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Adsorption Study of phosphorus in water by CeramicPan Zeyou(College of Chemistry and Chemical Engineering, Dezhou University,Dezhou 253023, P. R. of China)Abstract:The adsorption of phosphate in water was studied by using ceramsites. The effect of the initial concentration of phosphate in the water, pH value, oscillating time, dosage of ceramsites and particle size of ceramsites on the removal of phosphate was investigated. The experimental results showed that: when the pH of wastewater containing phosphate was 4, dosage of ceramsites was 2.0 g/100 mL, particle size of ceramsites was more than 0.9 mm, oscillation time was 10 min, adsorption removal rate of ceramsites was the highest (reached 88%).Keywords: ceramsites; adsorption; phosphateIntroductionEutrophication in waterGrowing problem of eutrophication in China and widely valued by many ecologists. Eutrophication easily leads to reduced water clarity, so that sunlight cannot reach the bottom, further hampering photosynthesis in aquatic plants, lowering the volume of dissolved oxygen in the water, causing mass deaths of fish, so as to block and break the water features and the stability of ecosystems. Meanwhile, for the utilization of water resources in the community, such as aquaculture, water, tourism, and water brought huge economic losses [1]. According to the 2013 China environmental situation bulletin, in 2013, severe pollution, water quality pollution, light pollution and excellent major lakes (reservoirs) ratio was 11.5%, 1.6%, 26.2% and 60.7%, poor nutrition, the nutrients and eutrophication in Lake (reservoir) was 14.8% and 57.4% and 27.8%, respectively. Among them, moderate eutrophication of Dianchi Lake, Taihu Lake and chaohu Lake is mild eutrophication. Therefore, treatment remediation of contaminated water into the construction of ecological environment and the urgent need for social progress, looking for cheaper and effective technology is around the corner.Common of eutrophication control techniquesIn recent years, as the impact of human activity, and inorganic nutrients such as nand p, and so on, into velocity shallow bodies of water such as rivers, lakes, caused by rapid proliferation of algae and water hyacinth, rapidly reducing the amount of dissolved oxygen in the water, declining water quality, fish, shrimp and other creatures most deaths caused, as well as water and the red tide phenomenon. By causing eutrophication of n and p are difficult to remove, and p is the cause of most water bodies eutrophication main-control factors. Therefore, removal of phosphate as first choice for harnessing eutrophication problems [2]. At present, the main methods of phosphorus removal of biological phosphorus removal, adsorption and chemical removal of phosphorus removal.Biological phosphorus removalBiological method except p principle can is divided into two species: first species is to poly p bacteria (PAOs) mainly of microbial biological except p technology, using PAOs can from bacteria body external environment in the absorption over its physiological by needs of p volume, and through aggregate will its storage in bacteria body, formed containing p volume super high of sludge, effective of will p from wastewater in the transfer to sludge in the, through discharge sludge, to reached reduced wastewater in the p concentration. In anaerobic environments, the phosphate accumulating organisms by decomposing the phosphorus in the body release energy, in which part of the energy is used to absorb fatty acid soluble, formation of intracellular c energy storage (PHB), and phosphate. In aerobic environments, PAOs revitalization of PHB produced from the decomposition of energy, part of the energy for the active p in excessive absorption of water, by means of Polyphosphate, p removed from the wastewater. In a suitable environment, in the process of removing waste 91% P[4]. Second is dominated by denitrifying phosphorus removal bacteria microbial phosphorus removal technology. Anaerobic denitrification phosphorus removal bacteria by polymers dissolved organic carbon into molecules of volatile organic acids, this organic acid intake to intracellular storage within cells in the form of carbon storage, and intracellular hydrolysis of Polyphosphate, phosphorus released into the water to get the energy you need. In hypoxia, the intracellular Polyphosphate bodies of carbon storage as a carbon source, energy, electron acceptors nitrate ion, excessive absorption of p from wastewater, and thus achieve the purpose of denitrifying