CN117550659A - Ruthenium trichloride and preparation method thereof - Google Patents
Ruthenium trichloride and preparation method thereof Download PDFInfo
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- CN117550659A CN117550659A CN202311587922.2A CN202311587922A CN117550659A CN 117550659 A CN117550659 A CN 117550659A CN 202311587922 A CN202311587922 A CN 202311587922A CN 117550659 A CN117550659 A CN 117550659A
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 64
- 239000000047 product Substances 0.000 claims abstract description 32
- 239000000706 filtrate Substances 0.000 claims abstract description 29
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 2
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention belongs to the technical field of ruthenium trichloride preparation, and discloses a preparation method of ruthenium trichloride, which comprises the following steps: step 1: heating, evaporating and concentrating chlororuthenic acid under the pressure of-0.06 to-0.08 Mpa to obtain concentrated solution with the density of 1.30-1.40 g/ml; step 2: vacuum filtering the concentrated solution to obtain filtrate; step 3: and baking the filtrate to obtain a finished product. According to the invention, the ruthenium content of ruthenium trichloride is controlled cooperatively and precisely by fine control in each of the evaporation concentration stage, the filtration stage and the baking stage, the contents of insoluble alpha-ruthenium trichloride and ruthenium dioxide in ruthenium trichloride are effectively reduced, the purity of ruthenium trichloride is effectively improved, and the product quality is improved.
Description
Technical Field
The invention relates to the technical field of ruthenium trichloride preparation, in particular to ruthenium trichloride.
Background
Ruthenium trichloride is one of the most important compounds of ruthenium, is an important noble metal inorganic compound, can form a complex with other reagents, is a catalyst for heterogeneous catalysis, homogeneous catalysis, organic isomerization, polymerization, hydrogenation and other reactions, is an important chemical raw material in the fields of electroplating and the like, and is widely applied to the industries of chemistry, chemical industry, electronics, electroplating and the like.
Ruthenium trichloride is also a main raw material of the metal anode coating of the electrolytic cell, is a catalytic active material, and the quality of the ruthenium trichloride directly affects the quality of the metal anode coating; the solid ruthenium trichloride has alpha-crystal form and beta-crystal form, and the alpha-crystal form ruthenium trichloride is insoluble and has no activity; the ruthenium trichloride used in the production of the metal anode coating must be soluble and have an active beta-form, so that for the ruthenium trichloride product used in the metal anode coating of the electrolytic cell, the content of the two crystal forms of ruthenium trichloride needs to be strictly controlled, the generation of alpha-form ruthenium trichloride in the ruthenium trichloride is reduced as much as possible, and the high content of ruthenium in the ruthenium trichloride product can possibly generate insoluble alpha-form ruthenium trichloride, meanwhile, because the solid ruthenium trichloride is easy to absorb moisture, the water contained is unstable, and when the content of ruthenium is lower than a certain value, the water content is larger, so that the ruthenium trichloride is easy to wall and is unfavorable for use; thus, in the preparation of ruthenium trichloride, it is necessary to strictly control the ruthenium content.
The ruthenium content of ruthenium trichloride solid in industry is generally required to be between 35% and 38%; since the detection of the crystal form of ruthenium trichloride has very high requirements on instruments and detection technology, the crystal form of ruthenium trichloride is not detected independently, whether the crystal form of ruthenium trichloride is qualified or not is usually judged by measuring the amount of insoluble substances in the crystal form, and the content of n-butanol insoluble substances of ruthenium trichloride which is an I product is not higher than 0.5% is clearly determined by using the ruthenium trichloride chemical industry standard for the metal anode coating of the HGT3679-2011 electrolytic tank.
