CN112808273A - MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed - Google Patents
MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed Download PDFInfo
- Publication number
- CN112808273A CN112808273A CN202110154477.5A CN202110154477A CN112808273A CN 112808273 A CN112808273 A CN 112808273A CN 202110154477 A CN202110154477 A CN 202110154477A CN 112808273 A CN112808273 A CN 112808273A
- Authority
- CN
- China
- Prior art keywords
- based catalyst
- hydrotalcite
- layered porous
- magnesium
- mgfe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 81
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 80
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 80
- 239000000725 suspension Substances 0.000 title claims abstract description 52
- 239000003225 biodiesel Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 16
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 235000019482 Palm oil Nutrition 0.000 claims abstract description 19
- 239000002540 palm oil Substances 0.000 claims abstract description 19
- 239000003921 oil Substances 0.000 claims abstract description 11
- 235000019198 oils Nutrition 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 21
- 239000011550 stock solution Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 7
- 229910000856 hastalloy Inorganic materials 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 244000309465 heifer Species 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention discloses a layered porous magnesium-iron hydrotalcite-based catalyst (MgFe-LMOs) and application thereof in producing biodiesel by hydrogenation and deoxidation in a suspension bed. The invention firstly adopts a hydrothermal-coprecipitation method to prepare the intercalation junctionAnd (3) roasting the MgFe-LDHs binary hydrotalcite in the air atmosphere to obtain the layered porous magnesium-iron catalyst material. The catalyst is applied to the suspension bed hydrodeoxygenation production of biodiesel by taking palm oil as raw oil, has higher hydrodeoxygenation reaction activity and selectivity, and the product mainly contains C10‑C18The alkane is the main one, and has higher combustion heat value, thereby having good application prospect in industry.
Description
Technical Field
The invention belongs to the technical field of energy chemical industry, and particularly relates to a layered porous magnesium-iron hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation in a suspension bed.
Background
With the increasing exhaustion of conventional fossil energy, the increasing pollution of the atmosphere, and the stricter requirements of various countries on the emission of greenhouse gases, the world is facing the dual challenges of coping with the climate change process and searching for alternatives of fossil energy. In order to solve the environmental and energy problems and realize sustainable development of human society, the search and development of new energy sources become a research hotspot at present. In order to achieve the purposes of reducing emission and cost and reducing the harm of conventional petrochemical energy to living environment, renewable energy is widely concerned. The raw material source of the biological fuel oil is wide, the biological fuel oil has reproducibility, the obtained product is clean, and the recycling of carbon can be realized. Therefore, the development and utilization of biofuel oil are the focus and emphasis of the research in the energy field at present.
In the process of producing the biofuel oil by hydrodeoxygenation, the catalyst plays a crucial role and influences the reaction process of the hydrodeoxygenation and the distribution of reaction products. Currently, one of the main types of hydrodeoxygenation catalysts that have been researched and developed is a noble metal catalyst, which is of interest to researchers due to high activity, s. Lestari et al use a noble metal catalyst Pd/SBA-15 to catalyze stearic acid to produce biodiesel (s. Lestari, p. M ä ki-Arvela, k. Er ä nen, j. Beltramini, et al, Catalysis Letters, 134 (2009) 250-. Therefore, the noble metal catalyst is difficult to be widely applied to the biodiesel production industry by hydrodeoxygenation.
The invention patent (CN 105087083B) discloses a method for producing biodiesel by catalytic conversion of grease by transition metal (Ni, Fe, Co, Mo and the like) sulfide, wherein the catalyst is gradually deactivated due to sulfur loss in the reaction process, and sulfur must be continuously supplemented into the raw materials in order to maintain the activity of the catalyst. On one hand, the production cost is improved, and on the other hand, the lost sulfur enters the oil product, so that the quality of the oil product is reduced.
