L-苹果酸中富马酸钙与苹果酸钙溶解动力学

采用反应分离耦合技术以富马酸钙为底物生产Ｌ－苹果酸是目前该产品生产的最佳方式,因此,研究该工艺过程中底物富马酸钙与产物苹果酸钙的溶解行为显得十分重要。详细考察了底物富马酸钙、产物苹果酸钙的溶解过程,讨论了温度、ｐＨ对溶解过程的影响,得出不同温度下溶解的Ｃ－ｔ曲线及动力学方程,结果如下。底物富马酸钙溶解动力学方程：４０℃：ｄＣ／ｄｔ＝２．７６１×１０－２（０．０９１２６－Ｃ）０．５６８２２０℃：ｄＣ／ｄｔ＝２．８７８×１０－３（０．０７５２２－Ｃ）０．２６７９产物苹果酸钙溶解动力学方程：４０℃：ｄＣ／ｄｔ＝４．０４１×１０－３（０．０６７５２－Ｃ）０．４０７１２０℃：ｄＣ／ｄｔ＝９．０９６×１０－３（０．０５１９５－Ｃ）０．７６７６     

合成三聚氯氰的氯化和聚合反应宏观动力学研究

利用非等温固定床反应器，研究了三聚氯氰合成的氯化和聚合反应宏观动力学，实验表明氢氰酸与氯气的氯化反应为气相均相反应，而氯氰的聚合反应为吸附在活性炭表面上的氯氰表面反应为控制步骤的气固催化反应。实验测得氯化反应的宏观反应动力学方程为对氢氰酸的一级反应，即（－ｒＡ）１＝２．４５×１０７ｅｘｐ（－２．９０×１０４／ＲＴ）ｃＡ测得聚合反应的宏观动力学方程为（－ｒＡ）２＝ｋ［ｐ３Ａ－ｐＲ／Ｋｐ］／［１＋ＫＡｐＡ＋ＫＲｐＲ］３ｋ＝４．０×１０７ｅｘｐ（－４．３５×１０４／ＲＴ）Ｋｐ＝６．７６×１０－２３ｅｘｐ（３．５２×１０５／ＲＴ）ＫＡ＝４．０×１０３ｅｘｐ（－３．３９×１０４／ＲＴ）ＫＲ＝１．０５×１０３ｅｘｐ（－５．０２×１０４／ＲＴ     

固定化细胞生产L－苹果酸新工艺及动力学研究

对产氨短杆菌ＭＡ－２固定化细胞在富马酸铵体系中转化生成Ｌ－苹果酸的优化工艺条件做了探讨，结果表明，富马酸铵浓度为１．８ｍｏｌ／Ｌ，ｐＨ７．０～８．０，反应温度为３７℃时，Ｌ－苹果酸得率达２００ｇ／Ｌ左右。同时，对固定化细胞的动力学进行了研究，结果为：ｒ（ｍａｘ）＝５８ｍｍｏｌ／（Ｌ·ｈ·ｇ固定化湿细胞）），Ｋｍ＝６．２５×１Ｏ￣（－２）ｍｏｌ／Ｌ，Ｐ＿ｍ＝１．５６ｍｏｌ／Ｌ     

丙烯氨氧化合成丙烯腈流化床反应器的模型拟合

基于反应动力学实验结果,分析考察了丙烯氨氧化反应的动力学行为,提出了关于反应转化率与目的产物收率的幂函数形式的拟合模型,藉此对某厂丙烯腈工业流化床反应器的操作数据进行了关联,在考虑反应器中气－固流动影响的前提下,建立了丙烯腈反应器的下述宏观数学模型：反应转化率Ｘ＝０．８３２５ｕ－０．１０５８Ｒ－０．０１６４ＮＨ３Ｒ０．２５０９Ｏ２ｅｘｐ（－０．７４５９＋３５９．７９／Ｔ）丙烯腈单收ＹＡＮ＝０．０８９６ｕ０．０３４２Ｒ０．２３３３ＮＨ３（５．８２４５ｅｘｐＲ１．１３３７Ｏ２－Ｒ４．７４４５Ｏ２）ｅｘｐ（－２．０６５１＋５２２．９８／Ｔ）模型拟合的相对误差小于１０％．     

