CN102616868B - 利用含钌废催化剂制备固体亚硝酰硝酸钌的方法 - Google Patents
利用含钌废催化剂制备固体亚硝酰硝酸钌的方法 Download PDFInfo
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 77
- 239000007787 solid Substances 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 35
- NSNVGCNCRLAWOJ-UHFFFAOYSA-N [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] NSNVGCNCRLAWOJ-UHFFFAOYSA-N 0.000 title abstract 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007789 gas Substances 0.000 claims abstract description 36
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 8
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000010792 warming Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 7
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 235000010333 potassium nitrate Nutrition 0.000 abstract 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000008676 import Effects 0.000 description 7
- -1 platinum metals Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- OABGXMCYPSFWJF-UHFFFAOYSA-N [Ru].N(=O)O Chemical compound [Ru].N(=O)O OABGXMCYPSFWJF-UHFFFAOYSA-N 0.000 description 1
- FTOVVAILFPXDLK-UHFFFAOYSA-N [Ru].N(=O)O[N+](=O)[O-].C(C)OCC Chemical compound [Ru].N(=O)O[N+](=O)[O-].C(C)OCC FTOVVAILFPXDLK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali 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
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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Abstract
本发明公开了一种利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其步骤为:将含钌废催化剂干燥后煅烧,获得含钌黑色固体,然后将含钌黑色固体研磨至粉末并通入氢气还原成金属钌,再利用臭氧和空气的混合气氧化金属钌,产生四氧化钌气体,收集气体通入硝酸溶液后加入固体亚硝酸钠,制得含亚硝酰硝酸钌的溶液,最后利用乙醚萃取,蒸发乙醚后获得亚硝酰硝酸钌固体。本发明可以有效地回收多种负载型含钌废催化剂中的贵金属钌,实现钌资源的有效回收再利用,操作步骤简单,不涉及钌中间体的引入,产品收率高,获得的固体亚硝酰硝酸钌不含卤素,纯度高,可直接用于催化剂的制备。
Description
技术领域
本发明涉及铂族金属的回收再利用,具体地指一种利用含钌废催化剂制备固体亚硝酰硝酸钌的方法。
背景技术
钌具有优良的催化性能,在催化剂行业用途广泛,多用于合成氨、苯选择加氢制环己烯和二氧化碳加氢制甲醇等,然而钌资源有限、价格昂贵、全球年产量仅有几十吨,限制了钌在上述领域的应用。从含钌废催化剂中回收钌用于再次生产钌基催化剂,可大幅降低该催化剂的使用成本,有效减少废催化剂对环境的污染,具有广泛的应用前景。
由于固体亚硝酰硝酸钌Ru(NO)(NO3)3不含卤素、硫、磷等易引起催化剂中毒的元素,且易溶于水、乙醚、丙酮等有机溶剂,因此成为众多含钌催化剂制备过程中的理想前驱体。如何有效地从负载型含钌废催化剂中制备高纯固体亚硝酰硝酸钌,具有重要的工业应用价值。
目前,文献关于亚硝酰硝酸钌的制备方法有两种:一种是将RuO4直接吸收在冷却的硝酸溶液中;另一种是用硝酸溶解回流亚硝酰氢氧化钌。专利CN101638727A公开了一种活性碳负载钌催化剂中钌的回收方法,其中涉及到亚硝酰硝酸钌的制备。该方法通过碱熔等一系列步骤将得到的氢氧化钌或RuO2·2H2O在回流装置中用微沸的硝酸搅拌、溶解,得到Ru(NO)(NO3)3的硝酸溶液。以上方法得到的产品均为亚硝酰硝酸钌的酸溶液,但由于其酸度较高,不易于储存及运输。