Prior art 1: chinese patent application CN107540025a discloses a method for preparing ruthenium trichloride hydrate, firstly, mixing metallic ruthenium powder with sodium chloride, melting at high temperature, adding trace starch to maintain the early temperature rising stage as weak reducing atmosphere; then introducing chlorine into the molten melt to convert most of ruthenium powder into sodium chlororuthenate; the ruthenium tetroxide gas produced in the melting process is absorbed by adopting a mixed solution of dilute hydrochloric acid and ethanol; and (3) merging the molten sodium chlororuthenate with a dilute hydrochloric acid solution for absorbing ruthenium tetroxide, adding sodium hydroxide for neutralization to obtain black ruthenium hydroxide or hydrated ruthenium dioxide, filtering the product, washing for multiple times to remove sodium ions, adding hydrochloric acid for dissolution, and concentrating and crystallizing to obtain the hydrated ruthenium trichloride crystal.
The method disclosed by the patent can be used for efficiently promoting the conversion of ruthenium and has the advantages of high reaction speed and high reaction efficiency; however, the method has harsh high-temperature chlorination conditions and higher production safety hidden trouble, sodium ions carried by the neutralization product ruthenium hydroxide or hydrated ruthenium dioxide are difficult to remove, more waste water is generated by repeated washing, the hydrated ruthenium dioxide is relatively indissolvable in hydrochloric acid, and the conversion efficiency of the hydrated ruthenium dioxide into chlororuthenic acid is to be examined.
Likewise, prior art 2: chinese patent application CN115745031a discloses a method for preparing ruthenium trichloride, which comprises stirring ruthenium oxide and hydrochloric acid aqueous solution in a container equipped with a reflux condenser and an inlet/outlet gas pipeline, adding a cosolvent, heating to 100-110 ℃ for reflux reaction, and continuing to react at reflux temperature for 1 hour when the system changes from dark blue to reddish brown; finally cooling the system to room temperature, adding oxalic acid aqueous solution, stirring for 2 hours at normal temperature, filtering, distilling under reduced pressure, concentrating, and drying to obtain the ruthenium trichloride product with the purity of more than 99.9% and the sodium ion content of 10-20 ppm.
Compared with the prior art 1, the technical scheme has the advantages that the purity of the obtained product is higher, but the ruthenium dioxide raw material without sodium ions is difficult to obtain; because ruthenium dioxide is relatively insoluble in hydrochloric acid, the reaction efficiency may not be high although a cosolvent is added; in addition, the ruthenium trichloride slurry is possibly heated unevenly when being dried in an anti-corrosion oven, and the uneven local temperature leads to uneven products and difficult control of insoluble matters.
Based on this, prior art 3 discloses a reaction-controllable technical solution, prior art 3: chinese patent application CN106335932A discloses a process for producing ruthenium trichloride by conventional method 4 A gas; then dilute hydrochloric acid is adopted to absorb RuO 4 The concentration of Ru in the gas to solution is 59-61 g/L, and meanwhile, the pH value is regulated to 1.9-2.1, thus obtaining ruthenium-containing solution; adding a dispersing solvent into the ruthenium-containing solution, wherein the adding volume of the dispersing solvent is 9 of the volume of the ruthenium-containing solution8 to 10.2 percent to obtain a dispersed ruthenium-containing solution; the dispersion solvent is hydrogen peroxide, ethanol and acetone according to the volume ratio of 1 (7.9-8.1): (0.95-1.05) and then spray-drying the resulting dispersed ruthenium-containing solution with a spray dryer to obtain ruthenium trichloride powder.
The method improves the traditional ruthenium trichloride production process, realizes continuous, large-scale and equipment production, and achieves the purposes of short production period, low cost and no environmental pollution; however, the method has high requirements on spraying equipment and great engineering difficulty; the concentration of ruthenium in the absorption liquid is 59-61 g/L, the spray feed amount is 800-1000 mL/h, the yield rate of 37% ruthenium trichloride solid is calculated to be lower than 165g/h, the production efficiency is insufficient to meet the production requirements of the technical development at present, in addition, the PH of the ruthenium-containing solution is regulated to be 1.9-2.1, alkaline substances are usually required to be added, new impurities can be introduced in the process, and the purity of the product is affected.
