Characterization of cation‐exchange membrane fouling during bipolar membrane electrodialysis of monosodium glutamate isoelectric supernatant

BACKGROUND: A novel procedure that involved regeneration and recycling of ammonia and sulfuric acid from monosodium glutamate isoelectric supernatant with bipolar membrane electrodialysis (BMED) was proposed. As the performance of the membranes deteriorated during the batch runs, fouling of the cation‐exchange membrane (CEM) in contact with the base cell was studied. RESULTS: During ten consecutive batches of BMED, some operating parameters deteriorated gradually. Using scanning electron microscopy observations, fouling deposits were found on the CEM surface on the base cell side. Using Fourier transform infrared spectroscopy and reversed‐phase high‐performance liquid chromatography (RP‐HPLC), the organic fouling fraction of the CEM foulants was found to contain eight amino acids. Using X‐ray energy‐dispersive analysis, the mineral fouling fraction was shown to be mainly O and Ca elements, and a little Mg. Using X‐ray diffraction, the inorganic foulant was identified as CaCO₃, mainly in the form of calcite and a little aragonite. CONCLUSION: The CEM was subject to membrane fouling consisting of an organic fouling fraction and a mineral fraction. The organic fraction occurred as ions with some positive charges from the isoelectric supernatant and probably existed in the form of amino acids or their peptides. The mineral fraction was mainly CaCO₃ calcite and aragonite, and probably a little amorphous Ca and Mg hydroxides. Copyright © 2011 Society of Chemical Industry     

沸石吸附-SBR工艺对味精废水脱氮的试验研究

针对味精废水高氨氮的特点,提出并利用沸石吸附—SBR组合工艺进行味精废水脱氮。研究结果表明:沸石吸附—SBR组合工艺对味精废水中的氨氮具有较好的去除效果。沸石吸附氨氮可以减轻后续生化处理负荷,为最终出水氨氮能够达标排放创造条件。SBR进水阶段采用限制性曝气方式;运行工况为进水曝气8h、厌氧搅拌1h、后段曝气1h、沉淀lh、排水0.5h;硝化反应过程pH控制在8左右;硝化阶段、反硝化阶段溶解氧(DO)质量浓度分别控制在2.0mg/L和0.5mg/L左右。组合工艺出水NH3-N能满足《味精工业污染物排放标准》(GB19431—2004)中50mg/L的限值要求,组合工艺对NH3-N的平均去除率达96.7%。     

二水硫酸钙在铵盐溶液中溶解度测定及热力学计算

利用溶解法测定了二水硫酸钙(CaSO4×2H2O)在NH4Cl-H2O体系和NH4Cl-(NH4)2SO4-H2O体系中298.15~343.15 K温度范围内的溶解度. 结果表明,CaSO4×2H2O在2个体系中的溶解度均随NH4Cl浓度增加而增大;温度对CaSO4×2H2O的溶解度影响不明显. 利用混合电解质NRTL模型对实验数据进行模拟计算,得到了新的能量相互作用参数,建立了CaSO4×2H2O(s)-NH4Cl-(NH4)2SO4-H2O体系的混合电解质模型,计算值与实验值相对偏差为2.36%.     

298K时(NH_4)_2S_2O_3-(NH_4)_2SO_4-H_2O三元体系相平衡研究

通过改良合成复体法对(NH4)2S2O3-(NH4)2SO4-H2O三元体系在298 K下的溶液相平衡进行研究。利用X-射线粉末衍射法(XRD)表征平衡固相组成。结果证实:该方法能很好地用于(NH4)2S2O3-(NH4)2SO4-H2O三元体系平衡固相组成的分析。依据水、硫酸铵及硫代硫酸铵组成的饱和溶液各组分的质量分数绘制了(NH4)2S2O3-(NH4)2SO4-H2O在298 K下的三元体系相图。依据三元体系相图,结果显示:硫代硫酸铵的结晶区远远大于硫酸铵的结晶区,同时在该温度下,硫代硫酸铵、硫酸铵及水形成简单三元体系,体系中没有水合物形成。     