专利CN102167405A公开了一种制备固体亚硝酰硝酸钌的方法,该方法将三氯化钌和亚硝酸钠反应合成亚硝酰氯化钌中间体,中间体与硝酸银作用得到亚硝酰硝酸钌溶液,再用乙醚萃取亚硝酰硝酸钌,最后将乙醚萃取液蒸发,得到亚硝酰硝酸钌固体。该方法虽然可以制得固体亚硝酰硝酸钌,但仍然存在缺点:其一,由于制备过程中引入氯化物,导致产品中含有杂质氯,容易引起催化剂中毒;其二,该方法在实施过程中需要通过制备钌中间体以获得最终产品,导致产品收率偏低;其三,该方法使用的原料RuCl3·xH2O本身可以直接用作催化剂的制备,以该结晶水合物作为原料制备亚硝酰硝酸钌,成本较高。
发明内容
本发明的目的就是要提供一种利用含钌废催化剂制备固体亚硝酰硝酸钌的方法。该方法简单、高效,可以从负载型含钌废催化剂中直接制备出高纯固体亚硝酰硝酸钌,所得的固体亚硝酰硝酸钌可以作为原料再次制备含钌催化剂。
为实现上述目的,本发明所设计的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,包括以下步骤:
1)将含钌废催化剂干燥后,于300~500℃煅烧2~4h,降温至室温,得到含钌黑色固体;
2)将步骤1)中得到的含钌黑色固体研磨至粉末,置于流化床反应器中,通氮气或惰性气体置换0.5~2h后切换为氢气,升温至100~600℃,恒温还原,将废催化剂中的氧化钌还原为金属钌;
3)将臭氧和空气的混合气通入步骤2)中得到的金属钌,对金属钌进行氧化,温度控制在600~650℃,产生四氧化钌气体;
4)将步骤3)中产生的四氧化钌气体导入盛有硝酸溶液的三级吸收装置中,得到硝酸钌的酸溶液;
5)将亚硝酸钠固体加入步骤4)中得到的硝酸钌的酸溶液中,适当搅拌,加热至溶液微沸回流,制得含亚硝酰硝酸钌的溶液;
6)将步骤5)中得到的含亚硝酰硝酸钌的溶液用无水乙醚萃取,收集乙醚萃取液,再将乙醚蒸发,得到亚硝酰硝酸钌固体。
其中,所述步骤1)中,含钌废催化剂的干燥条件可选为在氮气或惰性气体氛围中升温至100~150℃,干燥1~2h,含钌废催化剂可置于马弗炉中煅烧。
所述步骤2)中,还原反应时,氢气的流速无特别限制,但优选为1200~4000h-1,还原时间为1~12h,优选为6~12h。利用氢气将含钌废催化剂中被氧化的钌还原,其反应的化学方程式如下:
RuO2+2H2=Ru+2H2O
所述步骤3)中,臭氧和空气的混合气的流速无特别限制,但优选为1200~4000h-1,臭氧在所述混合气中的体积分数为1~20%,优选为15%,氧化时间为1~12h,优选为8~12h。金属钌被混合气氧化为四氧化钌气体,其反应的化学方程式如下:
Ru+2O2=RuO4↑,3Ru+4O3=3RuO4↑
所述步骤4)中,所述硝酸溶液的温度为50~95℃、质量浓度为45~68%,根据含钌废催化剂中钌的负载量计算硝酸溶液的理论用量,取理论用量的1.2~2.0倍作为硝酸溶液的实际用量。所述三级吸收装置为三个串联的棕色容器。四氧化钌气体通入硝酸溶液中,四氧化钌气体被吸收,在加热的条件下生成硝酸钌溶液,其反应的化学方程式如下:
2RuO4+16HNO3=2Ru(NO3)3+8H2O+5O2↑+10NO2↑
所述步骤5)中,根据含钌废催化剂中钌的负载量计算亚硝酸钠固体的理论用量,取理论用量的1.5~2.0倍作为亚硝酸钠固体的实际用量。亚硝酸钠固体适宜缓慢地加入硝酸钌的酸溶液中且伴随适当搅拌,以使其均匀扩散在硝酸钌的酸溶液中,加热该溶液至微沸进行回流,该反应回流时间为1~8h,优选为4~8h。加热回流的反应容器为常用的三颈圆底烧瓶,为本领域常用技术手段,此处不做赘述。硝酸钌的硝酸溶液与亚硝酸钠发生反应的化学方程式如下:
Ru(NO3)3+2NaNO2+2HNO3=Ru(NO)(NO3)3+2NaNO3+NO2↑+H2O
所述步骤6)中,可进行多次无水乙醚萃取,提高亚硝酰硝酸钌固体的收率。
所述含钌废催化剂为负载型含钌废催化剂,其载体范围广,可为氧化铝、二氧化硅、二氧化锆、二氧化钛和沸石中的一种或几种混合物的组合。载体可以为任何形状,常见的球型、圆柱型、三叶草型、四叶草型、环型、蜂窝型等均可利用本发明所述的方法回收钌。
本发明的有益效果:其一,利用本发明所述的方法可以由负载型含钌的废催化剂直接制备固体亚硝酰硝酸钌,回收成本低,所得固体产品便于储存及运输;其二,本发明方法制得的固体亚硝酰硝酸钌不含卤素,避免了含钌催化剂在反应过程中由于卤素而引起的中毒现象;其三,本发明方法操作步骤简单,不涉及钌中间体的引入,有效地提高了固体产品亚硝酰硝酸钌的收率。综上所述,本发明方法实现了钌资源的再利用,回收成本低,操作简单,产品收率高、纯度高,适于规模化生产。
附图说明
图1为本发明利用含钌废催化剂制备固体亚硝酰硝酸钌的方法的流程示意图。
具体实施方式
以下结合附图和具体实施例对本发明作进一步的详细描述,本发明的保护范围并不受这些实施例的限制。
