CN106698529A - Two-step synthesis method of ruthenium nitrosyl nitrate - Google Patents
Two-step synthesis method of ruthenium nitrosyl nitrate Download PDFInfo
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- CN106698529A CN106698529A CN201710023096.7A CN201710023096A CN106698529A CN 106698529 A CN106698529 A CN 106698529A CN 201710023096 A CN201710023096 A CN 201710023096A CN 106698529 A CN106698529 A CN 106698529A
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- ruthenium
- nitric acid
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- nitrosyl
- solution
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- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000001308 synthesis method Methods 0.000 title abstract 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000004821 distillation Methods 0.000 claims abstract description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 7
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000006396 nitration reaction Methods 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000002390 rotary evaporation Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000009635 nitrosylation Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- -1 Nitrosyl nitric acid ruthenium Chemical compound 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a two-step synthesis method of ruthenium nitrosyl nitrate, and belongs to the field of synthesis of ruthenium nitrosyl nitrate. The method comprises the following steps of: taking ruthenium as a raw material, obtaining a ruthenium nitrosyl nitrate solution by two steps of nitric acid absorption by oxidative distillation and nitrosylation of gas, and obtaining a ruthenium nitrosyl nitrate solution or crystal required by customers by rotary evaporation, wherein the product reaches the YS/T 755-2011 standard. The method provided by the method not only solves the problems that the ruthenium nitrosyl nitrate prepared by the traditional method carries a large number of impurity elements and the process flow is complicated and the like, but also has the advantages of short process, simple operation, low energy consumption and the like, and is suitable for industrial production.
Description
Technical field
The invention belongs to the synthesis field of nitrosyl nitric acid ruthenium, and in particular to a kind of two step synthesizes the side of nitrosyl nitric acid ruthenium
Method.
Background technology
Nitrosyl nitric acid ruthenium (Ru (NO) (NO)3), brown color or dark red-brown solid, soluble in water, acetone equal solvent.By
Being free of halogen, sulphur, phosphorus etc. in it easily makes the element of catalyst poisoning, therefore as preparing the preferable presoma of ruthenium-based catalyst.
Ruthenium-based catalyst except be applied to synthesis ammonia in addition to, be also applied to producing cyclohexene with benzene selective hydrogenation and hydrogenation of carbon dioxide methyl alcohol
Deng.
Report on nitrosyl nitric acid ruthenium technology of preparing, patent CN102167405A report with ruthenium trichloride as raw material,
Natrium nitrosum high―temperature nuclei nitrosyl ruthenic chloride is added, then nitrosyl ruthenic chloride and silver nitrate reaction are obtained nitrosyl nitric acid ruthenium
Solution, solution obtains solid nitrosonitric acid ruthenium through ether extracting, evaporating；Patent CN104556250A is reported the nitrous of brand-new
Acid and ruthenium trichloride backflow are obtained nitrosyl ruthenic chloride, and nitrosyl ruthenic chloride and silver nitrate reaction equally are obtained into nitrosyl nitric acid
Ruthenium solution, solution obtains solid nitrosonitric acid ruthenium through ether extracting, evaporating.Nitrosyl nitric acid ruthenium prepared by above method can band
Enter substantial amounts of impurity element Cl-, Ag+, Na+Deng the ruthenium-based catalyst catalytic performance for directly resulting in preparation is poor, even without activity.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method that two step synthesizes nitrosyl nitric acid ruthenium, the preparation side
Method is absorbed with ruthenium as raw material using oxidation distillation nitric acid, and gas is nitrosylated, and two steps are prepared into nitrosyl nitric acid ruthenium solution, warp
Rotary evaporation is obtained the nitrosyl nitric acid ruthenium solution or crystal for meeting demand；The method has that process route is short, simple to operate, energy
Consumption is low, does not bring other metal impurities and Na into+The features such as.
The present invention is adopted the following technical scheme that：Two steps synthesize the method for nitrosyl nitric acid ruthenium, and methods described includes following step
Suddenly：
(1), ruthenium oxidation distillation nitric acid absorbs：
Raw material ruthenium is placed in distillation reactor, oxidation distillation generates the RuO of yellow4Gas；The RuO4Gas is through 2 grades
After deionized water washing, it is passed through 3 grades of 4~8mol/L salpeter solutions and absorbs, obtains the nitric acid absorbing liquid of ruthenium；Unabsorbed tail gas
Processed through 2 grades of NaOH solutions of 13~18wt%；The ruthenium is 1~10 ︰ 100 with the mass ratio of salpeter solution；
(2), gas is nitrosylated：
The nitric acid absorbing liquid of ruthenium obtained above is heated to 50~110 DEG C, to gas is slowly introducing in solution, until molten
Liquid is transformed into the nitrosyl nitric acid ruthenium solution of shiny red by furvous, stops reaction；The nitrosyl nitric acid ruthenium solution for obtaining is through rotation
Turn evaporimeter concentration, obtain finished product.
