CN105540950A - Resource-converting treatment method for iron oxide yellow reaction solution - Google Patents
Resource-converting treatment method for iron oxide yellow reaction solution Download PDFInfo
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- CN105540950A CN105540950A CN201510990356.9A CN201510990356A CN105540950A CN 105540950 A CN105540950 A CN 105540950A CN 201510990356 A CN201510990356 A CN 201510990356A CN 105540950 A CN105540950 A CN 105540950A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F2305/00—Use of specific compounds during water 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention relates to a resource-converting treatment method for an iron oxide yellow reaction solution. The method comprises the following steps: adding manganese sulfate into the iron oxide yellow reaction solution, carrying out stirring so as to dissolve manganese sulfate, and then, adjusting the pH of the reaction solution to 7 to 9 by a NaOH solution; continuously introducing air into the solution so as to carry out an oxidation reaction for 5 to 15 hours, carrying out filtering separation so as to obtain filter liquor and filter cake, and subjecting the filter cake to rinsing, baking, crushing and calcining, thereby obtaining a manganese ferrite black product; subjecting the filter liquor to bipolar membrane electrodialysis treatment, so as to obtain the NaOH solution, a H2SO4 solution and dilute brine; recycling the NaOH solution to the step (1), recycling the H2SO4 solution to an acid dissolving section of an iron oxide yellow production process, and recycling the dilute brine to a filter cake rinsing section of the step (2). According to the method, the manganese ferrite black with a high economic added value is prepared by using ferrous sulfate in the iron oxide yellow reaction solution, sodium sulfate in the reaction solution is dissociated into sulfuric acid and the sodium hydroxide solution by using a bipolar membrane technology, and the sulfuric acid, the sodium hydroxide solution and the dilute brine are recycled to the process. Thus, the problem in the treatment of the iron oxide yellow reaction solution is solved, valuable resources in the reaction solution are utilized, and the cyclic utilization of the resources is realized.
Description
Technical field
The present invention relates to iron pigment waste water reclaiming process field, be specifically related to a kind of method of iron oxide yellow reaction solution recycling treatment.
Background technology
Output deironing in iron pigment of iron oxide yellow is infrared, occupies second.The main raw material of industrial iron oxide yellow is scrap iron skin, iron filings and ferrous sulfate, is industrial waste and utilizes.Iron oxide yellow deposits in case at nucleus, the oxygen reaction in ferrous sulfate and air and obtaining.Often consume 1mol ferrous sulfate in production process and just produce 1mol sulfuric acid, 1mol sulfuric acid reacts with scrap iron again produces 1mol ferrous sulfate.Though the important source material that ferrous sulfate is produced for iron oxide yellow, when scrap iron skin and waste iron filing abundance, the ferrous sulfate in solution maintains equilibrium state substantially.After the completion of reaction, in solution, ferrous sulfate content reaches 8 ~ 12%, and for remaining ferrous sulfate, general factory directly discharges with water in filter-press water-washing process, contaminate environment.Often produce 1t iron oxide yellow, by discharge 1.2 ~ 1.3t ferrous sulfate.
Bipolar membrane electrodialysis system is made up of Bipolar Membrane, anion-exchange membrane and cationic exchange membrane.Wherein, Bipolar Membrane is a kind of novel ion-exchange composite membranes, is composited by cation exchange layer (N-type film), interface hydrophilic layer (Catalytic Layer) and anion exchange layer (P type film).When Bipolar Membrane is oppositely pressurizeed, positive and negative ion is moved to bulk solution from ion-exchange bed interface respectively by yin, yang layer, thus exhausts at interfacial layer generation ion, forms high electrical potential gradient, finally causes water molecules to dissociate.The H that water decomposition produces
+and OH
-respectively to the migration of film both sides bulk solution, when not introducing new component, the salt in solution can be converted into corresponding bronsted lowry acids and bases bronsted lowry.
Because iron oxide yellow reaction liquid C OD is extremely low, and main containing ferrous sulfate and sodium sulfate, direct discharge not only pollutes surrounding enviroment, and causes the significant wastage of resource.The ferromanganese that ferrous sulfate in iron oxide yellow reaction solution is converted into high economic value added by the present invention is black, then utilize bipolar membrane electrodialysis technology that the sodium sulfate in reaction solution is converted into sulfuric acid and sodium hydroxide solution, and be back in technique, both a difficult problem for iron oxide yellow reaction solution process had been solved, take full advantage of again the ferrous sulfate in reaction solution and sodium sulfate resource, reduce production cost.
