CN114522554A - Preparation and application of superfine suspended calcium hydroxide - Google Patents
Preparation and application of superfine suspended calcium hydroxide Download PDFInfo
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- CN114522554A CN114522554A CN202210153939.6A CN202210153939A CN114522554A CN 114522554 A CN114522554 A CN 114522554A CN 202210153939 A CN202210153939 A CN 202210153939A CN 114522554 A CN114522554 A CN 114522554A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/02—Lime
- C04B2/04—Slaking
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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
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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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
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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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a preparation method and application of superfine suspended calcium hydroxide. The superfine suspension calcium hydroxide prepared by the invention can be kept stable continuously, and the appearance does not change obviously within 4 weeks of standing. The treatment effect of the ultrafine suspended calcium hydroxide is superior to the indexes (total phosphorus, chromium, nickel, fluoride and the like) of the similar products sold in the market, so that the use amount of the medicament is saved, and the treatment cost of the acidic wastewater is reduced.
Description
Technical Field
The invention relates to the field of water treatment agents, in particular to preparation and application of ultrafine suspended calcium hydroxide products for treating phosphorus-containing wastewater, heavy metal-containing wastewater and fluorine-containing wastewater.
Background
Calcium-based compounds, e.g. quicklime (CaO as the main component) and slaked lime (Ca (OH) as the main component)2) And has many practical applications. For example, calcium-based compounds are used in coatings for architectural decoration, disinfection in medicine, treatment of drinking water, wastewater and sewage, removal of sulfur dioxide in power plants, and as neutralizing agents for acid soils, and as raw materials for chemical products.
In water treatment, lime is added in two ways, namely dry adding and wet adding. The dry feeding is to directly feed lime into the wastewater, the equipment is simple, but the reaction is slow and incomplete, and the feeding amount is 1.4 to 1.5 times of the theoretical value. The wet feeding is to decompose lime and prepare lime milk (5-10%) with a certain concentration, and then to feed the lime milk into wastewater through a dispenser, and the method has rapid reaction. However, in the digestion process, dust is more, the operation sanitary condition is poor, raw or over-burnt calcium oxide exists in the raw materials, the raw or over-burnt calcium oxide is not digested basically, and during use, the equipment is easily abraded, and the pipelines, the metering valve and the like are blocked and damaged, so that the normal operation of the sewage treatment equipment is seriously influenced.
In actual industrial production and application, in order to improve the convenience of use of such calcium-based compounds, quicklime or slaked lime is generally mixed with water to react to form an aqueous suspension, which is a fluid suspension of slaked lime. The resulting aqueous suspension is characterized by the following parameters: alkalinity content, viscosity of the suspension, and size distribution of the particles in the suspension. The size distribution of the particles in the suspension largely determines the reactivity of the suspension. The narrower the size distribution, the finer the particles and the higher the reactivity.
ZL201580036684.3 discloses a process for preparing a milk of very fine slaked lime, which adds water to quicklime instead of adding quicklime to water to obtain a lime slurry. However, this method is liable to cause the lime milk to stick to the bottom of the reactor during the actual production process, resulting in an in-situ homogeneous slurry.
In order to solve the problems of dust generated by the on-site preparation of lime emulsion and easy sedimentation of the prepared emulsion, the invention prepares the superfine suspended calcium hydroxide, and the superfine suspended calcium hydroxide prepared by the method has the characteristics of high activity, narrow particle size distribution, small particle size, strong suspension performance and low viscosity, and can be used for treating phosphorus-containing wastewater, heavy metal-containing wastewater and fluorine-containing wastewater.
Disclosure of Invention
The invention aims to provide a preparation method of an ultrafine suspended calcium hydroxide product and application of the ultrafine suspended calcium hydroxide product in phosphorus-containing wastewater, heavy metal-containing wastewater and fluorine-containing wastewater, so as to solve the problem of overlarge dosage caused by large particle size, low reaction activity and easy sedimentation of the existing lime products, and the ultrafine suspended calcium hydroxide product is used for treating the phosphorus-containing wastewater, the heavy metal-containing wastewater and the fluorine-containing wastewater, thereby reducing the dosage of a medicament for wastewater treatment and saving the operation cost of wastewater treatment.
The invention relates to a superfine suspension calcium hydroxide product, which is characterized in that: the superfine suspension calcium hydroxide is prepared by carrying out a digestion reaction on quicklime and water in a digester, adding an additive, removing slag and grinding. The superfine suspension calcium hydroxide can be used for efficiently removing phosphate radicals, heavy metals and fluorides in the acidic wastewater.
