CN114192182A - 催化裂化汽油加氢脱硫催化剂及其制备方法与应用 - Google Patents
催化裂化汽油加氢脱硫催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
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- 238000000034 method Methods 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 34
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 7
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 6
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 4
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
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- 239000010703 silicon Substances 0.000 claims description 6
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- 239000001257 hydrogen Substances 0.000 claims description 5
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 3
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
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- 244000282866 Euchlaena mexicana Species 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
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- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical group O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
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- 229910020057 NbOPO4 Inorganic materials 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
本发明公开了一种催化裂化汽油加氢脱硫催化剂及其制备方法与应用。该催化剂包括载体和活性组分;载体为SBA‑15、MCFs及氧化铝的复合物或混合物;活性组分为氧化钼MoO3和氧化钴CoO,其含量分别为10~20wt%和2~5wt%;改性剂为硝酸镁、硼酸、硝酸钾、磷酸和磷酸二氢钾等。本发明中催化剂载体15~20nm的孔径占20%以上,48~53nm的孔径占15%以上,比表面积为400~600m2/g,孔容为1.0~2.0cm3/g,侧压强度大于120N/cm。该催化剂适用于烯烃含量较高的催化汽油加氢脱硫过程,具有脱硫活性高,选择性好,烯烃饱和程度低,辛烷值损失小的优点。
Description
技术领域
本发明涉及一种汽油选择性加氢脱硫催化剂及其制备方法,特别是涉及一种用于催化裂化汽油(FCC汽油)加氢脱硫催化剂及其制备方法与应用,更具体的说是一种用于催化裂化汽油全馏分或者重汽油馏分深度加氢脱硫的催化剂,深度脱硫过程中烯烃饱和少,辛烷值损失小。
背景技术
