CN102994142B - Method for hydrofining pyrolysis gasoline - Google Patents
Method for hydrofining pyrolysis gasoline Download PDFInfo
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- CN102994142B CN102994142B CN201110274173.9A CN201110274173A CN102994142B CN 102994142 B CN102994142 B CN 102994142B CN 201110274173 A CN201110274173 A CN 201110274173A CN 102994142 B CN102994142 B CN 102994142B
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- catalyzer
- catalyst
- carrier
- pyrolysis gasoline
- hydrogenation
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000010937 tungsten Substances 0.000 claims abstract 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 40
- 239000003921 oil Substances 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 3
- 239000007788 liquid Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052976 metal sulfide Inorganic materials 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000009183 running Effects 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910017313 Mo—Co Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl alkenyl arene Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- AWOORJZBKBDNCP-UHFFFAOYSA-N molybdenum;oxotungsten Chemical compound [Mo].[W]=O AWOORJZBKBDNCP-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for hydrofining pyrolysis gasoline; catalyst: the active components are one or more metal sulfides of cobalt, molybdenum, nickel and tungsten and Ni2A composite catalyst of P; dissolving metal salt, hypophosphite, assistant and complexing agent in deionized water to form co-immersion liquid, adding carrier into the co-immersion liquid in saturated immersion mode, and roasting to obtain Ni-containing carrier2The temperature of the P phase catalyst is 200-400 ℃, and the time is 2-6 h; vulcanizing the catalyst at 250-450 ℃ for 3-15 hours; the catalyst has small active component size, high dispersivity, high activity and high stability, and may be used in converting sulfur containing compound and olefin in cracked gasoline basically.
Description
Technical field
The present invention relates to oil-refining chemical field, is a kind of refining method of pyrolysis gasoline hydrogenation.
Background technology
Along with the raising of ethylene production capacity, ethylene by-product pyrolysis gasoline also increases thereupon, and since American UOP company in 1958 publishes the industrial technology of pyrolysis gasoline secondary hydrogenation production aromatic hydrocarbons first, pyrolysis gasoline hydrogenation device is successively gone into operation.The Manufacturing Technology Development of external pyrolysis gasoline hydrogenation catalyst is very fast, and French IFP secondary hydrogenation adopts the catalyzer of LD and two kinds of models of HR, and LD-145 is Mo-Ni type catalyzer, and HR-304B is Mo-Co type catalyzer.The G-35B of the Girdler catalyst company exploitation of Japan and the S-12 catalyzer of Uop Inc.'s exploitation are all Co-Mo/Al
2o
3catalyzer.
Comparatively ripe to the treatment technology of pyrolysis gasoline cut fraction in prior art, the general two-stage method hydrogen addition technology that adopts, one section of pyrolysis gasoline is selective hydrogenation, object is to make active component wherein (as alkynes, diolefin and alkyl alkenyl arene) generate corresponding monoolefine and alkylaromatic hydrocarbon, adopt noble metal hydrogenation catalyst or non-noble metal Ni series catalysts these active unsaturated components in saturated oil product at a lower temperature, to reduce the coking at second segment beds, thereby the running period of assurance device, second segment adopts conventional Mo-Co system to wait non-precious metal catalyst to remove the sulphur in oil product, the impurity such as nitrogen, and saturated remaining monoolefine.Product is used for producing BTX (benzene, toluene and dimethylbenzene) product as the raw material of aromatic extraction unit.But the method also exists technical process longer, first paragraph hydrogenation and second segment hydrogenation need adopt two to overlap independently reactive system, recycle hydrogen system, separation system and power system etc., and facility investment and process cost be the problem such as higher all.
Pyrolysis gasoline secondary hydrogenation had both needed to take into account olefin saturated, hydrogenating desulfurization, prevented again aromatic hydrocarbons loss simultaneously, and this requires support of the catalyst to have suitable acidity.Traditional pyrolysis gasoline secondary hydrogenation catalyzer is using Mo, Co, Ni as active ingredient, Al
2o
3adopt pickling process preparation as carrier, active ingredient does not reach desirable dispersion effect on carrier, and these catalyzer often exist hydrogenation activity too high or active too low and stability is poor, the problem of easy coking.
CN101265421A discloses a kind of sulfur method of hydrocarbon fractions from steam cracking effluents, relate to the treatment process of pyrolysis gasoline raw material, comprise the process of at least one material choice hydrotreating stage and a distillation tower operation, to produce at least one C5 lighting end, C6-C8 middle runnings for aromatic hydrocarbon product, for the last running of gasoline products.Middle runnings is used at least one hydrogenating desulfurization and deep hydrogenation stage, and last running is used an alkylation stage to make sulfur component weightening finish, as middle runnings or oil fuel, realizes cleaning of oil product and produces and can save the hydrogen consumption of shortage of resources in refinery.