The diameter of the quicklime raw material is less than 5cm, preferably less than 3 cm; the total content of calcium oxide and magnesium oxide is more than 90 percent, the content of magnesium oxide is less than 5 percent, and the content of carbon dioxide is less than 4 percent; the pulp yield is more than 26dm 310 kg; the 0.2mm screen residue rate is less than 2 percent. SaidThe water is city tap water, and preferably deionized water. The adding proportion of water to quicklime is 3: 1 to 10: 1, the preferable adding proportion is 3.5: 1 to 6: 1.
the digestion reaction is two-stage digestion, the digestion time is 20-60min, and the preferable digestion time is 40-50 min; the digestion temperature is 65 to 90 ℃, preferably 70 to 80 ℃.
The deslagging process is two-stage rotary vibration sieve screening, the size of a first-stage sieve pore is 60 meshes, and the size of a second-stage sieve pore is 200 meshes. The residue is discharged through a residue extraction machine.
The additive is at least one of sodium pyrophosphate, sodium orthophosphate, sodium citrate, potassium citrate, sodium aluminate and sodium aluminosilicate; preferred are sodium pyrophosphate, sodium orthophosphate; sodium pyrophosphate is particularly preferred. The dosage of the additive is 0.01-3% of the content of the quicklime, and the optimized dosage is 0.03-0.1%.
The grinding process is a horizontal overflow type stirring ball mill, the grinding medium ball body is an alumina-based grinding ball, preferably an aluminum-zirconium composite ball, and the diameter of the grinding ball body is 1-5 mm. The grinding medium accounts for 20-50% of the grinding volume proportion, and the optimized proportion is 30-40%; the grinding time is 15-45min, and the optimized grinding time is 20-30 min.
The alkalinity of the superfine suspended calcium hydroxide is 20 to 30 percent, and the optimal alkalinity is 22 to 28 percent; particle size distribution D50 is less than 10um, with a preferred particle size distribution D50 being less than 6 um; at 60rpm, the viscosity is less than 1200 mPas, preferably less than 600 mPas.
The superfine suspended calcium hydroxide has the characteristics of high activity, narrow particle size distribution, small particle size, strong suspension performance and low viscosity, and can be used for treating phosphorus-containing wastewater, heavy metal-containing wastewater and fluorine-containing wastewater.
The invention has the beneficial effects that:
1. the invention prepares the superfine suspension calcium hydroxide through two-stage digestion reaction, additive addition, slag removal process and grinding process, the product has narrow particle size distribution, small particle size, strong suspension performance and low viscosity, and solves the problems of large particle size, low reaction activity and easy sedimentation of the traditional calcium-based product.
2. The ultrafine suspended calcium hydroxide can be used for removing total phosphorus, heavy metals and fluoride in sewage, and can realize automatic dosing through an automatic dosing system.
Drawings
FIG. 1 is a flow chart of the preparation process of the ultrafine suspension calcium hydroxide. In the figure, raw materials of quicklime and water are added into a digester for digestion, then slag is removed through a slag extractor, after slag is discharged, slurry is added with additives for grinding, and the ground slurry overflows into a finished product tank.
FIG. 2 is a graph showing the particle size distribution of sample A in example 1. The particle size distribution interval of sample A is between 0.7um and 25 um. Among them, the differential distribution of the particle size is most concentrated on 7 um. Sample a had a particle size distribution D50 of 5.3 um.
FIG. 3 is a graph showing the particle size distribution of sample B in example 2. The particle size distribution interval of sample B is between 0.1um and 100 um. Among them, the differential distribution of the particle size is most concentrated on 8 um. Sample B had a particle size distribution D50 of 7.8 um.
FIG. 4 is a graph showing the particle size distribution of sample C in example 3. The particle size distribution interval of sample C is between 0.1um and 90 um. Among them, the differential distribution of the particle size is most concentrated at 6 um. Sample C had a particle size distribution D50 of 5.7 um.
FIG. 5 is a graph showing the particle size distribution of the non-milled sample D obtained after digestion in the digester and deslagging in example (1). The particle size distribution interval of sample D was between 1um and 300 um. Among them, the differential distribution of the particle size is most concentrated at 80 um. Sample D had a particle size distribution D50 of 60.1 um. The particle size distribution diagram of the sample A, B, C, D in the embodiment can obviously show that the particle size of the sample which is not ground is larger, and the particle size of the material can be greatly reduced after the grinding process, so that the suspension of the material is facilitated.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example (1)
Sample a: as shown in the process flow diagram 1, in
2t of quicklime is added into the digester, the diameter of the quicklime is 3cm, the total content of calcium oxide and magnesium oxide is 93.1 percent, the content of carbon dioxide is 2.3 percent, and the content of magnesium oxide is 1.8 percent. Adding 10t of water for digestion, wherein the digestion time is 50min and the digestion temperature is 75 ℃. After digestion, two-stage rotary vibration deslagging is carried out, wherein the size of a first-stage sieve pore is 60 meshes, and the size of a second-stage sieve pore is 200 meshes. The residue is discharged through a residue extraction machine. Transferring the slurry into a stirring tank, adding 2kg of sodium orthophosphate, stirring for 20min, pumping the slurry into a horizontal overflow type stirring ball mill, wherein the grinding medium in the ball mill is aluminum-zirconium composite balls, the diameter of the grinding balls is 3mm, the grinding medium accounts for 30% of the volume of a grinding cavity, and the grinding time is 25 min. And after grinding is finished, overflowing into a finished product tank. The prepared ultrafine suspended calcium hydroxide was sample a.