Summary of the invention
The invention discloses a kind of method of iron oxide yellow reaction solution recycling treatment, on the one hand the ferrous sulfate in reaction solution is converted into the ferromanganese mineral black of high economic value added, utilize bipolar membrane electrodialysis technology that the sodium sulfate in reaction solution is converted into sulfuric acid and sodium hydroxide solution on the other hand, and be back in explained hereafter, reduce production cost.
A method for iron oxide yellow reaction solution recycling treatment, is characterized in that, comprise the following steps:
Add manganous sulfate, stirring and dissolving in step 1, iron oxide yellow reaction solution, then regulate reaction solution pH to 7 ~ 9 by NaOH solution;
Step 2, pass into air, reaction solution oxidizing reaction 5 ~ 15h, filtering separation obtains filtrate and filter cake, and filter cake is through rinsing, oven dry, pulverizing and calcine and obtain the black product of ferromanganese;
The filtrate that step 3, step 2 obtain, through bipolar membrane electrodialysis process, obtains NaOH solution, H
2sO
4solution and weak brine; The reaction conditions of Bipolar Membrane: pole liquid is 1 ~ 5%Na
2sO
4solution, temperature of reaction is 1 ~ 40 DEG C, and current density is 100 ~ 700A/m
2;
The NaOH solution that step 4, step 3 obtain is back in step 1 and regulates reaction solution pH, H
2sO
4solution is back to the acid-soluble workshop section in iron oxide yellow production technique, and weak brine is back to the filter cake rinsing workshop section in step 2 or is used as the pole liquid of bipolar membrane electrodialysis.
Iron oxide yellow reaction solution of the present invention is that ferrous sulfate oxidation style produces the reaction solution produced in iron oxide yellow, mainly containing Fe
2+, SO
4 2-and Na
+.Ferrous sulfate oxidation style: sulfuric acid and iron filings react and generate ferrous sulfate, add sodium hydroxide and pass into atmospheric oxidation and prepare nucleus, in nucleus suspension, add ferrous sulfate and iron filings again, heating blasts atmospheric oxidation, obtains iron oxide yellow through press filtration, rinsing, drying, pulverizing.
As preferably, the present invention is equally applicable to the recycling treatment of iron oxide red reaction solution, and described iron oxide yellow reaction solution can replace with iron oxide red reaction solution.In red iron oxide, transparent iron oxide red, iron oxide yellow and transparent yellow iron oxide reaction solution, COD is all lower, and main containing ferrous sulfate and sodium sulfate.
Black (the MnFe of ferromanganese
2o
4, Fe
2o
3mnO) be a kind of black pigment of slightly red phase, calcined by the oxide compound of manganese and iron and obtain.Compared with Organic Black, titanium are black, it has higher temperature tolerance; Compared with black with chromium-copper, its tinting strength is lower, but has price advantage.Ferromanganese is black has the advantages such as excellent thermotolerance, photostabilization, resistance to acids and bases, solvent resistant, weather-proof and environment-protecting asepsis, is mainly used in the fields such as stove and accessory, vapor pipe, high-temperature boiler and glass enamel tinting pigment.
As preferably, in step 1, ferrous sulfate and manganous sulfate mol ratio are 2:1 ~ 2:1.1.
As preferably, in step 1, sodium hydroxide dosage is 1.05 ~ 1.25 times of the required theoretical amount of chemistry.The reaction that NaOH participates in is:
FeSO
4+2NaOH＝Fe(OH)
2↓+Na
2SO
4
MnSO
4+2NaOH＝Mn(OH)
2↓+Na
2SO
4。
As preferably, in step 2, in air, effective oxygen aequum is 1.05 ~ 1.3 times of chemical theory amount.The reaction that oxygen participates in is:
4Fe(OH)
2+2H
2O+O
2＝4Fe(OH)
3
2Mn(OH)
2+O
2＝2MnO(OH)
2。
As preferably, the calcining temperature that in step 2, ferromanganese is black is 930 ~ 970 DEG C.When temperature is on the low side, the crystalline structure of Manganese Ferrite can not be made fully to be formed, the result caused is that pigment powder blackness is not enough, and form and aspect are partially brown; Temperature is too high, and pigment sinters, and crystalline structure is destroyed, and causes pigmenting power greatly to reduce.