p.Rapid development of biological phosphorus removal from in the 1970 of the 20th century, due to which the full use of existing facilities for wastewater treatment, can also remove organic matter, low running costs, many researchers agree [6]. However, the disadvantage of biological method is: the BOD of water is too high, p concentrations higher than 10 mg/l, or organic matter concentrations below the minimum range, p concentrations of effluent to meet emissions requirements, which often requires removal once again approach to water.Chemical phosphorus removalChemical removal of phosphorus is added to the water by iron, aluminum salts and other chemical phosphorus removal agents will convert p solubility in water insolublesolid state p, by flocculation besides p, in order to achieve the purpose of reducing phosphorus concentration in the water. Common chemical removal of phosphorus and reagents are mainly aluminum salts, lime and ferric salts, [8]. According to the running process of adding phosphorus removal at different stages, and can be divided into front-precipitation, rear-mounted synergistic precipitation and precipitation. Chemical removal of phosphorus is the most commonly used technology to manipulate simple p high removal rate, reaching 81%-91% p removal rate and applicable conditions of low, difficult to produce secondary pollution, wide application range. But the disadvantage is: high cost of treatment, dose, and vulnerable to a large number of chemical sludge, handling difficult.Adsorption and phosphorusPhosphorus in waste water mainly to organophosphorus compounds, PO43-, HPO42-, P2O74-and P3O105-and other forms exist. Daily waste water, generally 4-16 mg/l total phosphorus content in the original daily waste water, proportion of p can be divided into: P2O74--1 mg/L, P3O105--3 mg/L, PO43-, HPO42-, such as 5 mg/l and organic phosphorus is 1 mg/l. Because phosphate can be hydrolyzed under acidic conditions such as PO43-, HPO42-, and therefore in the process of adsorption phosphorus, focus on PO43-, HPO42-.Phosphorus adsorption method is the use of adsorbent surface polar group and metal ions, high porosity and large specific surface area from the high efficiency and low consumption technology of low concentration solution in addition to the p. Adsorbent selected were required to meet the following: (1) raw materials readily available and inexpensive, (2) regeneration of adsorbent for easy, stable performance, (3) no harmful substance; (4) the strong anti-jamming ability of other ions (5) fast response (6) on the adsorbent is selective and (7) adsorption. Currently used for wastewater containing phosphorus adsorbents can be classified as non-clay and clay. Non-clay mainly synthetic materials, such as building materials, such as fly ash and slag [11], clay consists of silicates and non-silicate.ExperimentLab equipment and raw materialsExperimental equipmentPh meter ( pHS-25, Shanghai Precision Scientific Instruments Ltd ) ;Bench - type centrifuge ( TGL-16GB, Shanghai Anting Scientific Instrument Factory ) ;UV - Vis spectrophotometer ( 752, Shanghai Scientific Instrument Company ) ; Speed oscillator ( HY-4, ronghua geraetebau Gmbh in Jintan City, Jiangsu Province ) ; Electronic analytical balance ( AL204, mettler - toledo instruments Shanghai ) ; Beaker ( 1 L, 500 ML ), moving fluid tubes, graduated cylinder ( 5 ML ), the colorimetric Tube ( 50 ML ), ear syringe, glass rod and cone - shaped bottle, plastic head the eyedropper, capacity bottle of experimental conventional instruments. Experimental material(1) Pottery grain, experimental with ceramic for Texas college north campus building garbage, with Hammer knock on broken, with TO Ion Water repeatedly washing three times, filter, with oven drying, grinding to grain diameter $literal 20 accounts ( Aperture $literal 0.9 mm ), and 20-40 accounts ( aperture for 0.45-0.9 mm ), and 40-60 accounts ( aperture for 0.3-0.45 mm ), and 60-80 accounts ( aperture for 0.2-0.3 mm ), and less than 80 accounts ( Aperture less than 0.2 mm ) alternate.(2) Potassium persulfate, 50 g/L solution. Take 5 g of Potassium Sulphate ( K2S2O8, analytical grade ) in the Beaker, add deionized water, dissolved, and moved to 100 ML volumetric flask, add water, dilute to the mark.(3) Ascorbic acid, 100 g/L solution. Take 10 g of ascorbic acid (C6H8O6, analytical grade) in the Beaker, mixed with deionized water dissolves in 100 ML volumetric flask and dilute with water to them.This solution needs to be stored in brown color reagent bottle can be stored in a cool place for a month.