CN109201073B - 一种汽油加氢脱硫催化剂及制备方法 - Google Patents
一种汽油加氢脱硫催化剂及制备方法 Download PDFInfo
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- CN109201073B CN109201073B CN201811057444.3A CN201811057444A CN109201073B CN 109201073 B CN109201073 B CN 109201073B CN 201811057444 A CN201811057444 A CN 201811057444A CN 109201073 B CN109201073 B CN 109201073B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 24
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 56
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract 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 abstract description 53
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 22
- 229920000620 organic polymer Polymers 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 10
- 241000219782 Sesbania Species 0.000 claims description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
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- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000002253 acid Substances 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
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 230000004048 modification Effects 0.000 description 3
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000003921 oil Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
本发明公开一种汽油加氢脱硫催化剂,催化剂的载体为包含钨掺杂铁酸镧的氧化铝,催化剂的组成以氧化物质量计,包括如下组分:含钨掺杂铁酸镧的氧化铝载体70.0‑93.5 wt%,活性组分氧化钴3.0‑12 wt%、氧化钼3.5‑18.0 wt%。本发明的加氢脱硫催化剂用于生产超低硫、低烯烃、高辛烷值的清洁汽油。
Description
技术领域
本发明涉及石油化工领域,具体涉及一种汽油加氢脱硫催化剂及制备方法。
背景技术
目前,催化裂化汽油中高烯烃含量和硫含量已成为困扰世界清洁汽油生产的关键问题。为满足日益严格的清洁汽油标准要求,FCC汽油的加氢改质就成为满足国六标准车用汽油生产的关键技术之一。氧化铝载体广泛用于多相催化剂、催化剂载体等领域,载体氧化铝的热稳定性、水热稳定性、抗结焦性能等不理想,通常添加助剂进行改性,提高载体性能。
