CN104415759B - The sulfur method of desulphurization catalyst and preparation method thereof and sulfurous fuels oil - Google Patents
The sulfur method of desulphurization catalyst and preparation method thereof and sulfurous fuels oil Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- 238000000034 method Methods 0.000 title claims abstract description 71
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 41
- 239000011593 sulfur Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000446 fuel Substances 0.000 title description 5
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 197
- 230000023556 desulfurization Effects 0.000 claims abstract description 197
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 172
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011787 zinc oxide Substances 0.000 claims abstract description 81
- 239000002184 metal Substances 0.000 claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 54
- 239000011247 coating layer Substances 0.000 claims abstract description 49
- 239000000295 fuel oil Substances 0.000 claims abstract description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 88
- 239000002002 slurry Substances 0.000 claims description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- 239000010410 layer Substances 0.000 claims description 37
- 238000005253 cladding Methods 0.000 claims description 34
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003929 acidic solution Substances 0.000 claims description 24
- 239000012018 catalyst precursor Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 150000002739 metals Chemical class 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000007771 core particle Substances 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000004684 trihydrates Chemical class 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N phenyl acetate Chemical group CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 67
- 239000003502 gasoline Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 28
- 239000004005 microsphere Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 23
- 238000006722 reduction reaction Methods 0.000 description 20
- 239000000377 silicon dioxide Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000012921 fluorescence analysis Methods 0.000 description 12
- 238000001694 spray drying Methods 0.000 description 12
- 239000005995 Aluminium silicate Substances 0.000 description 11
- 235000012211 aluminium silicate Nutrition 0.000 description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000010451 perlite Substances 0.000 description 6
- 235000019362 perlite Nutrition 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000005065 mining Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 238000011988 family based association test Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 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 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000005243 fluidization Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- -1 methane hydrocarbons Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
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- 150000003567 thiocyanates Chemical class 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
本发明公开了一种脱硫催化剂，该催化剂包括内核和包覆层：内核含有氧化铝、氧化硅和活性金属；包覆层含有氧化铝、氧化硅和氧化锌。本发明还公开了一种脱硫催化剂的制备方法，由该方法得到的脱硫催化剂以及含硫燃料油的脱硫方法。本发明提供的脱硫催化剂具有层状结构，可以具有更好的脱硫性能，并且脱硫催化剂有更好的耐磨损强度。
The invention discloses a desulfurization catalyst, which comprises an inner core and a coating layer: the inner core contains aluminum oxide, silicon oxide and active metal; the coating layer contains aluminum oxide, silicon oxide and zinc oxide. The invention also discloses a preparation method of the desulfurization catalyst, the desulfurization catalyst obtained by the method and a desulfurization method of sulfur-containing fuel oil. The desulfurization catalyst provided by the invention has a layered structure, can have better desulfurization performance, and the desulfurization catalyst has better wear resistance strength.
Description
技术领域technical field
本发明涉及一种脱硫催化剂及其制备方法与含硫燃料油的脱硫方法，具体地，涉及一种具有层状结构的脱硫催化剂，一种具有层状结构的脱硫催化剂的制备方法，以及由该方法制备的具有层状结构的脱硫催化剂，和一种含硫燃料油的脱硫方法。The present invention relates to a desulfurization catalyst and a preparation method thereof and a desulfurization method of sulfur-containing fuel oil, in particular to a desulfurization catalyst with a layered structure, a method for preparing a desulfurization catalyst with a layered structure, and the desulfurization catalyst with a layered structure. A desulfurization catalyst with a layered structure prepared by the method, and a desulfurization method for sulfur-containing fuel oil.
背景技术Background technique
车用燃料中的硫燃烧后产生的硫氧化物，会抑制汽车尾气转化器中的贵金属催化剂的活性并可使之发生不可逆地中毒，从而使汽车尾气中含有的未燃烧的非甲烷烃、氮的氧化物和一氧化碳排放增加。而这些排放气体被日光催化则容易形成光化学烟雾，引发酸雨，同时大气中的硫氧化物本身也是形成酸雨的主要原因之一。随着人们对环境保护的日益重视，环保法规也日渐严格，降低汽油和柴油的硫含量被认为是改善空气质量的最重要措施之一。The sulfur oxides produced by the combustion of sulfur in the vehicle fuel will inhibit the activity of the noble metal catalyst in the exhaust gas converter of the vehicle and cause it to be irreversibly poisoned, so that the unburned non-methane hydrocarbons and nitrogen contained in the vehicle exhaust Oxide and carbon monoxide emissions increase. These exhaust gases are easily catalyzed by sunlight to form photochemical smog and cause acid rain. At the same time, sulfur oxides in the atmosphere are also one of the main causes of acid rain. As people pay more and more attention to environmental protection, environmental protection regulations are becoming stricter day by day. Reducing the sulfur content of gasoline and diesel is considered to be one of the most important measures to improve air quality.
我国车用汽油中的硫大多数来自于热加工汽油，主要为催化裂化汽油调合组分。因此催化裂化汽油中硫含量的减少有助于降低车用汽油的硫含量。我国现行的汽油产品标准为GB17930-2011《车用汽油》，该标准对汽油中硫含量进一步作出限制，要求到2013年12月31日，汽油中硫含量下降至50ppm。在这种情况下，催化裂化汽油必须经过深度脱硫才能符合环保的要求。Most of the sulfur in my country's motor gasoline comes from thermally processed gasoline, mainly from catalytic cracking gasoline blending components. Therefore, the reduction of sulfur content in FCC gasoline is helpful to reduce the sulfur content of motor gasoline. my country's current gasoline product standard is GB17930-2011 "Automotive Gasoline", which further restricts the sulfur content in gasoline, requiring that the sulfur content in gasoline be reduced to 50ppm by December 31, 2013. In this case, FCC gasoline must undergo deep desulfurization to meet the requirements of environmental protection.
CN1151333A公开了一种制备吸附剂组合物的方法，包括（a）将下述组分接触：至少一种锌组分（包括氧化锌或可转化为氧化锌的化合物）、至少一种二氧化硅组分（包括二氧化硅或可转化为二氧化硅的化合物）、至少一种胶体氧化物组分和至少一种生孔剂组分，以形成一种湿组合物（具有以所述湿组合物重量计约22-33重量%的水分），（b）挤出所述湿组合物以形成一种挤压过的湿组合物，其中所述挤压过的、湿组合物具有以其重量计约22-33重量%的水分，和（c）将所述挤压过的、湿组合物制成球形以形成球状、挤压过的湿组合物，该组合物的粒径为约0.5-15毫米。该制备方法得到的颗粒为100-300微米，这对于流化过程不是最有利的。而且该方法通过加入易燃造孔剂提高孔体积，使得颗粒容易破粹，强度较差。CN1151333A discloses a method for preparing an adsorbent composition, comprising (a) contacting the following components: at least one zinc component (including zinc oxide or a compound that can be converted to zinc oxide), at least one silicon dioxide Components (comprising silica or compounds convertible to silica), at least one colloidal oxide component, and at least one porogen component to form a wet composition (with about 22-33% moisture by weight of the object), (b) extruding the wet composition to form an extruded wet composition, wherein the extruded, wet composition has about 22-33% by weight of moisture, and (c) spheroidizing said extruded, wet composition to form a spherical, extruded wet composition having a particle size of about 0.5- 15 mm. This preparation method results in particles of 100-300 microns, which are not optimal for the fluidization process. Moreover, this method increases the pore volume by adding a flammable pore-forming agent, so that the particles are easily broken and the strength is relatively poor.
US6150300公开一种制备吸附剂的方法，包括制备球形颗粒：（a）将含二氧化硅的组合物、含有分散在水性介质中的金属氧化物的组合物以及含有氧化锌的组合物混合形成第一混合物且不挤出所述第一混合物；（b）将所述第一混合物成球形形成具有直径10-1000mm的颗粒。其中步骤（a）还包括与金属促进剂混合。US6150300 discloses a method for preparing an adsorbent, including preparing spherical particles: (a) mixing a composition containing silicon dioxide, a composition containing metal oxide dispersed in an aqueous medium, and a composition containing zinc oxide to form a second a mixture without extruding said first mixture; (b) spherical said first mixture to form particles having a diameter of 10-1000mm. Wherein step (a) also includes mixing with a metal accelerator.
CN1355727A公开了一种适用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物，由氧化锌、氧化硅、氧化铝和镍组成，其中镍以基本上还原价态存在，其存在量能从在脱硫条件下与所述含镍吸附剂组合物接触的裂化汽油或柴油机燃料流中脱除硫。该组合物通过将氧化锌、氧化硅和氧化铝形成的混合物颗粒化形成颗粒，干燥、焙烧后用镍或含镍化合物浸渍，再干燥、焙烧、还原得到。CN1355727A discloses a kind of adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, silicon oxide, aluminum oxide and nickel, wherein nickel exists in a reduced valence state substantially, and its presence can Sulfur is removed from a cracked gasoline or diesel fuel stream contacted with the nickel-containing sorbent composition under desulfurization conditions. The composition is obtained by granulating the mixture of zinc oxide, silicon oxide and aluminum oxide to form particles, drying, calcining, impregnating with nickel or a compound containing nickel, drying, calcining and reducing.
CN1856359A公开了一种生产组合物的方法，包括：a）混合液体、含锌化合物、含二氧化硅材料、氧化铝和助催化剂，以形成其混合物；b）干燥该混合物，以形成经干燥的混合物；c）煅烧该经干燥的混合物，以形成经煅烧的混合物；d）用适当的还原剂在适当的条件下将该经煅烧的混合物还原，以生产其内具有还原价态的助催化剂内容物的组合物，以及e）回收改组合物。助催化剂含有选自镍等多种金属。该方法将含锌化合物与助催化剂一起混合以生产组合物，两者均分散在整个颗粒中。CN1856359A discloses a method of producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina and a cocatalyst to form a mixture thereof; b) drying the mixture to form a dried the mixture; c) calcining the dried mixture to form a calcined mixture; d) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a cocatalyst content having a reduced valence state therein the composition of the material, and e) the recovery composition. The cocatalyst contains various metals selected from nickel and the like. This method mixes a zinc-containing compound together with a co-catalyst to produce a composition, both dispersed throughout the particle.
CN1871063A公开了一种生产组合物的方法，该方法包括：a）将液体、含锌化合物、含二氧化硅材料、氧化铝混合以便形成其混合物；b）将所述混合物干燥该混合以形成第一经干燥混合物；c）将所述第一经干燥混合物煅烧以形成第一经煅烧混合物；d）将促进剂结合到所述第一经煅烧混合物之内或之上以形成经促进混合物；e）使所述经促进混合物与选自柠檬酸、酒石酸及其组合的酸接触以形成经接触混合物；f）将所述经接触混合物干燥以形成第二经干燥混合物；g）将所述第二经干燥混合物煅烧以形成第二经煅烧混合物；h）在适当的条件下采用适合的还原剂还原所述第二经煅烧混合物以生产其中含有还原价态促进剂内容物的组合物，和i）回收所述组合物。该方法先制备含有含锌化合物的混合物，再加入促进剂。CN1871063A discloses a method of producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, and alumina to form a mixture thereof; b) drying the mixture to form a second a dried mixture; c) calcining said first dried mixture to form a first calcined mixture; d) incorporating a promoter into or onto said first calcined mixture to form a promoted mixture; e ) contacting the accelerated mixture with an acid selected from citric acid, tartaric acid, and combinations thereof to form a contacted mixture; f) drying the contacted mixture to form a second dried mixture; g) drying the second calcining the dried mixture to form a second calcined mixture; h) reducing said second calcined mixture with a suitable reducing agent under appropriate conditions to produce a composition comprising reduced valence promoter content therein, and i) The composition is recovered. In this method, a mixture containing zinc-containing compounds is prepared first, and then an accelerator is added.
