CN109133450B - Method for preparing iron oxide black pigment by using steel pickling wastewater - Google Patents
Method for preparing iron oxide black pigment by using steel pickling wastewater Download PDFInfo
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- 239000000049 pigment Substances 0.000 title claims abstract description 41
- 238000005554 pickling Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 24
- 239000010959 steel Substances 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 title claims description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052742 iron Inorganic materials 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims abstract description 31
- -1 iron ion Chemical class 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 19
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 15
- 239000012716 precipitator Substances 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 26
- 239000001099 ammonium carbonate Substances 0.000 claims description 26
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000005273 aeration Methods 0.000 abstract description 4
- 238000001579 optical reflectometry Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- 239000002699 waste material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a method for preparing steel by using steel pickling wastewaterThe iron black pigment preparing process includes utilizing iron ion and outer iron ion in steel pickling effluent as iron source and CO content3 2‑Or HCO3 ‑The inorganic salt is a precipitator, and the iron black pigment is prepared by a precipitation method without an aeration oxidation process. In the reaction process, the control of the precipitation reaction temperature (60-80 ℃), the molar weight of the iron source in the reaction liquid and CO3 2‑(or HCO)3 ‑) Controlling the molar weight ratio (1: 0.6-1: 1.2), and controlling the aging pH value (pH is 6-9), the aging temperature (85-95 ℃) and the aging time (2-4 h) after the precipitation is finished to prepare the iron black pigment with high tinting strength. Compared with the same type of iron black pigment products sold in the market, the iron black pigment prepared by the invention has better color saturation, higher tinting strength and lower light reflectivity. The method takes the similar products in the market as standard products, and the delta c value of the sample measured by a color measuring instrument is a positive value (0.66-1.76), the delta L value is a negative value (-1.57-5.62), and the relative coloration is 102-113%.
Description
Technical Field
The invention relates to the field of chemical production wastewater recycling, in particular to a method for preparing iron black pigment by utilizing steel pickling wastewater.
Background
China becomes the first major steel producing country around the world, steel enterprises in China generate more than million cubic meters of pickling waste liquid every year, the pickling waste liquid contains a large amount of iron ions and a small amount of other metal ions, and the discharge of the pickling waste liquid causes serious pollution and toxicity to water and organisms. According to the relevant regulations in the national hazardous waste records, the acid (alkali) washing, oil removal, rust removal and washing processes of metal surface treatment generate waste corrosive liquid, washing liquid and sludge, so that the waste acid liquid and the acid washing sludge generated in the metal product processing surface treatment process belong to hazardous wastes and must be safely treated. At present, the most representative of the treatment and utilization technologies of the wastewater is a neutralization precipitation method and a waste acid comprehensive recovery method. The neutralization precipitation method is gradually eliminated due to the treatment cost and the secondary pollution problem of the sludge; the comprehensive recovery method mainly utilizes methods such as evaporative crystallization, solvent precipitation and the like to recover iron salt and secondary acid contained in the pickling waste liquid, and utilizes the recovered iron salt to further process and produce the iron-based chemical products. Among them, iron-based pigments are an important class of products.