改性氧化铝载体专利技术有很多,CN201310429334.6公开一种高性能催化剂载体及其制备方法,用于多相催化反应的催化剂载体材料。这种高性能催化剂载体的主要成分为Al、Zr、Mg、Ti、Si氧化物的混合物,以稀土元素或铬改性,制备方法包括载体颗粒的制备和载体颗粒的改性,制备的高温载体的比表面积在80m2/g以上,孔容在0.3ml/g以上,高温水蒸汽处理比表面积保留率在90%以上。该催化剂载体可用于高温反应催化剂的制备,能够承受600℃以上的高温,可以在400~650℃下使用。在高温反应时,活性组分金属或金属氧化物颗粒不易烧结,性能稳定,催化剂具有较长的寿命。
CN200780024779.9提供一种废气净化催化剂,其具有由具有细孔结构的二氧化硅构成的多孔二氧化硅载体、以及担载于该多孔二氧化硅载体的细孔结构内的钙钛矿型复合氧化物的粒子。这里,在该多孔二氧化硅载体中,在其细孔分布中,源于一次粒子间的间隙的峰处于3~100nm的范围。
发明内容
本发明目的在于提供一种汽油加氢脱硫催化剂,催化剂载体包含具有大孔结构的氧化铝,用于生产超低硫、低烯烃、高辛烷值的清洁汽油。
一种加氢脱硫催化剂,催化剂的载体为包含钨掺杂铁酸镧的氧化铝,催化剂的组成以氧化物质量计,包括如下组分:含钨掺杂铁酸镧的氧化铝载体70.0-93.5wt%,活性组分氧化钴3.0-12wt%、氧化钼3.5-18.0wt%。
进一步优选,活性组分氧化钴3.0-10wt%、氧化钼4.5-15.0wt%。
本发明还提供一种加氢脱硫催化剂的制备方法,包括如下步骤:将含钴和含钼的可溶性盐配成浸渍液,浸渍氧化铝载体,在120-180℃下干燥4-8小时,450-800℃下焙烧3-9小时,得到所述加氢脱硫催化剂。
上述氧化铝载体中包含0.1~12wt%的钨掺杂铁酸镧,载体介孔占总孔的1~85%,大孔占总孔的1~70%。优选地,介孔占总孔的5~70%,大孔占总孔的5~45%。
上述氧化铝载体的制备方法如下:将拟薄水铝石和田菁粉加入到捏合机中混合均匀,加入无机酸溶液和有机聚合物,捏合均匀,然后再加入钨掺杂铁酸镧,捏合均匀后,经过挤条、成型、干燥、焙烧,得到氧化铝载体。
对上述氧化铝载体进一步改进,得到改进型氧化铝载体,改进型氧化铝载体中包含0.1~12wt%的氧化硅,0.1~10wt%的钨掺杂铁酸镧,载体介孔占总孔的1~80%,大孔占总孔的1~55%。优选地,介孔占总孔的1~65%,更优选5~55%。优选地,大孔占总孔的5~45%,更优选10~35%,载体中微孔、介孔、大孔不均匀分布。
所述改进型氧化铝载体的制备方法如下:将拟薄水铝石和田菁粉加入到捏合机中混合均匀,加入无机酸溶液和有机聚合物,捏合均匀,然后再加入钨掺杂铁酸镧,混合均匀得到氧化铝前驱体,备用;在有机聚合物的酸液中加入硅源混合均匀,得到硅源-有机聚合物混合物,氧化铝前驱体中单位含量的有机聚合物比硅源-有机聚合物混合物中有机聚合物的含量高1.5倍以上,然后将硅源-有机聚合物混合物与氧化铝前驱体混合,经挤条、成型、干燥、焙烧,得到氧化铝载体。所述硅源可以是硅酸钠或硅微粉。
氧化铝载体或改进型氧化铝载体的制备过程,所述有机聚合物为聚乙烯醇、聚丙烯酸钠、聚乙二醇、聚丙烯酸酯中的一种或几种,优选聚丙烯酸或聚丙烯酸钠。
优选地,上述氧化铝载体或改进型氧化铝载体中钨掺杂铁酸镧为0.3~9wt%,更优选0.3~5wt%,钨掺杂铁酸镧中钨占钨掺杂铁酸镧的0.1~8wt%。
进一步,上述氧化铝载体或改进型氧化铝载体中的钨掺杂铁酸镧最好具有微介孔,引入具有微介孔的钨掺杂铁酸镧,制备的催化剂有利于抑制副反应发生,提高目的产物选择性。因此,本发明还提供了一种具有微介孔的钨掺杂铁酸镧的制备方法:将柠檬酸溶于去离子水中搅拌溶解,然后将硝酸镧与硝酸铁加入柠檬酸中,搅拌溶解,加入聚丙烯酸钠或聚丙烯酸,聚丙烯酸钠或聚丙烯酸的加入量为钨掺杂铁酸镧的0.1~9wt%,优选0.1~6.0wt%。再加入含钨化合物,以氧化物记,钨占钨掺杂铁酸镧的0.1~8wt%,搅拌,反应后,经干燥、焙烧、研磨得到成品。
所述含钨化合物包括钨酸铵、偏钨酸铵、仲钨酸铵等。
氧化铝载体中加入钨掺杂铁酸镧,相比加入铁酸镧(LaFeO3),能够有效抑制烯烃聚合、过度裂化等副反应发生,提高目的产物选择性。
氧化铝前驱体中单位含量的有机聚合物比硅源-有机聚合物混合物中有机聚合物的含量高1.5倍以上,可以有效改善载体的孔结构,一方面使载体微孔、介孔、大孔不均匀分布,减少副反应发生,提高选择性;另一方面有利于载体表面产生出更多的活性位负载中心,提高催化剂活性。
