CN116790288B - Method for producing biological aviation kerosene by hydrogenating waste grease - Google Patents
Method for producing biological aviation kerosene by hydrogenating waste grease Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 239000004519 grease Substances 0.000 title claims abstract description 49
- 239000003350 kerosene Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 88
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000007670 refining Methods 0.000 claims abstract description 15
- 239000012263 liquid product Substances 0.000 claims abstract description 13
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 43
- 239000003921 oil Substances 0.000 claims description 27
- 235000019198 oils Nutrition 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 21
- 239000003225 biodiesel Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 235000019482 Palm oil Nutrition 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 239000002540 palm oil Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- -1 transition metal sulfide Chemical class 0.000 claims description 4
- 150000003657 tungsten Chemical class 0.000 claims description 4
- 235000019197 fats Nutrition 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 2
- 235000015278 beef Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims 1
- 239000003760 tallow Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000000295 complement effect Effects 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 208000036828 Device occlusion Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000000508 aqueous-phase reforming Methods 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010806 kitchen waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 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
- 239000000126 substance Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of biological oil products and discloses a method for producing biological aviation kerosene by hydrogenating waste grease, which comprises the following steps of mixing the waste grease with hydrogen and a hydrogenation pretreatment catalyst, and then feeding the mixture into a slurry bed hydrogenation reactor for hydrogenation; recycling a tailings part obtained by the effluent after hydrogenation through a hydrocyclone to a slurry bed hydrogenation reactor; the liquid product is subjected to gas-liquid separation, the hydrogen-rich gas is purified and recycled, and the liquid product is subjected to solid-liquid separation; the separated liquid phase product enters a hydrofining reactor, a hydrocracking reactor and a post-refining reactor which are connected in series for hydrogenation; and (3) carrying out gas-liquid separation on the hydrogenation product, and fractionating the liquid product to obtain the biological aviation kerosene. According to the invention, the slurry bed hydrogenation pretreatment is used for efficiently completing the hydrogenation conversion of non-ideal components such as oxygen-containing compounds in waste grease; obtaining high-quality biological aviation kerosene fraction through deep complementary hydrotreatment; the adaptability of raw materials is strong; the product yield is high; the running period of the device is long.
Description
Technical Field
The invention relates to the technical field of biological oil products, in particular to a method for producing biological aviation kerosene by hydrogenating waste grease.
Background
The aviation kerosene has proper density, high heat value, good combustion performance, small combustion area, less carbon deposition and difficult coking, and can be rapidly, stably, continuously and completely combusted; the low-temperature fluidity is good, and the requirements of cold low-temperature areas and high-altitude flight on the fluidity of oil products can be met; the heat stability and the oxidation stability are good, and the requirements of supersonic high-altitude flight can be met; high cleanliness, no harmful substances such as mechanical impurities, moisture and the like, low sulfur content, particularly mercaptan sulfur content, and small corrosion to parts.
Compared with the traditional fossil fuel, the biological aviation kerosene produced by taking the vegetable oil represented by the palm oil and the waste grease represented by the edible waste oil as raw materials can reduce the carbon emission by 55-92%.
The biodiesel is prepared from waste grease, belongs to waste energy regeneration, and compared with the conventional biofuel, the usage amount of the biodiesel in Europe is in accordance with the principle of double emission reduction count (namely, the actual addition amount is 1 percent and the calculated addition amount is 2 percent). If the biodiesel taking the waste grease as the raw material is added, the addition amount of the biodiesel can be reduced by the double emission reduction counting principle, so that the coordinated development of economy and environmental protection is realized.
Because of the characteristics of high viscosity, high oxygen content, unstable combustion, low heat value and the like of the biomass raw material, the biomass raw material cannot be directly used as a substitute for petroleum fuel, hydrodeoxygenation (Hydrodeoxygenation, HDO) treatment is required before the biomass raw material is used, and main types of oxygen-containing compounds in the biomass raw material comprise phenols, furans, ketones, aldehydes, esters and the like. The main oxygen-containing compound in palm oil and edible waste oil is triglyceride, and most of carbon chains are C 14～22, wherein C 18 and C 16 account for more than 95% of the total fatty acid.