(NH4)2SO4和Na2SO4混合溶液中(NH4)2SO4结晶动力学及铁/铝/锰/铬等离子对(NH4)2SO4结晶的影响规律

湿法冶金、三元前体制备等过程均会产生含硫酸钠与硫酸铵的高盐废水。研究高盐废水中硫酸铵的结晶动力学,并考察常见金属离子的影响规律对高盐废水处理具有重要意义。本文以含硫酸钠与硫酸铵混合溶液中硫酸铵的结晶过程为例,系统考察了硫酸铵的结晶动力学及铁、铝、锰、铬对硫酸铵结晶的影响规律。含硫酸钠与硫酸铵混合溶液硫酸铵结晶动力学研究结果表明,硫酸铵生长速率和成核速率方程分别为为B=1.303×10^-16G^1.069M_T^1.801,G=15.708σ^1.387;在硫酸钠与硫酸铵混合体系中,溶液过饱和度影响硫酸铵成核及生长速率,溶液过饱和度减小,晶体的成核及生长速率都会减小,与单体系硫酸铵结晶动力学结果相比,动力学参数均有所下降。铁、铝、锰、铬对硫酸铵结晶的影响规律研究结果表明,铁、铝抑制了硫酸铵晶面生长,结晶粒度减小;锰、铬对硫酸铵结晶有一定的促进作用,结晶粒度增大。金属离子改变了硫酸铵晶习,锰使结晶呈现三棱柱状,铁、铝使硫酸铵结晶片状生长。不同金属离子条件下的结晶动力学方程表明,铁和铝对结晶...     

(NH4)2S吸收净化冶炼烟气中SO2回收硫资源的方法

采用(NH₄)₂S溶液吸收净化高浓度SO₂烟气,得到(NH₄)₂S₂O₃和NH₄HSO₃的混合溶液并转移至高压反应釜中,控制反应条件,两种物质发生自氧化还原反应,生成硫磺和(NH₄)₂SO₄.实验考察了吸收SO₂过程和自氧化还原过程的影响条件,结果表明:在pH=3～7,SO₂气体流速300 ml·min^-1,(NH₄)₂S浓度为0.2～1.2 mol·L^-1,常温条件下,烟气中二氧化硫的吸收率达到99.8%以上,且无H₂S生成;在pH=2.5～3.0,温度为130℃条件下,反应进行1 h,硫磺收率达到95%以上,溶液经过蒸发结晶得到(NH₄)₂SO₄.用X射线衍射(XRD)和X射线荧光光谱(XRF)对硫磺和硫酸铵进行表征分析,结果表明:硫磺的纯度为99.14%,硫酸铵中氮元素含量为23.6%.     

Application of response surface methodology to optimize the operation process for regeneration of acid and base using bipolar membrane electrodialysis

BACKGROUND: Bipolar membrane electrodialysis (BMED) has been widely used for desalination, concentration, separation, and purification in many fields. The purpose of this study is to optimize the operation conditions using response surface methodology (RSM) for the regeneration of sulfuric acid and ammonia from ammonium sulfate solution by BMED coupled with ammonia in situ stripping. RESULTS: A three‐factor central composite design of RSM was used to analyze the effect of operation conditions (current density, flow rate, initial acid concentration) on average current efficiency (ACE) and establish the optimal operation conditions. The ACE was 76.7 ± 2.2% under optimal operation conditions (current density 23.8 mA cm^?2, flow rate 27.3 L h^?1, initial acid concentration 0.09 mol L^?1). CONCLUSION: A suitable regression model for predicting ACE within the ranges of variables used was developed based on experimental results. The operation conditions were optimized by RSM and the ACE obtained under the optimal operation conditions was in good agreement with the value predicted by the regression model (78%), which proved the validity of the model. Copyright © 2007 Society of Chemical Industry     

硫酸铵焙烧与浸出提取碳素铬铁冶炼渣中有价金属

用(NH4)2SO4焙烧分解碳素铬铁冶炼渣,提取有价金属,考察了焙烧温度、硫酸铵用量和焙烧时间对有价金属浸出率及过程相变的影响. 结果表明,焙烧过程中250~435℃间失重达65.5%,主要为NH3,H2O,SO3释放及(NH4)2SO4挥发. 优化的焙烧条件为(NH4)2SO4与铝镁渣质量比5:1、焙烧温度350℃,焙烧时间3.5 h. 有价金属转变为其相应的硫酸金属铵盐,且与(NH4)2SO4分解产物共存;该条件下的焙烧料90℃下浸出1 h,Mg, Al, Cr, Fe的浸出率分别为92%, 80%, 82%, 93%. 推测新生成的硫酸金属铵盐的片状聚集体阻碍碳素铬铁渣内部完全被(NH4)2SO4侵蚀.     