(4) Molybdate solution. Get 13 g of ammonium molybdate ( ( nh4 ) 2moo4, analysis of the pure ) in 100 ml of deionized water, stir to dissolve.Also 100 ml of deionized water dissolves 0.36 G potassium antimonyl tartrate ( k2sb2 ( c4h2o6 ) 2, analysis of the pure ).By continuously stirring of ( nh4 ) 2moo4 solution slowly added to the 300 mlh2so4 ( 1:1 ), and then join k2sb2 ( c4h2o6 ) 2 solution, with a glass rod churns. (5) Phosphorus standard stock solution. Weigh ( 0.2197 v 0.001 ) g of potassium dihydrogen phosphate ( kh2po4, analysis of the pure ), after mixing with water dissolved in the transfer to 1000 ML volumetric flask, and then joined About 800 ml water, and then slowly add 5 ML h2so4 ( 1:1 ), dilute to the mark with water and mixing.50 / g of phosphorus - containing 1.00 ml of the standard solution.(6) The standard use of phosphorus liquid. Get 10 ML standard reserves of phosphorus in liquid transfer to 250 ML volumetric flask, dilute to the mark with water, into a stopper and shake uniform.2 / g of phosphorus - containing 1.00 ml of the standard solution. Using the same day match on that day.( 7 ) sulphuric acid, 1:1.( 8 ) sodium hydroxide ,1 MOL / l solution.( 9 ) hydrochloric acid, 1 MOL / l solution.The experimental processDrawing standard curves of phosphorusPhosphorus standard curve as shown in figure 2-1Figure 2-1 the standard curveTake 7 scale brace tube, add 0, 0.5, 1.0, 3.0 and 5.0, respectively, 10.0, 15.0 ML of standard solution of phosphates.Added 1.0 mL10 C6H8O6 solution, shake, after 30 S joining 2.0 ML ( NH4 ) 2MoO solution, shake, static 15 Min.At 700 nm wavelength, determination of phosphorus by 30 mm telflon absorbance of the standard solution ( in deionized water as the blank Reference ), and calculates the corresponding phosphorus content and drawing work curve.Adsorption effect of time on phosphorus removal in waterTake a certain volume of phosphorus standard stock solution, add simulation of water diluted into 1 mg/l initial concentration of phosphorus wastewater, each 25 ML, respectively, in the Sung in the 7 cone - shaped bottle.Join 0.2 G ceramsite in the conical flask ( 80 WS ), in oscillator at a certain speed, oscillation, respectively 0, 5, 10, 15, 30, 45, 60 Min, and then in bench - type centrifuge at 2000 r/min speed centrifugal 10 Min, with ammonium molybdate Spectrophotometric Method for the determination of the supernatant solution absorption spectrophotometry after processing, the record data.Ceramic particle size effects on phosphorus removal in waterTake a certain volume of phosphorus standard stock solution, add simulation of water diluted into 1 mg/l initial concentration of phosphorus wastewater, each 25 ML, respectively, in the Sung in the 4 cone - shaped bottle.Join 0.2 G in the conical flask size of more than 20, 20-40, 40-60, is 80 the purpose of ceramsite, in oscillator Oscillation 10 Min ( An Experiment on of the best values ), centrifugal 10 Min, with ammonium molybdate Spectrophotometric Method for the determination of the supernatant solution absorption spectrophotometry after processing, the record data. Ceramic dosage effects on phosphorus removal in waterTake a volume of phosphorus standard stock solution, diluted with water intoa simu lation of the initial concentration of 1 mg/l phosphorus effluent,take 25 mL separately into 8 an Erlenmeyer flask. In tapered bottle in the the joined 0.05, and 0.10, and 0.20, and 0.40, and 0.60, and 1.00, and 1.50, and 2.00 g pottery grain (≥ 20 accounts, last experiment obtained of best value), in oscillation device Shang to must of speed oscillation 10 min, then in desktop centrifugal machine Shang centrifugal 10 min, with MO acid ammonium points light photometric method determination processing Hou solution Shang clear liquid of sucking photometric, records data.Effect of pH on Removal of phosphorus in the waterTake a certain volume of phosphorus standard stock solution, add simulation of water diluted into 1 mg/l initial concentration of phosphorus wastewater, each 25 ML, respectively, in the Sung in the 6 cone - shaped bottle.In the cone - shaped bottle of joining 0.2 G ( An Experiment on the optimum value ), ceramic ( more than 20 mesh ), adjust PH to 2, 4, 6, 8, 10, 12, in oscillator Oscillation 10 Min respectively, and then to 2000 r/min centrifugal 10 Min, with ammonium molybdate Spectrophotometric Method for the determination of the supernatant solution absorption spectrophotometry after processing, the record data.Initial solution concentration of phosphorus removal efficiency ofphosphorus in water impactTake