本发明加氢脱硫催化剂以具有大孔结构的氧化铝为载体,制备的高活性催化剂脱硫率高,辛烷值损失低,烯烃饱和率低,收率高。
具体实施方式
以下通过实施例进一步详细描述本发明,但这些实施例不应认为是对本发明的限制。本发明所用的原料试剂均为市售产品。
实施例1
1、制备具有微介孔的钨掺杂铁酸镧
搅拌条件下,将2.2mol La(NO3)3溶于100mL水中,加入柠檬酸搅拌溶解;再加入4.2mol Fe(NO3)3,然后再加入160g聚丙烯酸钠,再加入含10g偏钨酸铵的水溶液,继续搅拌30min,经烘干、焙烧、研磨得到微介孔钨掺杂铁酸镧(LaFeO3)。
2、制备氧化铝载体
2.2g微介孔钨掺杂铁酸镧中加入柠檬酸备用,将300g拟薄水铝石粉子和20.0g田菁粉加入到捏合机中,并混合均匀,再加入硝酸、8g聚丙烯酸钠,捏合均匀,然后加入微介孔钨掺杂铁酸镧,混合均匀,经过捏合-挤条成型为三叶草形状。在120℃干燥8小时,700℃焙烧4小时,得到含微介孔钨掺杂铁酸镧的氧化铝载体1。载体孔结构如表1所示。
3、制备催化剂
将七钼酸铵和硝酸钴加入到蒸馏水中,配成浸渍液浸渍上述氧化铝载体,得到的催化剂前躯体在140℃烘干后,在650℃焙烧7h,得到催化剂1。催化剂1主要组成:含微介孔钨掺杂铁酸镧的氧化铝载体为81.0wt%,氧化钴含量为8.4wt%,氧化钼含量为10.6wt%。
对比例1
对比催化剂的制备同实施例1,只是用铁酸镧代替含微介孔钨掺杂铁酸镧,反应评价条件同实施例1,反应结果见表2。
实施例2
1、制备钨掺杂铁酸镧
搅拌条件下,将2.2mol La(NO3)3溶于100mL水中,加入柠檬酸搅拌溶解;再加入4.2mol Fe(NO3)3,再加入含10g偏钨酸铵的水溶液,继续搅拌30min,经烘干、焙烧、研磨得到钨掺杂铁酸镧。
2、制备氧化铝载体
2.2g钨掺杂铁酸镧中加入柠檬酸,将300g拟薄水铝石粉子和20.0g田菁粉加入到捏合机中,并混合均匀,再加入硝酸、8g聚丙烯酸钠,捏合均匀,然后加入钨掺杂铁酸镧,混合均匀,经过捏合-挤条成型为三叶草形状。在120℃干燥8小时,700℃焙烧4小时,得到含钨掺杂铁酸镧的氧化铝载体2。载体孔结构如表1。
3、制备催化剂
将七钼酸铵和硝酸钴加入到蒸馏水中,配成浸渍液浸渍氧化铝载体,得到的催化剂前躯体在140℃烘干后,在650℃焙烧7h,得到催化剂2。催化剂2主要组成:含钨掺杂铁酸镧的氧化铝载体为81.2WT%,氧化钴含量为6.3WT%,氧化钼含量为12.5WT%。
实施例3
载体的制备同实施例1,所不同的是微介孔钨掺杂铁酸镧占载体6wt%。催化剂的制备同实施例1,催化剂3主要组成:微介孔钨掺杂铁酸镧的氧化铝载体为78.8wt%,氧化钴含量为11.5wt%,氧化钼含量为9.7wt%。
实施例4
制备改进型氧化铝载体
2g聚丙烯酸钠溶于硝酸中,再加入28g硅微粉,搅拌均匀,得到硅微粉-聚丙烯酸钠混合物,取1/10的量备用,2.0g微介孔钨掺杂铁酸镧中加入柠檬酸备用。将310g拟薄水铝石粉子和22.0g田菁粉加入到捏合机中,加入硝酸,再加入28g聚丙烯酸钠硝酸溶液,并混合均匀,再加入上述硅微粉-聚丙烯酸钠混合物,捏合均匀,然后加入微介孔钨掺杂铁酸镧,混合均匀,经过捏合-挤条成型为三叶草形状。在130℃干燥7小时,650℃焙烧5小时,得到微介孔钨掺杂铁酸镧和氧化硅的氧化铝载体4。
催化剂的制备同实施例1,催化剂4主要组成:含微介孔钨掺杂铁酸镧的氧化铝载体为78.0wt%,氧化钴含量为7.4wt%,氧化钼含量为14.6wt%。
实施例5
搅拌条件下,将2.0mol La(NO3)3溶于100mL水中,加入柠檬酸搅拌溶解;再加入4.0mol Fe(NO3)3,再加入含12g偏钨酸铵的水溶液,继续搅拌30min,经烘干、焙烧、研磨得到钨掺杂铁酸镧。
载体的制备同实施例4,所不同的是钨掺杂铁酸镧占载体3wt%。催化剂5主要组成:含钨掺杂铁酸镧和氧化硅的氧化铝载体为78.7wt%,氧化钴含量为10.1wt%,氧化钼含量为11.2wt%。
表1大孔的氧化铝载体比表面积与孔径分布
表2催化剂加氢脱硫反应结果