Among iron pigments, iron black pigments have been widely used in the fields of paints, copying powders, sewage treatment, etc. because of their characteristics of good tinting strength, dispersibility, water resistance, medium compatibility, ferromagnetism, etc. At present, the mainstream technology is to prepare iron oxide black by adopting a precipitation aeration oxidation method, and Fe (OH) is adopted in the preparation process2The oxidation of the precipitate is a key step in the preparation of iron black pigments and is also a very difficult step to control, and the oxidation end point is very difficult to control.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing iron black pigment by utilizing steel pickling wastewater, which takes iron ions and external iron ions in the steel pickling wastewater as iron sources in a synergetic way, and takes CO contained in the iron sources3 2-The inorganic salt is a precipitator, and the iron black pigment is directly prepared by a precipitation method without an aeration oxidation process. In the reaction process, the control of the precipitation reaction temperature, the molar quantity of the iron source and CO in the reaction liquid3 2-(or HCO)3 -) Controlling the molar weight ratio, and controlling the aging pH value, the aging temperature and the aging time after the precipitation is finished to prepare the iron black pigment with high tinting strength.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for preparing iron black pigment from the waste water generated by pickling iron or steel includes such steps as providing the iron ions and iron ions in the waste water generated by pickling iron or steel plant, and using CO as iron source3 2-Or HCO3 -The inorganic salt is used as a precipitator to prepare the iron black pigment, and the method comprises the following steps:
(1) pretreatment of pickling wastewater: adding reduced iron powder into the pickling wastewater according to a solid-liquid ratio of 1: 400-1: 1000, carrying out ultrasonic dispersion treatment, adjusting the pH value to 5-6, and then adjusting the pH value to Zn in the pickling wastewater according to the solid-liquid ratio2+Adding Na into the mixture according to the molar ratio of 1:12S, pretreating, stirring and dispersing for 10min, carrying out suction filtration on the solution, taking filtrate and measuring Fe in the filtrate2+The content of the organic silicon compound is calculated according to the mole percentage,is marked as m1And adding Fe thereto2+The molar content is m2FeSO of (2)4·7H2O, stirring and dissolving to obtain an iron-containing solution, pouring the iron-containing solution into a reactor, and stirring for later use;
(2) precipitation reaction: after the iron-containing solution obtained in the step (1) is heated to 60-80 ℃, weighing CO3 2-Or HCO3 -The molar content is m3Dissolving the inorganic salt in water, dropwise adding the inorganic salt into the iron-containing solution for 15-30min, adjusting the pH value to 6-9 after dropwise adding, and continuously stirring the solution for 10 min;
(3) aging reaction: continuing to heat the reaction liquid, aging and preserving heat for 2-4 hours at 85-95 ℃, then carrying out heat filtration on the reaction liquid, washing a filter cake with distilled water, drying at 90 ℃, and grinding to obtain the iron black pigment, wherein (m) is1+m2):m3＝1:(0.6～1.2)。
The inorganic salt is one or more of sodium carbonate, ammonium carbonate, sodium bicarbonate and ammonium bicarbonate.
And (2) adding ammonia water to adjust the pH value to 5-6 in the step (1).
In the step (1), a NaOH solution with the mass percentage concentration of 5% and a HCl solution with the mass percentage concentration of 5% are adopted to adjust the pH value of the reaction solution to 6-9.
The invention has the beneficial effects that:
(1) the preparation method is simple, and realizes the reclamation of the wastewater. In addition, compared with the traditional preparation method, the preparation method of the iron black pigment does not need precipitation, aeration and oxidation, and the performance of the prepared pigment product is easy to control.
(2) Compared with the same type of iron black pigment products sold in the market, the iron black pigment prepared by the invention has better color saturation, higher tinting strength and lower light reflectivity. The method takes the similar products in the market as standard products, and the delta c value of the sample measured by a color measuring instrument is a positive value (0.66-1.76), the delta L value is a negative value (-1.57-5.62), and the relative coloration is 102-113%.
Detailed Description
The method for preparing iron black pigment by using the steel pickling wastewater of the present invention will be described with reference to examples.
