概述
In processes for removing ruthenium by distilling RuO4from ruthenate-containing solutions with these steps of
the treatment of the ruthenate-containing solution with an oxidising agent,
distilling off of the RuOformed,
absorbing the RuOfrom step II in hydrochloric acid,
the oxidising agent is recycled into step I following step II. The processes can be carried out in reactor modules with
A a reactor with a stirrer,gas inlet and gas outlet,
B at least one scrubber connected in series downstream with the gas outlet via a line,
C one or several gas absorbers connected in series down- stream with the at least one scrubber via lines,
E at least one line from the optionally last absorber for recycling into the gas inlet of the reactor
or into a further module
or into a facility for off-gas treatment.
通过以下步骤从含钌酸盐的溶液中蒸馏RuO4来去除钌的方法中：
用氧化剂处理含钌酸盐的溶液，蒸馏RuO形成，吸收RuO从步骤II的盐酸中，氧化剂在步骤II之后再循环到步骤I中。该过程可以在具有一种具有搅拌器、气体入口和气体出口的反应器，B至少一个洗涤器，所述洗涤器经由管线在所述气体出口的下游串联连接，C一个或多个气体吸收器，其通过管线与至少一个洗涤器串联在下游，E来自任选*后一个吸收器的至少一条管线，用于再循环到反应器的气体入口中或进入另一个模块或者进入用于废气处理的设施。
[0001] The invention relates to processes and devices for removing ruthenium as RuO4 from ruthenate-containing solutions by distillation.
本发明涉及通过蒸馏从含钌酸盐的溶液中以RuO4形式除去钌的方法和装置。
[0002] Parting products containing ruthenium(and,if applicable,osmium)are treated initially with an alkaline oxi- dising melt,forexample,to recover the noble metals.Follow- ing leaching,solutions are obtained therefrom which contain K
RuO(and,if applicable,KOsO).The elements Ru and Os are advantageously partitioned oxidatively as tetroxides. Suitable oxidising agents for this purpose are e.g.oxygen/ ozone,H
O/sulphuric acid,peroxodisulphate,bromine or chlorine.The tetroxides are separated off by distillation.
例如，含有钌（以及锇，如果适用）的分离产物*初用碱性氧气熔体处理，以回收贵金属。在浸出之后，从中获得含有K的溶液RuO（如果适用，KOsO).元素Ru和Os有利地被氧化分配为四氧化二磷。适用于此目的的氧化剂有：氧气/臭氧、HO/硫酸、过氧二硫酸盐、溴或氯。四氧化二磷通过蒸馏分离出来
[0003] From JP61006130A,it is known to saturate ruthen- ate-containing aqueous solutions from alkaline melt leaching with chlorine gas,to decompose the hypochlorite formed by acidification,to distill off RuO
and to take it up in HCl.A yield of 99%is indicated as being obtained on a laboratory scale.
从JP61006130A中，已知用氯气饱和来自碱性熔融浸出的含钌酸盐的水溶液，以分解通过酸化形成的次氯酸盐，从而蒸馏出RuO并将其吸收在HCl中。99%的产率表明是在实验室规模上获得的。
[0004] To liberate RuO,chlorine is consumed: 解放鲁,氯被消耗：
2K+RuO-+Cl→RuO+2KCl (I)
[0005] During absorption in HCl,twice the quantity of chlorine is liberated:
在吸收HCl的过程中，释放出两倍量的氯：
RuO+10HCl→HRuCl+2Cl+4HO (I)
[0006] When an oxidising agent such as chlorine or a chlo- rine/air mixture is passed through the ruthenate-containing solution on an industrial scale and acts as entrainer for RuO
, a large quantity of oxidising agent is consumed in the process.
当氧化剂（如氯或氯/空气混合物）在工业规模上通过含钌酸盐的溶液并作为钌的夹带剂时, 在该过程中消耗了大量的氧化剂。
[0007] The invention attempts above all to remedy this problem.It has the object of providing a process forremoving ruthenium as RuO
from ruthenate-containing solutions by distillation,in which process the oxidising agent is used as efficiently as possible with a high yield.
本发明首先试图解决这个问题。其目的是提供一种以RuO形式去除钌的方法通过蒸馏从含有钌酸盐的溶液中提取，在该过程中，氧化剂以尽可能高的产率被有效地使用。
[0008] A furtherobject is the provisionofa process suitable for automation. 另一个目标是提供一个适合自动化的过程。
[0009] The object is achieved by way of processes accord- ing to claim 1.Advantageous embodiments can be found in the further claims.
该目的是通过根据权利要求1的方法实现的。在进一步的权利要求中可以找到有利的实施方案。
[0010 ] In this process,the oxidising agent,e.g.a chlorine/ air mixture,is recycled within a distillation facility.
在这个过程中，氧化剂，例如氯/空气混合物，在蒸馏设备中循环使用
[0011] Advantageously,the reactor is heatable and cool- able such that the temperature development can be controlled in an automated manner.
有利的是，反应器是可加热和可冷却的，从而可以以自动方式控制温度发展。
[0012] It is advantageous to connect several distillation facilities in series as modules.Appropriately,the process is controlled in such a way that as soon as excess oxidising agent,e.g.chlorine,is developed in a facility,its gas mixture is pumped into the next facility.In this way,ifchlorine is used as oxidising agent,chlorine produced in the process,too,is utilised for the oxidation of ruthenate.With this method of operation,approximately 1.9 kg of chlorine per kg of Ru,for example,are introduced from outside.As a result of the recycling operation,approximately 0.2 kg of chlorine per kg of Ru pass into the off-gas purification facility.