The existing production process of the second generation biodiesel mainly adopts a fixed bed hydrogenation process, and the waste grease raw materials have the defects of high acid value and excessively high content of Fe, na, ca metal elements, O, N, P and other elements, and are easy to deposit on the active components of a hydrogenation catalyst in the hydrogenation reaction process so as to quickly poison the catalyst; in addition, the presence of long-chain olefins and oxygenates can cause agglomeration and plugging of the catalyst bed, causing rapid rise in reactor pressure drop and shut down; in addition, due to different sources and complex composition of biomass raw materials, the problems of device blockage, corrosion and the like commonly exist in the conventional fixed bed hydrogenation process, and high requirements are put on the continuity and long-period stable operation of the hydrodeoxygenation process, wherein the long-period stable operation of the hydrodeoxygenation process is the pain point of the biological aviation kerosene production technology.
The carrier of the supported catalyst has a direct influence on the service life and stability of the catalyst. Currently, the most used support for Hydrodeoxygenation (HDO) catalysts is γ -Al 2O3. However, the high oxygen content of the bio-oil raw material can lead to a certain amount of water generation in the hydrodeoxygenation process, and Al 2O3 can generate boehmite in water vapor with a certain pressure, so that the catalyst structure collapses, the specific surface area and the pore volume are reduced, the mechanical strength is reduced, and the catalytic activity of the catalyst is reduced. Conventional supported catalysts have great limitations in the hydroprocessing of waste oils and fats.
Currently, the main processes used for producing the second generation biodiesel are fixed bed hydrogenation processes, the catalysts used are mainly supported transition metal sulfidic catalysts, the catalyst carriers used are mainly alumina, for example, NExBTL process ((US Patent: 7232935) adopted by Neste oil industry group (Neste oil) in Finland, and Econfining process (US Patent: 20060264684) jointly developed by UOP and Italian hydrocarbon company (Ente Nazionale ldrocarburi) in the United states, and the domestic production process is basically similar to the two processes.
The patent with the application number of CN20110373951. X discloses a production method of biodiesel, which uses kitchen waste oil and mineral diesel as raw materials, and the addition of the mineral diesel solves the problem that H 2 O generated in hydrodeoxygenation affects the service life of a catalyst to a certain extent, but the addition of the mineral diesel ensures that the produced finished biodiesel does not accord with the national definition of biodiesel, cannot enjoy corresponding tax preference, and loses economic benefit.
The patent with the application number of CN202110261877.6 discloses a process for directly producing aviation kerosene by utilizing waste grease, which comprises the processes of pretreatment of raw oil, hydrolysis of high-carbon-number hydrocarbons to obtain fatty acid, hydrofining and the like, and has complex operation process, and the operation of obtaining fatty acid through hydrolysis increases construction cost and running cost.
The patent with the application number of CN200610083300.6 discloses a method for preparing biodiesel, which comprises the steps of carrying out transesterification reaction on a biological grease raw material and short-chain alcohol, recovering methanol and glycerin, wherein the product prepared by the method is first-generation biodiesel, and has the defects of high energy consumption and difficult recovery of methyl ester products, and the catalyst used in the transesterification process is a Bronsted acid ionic liquid catalyst, so that the production cost is high.
The patent with the application number of CN201110192761.8 discloses a method for preparing biodiesel by hydrogenation, which uses excellent vegetable oil as a raw material, mainly comprises the processes of hydrofining, hydrodewaxing and the like, uses a catalyst in a sulfurized state, needs to presulfiding an oxidized catalyst active component by using a sulfur-containing compound (such as carbon disulfide, thioether, derivative thereof and the like), has a complex operation process and serious pollution to water. The catalyst carrier is gamma-Al 2O3, which can collapse the catalyst structure under the long-term hydrothermal condition, reduce the specific surface area and pore volume and lower the mechanical strength.