由现有的制备脱硫吸附剂的方法得到的脱硫吸附剂所具有的颗粒结构，不利于该脱硫吸附剂用于从裂化汽油和柴油机燃料中更深度地脱除硫，难以使裂化汽油产品或柴油机燃料满足国家标准。The particle structure of the desulfurization adsorbent obtained by the existing method for preparing the desulfurization adsorbent is unfavorable for the desulfurization adsorbent to be used for deeper removal of sulfur from cracked gasoline and diesel fuel, and it is difficult to make cracked gasoline products or diesel engine fuels The fuel meets the national standard.
因此，为了克服现有脱硫吸附剂的缺陷，需要提供新的能够有更好脱硫活性、促进脱硫反应进行的脱硫催化剂。Therefore, in order to overcome the defects of existing desulfurization adsorbents, it is necessary to provide new desulfurization catalysts that can have better desulfurization activity and promote desulfurization reactions.
发明内容Contents of the invention
本发明的目的是为了克服现有脱硫吸附剂存在的缺陷，提供一种用于从裂化汽油和柴油机燃料中脱除硫的具有层状结构的脱硫催化剂及其制备方法与含硫燃料油的脱硫方法。The purpose of the present invention is to overcome the defect that existing desulfurization adsorbent exists, provide a kind of desulfurization catalyst with layered structure for removing sulfur from cracked gasoline and diesel engine fuel and its preparation method and the desulfurization of sulfur-containing fuel oil method.
为了实现上述发明目的，本发明提供一种脱硫催化剂，以该脱硫催化剂的总重量为基准，该脱硫催化剂含有5-35重量%的氧化铝、5-35重量%的氧化硅、10-70重量%的氧化锌和5-30重量%的活性金属；该脱硫催化剂包括内核和附着在所述内核的至少部分表面上的包覆层：1）内核含有氧化铝、氧化硅和活性金属；2）包覆层含有氧化铝、氧化硅和氧化锌；且所述包覆层中的活性金属与脱硫催化剂中的活性金属的重量比为0.3以下，所述包覆层中的氧化锌与脱硫催化剂中的氧化锌的重量比为大于1.5；所述活性金属选自VIII族金属中的至少一种。In order to achieve the purpose of the above invention, the present invention provides a desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 5-35% by weight of alumina, 5-35% by weight of silicon oxide, 10-70% by weight % zinc oxide and 5-30% by weight of active metals; the desulfurization catalyst includes an inner core and a cladding layer attached to at least part of the surface of the inner core: 1) the inner core contains alumina, silicon oxide and active metals; 2) The cladding layer contains aluminum oxide, silicon oxide and zinc oxide; and the weight ratio of the active metal in the cladding layer to the active metal in the desulfurization catalyst is 0.3 or less, and the zinc oxide in the cladding layer and the active metal in the desulfurization catalyst The weight ratio of zinc oxide is greater than 1.5; the active metal is at least one selected from group VIII metals.
本发明还提供一种脱硫催化剂的制备方法，该方法包括：（1）将粘结剂、氧化硅源、活性金属前体、水和第一酸性溶液进行第一混合，得到酸化浆液，将酸化浆液成型、干燥和焙烧，得到内核颗粒；（2）将粘结剂、氧化硅源、氧化锌源、水和第二酸性溶液进行第二混合，形成包覆层浆液；将步骤（1）得到的内核颗粒加入所述包覆层浆液中，再次进行成型、干燥和焙烧，得到催化剂前体；（3）将步骤（2）得到的催化剂前体在含氢气气氛下还原，得到脱硫催化剂；所述第一酸性溶液和所述第二酸性溶液为相同或不同，各自为无机酸和/或有机酸的水溶液。The present invention also provides a method for preparing a desulfurization catalyst, the method comprising: (1) first mixing a binder, a silicon oxide source, an active metal precursor, water, and a first acidic solution to obtain an acidified slurry; Slurry molding, drying and roasting to obtain core particles; (2) second mixing of binder, silicon oxide source, zinc oxide source, water and a second acidic solution to form a coating layer slurry; step (1) to obtain Add the inner core particles into the coating layer slurry, shape, dry and roast again to obtain a catalyst precursor; (3) reduce the catalyst precursor obtained in step (2) under a hydrogen-containing atmosphere to obtain a desulfurization catalyst; The first acidic solution and the second acidic solution are the same or different, and each is an aqueous solution of an inorganic acid and/or an organic acid.
本发明还提供了由本发明提供的方法制备的脱硫催化剂。The invention also provides the desulfurization catalyst prepared by the method provided in the invention.
本发明还提供了一种含硫燃料油的脱硫方法，该方法包括：将含硫燃料油与脱硫催化剂接触，其中，所述脱硫催化剂为本发明提供的脱硫催化剂。The present invention also provides a method for desulfurizing sulfur-containing fuel oil, the method comprising: contacting sulfur-containing fuel oil with a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst provided by the present invention.
本发明提供的脱硫催化剂具有层状结构，可以具有更好的脱硫性能，并且脱硫催化剂有更好的耐磨损强度。例如实施例1得到的脱硫催化剂A1组成为氧化铝22.7重量%，氧化硅15.3重量%，氧化锌36.0重量%，镍23.9重量%；并且包覆层中的Ni与A1中的Ni的重量比为0.29，包覆层中的氧化锌与A1中的氧化锌的重量比为1.6；内核与包覆层的厚度比为1：0.33；通过XPS测定测得的包覆层中Ni：Zn的摩尔比为1：6。脱硫催化剂A1的FBAT指数为4.6，循环6次得到的产品汽油硫含量为14μg/g。而对比例1得到的脱硫催化剂B1虽然组成与A1相同，但是以现有技术将活性金属镍全部通过浸渍方法负载在脱硫催化剂B1的表面。采用XPS测定，B1表面上Ni：Zn的摩尔比为2：1；通过荧光分析和XPS测定，B1包覆层中的Ni与B1中的Ni的重量比为1.5，包覆层中的氧化锌与B1中的氧化锌的重量比为0.72。B1没有形成如脱硫催化剂A1中内核富含镍和包覆层富含氧化锌的层状结构。脱硫催化剂B1的FBAT指数为5.7，循环6次得到的产品汽油硫含量为34μg/g。The desulfurization catalyst provided by the invention has a layered structure, can have better desulfurization performance, and the desulfurization catalyst has better wear resistance strength. For example, the composition of the desulfurization catalyst A1 obtained in Example 1 is 22.7% by weight of aluminum oxide, 15.3% by weight of silicon oxide, 36.0% by weight of zinc oxide, and 23.9% by weight of nickel; and the weight ratio of Ni in the coating layer to Ni in A1 is 0.29, the weight ratio of zinc oxide in the cladding layer to zinc oxide in A1 is 1.6; the thickness ratio of the inner core to the cladding layer is 1:0.33; the molar ratio of Ni:Zn in the cladding layer measured by XPS It is 1:6. The FBAT index of the desulfurization catalyst A1 is 4.6, and the sulfur content of the product gasoline obtained after 6 cycles is 14 μg/g. Although the composition of the desulfurization catalyst B1 obtained in Comparative Example 1 is the same as that of A1, all the active metal nickel is loaded on the surface of the desulfurization catalyst B1 by impregnation method in the prior art. As determined by XPS, the molar ratio of Ni:Zn on the surface of B1 is 2:1; by fluorescence analysis and XPS, the weight ratio of Ni in the coating layer of B1 to Ni in B1 is 1.5, and the zinc oxide in the coating layer The weight ratio to the zinc oxide in B1 was 0.72. B1 does not form a layered structure such as the core rich in nickel and the cladding layer rich in zinc oxide in the desulfurization catalyst A1. The FBAT index of the desulfurization catalyst B1 is 5.7, and the sulfur content of the product gasoline obtained after 6 cycles is 34 μg/g.
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present invention will be described in detail in the following detailed description.
附图说明Description of drawings
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:
图1为脱硫催化剂A1的TPR谱图；Fig. 1 is the TPR spectrogram of desulfurization catalyst A1;
图2为脱硫催化剂的层状结构示意图。Figure 2 is a schematic diagram of the layered structure of the desulfurization catalyst.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
本发明提供一种脱硫催化剂，以该脱硫剂的总重量为基准，该脱硫催化剂含有5-35重量%的氧化铝、5-35重量%的氧化硅、10-70重量%的氧化锌和5-30重量%的活性金属；该脱硫催化剂包括内核和附着在所述内核的至少部分表面上的包覆层：1）内核含有氧化铝、氧化硅源和活性金属；2）包覆层含有氧化铝、氧化硅源和氧化锌；且所述包覆层中的活性金属与脱硫催化剂中的活性金属的重量比为0.3以下，所述包覆层中的氧化锌与脱硫催化剂中的氧化锌的重量比为大于1.5；所述活性金属选自VIII族金属中的至少一种；优选地，以脱硫催化剂总重量为基准，所述脱硫催化剂含有12-30重量%的氧化铝、15-30重量%的氧化硅、30-55重量%的氧化锌和10-25重量%的活性金属。The invention provides a desulfurization catalyst, based on the total weight of the desulfurizer, the desulfurization catalyst contains 5-35% by weight of alumina, 5-35% by weight of silicon oxide, 10-70% by weight of zinc oxide and 5 - 30% by weight of active metal; the desulfurization catalyst comprises an inner core and a cladding layer attached to at least part of the surface of said inner core: 1) the inner core contains alumina, a source of silica and active metal; 2) the cladding layer contains oxide Aluminum, silicon oxide source, and zinc oxide; and the weight ratio of the active metal in the cladding layer to the active metal in the desulfurization catalyst is 0.3 or less, and the ratio of the zinc oxide in the cladding layer to the zinc oxide in the desulfurization catalyst The weight ratio is greater than 1.5; the active metal is selected from at least one of Group VIII metals; preferably, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 12-30% by weight of alumina, 15-30% by weight % of silicon oxide, 30-55% by weight of zinc oxide and 10-25% by weight of active metals.
本发明中，尽管具有MFI结构的分子筛通常用氧化铝和氧化硅的含量来表示分子筛的组成，但本发明中氧化硅、氧化铝的含量并不包含具有MFI结构的分子筛中氧化铝和氧化硅的量，而是指除具有MFI结构的分子筛中之外的氧化硅和氧化铝的量。上述组成按照投料计算得到。In the present invention, although the molecular sieve with MFI structure usually uses the content of alumina and silica to represent the composition of molecular sieve, the content of silica and alumina in the present invention does not include alumina and silica in molecular sieves with MFI structure Instead, it refers to the amount of silica and alumina except in molecular sieves with MFI structure. The above composition is calculated according to the feeding.
根据本发明，优选情况下，所述内核与所述包覆层的厚度比为1：0.2-0.6。According to the present invention, preferably, the thickness ratio of the inner core to the cladding layer is 1:0.2-0.6.
根据本发明，如图2所示，所述脱硫催化剂包括内核和包覆层，并且活性金属主要包含在内核，氧化锌主要包含在包覆层，即形成内核富含活性金属、包覆层富含氧化锌的层状结构。具有这样结构的脱硫催化剂可以在脱硫反应过程中更有利于进行活性金属还原氧化态硫和氧化锌吸附存储硫；并且所述脱硫催化剂含有的各组分的含量在上述范围内，可以有更好的脱硫效果。According to the present invention, as shown in Figure 2, the desulfurization catalyst includes an inner core and a cladding layer, and the active metal is mainly contained in the core, and zinc oxide is mainly contained in the cladding layer, that is, the core is rich in active metals, and the cladding layer is rich in active metals. Layered structure containing zinc oxide. The desulfurization catalyst with such a structure can be more conducive to the reduction of oxidized sulfur by active metals and the adsorption and storage of sulfur by zinc oxide during the desulfurization reaction process; and the content of each component contained in the desulfurization catalyst is within the above range, which can have better desulfurization effect.
