CN115872433A - Method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid - Google Patents
Method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid Download PDFInfo
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Abstract
The invention is suitable for the field of waste acid recycling, and provides a method for producing a calcium chloride solution and an iron oxide black raw material from iron-containing waste hydrochloric acid, which comprises the following steps: slowly adding calcium oxide or calcium hydroxide powder into waste acid containing hydrochloric acid and ferrous chloride, and stirring at a high speed; until the pH value is 11-13; adding an initiator into the second step, and carrying out aeration oxidation on the reaction kettle by adopting a micro-nano aeration system, wherein the initiator is calcium hypochlorite; the reaction process detects whether the reaction end point is reached or not by sampling; after the reaction is finished, the materials are subjected to vacuum filtration to obtain a black Fe3O4 filter cake and a high-purity transparent calcium chloride liquid; black Fe 3 O 4 Drying the filter cake at 105 ℃, naturally cooling, and grinding to obtain the superfine nano Fe 3 O 4 And (3) powder. The air oxidation methodIs a gas, solid and liquid three-phase reaction, although the reaction mechanism and the process condition are more complicated, the colloid formation and the Fe can be effectively prevented as long as the pH value, the stirring speed and the aeration quantity are well controlled 3 O 4 And (4) agglomeration.
Description
Technical Field
The invention belongs to the field of waste acid recycling, and particularly relates to a method for producing a calcium chloride solution and an iron oxide black raw material from iron-containing waste hydrochloric acid.
Background
The steel needs to consume a large amount of hydrochloric acid for pickling before surface treatment such as hot galvanizing, electroplating, plastic spraying, electrophoresis and the like so as to remove the iron scale on the surface. For steel surface treatment enterprises, the waste acid discharged every day is up to hundreds of tons, and the waste acid contains hydrochloric acid and ferrous chloride with certain concentration, generally comprises 1-10% of free acid and 5-30% of ferrous chloride, and is accompanied with partial heavy metals and other impurities.
At present, the neutralization method is mostly adopted for treating the waste acid liquid in domestic factories. The method is simple, has low requirements on equipment, has low one-time investment but high operating cost, and has the fatal defects of generating a large amount of sludge and a large amount of waste water, ensuring that the COD (chemical oxygen demand) and heavy metal values of the waste water do not easily reach the national discharge standard, and generating secondary pollution. In recent ten years, the iron-containing hydrochloric acid wastewater is treated by an extraction method, a spray roasting method, a fluidized bed roasting method, an evaporation crystallization roasting method and a chlorine oxidation method to prepare polyferric chloride or polyferric chloride. The disadvantages of these methods are:
1. large equipment investment, high technical difficulty, complex process flow and large occupied area.
2. High requirements on fuel gas and high energy consumption, and if the fuel gas is improperly operated, leakage can occur, thereby causing serious consequences.
3. The salt concentrate and the iron oxide are liable to cause clogging and scarring in the equipment during the roasting process, and the salt concentrate and the iron oxide are liable to cause clogging and scarring in the equipment.
4. In the extraction process, iron and waste acid in the extraction waste liquid are continuously kept in the water phase, and the waste acid cannot be thickened in the treatment process, so that the volume is gradually increased.
5. The use of hydrogen peroxide solution as the oxidizing agent increases costs.
6. Hazardous chemicals such as sulfuric acid and other strong oxidizing reagents are required for the project, reduced pressure distillation is required, the energy consumption is high, the equipment investment of a distillation system is high, the equipment is easy to corrode, the recycled hydrochloric acid relates to production and management of the hazardous chemicals, the environmental protection and industry admission thresholds are high, and the product added value is low.
Disclosure of Invention
The embodiment of the invention aims to provide a method for producing a calcium chloride solution and a black iron oxide raw material from iron-containing waste hydrochloric acid, and aims to solve the problems of high cost and high difficulty of the conventional waste acid treatment.
The invention is realized in such a way that the method for producing the calcium chloride solution and the iron oxide black raw material from the iron-containing waste hydrochloric acid comprises the following steps:
step one, slowly adding calcium oxide or calcium hydroxide powder into waste acid containing hydrochloric acid and ferrous chloride, stirring at a high speed, and controlling the reaction temperature within 40 ℃;
step two, detecting the pH change in the reaction process in the step two until the pH does not fluctuate between acidity and alkalinity any more and the pH value is 11-13;
step three, adding an initiator into the step two, and carrying out aeration oxidation on the reaction kettle by adopting a micro-nano aeration system, wherein the initiator is calcium hypochlorite;
step four, detecting whether the reaction process reaches the reaction end point or not by sampling;
after the reaction is finished, performing vacuum filtration on the materials to obtain a black Fe3O4 filter cake and a high-purity transparent calcium chloride liquid;
step six, black Fe 3 O 4 Drying the filter cake at 105 ℃, naturally cooling, and grinding to obtain the superfine nano Fe 3 O 4 And (3) powder.