Patent application number CN201910190312.6 discloses a method for preparing biodiesel, which comprises the steps of hydrolysis of glyceride, water phase reforming of glycerol to generate hydrogen, hydrofining and the like. The method does not need to additionally introduce high-purity nitrogen, and has low energy consumption. However, the subsequent hydrogenation reaction at too high a temperature can inhibit the aqueous phase reforming reaction of glycerol from generating hydrogen, and the product separation is complex.
The patent with the application number of CN201911163276.6 discloses a method for preparing hydrogenated biodiesel by catalyzing grease to carry out directional hydrodeoxygenation, waste grease and the like are used as raw materials, a molecular sieve supported catalyst is Ni 2 P/SAPO-11, a large amount of phosphating wastewater is caused by the existence of phosphide, the treatment cost is high, and the produced wastewater has serious pollution to the environment.
The patent with the application number of CN201510263141.7 discloses a method for producing aviation biofuel from waste animal and vegetable oil, which consists of a pretreatment unit, a hydrotreatment unit, a degassing and dehydration unit, a hydroconversion unit and a rectification unit, has complex treatment procedures, and needs to fill a protective agent in the hydrotreatment unit and also needs to adopt a special catalyst grading process so as to prevent H 2 O generated in the grease hydrogenation process from influencing the catalyst activity. The operation flexibility is low.
In summary, the following problems are generally encountered in the process of producing bio-aviation kerosene using waste grease: on the one hand, the composition of the waste grease is complex, the waste grease raw material has the defects of high acid value and excessively high contents of Fe, na, ca metal elements, O, N, P and other elements, the fixed bed catalyst is easy to poison and deactivate, the coking and blocking are difficult to realize long-period operation, and the fixed bed hydrodeoxygenation industrialization is hindered. On the other hand, the carrier of the supported catalyst has a direct influence on the service life and stability of the catalyst. However, the high oxygen content of the bio-oil raw material can lead to a certain amount of water generation in the hydrodeoxygenation process, and Al 2O3 can generate boehmite in water vapor with a certain pressure, so that the catalyst structure collapses, the specific surface area and the pore volume are reduced, the mechanical strength is reduced, and the catalytic activity of the catalyst is reduced. Conventional supported catalysts have great limitations in the hydroprocessing of waste oils and fats. Therefore, eliminating various defects of a fixed bed in the hydrodeoxygenation process, developing a treatment process with strong adaptability to raw materials and capable of realizing large-scale and long-period operation of a device is an important problem to be solved in the field.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for producing biological aviation kerosene by hydrogenating waste grease, which has the following technical scheme:
a method for producing biological aviation kerosene by hydrogenating waste grease comprises the following steps:
s101: fully mixing the waste grease with the mechanical impurities removed, hydrogen and a hydrogenation pretreatment catalyst, and then entering a slurry bed hydrogenation reactor for hydrogenation pretreatment;
S102: recycling a part of tailings obtained by the effluent after hydrogenation through a hydrocyclone to an inlet of a slurry bed hydrogenation reactor, and discharging a small amount of tailings;
s103: the liquid product obtained by separation of the cyclone liquid separator enters a gas-liquid separator for gas-liquid separation, the obtained hydrogen-rich gas is purified and recycled, and the obtained liquid product enters a solid-liquid separator;
s104: taking the liquid phase product separated by the solid-liquid separator as a product after hydrogenation pretreatment, and discharging the solid residue out of the device;
s105: the product after the hydrogenation pretreatment enters a fixed bed hydrofining reactor, a fixed bed hydrocracking reactor and a fixed bed post-refining reactor which are sequentially connected in series for hydrogenation treatment;
S106: the hydrogenation product enters a gas-liquid separation unit to carry out gas-liquid separation, and the obtained liquid product enters a fractionation unit to obtain naphtha fraction, biological aviation kerosene fraction and biodiesel fraction.