将加氢脱硫催化剂1-5分别装入10ml固定床绝热反应器中,评价催化剂反应性能。用硫化油对催化剂进行预硫化,硫化油为直馏汽油,硫化剂为CS2,硫化处理结束后,切换为全馏分FCC汽油置换处理7h,待预硫化过程结束后,调整到反应工艺条件,进行催化裂化汽油反应。反应工艺条件为:反应器温度265℃,反应压力1.6MPa,体积空速3.5h-1,氢油体积比325。反应约60h后取样分析,结果如表2所示。
加氢脱硫催化剂1-5辛烷值损失低,烯烃降量小,液体收率高,脱硫率高,活性好,具有良好的加氢脱硫选择性。反应运行600h,加氢脱硫催化剂1和4产品脱硫率为80.3%、82.9%,烯烃降量3.2%、2.4%,辛烷值损失为0.4个单位、0.3个单位,烯烃饱和率(HYD)为10%、8%,积碳率3.1、2.4,液体收率97.7%、98.4%。催化剂能够有效抑制烯烃聚合、过度裂化等副反应发生,提高目的产物选择性,热稳定性好。催化剂的载体表面产生出更多的活性位负载中心,有效提高催化剂脱硫活性,催化剂反应性能稳定。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明的保护范围。
Claims (10)
1.一种加氢脱硫催化剂,其特征在于:催化剂的载体为包含钨掺杂铁酸镧的氧化铝载体,所述氧化铝载体包含0.1~12 wt%的钨掺杂铁酸镧,载体介孔占总孔的1~85%,大孔占总孔的1~70%, 钨掺杂铁酸镧中钨占钨掺杂铁酸镧的0.1~8 wt%,催化剂的组成以氧化物质量计,包括如下组分:含钨掺杂铁酸镧的氧化铝载体70.0-93.5 wt %,活性组分氧化钴3.0-12wt %、氧化钼3.5-18.0 wt %。
2.根据权利要求1所述的加氢脱硫催化剂,其特征在于:所述活性组分氧化钴3.0-10wt %、氧化钼4.5-15.0 wt %。
3.一种如权利要求1所述的加氢脱硫催化剂的制备方法,其特征在于:包括如下步骤:将含钴和含钼的可溶性盐配成浸渍液,浸渍氧化铝载体,在120-180℃下干燥4-8小时,450-800℃下焙烧3-9小时,得到所述加氢脱硫催化剂。
4.根据权利要求1所述的加氢脱硫催化剂,其特征在于:所述氧化铝载体包含0.1~12wt%的氧化硅,0.1~10 wt%的钨掺杂铁酸镧,介孔占总孔的1~80%,大孔占总孔的1~55%,载体中微孔、介孔、大孔不均匀分布。
5.根据权利要求1、2、4任一项所述的加氢脱硫催化剂,其特征在于:所述氧化铝载体中钨掺杂铁酸镧为0.3~9 wt%,钨掺杂铁酸镧中钨占钨掺杂铁酸镧的0.1~8 wt%。
6.根据权利要求1、2、4任一项所述的加氢脱硫催化剂,其特征在于:所述钨掺杂铁酸镧为具有微介孔的钨掺杂铁酸镧。
7.根据权利要求6所述的加氢脱硫催化剂,其特征在于:所述具有微介孔的钨掺杂铁酸镧由以下方法制备而成:将柠檬酸溶于去离子水中搅拌溶解得到柠檬酸溶液,然后将硝酸镧与硝酸铁加入柠檬酸溶液中,搅拌溶解,再加入聚丙烯酸钠或聚丙烯酸,所述聚丙烯酸钠或聚丙烯酸的加入量为钨掺杂铁酸镧的0.1~9wt%,再加入含钨化合物,以氧化物计,钨占钨掺杂铁酸镧的0.1~8 wt%,搅拌,反应后,经干燥、焙烧、研磨得到成品。
8.根据权利要求1所述的加氢脱硫催化剂,其特征在于:所述氧化铝载体的制备方法包括如下步骤:将拟薄水铝石和田菁粉加入到捏合机中混合均匀,然后加入无机酸溶液和有机聚合物,捏合均匀,再加入钨掺杂铁酸镧,捏合均匀后,经过挤条、成型、干燥、焙烧,得到氧化铝载体。
9.根据权利要求4所述的加氢脱硫催化剂,其特征在于:所述氧化铝载体的制备方法包括如下步骤:将拟薄水铝石和田菁粉加入到捏合机中混合均匀,然后加入无机酸溶液和有机聚合物,捏合均匀,再加入钨掺杂铁酸镧,混合均匀得到氧化铝前驱体;
在有机聚合物的酸液中加入硅源硅酸钠或硅微粉,混合均匀得到硅源-有机聚合物混合物,然后与上述氧化铝前驱体混合,经挤条、成型、干燥、焙烧,得到氧化铝载体。
10.根据权利要求9所述的加氢脱硫催化剂,其特征在于:所述氧化铝前驱体中单位含量的有机聚合物比硅源-有机聚合物混合物中有机聚合物的含量高1.5倍以上。
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