CN109437629B - Composite waste tailing porous material and preparation method and application thereof - Google Patents
Composite waste tailing porous material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a composite waste tailing porous material and a preparation method and application thereof. The material is a spherical porous ceramsite material, the diameter of the material is 5-8 mm, and the porosity is 43% -52%; the raw material components by mass percentage are as follows: waste copper tailings: 58% -65%; waste iron tailings: 9% -18%; sodium bicarbonate: 4% -12%; water glass: 5% -10%; corn starch: 3-14% and activated carbon powder: 3 to 9 percent. The method uses waste copper tailings and iron tailings as main raw materials, calculates the material ratio required by target ceramsite, and uses water glass as a binder to prepare a porous carrier material which has certain mechanical strength and high porosity and can be repeatedly used for wastewater treatment through processing. The carrier material can be used for a catalyst for catalytic oxidation of ozone loaded with cyanide, and the highest degradation efficiency of the cyanide can reach 92.11%.
Description
Technical Field
The invention belongs to the fields of comprehensive utilization of mineral resources and sewage purification treatment, and particularly relates to a composite waste tailing porous material and a preparation method and application thereof.
Background
The industrial wastewater containing cyanide is called cyanide-containing wastewater, and the cyanide-containing wastewater mainly comes from metallurgical plants, fertilizer plants, coking plants, electroplating plants and the like. Cyanide belongs to a highly toxic substance, the emission concentration of the cyanide must be controlled according to national standards, if the cyanide cannot be properly treated, the efficient and stable operation of a biochemical treatment process is seriously influenced, and meanwhile, the cyanide also has great harm to the life of people and the natural environment. Generally, the cyanide-containing wastewater with high concentration is recycled, and the cyanide-containing wastewater with low concentration is subjected to oxidative destruction, such as ozone catalytic oxidation, hydrogen peroxide catalytic oxidation, photocatalytic oxidation, electrocatalytic oxidation, and photoelectrocatalytic oxidation.
The hydrogen peroxide is oxidizing, and the cyanide can be oxidized to cyanate CNO by the hydrogen peroxide under alkaline condition-The cyanate will then continue to hydrolyze into carbonic acid or bicarbonate. Since the reaction rate of hydrogen peroxide and cyanide is slow, a metal ion catalyst such as copper, cobalt, nickel, iron, etc. is added during the reaction process to accelerate the reaction rate. This reaction is known as catalytic hydrogen peroxide chemical oxidation. Ozone can react with a target substance in a direct and indirect way, wherein the indirect ozone oxidation reaction is a free radical type reaction, ozone is decomposed to form-OH free radicals, and the-OH free radicals can be combined with organic matters in a nonselective way. The catalysts for heterogeneous catalytic oxidation mainly comprise: MnO2、Al2O3、CeO/Al2O3、TiO2And MnO2Activated carbon, etc.
The application range of the metal copper and the metal iron is very wide, the demand of the metal copper and the metal iron is increased along with the development of global economy, and on the contrary, the mining amount of copper ores and iron ores is increased day by day in order to meet the demand of people on the metal copper and the steel. Therefore, a large amount of copper-selecting tailings and iron tailings are generated, the geological environment around the waste tailings is complex, geological disasters such as landslide and debris flow are easy to occur, and the destructiveness is great; in addition, the accumulation of the tailings causes serious pollution to the surrounding environment, and harmful substances are enriched in vegetation and enter a food chain in the biological world, so that the harmful substances continuously cause greater harm and are finally absorbed by human beings. The comprehensive recycling of the copper tailings and the iron tailings in China comprises the following steps: filling mines or reclaimed lands, being used as building material production raw materials, firing glass ceramics and firing ceramics. In addition, the novel research on the comprehensive utilization of the copper tailings also comprises the following steps: the recovery of metals such as copper, iron, zinc, bismuth and the like and non-metals such as sulfur and the like in the copper tailings is carried out by utilizing a microbial leaching technology; and (4) screening the copper-tailing-resistant sand-mold plants to realize the treatment of the copper-tailing-polluted soil and the restoration of the polluted plants. The novel research on the comprehensive utilization of the iron tailings comprises the following steps: can be used as soil conditioner, microelement fertilizer and reclamation vegetation in mining area.