本发明中，包覆层中的活性金属和氧化锌分别与脱硫催化剂中的活性金属和氧化锌的重量比，可以通过荧光分析得到脱硫催化剂的组分含量和X射线光电子能谱分析（XPS）测定分析得到的包覆层中的组分含量来确定。In the present invention, the weight ratio of the active metal and zinc oxide in the cladding layer to the active metal and zinc oxide in the desulfurization catalyst can be obtained by fluorescence analysis and X-ray photoelectron spectroscopy (XPS) The content of the components in the coating layer obtained by the measurement analysis is determined.
本发明中，所示脱硫催化剂的内核与包覆层的厚度比，可以通过扫描电子显微镜及能谱仪（即SEM-EDX）测定的数据计算得出。具体地，通过SEM-EDX扫描脱硫催化剂的截面，通过EDX测定活性金属和锌元素沿该截面直径上各处的含量，得到活性金属元素和锌元素沿所述脱硫催化剂截面的径向的含量分布，由此分布得到上述厚度比。所述厚度比为形成所述内核的颗粒的半径与所述包覆层的厚度之间的比值。In the present invention, the thickness ratio of the inner core to the cladding layer of the desulfurization catalyst can be calculated from data measured by a scanning electron microscope and an energy spectrometer (ie, SEM-EDX). Specifically, scan the cross section of the desulfurization catalyst by SEM-EDX, measure the content of active metal and zinc element along the diameter of the cross section by EDX, and obtain the content distribution of active metal element and zinc element along the radial direction of the cross section of the desulfurization catalyst , from which the above-mentioned thickness ratios are obtained. The thickness ratio is a ratio between the radius of the particles forming the inner core and the thickness of the cladding layer.
根据本发明，所述脱硫催化剂的包覆层含有氧化锌，内核含有活性金属。也可以有少量活性金属在所述脱硫催化剂经历制备过程中的焙烧时迁移到包覆层中，但是所述脱硫催化剂中的活性金属还是主要存在于内核中；所述脱硫催化剂含有的氧化锌组分被制备主要存在于所述脱硫催化剂的包覆层。因此在包覆层中存在的锌的量要高于活性金属的量。优选情况下，所述包覆层以X射线光电子能谱分析（XPS），所述活性金属与锌的摩尔比在1：3以下；优选地，所述包覆层以X射线光电子能谱分析，所述活性金属与锌的摩尔比在1：5以下。According to the present invention, the cladding layer of the desulfurization catalyst contains zinc oxide, and the inner core contains active metal. There may also be a small amount of active metals that migrate into the cladding layer when the desulfurization catalyst undergoes roasting in the preparation process, but the active metals in the desulfurization catalyst still mainly exist in the inner core; the zinc oxide group contained in the desulfurization catalyst Particles are prepared mainly present in the coating layer of the desulfurization catalyst. The amount of zinc present in the coating is therefore higher than the amount of active metal. Preferably, the coating layer is analyzed by X-ray photoelectron spectroscopy (XPS), and the molar ratio of the active metal to zinc is below 1:3; preferably, the coating layer is analyzed by X-ray photoelectron spectroscopy , the molar ratio of the active metal to zinc is below 1:5.
根据本发明，所述活性金属可以为将氧化态硫还原为硫化氢的金属，更优选地，所述活性金属可以为钴和/或镍；进一步优选地，所述活性金属可以为镍。According to the present invention, the active metal can be a metal that reduces oxidized sulfur to hydrogen sulfide, more preferably, the active metal can be cobalt and/or nickel; further preferably, the active metal can be nickel.
本发明还提供一种具有层状结构的脱硫催化剂的制备方法，该方法包括：（1）将粘结剂、氧化硅源、活性金属前体、水和第一酸性溶液进行第一混合，得到酸化浆液，将酸化浆液成型、干燥和焙烧，得到内核颗粒；（2）将粘结剂、氧化硅源、氧化锌源、水和第二酸性溶液进行第二混合，形成包覆层浆液；将步骤（1）得到的内核颗粒加入所述包覆层浆液中，再次进行成型、干燥和焙烧，得到催化剂前体；（3）将步骤（2）得到的催化剂前体在含氢气气氛下还原，得到脱硫催化剂；所述第一酸性溶液和所述第二酸性溶液为相同或不同，各自为无机酸和/或有机酸的水溶液。The present invention also provides a method for preparing a desulfurization catalyst with a layered structure, the method comprising: (1) first mixing a binder, a silicon oxide source, an active metal precursor, water and a first acidic solution to obtain Acidify the slurry, forming, drying and roasting the acidified slurry to obtain core particles; (2) secondly mixing the binder, silicon oxide source, zinc oxide source, water and a second acidic solution to form a coating layer slurry; adding the core particles obtained in step (1) into the coating layer slurry, forming, drying and roasting again to obtain a catalyst precursor; (3) reducing the catalyst precursor obtained in step (2) in a hydrogen-containing atmosphere, A desulfurization catalyst is obtained; the first acidic solution and the second acidic solution are the same or different, and each is an aqueous solution of an inorganic acid and/or an organic acid.
根据本发明，优选情况下，所述粘结剂、氧化硅源、氧化锌源和活性金属前体的加入量使得得到的脱硫催化剂中，以该脱硫催化剂总重量为基准，氧化铝的含量为5-35重量%，氧化硅的含量为5-35重量%，氧化锌的含量为10-70重量%，活性金属的含量为5-30重量%。优选地，所述粘结剂、氧化硅源、氧化锌源和活性金属前体的加入量使得得到的脱硫催化剂中，以该脱硫催化剂总重量为基准，氧化铝的含量为12-30重量%，氧化硅的含量为15-30重量%，氧化锌的含量为30-55重量%，活性金属的含量为10-25重量%。According to the present invention, preferably, the addition amount of the binder, the silicon oxide source, the zinc oxide source and the active metal precursor makes the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of aluminum oxide is 5-35% by weight, the content of silicon oxide is 5-35% by weight, the content of zinc oxide is 10-70% by weight, and the content of active metal is 5-30% by weight. Preferably, the amount of the binder, silicon oxide source, zinc oxide source and active metal precursor is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of alumina is 12-30% by weight , the content of silicon oxide is 15-30% by weight, the content of zinc oxide is 30-55% by weight, and the content of active metal is 10-25% by weight.
本发明中制备所述脱硫催化剂所使用的原料可以为化学纯的物料，也可以使用一般可以商购得到的工业用料。在使用工业用料时，获得的脱硫催化剂中会含有部分杂质，但是只要脱硫催化剂的主要组分和含量仍然在上述限定范围内，就不影响脱硫催化剂的性能。本发明的实施例和对比例中列出的得到的脱硫催化剂的组成含量，是脱硫催化剂含有的主要组分的含量。这些含量加和小于等于100重量%，与100重量%相差的含量即为杂质的含量。由于上述含量的杂质并不影响脱硫催化剂的性能，因此本发明未具体列出杂质的组成。The raw materials used in the preparation of the desulfurization catalyst in the present invention can be chemically pure materials, or generally commercially available industrial materials. When using industrial materials, the obtained desulfurization catalyst will contain some impurities, but as long as the main components and content of the desulfurization catalyst are still within the above-mentioned limited range, the performance of the desulfurization catalyst will not be affected. The composition contents of the obtained desulfurization catalysts listed in the examples and comparative examples of the present invention are the contents of the main components contained in the desulfurization catalysts. The sum of these contents is less than or equal to 100% by weight, and the content that differs from 100% by weight is the content of impurities. Since the impurities in the above content do not affect the performance of the desulfurization catalyst, the composition of the impurities is not specifically listed in the present invention.
根据本发明，所述活性金属前体是可以在步骤（1）的焙烧条件下转化为金属氧化物的物质，优选情况下，所述活性金属可以选自VIII族金属的醋酸盐、碳酸盐、硝酸盐、硫酸盐、硫氰酸盐和氧化物中的至少一种。According to the present invention, the active metal precursor is a substance that can be converted into a metal oxide under the roasting conditions of step (1). Preferably, the active metal can be selected from the group VIII metal acetate, carbonic acid at least one of salts, nitrates, sulfates, thiocyanates and oxides.
根据本发明，优选情况下，所述氧化锌源可以为氧化锌和/或在步骤（2）的所述焙烧的条件下能够转化为氧化锌的氧化锌前体；所述氧化锌前体可以为硫化锌、硫酸锌、氢氧化锌、碳酸锌、醋酸锌和硝酸锌中的至少一种。According to the present invention, preferably, the zinc oxide source can be zinc oxide and/or a zinc oxide precursor that can be converted into zinc oxide under the conditions of the calcination in step (2); the zinc oxide precursor can be It is at least one of zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate.
根据本发明，优选情况下，所述氧化硅源可以为纯氧化硅或氧化硅含量大于45重量%的天然矿物。优选地，所述氧化硅源可以选自硅藻土、膨胀珍珠岩、高岭土、硅质岩、水解氧化硅、大孔氧化硅以及硅胶中的至少一种。According to the present invention, preferably, the silicon oxide source may be pure silicon oxide or natural minerals with a silicon oxide content greater than 45% by weight. Preferably, the silica source may be selected from at least one of diatomaceous earth, expanded perlite, kaolin, silicalite, hydrolyzed silica, macroporous silica and silica gel.
根据本发明，所述粘结剂是指焙烧后能形成耐热无机氧化物的物质，其中耐热无机氧化物可以为氧化铝、氧化硅和无定型硅铝中的一种或几种，优选氧化铝。优选情况下，所述粘结剂可以为水合氧化铝、铝溶胶、一水软铝石（薄水铝石）、假一水软铝石（拟薄水铝石）、三水合氧化铝和无定形氢氧化铝中的至少一种。这些不同形式的粘结剂在步骤（1）或（2）中的焙烧后可以以γ-Al2O3的形式存在。具体地，本发明中所使用的粘结剂可以为本领域技术人员所公知的。According to the present invention, the binder refers to a substance capable of forming heat-resistant inorganic oxides after firing, wherein the heat-resistant inorganic oxides can be one or more of alumina, silicon oxide and amorphous silicon-alumina, preferably alumina. Preferably, the binder can be hydrated alumina, alumina sol, boehmite (boehmite), pseudoboehmite (pseudoboehmite), alumina trihydrate and At least one of shaped aluminum hydroxide. These different forms of binders may exist in the form of γ-Al 2 O 3 after firing in step (1) or (2). Specifically, the binder used in the present invention may be known to those skilled in the art.