In a further technical scheme, the pH change in the second step is detected by a pH meter.
According to a further technical scheme, in the step one, iron powder is added before calcium oxide or calcium hydroxide powder is slowly added into waste acid.
According to a further technical scheme, in the third step, the materials are heated by using a heating device, and the reaction temperature is controlled to be 80 ℃.
According to a further technical scheme, the concrete steps of detecting whether the reaction end point is reached or not by sampling in the reaction process in the fourth step are as follows:
firstly, moving a sample to a sample tube and standing for 5 minutes;
b, if the water sample becomes clear and transparent, indicating that the reaction is finished, and pouring the sample tube product on white filter paper;
and c, drying the product on the white filter paper in an oven at 105 ℃ for 10 minutes, wherein the product is black and does not yellow, which indicates that the reaction is finished.
The method for producing the calcium chloride solution and the iron oxide black raw material from the iron-containing waste hydrochloric acid provided by the embodiment of the invention is a gas-solid-liquid three-phase reaction in the air oxidation method, and can effectively prevent colloid formation and Fe as long as the pH value, the stirring speed and the aeration quantity are controlled well although the reaction mechanism and the process conditions are relatively complex 3 O 4 And (4) agglomeration. The industrial production process adopts an automatic precise batch feeding control technology, so that the pH value, the stirring speed and the aeration quantity are conveniently controlled, the implementation of the technical scheme can realize controllable product appearance and complete crystal lattice development; the product purity is high; the process has the advantages of less energy consumption, less pollution and the like, and Fe 3 O 4 The product has the characteristics of superfine particles, good hydrophobicity, high filtering speed, less calcium chloride residue, easy drying and difficult moisture regain; meanwhile, the calcium chloride liquid has high purity (the iron ion content in the product is extremely low), and the product has wide application field.
One-step ultra-pure Fe separation method adopting micro-nano aeration oxidation 3 O 4 With calcium chloride solution, the whole production process does not use dangerous chemicals, fe 3 O 4 The product reaches the nanometer level, the calcium chloride solution has high purity, colorless and transparent appearance and low content of iron and heavy metals; the technology for treating the iron-containing hydrochloric acid waste liquid can change one waste acid into two products, namely ferroferric oxide and industrial calcium chloride, and the waste acid and the industrial calcium chloride both reach ferric oxideBlack pigment standard and industrial calcium chloride liquid standard; the method has the advantages of simple process, easy operation, low investment, wide application range, no organic solvent, good safety, no introduction of dangerous chemical raw materials, no product belonging to dangerous chemicals, and no secondary pollution in the production process; compared with the foreign spray roasting method, the method has the advantages of less equipment investment and low energy consumption. Compared with an extraction method (CN 8518552A and CN 1041742A), strong oxidation operation is not needed before extraction, expensive oxidant is saved, and an organic solvent is not used, so that the recovery cost is reduced.
Drawings
Fig. 1 is a schematic flow chart of a method for producing a calcium chloride solution and a black iron oxide raw material from iron-containing waste hydrochloric acid according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example one
A method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid comprises the following steps:
step one, slowly adding calcium hydroxide powder into waste acid containing hydrochloric acid and ferrous chloride, stirring at a high speed, and controlling the reaction temperature within 40 ℃;
step two, detecting the pH change in the reaction process in the step two until the pH value is not fluctuated between acidity and alkalinity any more, the pH value is 11-13, and detecting the pH change by adopting a pH instrument;
step three, adding an initiator into the step two, and carrying out aeration oxidation on the reaction kettle by adopting a micro-nano aeration system, wherein the initiator is calcium hypochlorite;
step four, detecting whether the reaction process reaches the reaction end point or not by sampling; the concrete steps of sampling and detecting whether the reaction end point is reached are as follows:
firstly, moving a sample to a sample tube and standing for 5 minutes;
b, if the water sample becomes clear and transparent, indicating that the reaction is finished, and pouring the sample tube product on white filter paper;
c, putting the product on the white filter paper into a drying oven at 105 ℃ for drying for 10 minutes, wherein the product is black and does not yellow, which indicates that the reaction is finished;
step five, after the reaction is finished, vacuum filtering the materials to obtain black Fe 3 O 4 Filter cake and high-purity transparent calcium chloride liquid;
step six, black Fe 3 O 4 Drying the filter cake at 105 ℃, naturally cooling, and grinding to obtain the superfine nano Fe 3 O 4 And (3) powder.