(NH4)2SO4作助熔剂对单氟磷酸钠合成的影响

以六偏磷酸钠和氟化钠为合成单氟磷酸钠的主要反应原料,根据助熔剂的性质,筛选出(NH4)2SO4为较佳助熔荆.采用单因素实验法考察了干燥温度、干燥时间、合成温度、合成时间、氟磷比、n[(NH4)2SO4]:n(NaPO3)6+NaF]对反应的影响.通过正交实验优选,确定了最佳工艺条件.     

用Na2SO4提高牛眼透明质酸回收率的研究

通过 Ｎａ Ｃｌ和 Ｎ ａ２ Ｓ Ｏ ４ 溶解牛眼透明 质酸粗制品对透明质酸（ Ｈ Ａ ）提取率及纯度影响的比较研究,发现 Ｎ ａ２ Ｓ Ｏ ４ 比 Ｎ ａ Ｃｌ 对 Ｈ Ａ 提取率提高 ５ 倍以上,实验品的纯度达到 ９９３％ 。     

膜法除硝技术在氯碱盐水生产中的应用

介绍了膜法除硝技术在氯碱盐水生产中的应用情况,比较了2种处理装置的运行情况.     

Preparation of synthetic rutile via selective sulfation of ilmenite with (NH4)2SO4 followed by targeted removal of impurities

This paper describes a novel, facile chemical pathway for preparing synthetic rutile from ilmenite. The pathway consists of two primary units, i.e., selectively sulfating ilmenite, which was realized via roasting ilmenite with(NH_4)_2SO_4followed by selective thermal decomposition of the sulfated ilmenite, and targeted leaching of the impurities. The effects of the process parameters were systematically investigated. The results showed that the optimum sulfation conditions were a mass ratio of(NH_4)_2SO_4to ilmenite of 14, temperature of 360 °C, and time of 120 min with a sulfation ratio of ~ 95%. The optimum thermal decomposition conditions were480 °C in N_2 atmosphere, and nearly all Ti OSO_4 were decomposed with co-decomposition of Fe SO_4 of 23%. For acid leaching, the optimum conditions were 2.5 wt% HCl, 98 °C and 120 min. Under those conditions, 94.2% iron was removed with a Ti O_2 dissolution loss b 1%. For alkali leaching, 67% Si O_2 was removed in 5 wt% Na OH at102 °C for 1 h. A synthetic rutile with a Ti O_2 content N 92 wt% and total Mg O + Ca O b 1.5 wt% was obtained.Based on these results, a schematic flowsheet was proposed. Additionally, it was found that the decomposition of Fe SO_4 mixed with Ti OSO_4 under N_2was inhibited due to its oxidation to a higher thermal stability Fe_2(SO_4)_3by oxygen emitted from the decomposition of Ti OSO_4. At the same time, Ti OSO_4 decomposition was promoted due to the immediate in situ consumption of oxygen by Fe SO_4. The synergetic effect might be responsible for the enhanced selectivity of sulfated ilmenite thermal decomposition.     

i(SO4)2/SiO2催化合成苯甲酸异戊酯的研究

以Ti(SO₄)₂/SiO₂为催化剂，苯甲酸和异戊醇为原料，合成了苯甲酸异戊酯。对影响酯化反应的因素进行了研究。优化的工艺条件：负载硫酸钛质量分数为10%，催化剂用量为2.5 g·(0.05 mol-苯甲酸)^-1，醇酸物质的量比为4∶1，反应时间为90 min，苯甲酸的酯化率可达96.6%。     

利用氢氧化镁热分解氯化铵制氨气工艺的研究

对利用氢氧化镁热分解氯化铵制氨气反应体系进行了热力学计算分析,以反应温度、反应物的物质的量比、反应时间为变量,以固体产物中的含氮量、氯收率以及氨气收率等为评价指标,对氢氧化镁热分解氯化铵制氨气的工艺条件进行了研究。实验结果表明,在反应温度为375 ℃,氢氧化镁与氯化铵的物质的量比为1∶0.75,反应时间为50 min时,氯收率和氨气收率均可达到90%以上,同时氢氧化镁分解氯化铵能够直接生成碱式氯化镁,不需向反应器中通入水蒸气。     