The Chinese patent CN105693277A discloses a preparation method and application of an iron tailing porous material used as a microorganism ceramsite filter material, wherein the used raw materials are high-silicon iron tailings, clay, pore-forming agent and calcium carbonate, and because the content of the high-silicon iron tailings in the raw materials is higher, and SiO in the high-silicon iron tailings2The content is very high, so that the firing of the ceramsite needs higher sintering temperature, the prepared ceramsite cannot ensure higher utilization rate of the iron tailings and higher porosity, the content of the iron tailings is increased, and the porosity is inevitably greatly reduced; meanwhile, the content of Fe is low, and Fe is oxidized into Fe under the high temperature condition of 1100 DEG C2O3Therefore, the application of the method can only be spraying the bacteria liquid treated in the bacteria culture process to the ceramsite filter material to obtain the porous material used as the microbial ceramsite filter material, and the method has higher process requirement and consumes long time in the bacteria culture process. The Chinese invention patent CN108440013A discloses a ceramsite filter material for a biological aerated filter and a preparation method thereof, wherein the raw materials used in the ceramsite filter material are iron tailings, fly ash and a binder, the method also adopts high-silicon iron tailings, but the raw material proportion does not involve the addition of a cosolvent, so that the preparation method has larger energy consumption, and the method does not involve the utilization of waste copper tailings. The invention of China patent CN105669157A discloses a method for preparing ceramsite containing copper tailings for landscaping, which comprises the steps of mixing the pretreated copper tailings with raw materials such as sludge, red mud, coal gangue, fly ash, silica fume and alumina solution, molding, and performing steam curing treatment to finally prepare the target ceramsite.
Disclosure of Invention
The invention aims to provide a composite waste tailing porous material and a preparation method and application thereof aiming at the defects in the prior art. The method takes waste copper tailings and iron tailings as main raw materials, accurately calculates the material ratio required by target ceramsite, and takes water glass as a binder to prepare the porous carrier material which has certain mechanical strength, high porosity and can be repeatedly used for wastewater treatment through processing. The carrier material can be used for a catalyst for catalytic oxidation of ozone loaded with cyanide, and the highest degradation efficiency of the cyanide can reach 92.11%.
The technical scheme of the invention is as follows:
a composite porous material of waste tailings is a spherical porous ceramsite material, the diameter of the material is 5-8 mm, and the porosity is 43% -52%; the raw material components by mass percentage are as follows:
waste copper tailings: 58% -65%;
waste iron tailings: 9% -18%;
sodium bicarbonate: 4% -12%;
water glass: 5% -10%;
corn starch: 3% -14%;
activated carbon powder: 3 to 9 percent.
The waste copper tailings comprise the following main chemical components in percentage by mass: SiO 22：55.6％～60.3％，(Al2O3+Fe2O3)：15.7％～22.5％，Cu：0.04％～0.10％；
The waste iron tailings comprise the following main chemical components in percentage by mass: SiO 22：33.4％～38.7％；(Al2O3+Fe2O3)：13.6～14.9％；Fe：17.1％～18.5％。
The preparation method of the composite waste tailing porous material comprises the following steps:
(1) pretreatment of raw materials: ball-milling the dried copper tailings and iron tailings respectively, sieving the copper tailings and the iron tailings with a 200-mesh sieve, and taking undersize products to obtain copper tailing powder and iron tailing powder;
(2) preparing materials: respectively weighing waste copper tailing powder, waste iron tailing powder, calcium carbonate, corn starch and activated carbon powder according to the mass percentage;
(3) mixing materials: mixing the weighed raw materials, performing ball milling mixing for 20-40 min, then sieving by a 60-mesh sieve, and taking undersize materials as the raw materials after mixing.
(4) Molding: adding the water glass in the ratio into the mixed raw materials, mixing, and granulating by a pill rolling plate forming method; the particle size range is 5-8 mm;
(5) and (3) ageing and drying: standing and ageing the obtained ceramsite for 12-15 h at room temperature, and drying for 3-5 h at 100-110 ℃.
