常州丰硕化工有限公司

地址: 江苏省常州市百丈工业园 
邮编: 213000 
电话: 0519-88290710
 手机:13776880578
传真: 0519-88290710
e-mail: czfengshuo@163.com

繁體中文
当前位置:首页 > 技术指导 > 详细内容
氯化法钛白粉生产工艺
发布时间:2014-6-2  阅读次数:2708  字体大小: 【】 【】【

氯化法钛白粉的生产工艺过程
The production process of chlorination process titanium dioxide
氯化法对于硫酸法而言是一个技术进步,它可以高效率的连续化、自动化操作,产品质量好,直接排放的“三废”比硫酸法少得多,这是它可以取而代之硫酸法的基本原因。但是氯化法“三废”少主要取决于它的原料,大部分氯化法工厂使用的原料是TiO2含量95%以上的天然金红石或TiO2含量90%左右的人造金红石和钛渣,只有美国杜邦公司的氯化法工艺使用TiO2含量60%~84%的混合矿,当然这种工艺的“三废”排放量要比使用天然金红石和人造金红石或钛渣工艺的高,氯化法一般只能生产金红石型。
Chlorination is a technology for sulfuric acid method, continuous, automatic operation which can be high efficiency, good quality of product, the direct discharge of "three wastes" much less than sulfuric acid method, which is the basic reason which can replace sb. sulfuric acid method. But by "three wastes" less depends mainly on the material, most of the raw materials used by factory is a 90% natural rutile or TiO2 content more than 95% of the TiO2 content of synthetic rutile and titanium slag, mixed ore only chlorination process America DuPont Co use TiO2 content 60%~84%, of course, the process of "three wastes" emissions over the use of natural rutile and synthetic rutile or high titanium slag process, chlorination process can only produce rutile.
氯化法的工艺流程比硫酸法短得多,主要包括四氯化钛制备、四氯化钛的氧化和二氧化钛的表面处理三大部分。
Process of chlorination is much shorter than sulfuric acid method, mainly including oxide and titanium dioxide titanium chloride four four titanium chloride preparation, surface treatment of three parts.
1、四氯化钛的制备与精制
Preparation and purification of the 1, four titanium chloride system
氯化法对原料的要求比硫酸法苛刻得多,它要求使用TiO2含量在90%以上的钛矿,目前常用的有天然金红石矿、人造金红石和高钛渣。氯化法对矿粉的细度和湿度要求比硫酸法严,因为在沸腾氯化时要使质量较重的钛矿和质量较轻的石油焦或焦碳都能顺利的流态化,矿粉细度的均匀是很重要的,此外湿度大水分含量高,在氯化过程中会产生氯化氢和氯化氧钛,前者会腐蚀设备,后者会堵塞管道、阀门。
The chlorination process requirements on raw materials than the sulfuric acid method much more demanding, it requires the use of TiO2 content in more than 90% of titanium, the commonly used natural rutile ore, rutile and titanium slag. Chlorination of powder fineness and humidity requirements than the sulfuric acid method strictly, because of the lighter titanium and quality in boiling chlorination to make quality heavier petroleum coke or a coke can flow smoothly, powder fineness uniformity is very important in high humidity, high moisture content, can be generated in the process of titanium in chloride hydrogen chloride and oxygen chloride, the former will corrode the equipment, the latter will plug the pipe, valve.
二氧化钛的氯化反应是一个可逆的吸热反应,而且必须有还原剂的存在下才能进行,否则温度高达1800℃也无法氯化,反应式如下:
Chlorination of titanium dioxide is a reversible endothermic reaction, and must have the presence of a reducing agent can be carried out, otherwise the temperature up to 1800 ℃ cannot chloride, the reaction equation as follows:
TiO2+C+Cl2→TiCl4+CO(CO2)
