Figures (8)  Tables (3)

    • Figure 1. 

      The TIC diagrams of the tar obtained by the co-pyrolysis of rich-oil coal and phosphorus-containing compounds at different ratios. Ratio is all rich-oil coal : phosphorus compounds, (a) 1:1, (b) 1:3, (c) 1:5.

    • Figure 2. 

      Speculation on the mechanism of the co-pyrolysis products of phosphoric acid and coal.

    • Figure 3. 

      GC diagram of the co-pyrolysis products of POCl3 and oil-rich coal. (a) GC-MS; (b) GC-FPD.

    • Figure 4. 

      31P NMR images of the co-pyrolysis products of phosphorus oxychloride and oil-rich coal, and the structures of phosphine compounds in various regions.

    • Figure 5. 

      NMR spectra and mechanism diagrams of the co-pyrolysis products of dimethyl phenylphosphonate and oil-rich coal. (a) 31P NMR spectrum; (b) 1H-31P HMBC NMR spectrum; (c) mechanism diagram.

    • Figure 6. 

      The 31P NMR spectrum of the co-pyrolysis products of triphenyl phosphite and oil-rich coal.

    • Figure 7. 

      NMR spectra and mechanism diagrams of the co-pyrolysis products of phenyldichlorophosphine and oil-rich coal. (a) 31P NMR spectrum; (b) 1H-31P HMBC NMR spectrum; (c) mechanism diagram.

    • Figure 8. 

      NMR spectra and mechanism diagrams of the co-pyrolysis products of chlorinated diphenylphosphine and oil-rich coal. (a) 31P NMR spectrum; (b) 1H-31P HMBC NMR spectrum; (c) mechanism diagram.

    • Sample Industrial analysis (%) Elemental analysis (%)
      Mad Aad Vad FCad C H O N S H/C
      Coal of
      Zhangjiamao      		 3.78 6.92 32.51 56.79 77.89 4.62 16.51 0.60 0.38 0.71

      Table 1. 

      Industrial analysis and elemental analysis of oil-rich coal samples.

    • No. Compound name Solvent δP (ppm)
      1 Triphenyl phosphite CDCl3 128.5
      2 Methyl diphenylphosphinite CDCl3 116.92
      3 Chlorodiphenylphosphine CDCl3 81.88
      4 Diphenylphosphinic chloride CDCl3 44.68
      5 Dichlorophenylphosphine CDCl3 36.02
      6 Phenylphosphonic dichloride CDCl3 35.98
      7 Methyldiphenylphosphine oxide CDCl3 29.90
      8 Phenylphosphonic acid dimethyl ester CDCl3 27.04
      9 Phosphate radical (Na3PO4) CDCl3 6
      10 Phosphoric acid CDCl3 0
      11 Triphenylphosphine CDCl3 −5.38
      12 (±) 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl C6D6 −15.61
      13 Triethylphosphine CDCl3 −20
      14 Methyl(diphenyl)phosphane CDCl3 −26.7
      15 Tri(1-naphthyl)phosphine D6-DMSO −33.14
      16 Dimethylphenylphosphine CDCl3 −45.46
      17 Trimethylphosphine CDCl3 −62
      18 Phosphorus pentachloride CDCl3 −80

      Table 2. 

      31P NMR chemical shifts of phosphorus-containing standards.

    • Sample name Treatment method Content of P (mg/L)
      Coal pyrolysis tar Microwave digestion 1.04
      Phosphorus-containing co-pyrolysis tar Microwave digestion 546.84

      Table 3. 

      Comparison of P content in raw coal pyrolysis tar and co-pyrolysis coal tar.