Example two
A method for producing a calcium chloride solution and a black iron oxide raw material from iron-containing waste hydrochloric acid comprises the following steps:
step one, slowly adding calcium oxide powder into waste acid containing hydrochloric acid and ferrous chloride, stirring at a high speed, and controlling the reaction temperature within 40 ℃;
step two, detecting the pH change in the reaction process in the step two until the pH value is not fluctuated between acidity and alkalinity any more, the pH value is 11-13, and detecting the pH change by adopting a pH instrument;
step three, adding an initiator into the step two, and carrying out aeration oxidation on the reaction kettle by adopting a micro-nano aeration system, wherein the initiator is calcium hypochlorite;
step four, detecting whether the reaction process reaches the reaction end point or not by sampling; the concrete steps of sampling and detecting whether the reaction end point is reached are as follows:
firstly, moving a sample to a sample tube and standing for 5 minutes;
b, if the water sample becomes clear and transparent, indicating that the reaction is finished, and pouring the sample tube product on white filter paper;
c, putting the product on the white filter paper into a drying oven at 105 ℃ for drying for 10 minutes, wherein the product is black and does not yellow, which indicates that the reaction is finished;
step five, after the reaction is finished, vacuum filtering the materials to obtain black Fe 3 O 4 Filter cake and high-purity transparent calcium chloride liquid;
step six, black Fe 3 O 4 Drying the filter cake at 105 ℃, naturally cooling, and grinding to obtain the superfine nano Fe 3 O 4 Powder;
heating the materials by using a heating device, and controlling the reaction temperature to be 80 ℃;
in the first step, iron powder is added before calcium oxide or calcium hydroxide powder is slowly added into the waste acid. The purpose of adding iron powder is to prevent premature oxidation of Fe2+ to Fe3+ in the system.
EXAMPLE III
A method for producing a calcium chloride solution and a black iron oxide raw material from iron-containing waste hydrochloric acid comprises the following steps:
firstly, adding iron powder into waste acid containing hydrochloric acid and ferrous chloride;
step two, stirring the solution obtained in the step one at a high speed, slowly adding calcium oxide powder, and controlling the reaction temperature within 40 ℃;
step three, detecting the pH change in the reaction process in the step two until the pH value is not fluctuated between acidity and alkalinity any more and is between 11 and 13;
fourthly, adjusting the pH value to 6-9 by using ferrous chloride;
fifthly, heating the materials by using a heating device, and controlling the reaction temperature to be 80 ℃;
step six, carrying out aeration oxidation on the reaction kettle by adopting a micro-nano aeration system;
step seven, detecting whether the reaction process reaches the reaction end point or not through sampling;
step eight, after the reaction is finished, vacuum filtering the materials to obtain black Fe 3 O 4 Filter cake and high-purity transparent calcium chloride liquid;
step nine, black Fe 3 O 4 Drying the filter cake at 105 ℃, naturally cooling, and grinding to obtain superfine nano Fe 3 O 4 Powder;
detecting the pH change in the third step by using a pH instrument;
the reaction process in the fourth step detects whether the reaction end point is reached or not by sampling, and the specific steps are as follows:
firstly, moving a sample to a sample tube and standing for 5 minutes;
b, if the water sample becomes clear and transparent, indicating that the reaction is finished, and pouring the sample tube product on white filter paper;
and c, drying the product on the white filter paper in an oven at 105 ℃ for 10 minutes, wherein the product is black and does not yellow, which indicates that the reaction is finished.
The purpose of adding iron powder in the first step and the second step and controlling the temperature at 40 ℃ is to prevent Fe < 2+ > in the system from being oxidized into Fe < 3+ > prematurely, and because the solubility of calcium oxide in water is low, the solubility is greatly enhanced only after the calcium oxide reacts with ferrous chloride free acid and is converted into calcium chloride, the process of the third step can effectively prevent the pH from showing false appearance, and can effectively prevent the formation of colloid and Fe in the subsequent oxidation process 3 O 4 And (5) agglomeration, wherein the oxygen content and oxygen retention time in the reaction system can be improved by micro-nano aeration in the sixth step, bubbles are prevented from rising rapidly, so that the oxidation contact time is reduced, and the suction filtration mother liquor in the eighth step is high-purity transparent calcium chloride liquid and can be directly canned for sale.