(6) Roasting: and (3) preheating the dried ceramsite in a sintering furnace at 150 ℃ for 30min, roasting at 900-1000 ℃ for 20-30 min, wherein the temperature rise rate of the sintering furnace is 10-15 ℃/min, and thus obtaining the porous material.
The composite waste tailing porous material is applied to a catalyst for loading catalytic oxidation of cyanide.
The application of the composite waste tailing porous material comprises the following steps:
dripping ethylene glycol aqueous solution into the mixed solution at room temperature under the ultrasonic condition to obtain TiO2Precursor solution; adding ceramsite into TiO2Immersing the precursor solution for 3-5 h under stirring, taking out the ceramsite, drying the ceramsite for 3-5 h at 90-100 ℃, taking out the ceramsite, and calcining the ceramsite for 1.5-2.5 h at 600-700 ℃ to obtain the ceramsite loaded with the catalyst for catalytic oxidation of cyanide;
wherein the mixed solution comprises butyl titanate, glycol and citric acid, and the molar ratio of the butyl titanate to the glycol is as follows: ethylene glycol: 4-5 of citric acid: 20-25: 5.5 to 6.5; in the ethylene glycol aqueous solution, the volume ratio is ethylene glycol: water 7: 5, adjusting ph to be 6-7 by using ammonia water; the volume ratio of the mixed solution to the ethylene glycol aqueous solution is 4-5: 1; the stirring speed is 50-100 rad/min.
The invention has the substantive characteristics that:
the waste copper tailings and iron tailings are used as main raw materials, water glass is used as a binder, and the porous carrier material which has certain mechanical strength and high porosity and can be repeatedly used and used for wastewater treatment is prepared by processing, and is characterized in that: the variety of the auxiliary agents is less; the proportion of silicon dioxide is lower, is 35.25 to 46.16 percent, the sintering temperature is low, and the method is energy-saving and environment-friendly; the raw material contains a small amount of copperThe simple substance and more iron simple substances are respectively mixed with CuO and FeO or Fe after being sintered3O4The copper ions and the ferrous ions have the catalytic action in the catalytic oxidation of cyanide, and the ceramsite is loaded with TiO2Copper ion, ferrous ion and TiO2The maximum degradation rate of cyanide can reach 92.11%, and the catalyst is a high-efficiency catalyst.
Advantageous effects of the invention
The invention has the beneficial effects that:
(1) the method is characterized in that waste copper tailings and iron tailings are used as main raw materials, a target ceramsite is prepared through the processing processes of raw material pretreatment, batching, mixing, forming and the like, titanium dioxide prepared by a sol-gel method is loaded on the surface of the ceramsite, the ceramsite loaded with a catalyst used for catalytic oxidation of cyanide can be obtained, the ceramsite is used for catalytic oxidation of the cyanide by ozone under an alkaline condition, and the cyanide breaking efficiency of the ceramsite is over 80%. Has the characteristics of wide raw material source, high availability, simple preparation process, easy recovery and the like.
(2) According to the results of mercury intrusion instrument tests and ceramsite SEM results, the prepared ceramsite has high porosity and a large number of communicated pores, the soaking method is used for obtaining that the ceramsite has high water absorption rate which can reach 10% at most, the soaking method and the fractal theory are combined for calculation to obtain that the ceramsite has high surface roughness, the characteristics enable the ceramsite to be capable of loading a target catalyst as much as possible, and the contact between the ceramsite loaded with the catalyst and target wastewater is wider and deeper, and the experiment results are as follows: the ceramsite after loading the catalyst is subjected to cyanide catalytic oxidation, and the highest degradation efficiency of cyanide can reach 92.11 percent, so the ceramsite is a good catalyst carrier.
Drawings
For the purpose of more clearly illustrating the objects, technical solutions and features of the present invention, the present invention will be described in further detail below with reference to the accompanying drawings.