实施例1
称取60g含钌催化剂(球型,Ru/Al2O3,Ru负载量5%)装在坩埚中,将其置于马弗炉中,通入N2,120℃干燥2h,随后在450℃煅烧3h,除去废催化剂中残留的有机物质,冷却至室温称重得到58.6g固体。将黑色固体研磨呈均匀粉末,转移至流化床反应器中,通氮气置换30min后切换为氢气,氢气空速为1200h-1,升温至300℃,恒温还原12h,继续升温至600℃,再通入混合气15vol%O3/空气,保持混合气空速1200h-1流通12h。将产生的RuO4气体依次导入3个装有40g质量浓度为68%的硝酸溶液的吸收瓶中,并控制硝酸溶液温度为75℃附近,得到Ru(NO3)3的酸溶液。
收集上述得到的Ru(NO3)3酸溶液于三颈圆底烧瓶中,缓慢加入理论用量1.5倍(6g)的NaNO2粉末,搅拌并加热回流8h,溶液逐渐变为深红黑色。冷却该溶液,用130ml无水乙醚萃取3次,收集乙醚萃取液,并将乙醚蒸发,得到棕黄色固体8.84g。经KBr压片红外分析,其特征峰位于1924cm-1,与Ru(NO)(NO3)3特征结构参数吻合,计算收率为96.2%,杂质金属含量<30ppm。
实施例2
称取50g含钌催化剂(圆柱型,Ru/SiO2,Ru负载量3%)装在坩埚中,将其置于马弗炉中,通入N2,120℃干燥2h,随后在450℃煅烧3h,冷却至室温称重得到48.9g固体。将黑色固体研磨呈均匀粉末,转移至流化床反应器中,通氮气置换30min后切换为氢气,氢气空速为2500h-1,升温至350℃,恒温还原10h,继续升温至620℃,再通入混合气15vol%O3/空气,保持混合气空速2500h-1流通10h,将产生的RuO4气体依次导入3个装有24g质量浓度为60%的硝酸溶液的吸收瓶中,控制硝酸溶液温度为75℃附近,得到Ru(NO3)3的酸溶液。
将得到的Ru(NO3)3的酸溶液转移至三颈圆底烧瓶中,缓慢加入理论用量1.8倍(3.6g)的NaNO2粉末,搅拌并加热回流4h,溶液逐渐变为深红黑色。冷却该溶液,用80ml无水乙醚萃取3次,收集乙醚萃取液,并将乙醚蒸发,得到棕黄色固体4.41g。经KBr压片红外分析,其特征峰位于1924cm-1,与Ru(NO)(NO3)3特征结构参数吻合,计算收率为95.8%,杂质金属含量<30ppm。
实施例3
称取120g含钌催化剂(三叶草型,Ru/ZrO2,Ru负载量4‰)装在坩埚中,将其置于马弗炉中,通入N2,120℃干燥2h,随后在450℃煅烧3h,冷却至室温称重得到118.2g固体。将黑色固体研磨呈均匀粉末,转移至流化床反应器中,通氮气置换30min后切换为氢气,氢气空速为4000h-1,升温至350℃,恒温还原6h,继续升温至650℃,再通入混合气15vol%O3/空气,保持混合气空速4000h-1流通8h,将产生的RuO4气体依次导入3个装有13g质量浓度为45%的硝酸溶液的吸收瓶中,控制硝酸溶液温度为75℃附近,得到Ru(NO3)3的酸溶液。
将得到的Ru(NO3)3的酸溶液转移至三颈圆底烧瓶中,缓慢加入理论用量2.0倍(1.29g)的NaNO2粉末,搅拌并加热回流6h,溶液逐渐变为深红黑色。冷却该溶液,用60ml无水乙醚萃取3次,收集乙醚萃取液,并将乙醚蒸发,得到棕黄色固体1.44g。经KBr压片红外分析,其特征峰位于1924cm-1,与Ru(NO)(NO3)3特征结构参数吻合,计算收率为97.3%,杂质金属含量<30ppm。
实施例4
称取60g含钌催化剂(四叶草型,Ru/TiO2,Ru负载量5%)装在坩埚中,将其置于马弗炉中,通入N2,120℃干燥2h,随后在450℃煅烧3h,除去废催化剂中残留的有机物质,冷却至室温称重得到58.1g固体。将黑色固体研磨呈均匀粉末,转移至流化床反应器中,通氮气置换30min后切换为氢气,氢气空速为2000h-1,升温至350℃,恒温还原8h,继续升温至620℃,再通入混合气10vol%O3/空气,保持混合气空速1500h-1流通5h。将产生的RuO4气体依次导入3个装有27g质量浓度为68%的硝酸溶液的吸收瓶中,并控制硝酸溶液温度为75℃附近,得到Ru(NO3)3的酸溶液。
收集上述得到的Ru(NO3)3酸溶液于三颈圆底烧瓶中,缓慢加入理论用量0.9倍的(3.56g)NaNO2粉末,搅拌并加热回流6h,溶液逐渐变为深红黑色。冷却该溶液,用100ml无水乙醚萃取3次,收集乙醚萃取液,并将乙醚蒸发,得到棕黄色固体8.21g。经KBr压片红外分析,其特征峰位于1924cm-1,与Ru(NO)(NO3)3特征结构参数吻合,计算收率为90.3%,杂质金属含量<30ppm。
实施例5
称取60g含钌催化剂(环型,Ru/Al2O3-ZSM-5,Ru负载量1%)装在坩埚中,将其置于马弗炉中,通入N2,120℃干燥2h,随后在450℃煅烧3h,除去废催化剂中残留的有机物质,冷却至室温称重得到59.0g固体。将黑色固体研磨呈均匀粉末,转移至流化床反应器中,通氮气置换30min后切换为氢气,氢气空速为2000h-1,升温至350℃,恒温还原8h,继续升温至620℃,再通入混合气15vol%O3/空气,保持混合气空速3000h-1流通8h。将产生的RuO4气体依次导入3个装有16g质量浓度为45%的硝酸溶液的吸收瓶中,并控制硝酸溶液温度为75℃附近,得到Ru(NO3)3的酸溶液。