Based on the problems that the production efficiency of the 3 prior art is difficult to meet the latest technical development, the productivity is insufficient, insoluble substances are difficult to control or the purity is insufficient, and the like, the method for preparing the ruthenium trichloride, which can effectively balance the productivity, can control the insoluble substances and can control the product purity, is finally determined through experiments: concentrating and crystallizing the chlororuthenic acid solution, and drying to obtain hydrated ruthenium trichloride solid, wherein a glass container is adopted for baking under an infrared lamp during concentrating and crystallizing; however, the method is easy to cause the problem of poor consistency of products in each batch under the conventional condition, the particles of the products are uneven, basically the particles and the powder are all in blocks, the ruthenium metal content of the products can only be controlled by the experience of workers, the ruthenium content is suddenly high and suddenly low, the re-drying is required to be carried out, and more insoluble substances are probably generated, so that the qualification rate of the products is low.
Therefore, further development is needed to develop a ruthenium trichloride preparation method which can efficiently produce ruthenium trichloride and has controllable ruthenium trichloride content and insoluble matters.
Disclosure of Invention
The invention aims to provide a preparation method of ruthenium trichloride, which aims to solve the problems that the production efficiency of ruthenium trichloride is insufficient and the content of ruthenium and insoluble matters are difficult to control in the prior art.
The invention further aims to provide ruthenium trichloride, which is prepared by the preparation method of the ruthenium trichloride, has the advantage of controllable ruthenium content, has low content of insoluble alpha-type ruthenium trichloride and ruthenium dioxide, and improves the production efficiency obviously.
In order to achieve the above object, the present invention provides a method for preparing ruthenium trichloride, comprising the steps of:
step 1: heating, evaporating and concentrating chlororuthenic acid under the pressure of-0.06 to-0.08 Mpa to obtain concentrated solution with the density of 1.30-1.40 g/ml;
step 2: vacuum filtering the concentrated solution to obtain filtrate;
step 3: and baking the filtrate to obtain a finished product.
Preferably, the specific operation of the step 1 is as follows: adding chlororuthenic acid into a rotary evaporator, starting the rotary speed to be 20-40 RPM, vacuumizing the rotary evaporator to be-0.06 to-0.08 Mpa, evaporating and concentrating for a period of time at the heating temperature of 70-80 ℃ and the condensing temperature of 10-20 ℃, stopping heating when the density of the concentrated solution is 1.30-1.40 g/ml, and cooling.
Preferably, in the step 2, the vacuum degree of the vacuum filtration is-0.06 to-0.09 Mpa.
Further preferably, in the step 2, the funnel used for vacuum filtration is a sand core funnel with a filter membrane, the aperture of the sand core funnel is 16-30 um, the filter membrane is made of polytetrafluoroethylene membrane, and the aperture is 0.2 um.
Preferably, the specific operation of the step 3 is as follows: and (3) detecting the filtrate obtained in the step (2) to obtain the ruthenium content of W1, weighing the filtrate to obtain the filtrate with the mass of M1, uniformly baking the filtrate to form a baked material, weighing the baked material every 5 minutes of baking to obtain the baked material with the mass of M2, and ending baking when the ruthenium content W2 of the baked material reaches the target ruthenium content to obtain the finished product.
Preferably, the target ruthenium content of the ruthenium trichloride finished product is 35% -38%.
Wherein the ruthenium content W2 of the baked material can be calculated by the following formula: w2=w1×m1/M2.
The invention also provides ruthenium trichloride, which is prepared by adopting the preparation method of ruthenium trichloride.
Further, the content of alpha-type ruthenium trichloride and ruthenium dioxide in the ruthenium trichloride is low.
