含氟、鈾廢水深度凈化處理方法研究
發(fā)布時(shí)間：2018-09-01 20:07
【摘要】：隨著核工業(yè)的發(fā)展,產(chǎn)生了一批難于處理的含氟、鈾廢水。本研究以含氟、鈾廢水為研究對(duì)象,采用生物沉降、化學(xué)沉降以及離子交換纖維(IEF)技術(shù),分別實(shí)現(xiàn)了對(duì)氟和鈾的深度凈化要求,并以此提出了一條較為經(jīng)濟(jì)可行的含氟、鈾廢水深度凈化工藝。生物沉降采用固定化活體耐輻射奇球菌(IDR)進(jìn)行,結(jié)果表明,菌含量2.5%的IDR顆粒對(duì)鈾的沉降性能良好,p H=3.5,鈾初始濃度50mg/L,去除率最高可達(dá)95%以上,最大吸附量達(dá)103.82 mg/g(DW)。IDR的動(dòng)態(tài)柱吸附實(shí)驗(yàn)表明,其去除鈾的穩(wěn)定性較好,吸附后鈾易通過0.1 mol/L HCl再生,解吸率達(dá)90%以上,也可作為固定床填料考慮。經(jīng)SEM/EDS、XRD等分析可知,鈾在IDR顆粒表面以片狀鈾的磷酸鹽形式存在。經(jīng)過灰化處理后,減重比為254;灰分中鈾以Ca(UO2)(PO4)·3H2O和(Ca,U)(PO4)·2H2O的形式賦存。化學(xué)沉降鈾試驗(yàn)結(jié)果表明,優(yōu)選組合為p H=9,添加10%乙醇,磷酸二氫鈣用量為3g,鈾去除率達(dá)95%以上。經(jīng)SEM/EDS分析,沉淀是5~10μm片層狀堆積的顆粒,由Ca、P、U、O四種元素組成的混合物。在p H=9,加10%乙醇,投加磷酸二氫鈣3g條件下,易生成U(HPO4)2·6H2O;而p H=7,加30%乙醇,投加磷酸二氫鈣3g條件下易生成(UO2)3(PO4)2·8H2O�；瘜W(xué)沉淀氟采用鈣鹽進(jìn)行,廢水氟離子濃度控制在130%理論值的鈣鹽投加量條件下,除氟效果達(dá)到最佳,氟離子濃度可以降到30mg/L左右,進(jìn)一步處理首先調(diào)節(jié)p H=11左右,按照2:1的磷酸鹽:氟離子的比例投加磷酸鹽,可以使廢水中氟離子濃度降至5mg/L左右,達(dá)到可排放的水平。IEF篩選優(yōu)化靜態(tài)除鈾試驗(yàn)結(jié)果表明,純鈾體系下,強(qiáng)堿型纖維(SAIEF)處理效果最優(yōu),預(yù)處理采用酸堿洗的方式進(jìn)行,接觸時(shí)間在15~30 min內(nèi),其對(duì)鈾的去除率可達(dá)90%以上;p H最佳范圍為9.5~11,于10.5處最佳,投加量以1.5g/100mL為宜,鈾初始濃度20~100mg/L為宜;恒定投加量梯度遞降3次可使50mg/L的鈾降至0.05mg/L以下;采用0.1M鹽酸作為解吸劑效果較佳,10%的氯化鈉也可;解吸后濃水可采用化學(xué)沉降的方式回收利用。氟鈾體系下,設(shè)定氟離子濃度5g/L、10g/L、15g/L條件下,分別對(duì)應(yīng)5mg/LU和50mg/LU,SAIEF基本保持了在純鈾體系下對(duì)鈾的吸附性能,且?guī)缀鯇?duì)氟離子不去除。結(jié)合SEM/EDS、FTIR表征和模擬分析,SAIEF的主要離子交換方程如下:P-CH2N+(CH3)3Cl-+(UO2)2CO3(OH)3-→[P-CH2N+(CH3)3](UO2)2CO3(OH)3 + Cl-(pH 8~11.5)P-CH2N+(CH3)3Cl-+ UO2(OH)3-→[P-CH2N+(CH3)3]UO2(OH)3+ Cl-(p H 10~14)SAIEF動(dòng)態(tài)柱試驗(yàn)結(jié)果表明,純鈾體系下,流速10~20mL/min,SAIEF對(duì)鈾的飽和吸附量約為426.7mg/g;單級(jí)填料10~20 g、填料密度=0.1g/mL;填料高度10~20 cm;徑高比=1:3~6;進(jìn)水濃度2~50mg/L鈾時(shí),進(jìn)入量:30-60個(gè)柱體積;可保證出水維持10 h左右持續(xù)出水鈾濃度在0.05g/L以下,符合深度凈化要求。且該流速下高徑比對(duì)鈾去除的影響不大,動(dòng)態(tài)解吸流速減半,采用3倍柱體積的0.1M鹽酸或10%氯化鈉可完成。流速25ml/min時(shí),三級(jí)串連,填料密度0.1g/mL;填料高度20 cm;徑高比=1:7.6條件下,進(jìn)水50mg/L U,出水維持10 h左右持續(xù)出水鈾濃度0.05mg/L以下,此時(shí)進(jìn)水總體積為120個(gè)柱體積;當(dāng)進(jìn)水5mg/L U時(shí),出水維持28 h左右持續(xù)出水鈾濃度0.05mg/L以下,此時(shí)進(jìn)水總體積為1050個(gè)柱體積。吸附后纖維的灰化產(chǎn)物主要成分為UO4·4H2O,減重比為6.5左右。氟鈾體系下,流速10~20mL/min時(shí),兩級(jí)串連,填料密度=0.1g/mL;填料高度10 cm;徑高比=1:6,進(jìn)水50mg/L U、10g/L F,通水體積4.5L左右可保持出水鈾濃度在0.05mg/L以下,氟濃度維持在10g/L左右。流速25ml/min時(shí),三級(jí)串連,填料密度0.1g/mL;填料高度20 cm;徑高比=1:7.6條件下,進(jìn)水50mg/L U、10g/L F,5mg/L U、10g/L F條件下,均可保證至少8 h持續(xù)出水鈾濃度0.05mg/L以下,氟離子濃度維持進(jìn)水濃度左右。在純鈾體系下對(duì)SAIEF單元進(jìn)行小試和中試試驗(yàn),結(jié)果表明,設(shè)定濃度5~100mg/L,流速5~100L/h,高徑比4:1,單級(jí)纖維填充密度為0.1g/mL,3~4級(jí)串連條件下,對(duì)各初始濃度各流速條件下,均可完成對(duì)廢水中鈾的深度凈化,去污因子最高達(dá)3.762×105。同時(shí),對(duì)長(zhǎng)期使用后SAIEF進(jìn)行SEM分析,結(jié)果表明,纖維在反復(fù)多次使用后結(jié)構(gòu)完好,未有解體現(xiàn)象。從EDS結(jié)果可以看出,Cl含量增加,說明纖維的功能基團(tuán)正常,在反復(fù)使用過程中,其交換能力得到了進(jìn)一步優(yōu)化。結(jié)合以上研究,本文提出一條以沉降方法配合SAIEF技術(shù)的較經(jīng)濟(jì)可行的含氟、鈾廢水深度凈化工藝,為核工業(yè)含氟、鈾廢水的處理提供一定的參考。