收集上述得到的Ru(NO3)3酸溶液于三颈圆底烧瓶中,缓慢加入用量为理论用量1.5倍(1.2g)的NaNO2粉末,搅拌并加热回流6h,溶液逐渐变为深红黑色。冷却该溶液,用50ml无水乙醚萃取3次,收集乙醚萃取液,并将乙醚蒸发,得到棕黄色固体1.78g。经KBr压片红外分析,其特征峰位于1924cm-1,与Ru(NO)(NO3)3特征结构参数吻合,计算收率为96.6%,杂质金属含量<30ppm。
实施例6
称取160g含钌催化剂(蜂窝型,Ru/Al2O3-SiO2,Ru负载量2‰)装在坩埚中,将其置于马弗炉中,通入N2,120℃干燥2h,随后在450℃煅烧3h,除去废催化剂中残留的有机物质,冷却至室温称重得到156.4g固体。将黑色固体研磨呈均匀粉末,转移至流化床反应器中,通氮气置换30min后切换为氢气,氢气空速为2000h-1,升温至350℃,恒温还原8h,继续升温至620℃,再通入混合气15vol%O3/空气,保持混合气空速2500h-1流通8h。将产生的RuO4气体依次导入3个装有8.6g质量浓度为45%的硝酸溶液的吸收瓶中,并控制硝酸溶液温度为75℃附近,得到Ru(NO3)3的酸溶液。
收集上述得到的Ru(NO3)3酸溶液于三颈圆底烧瓶中,缓慢加入理论用量1.5倍(0.64g)的NaNO2粉末,搅拌并加热回流8h,溶液逐渐变为深红黑色。冷却该溶液,用30ml无水乙醚萃取3次,收集乙醚萃取液,并将乙醚蒸发,得到棕黄色固体0.95g。经KBr压片红外分析,其特征峰位于1924cm-1,与Ru(NO)(NO3)3特征结构参数吻合,计算收率为97.2%,杂质金属含量<30ppm。
结果分析:
根据实施例1~6的实验结果,可以得出,根据本发明所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,以含钌的废催化剂作为原料制备的固体亚硝酰硝酸钌收率均在90%以上,并且在优选条件下,其收率可达95%以上。所得的固体亚硝酰硝酸钌可以作为原料再次制备含钌催化剂,实现了钌资源的有效利用。本发明方法回收成本低,操作简单,制得的产品收率高、纯度高,适于规模化生产。
Claims (10)
1.一种利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,包括以下步骤:
1)将含钌废催化剂干燥后,于300~500℃煅烧2~4h,降温至室温,得到含钌黑色固体;
2)将步骤1)中得到的含钌黑色固体研磨至粉末,置于流化床反应器中,通氮气或惰性气体置换0.5~2h后切换为氢气,升温至100~600℃,恒温还原,将废催化剂中的氧化钌还原为金属钌;
3)将臭氧和空气的混合气通入步骤2)中得到的金属钌,对金属钌进行氧化,温度控制在600~650℃,产生四氧化钌气体;
4)将步骤3)中产生的四氧化钌气体导入盛有硝酸溶液的三级吸收装置中,硝酸溶液的温度为50~95℃、质量浓度为45~68%,得到硝酸钌的酸溶液;
5)将亚硝酸钠固体加入步骤4)中得到的硝酸钌的酸溶液中,适当搅拌,加热至溶液微沸回流,加热回流的时间为1~8h,制得含亚硝酰硝酸钌的溶液;
6)将步骤5)中得到的含亚硝酰硝酸钌的溶液用无水乙醚萃取,收集乙醚萃取液,再将乙醚蒸发,得到亚硝酰硝酸钌固体。
2.根据权利要求1所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤1)中,含钌废催化剂的干燥条件为在氮气或惰性气体氛围中升温至100~150℃,干燥1~2h。
3.根据权利要求1所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤2)中,氢气的流速为1200~4000h-1,还原时间为1~12h。
4.根据权利要求3所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤2)中,还原时间为6~12h。
5.根据权利要求1所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤3)中,臭氧和空气的混合 气的流速为1200~4000h-1,臭氧在所述混合气中的体积分数为1~20%,氧化时间为1~12h。
6.根据权利要求5所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤3)中,臭氧的体积分数为15%,氧化时间为8~12h。
7.根据权利要求1所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤4)中,硝酸溶液的温度为50~95℃、质量浓度为45~68%,根据含钌废催化剂中钌的负载量计算硝酸溶液的理论用量,取理论用量的1.2~2.0倍作为硝酸溶液的实际用量,且硝酸溶液的盛放容器为三个串联的棕色容器。