The invention patent (CN 102427880B) discloses a method for producing biodiesel by hydrogenating metal phosphide, and MoP/ZrO used in the method2The diesel selectivity of the catalyst is 97%, and the catalyst has certain isomerization performance and can obtain the biodiesel with low pour point. The invention patent (CN 103756794B) discloses a method for producing second-generation biodiesel by hydrogenation by taking illegal cooking oil as a raw material, wherein the biodiesel is obtained by hydrodeoxygenation reaction under the action of transition metal phosphide, and the produced biodiesel has high cetane number and low condensation point, but the production process is complex and the energy consumption is high. Although the transition metal phosphide catalyst has noble metal-like properties and excellent hydrogenation performance, the phosphide catalyst has the defects of easy oxidation in air, poor stability, easy inactivation when meeting water and the like, and the industrial production and application of the phosphide catalyst are limited to a great extent.
The invention patents (CN 103721741 a, CN 105944750 a and CN 107442166A) and the like disclose a method of producing a metal oxide with one or more transition metal oxides (Ni, Fe, Co, Mo,mn, etc.) as active center, molecular sieve or Al2O3，TiO2，SiO2，MgO，ZrO2The preparation of the catalyst taking the same as the carrier and the application thereof in the biodiesel have good hydrodeoxygenation and isomerization effects. However, these catalysts have complicated preparation steps, easily lost active components, excessively high reaction temperature and low carbon yield.
Hydrotalcite (LDH) as a functional material with a layered structure has excellent catalytic performance and great advantages in the preparation of biodiesel. T, Morgan et Al (T, Morgan, E, Santalin-Jimenez, A, E, Harman-Ware, et Al, Chemical Engineering Journal, 189-190 (2012) 346-355) use Ni-Al-LDHs, Ni-Mg-Al-LDHs and Mg-Al-LDHs as catalysts to research the deoxidation of soybean oil in a nitrogen atmosphere, the yield of the obtained hydrocarbon fuel is lower and is 46-52%, and the catalysts are easy to coke. Then T.Morgan et Al (E.Santillan-Jimenez, T.Morgan, J.Shoup, A.E.Harman-Ware, M.Crocker, Catalysis Today, 237 (2014) 136-144) again using Ni-Al-LDH catalyst at 10% H2/N2Or H2The conversion of fatty acids and triglycerides to fuel-like hydrocarbons was investigated under an atmosphere and the yield of fuel hydrocarbons was increased to about 70%. The invention patent (CN 111205931A) discloses a method for producing biodiesel by catalytic action of roasted Ca-Al hydrotalcite, which takes vegetable oil, dimethyl carbonate and methanol as raw materials to react, the yield of the product is more than 80 percent, but a certain amount of glycerol still exists.
At present, the production of biodiesel by a hydrodeoxygenation technology is mainly based on a fixed bed reaction process, however, the production of water is not avoided in the process of producing biodiesel by hydrodeoxygenation of animal and vegetable oil, which is a great challenge to the stability of a catalyst, and coke is produced in the reaction process. The accumulation of water and coke on the surface of the catalyst severely reduces the activity of the catalyst, resulting in rapid deactivation of the catalyst. Therefore, the development of a new hydrodeoxygenation process is of great importance. The suspension bed reaction process is characterized in that the catalyst and the raw materials pass through the reactor at one time, and the problem of catalyst deactivation caused by the production of water and coke can be well avoided. However, based on the characteristics of the suspension bed hydrogenation reaction, the catalyst is required to have the characteristics of high activity, low price and good stability.
In conclusion, the development of a suspension bed hydrodeoxygenation catalyst with high activity and selectivity, low cost and good stability is necessary in the aspect of producing biodiesel, and the key point is how to select a material with high hydrodeoxygenation activity and low cost as an active component and prepare a catalyst with high dispersion and high stability. In order to achieve the effect, the invention provides a layered porous magnesium-iron metal oxide material for preparing biodiesel, the material has the advantages of green and simple preparation process, cheap raw materials and very important guiding significance and practical value for the production of biodiesel, and the application of the layered porous magnesium-iron metal material in the field of producing biofuel oil by hydrodeoxygenation in a suspension bed is rarely reported at present.