根据本发明，具体地，制备脱硫催化剂可以按照以下方法进行：According to the present invention, specifically, preparing desulfurization catalyst can be carried out according to the following method:
步骤（1）中，所述第一混合可以没有特别的限定，可以是所述粘结剂、所述氧化硅源和所述活性金属前体加入所述水中得到浆液，然后再加入所述第一酸性溶液得到酸化浆液。所述粘结剂、所述氧化硅源和所述活性金属前体加入所述水中的顺序没有特别的限定，优选地，在其它组分加入之后再加入所述活性金属。各组分加入时需要充分搅拌。所述第一酸性溶液的用量可以不特别限定，优选所述第一酸性溶液的用量使浆液的pH值为2-5，优选为2-4。若所述活性金属前体本身为酸性，并且能够保证混合后得到的浆液的pH值为2-5（优选2-4）时，可以不用另加第一酸性溶液。所述第一酸性溶液可以为无机酸和/或有机酸的水溶液，优选地，可以为盐酸和/或硝酸。得到的所述酸化浆液可以进一步进行老化，可以是本领域常规使用的老化方法，优选地，所述老化的温度可以约为60-90℃，所述老化的时间可以约为1-4小时。In step (1), the first mixing may not be particularly limited, it may be that the binder, the silicon oxide source and the active metal precursor are added to the water to obtain a slurry, and then the second mixing is added. An acidic solution yields an acidified slurry. The order in which the binder, the silicon oxide source and the active metal precursor are added to the water is not particularly limited. Preferably, the active metal is added after other components are added. The ingredients need to be fully stirred when they are added. The amount of the first acidic solution is not particularly limited, preferably the amount of the first acidic solution is such that the pH of the slurry is 2-5, preferably 2-4. If the active metal precursor itself is acidic and the pH of the slurry obtained after mixing can be guaranteed to be 2-5 (preferably 2-4), it is not necessary to add the first acidic solution. The first acidic solution may be an aqueous solution of inorganic acid and/or organic acid, preferably, may be hydrochloric acid and/or nitric acid. The obtained acidified slurry may be further aged, which may be an aging method conventionally used in the art. Preferably, the aging temperature may be about 60-90° C., and the aging time may be about 1-4 hours.
步骤（1）中，优选情况下，以100重量份的所述粘结剂为基准，加入40-250重量份的所述氧化硅源，50-400重量份的活性金属前体和500-1000重量份的水。In step (1), preferably, based on 100 parts by weight of the binder, add 40-250 parts by weight of the silicon oxide source, 50-400 parts by weight of the active metal precursor and 500-1000 parts by weight parts by weight of water.
步骤（1）中，所述成型的方式可以根据所述酸化浆液的形式选择。所述酸化浆液可以是捏塑体、膏状混合物、湿混合物或浆液等形式，可以选择所述成型的方式为将所述酸化浆液成型为挤出物、片、丸粒、球或微球状颗粒。例如，所述酸化浆液为捏塑体或膏状混合物形式时，可以使所述酸化浆液成型（优选挤出成型）为颗粒，优选直径在1.0-8.0mm，长度在2.0-5.0mm的圆柱形挤出物，然后使所得的挤出物进行干燥、焙烧。所述酸化浆液为湿混合物形式时，可以使该混合物稠化，经过干燥后成型。所述酸化浆液为浆液形式时，可以通过喷雾干燥形成平均粒径（直径）为20-100微米的微球，优选为40-60微米的微球，达到成型的目的。为了便于喷雾干燥，干燥前浆液的固含量为10-60重量%，优选为20-50重量%。In step (1), the forming method can be selected according to the form of the acidified slurry. The acidified slurry can be in the form of a dough, a paste mixture, a wet mixture or a slurry, and the forming method can be selected to form the acidified slurry into extrudates, tablets, pellets, balls or microspherical particles . For example, when the acidified slurry is in the form of a dough or paste mixture, the acidified slurry can be shaped (preferably extruded) into granules, preferably cylindrical with a diameter of 1.0-8.0mm and a length of 2.0-5.0mm The extrudate is then dried and calcined. When the acidified slurry is in the form of a wet mixture, the mixture can be thickened, dried and shaped. When the acidified slurry is in the form of slurry, microspheres with an average particle size (diameter) of 20-100 microns, preferably 40-60 microns, can be formed by spray drying to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the slurry before drying is 10-60% by weight, preferably 20-50% by weight.
步骤（1）的干燥和焙烧的方法与条件可以为本领域技术人员所公知，例如干燥的方法可以是晾干、烘干、鼓风干燥。干燥的温度可以是室温至400℃，优选可以为100-350℃。干燥的时间可以约为0.5-8小时，更优选可以约为1-5小时。干燥后，在有氧气、或含氧气体存在的条件下进行焙烧，焙烧的温度可以约为300-800℃，更优选可以约为450-750℃，焙烧的时间可以约为0.5-4小时，优选约为1-3小时，直至挥发性物质被除去并且活性金属被转化为金属氧化物。The methods and conditions of drying and roasting in step (1) can be known to those skilled in the art, for example, the drying methods can be air drying, oven drying, and blast drying. The drying temperature can be from room temperature to 400°C, preferably 100-350°C. The drying time may be about 0.5-8 hours, more preferably about 1-5 hours. After drying, calcination is carried out in the presence of oxygen or oxygen-containing gas. The calcination temperature can be about 300-800°C, more preferably about 450-750°C, and the calcination time can be about 0.5-4 hours. Preferably about 1-3 hours until the volatile species are removed and the active metals are converted to metal oxides.
步骤（2）中，所述第二混合可以没有特别的限定，可以是所述粘结剂、所述氧化硅源和所述氧化锌源加入所述水中得到混合浆液，然后再加入所述第二酸性溶液得到包覆层浆液。所述包覆层浆液可以进一步进行老化，可以是本领域常规使用的老化方法，优选地，所述老化的温度可以约为60-90℃，所述老化的时间可以约为1-4小时。所述第二酸性溶液的用量可以不特别限定，优选所述第二酸性溶液的用量使所述包覆层浆液经所述老化后的pH值为2-5。所述第二酸性溶液可以为无机酸和/或有机酸的水溶液，优选地，可以为盐酸和/或硝酸。In step (2), the second mixing may not be particularly limited, it may be that the binder, the silicon oxide source and the zinc oxide source are added to the water to obtain a mixed slurry, and then the second mixing is added. The diacid solution yields a coating slurry. The coating layer slurry can be further aged, which can be an aging method commonly used in the art. Preferably, the aging temperature can be about 60-90° C., and the aging time can be about 1-4 hours. The amount of the second acidic solution is not particularly limited, and preferably, the amount of the second acidic solution is such that the pH of the coating layer slurry after the aging is 2-5. The second acidic solution may be an aqueous solution of inorganic acid and/or organic acid, preferably, may be hydrochloric acid and/or nitric acid.
步骤（2）中，优选情况下，以100重量份的所述粘结剂为基准，加入40-250重量份的所述氧化硅源，80-600重量份的氧化锌源，500-1000重量份的水。In step (2), preferably, based on 100 parts by weight of the binder, add 40-250 parts by weight of the silicon oxide source, 80-600 parts by weight of the zinc oxide source, 500-1000 parts by weight parts of water.
本发明中，所述第一酸性溶液和所述第二酸性溶液可以为相同或不同；优选为相同。In the present invention, the first acidic solution and the second acidic solution may be the same or different; preferably the same.
步骤（2）中的成型可以是实现使所述包覆层浆液包裹在所述内核颗粒的目的。将所述包覆层浆液进行成型的方法可以根据步骤（1）中得到的内核颗粒形状选择。例如步骤（2）中得到的是微球，可以将所述包覆层浆液进行喷雾干燥成型，形成微球的包覆层厚度为5-25微米，优选8-20微米。为了便于喷雾干燥，干燥前浆液的固含量为20-60重量%，优选为30-50重量%。步骤（1）得到的是条、片或小球时，可以在搅拌并加热的情况下，使所述包覆层浆液中的水分蒸发，包覆层浆液中的固体组分可以附着在内核颗粒的表面上以完成所述包覆层浆液在所述内核颗粒上成型的目的。The shaping in step (2) may be to achieve the purpose of wrapping the coating layer slurry on the core particles. The method for forming the coating layer slurry can be selected according to the shape of the inner core particles obtained in step (1). For example, microspheres are obtained in step (2), and the coating layer slurry can be spray-dried to form a coating layer of microspheres with a thickness of 5-25 microns, preferably 8-20 microns. In order to facilitate spray drying, the solid content of the slurry before drying is 20-60% by weight, preferably 30-50% by weight. When strips, flakes or pellets are obtained in step (1), the water in the coating layer slurry can be evaporated under the condition of stirring and heating, and the solid components in the coating layer slurry can be attached to the inner core particles on the surface of the inner core particle to complete the coating layer slurry forming purpose.
步骤（2）中的干燥方法与条件可以为本领域技术人员所公知，例如干燥的方法可以是晾干、烘干、鼓风干燥。干燥的温度可以是室温至400℃，优选可以为100-350℃。干燥的时间可以约为0.5-8小时，更优选可以约为1-5小时。The drying method and conditions in the step (2) can be known to those skilled in the art, for example, the drying method can be air drying, oven drying, and blast drying. The drying temperature can be from room temperature to 400°C, preferably 100-350°C. The drying time may be about 0.5-8 hours, more preferably about 1-5 hours.
步骤（2）中的焙烧方法与条件只要能将步骤（2）中形成包裹层浆液的各组分转变为各组分的氧化物形式，并且内核中的镍较少迁移到包裹层中即可。焙烧在有氧气、或含氧气体存在的条件下进行，焙烧的温度可以约为300-800℃，更优选可以约为450-750℃，焙烧的时间可以约为0.5-4小时，优选约为1-3小时。The roasting method and conditions in step (2) only need to be able to convert each component of the slurry forming the coating layer in step (2) into the oxide form of each component, and the nickel in the inner core is less likely to migrate into the coating layer. . Roasting is carried out in the presence of oxygen or an oxygen-containing gas, the temperature of the calcination can be about 300-800°C, more preferably about 450-750°C, and the time of calcination can be about 0.5-4 hours, preferably about 1-3 hours.
本发明中，步骤（1）和（2）中加入的粘结剂和氧化硅源的总量使得得到的脱硫催化剂中，以该脱硫催化剂总重量为基准氧化铝含量为5-35重量%，氧化硅含量为5-35重量%；优选地，氧化铝含量为12-30重量%，氧化硅含量为15-30重量%。In the present invention, the total amount of binder and silica source added in steps (1) and (2) makes the obtained desulfurization catalyst have an alumina content of 5-35% by weight based on the total weight of the desulfurization catalyst, The silicon oxide content is 5-35% by weight; preferably, the aluminum oxide content is 12-30% by weight, and the silicon oxide content is 15-30% by weight.
步骤（3）中，将催化剂前体还原可以在制得脱硫催化剂前体后立即进行，也可以在使用前（即用于脱硫催化前）进行。由于活性金属溶液氧化，而脱硫催化剂前体中的活性金属以氧化物形式存在，因此为便于运输和储存，优选步骤（3）中将催化剂前体还原在进行脱硫催化前进行。所述还原为使活性金属的氧化物中的金属基本上以还原态存在，得到本发明的脱硫催化剂。所述含氢气气氛可以为氢气含量为10-60体积%的气氛，还原的温度为300-600℃，还原的时间可以为0.5-6小时；优选地，还原的温度为400-500℃，还原的时间为1-3小时。In step (3), the reduction of the catalyst precursor can be performed immediately after the desulfurization catalyst precursor is prepared, or before use (that is, before being used for desulfurization catalysis). Since the active metal solution is oxidized, the active metal in the desulfurization catalyst precursor exists in the form of oxides, so for the convenience of transportation and storage, it is preferable to reduce the catalyst precursor in step (3) before performing desulfurization catalysis. The reduction means that the metal in the active metal oxide basically exists in a reduced state to obtain the desulfurization catalyst of the present invention. The hydrogen-containing atmosphere can be an atmosphere with a hydrogen content of 10-60% by volume, the reduction temperature is 300-600°C, and the reduction time can be 0.5-6 hours; preferably, the reduction temperature is 400-500°C, and the reduction The time is 1-3 hours.