Wherein, in the method and step (1) of above-mentioned two steps synthesis nitrosyl nitric acid ruthenium, the raw material ruthenium is ruthenium powder, metal Ru
Or ruthenium waste material.
Wherein, in the method and step (1) of above-mentioned two steps synthesis nitrosyl nitric acid ruthenium, the technique that the oxidation distillation is used
It is：The logical chlorine distillation of NaOH, sulfuric acid are added dropwise sodium chlorate distillation, sulfuric acid dropwise addition nitric acid distillation or hydrochloric acid and add hydrogen peroxide to steam
Evaporate.
Wherein, in the method and step (2) of above-mentioned two steps synthesis nitrosyl nitric acid ruthenium, the gas is nitric oxide and dioxy
Change the mixed gas of nitrogen.
Wherein, in the method for above-mentioned two step synthesis nitrosyl nitric acid ruthenium, the nitric oxide and nitrogen dioxide mixed gas
It is, by nitration acid heat to slight boiling condition, to be slowly added dropwise sodium nitrite solution acquisition.
Compared with prior art, the beneficial effects of the invention are as follows：This method not only solves the nitrous of conventional method preparation
Acyl nitric acid ruthenium can bring substantial amounts of impurity element Cl into-、Ag+、Na+It is short etc. problem, and process route, production process easy controlled operation,
Energy consumption is low, product quality stabilization, is suitable for industrialized production, and product meets YS/T755-2011 nitrosyl nitric acid ruthenium standards.
Specific embodiment
The invention provides the method that two steps synthesize nitrosyl nitric acid ruthenium, the described method comprises the following steps：
(1), ruthenium oxidation distillation nitric acid absorbs：
Raw material ruthenium is placed in distillation reactor, oxidation distillation generates the RuO of yellow4Gas；The RuO4Gas is through 2 grades
After deionized water washing, it is passed through 3 grades of 4~8mol/L salpeter solutions and absorbs, obtains the nitric acid absorbing liquid of ruthenium；Unabsorbed tail gas
Processed through 2 grades of NaOH solutions of 13~18wt%；The ruthenium is 1~10 ︰ 100 with the mass ratio of salpeter solution；
(2), gas is nitrosylated：
The nitric acid absorbing liquid of ruthenium obtained above is heated to 50~110 DEG C, to gas is slowly introducing in solution, until molten
Liquid is transformed into the nitrosyl nitric acid ruthenium solution of shiny red by furvous, stops reaction；The nitrosyl nitric acid ruthenium solution for obtaining is through rotation
Turn evaporimeter concentration, obtain finished product；The gas is the mixed gas of nitric oxide and nitrogen dioxide.
Wherein, in the method and step (1) of above-mentioned two steps synthesis nitrosyl nitric acid ruthenium, the raw material ruthenium is ruthenium powder, metal Ru
Or ruthenium waste material.
Wherein, in the method and step (1) of above-mentioned two steps synthesis nitrosyl nitric acid ruthenium, the technique that the oxidation distillation is used
It is：The logical chlorine distillation of NaOH, sulfuric acid are added dropwise sodium chlorate distillation, sulfuric acid dropwise addition nitric acid distillation or hydrochloric acid and add hydrogen peroxide to steam
Evaporate.
Wherein, in the method and step (2) of above-mentioned two steps synthesis nitrosyl nitric acid ruthenium, the nitric oxide and nitrogen dioxide are mixed
It is, by nitration acid heat to slight boiling condition, to be slowly added dropwise sodium nitrite solution acquisition to close gas, and gas synthesis speed is by addition nitrous
The amount of sour sodium is controlled.
Wherein, the present invention does not make the operation of specified otherwise, is this area routine operation.