FIG. 1 is a temperature rise curve for firing the ceramsite according to example 1
FIG. 2 is a 1000-fold SEM image of the ceramsite in example 2
FIG. 3 is a 4000-fold SEM image of the ceramsite in example 2
FIG. 4 is a graph of cyanide residual as a function of time as described in example 2
Detailed Description
The invention is further illustrated by the following specific examples:
the main components of the copper and iron tailings are as follows:
(1) the copper tailings mainly comprise the following chemical components in percentage by mass: SiO 22：55.6％～60.3％，(Al2O3+Fe2O3)：
15.7％～22.5％，Cu：0.04％～0.10％；
(2) The iron tailings mainly comprise the following chemical components in percentage by mass: SiO 22：33.4％～38.7％；(Al2O3+Fe2O3)：
13.6～14.9％；Fe：17.1％～18.5％；
Example 1
Ball-milling the dried copper tailings and iron tailings respectively, sieving the copper tailings and the iron tailings with a 200-mesh sieve, and taking undersize products to obtain copper tailing powder and iron tailing powder; weighing: 60g of waste copper tailing powder, 15g of waste iron tailing powder, 11g of calcium carbonate, 7.5g of corn starch and 7.5g of activated carbon powder. Mixing the weighed raw materials, performing ball milling and mixing, then sieving by a 60-mesh sieve, and taking undersize materials as the raw materials after mixing; measuring 8.5g of water glass as a binder, adding the mixed raw materials, uniformly mixing, and then molding and granulating by using a ball rolling plate to obtain particles with the particle size of 6 mm; the formed ceramsite is aged for 12 hours at room temperature, and then is put into an oven at 100 ℃ for drying for 3 hours; and (3) preheating the dried ceramsite raw material in a sintering furnace at 150 ℃ for 30min, and sintering at 1000 ℃ at the temperature rise rate of 10 ℃/min. The firing temperature-rising system of the ceramsite is shown in figure 1, after sintering, the ceramsite is cooled to about 150 ℃ in the air, and then the ceramsite is taken out of the furnace and is continuously cooled to room temperature.
After the test, the porosity of the obtained ceramsite clinker is 49% measured by a mercury porosimeter, the radial crushing force of the ceramsite clinker is 146.13N measured by an electronic universal tester, the water absorption of the ceramsite clinker is 8.7% measured by a soaking method, and the fractional dimension value of the ceramsite clinker is 2.65 (by the combined use of the soaking method and a fractal theory and calculation)The fractal value is a constant which is more than 1 and less than 3, theoretically, the larger the fractal value is, the higher the roughness is), and the ICP-AES analysis shows that: cu of ceramsite in water2+The elution amount was 0.01mg/L, Fe2+The amount eluted was 0.2 mg/L.
Example 2
Ball-milling the dried copper tailings and iron tailings respectively, sieving the copper tailings and the iron tailings with a 200-mesh sieve, and taking undersize products to obtain copper tailing powder and iron tailing powder; weighing: 65g of waste copper tailing powder, 10g of waste iron tailing powder, 11g of sodium bicarbonate, 11.25g of corn starch and 3.75g of activated carbon powder. Mixing the weighed raw materials, performing ball milling and mixing, then sieving by a 60-mesh sieve, and taking undersize materials as the raw materials after mixing; weighing 10g of water glass as a binder, adding the mixed raw materials, uniformly mixing, and then molding and granulating by using a ball rolling plate; the formed ceramsite is aged for 12 hours at room temperature, and then is put into an oven with the temperature of 100 ℃ for drying for 4 hours; and (3) preheating the dried ceramsite raw material in a sintering furnace at 150 ℃ for 30min, sintering at 1000 ℃, and obtaining the ceramsite clinker, wherein the heating rate of the sintering furnace is 10 ℃/min.
After the test, the porosity of the obtained ceramsite clinker is measured to be 53% by adopting a mercury intrusion instrument, the radial crushing force of the ceramsite clinker is measured to be 133.52N by adopting an electronic universal tester, the water absorption of the ceramsite clinker is measured to be 9.6% by adopting a soaking method, and the Cu of the ceramsite clinker in water is measured by adopting an ICP-AES method2+The elution amount was 0.01mg/L, Fe2+The amount eluted was 0.03 mg/L. The section SEM images of the obtained ceramsite are shown in figures 2 and 3, the aperture of the ceramsite is 5-60 mu m, macroscopic ultra-large pores with the aperture of more than 100 mu m are occasionally observed, the internal aperture of the ceramsite is developed, the number of connected pores is large, and the large pores are sleeved with small pores.