本发明中可以从采用H2-TPR方法对脱硫催化剂进行测定得到的H2-TPR谱图，如图1脱硫催化剂A1中的活性金属为镍，判断脱硫催化剂内核中活性金属经氢气还原已从氧化物转变为金属。在图1中，横坐标为脱硫催化剂进行还原所经历的温度，纵坐标为H2-TPR方法中，对应每个温度点采用TCD检测器检测到的经过脱硫催化剂表面的还原气氛所对应的TCD信号。TCD信号基线对应初始还原气氛中的氢气量，TCD信号偏离基线说明测定的还原气氛中氢气量比初始时发生了变化。从TCD信号出峰可以判断在出峰对应的温度范围，还原气氛中的氢气被消耗参与了某一氧化物的还原反应。该氧化物的还原反应结束后，TCD信号重回基线。首先脱硫催化剂A1中氧化硅、氧化铝被氢气还原的温度均在1000℃以上，氧化锌公知被氢气很难还原，因此图1显示的是氧化镍被还原为镍的过程，氧化镍还原的温度在200-300℃。由此可以说明步骤（3）中的还原是可以使脱硫催化剂内核的活性金属以还原态存在。In the present invention, the H2-TPR spectrogram obtained from the desulfurization catalyst can be measured by the H2-TPR method, as shown in Figure 1. The active metal in the desulfurization catalyst A1 is nickel, and it is judged that the active metal in the desulfurization catalyst core has been reduced from the oxide by hydrogen reduction. transformed into metal. In Figure 1, the abscissa is the temperature experienced by the desulfurization catalyst for reduction, and the ordinate is the TCD signal corresponding to the reducing atmosphere on the surface of the desulfurization catalyst detected by the TCD detector for each temperature point in the H2-TPR method . The baseline of the TCD signal corresponds to the amount of hydrogen in the initial reducing atmosphere, and the deviation of the TCD signal from the baseline indicates that the measured amount of hydrogen in the reducing atmosphere has changed from the initial value. From the peak of the TCD signal, it can be judged that in the temperature range corresponding to the peak, the hydrogen in the reducing atmosphere is consumed to participate in the reduction reaction of a certain oxide. After the reduction reaction of the oxide is completed, the TCD signal returns to baseline. First of all, the reduction temperature of silicon oxide and aluminum oxide in desulfurization catalyst A1 by hydrogen is above 1000°C. Zinc oxide is known to be difficult to reduce by hydrogen, so Figure 1 shows the process of nickel oxide being reduced to nickel, and the temperature of nickel oxide reduction At 200-300°C. It can thus be explained that the reduction in step (3) can make the active metal in the core of the desulfurization catalyst exist in a reduced state.
本发明还提供了一种由本发明提供的方法制备的具有层状结构的脱硫催化剂。The invention also provides a desulfurization catalyst with a layered structure prepared by the method provided by the invention.
根据本发明，该脱硫催化剂如前所述，在此不再赘述。According to the present invention, the desulfurization catalyst is as described above, and will not be repeated here.
本发明还提供了一种含硫燃料油的脱硫方法，该方法包括：将含硫燃料油与脱硫催化剂接触，其中，所述脱硫催化剂为本发明提供的脱硫催化剂。The present invention also provides a method for desulfurizing sulfur-containing fuel oil, the method comprising: contacting sulfur-containing fuel oil with a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst provided by the present invention.
根据本发明，所述含硫燃料油的脱硫方法中，所述接触可以在氢气气氛下进行，所述接触的条件包括：接触的温度可以为350-500℃，接触的压力可以为0.5-4MPa；优选接触的温度为400-450℃，接触的压力为1-3MPa。在上述条件下使含硫燃料油与本发明提供的脱硫催化剂充分接触。在此过程中含硫燃料油中的硫被催化到催化剂上，从而得到低硫含量的产物。According to the present invention, in the desulfurization method of sulfur-containing fuel oil, the contacting can be carried out under a hydrogen atmosphere, and the contacting conditions include: the contacting temperature can be 350-500°C, and the contacting pressure can be 0.5-4MPa ; The preferred contact temperature is 400-450°C, and the contact pressure is 1-3MPa. Under the above conditions, the sulfur-containing fuel oil is fully contacted with the desulfurization catalyst provided by the invention. During this process, the sulfur in the sulfur-containing fuel oil is catalyzed onto the catalyst, resulting in a product with low sulfur content.
根据本发明，所述含硫燃料油的脱硫方法还可以包括：接触后将经过接触的脱硫催化剂进行再生。再生的条件包括：在氧气气氛（氧气含量可以为10-80体积%）下进行再生；再生的温度为450-600℃，优选为480-520℃；再生的压力为常压。According to the present invention, the method for desulfurizing fuel oil containing sulfur may further include: regenerating the contacted desulfurization catalyst after contacting. Regeneration conditions include: regeneration under oxygen atmosphere (oxygen content can be 10-80% by volume); regeneration temperature is 450-600°C, preferably 480-520°C; regeneration pressure is normal pressure.
本发明中，所述含硫燃料油的脱硫方法还可以包括：再生后的脱硫催化剂在重新使用前进行还原。还原的条件包括：在氢气气氛（氢气含量可以为30-60体积%）下进行还原；还原的温度可以为350-500℃，优选400-450℃；还原的压力可以为0.2-2MPa，优选为0.2-1.5MPa。In the present invention, the method for desulfurizing fuel oil containing sulfur may further include: reducing the regenerated desulfurization catalyst before reuse. Reduction conditions include: reduction under hydrogen atmosphere (hydrogen content can be 30-60% by volume); reduction temperature can be 350-500°C, preferably 400-450°C; reduction pressure can be 0.2-2MPa, preferably 0.2-1.5MPa.
本发明中，经过再生-还原后的脱硫催化剂可以重新进行含硫燃料油的脱硫。In the present invention, the regenerated-reduced desulfurization catalyst can re-desulfurize fuel oil containing sulfur.
本发明中，所述接触优选在流化床中进行。In the present invention, the contacting is preferably performed in a fluidized bed.
本发明所用术语“裂化汽油”意指沸程为40-210℃的烃或其任何馏分，是来自使较大的烃分子裂化成较小分子的热或催化过程的产品。适用的热裂化过程包括但不限制于焦化、热裂化和减粘裂化等及其组合。适用的催化裂化过程的例子包括但不限于流化床催化裂化和重油催化裂化等及其组合。因此，适用的催化裂化汽油包括但不限于焦化汽油、热裂化汽油、减粘裂化汽油、流化床催化裂化汽油和重油裂化汽油及其组合。在某些情况下，在本发明方法中用作含烃流体时可在脱硫之前将所述裂化汽油分馏和/或加氢处理。The term "cracked gasoline" as used herein means a hydrocarbon or any fraction thereof having a boiling range of 40-210°C, the product from a thermal or catalytic process of cracking larger hydrocarbon molecules into smaller molecules. Applicable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, etc., and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking, heavy oil catalytic cracking, and the like, and combinations thereof. Accordingly, suitable catalytically cracked gasoline includes, but is not limited to, coker gasoline, thermally cracked gasoline, visbroken gasoline, fluid catalytically cracked gasoline, and heavy oil cracked gasoline, and combinations thereof. In some cases, the cracked gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in the process of the present invention.
本发明所用术语“柴油机燃料”意指沸程为170-450℃的烃混合物或其任何馏分组成的液体。此类含烃流体包括但不限于轻循环油、煤油、直馏柴油和加氢处理柴油等及其组合。The term "diesel fuel" as used in the present invention means a liquid composed of a hydrocarbon mixture or any fraction thereof having a boiling range of 170-450°C. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight-run diesel and hydrotreated diesel, and the like, and combinations thereof.
本发明所用术语“硫”代表任何形式的硫元素如含烃流体如裂化汽油或柴油机燃料中常存在的有机硫化合物。本发明含烃流体中存在的硫包括但不限于氧硫化碳（COS）、二硫化碳（CS2）、硫醇或其他噻吩类化合物等及其组合，尤其包括噻吩、苯并噻吩、烷基噻吩、烷基苯并噻吩和烷基二苯并噻吩，以及柴油机燃料中常存在的分子量更大的噻吩类化合物。The term "sulfur" as used herein denotes any form of elemental sulfur such as organic sulfur compounds commonly present in hydrocarbon-containing fluids such as cracked gasoline or diesel fuel. The sulfur present in the hydrocarbon-containing fluid of the present invention includes but is not limited to carbon oxysulfide (COS), carbon disulfide (CS 2 ), mercaptan or other thiophene compounds, etc., and combinations thereof, especially including thiophene, benzothiophene, alkylthiophene, Alkylbenzothiophenes and alkyldibenzothiophenes, as well as higher molecular weight thiophenes often found in diesel fuel.
本发明提供的脱硫催化剂具有良好的脱硫活性，而且该脱硫催化剂的耐磨损强度更好，可大大延长脱硫催化剂的使用寿命。The desulfurization catalyst provided by the invention has good desulfurization activity, and the desulfurization catalyst has better wear resistance strength, and can greatly prolong the service life of the desulfurization catalyst.
以下通过实施例对本发明作进一步说明。The present invention will be further described below through embodiment.
在以下实施例和对比例中，脱硫催化剂的组成通过荧光分析得出。荧光分析采用日本理学公司3271E型X射线荧光光谱仪进行测定。In the following examples and comparative examples, the composition of the desulfurization catalyst was obtained by fluorescence analysis. Fluorescence analysis was carried out using a 3271E X-ray fluorescence spectrometer from Japan Rigaku Corporation.
SEM-EDX测定采用日本日立S4800扫描电镜。事先把催化剂微球固定在树脂中，通过切割得到其剖面，采用SEM观察并结合EDX分析不同位置元素的组成，测得内核和包覆层的厚度。SEM-EDX was measured using a Hitachi S4800 scanning electron microscope. The catalyst microspheres were fixed in the resin in advance, and their cross-sections were obtained by cutting. The composition of elements at different positions was analyzed by SEM observation and combined with EDX, and the thickness of the inner core and the cladding layer were measured.
XPS测定采用英国VG公司MKII型光电子能谱仪测试，入射光为AlKα射线，入射光电子能量为1486.6eV，通过能为50eV。以C1s为内标，校正后BE=285.0eV。The XPS measurement was carried out using a MKII photoelectron spectrometer from VG Company of the United Kingdom. The incident light was AlKα rays, the incident photoelectron energy was 1486.6eV, and the passing energy was 50eV. With C1s as the internal standard, BE=285.0eV after correction.
TPR分析采用美国Micromeritics公司的2950高压吸附仪，在1.5MPa压力下，采用30体积%H2+70体积%Ar为还原气氛，从100℃至500℃以10℃/min的速率升温，通过TCD记录还原时还原气氛中氢气量的变化。The TPR analysis adopts the 2950 high-pressure adsorption instrument of Micromeritics Company in the United States. Under the pressure of 1.5MPa, 30vol%H 2 +70vol%Ar is used as the reducing atmosphere, and the temperature is raised from 100°C to 500°C at a rate of 10°C/min. Record the change of the amount of hydrogen in the reducing atmosphere during the reduction.
实施例1Example 1
本实施例用于说明本发明的脱硫催化剂的制备方法。This example is used to illustrate the preparation method of the desulfurization catalyst of the present invention.