The pyrolysis gasoline hydrogenation technology (as CN91109503.9) of Lanzhou chemical research institute exploitation, one section adopts aluminum oxide and supports the noble metal hydrogenation catalyst that the metallic palladium on it forms, for the selective hydrogenation of diolefine; Two sections adopt conventional non-noble metal hydrogenation catalyst to remove the impurity such as sulphur, nitrogen, have obtained comparatively satisfied effect.
CN1353168A discloses one and has been applicable to pyrolysis gasoline secondary hydrogenation catalyst for refining and preparation method thereof, use aluminum oxide precursor, in the time of its moulding, add superpolymer, IV subgroup metal after super-dry, roasting, to obtain shaping carrier, ammonia co-impregnated solution dipping through containing Mo, Co, Ni active ingredient, dry at 100-120 DEG C, under 400-700 DEG C of air, activation obtains catalyzer, the acid-basicity of adjustable carrier, suppress the coking and deactivation speed of catalyzer, because the lower specific surface area of carrier causes catalyst hydrogenation activity not high.
At present, metal phosphorizing nickel catalyzator generally adopts temperature-programmed reduction method preparation, and the method need to be carried out under comparatively high temps.Therefore, when adopting Al
2o
3during for carrier, in the process of high temperature reduction nickel ion, easily cause nickel aluminate to generate, make with Al
2o
3for the catalyst of phosphatizing nickel hydrodesulfurization activity of carrier lower.At present, efficient phosphide Hydrobon catalyst is generally with SiO
2for carrier, still, SiO
2the forming technique of carrier and Surface acidity thereof and Acidity have limited the industry of catalyzer and have promoted.The present invention is directed to the feature of above-mentioned phosphide, develop one to be easy to the Al of moulding
2o
3for carrier, add the modified support of IV subgroup metal, then make the sulphided state catalyzer of containing metal phosphide at carrier surface supported active metal, utilize the keying action between Ni-P-S, strengthen the stability of metallic sulfide Hydrogenation, the superelevation hydrodesulfurization performance of performance nickel phosphide, the pyrolysis gasoline secondary hydrogenation catalyst for refining of acquisition high reactivity and high stability.
Summary of the invention
The object of this invention is to provide a kind of refining method of pyrolysis gasoline hydrogenation, catalyzer used is a kind of catalyzer with high-activity hydrogenation ability, hydrogenation saturated mono alkene to greatest extent, adaptability to raw material is wide, processing inferior raw material and high-speed are required to have greater advantage, adapt to market demands.Method for preparing catalyst is simple, physical strength is high, bulk density is low.
Catalyzer is with resistant to elevated temperatures inorganic porous oxide material, as Al
2o
3, SiO
2, SiO
2-Al
2o
3, one or more in molecular sieve or activated carbon are carrier; Active ingredient is Co, Mo, Ni, W monomer or NiMo, NiW, CoMo, NiCoW, CoNiMo composition metal.Catalyzer is metallic sulfide and the Ni such as a kind of cobalt, molybdenum, nickel, nickel molybdenum, nickel tungsten, cobalt molybdenum, nickel cobalt molybdenum, nickel cobalt or cobalt molybdenum nickel
2the composite catalyst of P.In catalyzer, contain auxiliary agent phosphorus or/and boron, silicon and alkali metal promoter.Taking catalyst weight as 100%, catalyzer contains molybdenum oxide (tungsten) 10-18%, cobalt oxide 0-5%, and nickel oxide 1-15%, additive alkali metal content is 1-3%, and phosphorus is or/and boron is 1-10%, and silicon is 0-30%; The specific surface area of catalyzer is 170-280m
2/ g, pore volume is 0.4-0.7cm
3/ g.
Carrier preparation method is as follows:
First carrier preparation passes through powder kneading, extrusion, and dry, the method for roasting, is cloverleaf pattern.Mediate after extruded moulding, 80-150 DEG C of oven dry in air, 400-600 DEG C of roasting 3-5 hour, makes carrier.
Auxiliary agent phosphorus is or/and boron, silicon and the alkali-metal mode that adds can be that kneading can be to be also impregnated on carrier by the mode of dipping in powder, and silicon is preferably in carrier moulding and adds, and basic metal is preferably in steeping fluid and adds.