a volume of phosphorus standard stock solution, add water, diluted to 0.5, 1.0,1.5,2.0, 2.5,3.0 mg/l simulated phosphorus wastewater, take 25 mL, Sung in 6 an Erlenmeyer flask. Add 0.2 g of ceramsite in an Erlenmeyer flask (≥ 20), certain speed difference in the oscillator oscillate 10 min, then centrifuge 10 min on the bench-top centrifuges, with on ammonium molybdate Spectrophotometric method for the determination of the absorbance of the solution, the record data.After the experiment according to the following formula to calculate the removal rate:%100A 00⨯-=A A n (1) In the last: A0 to simulate the initial absorbance of phosphorus waste water;A is the absorbance of the solution after the treatment.Analysis of resultsEffect of removal efficiency of phosphorus in water absorption timeEffect of removal efficiency of phosphorus in water adsorption time is shown in table 3-1 and 3-1. Table 3-1 and 3-1 aggregate absorption rate with the extension of reaction time, is getting bigger. As the time approaches when 10 min, maximum adsorption rate of ceramic, which is due to increase over time, absorption close to saturation point, adsorption rate was 72%. Initially adsorbed faster is because most of the phosphorus adsorption on ceramic surfaces, over time, to reduce phosphorus concentration in the water, phosphorus needed by entering the aggregate voids can be adsorbed. As time grew, phosphorus removal rate, effect of ceramisite adsorption weakened [12]. This may be due to certain elements replace the phosphorus out of the solution, causing the phosphorus desorption behavior occurs, resulting in the removal effect of ceramisite reduced. By 3-1 know that reaction time should be 10 min.Table 3-1 time influence on removal efficiency of phosphorus in water吸附时间（min ）0 5 10 15 30 45 60 吸光度0.050 0.015 0.014 0.016 0.018 0.030 0.041 去除率（%） 070 72 68 64 40 18Figure 3-1 time influence on removal efficiency of phosphorus in waterAggregate effect of particle size on removal efficiency of phosphorus in waterCeramic particle removal efficiency of phosphorus in water, as illustrated in table 3-2 and 3-2. Tables 3-2 and 3-2 can be seen when ceramic particle diameter ≥ 20 meshes, and maximum removal rate at 90%. When the ceramic particle size becomes small, and phosphorus removal rate decreases, the adsorption effect of ceramisite gradually weakened. When ceramic particle ≤ 80 accounts, ceramic on phosphorus adsorption rate is 74%. Pottery grain size on p of removal effect of effect main performance in two a level: a, and pottery grain is more hole sex solid particles, dang pottery grain grain diameter variable small Hou, easy makes pottery grain of hole-like structure was damage; II, and grain diameter variable small helps enhanced p in pottery grain in the of diffusion speed, while increases pottery grain surface of than surface area [13]. When the ceramic particles smaller than 20 head, ceramic-like structure on the adsorption effect of significantly larger than the surface area increased and faster diffusion of phosphorus on adsorption effect of ceramisite and behaves as shown in Figure 3-2 removal rate and slow down. Therefore, the aggregate best ≥ 20 mesh particle size.Table 3-2 ceramic particle size effect on the removal efficiency of phosphorus inwater粒径（mm ）≥0.9 0.45-0.9 0.3-0.45 ≤0.2 吸光度0.005 0.006 0.01 0.013 去除率（%） 90 88 80 74Figure 3-2 aggregate effect of particle size on removal efficiency of phosphorus inwaterCeramic dosage effect of removal efficiency of phosphorus in waterCeramic dosage on removal efficiency of phosphorus in water, as illustratedintable 3-3 and 3-3. Table 3-3 and 3-3 phosphorus removal rate gradually increases with the quantity of ceramic, increasing the dosage of ceramic to improve phosphorus removal effect. When the aggregate dosing quantity close to 0.5 g, and effect of ceramisite on phosphate adsorption stabilized, balance. Thus, we know that aggregate maximum adsorption adsorption capacity exists, when the maximum adsorption capacity is exceeded, ceramic can no longer adsorbed phosphate. This may be due to residual phosphorus concentration in solution is too low, hindered the process of phosphorus in ceramic transfer, impact absorption, so there will be ceramic particle removal rate is no longer rising phenomenon [14].Table 3-3 ceramsite dosage effect of removal efficiency of phosphorus in water 陶粒投加量（g ）0.05 0.1 0.2 0.4 0.6 1 1.5 吸光度0.02 0.01 0.008 0.007 0.007 0.012 0.011 去除率（%） 60 80 84 86 86 82 78Figure 3-3 ceramsite dosage effect of removal efficiency of phosphorus in water Effect of pH on removal