Example (2)
Sample B: in that
2t of quicklime is added into the digester, the diameter of the quicklime is 3cm, the total content of calcium oxide and magnesium oxide is 93.1 percent, the content of carbon dioxide is 2.3 percent, and the content of magnesium oxide is 1.8 percent. Adding 12t of water for digestion, wherein the digestion time is 60min and the digestion temperature is 70 ℃. After digestion, two-stage rotary vibration deslagging is carried out, wherein the size of a first-stage sieve pore is 60 meshes, and the size of a second-stage sieve pore is 200 meshes. The residue is discharged through a residue extraction machine. Transferring the slurry into a stirring tank, adding 1.2kg of sodium pyrophosphate, stirring for 20min, pumping the slurry into a horizontal overflow type stirring ball mill, wherein a grinding medium in the ball mill is an aluminum-zirconium composite ball, the diameter of a grinding ball body is 3mm, the grinding medium accounts for 30% of the volume of a grinding cavity, and the grinding time is 35 min. And after grinding is finished, overflowing into a finished product tank.
The prepared ultrafine suspended calcium hydroxide was sample B.
Example (3)
Sample C: in that
1.5t of quicklime is added into the digester, the diameter of the quicklime is 3cm, the total content of calcium oxide and magnesium oxide is 93.1 percent, the content of carbon dioxide is 2.3 percent, and the content of magnesium oxide is 1.8 percent. Adding 10t of water for digestion, wherein the digestion time is 30min and the digestion temperature is 68 ℃. After digestion, two-stage rotary vibration deslagging is carried out, wherein the size of a first-stage sieve pore is 60 meshes, and the size of a second-stage sieve pore is 200 meshes. The residue is discharged through a residue extraction machine. Transferring the slurry to a stirring tank, adding 0.6kg of potassium citrate, stirring for 20min, pumping the slurry into a horizontal overflow type stirring ball mill, wherein the grinding medium in the ball mill is aluminum-zirconium composite balls, the diameter of the grinding balls is 3mm, the grinding medium accounts for 30% of the volume of a grinding cavity, and the grinding time is 45 min. And after grinding is finished, overflowing into a finished product tank. The prepared ultrafine suspended calcium hydroxide was sample C.
Example (4)
The A, B, C samples of examples (1), (2) and (3) and the unmilled D sample which had been digested by the digestor and had been removed from the slag were taken and put into a 1000mL measuring cylinder, respectively, and the suspension properties of calcium hydroxide after standing for 1 to 4 weeks were observed, and the suspension properties were expressed in terms of solid content (as shown in Table 1). Wherein the solid content ratio is solid volume/total volume is solid volume/(supernatant volume + solid volume). The viscosity of the sample was measured by a viscometer under the conditions of 60rpm, rotor No. 3, 25 ℃ and the viscosity of the sample A, B, C, D was 548, 496, 537, 916 mPas, respectively.
TABLE 1, examples (1), (2), (3) preparation of samples the suspension properties of calcium hydroxide after 4 weeks
After 4 weeks, sample A, B, C had a solids content of 94% or more, had good suspension properties, and was stable in storage.
Example (5)
The samples A, B, C of examples (1), (2) and (3) and the sample D of example (1) which was digested by a digester and then deslagged and not ground were taken, and the particle size distribution was measured by a laser particle sizer. FIGS. 2, 3, 4, and 5 correspond to particle size distribution plots for sample A, B, C, D, respectively. As is evident from the particle size distribution plots of sample A, B, C, D in the examples, sample D has a particle size D50 of 60um, while sample A, B, C has a particle size of less than 10 um.
Example (6)
Taking the sample A in the example (1) and the sample D which is digested by the digester and subjected to deslagging and then not ground in the example (1) to treat wastewater of a hardware electroplating plant in the city of Huizhou city, wherein the technical parameters of the wastewater comprise pH value, total phosphorus, chromium, nickel, fluorine ions and the like, and are specifically shown in Table 2. From the experimental results in table 2, the effect of sample a on treating wastewater is significantly better than that of sample D, which shows that the treatment effect of wastewater can be improved by the process.