The method for preparing the iron oxide black pigment by using the steel pickling wastewater utilizes the iron ions and the added iron ions in the steel pickling wastewater to be cooperated as an iron source and contains CO3 2-Or HCO3 -The inorganic salt is used as a precipitator to prepare the iron black pigment, and the method comprises the following steps:
(1) pretreatment of pickling wastewater: adding reduced iron powder into the pickling wastewater according to a solid-liquid ratio of 1: 400-1: 1000, carrying out ultrasonic dispersion treatment, adjusting the pH value to 5-6, and then adjusting the pH value to Zn in the pickling wastewater according to the solid-liquid ratio2+Adding Na into the mixture according to the molar ratio of 1:12S, pretreating, stirring and dispersing for 10min, carrying out suction filtration on the solution, taking filtrate and measuring Fe in the filtrate2+Molar content, denoted m1And adding Fe thereto2+The molar content is m2FeSO of (2)4·7H2O, stirring and dissolving to obtain an iron-containing solution, pouring the iron-containing solution into a reactor, and stirring for later use;
(2) precipitation reaction: after the iron-containing solution obtained in the step (1) is heated to 60-80 ℃, weighing CO3 2-Or HCO3 -The molar content is m3Dissolving the inorganic salt in water, dropwise adding the inorganic salt into the iron-containing solution for 15-30min, adjusting the pH value to 6-9 after dropwise adding, and continuously stirring the solution for 10 min;
(3) aging reaction: continuing to heat the reaction liquid, aging and preserving heat for 2-4 hours at 85-95 ℃, then carrying out heat filtration on the reaction liquid, washing a filter cake with distilled water, drying at 90 ℃, and grinding to obtain the iron black pigment, wherein (m) is1+m2):m3＝1:(0.6～1.2)。
The inorganic salt is one or more of sodium carbonate, ammonium carbonate, sodium bicarbonate and ammonium bicarbonate.
And (2) adding ammonia water to adjust the pH value to 5-6 in the step (1).
In the step (1), NaOH solution with the mass percentage concentration of 5% and HCl solution with the mass percentage concentration of 5% are adopted to adjust the pH value of the reaction solution to 6-9.
The invention aims at the difficulty in the preparation process of the iron black pigmentTo contain CO3 2-The inorganic salt is used as a precipitator, and the method for preparing the iron black pigment by using the steel pickling wastewater is provided by controlling the reaction process conditions and the dosage ratio of the raw materials.
Example 1
Ammonium carbonate is used as precipitant, and the molar weight of iron ions in reaction liquid and CO in the precipitant3 2-Example of molar ratio between molar amounts of 1:0.7
Measuring 200mL of steel pickling wastewater, adding 0.2g of reduced iron powder into the steel pickling wastewater, performing ultrasonic dispersion treatment for 10min, dropwise adding ammonia water into the steel pickling wastewater to adjust the pH value of the solution to 5-6, and then adding Na into the solution2S0.75g to remove Zn from wastewater by precipitation2+Then the solution was filtered with suction to obtain a filtrate, and 5g of FeSO was added thereto4·7H2O is dissolved and then the iron containing solution is transferred into a four-necked flask and the solution is heated to elevated temperature with mechanical agitation.
Weighing 3g of ammonium carbonate, dissolving the ammonium carbonate in water, dropwise adding an ammonium carbonate solution into the iron-containing solution when the temperature of the iron-containing solution is raised to 75 ℃, wherein the dropwise adding time is 15min, after the dropwise adding is finished, adjusting the pH value of the reaction solution to 8 by using a prepared 5% NaOH solution and a prepared 5% HCl solution, and continuously stirring for 10 min. And then continuing heating the solution, aging and preserving heat for 3 hours at 85 ℃, carrying out suction filtration on the solution, washing a filter cake, drying the filter cake at 90 ℃, and grinding to obtain the iron black pigment product. The color performance of the same kind of commercial products is tested by a color measuring instrument, the obtained color performance parameters are that delta L is-4.17, delta a is-0.64, delta b is 0.13, delta c is 0.66, delta H is 0.14, and the relative tinting strength is 105%.
Example 2
Sodium carbonate is used as a precipitator, and the molar weight of iron ions in reaction liquid and CO in the precipitator3 2-Example of molar ratio between molar amounts of 1:0.7
The precipitant ammonium carbonate (3.00g) in example 1 was adjusted to sodium carbonate (2.03g), the amount of reduced iron powder was adjusted to 0.5g, the precipitation reaction temperature was 60 ℃, the precipitant dropping time was adjusted to 30min, the pH of the reaction solution was adjusted to 9 with the prepared 5% NaOH solution and 5% HCl solution, the aging temperature was adjusted to 90 ℃, the aging time was 3.5h, and other reaction conditions were unchanged, to obtain an iron black pigment product using sodium carbonate as precipitant. The color performance of the same kind of commercial products is tested by a color measuring instrument, the obtained color performance parameters are that delta L is-5.42, delta a is-0.51, delta b is 0.95, delta c is 0.86, delta H is 1.03, and the relative tinting strength is 102%.
