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    廢催化劑中鉑族金屬回收現狀與研究進展

    丁云集 張深根

    丁云集, 張深根. 廢催化劑中鉑族金屬回收現狀與研究進展[J]. 工程科學學報, 2020, 42(3): 257-269. doi: 10.13374/j.issn2095-9389.2019.11.26.001
    引用本文: 丁云集, 張深根. 廢催化劑中鉑族金屬回收現狀與研究進展[J]. 工程科學學報, 2020, 42(3): 257-269. doi: 10.13374/j.issn2095-9389.2019.11.26.001
    DING Yun-ji, ZHANG Shen-gen. Status and research progress on recovery of platinum group metals from spent catalysts[J]. Chinese Journal of Engineering, 2020, 42(3): 257-269. doi: 10.13374/j.issn2095-9389.2019.11.26.001
    Citation: DING Yun-ji, ZHANG Shen-gen. Status and research progress on recovery of platinum group metals from spent catalysts[J]. Chinese Journal of Engineering, 2020, 42(3): 257-269. doi: 10.13374/j.issn2095-9389.2019.11.26.001

    廢催化劑中鉑族金屬回收現狀與研究進展

    doi: 10.13374/j.issn2095-9389.2019.11.26.001
    基金項目: 國家自然科學基金資助項目(51672024);工信部綠色制造系統集成資助項目;中央基本科研業務費資助項目(FRF-TP-19-003B1)
    詳細信息
      通訊作者:

      E-mail:zhangshengen@mater.ustb.edu.cn

    • 中圖分類號: TF83;X742;X734.2

    Status and research progress on recovery of platinum group metals from spent catalysts

    More Information
    • 摘要: 我國鉑族金屬(Platinum group metals, PGMs)儲量少,消費量大,對外依存度高,PGMs二次資源的回收利用是緩解我國PGMs短缺最重要的途徑。廢催化劑是PGMs最主要的來源,其回收成為研究的熱點。本文詳細介紹了PGMs消費結構與回收現狀,全球PGMs回收量約占原礦產量的20%~30%,且將保持持續增長的趨勢。樣品的精準分析對PGMs回收有至關重要的作用,同時還原、焙燒、機械球磨等預處理能提高PGMs回收率。相對于傳統氰化法和王水溶解,近年來開發出氯化浸出法、超臨界萃取法、載體溶解法等較環保的浸出工藝。盡管部分濕法浸出工藝已經產業化應用,但存在廢水量大、產生有毒氣體及回收率低(特別是Rh)的問題。火法富集是以鉛、銅、鐵、鎳锍為捕集劑,與PGMs形成合金富集,載體熔化造渣。本文對上述富集方法進行了綜述并總結了優缺點,基于現有技術存在的污染嚴重、PGMs回收率不高等問題,展望了PGMs綠色高效回收技術,如活化預處理、協同提取有價金屬和載體利用、賤金屬協同冶煉和鐵捕集–電解等,為從事該領域的科研工作者提供了良好的參考。

       

    • 圖  1  2007—2018年全球主要國家原生Pt(a)和原生Pd產量(b)

      Figure  1.  Global mineral production of Pt (a) and Pd (b) during 2007—2018

      圖  2  全球Pt和Pd在主要領域的消費結構分布

      Figure  2.  Main worldwide consumption distributions of Pt and Pd

      圖  3  鐵合金物相分析. (a)掃描透射電子顯微鏡微區;(b)能譜成分分析;(c)高分辨透射電鏡;(d)選區電子衍射圖譜

      Figure  3.  Analysis of Fe-PGMs alloy: (a) STEM; (b) EDS analysis; (c) HRTEM; (d) SAED

      表  1  不同廢催化劑的分析方法及結果

      Table  1.   Determination of PGMs in spent catalysts by various methods

      Catalysts (carriers)ElementsAnalysis methodsRSD/%Ref
      Spent automotive catalystsPt, Pd, RhCarius tube+ICP–AES1~2[12]
      HCl–H2O2+ICP–AES4.5~5.1[13]
      Spent catalysts (Al2O3/SiO2)PtICP–AES standard curve method<3[14]
      Spent Oxo-alcohols CatalystRhH2SO4–H2O2–HCl+ICP–OES0.92[15]
      Spent catalysts (SiO2)RhChemical vapour generation+ICP–AES1.6[16]
      Spent catalyst (Al2O3/SiO2)Pt, PdFire assaying+ICP–AES<2[17]
      Spent dehydrogenation catalystPtAqua regia+FAAS<3.45[18]
      Spent Pd–C catalystPdH2SO4–HNO3+ICP–AES1.52[19]
      下載: 導出CSV

      表  2  25 ℃ PGMs的標準電極電位

      Table  2.   Standard electrode potentials of PGMs at 25 ℃

      Electrode reactionsε0/V
      ${\rm{PdBr}}_4^{2 - }$+2e?=Pd+4Br?0.60
      ${\rm{PdCl}}_4^{2 - }$+2e?=Pd+4Cl?0.62
      ${\rm{PdCl}}_6^{2 - }$+2e?=${\rm{PdCl}}_4^{2 - }$+2Cl?1.29
      ${\rm{PtBr}}_4^{2 - }$+2e?=Pt+4Br?0.58
      ${\rm{PtBr}}_6^{2 - }$+2e?=${\rm{PtBr}}_4^{2 - }$+2Br?0.59
      ${\rm{PtCl}}_6^{2 - }$+4e?=Pt+6Cl?0.74
      ${\rm{RhCl}}_6^{3 - }$+3e?=Rh+6Cl?0.43
      ${\rm{PdCN}}_4^{2 - }$+2e?=Pd+4CN?0.40
      ${\rm{PtCN}}_4^{2 - }$+2e?=Pt+4CN?0.09
      下載: 導出CSV

      表  3  部分典型賤金屬捕集PGMs工藝

      Table  3.   Some typical pyrometallurgical processes for PGM recycling

      CountriesCompany namesFurnacesCollectors
      BelgiumUmicoreIsasmelt furnaceCopper
      AmericaMultimetcoDC electrical arc furnaceCopper
      JapanTanakaPlasma melting furnaceIron
      EnglandJohnson-MattheyPlasma melting furnaceIron
      ChinaSino-Platinum MetalsPlasma melting furnaceIron
      下載: 導出CSV
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