TABLE 2 results of indexes of samples prepared in example (1) and other products after treatment of acid wastewater from electroplating plants
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made in the formulation and preparation process of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. An ultrafine suspended calcium hydroxide product, which is characterized in that: the superfine suspension calcium hydroxide is prepared by carrying out a digestion reaction on quicklime and water in a digester, adding an additive, removing slag and grinding; the superfine suspended calcium hydroxide can be used for efficiently removing phosphate radicals, heavy metals and fluorides in the acidic wastewater.
2. A quicklime material as claimed in claim 1 having a diameter of less than 5cm, preferably less than 3 cm; the total content of calcium oxide and magnesium oxide is more than 90 percent, the content of magnesium oxide is less than 5 percent, and the content of carbon dioxide is less than 4 percent; the pulp yield is more than 26dm310kg of a reaction product; the 0.2mm screen residue rate is less than 2 percent.
3. Water according to claim 1, being city tap water, preferably deionized water; the adding proportion of water to quicklime is 3: 1 to 10: 1, the preferable adding proportion is 3.5: 1 to 6: 1.
4. the ultra-fine suspended calcium hydroxide according to claim 1, wherein the digestion reaction is a two-stage digestion, the digestion time is 20-60min, preferably 40-50 min; the digestion temperature is 65 to 90 ℃, preferably 70 to 80 ℃.
5. The ultra-fine suspended calcium hydroxide as claimed in claim 1, wherein the deslagging process is two-stage rotary vibrating screen sizing, the first stage screen size is 60 mesh, the second stage screen size is 200 mesh; the residue is discharged through a residue extraction machine.
6. The additive of claim 1 being at least one of sodium pyrophosphate, sodium orthophosphate, sodium citrate, potassium citrate, sodium aluminate, sodium aluminosilicate; preferred are sodium pyrophosphate, sodium orthophosphate; particularly preferred is sodium pyrophosphate; the dosage of the additive is 0.01-3% of the content of the quicklime, and the optimized dosage is 0.03-0.1%.
7. The ultra-fine suspended calcium hydroxide as claimed in claim 1, wherein the grinding process is a horizontal overflow type stirred ball mill, the grinding medium balls are alumina-based grinding balls, preferably aluminum-zirconium composite balls, and the diameter of the grinding balls is 1-5 mm; the grinding medium accounts for 20-50% of the grinding volume proportion, and the optimized proportion is 30-40%; the grinding time is 15-45min, and the optimized grinding time is 20-30 min.
8. The ultrafine suspended calcium hydroxide according to claim 1, wherein the alkalinity of the ultrafine suspended calcium hydroxide is 20% to 30%, preferably 22% to 28%; particle size distribution D50 is less than 10um, with a preferred particle size distribution D50 being less than 6 um; the viscosity is less than 1200 mPas, preferably less than 600 mPas, under the test conditions of 60rpm, spindle No. 3.
9. The ultra-fine suspended calcium hydroxide of claim 1, which is used for removing total phosphorus, heavy metals and fluoride in sewage.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853368A (en) * | 2022-06-21 | 2022-08-05 | 安徽前江超细粉末科技有限公司 | Low-viscosity calcium hydroxide suspension and preparation method thereof |
| CN114956609A (en) * | 2022-06-21 | 2022-08-30 | 安徽前江超细粉末科技有限公司 | Low-cost calcium hydroxide suspension and preparation method thereof |
| CN114956608A (en) * | 2022-06-21 | 2022-08-30 | 安徽前江超细粉末科技有限公司 | Low-viscosity and low-cost calcium hydroxide suspension and preparation method thereof |
| CN115108738A (en) * | 2022-06-21 | 2022-09-27 | 安徽前江超细粉末科技有限公司 | Calcium hydroxide suspension and preparation method thereof |
-
2022
- 2022-02-20 CN CN202210153939.6A patent/CN114522554A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853368A (en) * | 2022-06-21 | 2022-08-05 | 安徽前江超细粉末科技有限公司 | Low-viscosity calcium hydroxide suspension and preparation method thereof |
| CN114956609A (en) * | 2022-06-21 | 2022-08-30 | 安徽前江超细粉末科技有限公司 | Low-cost calcium hydroxide suspension and preparation method thereof |
| CN114956608A (en) * | 2022-06-21 | 2022-08-30 | 安徽前江超细粉末科技有限公司 | Low-viscosity and low-cost calcium hydroxide suspension and preparation method thereof |
| CN115108738A (en) * | 2022-06-21 | 2022-09-27 | 安徽前江超细粉末科技有限公司 | Calcium hydroxide suspension and preparation method thereof |
| CN114956608B (en) * | 2022-06-21 | 2023-04-21 | 安徽前江超细粉末科技有限公司 | Low-viscosity low-cost calcium hydroxide suspension and preparation method thereof |
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