Bipolar Membrane and anions and canons one pole film are combined to form by bipolar membrane electrodialysis in different ways, and successfully being dissociated by common electrodialytic salt dissociates with the water molecules of Bipolar Membrane combines, and makes the H that in solution, corresponding salt ion and Bipolar Membrane water decomposition produce
+and OH
-in conjunction with being converted into corresponding bronsted lowry acids and bases bronsted lowry.The core of bipolar membrane electrodialysis system is Bipolar Membrane, and it is composited by cation exchange layer (N-type film), interface hydrophilic layer (Catalytic Layer) and anion exchange layer (P type film).When after applying voltage, the electrolyte ion in Bipolar Membrane middle layer will move to bulk solution, and after the migration of all electrolyte ions exhausts, electric current must by H
+and OH
-load completes, and is supplemented by the water decomposition in Bipolar Membrane middle layer, and the water consumed is supplemented to the diffusion of Bipolar Membrane middle layer by the water in surrounding medium.Schematic diagram is illustrated in fig. 1 shown below.
Compared with traditional iron oxide yellow reaction solution treatment process, advantage of the present invention is:
1, present invention process flow process advantage be simple to operate understandable, reaction conditions is gentle, do not introduce other organism, take up an area less and be easy to industrialization etc.;
2, to utilize ferrous sulfate in iron oxide yellow reaction solution to prepare the ferromanganese of high economic value added black in the present invention, in addition, utilize Bipolar membrane water splitting that the sodium sulfate in iron oxide yellow reaction solution is dissociated into sulfuric acid and sodium hydroxide solution, and sulfuric acid, sodium hydroxide solution and weak brine are back in technique.Both solve a difficult problem for iron oxide yellow reaction solution process, once more make use of the valuable resource in iron oxide yellow reaction solution.
Accompanying drawing explanation
Fig. 1 is Bipolar Membrane hydrolysis schematic diagram.
Fig. 2 is the schema of the method for a kind of iron oxide yellow reaction solution of the present invention recycling treatment.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, it is noted that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not played to it.
Embodiment 1
The reaction solution produced in common iron oxide yellow production process, mainly containing Fe
2+, SO
4 2-and Na
+, the concentration of ferrous sulfate is 27g/L after measured.
Add manganous sulfate (ferrous sulfate and manganous sulfate mol ratio are 2:1) in step 1, iron oxide yellow reaction solution, stirring and dissolving, then regulate reaction solution pH=8 by NaOH solution;
FeSO
4+2NaOH＝Fe(OH)
2↓+Na
2SO
4
MnSO
4+2NaOH＝Mn(OH)
2↓+Na
2SO
4
Step 2, continue to pass into air, reaction solution oxidizing reaction 10h, filtering separation obtains filtrate and filter cake, and filter cake is through rinsing, oven dry, pulverizing and calcine and obtain the black product of ferromanganese, and wherein calcining temperature is 950 DEG C.
4Fe(OH)
2+2H
2O+O
2＝4Fe(OH)
3
2Mn(OH)
2+O
2＝2MnO(OH)
2
Contrast with standard substance Lockwood 303T, the black quality of ferromanganese is as follows:
| △ L (lightness) | △ a (red green phase) | △ b (champac phase) | △ c (saturation ratio) | △ E (aberration) | Pigment intensity |
| 2.49 | -0.26 | -0.25 | 0.29 | 2.52 | 83.43％ |
As seen from the above table, a, b value is negative value, sample phase greener than standard specimen is described, more blue phase, is good form and aspect concerning mineral black.C value be on the occasion of, illustrate that sample has better saturation ratio than standard specimen.Shortcoming is pigment undercapacity, only has 83.43% of standard specimen.From data analysis, calcining temperature is too high, can reduce by 10 ~ 20 DEG C, and tinting strength will improve.
The filtrate that step 3, step 2 obtain is colourless, COD is 15mg/L, and the content of sodium sulfate is about 17.5%, adopts bipolar membrane electrodialysis process, obtains 9%NaOH solution, 11%H
2sO
4solution and weak brine; Bipolar Membrane reaction conditions: adopt 3% metabisulfite solution to be pole liquid, temperature of reaction is 30 DEG C, and current density is 500A/m
2.
The NaOH solution that step 4, step 3 obtain is back in step 1 and regulates reaction solution pH, H
2sO
4solution is back to the acid-soluble workshop section in iron oxide yellow production technique, and weak brine is back to the filter cake rinsing workshop section in step 2 or is used as the pole liquid of bipolar membrane electrodialysis.
Comparative example 1
The reaction solution produced in common iron oxide yellow production process, mainly containing Fe
2+, SO
4 2-and Na
+, the concentration of ferrous sulfate is 27g/L after measured.