The inventive method is absorbed using oxidation distillation nitric acid and gas is nitrosylated with ruthenium as raw material, and two steps are prepared into Asia
Nitryl nitric acid ruthenium solution, rotated evaporation is obtained the nitrosyl nitric acid ruthenium solution or crystal for meeting demand；It is sub- obtained in the method
Foreign ion Cl is not contained in nitryl nitric acid ruthenium-, Ag+, Na+Deng；And process route is short, production process easy controlled operation, energy consumption
Low, product quality stabilization is suitable for industrialized production, and product meets YS/T755-2011 nitrosyl nitric acid ruthenium standards.
The present invention is further explained and illustrated below in conjunction with specific embodiment, but and is not so limited guarantor of the invention
Shield scope.
The method of 1 liang of step synthesis nitrosyl nitric acid ruthenium of embodiment is as follows：
(1), 300g ruthenium powder is thrown in distillation reactor, using the logical chlorine distillation technique of NaOH, distillation generation is yellow
Color RuO4Gas, RuO4After gas is washed through 2 grades of deionized waters, it is passed into 3 grades of 4mol/L salpeter solutions and absorbs, obtains ruthenium
The common 6000g of nitric acid absorbing liquid；Unabsorbed tail gas is using 2 grades of NaOH solution absorption treatment of 15wt%；Wherein, ruthenium and nitric acid
The mass ratio of solution is 8 ︰ 100；
(2) the nitric acid absorbing liquid of furvous ruthenium obtained above, is heated to 60 DEG C, existing system is slowly introducing from solution bottom
Nitric oxide and nitrogen dioxide mixed gas, after being passed through gas 2h, solution colour is transformed into shiny red, obtains nitrosyl nitric acid
Ruthenium solution, stops reaction；After the nitrosyl nitric acid ruthenium solution filtering that will be obtained, rotated evaporimeter concentration is prepared into 10wt%'s
Nitrosyl nitric acid ruthenium solution 2898.34g, product yield is 96.61%, and product meets YS/T 755-2011 nitrosyl after testing
Nitric acid ruthenium standard.
The method of 2 liang of step synthesis nitrosyl nitric acid rutheniums of embodiment is as follows：
(1), 200g ruthenium powder is thrown in distillation reactor, sodium chlorate distillation technique is added dropwise using sulfuric acid, distillation generation is yellow
The RuO of color4Gas, RuO4After gas is washed through 2 grades of deionized waters, it is passed into 3 grades of 6mol/L salpeter solutions and absorbs, obtains ruthenium
The common 6000g of nitric acid absorbing liquid；Unabsorbed tail gas is using 2 grades of NaOH solution absorption treatment of 15wt%；Wherein, ruthenium and nitre
The mass ratio of acid solution is 6 ︰ 100；
(2) the nitric acid absorbing liquid of furvous ruthenium obtained above, is heated to 80 DEG C, existing system is slowly introducing from solution bottom
Nitric oxide and nitrogen dioxide mixed gas, after being passed through gas 1.5h, solution colour is transformed into shiny red, obtains nitrosyl nitre
Sour ruthenium solution, stops reaction；After the nitrosyl nitric acid ruthenium solution filtering that will be obtained, rotated evaporimeter concentration is prepared into 5wt%
Nitrosyl nitric acid ruthenium solution 3894.15g, product yield is 97.35%, and product meets YS/T 755-2011 nitrous after testing
Acyl nitric acid ruthenium standard.