Further, the waste grease, hydrogen and the hydrogenation pretreatment catalyst in the step S101 are mixed and then enter a slurry bed hydrogenation reactor from the bottom to flow from bottom to top; the reaction conditions of the slurry bed hydrogenation reactor are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 340-410 ℃, the liquid hourly space velocity is 0.5-1.5 h -1, and the volume ratio of hydrogen to waste grease is 300-1200 Nm 3/m3; the axial temperature distribution of the slurry bed hydrogenation reactor is uniform, and the maximum temperature difference is not more than 15 ℃.
Further, the adding amount of the hydrogenation pretreatment catalyst in the S101 accounts for 0.005-0.2% of the weight of the waste grease.
Further, the operating conditions of the hydrocyclone in S102 are as follows: the pressure is 4-20 MPa, and the temperature is 200-300 ℃; the tailings obtained by the hydrocyclone in the S102 are recycled to the inlet of the slurry bed hydrogenation reactor, the amount of the tailings is 80-99 wt% of the total amount of the tailings, and the external discharge amount is 1-20 wt% of the total amount of the tailings.
Further, the reaction conditions of the fixed bed hydrofining reactor in S105 are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 280-380 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3; the reaction conditions of the fixed bed hydrocracking reactor in S105 are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 340-390 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3; the reaction conditions of the fixed bed post-refining reactor in S105 are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 240-320 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3.
Further, the hydrogenation pretreatment catalyst in S101 is a VIB group metal Mo or W and a VIIIB group metal Co or Ni which are supported on a carrier, and the catalyst active component accounts for 10-30% of the weight of oxide.
Further, the composition of the hydrotreating catalyst in S101 is: 1 to 6 weight percent of nickel oxide and/or cobalt oxide, 6 to 24 weight percent of molybdenum oxide and/or tungsten oxide, and the balance of carbon carrier.
Further, the preparation steps of the hydrogenation pretreatment catalyst in S101 are as follows:
(1) Preparing a solution with a required concentration from soluble salt of active metal, impregnating a carbon carrier by adopting an isovolumetric impregnation method, and drying for 1-10 hours at 80-200 ℃ to obtain an active carbon supported metal catalyst; the active metal soluble salts comprise nickel salts, cobalt salts, molybdenum salts and tungsten salts, wherein the nickel salts comprise nickel nitrate and basic nickel carbonate, the cobalt salts comprise cobalt nitrate, cobalt acetate and basic cobalt carbonate, the molybdenum salts comprise molybdenum oxide and ammonium molybdate, and the tungsten salts comprise tungsten oxide and ammonium metatungstate;
(2) Adding the active carbon supported metal catalyst obtained in the step (1) and a vulcanizing agent into a reaction kettle for hydrothermal treatment, wherein the molar ratio of the sulfur content of the vulcanizing agent to the active metal content is 3-5:1, the active metal content is the sum of nickel and/or cobalt and molybdenum and/or tungsten, the reaction temperature is 80-200 ℃, and the reaction time is 2-6 hours, so that the active carbon supported transition metal sulfide catalyst can be obtained.
Further, the hydrogenation pretreatment catalyst is granular, and the outer diameter is 50-500 mu m; the vulcanizing agent is one or more of ammonium sulfide, ammonium polysulfide, elemental sulfur, thiourea and ammonium thiosulfate.
Further, the waste grease comprises one or more of acidized oil, edible waste oil, animal internal oil, condensate oil of a range hood, clay refining desorption oil, fatlute generated in the oil pressing process, beef and mutton skin oil, palmitoized oil, coconut oil and palm oil.