（1）内核制备。1.20千克高岭土（苏州高岭土厂，S1，含干基0.90千克），水合氧化铝1.0千克（拟薄水铝石，山东铝厂出品，含干基0.8千克），160克30重量%的硝酸（化学纯，北京化工厂出品）和5.0千克中性水在搅拌下混合均匀后，搅拌酸化1小时。然后加入3.07千克氧化镍（分析纯，国药化学试剂公司），搅拌均匀后得到酸化浆液，其pH值为3.0。(1) Core preparation. 1.20 kg of kaolin (Suzhou Kaolin Factory, S1, containing 0.90 kg on a dry basis), 1.0 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Factory, containing 0.8 kg on a dry basis), 160 grams of 30% by weight nitric acid (chemical Pure, produced by Beijing Chemical Plant) and 5.0 kg of neutral water were mixed evenly under stirring, and acidified by stirring for 1 hour. Then add 3.07 kg of nickel oxide (analytical grade, Sinopharm Chemical Reagent Company), and stir evenly to obtain an acidified slurry with a pH value of 3.0.
所述混合浆液采用NiroBowenNozzleTowerTM型号的喷雾干燥机进行喷雾干燥：采用1.4mm的喷嘴，喷雾干燥压力为8.5-9.5MPa，入口温度500℃以下，出口温度约为150℃。由喷雾干燥得到的微球先在180℃下干燥1小时，然后在635℃下焙烧1小时得到内核微球。测定获得的内核微球的平均粒径（半径）为27微米。The mixed slurry is spray-dried with a NiroBowenNozzleTowerTM type spray dryer: a 1.4mm nozzle is used, the spray drying pressure is 8.5-9.5MPa, the inlet temperature is below 500°C, and the outlet temperature is about 150°C. The microspheres obtained by spray drying were first dried at 180° C. for 1 hour, and then calcined at 635° C. for 1 hour to obtain inner core microspheres. The average particle diameter (radius) of the obtained core microspheres was determined to be 27 microns.
（2）包覆层制备。取1.52千克膨胀珍珠岩（世界矿业公司，M27，含干基1.50千克）、水合氧化铝1.0千克（拟薄水铝石，山东铝厂出品，含干基0.8千克）以及9.0千克去离子水，搅拌混合均匀，加入160克30重量%的硝酸（化学纯，北京化工厂出品）搅拌酸化1小时。加入3.6千克氧化锌粉末，搅拌0.5小时，再加入步骤（1）中得到的内核微球，搅拌均匀后得到包覆层浆液。(2) Preparation of coating layer. Take 1.52 kg of expanded perlite (World Mining Company, M27, including 1.50 kg on a dry basis), 1.0 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Plant, including 0.8 kg on a dry basis) and 9.0 kg of deionized water, Stir and mix evenly, add 160 grams of 30% by weight nitric acid (chemically pure, produced by Beijing Chemical Factory) and stir for 1 hour to acidify. Add 3.6 kg of zinc oxide powder, stir for 0.5 hour, then add the inner core microspheres obtained in step (1), and stir evenly to obtain a coating layer slurry.
包覆层浆液采用NiroBowenNozzleTowerTM型号的喷雾干燥机进行喷雾干燥：采用2.0mm的喷嘴，喷雾干燥压力为2.0-2.5MPa，入口温度500℃以下，出口温度约为150℃。由喷雾干燥得到的微球先在180℃下干燥1小时，然后在635℃下焙烧1小时得到催化剂前体。测定催化剂前体的平均粒径（半径），与步骤（1）中测定得到的内核微球的平均粒径（半径）相减得到包覆层的厚度为9微米。The coating layer slurry is spray-dried by a NiroBowenNozzleTower TM type spray dryer: a 2.0mm nozzle is used, the spray drying pressure is 2.0-2.5MPa, the inlet temperature is below 500°C, and the outlet temperature is about 150°C. The microspheres obtained by spray drying were first dried at 180°C for 1 hour, and then calcined at 635°C for 1 hour to obtain a catalyst precursor. The average particle size (radius) of the catalyst precursor was measured, and subtracted from the average particle size (radius) of the inner core microspheres measured in step (1) to obtain a thickness of the coating layer of 9 microns.
（3）还原。催化剂前体在425℃的氢气气氛（氢气含量为30体积%）中还原2小时即可得到脱硫催化剂，记为脱硫催化剂A1。另外将脱硫催化剂A1进行H2-TPR测试，得H2-TPR谱图，如图1所示。图1中TCD信号出峰说明脱硫催化剂A1中的氧化镍已被还原为金属镍。(3) Restore. The desulfurization catalyst can be obtained by reducing the catalyst precursor in a hydrogen atmosphere (hydrogen content: 30% by volume) at 425°C for 2 hours, which is denoted as desulfurization catalyst A1. In addition, the desulfurization catalyst A1 was subjected to the H2-TPR test to obtain the H2-TPR spectrum, as shown in FIG. 1 . The peak of the TCD signal in Figure 1 indicates that the nickel oxide in the desulfurization catalyst A1 has been reduced to metallic nickel.
脱硫催化剂A1的化学组成为：氧化铝22.7重量%，氧化硅15.3重量%，氧化锌36.0重量%，镍23.9重量%。The chemical composition of the desulfurization catalyst A1 is: 22.7% by weight of alumina, 15.3% by weight of silicon oxide, 36.0% by weight of zinc oxide, and 23.9% by weight of nickel.
将脱硫催化剂A1进行SEM-EDX测定分析，根据得到的镍、锌沿A1截面径向的含量分布，得出内核与包覆层的厚度比为1：0.33。The desulfurization catalyst A1 was subjected to SEM-EDX measurement and analysis. According to the obtained content distribution of nickel and zinc along the radial direction of the section of A1, the thickness ratio of the inner core to the cladding layer was 1:0.33.
脱硫催化剂A1进行XPS测定，包覆层中Ni：Zn的摩尔比为1：6。Desulfurization catalyst A1 was determined by XPS, and the molar ratio of Ni:Zn in the cladding layer was 1:6.
通过荧光分析和XPS测定，脱硫催化剂A1包覆层中的Ni与A1中的Ni的重量比为0.29，包覆层中的氧化锌与A1中的氧化锌的重量比为1.60。According to fluorescence analysis and XPS measurement, the weight ratio of Ni in the coating layer of desulfurization catalyst A1 to Ni in A1 is 0.29, and the weight ratio of zinc oxide in the coating layer to zinc oxide in A1 is 1.60.
实施例2Example 2
本实施例用于说明本发明的脱硫催化剂的制备方法。This example is used to illustrate the preparation method of the desulfurization catalyst of the present invention.
（1）内核制备。1.02千克膨胀珍珠岩（世界矿业公司，M27，含干基1.00千克），水合氧化铝0.86千克（拟薄水铝石，山东铝厂出品，含干基0.69千克），9.9千克六水硝酸镍（分析纯，国药化学试剂公司）和4.0千克中性水在搅拌下均匀，得到浆液，其pH值为2.6。(1) Core preparation. 1.02 kg of expanded perlite (World Mining Company, M27, containing 1.00 kg on a dry basis), 0.86 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Plant, containing 0.69 kg on a dry basis), 9.9 kg of nickel nitrate hexahydrate ( Analytical grade, Sinopharm Chemical Reagent Company) and 4.0 kg of neutral water were homogenized under stirring to obtain a slurry with a pH value of 2.6.
按照实施例1步骤（1）中的方法进行喷雾干燥，得到内核微球。测定获得的内核微球的平均粒径（半径）为25微米。Spray drying was carried out according to the method in step (1) of Example 1 to obtain inner core microspheres. The average particle diameter (radius) of the obtained core microspheres was determined to be 25 microns.
（2）包覆层制备。取1.23千克膨胀珍珠岩（世界矿业公司，M27，含干基1.21千克）、水合氧化铝0.75千克（拟薄水铝石，山东铝厂出品，含干基0.6千克）以及9.0千克去离子水，搅拌混合均匀，加入130克30重量%的盐酸（化学纯，北京化工厂出品）搅拌酸化1小时。加入4.5千克氧化锌粉末，搅拌0.5小时，再加入步骤（1）中得到的内核微球，搅拌均匀后得到包覆层浆液。(2) Preparation of coating layer. Take 1.23 kg of expanded perlite (World Mining Company, M27, including 1.21 kg on a dry basis), 0.75 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Plant, including 0.6 kg on a dry basis) and 9.0 kg of deionized water, Stir and mix evenly, add 130 g of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Factory) and stir for 1 hour to acidify. Add 4.5 kg of zinc oxide powder, stir for 0.5 hours, then add the inner core microspheres obtained in step (1), and stir evenly to obtain a coating layer slurry.
按照实施例1步骤（2）中的方法进行包覆层浆液的喷雾干燥成型并焙烧处理，得到催化剂前体。测定催化剂前体的平均粒径（半径），与步骤（1）中测定得到的内核微球的平均粒径（半径）相减得到包覆层的厚度为11微米。According to the method in step (2) of Example 1, the coating layer slurry was spray-dried and calcined to obtain a catalyst precursor. The average particle size (radius) of the catalyst precursor was measured, and subtracted from the average particle size (radius) of the inner core microspheres measured in step (1) to obtain a thickness of the coating layer of 11 microns.
（3）还原。按照实施例1步骤（3）中的方法进行催化剂前体的还原，得到脱硫催化剂A2。按照实施例1中方法进行H2-TPR测试，显示脱硫催化剂A2中的氧化镍被还原为金属镍。(3) Restore. The catalyst precursor was reduced according to the method in step (3) of Example 1 to obtain desulfurization catalyst A2. The H2-TPR test was carried out according to the method in Example 1, which showed that the nickel oxide in the desulfurization catalyst A2 was reduced to metallic nickel.
脱硫催化剂A2的化学组成为：氧化铝16.9重量%，氧化硅15.9重量%，氧化锌45.0重量%，镍20.0重量%。The chemical composition of the desulfurization catalyst A2 is: 16.9% by weight of alumina, 15.9% by weight of silicon oxide, 45.0% by weight of zinc oxide, and 20.0% by weight of nickel.
按照实施例1中方法进行SEM-EDX测定分析，得出内核与包覆层的厚度比为1：0.44。脱硫催化剂A2进行XPS测定，包覆层中Ni：Zn的摩尔比为1：12。通过荧光分析和XPS测定，脱硫催化剂A2包覆层中的Ni与A2中的Ni的重量比为0.25，外层中的氧化锌与A2中的氧化锌的重量比为1.72。SEM-EDX measurement and analysis was carried out according to the method in Example 1, and it was found that the thickness ratio of the inner core to the cladding layer was 1:0.44. Desulfurization catalyst A2 was determined by XPS, and the molar ratio of Ni:Zn in the cladding layer was 1:12. According to fluorescence analysis and XPS measurement, the weight ratio of Ni in the coating layer of desulfurization catalyst A2 to Ni in A2 is 0.25, and the weight ratio of zinc oxide in the outer layer to zinc oxide in A2 is 1.72.
实施例3Example 3
本实施例用于说明本发明的脱硫催化剂的制备方法。This example is used to illustrate the preparation method of the desulfurization catalyst of the present invention.
（1）内核制备。1.33千克高岭土（苏州高岭土厂，S1，含干基1.0千克），水合氧化铝0.56千克（拟薄水铝石，山东铝厂出品，含干基0.45千克），4.95千克六水硝酸镍（分析纯，国药化学试剂公司）和4.0千克中性水在搅拌下均匀，得到浆液，其pH值为3.1。(1) Core preparation. 1.33 kg of kaolin (Suzhou Kaolin Factory, S1, containing 1.0 kg on a dry basis), 0.56 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Plant, containing 0.45 kg on a dry basis), 4.95 kg of nickel nitrate hexahydrate (analytical pure , Sinopharm Chemical Reagent Company) and 4.0 kg of neutral water were uniformly stirred to obtain a slurry with a pH value of 3.1.