Example 3
Sodium bicarbonate is used as a precipitator, and the molar weight of iron ions in reaction liquid and CO in the precipitator3 2-Example of molar ratio between molar amounts of 1:0.7
The precipitant ammonium carbonate (3.00g) in example 1 was adjusted to sodium carbonate (1.61g), the precipitation reaction initiation temperature was 80 ℃, the precipitant dropping time was adjusted to 25min, the pH of the reaction solution was adjusted to 9 with the prepared 5% NaOH solution and 5% HCl solution, the aging temperature was adjusted to 90 ℃, the aging time was 3h, and other reaction conditions were unchanged, to obtain an iron black pigment product using sodium bicarbonate as a precipitant. The color performance of the same kind of commercial products is tested by a color measuring instrument, the obtained color performance parameters are that delta L is-4.97, delta a is-0.54, delta b is 0.95, delta c is 0.86, delta H is 1.06, and the relative tinting strength is 113%.
Example 4
Ammonium bicarbonate is used as precipitant, the molar weight of iron ions in reaction liquid and CO in the precipitant3 2-Example of molar ratio between molar amounts of 1:0.7
The precipitant ammonium carbonate (3.00g) in example 1 was adjusted to sodium carbonate (1.51g), the precipitant dropping time was adjusted to 25min, the pH of the reaction solution was adjusted to 6 with the prepared 5% NaOH solution and 5% HCl solution, the aging temperature was adjusted to 90 ℃, the aging time was 4h, and other reaction conditions were unchanged, to obtain an iron black pigment product using sodium bicarbonate as a precipitant. The color performance of the same kind of commercial products is tested by a color measuring instrument, the obtained color performance parameters are that delta L is-3.96, delta a is-0.17, delta b is 2.80, delta c is 1.10, delta H is 2.58, and the relative tinting strength is 104%.
Example 5
Ammonium carbonate is used as precipitant, and the molar weight of iron ions in reaction liquid and CO in the precipitant3 2-Example of molar ratio between molar amounts of 1:0.6
The amount of ammonium carbonate used as a precipitant in example 1 was adjusted to 2.57g, and other reaction conditions were not changed to obtain ammonium carbonate as a precipitant, and the molar amount of iron ions in the reaction solution and CO in the precipitant used were calculated3 2-Iron black pigment products having a molar ratio between molar amounts of 1:0.6 for example. The color performance of the same kind of commercial products is tested by a color measuring instrument, the obtained color performance parameters are that delta L is-2.93, delta a is-0.62, delta b is-0.01, delta c is 1.56, delta H is-0.02, and the relative tinting strength is 102%.
Example 6
Ammonium carbonate is used as precipitant, and the molar weight of iron ions in reaction liquid and CO in the precipitant3 2-Example of molar ratio between molar amounts of 1:0.8
The amount of ammonium carbonate used as a precipitant in example 1 was adjusted to 3.43g, and other reaction conditions were not changed to obtain ammonium carbonate as a precipitant, and the molar amount of iron ions in the reaction solution and CO in the precipitant used were calculated3 2-Iron black pigment products having a molar ratio between molar amounts of 1: 0.8. The color performance of the same kind of commercial products is tested by a color measuring instrument, the obtained color performance parameters are that delta L is-1.76, delta a is-0.37, delta b is 0.61, delta c is 1.68, delta H is 1.06, and the relative tinting strength is 106%.