Compared with embodiment 1, other condition remains unchanged, the calcining temperature to 930 DEG C that in set-up procedure 2, ferromanganese is black, and with standard substance Lockwood 303T, the black quality of ferromanganese is as follows:
| △ L (lightness) | △ a (red green phase) | △ b (champac phase) | △ c (saturation ratio) | △ E (aberration) | Pigment intensity |
| 1.99 | 0.19 | -0.29 | 0.32 | 2.52 | 89.28％ |
As seen from the above table, the black product of ferromanganese that calcining temperature obtains after slightly reducing has better form and aspect, saturation ratio and tinting strength.
Comparative example 2
The reaction solution produced in common iron oxide yellow production process, mainly containing Fe
2+, SO
4 2-and Na
+, the concentration of ferrous sulfate is 27g/L after measured.
Compared with embodiment 1, other condition remains unchanged, the calcining temperature to 970 DEG C that in set-up procedure 2, ferromanganese is black, and with standard substance Lockwood 303T, the black quality of ferromanganese is as follows:
| △ L (lightness) | △ a (red green phase) | △ b (champac phase) | △ c (saturation ratio) | △ E (aberration) | Pigment intensity |
| 3.84 | -2.56 | 0.78 | -0.75 | 4.92 | 78.71％ |
As seen from the above table, because calcining temperature is too high, cause pigment powder sintering, pigmenting power is reduced greatly.Adjustment calcining temperature gets final product head it off.
From embodiment 1, comparative example 1 and comparative example 2, calcining temperature is larger on the impact of ferromanganese black product quality.
Comparative example 3
The reaction solution produced in common iron oxide yellow production process, mainly containing Fe
2+, SO
4 2-and Na
+, the concentration of ferrous sulfate is 27g/L after measured.
Compared with embodiment 1, other condition remains unchanged, and in set-up procedure 3, the current density of bipolar membrane electrodialysis system is to 300A/m
2, found by test, the efficiency of bipolar membrane electrodialysis system reduces 38%.
Embodiment 2
The reaction solution produced in transparent yellow iron oxide production process, mainly containing Fe
2+, SO
4 2-and Na
+, the concentration of ferrous sulfate is 26g/L after measured.
Add manganous sulfate (ferrous sulfate and manganous sulfate mol ratio are 2:1.05), stirring and dissolving in step 1, thoroughly iron oxide yellow reaction solution, then regulate reaction solution pH=8 by NaOH solution;
FeSO
4+2NaOH＝Fe(OH)
2↓+Na
2SO
4
MnSO
4+2NaOH＝Mn(OH)
2↓+Na
2SO
4
Step 2, continue to pass into air, reaction solution oxidizing reaction 10h, filtering separation obtains filtrate and filter cake, and filter cake is through rinsing, oven dry, pulverizing and calcine and obtain the black product of ferromanganese, and wherein calcining temperature is 950 DEG C.
4Fe(OH)
2+2H
2O+O
2＝4Fe(OH)
3
2Mn(OH)
2+O
2＝2MnO(OH)
2
The filtrate that step 3, step 2 obtain is colourless, COD is 12mg/L, and the content of sodium sulfate is about 17%, adopts bipolar membrane electrodialysis process, obtains 9%NaOH solution, 11%H
2sO
4solution and weak brine; Bipolar Membrane reaction conditions: adopt 3% metabisulfite solution to be pole liquid, temperature of reaction is 30 DEG C, and current density is 500A/m
2.
The NaOH solution that step 4, step 3 obtain is back in step 1 and regulates reaction solution pH, H
2sO
4solution is back to the acid-soluble workshop section in iron oxide yellow production technique, and weak brine is back to the filter cake rinsing workshop section in step 2 or is used as the pole liquid of bipolar membrane electrodialysis.
Embodiment 3
The reaction solution produced in red iron oxide production process, mainly containing Fe
2+, SO
4 2-and Na
+, the concentration of ferrous sulfate is 28g/L after measured.
Add manganous sulfate (ferrous sulfate and manganous sulfate mol ratio are 2:1.05) in step 1, red iron oxide reaction solution, stirring and dissolving, then regulate reaction solution pH=8 by NaOH solution;
FeSO
4+2NaOH＝Fe(OH)
2↓+Na
2SO
4
MnSO
4+2NaOH＝Mn(OH)
2↓+Na
2SO
4
Step 2, continue to pass into air, reaction solution oxidizing reaction 10h, filtering separation obtains filtrate and filter cake, and filter cake is through rinsing, oven dry, pulverizing and calcine and obtain the black product of ferromanganese, and wherein calcining temperature is 950 DEG C.