Compared with the prior art, the invention has the following beneficial technical effects:
1. By adopting the slurry bed hydrogenation pretreatment process, the hydrodeoxygenation of the waste grease and the deep removal of chlorine, metal, phospholipid and other hetero atoms can be efficiently realized, and the hydroconversion of non-ideal components such as oxygen-containing compounds in the waste grease can be completed. Wherein the deoxidization rate of the waste grease after the slurry bed hydrogenation pretreatment is higher than 99 percent.
2. The hydrofining reactor, the hydroisomerization reactor and the post-refining reactor are connected in series to realize the deep hydrotreatment of the waste grease, thereby obtaining the high-quality biological aviation kerosene fraction.
3. The process flow is simple.
4. The operation is flexible.
5. The adaptability of raw materials is strong.
6. The yield of the biological aviation kerosene product is high.
7. The operating cycle of the waste grease hydrotreater can be remarkably prolonged.
8. Provides technical support for the high added value utilization of waste grease, and has very wide application prospect.
Drawings
FIG. 1 is a flow chart of a process for producing biological aviation kerosene by hydrogenating waste grease;
In the figure: the method comprises the following steps of 1-waste grease, 2-hydrogen, 3-hydrogenation pretreatment catalyst, 4-slurry bed hydrogenation reactor, 5-hydrogenation pretreatment reaction product, 6-hydrocyclone, 7-hydrocyclone separation solid-containing tailings, 8-hydrocyclone separation liquid product, 9-gas-liquid separator, 10-hydrogen-rich gas, 11-solid-liquid separator, 12-hydrogenation pretreatment product, 13-solid tailings, 14-fixed bed hydrofining reactor, 15-fixed bed hydrocracking reactor, 16-fixed bed post-refining reactor, 17-gas-liquid separation unit and 18-fractionation unit.
Detailed Description
The method provided by the invention is further described below with reference to the accompanying drawings. Many devices such as pumps, heat exchangers, compressors, etc. are omitted from the figures, but are well known to those of ordinary skill in the art.
As shown in FIG. 1, the method for producing biological aviation kerosene by hydrogenation of waste grease of the invention has the following detailed flow:
The waste grease 1 from the pipeline is fully mixed with hydrogen 2 and a hydrogenation pretreatment catalyst 3 and then enters a slurry bed hydrogenation reactor 4 for hydrogenation pretreatment, and the reaction conditions are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 340-410 ℃, the liquid hourly space velocity is 0.5-1.5 h -1, and the volume ratio of hydrogen to waste grease is 300-1200 Nm 3/m3; Separating the slurry bed hydrogenation pretreatment reaction product 5 by a hydrocyclone 6 to obtain a hydrocyclone separated solid-containing tailings 7, wherein part of the tailings are circulated to the inlet of the slurry bed hydrogenation reactor 6, and the rest of the tailings are discharged; the cyclone liquid separation liquid product 8 obtained by the separation of the cyclone liquid separator 6 enters a gas-liquid separator 9 for gas-liquid separation, the obtained hydrogen-rich gas 10 is purified and recycled, and the liquid phase product enters a solid-liquid separator 11; the liquid phase product separated by the solid-liquid separator 11 is a product 12 after hydrogenation pretreatment, and the solid tailings 13 are discharged out of the device. the product 12 after hydrogenation pretreatment enters a fixed bed hydrofining reactor 14, a fixed bed hydrocracking reactor 15 and a fixed bed post-refining reactor 16 which are connected in series for hydrogenation reaction, wherein the reaction conditions of the fixed bed hydrofining reactor 14 are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 280-380 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3; the reaction conditions of the fixed bed hydrocracking reactor are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 340-390 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3; the reaction conditions of the fixed bed post-refining reactor are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 240-320 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3. the hydrogenation product enters a gas-liquid separation unit 17 for gas-liquid separation, and the obtained liquid product enters a fractionation unit 18 to finally obtain high-quality biological aviation kerosene fraction.
The properties of the raw materials used in the examples are shown in Table 1.