按照实施例1步骤（1）中的方法进行喷雾干燥，得到内核微球。测定获得的内核微球的平均粒径（半径）为25微米。Spray drying was carried out according to the method in step (1) of Example 1 to obtain inner core microspheres. The average particle diameter (radius) of the obtained core microspheres was determined to be 25 microns.
（2）包覆层制备。取1.70千克硅藻土（北京化学试剂厂，含干基1.65千克）、水合氧化铝0.63千克（拟薄水铝石，山东铝厂出品，含干基0.5千克）以及8.0千克去离子水，搅拌混合均匀，加入120克30重量%的盐酸（化学纯，北京化工厂出品）搅拌酸化1小时。加入5.4千克氧化锌粉末，搅拌0.5小时，再加入步骤（1）中得到的内核微球，搅拌均匀后得到包覆层浆液。(2) Preparation of coating layer. Take 1.70 kg of diatomite (Beijing Chemical Reagent Factory, containing 1.65 kg on a dry basis), 0.63 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Factory, containing 0.5 kg on a dry basis) and 8.0 kg of deionized water, and stir Mix evenly, add 120 g of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Factory) and stir for 1 hour to acidify. Add 5.4 kg of zinc oxide powder, stir for 0.5 hours, then add the inner core microspheres obtained in step (1), and stir evenly to obtain a coating layer slurry.
按照实施例1步骤（2）中的方法进行包覆层浆液的喷雾干燥成型并焙烧处理，得到催化剂前体。测定催化剂前体的平均粒径（半径），与步骤（1）中测定得到的内核微球的平均粒径（半径）相减得到包覆层的厚度为15微米。According to the method in step (2) of Example 1, the coating layer slurry was spray-dried and calcined to obtain a catalyst precursor. The average particle size (radius) of the catalyst precursor was measured, and subtracted from the average particle size (radius) of the inner core microspheres measured in step (1) to obtain a thickness of the coating layer of 15 microns.
（3）还原。按照实施例1步骤（3）中的方法进行催化剂前体的还原，得到脱硫催化剂A3。按照实施例1中方法进行H2-TPR测试，显示脱硫催化剂A3中的氧化镍被还原为金属镍。(3) Restore. The catalyst precursor was reduced according to the method in step (3) of Example 1 to obtain desulfurization catalyst A3. The H2-TPR test was carried out according to the method in Example 1, which showed that the nickel oxide in the desulfurization catalyst A3 was reduced to metallic nickel.
脱硫催化剂A3的化学组成为：氧化铝14.0重量%，氧化硅21.2重量%，氧化锌54.0重量%，镍10.0重量%。The chemical composition of the desulfurization catalyst A3 is: 14.0% by weight of alumina, 21.2% by weight of silicon oxide, 54.0% by weight of zinc oxide, and 10.0% by weight of nickel.
按照实施例1中方法进行SEM-EDX测定分析，得出内核与包覆层的厚度比为1：0.6。The SEM-EDX measurement and analysis was carried out according to the method in Example 1, and it was found that the thickness ratio of the inner core to the cladding layer was 1:0.6.
脱硫催化剂A3进行XPS测定，包覆层中Ni：Zn的摩尔比为1：20。Desulfurization catalyst A3 was determined by XPS, and the molar ratio of Ni:Zn in the cladding layer was 1:20.
通过荧光分析和XPS测定，脱硫催化剂A3包覆层中的Ni与A3中的Ni的重量比为0.18，内核中的氧化锌与A3中的氧化锌的重量比为1.79。According to fluorescence analysis and XPS measurement, the weight ratio of Ni in the cladding layer of desulfurization catalyst A3 to Ni in A3 is 0.18, and the weight ratio of zinc oxide in the inner core to zinc oxide in A3 is 1.79.
实施例4Example 4
本实施例用于说明本发明的脱硫催化剂的制备方法。This example is used to illustrate the preparation method of the desulfurization catalyst of the present invention.
（1）内核制备。取0.98千克硅藻土（北京化学试剂厂，含干基0.95千克），水合氧化铝0.75千克（拟薄水铝石，山东铝厂出品，含干基0.6千克），120克30重量%的硝酸（化学纯，北京化工厂出品）克和4.5千克中性水在搅拌下均匀。然后加入2.04千克氧化镍（分析纯，国药化学试剂公司），搅拌均匀后得到酸化浆液，其pH值为3.3。(1) Core preparation. Take 0.98 kg of diatomite (Beijing Chemical Reagent Factory, containing 0.95 kg on a dry basis), 0.75 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Factory, containing 0.6 kg on a dry basis), and 120 grams of 30% by weight nitric acid (Chemically pure, produced by Beijing Chemical Plant) and 4.5 kg of neutral water were mixed evenly under stirring. Then add 2.04 kg of nickel oxide (analytical grade, Sinopharm Chemical Reagent Company), and stir to obtain an acidified slurry with a pH value of 3.3.
按照实施例1步骤（1）中的方法进行喷雾干燥，得到内核微球。测定获得的内核微球的平均粒径（半径）为23微米。Spray drying was carried out according to the method in step (1) of Example 1 to obtain inner core microspheres. The average particle diameter (radius) of the obtained core microspheres was determined to be 23 microns.
（2）包覆层制备。1.50千克白土（苏州高岭土厂，含干基1.25千克）、水合氧化铝0.75千克（拟薄水铝石，山东铝厂出品，含干基0.6千克）以及8.0千克去离子水，搅拌混合均匀，加入140克30重量%的硝酸（化学纯，北京化工厂出品）搅拌酸化1小时。加入5.0千克氧化锌粉末，搅拌0.5小时，再加入步骤（1）中得到的内核微球，搅拌均匀后得到包覆层浆液。(2) Preparation of coating layer. 1.50 kg of white clay (Suzhou Kaolin Factory, including 1.25 kg on a dry basis), 0.75 kg of hydrated alumina (pseudoboehmite, produced by Shandong Aluminum Plant, including 0.6 kg on a dry basis) and 8.0 kg of deionized water, stir to mix evenly, add 140 grams of 30% by weight nitric acid (chemically pure, produced by Beijing Chemical Plant) was stirred and acidified for 1 hour. Add 5.0 kg of zinc oxide powder, stir for 0.5 hours, then add the inner core microspheres obtained in step (1), and stir evenly to obtain a coating layer slurry.
按照实施例1步骤（2）中的方法进行包覆层浆液的喷雾干燥成型并焙烧处理，得到催化剂前体。测定催化剂前体的平均粒径（半径），与步骤（1）中测定得到的内核微球的平均粒径（半径）相减得到包覆层的厚度为10微米。According to the method in step (2) of Example 1, the coating layer slurry was spray-dried and calcined to obtain a catalyst precursor. The average particle size (radius) of the catalyst precursor is measured, and subtracted from the average particle size (radius) of the inner core microspheres measured in step (1) to obtain a thickness of the coating layer of 10 microns.
（3）还原。按照实施例1步骤（3）中的方法进行催化剂前体的还原，得到脱硫催化剂A4。按照实施例1中方法进行H2-TPR测试，显示脱硫催化剂A4中的氧化镍被还原为金属镍。(3) Restore. The catalyst precursor was reduced according to the method in step (3) of Example 1 to obtain desulfurization catalyst A4. The H2-TPR test was carried out according to the method in Example 1, which showed that the nickel oxide in the desulfurization catalyst A4 was reduced to metallic nickel.
脱硫催化剂A4的化学组成为：氧化铝17.2重量%，氧化硅15.6重量%，氧化锌50.0重量%，镍16.0重量%。The chemical composition of the desulfurization catalyst A4 is: 17.2% by weight of alumina, 15.6% by weight of silicon oxide, 50.0% by weight of zinc oxide, and 16.0% by weight of nickel.
按照实施例1中方法进行SEM-EDX测定分析，得出内核与包覆层的厚度比为1：0.43。The SEM-EDX measurement and analysis was carried out according to the method in Example 1, and it was obtained that the thickness ratio of the inner core to the cladding layer was 1:0.43.
脱硫催化剂A4进行XPS测定，包覆层中Ni：Zn的摩尔比为1：13。Desulfurization catalyst A4 was determined by XPS, and the molar ratio of Ni:Zn in the cladding layer was 1:13.
通过荧光分析和XPS测定，脱硫催化剂A4包覆层中的Ni与A4中的Ni的重量比为0.21，中的氧化锌与A4中的氧化锌的重量比为1.73。According to fluorescence analysis and XPS measurement, the weight ratio of Ni in the cladding layer of desulfurization catalyst A4 to Ni in A4 is 0.21, and the weight ratio of zinc oxide in A4 to zinc oxide in A4 is 1.73.
对比例1Comparative example 1
取1.52千克膨胀珍珠岩（世界矿业公司，M27，含干基1.50千克）、1.20千克高岭土（苏州高岭土厂，S1，含干基0.90千克），水合氧化铝2.0千克（拟薄水铝石，山东铝厂出品，含干基1.6千克）和14.0千克中性水在搅拌下混合均匀后，加入300克30重量%的硝酸（化学纯，北京化工厂出品）搅拌酸化1小时。加入3.6千克氧化锌粉末混合后搅拌1小时得到载体浆液。Take 1.52 kg of expanded perlite (World Mining Company, M27, containing 1.50 kg on a dry basis), 1.20 kg of kaolin (Suzhou Kaolin Factory, S1, containing 0.90 kg on a dry basis), 2.0 kg of hydrated alumina (pseudoboehmite, Shandong Produced by an aluminum factory, containing 1.6 kg on a dry basis) and 14.0 kg of neutral water are mixed evenly under stirring, and then 300 g of 30% by weight nitric acid (chemically pure, produced by Beijing Chemical Plant) is added to acidify for 1 hour. 3.6 kg of zinc oxide powder was added, mixed and then stirred for 1 hour to obtain a carrier slurry.
所述载体浆液采用NiroBowenNozzleTowerTM型号的喷雾干燥机进行喷雾干燥：采用2.0mm的喷嘴，喷雾干燥压力为8.5-9.5MPa，入口温度500℃以下，出口温度约为150℃。由喷雾干燥得到的微球先在180℃下干燥1小时，然后在635℃下焙烧1小时得到催化剂载体。The carrier slurry is spray-dried using a NiroBowenNozzleTowerTM type spray dryer: a 2.0mm nozzle is used, the spray drying pressure is 8.5-9.5MPa, the inlet temperature is below 500°C, and the outlet temperature is about 150°C. The microspheres obtained by spray drying were first dried at 180° C. for 1 hour, and then calcined at 635° C. for 1 hour to obtain a catalyst carrier.
将3.88千克的催化剂载体（干基3.8千克）用4.8千克六水合硝酸镍、1.9千克去离子水溶液分两次浸渍，得到的混合物经过180℃干燥4小时后，在空气气氛635℃焙烧1小时即可制得催化剂前体。催化剂前体在425℃的氢气气氛中还原2小时即可得到脱硫催化剂，记为脱硫催化剂B1。3.88 kg of catalyst carrier (3.8 kg on a dry basis) was impregnated twice with 4.8 kg of nickel nitrate hexahydrate and 1.9 kg of deionized aqueous solution, and the resulting mixture was dried at 180°C for 4 hours, and then calcined at 635°C in an air atmosphere for 1 hour. Catalyst precursors can be prepared. The desulfurization catalyst can be obtained by reducing the catalyst precursor in a hydrogen atmosphere at 425° C. for 2 hours, which is designated as desulfurization catalyst B1.