Disclosure of Invention
The invention aims to provide a layered porous MgFe hydrotalcite-based catalyst and application thereof in producing biodiesel by hydrogenation and deoxidation in a suspension bed. The MgFe-LDHs material with a layered structure is used as a precursor, and is calcined to generate a composite metal oxide (MgFe-LMOs) with closely-packed and stable crystal units, the composite metal oxide has metal active sites and oxygen vacancy sites, is favorable for carrying out hydrodeoxygenation reaction, has good stability, is difficult for loss of active components, and simultaneously has relatively large aperture of the synthesized catalyst, and is favorable for diffusion of macromolecules in raw materials. The catalyst shows excellent catalytic performance in a palm oil suspension bed hydrodeoxygenation reaction, can remove oxygen in raw materials, has high yield of biodiesel, and has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a layered porous MgFe hydrotalcite-based catalyst is prepared through the hydrothermal-coprecipitation process to generate precipitation reaction between alkaline solution and Mg and Fe metal salt ions at a certain temp to generate a binary hydrotalcite-like precursor (MgFe-LDHs), and calcining in air atmosphere to obtain the highly dispersed and stable layered porous MgFe catalyst (MgFe-LMOs). The preparation method comprises the following steps:
(1) mixing and dissolving a magnesium salt and an iron salt in a certain molar ratio into deionized water to form a mixed metal salt solution;
(2) stirring and dissolving the mixed alkaline substance in deionized water to form an alkaline solution;
(3) slowly adding the alkaline solution obtained in the step (2) into the mixed metal salt solution obtained in the step (1) dropwise under the condition of vigorous stirring to form a uniform suspension, then vigorously stirring at normal temperature, and aging for 0.5-8 h (preferably 1-6 h);
(4) transferring the suspension aged in the step (3) to a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing for 6-48 h (preferably 8-36 h) at 70-180 ℃ (preferably 80-160 ℃), taking out and cooling to room temperature, filtering and washing the obtained precipitate, and drying in an oven at 80-180 ℃ to obtain a binary magnesium-iron hydrotalcite precursor;
(5) and (3) roasting the binary magnesium iron hydrotalcite precursor obtained in the step (4) for 2-12 h (preferably 2-8 h) in an air atmosphere at the temperature of 200-900 ℃ (preferably at the temperature of 300-800 ℃), and cooling to obtain the layered porous MgFe hydrotalcite-based catalyst for producing the biodiesel.
The amount of the magnesium salt and the iron salt used in the step (1) is converted according to the molar ratio of Mg to Fe of 1: 0.1-10. The ferric salt is any one of ferric nitrate, ferric acetate, ferric chloride, ferric oxalate or ferric sulfate; the magnesium salt is any one of magnesium nitrate, magnesium sulfate, magnesium chloride or magnesium acetate. The total molar concentration of the mixed metal salt solution obtained is 0.1-10 mol/L.
The mixed alkaline substance in the step (2) is NaOH, KOH, LiOH, ammonia water and Na2CO3、K2CO3、Li2CO3、(NH4)2CO3、NH4HCO3Two or more of urea, water and hydrazine, hexamethylenetetramine. The total molar concentration of the obtained alkaline solution is 0.1-20 mol/L.
The volume ratio of the mixed metal salt solution to the alkaline solution used in the step (3) is 1: 0.1-10. The stirring rate is 300-1500 rpm.
The obtained layered porous MgFe hydrotalcite-based catalyst can be applied to the production of biodiesel by suspension bed hydrodeoxygenation, and the application method specifically comprises the steps of taking palm oil (one or more of 24, 33, 44 and 52 degrees) as raw material oil, putting the raw material oil and the layered porous MgFe hydrotalcite-based catalyst into a suspension bed reactor together, purging air in the reactor and a pipeline by nitrogen, then filling high-purity hydrogen into the suspension bed reactor for hydrodeoxygenation reaction, and filtering and separating the obtained reaction product to obtain the biodiesel; the conditions of the hydrodeoxygenation reaction are as follows: the temperature is 200-400 ℃ (preferably 280-380 ℃), the hydrogen pressure is 2-8 MPa (preferably 2-6 MPa), the stirring speed is 300-1000 rpm (preferably 300-800 rpm), and the catalyst is 0.5-30wt% (preferably 4 wt%).