[Abstract]:With the development of nuclear industry, a number of wastewater containing fluorine and uranium are produced which are difficult to be treated. In this study, biological sedimentation, chemical sedimentation and ion exchange fiber (IEF) technology are used to purify fluorine and uranium, and a more economical and feasible method is proposed to purify fluorine and uranium wastewater. Biological sedimentation was carried out by immobilized in vivo Mycoccus radiodurans (IDR). The results showed that the sedimentation performance of uranium by 2.5% IDR particles was good, P H=3.5, the initial concentration of uranium was 50mg/L. The removal rate of uranium was up to 95%, and the maximum adsorption capacity was 103.82 mg/g (DW). The dynamic column adsorption experiment of IDR showed that the removal stability of uranium was better. Good, uranium can be easily regenerated by 0.1 mol/L HCl after adsorption, and the desorption rate is over 90%. It can also be considered as a fixed bed packing. The results of chemical precipitation uranium test show that the optimum combination is p H=9, 10% ethanol is added, the dosage of calcium dihydrogen phosphate is 3 g, and the uranium removal rate is more than 95%. When the concentration of fluoride in wastewater is controlled at 130% of the theoretical value of calcium salt, the effect of fluoride removal is the best. The concentration of fluoride ion can be reduced to about 30mg/L. The further treatment is first regulated about P H = 11 according to the 2. Phosphate: 1. Phosphate: The proportion of fluoride ions added to phosphate can reduce the concentration of fluoride ions in wastewater to about 5 mg / L, reaching the level of discharge. IEF screening and optimization of static uranium removal test results show that under the pure uranium system, strong alkali fiber (SAIEF) treatment effect is the best, the pretreatment is carried out by acid-alkali washing, contact time is 15-30 minutes, and its contact time is within 15-30 minutes. The removal rate of uranium can reach more than 90%; the optimum range of P H is 9.5-11 and 10.5, the optimum dosage is 1.5 g/100 mL, and the initial concentration of uranium is 20-100 mg/L; the constant dosage gradient three times can reduce uranium to less than 0.05 mg/L; 0.1M hydrochloric acid as a desorbent, 10% sodium chloride can also be used; after desorption, concentrated water can be used. Under the condition of 5 g/L, 10 g/L, 15 g/L fluoride ion concentration, 5 mg/LU and 50 mg/LU respectively, SAIEF basically maintains the adsorption performance of uranium in the pure uranium system, and almost does not remove fluoride ions. Combined with SEM/EDS, FTIR characterization and simulation analysis, the main ion exchange equations of SAIEF are as follows: H2N + (CH3) 3Cl - + (CH3) 3Cl - + (UO2) 2CO3 (OH) 3 - 85 [[P - CH2N + (CH3) 3 3] (UO2) 2CO3 (OH) 3 + Cl - (pH 8 ~ 11.5) P - CH2N + (CH3) 3Cl - + UO2 (OH) 3 (OH) 3 (OH 3) 3 - 85 85 [P - CH2N + (CH3) 2SAN + (CH3) 3) 3] UO2 (OH) 