固体酸Zr(SO4)2/TiO2催化合成棕榈酸甲酯

以固体酸Zr(SO4)2/TiO2为催化剂,工业棕榈酸与甲醇为原料合成棕榈酸甲酯生物柴油。考察了Zr(SO4)2负载量、催化剂焙烧温度、焙烧时间、m(棕榈酸)∶m(甲醇)、催化剂用量和反应时间对酯化率的影响,并采用GC-MS、红外光谱仪、热重差热综合热分析仪对催化剂和产物进行表征分析。结果表明,与Zr(SO4)2催化剂相比,固体酸催化剂Zr(SO4)2/TiO2在工业棕榈酸和甲醇的酯化反应中具有较高的催化活性。适宜的反应条件为:以400℃焙烧制得的Zr(SO4)2负载量为65%的固体酸Zr(SO4)2/TiO2为催化剂,醇酸质量比为12∶25,催化剂用量为棕榈酸质量的8.0%,反应时间5 h。在该条件下,酯化率可达98.9%。经GC-MS分析,酯产物主要为直链十六烷酸甲酯和10-十八碳烯酸甲酯。     

乙醇/硫酸铵双水相体系萃取甘草酸钾的研究

实验考察了乙醇/硫酸铵双水相萃取甘草酸钾的可能性及其影响因素,结果表明,甘草酸钾在该体系的分配系数K和收率均随乙醇、硫酸铵质量分数的增加而增大,而随着pH的增加先增加后减小。且在w(乙醇)=35 1%,w(硫酸铵)=17 7%,pH=6 0左右时,分配系数K可达13 7,收率η可达96 3%。这将为甘草酸钾的提取分离提供一种新的可能。     

Pd(OH)_2胶体预处理及化学镀法修补复合Pd膜

提出了一种有效的膜缺陷修补方法,即预先采用Pd(OH)2胶体浸渍有缺陷的Pd膜,还原后再化学镀金属Pd。通过扫描电镜(SEM)和金相显微镜对膜的表面和断面进行表征,并结合透氢性能测试对膜的修补效果进行了评价。研究结果表明:预处理后所形成的Pd金属微粒可富集在膜缺陷处且对后续的化学镀反应有良好的催化作用,从而促进了金属Pd在缺陷处的沉积,使膜缺陷得到有效修补。文中修补工艺可在几乎不损失氢通量的前提下大大提高Pd膜的选择性。     

氟硅酸铵改性纳米HZSM-5分子筛的表征及催化甲醇制低碳烯烃

对纳米HZSM-5分子筛进行氟硅酸铵改性,系统考察氟硅酸铵浓度、改性温度、改性时间及缓冲剂用量的影响。利用X射线衍射、透射电镜、N_2吸附、X荧光光谱和吡啶吸附-红外光谱技术,对改性前后的纳米HXSM-5分子筛进行表征,并在常压、500℃和甲醇空速6 h^(-1)条件下,采用连续流动微型固定床反应器考察其催化甲醇制低碳烯烃的性能。结果表明,通过调变氟硅酸铵改性条件可以有效调节纳米HZSM-5分子筛的孔结构和酸性等,氟硅酸铵改性纳米HZSM-5分子筛的乙烯、丙烯和丁烯选择性可达65.1%,比未改性的纳米HZSM-5分子筛提高了27.8个百分点。     

强酸性离子交换膜催化合成二氢嘧啶酮药物中间体

在HF 101强酸性离子交换膜的存在下,由对羟基苯甲醛、乙酰乙酸甲酯与脲一步合成了5 甲氧羰基 4 (4 甲氧苯基) 6 甲基 3,4 二氢嘧啶 2(1H) 酮。当对羟基苯甲醛、乙酰乙酸甲酯与脲的摩尔比为1∶2∶5,乙醇作溶剂,3g离子交换膜,回流2h,产物收率达95.4%。同时研究了离子交换膜作为催化剂的重复使用情况。