近年来,雾霾天气笼罩着全国各大城市,给人们的健康和出行造成了很大危害。研究发现,机动车尾气是造成雾霾天气的主要来源之一,且机动车尾气中的硫化物是主要污染物之一。我国汽油构成以FCC汽油组份为主,占80%左右,其特点是高硫、高烯烃及高辛烷值组份不足。而且,随着FCC加工的原料向重质化方向发展,将导致FCC汽油中的硫含量和烯烃含量进一步增高。因此FCC汽油脱硫、降烯烃、保持辛烷值就成为我国清洁汽油生产技术需要解决的关键问题。
在对加氢脱硫催化剂的长期研究过程中,载体的研究是重点之一。对于负载型催化剂,载体对催化剂的催化性能有着重要的影响。载体不仅需要提供较大的比表面积,使催化剂的活性组分得到充分利用,降低经济成本,而且还可通过与活性组分发生相互作用来改善催化剂的性能,如可作为催化剂的骨架,提高其稳定性和机械强度,并保证催化剂有一定的形状和大小,使之符合工业反应器中流体力学条件的需要,减少流体流动阻力等众多优点。目前,最常用的催化剂载体有γ-Al2O3、活性炭和分子筛等。近年来,研究发现以SBA-15、介孔二氧化硅泡沫材料(MCFs)等介孔材料与ZSM-5、Beta等微孔材料混合或者复合作为载体。CN106433758A公开了一种FCC汽油加氢脱硫工艺,所述催化剂包括载体和活性组分;所述载体为MSU-G、SBA-15和HMS的复合物或混合物,所述的催化剂还含有催化助剂,所述催化助剂为Cr2O3、ZrO2、CeO2、V2O5和NbOPO4的混合物。该工艺可以将FCC汽油中的总硫含量降低到5ppm以下,以满足汽油国五标准。同时,该工艺还使得FCC汽油的辛烷值不明显降低。但是,该方法制备的载体材料为简单混合或者复合,不能形成渐变的梯级孔结构,载体材料合成有进一步提升的空间。
发明内容
本发明的目的在于提供一种催化裂化汽油加氢脱硫催化剂的制备方法,通过该制备方法得到的催化剂具有高脱硫活性以及高脱硫选择性。
为达上述目的,本发明提供一种催化裂化汽油加氢脱硫催化剂的制备方法,包括以下步骤:
步骤1:以F127或P123为模板剂,在酸性环境下加入硅源、扩孔剂以及去离子水,经晶化、焙烧,得到SBA-15和MCFs复合载体,将复合载体与氧化铝粉末混捏、挤条成型,100-150℃干燥3-6h,550-750℃焙烧3-6h,制得催化剂载体;
步骤2:使用改性剂对催化剂载体进行改性;
步骤3:将活性组分溶解于络合剂中,配成活性金属组分络合溶液,使用活性金属组分络合溶液等体积浸渍催化剂载体,静置6-12h,经100-150℃干燥3-6h,400-600℃焙烧3-6h后,制得催化裂化汽油加氢脱硫催化剂。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,催化剂载体中SBA-15含量为28~44wt%、MCFs含量为26~44wt%以及氧化铝含量为6~19wt%。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,活性组分为钴盐和钼盐,钴盐为碱式碳酸钴、硝酸钴、氧化钴和乙酸钴中的至少一种,钼盐为钼酸铵和氧化钼中的至少一种。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,钼盐为氧化钼MoO3,钴盐为氧化钴CoO,含量分别为10~20wt%和2~5wt%。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,MoO3含量为10~15wt%,CoO含量为2.5~3.5wt%。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,改性剂为硝酸镁、硼酸、硝酸钾、磷酸和磷酸二氢钾中的至少一种。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,络合剂为柠檬酸、氨水和磷酸中的至少一种。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,催化剂载体15~20nm的孔径占20%以上,48~53nm的孔径占15%以上,比表面积为400~600m2/g,孔容为1.0~2.0cm3/g,侧压强度大于120N/cm。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,催化剂比表面积为480~520m2/g,孔容为1.5~1.8cm3/g,15~20nm的孔径占20%以上,48~53nm的孔径占15%以上。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,步骤1中,酸性环境为pH 1~3,晶化温度为100~200℃,晶化时间为24h,焙烧温度为400~600℃,焙烧时间为6h。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,硅源为正硅酸四乙酯、水玻璃、硅胶和硅酸钠中的至少一种;扩孔剂为己烷、环己烷、1,3,5-三异丙基苯和均三甲苯中至少一种,加入量为模板剂的30~60wt%。