Method for preparing catalyst is as follows:
First will contain the metal-salt of Co, Ni, Mo and/or W, and hypophosphite, auxiliary agent and complexing agent form co-impregnated solution with deionized water dissolving, after moulding, carrier adds metal co-impregnated solution with saturated impregnation method.Obtain containing Ni by calcination process
2the catalyzer of P thing phase, 200～400 DEG C for the treatment of temps, the treatment time is 2～6h, the mass loading amount of nickel phosphide is 1～15%.Then will contain Ni
2the catalyzer of P thing phase vulcanizes, and the pre-curing temperature of catalyzer is 250～450 DEG C, and the prevulcanized time is 3-15 hour.The mol ratio of described complexing agent and metal Ni or Co is 0.5～5: 1.
It can be the soluble metallic salt of various ways that metal in steeping fluid adds, and as Ni comprises ortho phosphorous acid nickel, can also comprise other forms of nickel salt, as nickelous nitrate, basic nickel carbonate, nickel acetate etc.Active ingredient salt, auxiliary agent and complexing agent are dissolved and form steeping fluid, be impregnated on carrier.Complexing agent can be one or more in ammoniacal liquor, EDTA, organic acid, and the add-on of complexing agent is relevant to loaded metal amount.
The refining method of pyrolysis gasoline secondary hydrogenation of the present invention, is specially adapted to intermediate oil C5-C9, the preferably secondary hydrogenation of C6-C8 distillate, and at pressure 2.0-5.0MPa, temperature 210-300 DEG C, air speed are 1.5-5.0h
-1under the hydrogen-oil ratio condition that is 150-450/1, in hydrogenating desulfurization, hydrogenation saturated mono alkene to greatest extent, can adapt to the variation of feed sulphur content and the requirement of high-speed.
Embodiment
Embodiment 1
With industrial Al (OH)
3for raw material, get 104.3g powder, boric acid 4.44g, phosphoric acid 3.21g are joined in 105ml water and dissolved, through kneading, extruded moulding, at 120 DEG C, dry 8h, then through 500 DEG C of roasting 4h, make support of the catalyst.Ortho phosphorous acid nickel 7.79g, ammonium molybdate 14.33g, potassium hydroxide 1.55g are dissolved in ammoniacal liquor-aqueous solution, and constant volume is at 45ml, and dipping solution is immersed on 50g carrier, dries, then obtain containing Ni through 450 DEG C of roastings at 120 DEG C
2the precursor of the catalyzer of the active phase of P.By logical the catalyzer precursor of gained H
2s vulcanizes, and obtains catalyst n i
2p-MoS/ γ-Al
2o
3.
Embodiment 2
The catalyzer of embodiment 2 is prepared according to the same method of embodiment 1, and catalyst activity metal composition has difference, adds Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in the time of impregnated catalyst, specifically forms in table 2.
Embodiment 3
The catalyzer of embodiment 3 is prepared according to the same method of embodiment 1, and catalyst activity metal composition has difference, adds nickelous nitrate in the time of impregnated catalyst, specifically forms in table 2.
Embodiment 4
The catalyzer of embodiment 4 is prepared according to the same method of embodiment 1, and catalyst activity metal composition has difference, adds Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in the time of impregnated catalyst, specifically forms in table 2.
Comparative example 1
With industrial Al (OH)
3for raw material, get 104.3g powder, boric acid 4.44g, phosphoric acid 3.21g are joined in 105ml water and dissolved, through kneading, extruded moulding, at 120 DEG C, dry 8h, then through 500 DEG C of roasting 4h, make support of the catalyst.Nickelous nitrate 7.58g, ammonium molybdate 14.33g, potassium hydroxide 1.55g are dissolved in ammoniacal liquor-aqueous solution, and constant volume is at 45ml, and dipping solution is immersed on 50g carrier, dries, then obtain oxidized catalyst through 450 DEG C of roastings at 120 DEG C.By logical the catalyzer of gained H
2s vulcanizes, and obtains catalyst n iMoS/ γ-Al
2o
3.
Embodiment 5
This case introduction activity rating of catalyst process.
Adopting Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline product is raw material, and feedstock property is in table 1.
Catalyzer in embodiment and comparative example is carried out to the evaluation tests in 300 hours of the same terms, every 24 hours sampling analysis product bromine valencys, sulphur content, analytical results is averaged in table 2 and table 3.Catalyst loading and appreciation condition are as follows:
Evaluate with device be 20ml fixed-bed reactor, reactor interlude can be realized thermostatic control, evaluate catalysts is got length between 2-5mm, is seated in reactor interlude and is beneficial to the control of temperature of reaction, upper-lower section loads with 20-30 order quartz sand, N
2airtight qualified rear temperature programming, 150 DEG C of dry 2h, then enter straight-run spirit, are raised to 240 DEG C of swap-in stock oils of temperature of reaction with the speed of 20 DEG C/h.Appreciation condition: reaction pressure 3.0MPa, raw material volume space velocity 3.0h
-1, hydrogen-oil ratio 300: 1.