The innovation of the invention is that:
(1) the preparation process of the layered porous magnesium iron hydrotalcite-based catalyst provided by the invention is green and simple, the cost is low, the prepared catalyst has metal active sites and oxygen defect sites, the hydrogenation reaction is favorably carried out, the stability is good, the active components are not easy to lose, the pore size is relatively large, and the conversion of macromolecules in raw materials is favorably realized.
(2) The hydrotalcite-based catalyst is applied to the process for producing the biodiesel by the hydrodeoxygenation of the suspension bed for the first time, the oxygen in the raw materials can be removed, the yield of the biodiesel is high, and the method has a good application prospect in industry.
Drawings
Fig. 1 is an XRD pattern of the binary magnesium iron hydrotalcite precursor prepared in example 1.
Fig. 2 is an XRD pattern of the layered porous magnesium iron hydrotalcite-based catalyst prepared in example 1.
Fig. 3 is a TEM image of the layered porous magnesioferrite-based catalyst prepared in example 1.
FIG. 4 is a graph showing FT-IR comparison of the product obtained after the deoxygenation reaction of examples 1-3 with the starting material.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The raw materials used in the examples are all reagent grade. XRD detection IS carried out by adopting an Ultima type X-ray powder diffractometer produced by Japan, the specific surface area and the pore size distribution of the catalyst are observed by adopting an ASAP 2460 full-automatic specific surface and porosity analyzer of American Mimmeritek corporation, the components of the biodiesel are measured by adopting a gas chromatography-mass spectrometer of TRACE GC1300/ISQ 7000 type of American Sammelier corporation, and the oxygen-containing functional groups are measured by adopting a Nicolet IS 10 type Fourier infrared spectrometer of American Sammelier heifer corporation.
Example 1
Adding 0.03 mol of MgCl2•6H2O and 0.01 mol FeCl3•6H2Dissolving O in 100 ml deionized water to form 0.4mol/L solution A, adding 0.08 mol NaOH and 0.005 mol Na2CO3Adding the solution B into 80 ml of deionized water to obtain 1.0mol/L clear solution B, dropwise and slowly adding the solution B into the solution A under the condition of vigorous stirring (the speed is 800 rpm) to form uniform suspension, then vigorously stirring and aging for 1 h at normal temperature, transferring the aged suspension into a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing at 140 ℃ for 12 h, taking out and cooling to room temperature, filtering and washing the obtained precipitate, drying in a 120 ℃ drying oven to constant weight to obtain a binary magnesium-iron hydrotalcite precursor, finally placing the binary magnesium-iron hydrotalcite precursor into a muffle furnace, and roasting at 500 ℃ for 6 h to obtain the layered porous magnesium-iron hydrotalcite-based catalyst.
Taking 50 g of palm oil stock solution and 2 g of prepared layered porous magnesium-iron hydrotalcite-based catalyst, loading the palm oil stock solution and the prepared layered porous magnesium-iron hydrotalcite-based catalyst into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 350 ℃, the hydrogen pressure is 4 MPa, the stirring speed is 300 rpm, the product after hydrodeoxygenation is filtered and separated, and the physical property analysis is carried out on the liquid phase product.