负温下NaNO2溶液中C3S水化动力学的研究

通过测定负温条件下掺ＮａＮＯ２的Ｃ３Ｓ悬浮液中５ｍｉｎ内的Ｃａ＾２＋浓度，回归出了Ｃ３Ｓ早期水化动力学方程和水化动力学参数（ｎ＝－１．２３～－１．１５，Ｋ＝２．２１～９．７５），并得到了Ｃ３Ｓ水化的表观活化能值（Ｅ＝１０．６９ｋＪ／ｍｏｌ）表明负温条件下，温度的改变只对水化反应速率影响显著，而对其机影响不大，且发现在负温对Ｃ３Ｓ水化反应的作用过程中，－１０℃为一转折点，建议在冬季施工中，将早期水化     

H2O2—Fe^2＋氧化法处理对氨基酚工业废水的研究

结果表明,利用Ｈ２Ｏ２－Ｆｅ２＋ 氧化法处理对氨基酚（ＰＡＰ）工业废水是切实可行的。当ＰＡＰ质量浓度在１．６ｇ／Ｌ～２．０ｇ／Ｌ范围内,在Ｈ２Ｏ２／ＰＡＰ＝ ４．０（质量比）,ＦｅＳＯ４·７Ｈ２Ｏ质量浓度为１．０ｇ／Ｌ条件下,反应１ｈ 后,工业废水中对氨基酚的去除率达９８％ ～９９％ 。降低了废水的色度并提高了废水的可生化性,该方法对反应条件（如温度和ｐＨ值等）没有严格要求,便于工业应用。     

利用棒杆菌由N－乙酰氨基肉桂酸制备L－苯丙氨酸

从土壤中分离到一株棒杆菌（ＣｏｒｙｎｅｂａｃｔｅｔｉｕｍＳｐ．），可利用Ｎ－乙酰氨基肉桂酸作底物，通过酰基转移和氨基转移两步酶促反应，生成Ｌ－苯丙氨酸。利用０．２ｍｏｌ／Ｌ的乙酰氨基肉桂酸可生成０．０６ｍｏｌ／Ｌ的Ｌ－苯丙氨酸，摩尔转化率可达３０％。     

极谱法测定冷却水中的乙二胺四甲叉膦酸钠

在６．８×１０＾－４ｍｏｌ．Ｌ柠檬酸钠，醋酸－醋酸钠缓冲溶液（ｐＨ＝５．２＋中，Ｃｕ＾２＋可与乙二胺四甲叉膦酸钠（ＥＤＴＭＰＳ）络合，使铜峰降低，峰电位Ｅｐ＝－０．２４Ｖ（银－氯化银电极）。乙二胺四甲叉膦酸钠浓度在３－５０ｍｇ／Ｌ范围内与峰高降低值呈线性关系。采用ＪＰ３－１型示波极谱仪，二次微分，起始电位０．００Ｖ，终止电位－１．２０Ｖ测定，检出银为１ｍｇ／Ｌ，变异系数为３．２％－６．０％，回收率     

浸渍活性炭脱除H2S的反应动力学

提出了浸渍活性炭脱除Ｈ２Ｓ的反应过程机理模型，认为脱硫过程主要是Ｈ２Ｓ在活性炭的吸附水膜内离解后被活化的Ｏ２分子以及活性氧原子氧化生成单质硫逐渐沉积在活性炭表面，同时应用最小二乘法回归实验数据得到了脱硫动力学方程ｄＷｓ／ｄｔ＝ｋ１ｋ２／ａｐｏ２／ｐＨ２Ｓ／１＋ｋ２ｐｏ２×（１－αＷｓ）＾２其中动力学参数ｋ１＝３．７５３×１０＾５ｅｘｐ「－３００６．５／Ｔｒ」ｋ２／０．２６３ｅｘｐ「１９４５．６／Ｔ     