TABLE 1 main Properties of waste fat Material
Example 1
The preparation method of the hydrogenation catalyst in the waste grease hydrogenation pretreatment process comprises the following steps: 28.8g of ammonium molybdate tetrahydrate is weighed and dispersed in 120ml of deionized water to obtain a clear solution A; 13.4g of nickel nitrate hexahydrate is weighed and dissolved in 30ml of ammonia water to obtain a clear solution B; mixing the clarified solution A and the clarified solution B to prepare an impregnating solution C; 100g of the carbon support is placed in an impregnating solution C by an isovolumetric impregnation method, and is dried for 120 minutes at 120 ℃ after 60 minutes of impregnation; and (3) adding the dried catalyst into a reaction kettle, performing hydrothermal treatment on thiourea solution, wherein the molar ratio of the sulfur content of thiourea to the active metal content (sum of nickel and molybdenum) is 4:1, the reaction temperature is 160 ℃, and the reaction time is 120 minutes, so that the active carbon-loaded NiMo sulfidic catalyst can be obtained. The catalyst calculates metal loading in terms of mass fractions of MoO 3 and NiO, wherein: moO 3 was 22.0: 22.0 wt% and NiO was 3.0% by weight. The catalyst particle size was 100. Mu.m. The reaction conditions of the slurry bed hydrogenation reactor are shown in Table 2, and the reaction results of the slurry bed hydrogenation reactor are shown in Table 3.
Example 2
The preparation method of the hydrogenation catalyst in the waste grease hydrogenation pretreatment process comprises the following steps: 30.5g of ammonium tungstate hexahydrate is weighed and dispersed in 120ml of deionized water to obtain a clear solution A; 13.6g of nickel nitrate hexahydrate is weighed and dissolved in 30ml of ammonia water to obtain a clear solution B; mixing the clarified solution A and the clarified solution B to prepare an impregnating solution C; 10g of acid-treated active carbon material is placed in an impregnating solution C by an isovolumetric impregnation method, the impregnating solution C is impregnated for 180 minutes and then dried for 180 minutes at 130 ℃, the dried catalyst is added into a reaction kettle, the hydrothermal treatment is carried out on thiourea solution, the molar ratio of sulfur content to active metal content (sum of nickel and tungsten) of thiourea is 4:1, the reaction temperature is 160 ℃, and the reaction time is 120 minutes, so that the active carbon-loaded NiW vulcanized catalyst can be obtained. The catalyst calculates the metal loading in terms of mass fractions of WO 3, niO, wherein: WO 3 was 22.0: 22.0 wt% and NiO was 3.0% by weight. The catalyst particle size was 100. Mu.m. The reaction conditions of the slurry bed hydrogenation reactor are shown in Table 2, and the reaction results of the slurry bed hydrogenation reactor are shown in Table 3.
Example 3
The adopted hydrogenation catalyst is waste agent of industrial diesel hydrofining catalyst, and the composition of the waste agent is as follows: 72 wt% of aluminum oxide, 4 wt% of nickel oxide and 24 wt% of molybdenum oxide. The catalyst particle size was 100. Mu.m. The reaction conditions of the slurry bed hydrogenation reactor are shown in Table 2, and the reaction results of the slurry bed hydrogenation reactor are shown in Table 3.
Example 4
This example used the oil-soluble molybdenum catalyst FGL-202 developed by heavy oil national emphasis laboratories. The reaction conditions of the slurry bed hydrogenation reactor are shown in Table 2, and the reaction results of the slurry bed hydrogenation reactor are shown in Table 3.