8.根据权利要求1所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤5)中,根据含钌废催化剂中钌的负载量计算亚硝酸钠固体的理论用量,取理论用量的1.5~2.0倍作为亚硝酸钠固体的实际用量,加热回流的时间为1~8h。
9.根据权利要求8所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述步骤5)中,加热回流的时间为4~8h。
10.根据权利要求1~9中任一项所述的利用含钌废催化剂制备固体亚硝酰硝酸钌的方法,其特征在于:所述含钌废催化剂为负载型含钌废催化剂,其载体为氧化铝、二氧化硅、二氧化锆、二氧化钛和沸石中的一种或几种混合物的组合。
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MX2014010569A MX358426B (es) | 2012-03-05 | 2013-03-04 | Metodo para la preparacion de nitrosil nitrato de rutenio solido mediante el uso de un catalizador residual que contiene rutenio. |
CA2866207A CA2866207C (en) | 2012-03-05 | 2013-03-04 | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium |
PL13758228T PL2823900T3 (pl) | 2012-03-05 | 2013-03-04 | Sposób wytwarzania nitrozyloazotanu rutenu w postaci ciała stałego z wykorzystaniem katalizatora odpadowego zawierającego ruten |
DK13758228.4T DK2823900T3 (en) | 2012-03-05 | 2013-03-04 | Process for the preparation of solid nitrosyl ruthenium nitrate using a waste catalyst containing ruthenium |
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RU2014140158/13A RU2580414C1 (ru) | 2012-03-05 | 2013-03-04 | Способ получения твердого нитрозилнитрата рутения с использованием отработанного катализатора, содержащего рутений |
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EP13758228.4A EP2823900B1 (en) | 2012-03-05 | 2013-03-04 | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium |
JP2014560228A JP5902324B2 (ja) | 2012-03-05 | 2013-03-04 | ルテニウムを含む廃触媒を使用することによる固形ニトロシル硝酸ルテニウムの調製方法 |
BR112014021848-0A BR112014021848A2 (pt) | 2012-03-05 | 2013-03-04 | Método para preparar nitrato de nitrosil rutênio sólido usando resíduo de catalisador contendo rutênio |
KR1020147027911A KR101567592B1 (ko) | 2012-03-05 | 2013-03-04 | 루테늄을 함유하는 폐촉매제를 이용하여 고형의 루테늄 니트로실 니트레이트를 제조하는 방법 |
SG11201405382UA SG11201405382UA (en) | 2012-03-05 | 2013-03-04 | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium |
ES13758228.4T ES2637517T3 (es) | 2012-03-05 | 2013-03-04 | Procedimiento de preparación de nitrosil nitrato de rutenio sólido mediante el uso de un catalizador gastado que contiene rutenio |
AP2014007986A AP2014007986A0 (en) | 2012-03-05 | 2013-03-04 | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium |
