in NaClO.
3. method according to claim 2, is characterized in that,
As the described O of employing
2during as oxygenant, the described O passed into
2be 1.5:1 ~ 3:1 with the mass ratio of iron ion in described acid waste liquid;
As the described Cl of employing
2during as oxygenant, the described Cl passed into
2be 3.2:1 ~ 4.8:1 with the mass ratio of iron ion in described acid waste liquid;
As the described H of employing
2o
2during as oxygenant, described H
2o
2be 0.3:1 ~ 0.45:1 with the mass ratio of iron ion in described acid waste liquid;
When adopting described NaClO as oxygenant, in described NaClO and described acid waste liquid, the mass ratio of iron ion is 0.67:1 ~ 1:1;
As the described NaClO of employing
3during as oxygenant, described NaClO
3be 0.32:1 ~ 0.48:1 with the mass ratio of iron ion in described acid waste liquid.
4. method according to claim 1, is characterized in that, adopt the mode of counter-current extraction to carry out separating-purifying to the described acid waste liquid after catalyzed oxidation, the progression of described counter-current extraction is 6 ~ 9 grades.
5. method according to claim 1, is characterized in that, in described step S2, described rich iron purification liquid is heated to 600 ~ 800 DEG C, calcines 0.5 ~ 1 hour.
6. method according to claim 1, is characterized in that, described rich iron purification liquid is concentrated into 8 ~ more than 10wt% and carries out calcination processing.
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| CN104150576B (en) * | 2014-07-20 | 2016-08-31 | 榆林学院 | A kind of coal ash for manufacturing is for the method for PAFC |
| CN104528995B (en) * | 2014-12-22 | 2017-01-04 | 中国神华能源股份有限公司 | The wastewater treatment equipment of aluminium oxide and method in a kind of acidity extraction flyash |
| CN106966415A (en) * | 2017-03-29 | 2017-07-21 | 西安航天动力试验技术研究所 | The process of aluminum oxide in a kind of acidity extraction coal-powder boiler flyash |
| CN107287421B (en) * | 2017-05-23 | 2019-04-05 | 清华大学 | A kind of process from hydrochloric acid leaching system extracting and refining molysite |
| CN109897961B (en) * | 2019-02-21 | 2020-09-29 | 山西大学 | Method for gradient separation and impurity removal and aluminum-gallium synergistic extraction from fly ash sulfuric acid system |
| CN110467223A (en) * | 2019-07-17 | 2019-11-19 | 李柏丛 | The iron oxide red preparation high-performance iron oxide of steel mill's pickling solution production is used for the new process of soft magnetic materials |
| CN110885931A (en) * | 2019-11-21 | 2020-03-17 | 神华准能资源综合开发有限公司 | Resource utilization technology for gallium extraction waste liquid in one-step acid dissolution process |
| CN113044865B (en) * | 2019-12-26 | 2022-03-22 | 国家能源投资集团有限责任公司 | Method for preparing aluminum oxide |
| CN113603150A (en) * | 2021-09-23 | 2021-11-05 | 广州大学 | Iron oxide red and preparation method thereof |
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