Example four
A method for producing a calcium chloride solution and a black iron oxide raw material from iron-containing waste hydrochloric acid comprises the following steps:
firstly, adding iron powder into waste acid containing hydrochloric acid and ferrous chloride;
step two, stirring the solution obtained in the step one at a high speed, slowly adding calcium hydroxide powder, and controlling the reaction temperature within 40 ℃;
step three, detecting the pH change in the reaction process in the step two until the pH value is not fluctuated between acidity and alkalinity any more and is between 11 and 13;
fourthly, adjusting the pH value to 6-9 by using ferrous chloride;
fifthly, heating the materials by using a heating device, and controlling the reaction temperature to be 80 ℃;
step six, carrying out aeration oxidation on the reaction kettle by adopting a micro-nano aeration system;
step seven, detecting whether the reaction process reaches the reaction end point or not by sampling;
step eight, after the reaction is finished, vacuum filtering the material to obtain black Fe 3 O 4 Filter cake and high-purity transparent calcium chloride liquid;
step nine, black Fe 3 O 4 Drying the filter cake at 105 ℃, naturally cooling, and grinding to obtain the superfine nano Fe 3 O 4 Powder;
detecting the pH change in the third step by using a pH instrument;
the reaction process in the fourth step detects whether the reaction end point is reached or not by sampling, and the specific steps are as follows:
a, moving a sample to a sample tube and standing for 5 minutes;
b, if the water sample becomes clear and transparent, indicating that the reaction is finished, and then pouring the sample tube product on white filter paper;
and c, drying the product on the white filter paper in an oven at 105 ℃ for 10 minutes, wherein the product is black and does not yellow, which indicates that the reaction is finished.
The purpose of adding iron powder in the first step and the second step and controlling the temperature at 40 ℃ is to prevent Fe < 2+ > in the system from being oxidized into Fe < 3+ > prematurely, and because the solubility of calcium oxide in water is low, the solubility is greatly enhanced only after the calcium oxide reacts with ferrous chloride free acid and is converted into calcium chloride, the process of the third step can effectively prevent the pH from showing false appearance, and can effectively prevent the formation of colloid and Fe in the subsequent oxidation process 3 O 4 And (4) agglomeration, wherein the oxygen content and oxygen retention time in the reaction system can be improved by micro-nano aeration in the sixth step, bubbles are prevented from rising rapidly, and the oxidation contact time is reduced, and the suction filtration mother liquor in the eighth step is high-purity transparent calcium chloride liquid and can be directly canned for sale.
The reaction equation involved in the reaction process is:
FeCl 2 +CaO+H 2 O＝Fe(OH) 2 ↓+CaCl 2
6Fe(OH) 2 +O 2 →2Fe 3 O 4 ↓+6H 2 O
the air oxidation method is a gas-solid-liquid three-phase reaction, although the reaction mechanism and the process conditions are complex, as long as the pH value, the stirring speed and the aeration quantity are well controlled, the formation of colloid and Fe can be effectively prevented 3 O 4 And (4) agglomeration. The problems can be effectively solved by adopting an automatic precise batch feeding control technology in the industrial production process, the implementation of the technical scheme can realize controllable product appearance and complete crystal lattice development; the product purity is high; the process has the advantages of less energy consumption, less pollution and the like, and Fe 3 O 4 The product has the characteristics of superfine particles, good hydrophobicity, high filtering speed, less calcium chloride residue, easy drying and difficult moisture regain; meanwhile, the calcium chloride liquid has high purity (the content of iron ions in the product is extremely low), and the product has wide application fields.
The invention provides a method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid, which is mainly technically characterized in that waste steel pickling solution containing ferrous chloride is added with calcium oxide or calcium hydroxide for neutralization, the pH value is adjusted, an initiator (calcium hypochlorite) is added, oxidation reaction is generated under the condition of introducing air, ferroferric oxide precipitate is formed, and after solid-liquid separation, ferroferric oxide solid and calcium chloride solution are formed. The process of the present invention is also applicable to other hydrochloric acid waste solutions containing metal ions of potassium (K +), sodium (Na +), calcium (Ca 2 +), magnesium (Mg 2 +), aluminum (Al 3 +), zinc (Zn 2 +), iron (Fe 2+, fe3 +), tin (Sn 2+, sn4 +), copper (Cu 2 +), chromium (Cr 3+, 6 +), manganese (Mn 2 +), titanium (Ti 4 +), nickel (Ni 2 +) and cobalt (Co 2+, co3 +). The content of free acid applicable to the invention is 1-10%, the content of ferrous chloride is 5-30%, and the concentration of other metal ions except iron in waste acid is 0-100 g/L.