According to the molar ratio of butyl titanate: ethylene glycol: weighing butyl titanate (C) 4.3:23.2:5.816H36O4Ti, molecular weight 340.30)29.24 g; ethylene glycol ((CH)2OH)2Molecular weight 62.07)28.76 g; 22.27g of citric acid (C6H8O7, molecular weight 192.14) to prepare 55mL of a butyl titanate mixed solution; measuring 7mL of ethylene glycol and 5mL of deionized water, and dropwise adding ammonia water to adjust ph to 6-7 to obtain ethylene glycolDropwise adding the mixed solution of glycol and water into the mixed solution of butyl titanate at the speed of 1mL/min at room temperature under the condition of ultrasound to obtain TiO2Precursor solution; soaking the obtained ceramsite clinker in TiO2Stirring the precursor solution for 5h at a rotation speed of 80rad/min, taking out the ceramsite, drying the ceramsite in an oven at 100 ℃ for 4h, taking out the ceramsite, and calcining the ceramsite at 650 ℃ for 1.5h to obtain the supported catalyst TiO for catalytic oxidation of cyanide2The ceramsite is prepared.
This supported TiO2Placing the ceramsite into a conical flask of a prepared solution with the concentration of cyanide (potassium cyanide) being 7mg/L, controlling the pH value of the solution to be 9-10, and carrying out ozone catalytic oxidation. Ozone is introduced from the bottom of the conical flask, the concentration of the ozone is 45mg/L, waste gas is absorbed by a KI absorption bottle connected with the conical flask, the change of the residual cyanide content along with time is shown in figure 4, and the graph shows that after the reaction is carried out for 30min, the residual total cyanide concentration in the solution is measured by adopting a spectrophotometry method, and the cyanide removal rate reaches 82.67%; after the reaction is carried out for 60min, the cyanide removal rate reaches 88.36 percent; after the reaction is carried out for 90min, the cyanide removal rate reaches 91.11%, and at the moment, the total cyanide concentration in the solution is 0.62mg/L, which reaches the three-level discharge standard of class II pollutants specified in Integrated wastewater discharge Standard GB 8978-1996.
The invention is not the best known technology.
Claims (3)
1. A composite porous material of waste tailings is characterized in that the material is a spherical porous ceramsite material, the diameter of the material is 5-8 mm, and the porosity of the material is 43% -52%; the raw material components by mass percentage are as follows:
waste copper tailings: 58% -65%;
waste iron tailings: 9% -18%;
sodium bicarbonate: 4% -12%;
water glass: 5% -10%;
corn starch: 3% -14%;
activated carbon powder: 3% -9%;
the waste copper tailings comprise the following main chemical components in percentage by mass: SiO 22：55.6％～60.3％，(Al2O3+Fe2O3)：15.7％～22.5％，Cu：0.04％～0.10％；
The waste iron tailings comprise the following main chemical components in percentage by mass: SiO 22：33.4％～38.7％；(Al2O3+Fe2O3)：13.6～14.9％；Fe：17.1％～18.5％；
The preparation method of the composite waste tailing porous material comprises the following steps:
(1) pretreatment of raw materials: ball-milling the dried copper tailings and iron tailings respectively, sieving the copper tailings and the iron tailings with a 200-mesh sieve, and taking undersize products to obtain copper tailing powder and iron tailing powder;
(2) preparing materials: respectively weighing waste copper tailing powder, waste iron tailing powder, calcium carbonate, corn starch and activated carbon powder according to the mass percentage;
(3) mixing materials: ball-milling and mixing the weighed raw materials for 20-40 min, then sieving the raw materials by a 60-mesh sieve, and taking undersize materials as the mixed raw materials;
(4) molding: adding the water glass in the ratio into the mixed raw materials, mixing, and granulating by a pill rolling plate forming method; the particle size range is 5-8 mm;
(5) and (3) ageing and drying: standing and ageing the obtained ceramsite for 12-15 h at room temperature, and drying at 100-110 ℃ for 3-5 h;
(6) roasting: and (3) preheating the dried ceramsite in a sintering furnace at 150 ℃ for 30min, roasting at 900-1000 ℃ for 20-30 min, wherein the temperature rise rate of the sintering furnace is 10-15 ℃/min, and thus obtaining the porous material.