The method of 3 liang of step synthesis nitrosyl nitric acid rutheniums of embodiment is as follows：
(1), the ruthenium waste material containing 100g rutheniums is thrown in distillation reactor, nitric acid distillation technique, distillation is added dropwise using sulfuric acid
Generate the RuO of yellow4Gas, RuO4After gas is washed through 2 grades of deionized waters, it is passed into 3 grades of 8mol/L salpeter solutions and absorbs,
Obtain the common 6000g of nitric acid absorbing liquid of ruthenium；Unabsorbed tail gas is using 2 grades of NaOH solution absorption treatment of 15wt%；Wherein,
Ruthenium is 3 ︰ 100 with the mass ratio of salpeter solution；
(2) the nitric acid absorbing liquid of furvous ruthenium obtained above, is heated to 100 DEG C, is slowly introducing from solution bottom existing
The nitric oxide and nitrogen dioxide mixed gas of system, after being passed through gas 2h, solution colour is transformed into shiny red, obtains nitrosyl nitre
Sour ruthenium solution, stops reaction；After the nitrosyl nitric acid ruthenium solution filtering that will be obtained, rotated evaporimeter concentration is prepared into 5wt%
Nitrosyl nitric acid ruthenium solution 1959.22g, product yield is 97.96%, and product meets YS/T 755-2011 nitrous after testing
Acyl nitric acid ruthenium standard.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned implementation method, also includes
Constituted technical scheme is combined by above technical characteristic.It should be pointed out that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (5)
1. the method that liang step synthesizes nitrosyl nitric acid ruthenium, it is characterised in that the described method comprises the following steps：
(1), ruthenium oxidation distillation nitric acid absorbs：
Raw material ruthenium is placed in distillation reactor, oxidation distillation generates the RuO of yellow4Gas；The RuO4Gas through 2 grades go from
After sub- water washing, it is passed through 3 grades of 4~8mol/L salpeter solutions and absorbs, obtains the nitric acid absorbing liquid of ruthenium；Unabsorbed tail gas is through 2
The NaOH solution treatment of 13~18wt% of level；The ruthenium is 1~10 ︰ 100 with the mass ratio of salpeter solution；
(2), gas is nitrosylated：
The nitric acid absorbing liquid of ruthenium obtained above is heated to 50~110 DEG C, to being slowly introducing gas in solution, until solution by
Furvous is transformed into the nitrosyl nitric acid ruthenium solution of shiny red, stops reaction；The nitrosyl rotated steaming of nitric acid ruthenium solution for obtaining
Hair instrument concentration, obtains finished product.
2. the method that two steps synthesize nitrosyl nitric acid ruthenium according to claim 1, it is characterised in that former described in step (1)
Material ruthenium is ruthenium powder, metal Ru or ruthenium waste material.
3. the method that two steps synthesize nitrosyl nitric acid ruthenium according to claim 1, it is characterised in that oxygen described in step (1)
Change distillation to adopt the technology that：The logical chlorine distillation of NaOH, sulfuric acid be added dropwise sodium chlorate distillation, sulfuric acid be added dropwise nitric acid distillation or
Hydrochloric acid adds hydrogen peroxide to distill.
4. the method that two steps synthesize nitrosyl nitric acid ruthenium according to claim 1, it is characterised in that gas described in step (2)
Body is the mixed gas of nitric oxide and nitrogen dioxide.
5. the method that two steps synthesize nitrosyl nitric acid ruthenium according to claim 4, it is characterised in that the nitric oxide and two
Oxidation nitrogen mixture gas are, by nitration acid heat to slight boiling condition, to be slowly added dropwise sodium nitrite solution acquisition.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142127A (en) * | 2020-09-02 | 2020-12-29 | 中国船舶重工集团公司第七一八研究所 | Method for preparing ruthenium nitrosyl nitrate solution |
| CN113582259A (en) * | 2021-08-25 | 2021-11-02 | 合创(无锡)环保科技有限公司 | Liquid ruthenium nitrate synthesis process method |
| CN115650322A (en) * | 2022-11-02 | 2023-01-31 | 金川集团股份有限公司 | Method for preparing nitrosyl ruthenium nitrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167405A (en) * | 2011-01-24 | 2011-08-31 | 昆明贵金属研究所 | New method for preparing ruthenium nitrosylnitrate solid |
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| CN104556250A (en) * | 2014-12-19 | 2015-04-29 | 昆明珀玺金属材料有限公司 | New method for preparing ruthenium nitrosyl nitrate solution or pure crystal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142127A (en) * | 2020-09-02 | 2020-12-29 | 中国船舶重工集团公司第七一八研究所 | Method for preparing ruthenium nitrosyl nitrate solution |
| CN112142127B (en) * | 2020-09-02 | 2022-07-15 | 中国船舶重工集团公司第七一八研究所 | Method for preparing ruthenium nitrosyl nitrate solution |
| CN113582259A (en) * | 2021-08-25 | 2021-11-02 | 合创(无锡)环保科技有限公司 | Liquid ruthenium nitrate synthesis process method |
| CN113582259B (en) * | 2021-08-25 | 2023-09-08 | 合创(无锡)环保科技有限公司 | Liquid ruthenium nitrate synthesis process |
| CN115650322A (en) * | 2022-11-02 | 2023-01-31 | 金川集团股份有限公司 | Method for preparing nitrosyl ruthenium nitrate |
| CN115650322B (en) * | 2022-11-02 | 2024-03-01 | 金川集团股份有限公司 | Method for nitrosyl ruthenium nitrate |
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| CN106698529B (en) | 2017-12-26 |
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