Table 1 catalyst activity is evaluated stock oil character
Investigate the catalyst activity of embodiment 1-4 and comparative example 1 with the appreciation condition of embodiment 5, result shows to adopt catalyzer prepared by the inventive method Hydrogenation compared with catalyzer in comparative example more excellent, and concrete outcome is in table 2.
Catalyzer preparation composition and the micro anti-evaluation result of table 2 embodiment 1-4 and comparative example 1
Embodiment 6
The siliceous Al (OH) preparing with coprecipitation method
3for raw material, get 101.6g powder, boric acid 4.44g, phosphoric acid 3.21g are joined in 110ml water and dissolved, through kneading, extruded moulding, at 120 DEG C, dry 8h, then through 500 DEG C of roasting 4h, make support of the catalyst.Ortho phosphorous acid nickel 7.69g, ammonium molybdate 11.79g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 3.98g, potassium hydroxide 1.53g are dissolved in ammoniacal liquor-aqueous solution, and constant volume is at 43ml, and dipping solution is immersed on 50g carrier, at 120 DEG C, dry, then obtain through 450 DEG C of roastings contain Ni
2the precursor of the catalyzer of the active phase of P.By logical the catalyzer precursor of gained H
2s vulcanizes, and obtains catalyst n i
2p-CoMoS/ γ-Al
2o
3.
Embodiment 7
The catalyzer of embodiment 7 is prepared according to the same method of embodiment 6, and catalyzer composition has difference, only adds boric acid aqueous solution in the time of carrier moulding, then through kneading, extrusion, specifically forms in table 3.
Embodiment 8
The catalyzer of embodiment 8 is prepared according to the same method of embodiment 6, and catalyzer composition has difference, only adds phosphate aqueous solution in the time of carrier moulding, then through kneading, extrusion, specifically forms in table 3.
Embodiment 9
The catalyzer of embodiment 9 is prepared according to the same method of embodiment 6, and catalyzer composition has difference, only adds the ammonia soln of metal-salt in the time of catalyst soakage, then mixing solutions be impregnated on carrier, specifically forms in table 3.
Comparative example 2
The siliceous Al (OH) preparing with coprecipitation method
3for raw material, get 101.6g powder, boric acid 4.44g, phosphoric acid 3.21g are joined in 110ml water and dissolved, through kneading, extruded moulding, at 120 DEG C, dry 8h, then through 500 DEG C of roasting 4h, make support of the catalyst.Nickelous nitrate 7.49g, ammonium molybdate 11.79g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 3.98g, potassium hydroxide 1.53g are dissolved in ammoniacal liquor-aqueous solution, and constant volume is at 43ml, and dipping solution is immersed on 50g carrier, at 120 DEG C, dry, then obtain through 450 DEG C of roastings contain Ni
2the precursor of the catalyzer of the active phase of P.By logical the catalyzer precursor of gained H
2s vulcanizes, and obtains catalyst n iCoMoS/ γ-Al
2o
3.
The catalyst activity of investigating embodiment 6-9 and comparative example 2 with the appreciation condition of embodiment 5, result shows to adopt catalyzer prepared by the inventive method to compare the catalyst hydrogenation excellent performance in ratio, and concrete outcome is in table 3.
Catalyzer preparation composition and the micro anti-evaluation result of table 3 embodiment 6-9 and comparative example 2
Catalyzer prepared by embodiment 6 carries out feedstock property and long period study on the stability, and feedstock property is in table 4, and raw material has the feature of high colloid, high bromine valency, low-sulfur.Catalyzer in embodiment is carried out to evaluation test in 1000 hours.Catalyst loading and appreciation condition are as follows:
Evaluate with device be 100ml fixed-bed reactor, evaluate catalysts is got length between 2-5mm, is seated in reactor interlude and is beneficial to the control of temperature of reaction, upper-lower section loads with 20-30 order quartz sand, N
2airtight qualified rear temperature programming, 150 DEG C of dry 2h, then enter straight-run spirit, are raised to 240 DEG C of swap-in stock oils of temperature of reaction with the speed of 20 DEG C/h.Appreciation condition: reaction pressure 3.0MPa, raw material volume space velocity 3.0h
-1, hydrogen-oil ratio 300: 1.
