氯化法钛白粉的生产工艺探究

从钛白粉及氯化法的基本原理介绍入手,分析了氯化法钛白粉生产工艺流程,在此基础上对氯化法钛白粉生产中废渣废水的处理及尾气的综合利用进行论述。期望通过研究能够对氯化法钛白粉生产工艺的推广使用有所帮助。     

国内外氯化法钛白粉生产技术的专利分布概况

为了解氯化法钛白粉相关生产技术的知识产权环境,降低企业知识产权风险,采用Innography专利分析平台对国内外氯化法钛白粉生产技术的专利申请进行了统计分析,并重点介绍了该技术在中国的相关专利布局情况。经研究分析发现：氯化法钛白粉生产技术的相关专利申请主要分布在美国、日本、德国、英国和中国;美国杜邦公司在氯化法钛白粉生产工艺的专利技术上有明显的优势;在中国,攀钢集团锦州钛业有限公司在氯化法钛白粉生产技术方面已形成相对完整的专利布局。最后,结合国内情况,给拟发展氯化法钛白粉的企业提出一些参考意见。     

硫酸法和氯化法钛白能耗分析与评述

钛白生产方法有硫酸法和氯化法两种,究竟哪一种方法好一直存在争议。从化学热力学角度,推算硫酸法和氯化法生产钛白的理论能耗,结果表明氯化法比硫酸法理论能耗低,氯化法具有节能优势。以钛铁矿原料为基态,比较硫酸法和氯化法的综合能耗,结果表明氯化法仍具有节能优势。以钛铁矿原料为基态,比较硫酸法产品（主产品为钛白,副产品为绿矾）和氯化法产品（主产品为钛白,副产品为粗铁）万元产值的能耗,结果表明氯化法仍具有明显的优势。究竟选择哪一种生产方法,能耗指标仅仅是一个方面,还要从投资、技术来源、运行成本、产品质量等方面综合考虑。     

钛白粉硫酸法与氯化法清洁生产比较

钛白粉其生产工艺主要分为硫酸法和氯化法两种,通过对比可知,氯化法钛白粉生产技术比硫酸法生产技术更先进、更环保,我国已将氯化法钛白粉技术列为清洁生产推行方案(推荐稿)中。     

国外氯化法生产钛白粉之进展

一、概述工业上生产钛白粉的方法仅有硫酸法与氯化法两种。硫酸法自1916年挪威建厂以来,一直沿用至今。氯化法的原理已了解了30余年,由于氯化法生产钛白粉与克鲁尔法生产海棉钛在四氯化钛发生与提纯方面极为相似     

三氯乙醛生产中杂质的影响

一、前言目前国内外生产三氯乙醛的工艺路线有乙醛氯化法和乙醇氯化法。国外生产多用乙醛氯化法。而我国大都是用乙醇氯化法。从理论上讲,乙醛比乙醇氯化法具有许多优点:即用氯量少;生成的副产氯化氢少;原料来源丰富(来自石油工业)等。而用乙醇氯化法生产三氯乙醛、据有关文献报道及生产实践证明,产生的杂质较多,由于这些杂质的存在,对制造敌百虫、氯仿等产品带来许多不利的因素,使产品的质量、收得率受到严     

天然气热氯化制四氯化碳生产装置降低原料消耗的途径

我国四氯化碳的生产厂家目前约有20多家,采用的生产方法除了传统的二硫化碳法外,主要有天然气热氯化法、一氯甲烷的热氯化法(或光氯化法)及废氯代烃高温气相氯化法等。其中以天然气热氯化法生产的四氯化碳为最多,全同已有生产装置10多家,生产能力约年4万吨左右。西南化工研究院于1986年受江苏金湖化肥厂的委托为该厂设训规模为2000t/a的四     

我国氯化法钛白技术的进展和展望

回顾了国内研制氯化法钛白的历史过程,特别介绍了锦州钛白粉公司1.5万t/a氯化法钛白生产技术的进展,分析认为国内具有发展氯化法钛白的有利条件.     