2. The use of the composite waste tailings porous material of claim 1, characterized by being used to support a catalyst for cyanide-catalyzed oxidation.
3. The use of the composite waste tailings porous material of claim 1, characterized by comprising the steps of:
under the conditions of room temperature and ultrasound, glycol water is addedDripping the solution into the mixed solution of butyl titanate to obtain TiO2Precursor solution; adding ceramsite into TiO2Dipping the precursor solution for 3-5 h under stirring, taking out the ceramsite, drying the ceramsite at 90-100 ℃ for 3-5 h, taking out the ceramsite, calcining the ceramsite at 600-700 ℃ for 1.5-2.5 h, and thus obtaining the ceramsite loaded with the catalyst for catalytic oxidation of cyanide;
wherein the mixed solution comprises butyl titanate, glycol and citric acid, and the molar ratio of the butyl titanate to the glycol is as follows: ethylene glycol: 4-5 of citric acid: 20-25: 5.5 to 6.5; in the ethylene glycol aqueous solution, the volume ratio is ethylene glycol: water 7: 5, adjusting the pH value to 6-7 by using ammonia water; the volume ratio of the mixed solution to the ethylene glycol aqueous solution is 4-5: 1; the stirring speed is 50-100 r/min.
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| CN111807814A (en) * | 2020-06-16 | 2020-10-23 | 日昌升建筑新材料设计研究院有限公司 | Process for preparing sintered heat-insulation building block from filter cake |
| CN112850858B (en) * | 2021-01-12 | 2023-04-07 | 山东中侨启迪环保装备有限公司 | A integrative electric ammonia nitrogen removal device for waste water treatment |
| CN115160015B (en) * | 2022-06-30 | 2023-09-29 | 武钢资源集团程潮矿业有限公司 | Low-silicon iron tailing high-strength ceramsite and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU657000A1 (en) * | 1977-10-20 | 1979-04-15 | Уральский научно-исследовательский и проектный институт строительных материалов | Raw mix for making light concrete |
| JPH06116057A (en) * | 1992-09-30 | 1994-04-26 | Ehime Pref Gov | Porous ceramic and its production |
| CN101747077A (en) * | 2009-12-30 | 2010-06-23 | 南京鑫翔新型建筑材料有限责任公司 | Sintered product of rejects and shale modular cellular bricks and preparing method thereof |
| CN103537272A (en) * | 2013-09-24 | 2014-01-29 | 苏磊 | Modified TiO2 loaded photocatalytic ceramsite and preparation method thereof |
| CN103980001A (en) * | 2014-05-19 | 2014-08-13 | 河北工业大学 | Porous ceramic material of iron tailings and preparation method thereof |
| CN105126760A (en) * | 2015-09-28 | 2015-12-09 | 福州大学 | Heavy metal poly-hole adsorption material and preparation method thereof |
-
2018
- 2018-12-03 CN CN201811465905.0A patent/CN109437629B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU657000A1 (en) * | 1977-10-20 | 1979-04-15 | Уральский научно-исследовательский и проектный институт строительных материалов | Raw mix for making light concrete |
| JPH06116057A (en) * | 1992-09-30 | 1994-04-26 | Ehime Pref Gov | Porous ceramic and its production |
| CN101747077A (en) * | 2009-12-30 | 2010-06-23 | 南京鑫翔新型建筑材料有限责任公司 | Sintered product of rejects and shale modular cellular bricks and preparing method thereof |
| CN103537272A (en) * | 2013-09-24 | 2014-01-29 | 苏磊 | Modified TiO2 loaded photocatalytic ceramsite and preparation method thereof |
| CN103980001A (en) * | 2014-05-19 | 2014-08-13 | 河北工业大学 | Porous ceramic material of iron tailings and preparation method thereof |
| CN105126760A (en) * | 2015-09-28 | 2015-12-09 | 福州大学 | Heavy metal poly-hole adsorption material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 尾矿回收的研究与应用;兰阳等;《2017 年中国非金属矿科技与市场交流大会》;20171231;第94-100页 * |
| 铜尾矿资源的利用现状及展望;张宏泉等;《现代矿业》;20171231(第1期);第127-131页 * |
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