本发明的催化裂化汽油加氢脱硫催化剂的制备方法,优选地,硅源为正硅酸四乙酯,加入量为模板剂的10~50wt%。
本发明还提供一种催化裂化汽油加氢脱硫催化剂,该催化剂由上述催化裂化汽油加氢脱硫催化剂的制备方法制得。
本发明又提供一种催化裂化汽油加氢脱硫催化剂的应用,选用上述催化裂化汽油加氢脱硫催化剂用于催化汽油或催化重汽油加氢脱硫反应,加氢脱硫反应条件为氢气压力1.5-2.5MPa、温度200-280℃、空速2.0-4.0h-1以及氢油比200:1-500:1。
本发明的催化裂化汽油加氢脱硫催化剂的应用,优选地,催化裂化汽油或催化重汽油的硫含量小于1000mg/kg,烯烃含量小于45v%,产品调和组分硫含量小于15mg/kg,烯烃含量降低小于10v%,辛烷值损失小于2.0。
介孔分子筛SBA-15具有高的比表面积,良好的水热稳定性和较大的孔径,有利于油品分子在其孔道内的扩散;MCFs是一种具有超大孔径、孔径分布均一、较大孔容以及较高比表面的新型介孔材料,将两种不同孔径大小和孔道结构的介孔材料与氧化铝粉末混合或者复合在一起,能够改变加氢精制催化剂的酸性,提高活性组分分散度,促进金属组分的还原硫化。因此,制备高比表面积、具有梯级孔结构和稳定性良好的介孔复合载体将成为提高加氢精制催化剂活性的一条重要途径。
本发明有如下优点:
(1)本发明提供的催化裂化汽油加氢脱硫催化剂中,SBA-15是一种具有体心立方结构的介孔材料;MCFs是一种具有超大孔径、孔径分布均一、较大孔容、较高比表面的新型介孔材料,将两种介孔材料与氧化铝复合或混合,形成梯级孔结构,孔径在15~20nm占20%以上,孔径在48~53nm占15%以上,能够实现加氢精制效果的协同提升。
(2)本发明提供的催化裂化汽油加氢脱硫催化剂,金属含量低,脱硫选择性高,针对富含烯烃的催化汽油,脱硫过程中烯烃饱和少,辛烷值损失小,起到了良好的加氢改质效果。
附图说明
图1为本发明实施例1的复合载体材料孔径分布曲线图;
图2为本发明实施例1的复合载体材料SEM图。
从图1中可以看出,所合成的复合载体材料孔径呈现梯级孔结构,且分布相对集中,大部分孔径集中在18nm和55nm之间。
从图2中可以看出,所合成的复合载体材料呈现出分散度较高的球形颗粒形貌。
具体实施方式
实施例1:
MCFs-SBA-15/Al2O3复合载体的制备
①以P123为模板剂,称取40g去离子水、60g一定浓度盐酸和2g P123模板剂,水浴35℃条件下搅拌直至形成均一溶液;
②称取模板剂30wt%的扩孔剂均三甲苯缓慢地滴加入到溶液①中,并继续水浴搅拌;
③称取模板剂10wt%的正硅酸四乙酯(TEOS),缓慢滴加到溶液②中,并置于密封环境中继续水浴搅拌,之后转入晶化釜并放置于120℃烘箱中晶化24h;
④待晶化过程结束后,取出晶化釜进行冷却水冷却处理,并将产物过滤、洗涤,120℃条件下干燥约6h,并于550℃马弗炉中焙烧6h即可得到介孔复合材料。
将模板剂1wt%的硝酸镁溶解在去离子水中,配成稳定的改性溶液,然后对催化剂载体进行改性。
将SBA-15-MCFs复合材料和氧化铝混合共100g,混合比例是2.1:0.4,加入3g田菁粉、5g硝酸、2.5g柠檬酸、100ml去离子水,混捏均匀,在单螺杆挤条机上用叶草孔板挤条,放置3h后120℃烘干4h,制得催化剂载体。
Co-Mo共浸液的配制及催化剂制备
按照等体积浸渍方法进行活性组分浸渍液的配制。首先称取50ml氨水,然后加入7.4gEDTA、7.4g碱式碳酸钴、5.6g钼酸铵搅拌至溶解,再加入9.6g硝酸镁,最后用氨水进行定容到78mL。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收活性组分浸渍液,然后放置12h后,对催化剂进行120℃干燥4h,在500℃下焙烧4h,制得加氢脱硫催化剂样品cat-1。