The TiO2+C+Cl2 → TiCl4+CO (CO2)
从上式可以看出反应的副产物不仅有CO,也可能有CO2,一般反应温度在700℃以上,以生成CO为主,反应温度在700℃以下,以生成CO2为主,因此测定炉气中的CO/CO2比值,可以掌握炉内的氯化状况。
From the type can be by-products that reaction not only have CO, and possibly CO2, reaction temperature 700 ℃ in general, to generate the CO, the reaction temperature is 700 ℃ below, to generate a CO2 based, so the determination of CO/CO2 ratio in the furnace gas, can master the furnace condition of chloride.
过去那种老式的固定床氯化法,现在已被沸腾化炉取代,固定床需要事先把金红石矿与石油焦按一定比例(钛渣:石油焦:沥青=7:2:1)混捏制团焦化,不利于连续化、自动化操作。大型沸腾氯化炉直径2~6m,内衬耐火砖,干燥的金红石矿(或钛渣)在氯化炉内先用空气使其流态化,并加热至650℃左右,然后加入干燥的焦碳或石油焦(金红石:石油焦=78:22),待温度升至900℃时用气化氯代替空气进入沸腾炉内,接着金红石矿(或钛渣)与焦碳(或石油焦)按一定的比例在保持沸腾床一定高度的情况下陆续加入,让氯化反应按一定的速率进行(氯气的气速一般为0.1~0.15m/s)。氯化反应一般维持在950~1000℃,正常生产时使用回收氯,不足部分用新鲜氯补充,如果反应温度超过1000℃,有可能使矿粉与反应的杂质氯化物烧结而造成死床,在这种情况下可以通入干燥的氮气来降温。
Old fixed bed chlorination, has now been fluidized bed furnace replaced, fixed bed need prior to the rutile ores and petroleum coke (according to a certain proportion of titanium slag: petroleum coke: asphalt =7:2:1) mixing kneading regiment coking, is not conducive to the continuous, automatic operation. Large boiling chlorination furnace lining refractory brick, 2~6m in diameter, dry Jin Hongshi mine (or titanium slag) in chlorinated furnace with the air to flow, and heated to 650 ℃, then add the dry coke and petroleum coke (Jin Hongshi: petroleum coke =78:22), when temperature is above 900 ℃ for gasification chloride instead of air into the boiling furnace, then Jin Hongshi ore (or titanium slag) and coke (or petroleum coke) according to a certain ratio in fluidized bed height circumstances be added, let the chlorination reaction in a certain rate (chlorine gas velocity is 0.1 ~0.15m/s). Chlorination is generally maintained at 950~1000 ℃, the use of the recovery of normal production, the insufficient part added fresh chlorine, if the temperature is over 1000 ℃, may make the impurity chloride sintered ore and reaction caused by the death bed, in this case can pass into the dry nitrogen to cool.
在二氧化钛氯化的同时,矿中的杂质也参与氯化反应生成FeCl3、SiCl4、AlCl3、VOCl3、MnCl2、NbCl5、SnCl2、MgCl2等,在反应气体出来冷却到200℃左右后,大部他杂质的氯化物冷凝在炉灰上而沉降下来,气体经过滤进一步冷凝到-12℃左右以尽可能的回收四氯化钛(通常用冷四氯化钛喷淋),不凝性气体主要是CO、CO2、H2、余氯和微量的四氯化钛,经气体处理装置用碱液吸收后排放。这种粗四氯化钛是一种红棕色的浑浊液体,在氯化前要通过蒸馏来精制。
In titanium dioxide chloride at the same time, impurity ore also participate in the chlorination reaction generated FeCl3, SiCl4, AlCl3, VOCl3, MnCl2, NbCl5, SnCl2, MgCl2, in the reaction gas from cooling to 200 ℃, most impurity chloride condensation in the ashes and settling down, gas through the filter further condensation to -12 ℃ to recycle four titanium chloride (usually with cold spray titanium chloride four), non condensable gas is mainly CO, CO2, H2, residual chlorine and trace four titanium chloride, the gas processing device for alkali absorption emission. This coarse four titanium chloride is turbid liquid a reddish brown, in the chlorination prior to the adoption of distillation refining.