4Fe(OH)
2+2H
2O+O
2＝4Fe(OH)
3
2Mn(OH)
2+O
2＝2MnO(OH)
2
The filtrate that step 3, step 2 obtain is colourless, COD is 18mg/L, and the content of sodium sulfate is about 19%, adopts bipolar membrane electrodialysis process, obtains 10%NaOH solution, 12%H
2sO
4solution and weak brine; Bipolar Membrane reaction conditions: adopt 3% metabisulfite solution to be pole liquid, temperature of reaction is 30 DEG C, and current density is 500A/m
2.
The NaOH solution that step 4, step 3 obtain is back in step 1 and regulates reaction solution pH, H
2sO
4solution is back to the acid-soluble workshop section in iron oxide yellow production technique, and weak brine is back to the filter cake rinsing workshop section in step 2 or is used as the pole liquid of bipolar membrane electrodialysis.
Claims (6)
1. a method for iron oxide yellow reaction solution recycling treatment, is characterized in that, comprises the following steps:
Add manganous sulfate, stirring and dissolving in step 1, iron oxide yellow reaction solution, then regulate reaction solution pH to 7 ~ 9 by NaOH solution;
Step 2, pass into air, reaction solution oxidizing reaction 5 ~ 15h, filtering separation obtains filtrate and filter cake, and filter cake is through rinsing, oven dry, pulverizing and calcine and obtain the black product of ferromanganese;
The filtrate that step 3, step 2 obtain, through bipolar membrane electrodialysis process, obtains NaOH solution, H
2sO
4solution and weak brine; The reaction conditions of Bipolar Membrane: pole liquid is 1 ~ 5%Na
2sO
4solution, temperature of reaction is 1 ~ 40 DEG C, and current density is 100 ~ 700A/m
2;
The NaOH solution that step 4, step 3 obtain is back in step 1 and regulates reaction solution pH, H
2sO
4solution is back to the acid-soluble workshop section in iron oxide yellow production technique, and weak brine is back to the filter cake rinsing workshop section in step 2 or is used as the pole liquid of bipolar membrane electrodialysis.
2. the method for a kind of iron oxide yellow reaction solution recycling treatment as claimed in claim 1, is characterized in that, described iron oxide yellow reaction solution can replace with iron oxide red reaction solution.
3. the method for a kind of iron oxide yellow reaction solution recycling treatment as claimed in claim 1, it is characterized in that, in step 1, ferrous sulfate and manganous sulfate mol ratio are 2:1 ~ 2:1.1.
4. the method for a kind of iron oxide yellow reaction solution recycling treatment as claimed in claim 1, is characterized in that, in step 1, sodium hydroxide dosage is 1.05 ~ 1.25 times of the required theoretical amount of chemistry.
5. the method for a kind of iron oxide yellow reaction solution recycling treatment as claimed in claim 1, is characterized in that, in step 2, in air, effective oxygen aequum is 1.05 ~ 1.3 times of chemical theory amount.
6. the method for a kind of iron oxide yellow reaction solution recycling treatment as claimed in claim 1, it is characterized in that, the calcining temperature that in step 2, ferromanganese is black is 930 ~ 970 DEG C.
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|---|---|---|---|
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|---|---|---|---|
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ID=55820580
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200159A (en) * | 1988-10-17 | 1993-04-06 | Chemirite, Ltd. | Purified solution containing iron and manganese, and method producing thereof |
| CN101314678A (en) * | 2008-06-20 | 2008-12-03 | 升华集团德清华源颜料有限公司 | Fire resistant black iron oxide pigment and preparation method thereof |
| CN101475276A (en) * | 2008-12-31 | 2009-07-08 | 莫一平 | Treatment process for ferric oxide production wastewater |
-
2015
- 2015-12-24 CN CN201510990356.9A patent/CN105540950A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200159A (en) * | 1988-10-17 | 1993-04-06 | Chemirite, Ltd. | Purified solution containing iron and manganese, and method producing thereof |
| CN101314678A (en) * | 2008-06-20 | 2008-12-03 | 升华集团德清华源颜料有限公司 | Fire resistant black iron oxide pigment and preparation method thereof |
| CN101475276A (en) * | 2008-12-31 | 2009-07-08 | 莫一平 | Treatment process for ferric oxide production wastewater |
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