实施例2:
MCFs-SBA-15/Al2O3复合载体的制备
①以F127为模板剂,称取40g去离子水、60g一定浓度盐酸和2g F127模板剂,水浴35℃条件下搅拌直至形成均一溶液;
②称取模板剂30wt%的扩孔剂己烷缓慢地滴加入到溶液①中,并继续水浴搅拌;
③称取模板剂30wt%的水玻璃,缓慢滴加到溶液②中,并置于密封环境中继续水浴搅拌,之后转入晶化釜并放置于120℃烘箱中晶化24h;
④待晶化过程结束后,取出晶化釜进行冷却水冷却处理,并将产物过滤、洗涤,120℃条件下干燥约12h,并于550℃马弗炉中焙烧6h即可得到SBA-15-MCFs复合材料。
⑤将复合材料3wt%的硼酸溶解在去离子水中,配成稳定的改性溶液,然后对催化剂载体进行改性。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收改性剂浸渍液,然后放置12h后,对材料进行120℃干燥4h,在500℃下焙烧4h,制得改性后复合材料。
⑥将SBA-15-MCFs复合材料和氧化铝混合共100g,混合比例是2.1:0.4,加入3g田菁粉、5g硝酸、2.5g柠檬酸、100ml去离子水,混捏均匀,在单螺杆挤条机上用叶草孔板挤条,放置3h后120℃烘干4h,制得催化剂载体。
Co-Mo共浸液的配制及催化剂制备
按照等体积浸渍方法进行活性组分浸渍液的配制。首先称取50ml氨水,然后加入7.4gEDTA、7.4g硝酸钴、5.6g氧化钼搅拌至溶解,再加入9.6g硝酸镁,最后用氨水进行定容到78mL。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收活性组分浸渍液,然后放置12h后,对催化剂进行120℃干燥4h,在500℃下焙烧4h,制得加氢脱硫催化剂样品cat-2。
实施例3:
MCFs-SBA-15/Al2O3复合载体的制备
①以F127为模板剂,称取40g去离子水、60g一定浓度盐酸和2g F127模板剂,水浴35℃条件下搅拌直至形成均一溶液;
②称取模板剂30wt%的扩孔剂己烷缓慢地滴加入到溶液①中,并继续水浴搅拌;
③称取模板剂50wt%的硅酸钠,缓慢滴加到溶液②中,并置于密封环境中继续水浴搅拌,之后转入晶化釜并放置于120℃烘箱中晶化24h;
④待晶化过程结束后,取出晶化釜进行冷却水冷却处理,并将产物过滤、洗涤,120℃条件下干燥约12h,并于550℃马弗炉中焙烧6h即可得到SBA-15-MCFs复合材料。
⑤将复合材料5wt%的硝酸钾溶解在去离子水中,配成稳定的改性溶液,然后对催化剂载体进行改性。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收改性剂浸渍液,然后放置12h后,对材料进行120℃干燥4h,在500℃下焙烧4h,制得改性后复合材料。
⑥将SBA-15-MCFs复合材料和氧化铝混合共100g,混合比例是2.1:0.4,加入3g田菁粉、5g硝酸、2.5g柠檬酸、100ml去离子水,混捏均匀,在单螺杆挤条机上用叶草孔板挤条,放置3h后120℃烘干4h,制得催化剂载体。
Co-Mo共浸液的配制及催化剂制备
按照等体积浸渍方法进行活性组分浸渍液的配制。首先称取50ml氨水,然后加入7.4gEDTA、7.4g乙酸钴、5.6g钼酸铵搅拌至溶解,再加入9.6g硝酸镁,最后用氨水进行定容到78mL。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收活性组分浸渍液,然后放置12h后,对催化剂进行120℃干燥4h,在500℃下焙烧4h,制得加氢脱硫催化剂样品cat-3。
实施例4:
MCFs-SBA-15复合载体的制备
①以F127为模板剂,称取40g去离子水、60g一定浓度盐酸和2g F127模板剂,水浴35℃条件下搅拌直至形成均一溶液;
②称取模板剂45wt%的扩孔剂己烷缓慢地滴加入到溶液①中,并继续水浴搅拌;
③称取模板剂50wt%的硅酸钠,缓慢滴加到溶液②中,并置于密封环境中继续水浴搅拌,之后转入晶化釜并放置于120℃烘箱中晶化24h;