Example 2
0.027 mol of MgCl2•6H2O and 0.013mol FeCl3•6H2Dissolving O in 100 ml deionized water to obtain 0.4mol/L solution A, adding 0.08 mol NaOH and 0.0067 mol Na2CO3Adding the solution B into 80 ml of deionized water to obtain 1.0mol/L clear solution B, dropwise and slowly adding the solution B into the solution A under the condition of vigorous stirring (the speed is 800 rpm) to form uniform suspension, then vigorously stirring and aging for 1 h at normal temperature, transferring the aged suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, statically crystallizing at 140 ℃ for 12 h, taking out and cooling to room temperature, filtering and washing the obtained precipitate, then placing the precipitate into a drying oven at 120 ℃ and drying to constant weight to obtain a binary magnesium-iron hydrotalcite precursor, finally placing the binary magnesium-iron hydrotalcite precursor into a muffle furnace, and roasting at 500 ℃ for 6 h to obtain the layered porous magnesium-iron hydrotalcite-based catalyst.
Taking 50 g of palm oil stock solution and 2 g of prepared layered porous magnesium-iron hydrotalcite-based catalyst, loading the palm oil stock solution and the prepared layered porous magnesium-iron hydrotalcite-based catalyst into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 350 ℃, the hydrogen pressure is 4 MPa, the stirring speed is 300 rpm, the product after hydrodeoxygenation is filtered and separated, and the physical property analysis is carried out on the liquid phase product.
Example 3
0.02 mol of MgCl2•6H2O and 0.02 mol FeCl3•6H2Dissolving O in 100 ml deionized water to form 0.4mol/L solution A, adding 0.08 mol NaOH and 0.01 mol Na2CO3Adding into 80 ml deionized water to obtain 1.0mol/L clear solution B, adding the obtained solution B into the solution A dropwise and slowly under the condition of vigorous stirring (speed is 800 rpm) to form uniform suspension, then vigorously stirring and aging at normal temperature for 1 h, transferring the aged suspension into a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing at 140 ℃ for 12 h, taking out and cooling to room temperature, filtering and washing the obtained precipitateAnd (3) drying the washed mixture in a 120 ℃ drying oven to constant weight to obtain a binary magnesium-iron hydrotalcite precursor, and finally, roasting the binary magnesium-iron hydrotalcite precursor in a muffle furnace at 500 ℃ for 6 hours to obtain the layered porous magnesium-iron hydrotalcite-based catalyst.
Taking 50 g of palm oil stock solution and 2 g of prepared layered porous magnesium-iron hydrotalcite-based catalyst, loading the palm oil stock solution and the prepared layered porous magnesium-iron hydrotalcite-based catalyst into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 350 ℃, the hydrogen pressure is 4 MPa, the stirring speed is 300 rpm, the product after hydrodeoxygenation is filtered and separated, and the physical property analysis is carried out on the liquid phase product.
Example 4
0.027 mol of MgCl2•6H2O and 0.013mol FeCl3•6H2Dissolving O in 100 ml deionized water to form 0.4mol/L solution A, adding 0.08 mol of urea, 0.0067 mol of water and hydrazine into 80 ml of deionized water to obtain 1.0mol/L clear solution B, the resulting solution B was slowly added dropwise to the solution A under vigorous stirring (at 800 rpm) to form a uniform suspension, then vigorously stirring and aging for 1 h at normal temperature, transferring the aged suspension into a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing at 140 ℃ for 12 h, taking out and cooling to room temperature, filtering and washing the obtained precipitate, then placing the precipitate in a 120 ℃ oven to dry to constant weight to obtain a binary magnesium iron hydrotalcite precursor, finally placing the binary magnesium iron hydrotalcite precursor in a muffle furnace, and roasting at 500 ℃ for 6 h to obtain the layered porous magnesium iron hydrotalcite-based catalyst.
Taking 50 g of palm oil stock solution and 2 g of prepared layered porous magnesium-iron hydrotalcite-based catalyst, loading the palm oil stock solution and the prepared layered porous magnesium-iron hydrotalcite-based catalyst into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 350 ℃, the hydrogen pressure is 4 MPa, the stirring speed is 300 rpm, the product after hydrodeoxygenation is filtered and separated, and the physical property analysis is carried out on the liquid phase product.