氯乙酰氯的合成工艺研究进展

综述了氯乙酰氯的合成工艺。氯乙酰氯的合成工艺有乙酸直接氯化法、氯乙酸氯化法、乙酰氯氯化法和乙烯酮氯化法等。国内主要以氯乙酸为原料，氯气氯化法生产氯乙酰氯，该法技术成熟、操作简便，但存在杂质较难控制、产品易残留硫等问题。光气氯化法具有杂质低、产品纯度高、收率高等优势，具有较好的工业化前景。     

出口有望退减税 钛白粉受瞩目

正中国钛白粉行业协会组织多家会员企业召开讨论会,为后期向主管部门申请氯化法钛白粉退减税做准备。氯化法生产钛白粉作为国际先进技术,施行减退税政策将提升国内行业国际市场竞争力,加快行业转型升级。钛白粉生产目前有硫酸法和氯化法两种工艺技术,氯化法具有工艺流程短、品质高、污染排放量小等优点,成为主流技术,全球产能占70%以上。由于海外化工巨头对氯化法技术高度封锁和垄断,中国氯化法产能占比不足10%。氯化法企业面临投资大、     

UV enhanced gas-solid synthesis of chlorinated poly vinyl chloride characterized by a UV-Vis online analysis method☆

Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as soon as UV lightwas affiliated, which demonstrated the intensified effect of UV radiation on PVC chlorination directly. Different affiliationmethods of UV light were then studied, proving that continuous UV radiation could enhance the chlorination process significantly while intermittent UV radiation was able to initiate the chlorination reaction once it was conducted. Besides, experiments were carried out to study the influences of parameters on the chlorination process such as UV wavelength, chlorination temperature, partial pressure of chlorine gas and PVC raw materials. Among all the parameters, chlorination temperature and partial pressure of chlorine gas were testified as two key factors to determine the chlorination performance. Thermal analysis of CPVC products showed that their corresponding properties such as the glass transition temperature (T_g) and the homogeneity of chlorine distribution in polymer phase were improved with the increase of chlorine content.     

乙酸光氯化反应制备氯乙酸工艺的研究

设计了一种新型实验室氯化反应器－－光照内环流气液反应器，应用于乙酸光氯化制氯乙酸的反应。该反应器具有光照效果好、易环流、密封性能好等。大环流反应器中考察了光照下不同反应温度对乙酸氯反应的影响，实测了不同温度下，乙酸、氯乙酸和二氯乙酸的浓度随反应时间的变化关系。将乙酸在环流反应器中的光氯伦反应结果与乙酐为催化剂的氯化反应结果进行了比较，发现光氯反应速率与乙酐为催化剂时的氯化速度时相当，但二氯乙酸生成量明显偏高，为了抑制二氯乙酸的生成，在光照的同时加入乙酐作为抑制剂，考察了不同的乙酐用量和加入方式对二氯乙酸生成的影响。     

提钛尾渣处理钛白废水试验研究

为了拓展攀钢提钛尾渣的利用途径及降低钛白企业废水处理成本,进行了提钛尾渣处理钛白废水的试验研究。试验表明,处理钛白废水的提钛尾渣中氯质量分数应≤0.24%,即必须使用洗后提钛尾渣处理钛白废水。随着废水酸浓度的增加及洗后提钛尾渣配比的增加,提钛尾渣与废水中和后pH越来越低;洗后提钛尾渣可代替20%石灰石液体中和废水,中和后pH、滤液及中和渣的化学成分在正常范围内。     

A kinetic model for glycerol chlorination in the presence of acetic acid catalyst

A kinetic model for the chlorination of glycerol with hydrochloric acid in the use of acetic acid as catalyst is presented in this study. The model is based on a comprehensive chlorination mechanism, taking the formation of 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol into account while ignoring the formation of any intermediate in the chlorination system. Simulations were carried out under different chlorination conditions to calculate the concentrations of the main chemical species in the reaction system. The validity of the model was examined via a comparison of the calculated data with the experimental data on the chlorination of glycerol with hydrochloric acid at 363–393 K. The results show the model is capable of describing the chlorination performance with good agreement with experimental data.     

The compatibility of poly(methyl methacrylate) and chlorinated polyethylene

The compatibility of poly(methyl methacrylate) with chlorinated polyethylene was studied using differential thermal analysis and dynamic mechanical measurements. For around 50% chlorination of polyethylene they were found to be compatible and show an LCST, but not at 27% chlorination as had previously been thought. The previous results were explained as due to a matching of refractive indices over some temperatures. The compatibility was explained by the heat of mixing which becomes favourable at chlorination levels above approximately 46%.     