Example 7
Ammonium carbonate is used as precipitant, and the molar weight of iron ions in reaction liquid and CO in the precipitant3 2-Example of molar ratio between molar amounts of 1:1.0
The amount of ammonium carbonate used as a precipitant in example 1 was adjusted to 4.29g, and other reaction conditions were not changed to obtain ammonium carbonate as a precipitant, and the molar amount of iron ions in the reaction solution and CO in the precipitant used were calculated3 2-Iron black pigment products having a molar ratio between molar amounts of 1: 1.0. The same kind of products sold in the market are taken as the standardThe product is tested for color performance by a color measuring instrument, and the obtained color performance parameters are that delta L is-1.57, delta a is-0.11, delta b is 2.24, delta c is 0.75, delta H is 2.12, and the relative tinting strength is 110%.
Example 8
Ammonium carbonate is used as precipitant, and the molar weight of iron ions in reaction liquid and CO in the precipitant3 2-Example of molar ratio between molar masses 1:1.2
The amount of ammonium carbonate used as a precipitant in example 1 was adjusted to 5.14g, and other reaction conditions were not changed to obtain ammonium carbonate as a precipitant, and the molar amount of iron ions in the reaction solution and CO in the precipitant used were calculated3 2-Iron black pigment products exemplified by a molar ratio between molar amounts of 1: 1.2. The color performance of the same kind of commercial products is tested by a color measuring instrument, the obtained color performance parameters are that delta L is-3.61, delta a is 0.41, delta b is 2.88, delta c is 1.76, delta H is 2.45, and the relative tinting strength is 106%.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.
Claims (4)
1. The method for preparing the iron oxide black pigment by using the steel pickling wastewater is characterized in that iron ions and external iron ions in the steel pickling wastewater are used as an iron source in a synergetic manner, and the iron source contains CO3 2-Or HCO3 -The inorganic salt is used as a precipitator to prepare the iron black pigment, and the method comprises the following steps:
(1) pretreatment of pickling wastewater: adding reduced iron powder into the pickling wastewater according to a solid-liquid ratio of 1: 400-1: 1000, carrying out ultrasonic dispersion treatment, adjusting the pH value to 5-6, and then adjusting the pH value to Zn in the pickling wastewater according to the solid-liquid ratio2+Adding Na into the mixture according to the molar ratio of 1:12S, pretreating, stirring and dispersing for 10min, carrying out suction filtration on the solution, taking filtrate and measuring Fe in the filtrate2+Molar content, denoted m1And adding Fe thereto2+Mole ofContent is m2FeSO of (2)4·7H2O, stirring and dissolving to obtain an iron-containing solution, pouring the iron-containing solution into a reactor, and stirring for later use;
(2) precipitation reaction: after the iron-containing solution obtained in the step (1) is heated to 60-80 ℃, weighing CO3 2-Or HCO3 -The molar content is m3Dissolving the inorganic salt in water, dropwise adding the inorganic salt into the iron-containing solution for 15-30min, adjusting the pH value to 6-9 after dropwise adding, and continuously stirring the solution for 10 min;
(3) aging reaction: continuing to heat the reaction liquid, aging and preserving heat for 2-4 hours at 85-95 ℃, then carrying out heat filtration on the reaction liquid, washing a filter cake with distilled water, drying at 90 ℃, and grinding to obtain the iron black pigment, wherein (m) is1+m2):m3＝1:(0.6～1.2)。
2. The method for preparing iron black pigment using steel pickling wastewater according to claim 1, wherein the inorganic salt is one or more of sodium carbonate, ammonium carbonate, sodium bicarbonate and ammonium bicarbonate.
3. The method for preparing iron black pigment by using steel pickling wastewater according to claim 1, wherein ammonia water is added in the step (1) to adjust the pH value to 5-6.
4. The method for preparing iron black pigment by using steel pickling wastewater according to claim 1, wherein in the step (1), a NaOH solution with a mass percentage concentration of 5% and a HCl solution with a mass percentage concentration of 5% are adopted to adjust the pH value of the reaction solution to 6-9.
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