3 + Cl - (p H 10 ~ 14) IEF dynamic column test results showed that in the pure uransystem, the flow rate of pure uransystem, flow rate of 20 mIEL / min, 20 m IEL / min, SAIEL / The saturated adsorption capacity of F to uranium is about 426.7 mg/g, the single stage packing is 10-20 g, and the packing density is 0.1 g/mL. The packing height is 10-20 cm, the ratio of diameter to height is 1:3-6, the inlet concentration is 2-50 mg/L uranium, the inlet volume is 30-60 column volume, and the effluent can be maintained for about 10 hours at a consistently effluent uranium concentration below 0.05 g/L, which meets the requirements of deep purification. 10% NaCl can be completed. When the flow rate is 25 ml/min, the three stages are connected in series, the packing density is 0.1 g/mL; the packing height is 20 cm; the diameter-to-height ratio is 1:7.6, the inlet water is 50 mg/L U, and the outlet water is maintained below 0.05 mg/L for about 10 hours, the total volume of the inlet water is 120 columns; when the inlet water is 5 mg/L U, the outlet water is maintained at 0.05 mg/L for about 28 hours. The main component of ashing product after adsorption is UO4.4H2O, and the weight loss ratio is about 6.5. In uranium fluoride system, when the flow rate is 10-20 mL/min, the two stages are in series, the packing density is 0.1 g/mL, the packing height is 10 cm, the diameter-height ratio is 1:6, the influent water volume is 50 mg/L, 10 g/L F, and the outlet water volume is about 4.5 L. Under the condition of 0.05 mg/L, fluorine concentration maintained at about 10 g/L, flow rate 25 ml/min, three stages in series, packing density 0.1 g/mL, packing height 20 cm, diameter-to-height ratio = 1:7.6, influent 50 mg/L U, 10 g/L F, 5 mg/L U, 10 g/L F, the influent concentration of uranium can be maintained at least 8 hours under 0.05 mg/L, fluoride ion concentration maintained at about the influent concentration. The results of pilot and pilot tests on SAIEF unit show that the deep purification of uranium in wastewater can be achieved under the conditions of setting concentration 5-100mg/L, flow rate 5-100L/h, height-diameter ratio 4:1, single-stage fiber packing density 0.1g/mL, 3-4 stages in series, and each initial concentration and flow rate. The maximum decontamination factor is 3.762 65507 The results of SEM analysis by post-SAIEF show that the structure of the fibers is intact after repeated use, and there is no disintegration. From the EDS results, it can be seen that the content of Cl increases, indicating that the functional groups of the fibers are normal. In the process of repeated use, the exchange capacity of the fibers is further optimized. SAIEF is an economical and feasible advanced purification process for fluorine-containing and uranium-containing wastewater, which provides a certain reference for the treatment of fluorine-containing and uranium-containing wastewater in nuclear industry.