Example 5
The liquid product obtained in the above example 1 is sequentially fed into a fixed bed hydrofining reactor, a fixed bed hydrocracking reactor and a fixed bed post-refining reactor, wherein the hydrofining catalyst, the hydrocracking catalyst and the post-refining catalyst can be common commercial catalysts in the field. This example employs hydrofining catalyst FGB-302, hydrocracking catalyst FGB-602, and post-refining catalyst FGB-502 developed by heavy oil national emphasis laboratories. The reaction conditions of the fixed bed hydrofining reactor are as follows: the hydrogen partial pressure in the reactor is 8MPa, the reaction temperature is 340 ℃, the liquid hourly space velocity is 2h -1, and the hydrogen volume ratio is 600Nm 3/m3; the reaction conditions of the fixed bed hydrocracking reactor are as follows: the hydrogen partial pressure in the reactor is 8MPa, the reaction temperature is 380 ℃, the liquid hourly space velocity is 1.5h -1, and the hydrogen volume ratio is 600Nm 3/m3; the reaction conditions of the fixed bed post-refining reactor are as follows: the hydrogen partial pressure in the reactor was 8MPa, the reaction temperature was 280 ℃, the liquid hourly space velocity was 3h -1, and the hydrogen volume ratio was 600Nm 3/m3. The results of the overall scheme are shown in Table 4.
TABLE 2 reaction conditions for waste oil slurry bed hydrogenation pretreatment
TABLE 3 results of waste oil slurry bed hydrogenation pretreatment reactions
TABLE 4 full flow reaction results for producing biological aviation kerosene by waste grease hydrogenation
As shown in Table 3, the waste grease is treated according to the slurry bed hydrogenation process adopted by the method of the invention, the oxygen content of the hydrotreatment product obtained by the industrial waste diesel hydrofining catalyst adopted in the example 3 is 1.52%, the oxygen content of the hydrotreatment products of the catalysts adopted in the other examples is less than 1%, and the deoxidization rate is more than 90%, wherein the deoxidization rates of the oil-soluble molybdenum-based catalyst and the carbon-supported NiMo catalyst are more than 99%, so that the high-efficiency conversion of non-ideal components in the waste grease is realized, and the requirement of the subsequent further hydrotreatment on raw materials is met.
As can be seen from the results in Table 4, the waste grease was treated according to the method of the present invention to obtain a high-quality bio-aviation kerosene fraction and a bio-diesel fraction. Therefore, the method for producing the biological aviation kerosene by the hydrogenation of the waste grease has the advantages of simple process flow, high oil liquid yield, good biological aviation kerosene quality and the like, and can realize full-fraction resource utilization of the waste grease.
It will be apparent to those skilled in the art that the present invention has been described in detail by way of illustration only, and it is not intended to be limited by the above-described embodiments, as long as various insubstantial modifications of the method concepts and aspects of the invention are employed or the inventive concepts and aspects of the invention are directly applied to other applications without modification, all within the scope of the invention.
Claims (2)
1. The method for producing the biological aviation kerosene by hydrogenating the waste grease is characterized by comprising the following steps of:
s101: fully mixing the waste grease with the mechanical impurities removed, hydrogen and a hydrogenation pretreatment catalyst, and then entering a slurry bed hydrogenation reactor for hydrogenation pretreatment;
S102: recycling a part of tailings obtained by the effluent after hydrogenation through a hydrocyclone to an inlet of a slurry bed hydrogenation reactor, and discharging a small amount of tailings;
s103: the liquid product obtained by separation of the cyclone liquid separator enters a gas-liquid separator for gas-liquid separation, the obtained hydrogen-rich gas is purified and recycled, and the obtained liquid product enters a solid-liquid separator;
s104: taking the liquid phase product separated by the solid-liquid separator as a product after hydrogenation pretreatment, and discharging the solid residue out of the device;
s105: the product after the hydrogenation pretreatment enters a fixed bed hydrofining reactor, a fixed bed hydrocracking reactor and a fixed bed post-refining reactor which are sequentially connected in series for hydrogenation treatment;