Advantageous effects
Compared with the prior art, the invention has at least the following advantages:
(1) The invention discloses a preparation method of ruthenium trichloride, which is characterized in that the evaporation concentration of chlororuthenic acid is carried out by using a decompression evaporation method in the evaporation concentration stage, so that the proper vacuum degree is controlled, the evaporation concentration efficiency is effectively improved, and meanwhile, the evaporation of ruthenium can be prevented;
(2) The method controls the production efficiency of the whole production step by controlling the density of the solution in the evaporation concentration stage, avoids the problem that the subsequent baking efficiency is influenced by too low ruthenium content in the solution, and simultaneously avoids the problem that the subsequent filtration rate is reduced due to the increase of the viscosity of the solution caused by too high ruthenium content, thereby effectively improving the whole production efficiency;
(3) The invention adds a filtering step before baking, thereby effectively reducing the content of insoluble substances in the ruthenium trichloride obtained by production;
(4) The invention discloses a preparation method of ruthenium trichloride, which controls the content of ruthenium by a ruthenium content calculation method in a baking stage so that the contents of alpha-type ruthenium trichloride and ruthenium dioxide in the prepared ruthenium trichloride are low, and the quality of the prepared ruthenium trichloride product is further improved;
(5) According to the invention, the ruthenium content of ruthenium trichloride is controlled cooperatively and precisely by fine control in each of the evaporation concentration stage, the filtration stage and the baking stage, the contents of insoluble alpha-ruthenium trichloride and ruthenium dioxide in ruthenium trichloride are effectively reduced, the purity of ruthenium trichloride is effectively improved, and the product quality is improved.
Detailed Description
The invention is further described below in connection with the examples, which are not to be construed as limiting the invention in any way, but rather as a limited number of modifications which are within the scope of the appended claims.
In order to explain the technical content of the present invention in detail, the following description will further explain the embodiments.
In the following examples and comparative examples, the funnel used for vacuum filtration was a sand core funnel with a filter membrane having a pore size of 16um, and a polytetrafluoroethylene membrane having a pore size of 0.2 μm;
in the following examples and comparative examples, the evaporation and concentration stage of step 1 was performed by sampling the test concentrate at intervals of 5 minutes.
Example 1
Ruthenium trichloride is prepared by the following steps:
step 1: adding 35kg of chlororuthenic acid into a rotary evaporator, wherein the ruthenium content of the chlororuthenic acid is 3.70%, the rotation speed is opened to 30RPM, then vacuumizing the rotary evaporator, the vacuum degree is minus 0.07Mpa, evaporating and concentrating for a period of time at the heating temperature of 75 ℃ and the condensing temperature of 15 ℃, stopping heating when the density of the concentrated solution is 1.35g/ml, and cooling to obtain the ruthenium content in the condensate liquid which is less than 0.2ppm;
step 2: vacuum filtering the concentrated solution to obtain filtrate, wherein the vacuum degree of vacuum filtration is-0.08 Mpa;
step 3: detecting the filtrate obtained in the step 2 to obtain a ruthenium content W1 of 18.5%, weighing the filtrate to obtain a filtrate mass M1 of 7kg, and uniformly baking the filtrate to obtain a baked material mass M2 of 3.477kg;
wherein, the target ruthenium content W2 of the baked ruthenium trichloride is set to be 37.25%, and the mass M2 of the baked material obtained by baking is 3.477kg according to the calculation of W2=W1×M1/M2.
Example 2
Ruthenium trichloride is prepared by the following steps:
step 1: adding 30kg of chlororuthenic acid into a rotary evaporator, wherein the ruthenium content of the chlororuthenic acid is 5.33%, the rotation speed is opened to 40RPM, then vacuumizing the rotary evaporator, the vacuum degree is-0.08 Mpa, evaporating and concentrating for a period of time at the heating temperature of 80 ℃ and the condensing temperature of 10 ℃, stopping heating when the density of the concentrated solution is 1.40g/ml, cooling, and measuring that the ruthenium content in the condensate is less than 0.2ppm;
step 2: vacuum filtering the concentrated solution to obtain filtrate, wherein the vacuum degree of vacuum filtration is-0.08 Mpa;
step 3: detecting the filtrate obtained in the step 2 to obtain a ruthenium content W1 of 20.0%, weighing the filtrate to obtain a filtrate mass M1 of 8kg, and uniformly baking the filtrate to obtain a baked material mass M2 of 4.244kg;
wherein, the target ruthenium content W2 of the baked ruthenium trichloride is set to be 37.70%, and the mass M2 of the baked material obtained by baking is calculated according to W2=W1×M1/M2 to be 4.244kg.