Example 5
0.027 mol of MgCl2•6H2O and 0.013mol FeCl3•6H2Dissolving O in 100 ml deionized water to obtain 0.4mol/L solution A, adding 0.08 mol NaOH and 0.0067 mol Na2CO3Adding the solution B into 80 ml of deionized water to obtain 1.0mol/L clear solution B, dropwise and slowly adding the solution B into the solution A under the condition of vigorous stirring (the speed is 800 rpm) to form uniform suspension, then vigorously stirring and aging for 1 h at normal temperature, transferring the aged suspension into a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing at 140 ℃ for 12 h, taking out and cooling to room temperature, filtering and washing the obtained precipitate, drying in a 120 ℃ drying oven to constant weight to obtain a binary magnesium-iron hydrotalcite precursor, finally placing the binary magnesium-iron hydrotalcite precursor into a muffle furnace, and roasting at 500 ℃ for 6 h to obtain the layered porous magnesium-iron hydrotalcite-based catalyst.
Taking 50 g of palm oil stock solution and 2 g of prepared layered porous magnesium-iron hydrotalcite-based catalyst, loading the palm oil stock solution and the prepared layered porous magnesium-iron hydrotalcite-based catalyst into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 320 ℃, the hydrogen pressure is 4 MPa, the stirring speed is 300 rpm, the product after hydrodeoxygenation is filtered and separated, and the physical property analysis is carried out on the liquid phase product.
Example 6
0.027 mol of MgCl2•6H2O and 0.013mol FeCl3•6H2Dissolving O in 100 ml deionized water to obtain 0.4mol/L solution A, adding 0.08 mol NaOH and 0.0067 mol Na2CO3Adding into 80 ml deionized water to obtain 1.0mol/L clear solution B, adding the obtained solution B into the solution A dropwise and slowly under the condition of vigorous stirring (speed is 800 rpm) to form uniform suspension, then vigorously stirring and aging at normal temperature for 1 h, transferring the aged suspension into a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing at 140 ℃ for 18 h, taking out and cooling to room temperature, filtering and washing the obtained precipitate, and placing the precipitate in a 120 ℃ oven for dryingDrying to constant weight to obtain a binary magnesium iron hydrotalcite precursor, and finally placing the binary magnesium iron hydrotalcite precursor in a muffle furnace, and roasting at 500 ℃ for 6 hours to obtain the layered porous magnesium iron hydrotalcite-based catalyst.
Taking 50 g of palm oil stock solution and 2 g of prepared layered porous magnesium-iron hydrotalcite-based catalyst, loading the palm oil stock solution and the prepared layered porous magnesium-iron hydrotalcite-based catalyst into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 380 ℃, the hydrogen pressure is 4 MPa, the stirring speed is 300 rpm, the product after hydrodeoxygenation is filtered and separated, and the physical property analysis is carried out on the liquid phase product.
Example 7
0.027 mol of MgCl2•6H2O and 0.013mol FeCl3•6H2Dissolving O in 100 ml deionized water to obtain 0.4mol/L solution A, adding 0.08 mol NaOH and 0.0067 mol Na2CO3Adding the solution B into 80 ml of deionized water to obtain 1.0mol/L clear solution B, dropwise and slowly adding the solution B into the solution A under the condition of vigorous stirring (the speed is 800 rpm) to form uniform suspension, then vigorously stirring and aging for 1 h at normal temperature, transferring the aged suspension into a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing at 140 ℃ for 12 h, taking out and cooling to room temperature, filtering and washing the obtained precipitate, drying in a 120 ℃ drying oven to constant weight to obtain a binary magnesium-iron hydrotalcite precursor, finally placing the obtained binary magnesium-iron hydrotalcite precursor in a muffle furnace, and roasting at 500 ℃ for 6 h to obtain the layered porous magnesium-iron hydrotalcite-based catalyst.