将几个蒸馏设施串联作为模块是有利的。适当地，控制该过程的方式是，一旦在一个设施中产生过量的氧化剂，如氯，其气体混合物就会被泵送到下一个设施。通过这种方式，如果氯被用作氧化剂，那么在该过程中产生的氯也被用于钌酸盐的氧化。利用这种操作方法，例如，从外部引入每千克Ru大约1.9千克氯。作为再循环操作的结果，每公斤Ru大约有0.2公斤氯进入废气净化设施。
[0013] If the pH of the alkaline ruthenate-containing solu- tion is reduced with acid before introducing the chlorine,the violence of the reaction is easier to control.
如果在引入氯之前用酸降低含钌酸盐的碱性溶液的pH，则反应的剧烈程度更容易控制。
[0014] It has proved to be advantageous to keep the con- centration of hydrochloric acid in which RuOis taken up at ahigh level,appropriately above 5 mole/1,by introducing HCl gas to prevent RuO
from accumulating.
事实证明，保持RuO中盐酸的浓度是有利的通过引入HCl气体以防止RuO，在较高水平（适当地高于5摩尔/1）下被吸收防止积累。
[0015] Appropriately,the process is integrated into a pro- cedure for recovering ruthenium from partitioning products. In this case,the absorbed H
RuCls and the mother liquors which have arisen are worked up in a manner known to the expert
适当地，将该过程整合到从分配产物中回收钌的过程中。在这种情况下，吸收的HRuCl和出现的母液是以专家已知的方式处理的
[0016] The process according to the invention is elucidated by way ofthe following example.Parts and percentages relate to the weight,as they do in the rest of the description,unless indicated otherwise.
根据本发明的方法通过以下实施例来阐明。除非另有说明，否则部分和百分比与重量有关，与说明书其余部分相同。
EXAMPLE 例子
[0017] Aruthenium-containing melt cake from the alkaline oxidising melt is leached with non-potable water with stir- ring.The potassium/sodium ruthenate solution obtained is introduced into a glass flask and subsequently pumped into a
receiving vessel.
用非饮用水通过搅拌环对碱性氧化熔体中的含砷熔体滤饼进行浸出。将获得的钌酸钾/钠溶液引入玻璃烧瓶中，随后泵入接收船。
[0018] A5001reactor with a gas inlet,stirrer,gas outlet and a 501 washing flask connected to it,which flask is connected to four absorber receiving vessels connected in series and filled with concentrated HCl (first receiving vessel),diluted HCl(2nd and 3rd receiving vessel)and water(4th receiving vessel)is supplied with 50-801 of the potassium/sodium ruthenate solution and filled with service water to a level of
3001.Depending on the predetermined concentration of potassium/sodium ruthenate solution,5-101 of concentrated technical grade HNO
are added to the solution and the tem- perature is raised to 50°C.
A5001反应器，具有气体入口、搅拌器、气体出口和与其相连的501洗涤烧瓶，该烧瓶连接到四个串联连接并填充有浓HCl的吸收塔接收容器（一级接收容器），向稀释的HCl（第二和第三接收容器）和水（第四接收容器）供应50-801的钌酸钾/钠溶液，并用厂用水填充至3001.根据钌酸钾/钠溶液的预定浓度，5-101的浓缩工业级HNO加入溶液中，温度升至50°C。
[0019] 2.5m³/hofchlorine are introduced into the solution via an inlet pipe.On termination of the temperature hike,
heating is carried out.
2.5立方米/小时的氯通过入口管引入溶液中。在温度升高终止时，进行加热。
[0020] All the liquid ruthenium tetroxide that has collected at the bottom of the distillation flask is distilled off and col- lected in the receiving vessels.
在蒸馏烧瓶底部收集的所有液态四氧化钌都被蒸馏掉，并在接收容器中收集。
[0021] Before the end of the RuOdistillation,HCl gas is introduced into the first receiving vessel.RuO4 reacts to form HRuCls according to equation(II)in this process.The intro- duction is started once a temperature 80-85°C.has been reached in the distillation flask.
在RuO结束之前将HCl气体引入一级接收容器中。RuO4反应生成H在该过程中根据方程（II）的RuCls。一旦蒸馏烧瓶中的温度达到80-85°C，就开始引入。
[0022] The reaction is terminated when the washing water in the washing flask becomes almost colourless,a tempera- ture of at least 98°C.has been reached in the reactor and no further RuOis visible at the bottom of the washing flask.
当洗涤烧瓶中的洗涤水几乎无色，反应器中的温度至少达到98°C，且没有进一步的RuO时，反应终止在洗涤烧瓶的底部可见。
[0023] The stream of chlorine is interrupted.
氯气流中断。
[0024] The stream of HCl into the receiving vessels is maintained for a further 1-2 h.
将进入接收容器的HCl流再维持1-2小时。
[0025] The residue in the reactor is treated with 3-41 of 45-50%technical grade NaOH.
反应器中的残留物用3-41的45-50%的工业级NaOH处理。
[0026] The HRuCl/RuClsolution obtained is removed from the absorber receiving vessels.
H氯化钌/氯化钌将获得的溶液从吸收器接收容器中移除。
[0027] The invention also relates to devices according to
claim 9 for carrying out the process described.
本发明还涉及根据权利要求9所述的方法。
[0028] FIG.1 shows a module of an exemplary device for
executing the process.
图1示出了用于执行该过程。
[0029] In the case of the module,a washing fask 2 is connected in series downstream to a reactor 1 with a stirrer 4, gas inlet 5 and gas outlet 6,in which washing flask the g