④待晶化过程结束后,取出晶化釜进行冷却水冷却处理,并将产物过滤、洗涤,120℃条件下干燥约12h,并于550℃马弗炉中焙烧6h即可得到SBA-15-MCFs复合材料(比例控制为1:1.1)。
⑤将复合材料5wt%的硝酸钾溶解在去离子水中,配成稳定的改性溶液,然后对催化剂载体进行改性。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收改性剂浸渍液,然后放置12h后,对材料进行120℃干燥4h,在500℃下焙烧4h,制得改性后复合材料。
⑥将SBA-15-MCFs复合材料100g与3g田菁粉、5g硝酸、2.5g柠檬酸、100ml去离子水,混捏均匀,在单螺杆挤条机上用叶草孔板挤条,放置3h后120℃烘干4h,制得催化剂载体。
Co-Mo共浸液的配制及催化剂制备
按照等体积浸渍方法进行活性组分浸渍液的配制。首先称取50ml氨水,然后加入7.4gEDTA、7.4g乙酸钴、5.6g钼酸铵搅拌至溶解,再加入9.6g硝酸镁,最后用氨水进行定容到78mL。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收活性组分浸渍液,然后放置12h后,对催化剂进行120℃干燥4h,在500℃下焙烧4h,制得加氢脱硫催化剂样品cat-4。
实施例5:
①以F127为模板剂,称取40g去离子水、60g一定浓度盐酸和2g F127模板剂,水浴35℃条件下搅拌直至形成均一溶液;
②称取模板剂50wt%的硅酸钠,缓慢滴加到溶液②中,并置于密封环境中继续水浴搅拌,之后转入晶化釜并放置于120℃烘箱中晶化24h;
③待晶化过程结束后,取出晶化釜进行冷却水冷却处理,并将产物过滤、洗涤,120℃条件下干燥约12h,并于550℃马弗炉中焙烧6h即可得到SBA-15。
④将SBA-15载体材料5wt%的硝酸钾溶解在去离子水中,配成稳定的改性溶液,然后对催化剂载体进行改性。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收改性剂浸渍液,然后放置12h后,对材料进行120℃干燥4h,在500℃下焙烧4h,制得改性后SBA-15。
⑤将SBA-15和氧化铝混合共100g,混合比例是1:0.4,加入3g田菁粉、5g硝酸、2.5g柠檬酸、100ml去离子水,混捏均匀,在单螺杆挤条机上用叶草孔板挤条,放置1-4h后120℃烘干4h,制得载体粉末。
Co-Mo共浸液的配制及催化剂制备
按照等体积浸渍方法进行活性组分浸渍液的配制。首先称取50ml氨水,然后加入7.4gEDTA、7.4g乙酸钴、5.6g钼酸铵搅拌至溶解,再加入9.6g硝酸镁,最后用氨水进行定容到78mL。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收活性组分浸渍液,然后放置12h后,对催化剂进行120℃干燥4h,在500℃下焙烧4h,制得加氢脱硫催化剂样品cat-5。
实施例6:
MCFs载体的制备
①以F127为模板剂,称取40g去离子水、60g一定浓度盐酸和2g F127模板剂,水浴35℃条件下搅拌直至形成均一溶液;
②称取模板剂60wt%的扩孔剂己烷缓慢地滴加入到溶液①中,并继续水浴搅拌;
③称取模板剂50wt%的硅酸钠,缓慢滴加到溶液②中,并置于密封环境中继续水浴搅拌,之后转入晶化釜并放置于120℃烘箱中晶化24h;
④待晶化过程结束后,取出晶化釜进行冷却水冷却处理,并将产物过滤、洗涤,120℃条件下干燥约12h,并于550℃马弗炉中焙烧6h即可得到MCFs载体材料。
⑤将复合材料5wt%的硝酸钾溶解在去离子水中,配成稳定的改性溶液,然后对催化剂载体进行改性。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收改性剂浸渍液,然后放置12h后,对材料进行120℃干燥4h,在500℃下焙烧4h,制得改性后MCFs。
⑥将MCFs载体材料100g与3g田菁粉、5g硝酸、2.5g柠檬酸、100ml去离子水,混捏均匀,在单螺杆挤条机上用叶草孔板挤条,放置3h后120℃烘干4h,制得催化剂载体。
Co-Mo共浸液的配制及催化剂制备