And the application also has the following advantages:
1. turning the harm into the benefit, and changing waste into valuable; the method for treating the iron-containing hydrochloric acid waste liquid can change one waste acid into two products, namely ferroferric oxide and industrial calcium chloride, and both reach the standard of black iron oxide pigment and the standard of industrial calcium chloride liquid.
2. The method has the advantages of simple process, easy operation, low investment, wide application range, no organic solvent, good safety, no introduction of dangerous chemical raw materials, no product belonging to dangerous chemicals, and no secondary pollution in the production process.
Compared with the foreign spray roasting method, the method has the advantages of less equipment investment and low energy consumption. Compared with extraction methods (CN 8518552A and CN 1041742A), strong oxidation operation is not needed before extraction, expensive oxidant is saved, and organic solvent is not used, so that the recovery cost is reduced.
Through research, development, experiments and improvement for more than 2 years, the iron-containing waste acid is comprehensively utilized to produce two high-added-value industrial calcium chloride solutions and industrial iron oxide black raw materials, which respectively reach the standard of calcium chloride solution in the industrial calcium chloride (GB/T26520-2021) and the standard of iron oxide black pigment (HG/T2250-91).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid is characterized by comprising the following steps:
step one, slowly adding calcium oxide or calcium hydroxide powder into waste acid containing hydrochloric acid and ferrous chloride, stirring at a high speed, and controlling the reaction temperature within 40 ℃;
step two, detecting the pH change in the reaction process in the step two until the pH does not fluctuate between acidity and alkalinity any more and the pH value is 11-13;
step three, adding an initiator into the step two, and carrying out aeration oxidation on the reaction kettle by adopting a micro-nano aeration system, wherein the initiator is calcium hypochlorite;
step four, detecting whether the reaction process reaches the reaction end point or not by sampling;
step five, after the reaction is finished, the material is subjected to vacuum filtration to obtain black Fe 3 O 4 Filter cake and high-purity transparent calcium chloride liquid;
step six, black Fe 3 O 4 Drying the filter cake at 105 ℃, naturally cooling, and grinding to obtain the superfine nano Fe 3 O 4 And (3) powder.
2. The method for producing a calcium chloride solution and a black iron oxide raw material from an iron-containing waste hydrochloric acid according to claim 1, wherein the change in pH in the second step is detected using a pH meter.
3. The method for producing the calcium chloride solution and the black iron oxide raw material from the iron-containing waste hydrochloric acid as claimed in claim 1, wherein in the first step, the iron powder is added before the calcium oxide or calcium hydroxide powder is slowly added into the waste acid.
4. The method for producing the calcium chloride solution and the black iron oxide raw material from the iron-containing waste hydrochloric acid as claimed in claim 1, wherein the third step uses a temperature raising device to raise the temperature, and the reaction temperature is controlled to be 80 ℃.
5. The method for producing the calcium chloride solution and the black iron oxide raw material from the iron-containing waste hydrochloric acid according to claim 1, wherein the concrete steps of the reaction process in the fourth step of detecting whether the reaction endpoint is reached through sampling are as follows:
firstly, moving a sample to a sample tube and standing for 5 minutes;
b, if the water sample becomes clear and transparent, indicating that the reaction is finished, and pouring the sample tube product on white filter paper;
and c, putting the product on the white filter paper into a drying oven at 105 ℃ for drying for 10 minutes, wherein the product is black and does not turn yellow, which indicates that the reaction is finished.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386764A (en) * | 2014-11-20 | 2015-03-04 | 周淑华 | Method for producing iron oxide black by acid waste water in titanium-dioxide industry |
| CN109264790A (en) * | 2018-10-25 | 2019-01-25 | 时文玲 | A method of ferroso-ferric oxide and calcium chloride are prepared using pickle liquor |
| CN111252950A (en) * | 2020-03-04 | 2020-06-09 | 南京皓安环境监测有限公司 | Organic amine wastewater treatment process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386764A (en) * | 2014-11-20 | 2015-03-04 | 周淑华 | Method for producing iron oxide black by acid waste water in titanium-dioxide industry |
| CN109264790A (en) * | 2018-10-25 | 2019-01-25 | 时文玲 | A method of ferroso-ferric oxide and calcium chloride are prepared using pickle liquor |
| CN111252950A (en) * | 2020-03-04 | 2020-06-09 | 南京皓安环境监测有限公司 | Organic amine wastewater treatment process |
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