脱硫催化剂B1的化学组成为：氧化铝22.7重量%，氧化硅15.3重量%，氧化锌36.0重量%，镍23.9重量%。The chemical composition of the desulfurization catalyst B1 is: 22.7% by weight of alumina, 15.3% by weight of silicon oxide, 36.0% by weight of zinc oxide, and 23.9% by weight of nickel.
脱硫催化剂B1进行XPS测定，脱硫催化剂B1的表面上Ni：Zn的摩尔比为2：1。Desulfurization catalyst B1 was measured by XPS, and the molar ratio of Ni:Zn on the surface of desulfurization catalyst B1 was 2:1.
通过荧光分析和XPS测定，脱硫催化剂B1表面的Ni与B1中的Ni的重量比为1.52，表面的氧化锌与B1中的氧化锌的重量比为0.72。According to fluorescence analysis and XPS measurement, the weight ratio of Ni on the surface of desulfurization catalyst B1 to Ni in B1 is 1.52, and the weight ratio of zinc oxide on the surface to zinc oxide in B1 is 0.72.
对比例2Comparative example 2
在6.2千克去离子水中加入4.5千克氧化锌粉末（北京化工厂出品）并搅拌30分钟，得到氧化锌浆液。Add 4.5 kg of zinc oxide powder (produced by Beijing Chemical Plant) into 6.2 kg of deionized water and stir for 30 minutes to obtain a zinc oxide slurry.
取2.24千克膨胀珍珠岩（世界矿业公司，M27，含干基2.21千克）水合氧化铝1.61千克（山东铝厂出品，含干基1.29千克）和6.8千克中性水在搅拌下混合均匀后，加入260克30重量%的硝酸（化学纯，北京化工厂出品）搅拌酸化1小时后，加入上述氧化锌浆液，并搅拌1小时得到载体浆液。Take 2.24 kg of expanded perlite (World Mining Company, M27, including 2.21 kg on a dry basis), 1.61 kg of hydrated alumina (produced by Shandong Aluminum Factory, including 1.29 kg on a dry basis) and 6.8 kg of neutral water, mix them evenly under stirring, and add 260 grams of 30% by weight nitric acid (chemically pure, produced by Beijing Chemical Plant) was stirred and acidified for 1 hour, then the above-mentioned zinc oxide slurry was added, and stirred for 1 hour to obtain a carrier slurry.
按照对比例1的方法进行载体的喷雾干燥成型并引入活性组分镍，得到脱硫催化剂B2。The carrier was spray-dried and molded according to the method of Comparative Example 1, and the active component nickel was introduced to obtain the desulfurization catalyst B2.
脱硫催化剂B2的化学组成为：氧化铝16.9重量%，氧化硅15.9重量%，氧化锌45.0重量%，镍20.0重量%。The chemical composition of the desulfurization catalyst B2 is: 16.9% by weight of alumina, 15.9% by weight of silicon oxide, 45.0% by weight of zinc oxide, and 20.0% by weight of nickel.
脱硫催化剂B2进行XPS测定，脱硫催化剂B2的表面上Ni：Zn的摩尔比为1.6：1。The desulfurization catalyst B2 was measured by XPS, and the molar ratio of Ni:Zn on the surface of the desulfurization catalyst B2 was 1.6:1.
通过荧光分析和XPS测定，脱硫催化剂B2表面的Ni与B2中的Ni的重量比为1.45，表面的氧化锌与B2中的氧化锌的重量比为0.83。According to fluorescence analysis and XPS measurement, the weight ratio of Ni on the surface of desulfurization catalyst B2 to Ni in B2 is 1.45, and the weight ratio of zinc oxide on the surface to zinc oxide in B2 is 0.83.
对比例3Comparative example 3
取1.70千克硅藻土（北京化学试剂厂，含干基1.65千克）、1.33千克高岭土（苏州高岭土厂，S1，含干基1.0千克），水合氧化铝1.19千克（山东铝厂出品，含干基0.95千克）和12.0千克中性水（pH值为6-8）在搅拌下混合均匀后，加入235克30重量%的盐酸（化学纯，北京化工厂出品）搅拌酸化2小时后升温至80℃老化2小时。待温度降低到40℃以下时，加入5.4千克氧化锌粉末混合后搅拌1小时得到载体浆液。Take 1.70 kg of diatomite (Beijing Chemical Reagent Factory, including 1.65 kg on dry basis), 1.33 kg of kaolin (Suzhou Kaolin Factory, S1, including 1.0 kg on dry basis), 1.19 kg of hydrated alumina (produced by Shandong Aluminum Factory, including dry basis 0.95 kg) and 12.0 kg of neutral water (pH value 6-8) are mixed evenly under stirring, then add 235 g of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stir for 2 hours, then heat up to 80°C Aged for 2 hours. When the temperature dropped below 40° C., 5.4 kg of zinc oxide powder was added for mixing and then stirred for 1 hour to obtain a carrier slurry.
按照对比例1的方法进行载体的喷雾干燥成型并引入活性组分镍，得到脱硫催化剂B3。The carrier was spray-dried and molded according to the method of Comparative Example 1, and the active component nickel was introduced to obtain the desulfurization catalyst B3.
脱硫催化剂B3的化学组成为：氧化铝14.0重量%，氧化硅21.2重量%，氧化锌54.0重量%，镍10.0重量%。The chemical composition of the desulfurization catalyst B3 is: 14.0% by weight of alumina, 21.2% by weight of silicon oxide, 54.0% by weight of zinc oxide, and 10.0% by weight of nickel.
脱硫催化剂B3进行XPS测定，脱硫催化剂B3的表面上Ni：Zn的摩尔比为1.18：1。Desulfurization catalyst B3 was measured by XPS, and the molar ratio of Ni:Zn on the surface of desulfurization catalyst B3 was 1.18:1.
通过荧光分析和XPS测定，脱硫催化剂B3表面的Ni与B3中的Ni的重量比为1.30，表面的氧化锌与B3中的氧化锌的重量比为0.90。According to fluorescence analysis and XPS measurement, the weight ratio of Ni on the surface of desulfurization catalyst B3 to Ni in B3 is 1.30, and the weight ratio of zinc oxide on the surface to zinc oxide in B3 is 0.90.
对比例4Comparative example 4
取0.98千克硅藻土（北京化学试剂厂，含干基0.95千克）、1.50千克白土（苏州高岭土厂，含干基1.25千克），水合氧化铝1.60千克（山东铝厂出品，含干基1.20千克）和14.0千克中性水（pH值为6-8）在搅拌下混合均匀后，加入225克30重量%的盐酸（化学纯，北京化工厂出品）搅拌酸化2小时后升温至80℃老化2小时。待温度降低到40℃以下时，加入5.0千克氧化锌粉末混合后搅拌1小时得到载体浆液。Take 0.98 kg of diatomite (Beijing Chemical Reagent Factory, including 0.95 kg on dry basis), 1.50 kg of white clay (Suzhou Kaolin Factory, including 1.25 kg on dry basis), 1.60 kg of hydrated alumina (produced by Shandong Aluminum Factory, including 1.20 kg on dry basis) ) and 14.0 kg of neutral water (pH value 6-8) were mixed evenly under stirring, then 225 g of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was added to acidify for 2 hours, then heated to 80°C for aging for 2 hours Hour. When the temperature dropped below 40° C., 5.0 kg of zinc oxide powder was added for mixing and then stirred for 1 hour to obtain a carrier slurry.
按照对比例1的方法进行载体的喷雾干燥成型并引入活性组分镍，得到脱硫催化剂B4。According to the method of Comparative Example 1, the carrier was spray-dried and molded and the active component nickel was introduced to obtain the desulfurization catalyst B4.
脱硫催化剂B4的化学组成为：氧化铝17.2重量%，氧化硅15.6重量%，氧化锌50.0重量%，镍16.0重量%。The chemical composition of the desulfurization catalyst B4 is: 17.2% by weight of alumina, 15.6% by weight of silicon oxide, 50.0% by weight of zinc oxide, and 16.0% by weight of nickel.
脱硫催化剂B4进行XPS测定，脱硫催化剂B4的表面上Ni：Zn的摩尔比为1.4：1。Desulfurization catalyst B4 was measured by XPS, and the molar ratio of Ni:Zn on the surface of desulfurization catalyst B4 was 1.4:1.
通过荧光分析和XPS测定，脱硫催化剂B4表面的Ni与B4中的Ni的重量比为1.36，表面的氧化锌与B4中的氧化锌的重量比为0.86。According to fluorescence analysis and XPS measurement, the weight ratio of Ni on the surface of desulfurization catalyst B4 to Ni in B4 is 1.36, and the weight ratio of zinc oxide on the surface to zinc oxide in B4 is 0.86.
测试例test case
测定脱硫催化剂A1-A4和B1-B4的耐磨损强度以及脱硫性能。The wear resistance and desulfurization performance of the desulfurization catalysts A1-A4 and B1-B4 were measured.
耐磨损强度采用直管磨损法进行评价，其评价方法参考企标Q/SH3360212-2009，数值越小，表明耐磨损强度越高。不同脱硫催化剂的磨损指数（FBAT）如表1所示。The wear resistance is evaluated by the straight pipe wear method. The evaluation method refers to the enterprise standard Q/SH3360212-2009. The smaller the value, the higher the wear resistance. The wear index (FBAT) of different desulfurization catalysts is shown in Table 1.
脱硫催化剂的脱硫性能采用固定床微反实验装置进行评价。评价使用的原料为硫含量为796μg/g的催化裂化汽油。将16克的脱硫催化剂装填在内径为30mm、长为1m的固定床反应器中。评价过程采用氢气气氛（氢气含量为30体积%），反应温度为410℃，评价使用的原料的进料的重量空速为4h-1。The desulfurization performance of the desulfurization catalyst was evaluated using a fixed-bed micro-reactor experimental device. The raw material used in the evaluation is catalytically cracked gasoline with a sulfur content of 796 μg/g. 16 grams of desulfurization catalyst was loaded into a fixed-bed reactor with an inner diameter of 30 mm and a length of 1 m. The evaluation process used a hydrogen atmosphere (the hydrogen content was 30% by volume), the reaction temperature was 410° C., and the weight space velocity of the raw materials used in the evaluation was 4 h −1 .
评价完成后脱硫催化剂进行再生处理，再生处理是在550℃的空气气氛下进行的。总共进行6次循环评价，以产品汽油中的硫含量代表催化剂的活性，硫含量采用离线色谱分析，采用安捷仑公司的GC6890-SCD仪器进行测定。After the evaluation is completed, the desulfurization catalyst is regenerated, and the regenerated treatment is carried out in an air atmosphere at 550°C. A total of 6 cycle evaluations were carried out, and the catalyst activity was represented by the sulfur content in the product gasoline. The sulfur content was analyzed by off-line chromatography and measured by the GC6890-SCD instrument of Agilent Company.
脱硫催化剂进行脱硫性能评价得到的产品汽油的硫含量如表2所示。Table 2 shows the sulfur content of product gasoline obtained by evaluating the desulfurization performance of the desulfurization catalyst.
表1Table 1
表2Table 2
从实施例和对比例的实验结果以及表1和表2的数据结果可以看出，本发明提供的脱硫催化剂因为形成具有内核和包覆层的层状结构，其中包覆层中含有氧化锌，内核富含活性金属，所以本发明提供的脱硫催化剂有更好的脱硫性能和耐磨损强度。As can be seen from the experimental results of Examples and Comparative Examples and the data results in Table 1 and Table 2, the desulfurization catalyst provided by the present invention has a layered structure with an inner core and a clad layer, wherein the clad layer contains zinc oxide, The inner core is rich in active metals, so the desulfurization catalyst provided by the invention has better desulfurization performance and wear resistance.
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