Every 96 hours sampling analysis product bromine valencys, sulphur content, analytical results is added up in table 5.Severe in stock oil character by the visible hydrogenation catalyst of the present invention of table 5, under hydrogenating materials innage air speed condition, still keep good Hydrogenation, Hydrogenation is stable, so the invention provides a kind of high reactivity, the refining method for preparing catalyst of high stability pyrolysis gasoline secondary hydrogenation.
Table 4 feedstock property table
Table 5 catalyzer long period activity rating result
Claims (3)
1. the refining method of pyrolysis gasoline hydrogenation, is characterized in that:
Pyrolysis gasoline hydrogenation catalyst for refining, in catalyst weight 100%, by molybdenum oxide or tungsten 10-18%, cobalt oxide 0-5%, nickel oxide 1-6%, basic metal 1-3%, phosphorus is or/and boron is 1-5%, and silicon is 0-20%, and nickel phosphide is 1～15%, and surplus is carrier composition;
Carrier is resistant to elevated temperatures inorganic porous oxide material, and specific surface area is 170-280m
2/ g, pore volume is 0.4-0.7cm
3/ g;
The preparation of catalyzer:
(1) first will contain Co, Ni, Mo or/and the metal-salt of W and ortho phosphorous acid nickel, auxiliary agent and complexing agent deionized water dissolving form co-impregnated solution, after moulding, carrier adds metal co-impregnated solution with saturated impregnation method, obtains containing Ni by calcination process
2the catalyzer of P thing phase, 200～400 DEG C for the treatment of temps, the treatment time is 2～6h;
(2) then will contain Ni
2the catalyzer of P thing phase vulcanizes, and the pre-curing temperature of catalyzer is 250～450 DEG C, and the prevulcanized time is 3-15 hour.
2. according to the refining method of pyrolysis gasoline hydrogenation claimed in claim 1, it is characterized in that: carrier is Al
2o
3, SiO
2, SiO
2-Al
2o
3, molecular sieve or activated carbon.
3. according to the refining method of pyrolysis gasoline hydrogenation claimed in claim 1, it is characterized in that: pyrolysis gasoline is that the secondary hydrogenation of intermediate oil C5-C9 distillate is when refining, adopt fixed-bed reactor, at pressure 2.0-5.0MPa, temperature 210-300 DEG C, air speed are 1.5-5.0h
-1with hydrogenating desulfurization under the hydrogen-oil ratio condition that is 150-450/1.
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| CN104588031B (en) * | 2013-10-31 | 2017-01-11 | 中国石油化工股份有限公司 | Distillate oil hydrotreatment catalyst and preparation method thereof |
| CN103611562B (en) * | 2013-11-29 | 2015-11-11 | 武汉科林精细化工有限公司 | A kind of cracking carbon nine secondary hydrogenation Catalysts and its preparation method |
| CN105087054B (en) * | 2014-05-08 | 2017-03-22 | 中国石油化工股份有限公司 | Hydrofining method of pyrolysis gasoline |
| CN105214697B (en) * | 2014-06-18 | 2017-12-01 | 天津大学 | A kind of low paraffin dehydrogenation alkene catalyst and preparation method |
| CN106890660A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN106552655A (en) * | 2016-11-26 | 2017-04-05 | 新疆佳宇恒能源科技有限公司 | A kind of preparation method of co-impregnated solution and wax oil hydrogenation catalyst for refining |
| CN109265305B (en) * | 2018-10-24 | 2020-01-07 | 濮阳市联众兴业化工有限公司 | Method for preparing cyclopentane by low-temperature hydrogenation of cracking carbon nine |
| CN114433092B (en) * | 2020-10-20 | 2024-01-30 | 中国石油化工股份有限公司 | Pre-sulfiding method of hydrogenation catalyst, obtained pre-sulfiding hydrogenation catalyst and application |
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| CN101011665A (en) * | 2007-01-09 | 2007-08-08 | 大连理工大学 | Double-metal phosphide hydrogenation refining catalyst |
| US7446075B1 (en) * | 2005-08-23 | 2008-11-04 | Uop Llc | Transition metal phosphides and hydrotreating process using the same |
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| US7446075B1 (en) * | 2005-08-23 | 2008-11-04 | Uop Llc | Transition metal phosphides and hydrotreating process using the same |
| CN101011665A (en) * | 2007-01-09 | 2007-08-08 | 大连理工大学 | Double-metal phosphide hydrogenation refining catalyst |
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