四磺化酞菁钴轴向配位反应研究

采用分光光度法研究了四磺化酞菁钴（ＣｏＴＳＰｃ）与配体Ｌ（Ｌ＝ｅｎ，ＮＨ３，ＣＮ）的配位反应，研究了配位反应学，测定了配合物的稳定常数Ｋ，并讨论了配位反应机理，研究表明：ＣｏＴＳＰｃ与Ｌ形成ＣｏＴＳＰｃ（Ｌ）２的配合物，动力学方程为：－ｄＣＭ／ｄｔ＝ｋＣＭＣＬ，ＣＭ、ＣＬ分别为ＣｏＴＳＰｃ的单体和配体的浓度（ｅｎ；ｎ＝１；ＮＨ３，ＣＮ：ｎ＝２）；ＣｏＴＳＰｃ（Ｌ）２的稳定常数为：Ｌ＝ｅｎ，ｌｇＫ＝     

ACETIC ACID AS AN OXYGEN CARRIER BETWEEN TWO PHASES FOR EPOXIDATION OF OLEIC ACID

Acetic acid was found to be an effective oxygen carrier for epoxidation of oleic acid. The reaction model of oleic acid epoxidation in the two-phase reaction system was systematically analyzed and the rate determining step was experimentally identified.

The results indicated that the rate of oxidation of the unsaturated acid was independent of the concentration of oleic acid and depended on the mixing rate and the rate of formation peracetic acid which in turn depended on the concentration of acetic acid, strength of acid catalyst and the oxygen source, hydrogen peroxide. In the region of reaction control, the rate equation of epoxidation was found to be

$

where k = 2.98 × 10^-2 M^-2 min^-1 at temperature of 35^°C.     

MODEL OF CHEMICAL REACTION EQUILIBRIUM OF SULFURIC ACID SALTS OF TRIOCTYLAMINE

The chemical reaction of trioctylamine (TOA) and sulfuric acid in organic solvent/aqueous solution was carried out. TOA salt products of various kinds were obtained based on different conditions of operation and organic solvents. An equilibrium model, based on the chemical reaction of sulfuric acid and trioctylamine, is proposed. The equilibrium constants of various reactions of trioctylamine and sulfuric acid were searched by means of the modified LETAGROP-DISTR computer program, from which the sum of the least-square error of the extraction of sulfuric acid per unit concentration of TOA salts was minimized. The corresponding concentration profiles of the various main products as a function of the activity of sulfuric acid in the aqueous solution were also obtained. The activity coefficient of the sulfuric acid in the aqueous phase and the density of the aqueous solution of sulfuric acid were considered in order to evaluate the activity of the sulfuric acid in the aqueous solution more accurately. The results obtained from the proposed model are consistent with that of Wilson's published model.     

外环流氨化反应器数学模型及其放大

研究了外环流氨化反应器的流动模型、传质模型和放大规律 .结果表明 ,在工业条件下 ,此反应器中的液相流动接近于全混流 ,传质模型为kGa =0 61W0 3a q1 2a应用此模型已将反应器放大到年产 60kt固体磷酸一铵规模 .     

稀醋酸催化精馏过程的反应动力学

研究了常压下温度308-328 K范围内用阳离子交换树脂作催化剂的稀醋酸合成醋酸甲酯本征反应动力学,得到基于Langmuir-Hinshelwood吸附理论用活度表示的通用动力学方程,在此基础上建立了数学模型并通过模拟计算证明了催化精馏过程是回收水溶液中醋酸的有效方案,为工业设计放大提供了理论依据.     