【學(xué)位授予單位】：西南科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703
本文編號(hào)：2218215
[Abstract]:With the development of nuclear industry, a number of wastewater containing fluorine and uranium are produced which are difficult to be treated. In this study, biological sedimentation, chemical sedimentation and ion exchange fiber (IEF) technology are used to purify fluorine and uranium, and a more economical and feasible method is proposed to purify fluorine and uranium wastewater. Biological sedimentation was carried out by immobilized in vivo Mycoccus radiodurans (IDR). The results showed that the sedimentation performance of uranium by 2.5% IDR particles was good, P H=3.5, the initial concentration of uranium was 50mg/L. The removal rate of uranium was up to 95%, and the maximum adsorption capacity was 103.82 mg/g (DW). The dynamic column adsorption experiment of IDR showed that the removal stability of uranium was better. Good, uranium can be easily regenerated by 0.1 mol/L HCl after adsorption, and the desorption rate is over 90%. It can also be considered as a fixed bed packing. The results of chemical precipitation uranium test show that the optimum combination is p H=9, 10% ethanol is added, the dosage of calcium dihydrogen phosphate is 3 g, and the uranium removal rate is more than 95%. When the concentration of fluoride in wastewater is controlled at 130% of the theoretical value of calcium salt, the effect of fluoride removal is the best. The concentration of fluoride ion can be reduced to about 30mg/L. The further treatment is first regulated about P H = 11 according to the 2. Phosphate: 1. Phosphate: The proportion of fluoride ions added to phosphate can reduce the concentration of fluoride ions in wastewater to about 5 mg / L, reaching the level of discharge. IEF screening and optimization of static uranium removal test results show that under the pure uranium system, strong alkali fiber (SAIEF) treatment effect is the best, the pretreatment is carried out by acid-alkali washing, contact time is 15-30 minutes, and its contact time is within 15-30 minutes. The removal rate of uranium can reach more than 90%; the optimum range of P H is 9.5-11 and 10.5, the optimum dosage is 1.5 g/100 mL, and the initial concentration of uranium is 20-100 mg/L; the constant dosage gradient three times can reduce uranium to less than 0.05 mg/L; 0.1M hydrochloric acid as a desorbent, 10% sodium chloride can also be used; after desorption, concentrated water can be used. Under the condition of 5 g/L, 10 g/L, 15 g/L fluoride ion concentration, 5 mg/LU and 50 mg/LU respectively, SAIEF basically maintains the adsorption performance of uranium in the pure uranium system, and almost does not remove fluoride ions. Combined with SEM/EDS, FTIR characterization and simulation analysis, the main ion exchange equations of SAIEF are as follows: H2N + (CH3) 3Cl - + (CH3) 3Cl - + (UO2) 2CO3 (OH) 3 - 85 [[P - CH2N + (CH3) 3 3] (UO2) 2CO3 (OH) 3 + Cl - (pH 8 ~ 11.5) P - CH2N + (CH3) 3Cl - + UO2 (OH) 3 (OH) 3 (OH 3) 3 - 85 85 [P - CH2N + (CH3) 2SAN + (CH3) 3) 3] UO2 (OH) 3 + Cl - (p H 10 ~ 14) IEF dynamic column test results showed that in the pure uransystem, the flow rate of pure uransystem, flow rate of 20 mIEL / min, 20 m IEL / min, SAIEL / The saturated adsorption capacity of F to uranium is about 426.7 mg/g, the single stage packing is 10-20 g, and the packing density is 0.1 g/mL. The packing height is 10-20 cm, the ratio of diameter to height is 1:3-6, the inlet concentration is 2-50 mg/L uranium, the inlet volume is 30-60 column volume, and the effluent can be maintained for about 10 hours at a consistently effluent uranium concentration below 0.05 g/L, which meets the requirements of deep purification. 