US14/475,547 US9005555B2 (en) | 2012-03-05 | 2014-09-02 | Method for preparing solid ruthenium nitrosyl nitrate |
ZA2014/07147A ZA201407147B (en) | 2012-03-05 | 2014-10-02 | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium |
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CN104556250B (zh) * | 2014-12-19 | 2016-06-01 | 昆明珀玺金属材料有限公司 | 一种制备亚硝酰硝酸钌溶液或纯净晶体的新方法 |
JP6562351B2 (ja) * | 2015-09-10 | 2019-08-21 | 学校法人上智学院 | ポリマーの製造方法およびニトロシルルテニウム錯体の使用 |
CN106698529B (zh) * | 2017-01-12 | 2017-12-26 | 郴州高鑫材料有限公司 | 两步合成亚硝酰硝酸钌的方法 |
CN106927514B (zh) * | 2017-03-20 | 2018-10-02 | 昆明理工大学 | 一种制备亚硝酰硝酸钌的方法 |
WO2020256007A1 (ja) * | 2019-06-21 | 2020-12-24 | 株式会社トクヤマ | 酸化ルテニウムガスの吸収液、酸化ルテニウムの分析方法およびトラップ装置、定量分析装置 |
CN112538573B (zh) * | 2020-11-18 | 2022-04-15 | 铜陵欣诺科新材料有限公司 | 从含钌废液中回收钌的方法 |
CN113582259B (zh) * | 2021-08-25 | 2023-09-08 | 合创(无锡)环保科技有限公司 | 一种液体硝酸钌合成工艺方法 |
CN115650322B (zh) * | 2022-11-02 | 2024-03-01 | 金川集团股份有限公司 | 一种亚硝酰基硝酸钌的方法 |
CN115536520A (zh) * | 2022-11-02 | 2022-12-30 | 金川集团股份有限公司 | 一种醋酸钌的制备方法 |
CN115874060A (zh) * | 2022-12-19 | 2023-03-31 | 本源精化环保科技有限公司 | 一种从废弃负载型复合催化剂中提取贵金属的方法 |
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KR20140130747A (ko) | 2014-11-11 |
EP2823900A1 (en) | 2015-01-14 |
RU2580414C1 (ru) | 2016-04-10 |
EP2823900B1 (en) | 2017-05-17 |
CA2866207C (en) | 2017-04-18 |
CA2866207A1 (en) | 2013-09-12 |
ZA201407147B (en) | 2016-01-27 |
ES2637517T3 (es) | 2017-10-13 |
DK2823900T3 (en) | 2017-09-04 |
JP2015514563A (ja) | 2015-05-21 |
SG11201405382UA (en) | 2014-10-30 |
CN102616868A (zh) | 2012-08-01 |
AU2013230403B2 (en) | 2015-10-08 |
AP2014007986A0 (en) | 2014-10-31 |
US9005555B2 (en) | 2015-04-14 |
MX2014010569A (es) | 2015-06-02 |
MY166186A (en) | 2018-06-07 |
EP2823900A4 (en) | 2015-11-25 |
US20140369905A1 (en) | 2014-12-18 |
KR101567592B1 (ko) | 2015-11-20 |
JP5902324B2 (ja) | 2016-04-13 |
PL2823900T3 (pl) | 2018-01-31 |
IN2014MN01924A (zh) | 2015-07-10 |
AU2013230403A1 (en) | 2014-10-16 |
BR112014021848A2 (pt) | 2021-05-18 |
MX358426B (es) | 2018-08-17 |
WO2013131451A1 (zh) | 2013-09-12 |
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