三辛胺萃取草酸的机理

选择草酸稀溶液为萃取对象 ,采用三辛胺 (TOA)为络合剂 ,正辛醇为稀释剂 ,开展了TOA萃取草酸的机理研究 .以红外谱图为分析手段 ,通过测定络合剂及被萃溶质的浓度对萃合物组成的影响 ,得到其萃合物以 1∶1和 1∶2 (酸 :碱 )两种形式存在于有机相中 ;并通过萃取平衡实验 ,获得了TOA萃取草酸的平衡特性 ,进一步验证了萃合物组成 .以此为基础建立了草酸与TOA两种萃合比情况下的数学模型 ,拟合求得了K₁₁及K₁₂ ,其中 1∶2萃合物的化学萃取平衡常数远远小于 1∶1的相应值     

EXTRACTION MECHANISM OF PHENOL BY SULFURIC ACID SALTS OF TRIOCTYLAMINE

In the present study, the extraction mechanism of phenol from an aqueous solution by sulfuric acid salts of trioctylamine (TOA salts) was investigated. Based on the experimental evidence that the affinity of sulfuric acid and amine is greater than that of phenol and amine, the procedure of the extraction mechanism is assumed to involve two independent steps, i.e., trioctylamine (TOA) is first reacted with sulfuric acid to form TOA salts and phenol is extracted from the aqueous phase by TOA salts. The Wilson model, which accounts for the reaction of trioctylamine and sulfuric acid to form different kinds of TOA-salts, is employed to predict the extraction of phenol in the present study. The number of water molecules in the neighborhood of the different TOA-salts, which directly reflects the extraction capability of phenol, was determined. This prediction from the Wilson model is fairly consistent with the experimental data.     

年青煤硝酸氧解制备硝基腐植酸的研究

对山东龙口的洼里褐煤、北皂长焰煤进行了稀硝酸氧化降解制备硝基腐植酸的实验研究，获得了影响硝基腐植酸产率的诸因素，如硝酸浓度、氧解温度、氧解时间、煤粒度等的影响规律。对氧解产物硝基腐植酸进行了ＦＴ－ＩＲ，光密度Ｅ＿４／Ｅ＿６以及主要活性基团的测定，论述了煤硝酸氧化降解的化学反应模式。     

SCRUBBING OF NITROGEN OXIDES WITH NITRIC ACID SOLUTIONS

A mathematical model is developed for an equilibrium stage analysis of nitrogen oxides absorption in nitric acid solutions. Using equilibrium data available from the literature, the model demonstrates that 15-35 wt% nitric acid may be efficiently used to reduce pollutant emissions in NO_x-containing gases having low degree of oxidation. Lower oxides of nitrogen accumulate in the liquid as nitrous acid which is carried away by the nitric acid solution. The scrubbed gas contains a reduced concentration of nitrogen oxides and has a higher degree of oxidation than the feed gas.     

THE EXTRACTION OF RHODIUM FROM AQUEOUS HITRIC ACID BY ORGANOPHOSPHINE SULPHIDES

The organophosphine sulphides, tri-phenyl phosphine sulphide (TPPS), tri-n-butyl phosphine sulphide (TBPS) and N,N',N"-tri-n-hexyl phosphorothioic-triamide (THPS) have been investigated for their potential use as extractants for the recovery of fission product rhodium from aqueous nitric acid solutions. The ease with which the extractions proceed can be rationalised in terms of the polarisability of the P=S bond, and in the case of THPS, the extraction is shown to proceed via a solvating type mechanism. Equilibration times for the extraction are of the order of 3-6 hours.     

对硝基苯甲酸催化加氢本征动力学

用活性炭载钯催化剂,在排除扩散影响的条件下,研究了对硝基苯甲酸加氢的动力学。实验测定了氢气压力、温度、催化剂浓度等因素对反应速率的影响。研究结果表明：对硝基苯甲酸催化加氢反应为一级反应,表面化学反应活化能Ｅ＝２５．９１０ｋＪ／ｍｏｌ,原子氢吸附热ＱＨ＝３８．４８７ｋＪ／ｍｏｌ,其总括动力学方程为ｒ＝Ｋｃ２ＴＫＨαＰＨ（１＋ＫＨα·ＰＨ）２·ｃＡ其中：ｃ２ＴＫ＝４．０３５×１０３ｅｘｐ［－２５９０９．４９／ＲＴ］,ｍｉｎ－１αＫＨ＝５．０１３×１０－６ｅｘｐ（３８４８６．９３／ＲＴ）,ＭＰ