S106: the hydrogenation product enters a gas-liquid separation unit to carry out gas-liquid separation, and the obtained liquid product enters a fractionation unit to obtain naphtha fraction, biological aviation kerosene fraction and biodiesel fraction;
The waste grease, hydrogen and the hydrogenation pretreatment catalyst in the S101 are mixed and then enter a slurry bed hydrogenation reactor from the bottom, and flow from bottom to top; the reaction conditions of the slurry bed hydrogenation reactor are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 340-410 ℃, the liquid hourly space velocity is 0.5-1.5 h -1, and the volume ratio of hydrogen to waste grease is 300-1200 Nm 3/m3; the axial temperature of the slurry bed hydrogenation reactor is uniformly distributed, and the maximum temperature difference is not more than 15 ℃;
The adding amount of the hydrogenation pretreatment catalyst in the S101 accounts for 0.005-0.2% of the weight of the waste grease;
The operation conditions of the hydrocyclone in S102 are as follows: the pressure is 4-20 MPa, and the temperature is 200-300 ℃; the tailings obtained by the hydrocyclone in the S102 are recycled to the inlet of the slurry bed hydrogenation reactor, the amount of the tailings is 80-99 wt% of the total amount of the tailings, and the external discharge amount is 1-20 wt% of the total amount of the tailings;
The reaction conditions of the fixed bed hydrofining reactor in the step S105 are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 280-380 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3; the reaction conditions of the fixed bed hydrocracking reactor in S105 are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 340-390 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3; the reaction conditions of the fixed bed post-refining reactor in S105 are as follows: the hydrogen partial pressure in the reactor is 4-20 MPa, the reaction temperature is 240-320 ℃, the liquid hourly space velocity is 0.5-4 h -1, and the volume ratio of hydrogen to the material entering the reactor is 300-1000 Nm 3/m3;
the hydrogenation pretreatment catalyst in S101 is a VIB group metal Mo or W and a VIII group metal Co or Ni which are loaded on a carrier, and the weight of the active components of the catalyst is 10-30% of that of the oxides;
The composition of the hydrogenation pretreatment catalyst in the S101 is as follows: 1 to 6 weight percent of nickel oxide and/or cobalt oxide, 6 to 24 weight percent of molybdenum oxide and/or tungsten oxide, and the balance of carbon carrier;
The preparation steps of the hydrogenation pretreatment catalyst in the step S101 are as follows:
(1) Preparing a solution with a required concentration from soluble salt of active metal, impregnating a carbon carrier by adopting an isovolumetric impregnation method, and drying for 1-10 hours at 80-200 ℃ to obtain an active carbon supported metal catalyst; the active metal soluble salt comprises nickel salt, cobalt salt, molybdenum salt and tungsten salt, wherein the nickel salt comprises nickel nitrate and basic nickel carbonate, the cobalt salt comprises cobalt nitrate, cobalt acetate and basic cobalt carbonate, the molybdenum salt is ammonium molybdate, and the tungsten salt is ammonium metatungstate;
(2) Adding the active carbon supported metal catalyst obtained in the step (1) and a vulcanizing agent into a reaction kettle for hydrothermal treatment, wherein the molar ratio of the sulfur content of the vulcanizing agent to the active metal content is 3-5:1, the active metal content is the sum of nickel and/or cobalt and molybdenum and/or tungsten, the reaction temperature is 80-200 ℃, and the reaction time is 2-6 hours, so that the active carbon supported transition metal sulfide catalyst can be obtained;
The hydrogenation pretreatment catalyst is granular, and the outer diameter is 50-500 mu m; the vulcanizing agent is one or more of ammonium sulfide, ammonium polysulfide, elemental sulfur, thiourea and ammonium thiosulfate.
2. The method for producing biological aviation kerosene by hydrogenating waste oil and fat according to claim 1, wherein the waste oil and fat comprises one or more of acidified oil, animal internal dirty oil, condensate oil of a smoke exhaust ventilator, clay refining desorption oil, fatlute generated in the oil pressing process, beef tallow oil, palmitoylated oil, coconut oil and palm oil.
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| CN114854462A (en) * | 2022-06-06 | 2022-08-05 | 中国石油大学(华东) | Method for preparing second-generation biodiesel by applying slurry bed process hydrogenation |
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