Example 3
Ruthenium trichloride is prepared by the following steps:
step 1: adding 25kg of chlororuthenic acid into a rotary evaporator, wherein the ruthenium content of the chlororuthenic acid is 5.33%, the rotating speed is started to be 20RPM, then vacuumizing the rotary evaporator, the vacuum degree is-0.06 Mpa, evaporating and concentrating for a period of time at the heating temperature of 70 ℃ and the condensing temperature of 20 ℃, stopping heating when the density of the concentrated solution is 1.36g/ml, cooling, and measuring that the ruthenium content in the condensate is less than 0.2ppm;
step 2: vacuum filtering the concentrated solution to obtain filtrate, wherein the vacuum degree of vacuum filtration is-0.08 Mpa;
step 3: detecting the filtrate obtained in the step 2 to obtain ruthenium content W1 of 19.6%, weighing the filtrate to obtain filtrate mass M1 of 6.8kg, and uniformly baking the filtrate to obtain baked material mass M2 of 3.652kg;
wherein, the target ruthenium content W2 of the baked ruthenium trichloride is set to be 36.5%, and the mass M2 of the baked material obtained by baking is 3.652kg according to the calculation of W2=W1×M1/M2.
Comparative example 1
Substantially the same as in example 1, except that step 2 was omitted.
Comparative example 2
Substantially the same as in example 1, except that the above-mentioned step 1 was changed to: 35kg of chlororuthenic acid was charged into a rotary evaporator, wherein the content of ruthenium in chlororuthenic acid was 3.70%, the rotation rate was turned on at 30RPM, then the solution was concentrated by evaporation at a heating temperature of 105℃and a condensing temperature of 15℃for a period of time, and when the density of the concentrate was 1.35g/ml, the heating was stopped, and the cooling was performed, and the content of ruthenium in the condensate was measured to be 10ppm, which took 2 times as long as in example 1, affecting the production efficiency and causing loss of ruthenium or increasing the secondary recovery cost.
Comparative example 3
Substantially the same as in example 1, except that the above-mentioned step 1 was changed to: adding 35kg of chlororuthenic acid into a rotary evaporator, wherein the ruthenium content of the chlororuthenic acid is 3.70%, the rotation speed is opened to 30RPM, then vacuumizing the rotary evaporator, the vacuum degree is minus 0.07Mpa, evaporating and concentrating for a period of time at the heating temperature of 75 ℃ and the condensing temperature of 15 ℃, stopping heating when the density of the concentrated solution is 1.25g/ml, and cooling to obtain the ruthenium content in the condensate liquid which is less than 0.2ppm;
wherein, the baking time of the step 3 is greatly increased due to the too low concentration liquid density, which affects the production efficiency.
Comparative example 4
Substantially the same as in example 1, except that the above-mentioned step 1 was changed to: adding 35kg of chlororuthenic acid into a rotary evaporator, wherein the ruthenium content of the chlororuthenic acid is 3.70%, the rotation speed is opened to 30RPM, then vacuumizing the rotary evaporator, the vacuum degree is minus 0.07Mpa, evaporating and concentrating for a period of time at the heating temperature of 75 ℃ and the condensing temperature of 15 ℃, stopping heating when the density of the concentrated solution is 1.45g/ml, and cooling to obtain the ruthenium content in the condensate liquid which is less than 0.2ppm;
the time consumption of the vacuum filtration in the step 2 is greatly increased due to the too high density of the concentrated solution, and the production efficiency is affected.
Comparative example 5
Substantially the same as in example 1, except that the above-mentioned step 3 was changed to: the ruthenium content is not controlled by a ruthenium content calculation method in the baking stage, and the end point of the material baking is observed and judged by means of the experience of personnel.
Results testing
The method for detecting the ruthenium content in the ruthenium trichloride product comprises the following steps: the ruthenium content in ruthenium trichloride is measured by using a hydrogen reduction gravimetric method which is common in the industry, and the allowable tolerance range for ruthenium content detection is +/-0.2%;
the method for detecting insoluble matters in ruthenium trichloride products comprises the following steps: reference is made to HGT3679-2011 under 6.3 of the chemical standard of ruthenium trichloride for metallic anode coating.