由于卤化物比较容易分级提纯,所以氯化法钛白粉的纯度比硫酸法高,这是它的主要优点之一。TiCl4的沸点是136℃,多数氯化物的沸点都与它有一定的距离,高于此沸点的主要有FeCl3、AlCl3等,低于此沸点的有SiCl4等,唯有钒的氯化物的沸点与它相近,工业生产中可以用传统的铜丝塔精馏除钒,或用不饱和矿物油处理成不挥发物后,再精馏后获得钒含量(以V2O5计)<×10-6级高纯四氯化钛液体,该液体无色透明、沸点136℃、凝固点-24℃、相对密度(20℃)1.726.
Because the halide easier fractionation purification, so the purity of the chlorination process titanium dioxide than the sulfuric acid method, which is one of its main advantages. TiCl4 boiling point is 136 ℃, the boiling point of the majority of chlorides have some distance from it, there are FeCl3, AlCl3 and other major above the boiling point, lower than the boiling point of SiCl4, the boiling point only vanadium chloride and its close, can remove vanadium with copper wire tower rectification of the traditional industrial production, or not saturated mineral oil into less volatile, then distillation obtained after vanadium (V2O5) < x 10-6 grade four titanium chloride liquid, the liquid is colorless and transparent, the boiling point of 136 DEG C, freezing point -24 ℃, relative density (20 ℃) 1.726.
四氯化钛遇水会立即发生强烈的放热反应,产生大量的白色HCl烟雾而污染环境、灼伤皮肤、刺激粘膜、损伤呼吸道组织、腐蚀设备,因此所有设备都要求严格密封、严禁泄漏。四氯化钛遇水的反应式如下:
Four titanium chloride water will occur immediately strong exothermic reaction, generate a lot of white HCl smoke and pollution of the environment, burn the skin, stimulate the mucosal injury, airway, equipment corrosion, so all equipment require strict sealing, no leakage. Reaction four titanium chloride in water:
TiCl4+H2O→TiOCl2+2HCl+Cl
The TiCl4+H2O → TiOCl2+2HCl+Cl
2、四氯化钛的氧化
Oxidation of 2, four titanium chloride
氧化是氯化法工艺核心,四氯化钛的氧化是气相反应,反应温度高达1400~1500℃左右,TiCl4生成TiO2的反应时间只有几毫秒,不像硫酸法从H2TiO3生成TiO2那样需要煅烧10余小时,其化学反应式如下:
Oxidation is chlorination process core, oxidation of four titanium chloride is a gas phase reaction, high reaction temperature was 1400~1500 ℃, reaction time TiCl4 generated TiO2 only a few milliseconds, unlike sulfuric acid generated from H2TiO3 TiO2 that requires more than 10 hours of calcination, the chemical reaction formula is as follows:
TiCl4(气)+O2(气)→TiO2[金红石(固)]+2Cl2(气)
TiCl4 (gas) +O2 (gas), TiO2[Jin Hongshi (solid)]+2Cl2 (gas)
氧化前先将精TiCl4液体在150~200℃下加热气化,分步或一步预热到900~1000℃,氧气同样也要预热到此温度,两者按一定比例同
The sperm TiCl4 liquid heating at 150~200 ℃ gasification first before oxidation, step by step or step preheating to 900~1000 ℃, oxygen also preheat this temperature, both according to a certain percentage of the same

关键词:金红石钛白粉

我要评论
  • 匿名发表
  • [添加到收藏夹]
  • 发表评论:(匿名发表无需登录,已登录用户可直接发表。) 登录状态:未登录
最新评论
所有评论[0]
    暂无已审核评论!

州丰硕化工有限公司 版权所

公司地址:江苏省常州市新北区百丈工业园  电话:0519-88290710  联系人:曹宏伟   18761199819   13776880578

金红石型钛白粉锐钛型钛白粉进口钛白粉立德粉滑石粉

 友情链接: 杜邦钛白粉  科美基钛白粉         超声波液位计 云母粉