Taking 50 g of palm oil stock solution and 2 g of prepared layered porous magnesium-iron hydrotalcite-based catalyst, loading the palm oil stock solution and the prepared layered porous magnesium-iron hydrotalcite-based catalyst into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 350 ℃, the hydrogen pressure is 6 MPa, the stirring speed is 300 rpm, the product after hydrodeoxygenation is filtered and separated, and the physical property analysis is carried out on the liquid phase product.
FIG. 1 is an XRD pattern of a binary magnesium iron hydrotalcite precursor (MgFe-LDH) prepared in example 1. As can be seen from the figure, the peaks at 2 θ =11.41 °, 22.97 °, 34.65 °, 38.99 °, 45.98 °, 59.94 °, 61.25 ° are characteristic diffraction peaks of hydrotalcite, corresponding to the (003), (006), (012), (015), (018), (110) and (113) crystal planes thereof, respectively, which proves that MgFe-LDHs binary hydrotalcite is successfully prepared by the hydrothermal-co-precipitation method.
FIG. 2 is an XRD pattern of a layered porous magnesium iron hydrotalcite based catalyst (MgFe-LMO) prepared in example 1. As can be seen from the figure, the diffraction peaks at 2 θ =37.01 °, 43.00 °, 62.45 ° correspond to the (111), (200), (220) crystal planes of MgO after being shifted, respectively, but Fe is not observed2O3Characteristic peak of (2), proving Fe2O3The bonding with MgO was good, and a solid solution was formed.
Fig. 3 is a TEM image of the layered porous magnesioferrite-based catalyst prepared in example 1. As can be seen from the figure, the layered porous mgferrite hydrotalcite-based catalyst prepared in example 1 is a layered structure stacked by sheets, is easily curled to generate wrinkles, and has an irregular pore structure and defect sites on the sheets.
FIG. 4 is a graph showing FT-IR comparison of the product obtained after dehydrogenation reaction of examples 1-3 with the feedstock. As can be seen from the figure, there is an ester bond with the oxygen-containing group-C = O (1740 cm)-1) -COOH carboxyl group (1710 cm)-1) and-C-O single bond (1160 cm)-1) The relevant tensile vibration band substantially disappeared, indicating that the layered porous magnesioferrite hydrotalcite-based catalyst has an excellent deoxidation effect.
Comparative example 1
In order to examine the effect of other metal species hydrotalcite-based catalysts on the yield of biodiesel, magnesium aluminum hydrotalcite-based catalysts (MgAl-LMOs) were prepared using the same synthesis conditions as in example 1, and the hydrodeoxygenation performance of the catalysts was evaluated using the same reaction conditions as in example 1.
Comparative example 2
In order to examine the effect of the hydrotalcite-based catalyst of other metal species on the yield of biodiesel, a nickel-alumina hydrotalcite-based catalyst (NiAl-LMOs) was prepared using the same synthesis conditions as in example 1, and the hydrodeoxygenation performance of the catalyst was evaluated using the same reaction conditions as in example 1.
Comparative example 3
In order to examine the influence of the reactor class on the yield of biodiesel, the hydrodeoxygenation performance of the catalyst was evaluated on a fixed bed reactor using the catalyst prepared in example 1, and the reaction conditions were kept consistent with those of example 1, and were: the temperature is 350 ℃, the hydrogen pressure is 4 MPa, and the liquid volume space velocity is 2.0 h-1The hydrogen-oil ratio is 300:1 (V/V).