10% NaCl can be completed. When the flow rate is 25 ml/min, the three stages are connected in series, the packing density is 0.1 g/mL; the packing height is 20 cm; the diameter-to-height ratio is 1:7.6, the inlet water is 50 mg/L U, and the outlet water is maintained below 0.05 mg/L for about 10 hours, the total volume of the inlet water is 120 columns; when the inlet water is 5 mg/L U, the outlet water is maintained at 0.05 mg/L for about 28 hours. The main component of ashing product after adsorption is UO4.4H2O, and the weight loss ratio is about 6.5. In uranium fluoride system, when the flow rate is 10-20 mL/min, the two stages are in series, the packing density is 0.1 g/mL, the packing height is 10 cm, the diameter-height ratio is 1:6, the influent water volume is 50 mg/L, 10 g/L F, and the outlet water volume is about 4.5 L. Under the condition of 0.05 mg/L, fluorine concentration maintained at about 10 g/L, flow rate 25 ml/min, three stages in series, packing density 0.1 g/mL, packing height 20 cm, diameter-to-height ratio = 1:7.6, influent 50 mg/L U, 10 g/L F, 5 mg/L U, 10 g/L F, the influent concentration of uranium can be maintained at least 8 hours under 0.05 mg/L, fluoride ion concentration maintained at about the influent concentration. The results of pilot and pilot tests on SAIEF unit show that the deep purification of uranium in wastewater can be achieved under the conditions of setting concentration 5-100mg/L, flow rate 5-100L/h, height-diameter ratio 4:1, single-stage fiber packing density 0.1g/mL, 3-4 stages in series, and each initial concentration and flow rate. The maximum decontamination factor is 3.762 65507 The results of SEM analysis by post-SAIEF show that the structure of the fibers is intact after repeated use, and there is no disintegration. From the EDS results, it can be seen that the content of Cl increases, indicating that the functional groups of the fibers are normal. In the process of repeated use, the exchange capacity of the fibers is further optimized. SAIEF is an economical and feasible advanced purification process for fluorine-containing and uranium-containing wastewater, which provides a certain reference for the treatment of fluorine-containing and uranium-containing wastewater in nuclear industry.
【學(xué)位授予單位】：西南科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 秦勝東;郭嘉f;劉玉存;馬慧;尹政;呂利剛;;固定化微生物技術(shù)研究進(jìn)展及其在水處理中的應(yīng)用[J];水處理技術(shù);2014年10期
2 劉明學(xué);董發(fā)勤;李姝;亢武;孫宇;杜旭光;茍清碧;;固定化耐輻射奇球菌對(duì)鍶柱吸附與減量化研究[J];環(huán)境科學(xué)與技術(shù);2014年06期
3 鄧欽文;丁德馨;劉冬;王永東;;耐輻射奇球菌對(duì)水中鈾(Ⅵ)的吸附試驗(yàn)[J];金屬礦山;2014年01期
4 辛蘊(yùn)甜;趙曉祥;;芽孢桿菌H-1菌株的固定化及降解動(dòng)力學(xué)研究[J];環(huán)境科學(xué)與技術(shù);2013年11期
5 李建華;王紅英;程威;鄧錦勛;李紅;;離子交換纖維處理含鈾礦井水[J];鈾礦冶;2012年02期
6 姚艷;楊道武;劉義;吳辰龍;;石灰乳-聚合氯化鋁處理高含氟廢水的研究[J];工業(yè)水處理;2011年08期
7 苗俊婷;;放射性廢水處理技術(shù)概述[J];科技信息;2011年23期
8 李興亮;宋強(qiáng);劉碧君;劉春霞;王航;耿俊霞;陳震;劉寧;李首建;;炭材料對(duì)鈾的吸附[J];化學(xué)進(jìn)展;2011年07期
9 凌俊;秦會(huì)敏;酈和生;;化學(xué)沉淀法處理高濃度含氟廢水的研究[J];石化技術(shù);2011年02期
10 吳偉;;探討含磷含氟廢水的處理工藝路線[J];能源研究與管理;2011年02期
相關(guān)碩士學(xué)位論文 前2條
1 譚翔;固定化真菌微球吸附鈾的研究[D];南華大學(xué);2013年
2 張道武;聚丙烯腈陰離子交換纖維的制備與應(yīng)用[D];北京服裝學(xué)院;2010年
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