CCl4低温氯化人造金红石制备TiCl4

为了开发低温钛氯化工艺及解决工业副产物CCl₄的再利用问题,在固定床和流化床反应器中考察了自贡法人造金红石原料与CCl₄低温氯化制备TiCl₄的反应过程,利用SEM、XRD、XPS等手段表征了人造金红石原料在反应前后的变化。结果显示,在450～500℃下,自贡法人造金红石能与CCl₄快速反应生成TiCl₄产品。少量Fe元素的掺杂是金红石相具备较高反应速率的关键原因。人造金红石原料制备过程中的弱氧化焙烧处理在颗粒表面形成的惰性金红石壳层,导致TiCl₄收率极限为90%,但该壳层能在酸解过程以及低温CCl₄氯化过程中维持颗粒粒度,使该原料能用于流化床操作。此过程具有显著的环保价值和工业应用前景。     

固相法合成涂料用高氯含量氯化聚乙烯

研究了固相合成高氯含量氯化聚乙烯过程中氯取代基，氯化温度、引发方式等对氯化速度的影响，及ＨＣＰＥ的降解。结果表明，大分子链上的氯取代代基对分子链进一步氯化起阻碍作用；氯化前期使用较高的温度或引发剂将使后面的氯化速度减慢；增大前期引发剂用量时，将会再次降低后期的氯化速度；通过机械剪切作用可使具有较高相对分子质量的ＨＣＰＥ大幅度降解。     

4,4-二甲基-3-氧戊腈合成的研究

对以丙酮为原料、先依次制得片呐醇、片呐酮、α 氯代片呐酮、最后由α 氯代片呐酮与NaCN反应制得 4,4 二甲基 3 氧 戊腈最后两步的反应条件进行了研究。片呐酮的α 卤代反应 ,氯代反应的产率比溴代反应的高 ,而且氯代产物与氰化钠反应的产率也比溴代产物的高。氯代反应在无水甲醇中进行 ,温度维持在 0～ 1 5℃。溶剂与片呐酮的质量比为 2 5∶1 0。氯气的通入量不应超过计算量 ,通入速度以维持反应体系温度不超过 0～ 1 5℃为宜 ,以防止反应温度过高而生成二氯化物。反应完成后 ,溶剂甲醇在减压下蒸出 ,并可以在下一次氯代反应中使用。将氰化钠的水溶液分批加入到α 氯代片呐酮的甲醇溶液中 ,然后在 0～ 1 0℃下酸化反应体系 ,制得 4,4 二甲基 3 氧 戊腈。     

3-氯-2,4-二氟苯甲酸的合成

提出了一种以2,6-氟苯胺为原料,经Sandmeyer反应、溴化和格氏反应三步得到3-氯-2,4-二氟苯甲酸的合成方法.其中Sandmeyer反应中氯代一步的最佳反应条件为:n(2,6二氯苯胺)∶n(氯化亚铜)=1 ∶0.55,氯代反应温度为70～90℃,氯代保温时间为2.5h.三步总摩尔产率约28％,纯度99.26 ...     

Improved peel strength in vulcanized sbr rubber roughened before chlorination with trichloroisocyanuric acid

The effectiveness of chlorination as surface treatment to improve the adhesion of synthetic vulcanized styrene-butadiene rubber (SBR) depends on several experimental variables. Solutions of trichloroisocyanuric acid (TCI) in methyl ethyl ketone (MEK) have been used as effective chlorination agents for several rubbers. In this study, the influence of roughening prior to chlorination treatment of a SBR rubber (R2) and the durability of the modifications produced as the time after chlorination increased have been considered. Two concentrations of the chlorination agent (0.5 and 2 wt% TCI/MEK) have been used and the chlorination treatment was applied on the R2 rubber surface using a brush. Characterization of the treated surfaces was carried out using contact angle measurements, ATR-IR spectroscopy and Scanning Electron Microscopy (SEM). T-peel tests of treated R2 rubber/polyurethane adhesive joints have been carried out to determine the adhesion properties. Roughening was an effective treatment to remove paraffin waxes (antiadherent moieties) from the R2 rubber surface. When the chlorination is produced on the roughened R2 rubber, more noticeable chemical and morphological modifications were produced, and higher adhesion was obtained. On the other hand, TCI particles appeared on the roughened and unroughened chlorinated R2 rubber surface, and the size of these TCI particles were decreased by increasing the time after treatment. Furthermore, similar peel strength values were obtained for time after halogenation higher than 2 hours; for shorter time, a decrease in peel strength was found by increasing the time, due to the migration of paraffin wax to the rubber surface.