The yields of biodiesel produced by the catalysts obtained in examples 1 to 7 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 comparison of the yields of biodiesel production in examples 1-7 and comparative examples 1-3
As can be seen from table 1, compared with comparative examples 1 and 2, the magnesium-iron hydrotalcite-based catalyst of the present invention has more excellent hydrodeoxygenation activity and higher biodiesel productivity than the magnesium-aluminum hydrotalcite-based catalyst and the nickel-aluminum hydrotalcite-based catalyst. Compared with a fixed bed reactor, the invention adopts a suspension bed reactor for reaction, can ensure that the catalyst is more fully contacted with the raw material, can inhibit the product from coking, and has the advantages of high conversion rate and high yield.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A layered porous MgFe hydrotalcite-based catalyst is characterized in that: the preparation method comprises the following steps:
(1) mixing and dissolving a magnesium salt and an iron salt in a certain molar ratio into deionized water to form a mixed metal salt solution;
(2) stirring and dissolving the mixed alkaline substance in deionized water to form an alkaline solution;
(3) slowly adding the alkaline solution obtained in the step (2) into the mixed metal salt solution obtained in the step (1) dropwise under the condition of vigorous stirring to form uniform suspension, then vigorously stirring at normal temperature, and aging for 0.5-8 h;
(4) transferring the suspension aged in the step (3) to a stainless steel reactor with a polytetrafluoroethylene lining, statically crystallizing at 70-180 ℃ for 6-48 h, taking out, cooling to room temperature, filtering, washing and drying the obtained precipitate to obtain a binary magnesium-iron hydrotalcite precursor;
(5) and (4) roasting the binary magnesium iron hydrotalcite precursor obtained in the step (4) at 900 ℃ under the air atmosphere for 2-12 h, and cooling to obtain the layered porous MgFe hydrotalcite-based catalyst for producing the biodiesel.
2. The layered porous MgFe hydrotalcite-based catalyst according to claim 1, characterized in that: the amount of the magnesium salt and the iron salt used in the step (1) is converted according to the molar ratio of Mg to Fe of 1: 0.1-10.
3. The layered porous MgFe hydrotalcite-based catalyst according to claim 1 or 2, characterized in that: in the step (1), the ferric salt is any one of ferric nitrate, ferric acetate, ferric chloride, ferric oxalate or ferric sulfate; the magnesium salt is any one of magnesium nitrate, magnesium sulfate, magnesium chloride or magnesium acetate.
4. The layered porous MgFe hydrotalcite-based catalyst according to claim 1, characterized in that: the total molar concentration of the mixed metal salt solution obtained in the step (1) is 0.1-10 mol/L.
5. The layered porous MgFe hydrotalcite-based catalyst according to claim 1, characterized in that: the mixed alkaline substance in the step (2) is NaOH, KOH, LiOH, ammonia water and Na2CO3、K2CO3、Li2CO3、(NH4)2CO3、NH4HCO3Two or more of urea, water, hydrazine and hexamethylenetetramine。
6. The layered porous MgFe hydrotalcite-based catalyst according to claim 1, characterized in that: the total molar concentration of the alkaline solution obtained in the step (2) is 0.1-20 mol/L.
7. The layered porous MgFe hydrotalcite-based catalyst according to claim 1, characterized in that: the volume ratio of the mixed metal salt solution to the alkaline solution used in the step (3) is 1: 0.1-10.
8. The layered porous MgFe hydrotalcite-based catalyst according to claim 1, characterized in that: the stirring rate in the step (3) is 300-1500 rpm.
9. Use of a layered porous MgFe hydrotalcite-based catalyst according to claim 1 in the production of biodiesel by suspension bed hydrodeoxygenation, characterized in that: taking palm oil as raw material oil, putting the raw material oil and the layered porous MgFe hydrotalcite-based catalyst into a suspension bed reactor together, purging air in the reactor and a pipeline by using nitrogen, then filling high-purity hydrogen into the suspension bed reactor to carry out hydrodeoxygenation reaction, and filtering and separating the obtained reaction product to obtain biodiesel;
the conditions of the hydrodeoxygenation reaction are as follows: the temperature is 200-400 ℃, the hydrogen pressure is 2-8 MPa, the stirring speed is 300-1000 rpm, and the catalyst dosage is 0.5-30 wt%.
10. The use of the layered porous MgFe hydrotalcite-based catalyst according to claim 9 in the production of biodiesel by suspension bed hydrodeoxygenation, characterized in that: the palm oil is one or more of 24 degrees, 33 degrees, 44 degrees and 52 degrees.
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