The ruthenium trichloride obtained in examples 1 to 3 and comparative examples 1 to 5 were subjected to detection of ruthenium content, insoluble matter and the like (the different sites were sampled and detected twice respectively to sufficiently verify uniformity of the product), and the production rates of ruthenium trichloride in the baking stages of examples 1 to 3 and comparative examples 1 to 5 were counted, and the results are shown in Table 1;
TABLE 1 test results of ruthenium content of ruthenium trichloride and insoluble content obtained in examples 1 to 3 and comparative examples 1 to 5
As can be seen from table 1:
as can be seen from the comparison of the data of example 1 and comparative example 1, the filtration step of the present invention can effectively reduce the content of insoluble substances in the finished product; after the filtration step is omitted in comparative example 1, the content of insoluble ruthenium trichloride obtained is too high, and the quality of the product is obviously reduced.
As is clear from the data of example 1 and comparative example 2, although the quality of the final ruthenium trichloride product was not affected, a small amount of ruthenium escaped to the condensate due to the higher evaporation temperature, resulting in loss of ruthenium or increase in secondary recovery cost, and the evaporation time was prolonged, wasting energy and affecting the production efficiency of the process.
Comparative example 3 the quality of the final ruthenium trichloride product was not affected, but the baking time of step 3 was greatly increased due to the excessively low concentration liquid density, which affected the production efficiency.
Likewise, in comparative example 4, the quality of the final ruthenium trichloride product was not affected, but the vacuum filtration time of step 2 was greatly increased due to the too high density of the concentrate, which affected the production efficiency.
As can be seen from the comparison of the example 1 and the comparative example 5, the invention adopts the control of the quality of the ruthenium trichloride obtained by drying to control the content of ruthenium, can precisely control the content and uniformity of ruthenium in the finished product, and effectively avoids the problem of inconsistent quality of ruthenium trichloride.
The embodiments presented herein are merely implementations selected from combinations of all possible embodiments. The following claims should not be limited to the description of the embodiments of the invention. Some numerical ranges used in the claims include sub-ranges within which variations in these ranges are also intended to be covered by the appended claims.
Claims (7)
1. The preparation method of ruthenium trichloride is characterized by comprising the following steps:
step 1: heating, evaporating and concentrating chlororuthenic acid under the pressure of-0.06 to-0.08 Mpa to obtain concentrated solution with the density of 1.30-1.40 g/ml;
step 2: vacuum filtering the concentrated solution to obtain filtrate;
step 3: and baking the filtrate to obtain a finished product.
2. The method for preparing ruthenium trichloride according to claim 1, wherein the specific operations of step 1 are: adding chlororuthenic acid into a rotary evaporator, starting the rotary speed to be 20-40 RPM, vacuumizing the rotary evaporator to be-0.06 to-0.08 Mpa, evaporating and concentrating for a period of time at the heating temperature of 70-80 ℃ and the condensing temperature of 10-20 ℃, stopping heating when the density of the concentrated solution is 1.30-1.40 g/ml, and cooling.
3. The method according to claim 1, wherein in the step 2, the vacuum degree of vacuum filtration is-0.06 to-0.09 Mpa.
4. The method according to claim 3, wherein in the step 2, the funnel used for vacuum filtration is a sand core funnel with a filter membrane, the pore diameter of the sand core funnel is 16-30 um, the filter membrane is made of polytetrafluoroethylene membrane, and the pore diameter is 0.2 μm.
5. The method for preparing ruthenium trichloride according to claim 1, wherein the specific operation of step 3 is: detecting the filtrate obtained in the step 2 to obtain the ruthenium content W1, weighing the filtrate to obtain the filtrate with the mass M1, uniformly baking the filtrate to form a baked material, weighing the baked material every 5min of baking to obtain the baked material with the mass M2, and ending baking when the ruthenium content W2 of the baked material reaches the target ruthenium content to obtain a finished product;
wherein the ruthenium content W2 of the baked material is calculated by the following formula: w2=w1×m1/M2.
6. Ruthenium trichloride, characterized in that it is produced by the process according to any one of claims 1 to 5.
7. The ruthenium trichloride of claim 6, wherein the ruthenium trichloride is low in alpha-form ruthenium trichloride and ruthenium dioxide.
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