efficiency of phosphorus in waterThe pH of the solution are important factors influencing the effect of ceramisite on phosphorus adsorption, phosphorus forms in solution, ceramic chemistry properties and property solutions has a great influence, and ceramic and phosphorus interaction between changes. Effect of pH on removal efficiency of phosphorus in water as shown in table 3-4 and 3-4. By the tables 3-4 and 3-4 can be seen, when the pH in the range of 2 to 4, aggregate absorption rate increasing, at the time of pH=4, effect of ceramisite on phosphate adsorption maximum removal rate is 70%. When you pH>4, effect of ceramisite on phosphate adsorption begin to weakens. This is caused by surface chemical properties of ceramic. When the solution pH<4, and ceramic surface adsorption of h + in solution, positively when solution when pH>4, aggregate absorption of Oh-in solution, a negative charge, and distances itself from pH=4, charge more for ceramic surfaces. However, the root itself negatively charged phosphate, reacts easily with H+ phosphate in acid conditions, so when pH<4, and phosphate content, increase the phosphorus adsorption capacity of ceramsite.Whenyou pH>4, ceramic adsorption OH – first, negatively charged and repulsion with the phosphate, ceramic reduced adsorption of phosphate from [15].Table 3-4 effects of pH on removal efficiency of phosphorus in waterpH2 4 6 8 10 12 吸光度0.019 0.016 0.019 0.023 0.027 0.031 去除率（%） 62 68 62 54 46 38Figure 3-4 effects of pH on removal efficiency of phosphorus in waterInitial solution concentration of phosphorus removal efficiency of phosphorus in water impactInitial solution concentration of phosphorus removal efficiency of phosphorus in water, as illustrated in table 3-5 and 3-5. The tables 3-5 and 3-5 showed that, when a simulating when ever-larger initial concentrations of phosphorus wastewater phosphorus removal efficiency increased. When the solution when the initial concentration of 2 mg/l phosphorus in phosphorus removal rate was 80%. Along with the phosphorus concentrations increased when, ceramic no longer phosphorus adsorption, phosphorus removal rate is no longer rising [16].Table 3-5 p solution influence of initial concentration on the removal efficiency ofphosphorus in water磷初始浓度（mg/L ）0.5 1 1.5 2 2.5 吸光度0.013 0.008 0.007 0.009 0.006 去除率（%） 74 84 86 8888Figure 3-5 phosphate solution influence of initial concentration on the removalefficiency of phosphorus in waterConclusionThrough these experiments, we know that in room temperature conditions, pH=4, dosage is 0.5 g of ceramic, ceramic particle diameter ≥ 20 mesh, reaction time is at 10 min, phosphorus removal, the best, and can be used to treat low concentrations of phosphorus waste water or as a filler in constructed wetlands. Because of the shards as a construction material everywhere, we can conduct resource recycling, low cost, easy to get, so ceramic in a certain prospect of phosphorus-containing wastewater. ProspectDue to absorption of phosphorus removal performance of high efficiency and low consumption, on phosphorus waste water treatment process. Have a significant effect, by ecologists and environmentalists are widely studied and discussed. Preparation of adsorbents using waste, can reach the waste and sludge reduction purposes, in line with the ecological requirements of green economic development, but also have a wide source of resources and advantages of adsorption effect in the future application of phosphorus removal in wastewater treatment by adsorption of an important direction [17].AcknowledgeMy thesis is my Advisor Wang Aili teacher's loving care and under the guidance of. Her no-nonsense attitude, spirit of strict educational standards, improving work style, deeply and inspired me. From subject selection to final completion after nearly three months of time, Mr Wang has always given me guidance and constant support, Wang expressed sincere gratitude and deep respect.Thank Mr Wang in the midst of our life and writing process of care and encouragement, thank my classmates doing experiments and writing papers for my help and support, also, special thanks to other teachers in the experimental medicine and equipment provide a lot of help.For Chemistry and chemical engineering leadership for spiritual encouragement and support as well as material provided, for all concerned, teachers and students have helped me. I wish them peace, happiness and health!Finally, many thanks to my instructor. Thanks again for all the people who helped me, sincerely wishes you, I wish you health, peace, and happiness!。