按照等体积浸渍方法进行活性组分浸渍液的配制。首先称取50ml氨水,然后加入7.4gEDTA、7.4g乙酸钴、5.6g钼酸铵搅拌至溶解,再加入9.6g硝酸镁,最后用氨水进行定容到78mL。采用等体积浸渍方法对载体进行浸渍,使催化剂载体充分吸收活性组分浸渍液,然后放置12h后,对催化剂进行120℃干燥4h,在500℃下焙烧4h,制得加氢脱硫催化剂样品cat-6。
实施例7:
采用实施例5中方法合成载体SBA-15,不再与氧化铝混合,其他条件不变,制得加氢脱硫剂样品cat-7。
实施例8:
采用实施例6中方法合成载体MCFs,不再与氧化铝混合,其他条件不变,制得加氢脱硫催化剂样品cat-8。
实施例9:
将实施例1中的载体改为氧化铝,其他条件不变,制得加氢脱硫催化剂样品cat-9。
由以上实施例所制备的催化裂化汽油加氢脱硫催化剂,具有梯级孔结构,15~20nm的孔径占20%以上,48~53nm的孔径占15%以上,比表面积为480~520m2/g,孔容为1.5~1.8cm3/g,可用于FCC汽油加氢脱硫过程。
催化剂的评价过程:将催化裂化汽油加氢脱硫剂装入固定床反应器中。首先对其进行预硫化,硫化油为含3wt%CS2的直馏汽油,硫化压力2.0MPa、氢油体积比300:1,230℃硫化处理8h,然后升温到320℃,然后在320℃下硫化处理约8h。硫化结束后,进原料油进行反应,原料油性质见表1,反应条件见表2。各实施例操作工艺条件相同(结果见表3和表4)。
表1催化裂化全馏分及重汽油馏分性质
表2操作工艺条件
工艺条件 | 全馏分催化汽油 | 重汽油 |
反应温度(℃) | 250 | 260 |
反应压力(MPa) | 2.0 | 2.0 |
体积空速(h<sup>-1</sup>) | 3.0 | 3.0 |
氢油比(V/V) | 400:1 | 400:1 |
表3实施例数据
表4实施例数据
表5催化剂的性质
结果表明:在表2所列工艺条件下,用cat-1处理全馏分汽油和重汽油,分别对其进行加氢脱硫,全馏分催化汽油硫含量由731.8mg/kg降至20mg/kg以下,且辛烷值基本不降低,重汽油硫含量由777.6mg/kg降至50mg/kg以下,辛烷值损失2个单位左右。说明该复合载体材料原料适应性强,与单一介孔材料载体相比(即cat-7~cat-9),本发明中提供的复合载体材料催化剂更适合用于催化汽油原料进行加氢改质。
当然,本发明还可有其他多种实施例,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所附的权利要求的保护范围。
Claims (13)
1.一种催化裂化汽油加氢脱硫催化剂的制备方法,其特征在于,包括以下步骤:
步骤1:以F127或P123为模板剂,在酸性环境下加入硅源、扩孔剂以及去离子水,经晶化、焙烧,得到SBA-15和MCFs复合载体,将复合载体与氧化铝粉末混捏、挤条成型,100-150℃干燥3-6h,550-750℃焙烧3-6h,制得催化剂载体;
步骤2:使用改性剂对催化剂载体进行改性;
步骤3:将活性组分溶解于络合剂中,配成活性金属组分络合溶液,使用活性金属组分络合溶液等体积浸渍催化剂载体,静置6-12h,经100-150℃干燥3-6h,400-600℃焙烧3-6h后,制得催化裂化汽油加氢脱硫催化剂。
2.根据权利要求1所述的催化裂化汽油加氢脱硫催化剂的制备方法,其特征在于,所述步骤1中,酸性环境为pH 1~3,晶化温度为100~200℃,晶化时间为24h,焙烧温度为400~600℃,焙烧时间为6h。
3.根据权利要求1所述的催化裂化汽油加氢脱硫催化剂的制备方法,其特征在于,所述扩孔剂为己烷、环己烷、1,3,5-三异丙基苯和均三甲苯中的至少一种,加入量为模板剂的30~60wt%。
4.根据权利要求1所述的催化裂化汽油加氢脱硫催化剂的制备方法,其特征在于,所述硅源为正硅酸四乙酯、水玻璃、硅胶和硅酸钠中的至少一种,加入量为模板剂的10~50wt%。
5.根据权利要求1所述的催化裂化汽油加氢脱硫催化剂的制备方法,其特征在于,所述改性剂为硝酸镁、硼酸、硝酸钾、磷酸和磷酸二氢钾中的至少一种。
6.根据权利要求1所述的催化裂化汽油加氢脱硫催化剂的制备方法,其特征在于,所述络合剂为柠檬酸、氨水和磷酸中的至少一种。
7.一种催化裂化汽油加氢脱硫催化剂,其特征在于,由权利要求1-6任一所述的催化裂化汽油加氢脱硫催化剂的制备方法制得,该催化剂具有梯级孔结构,15~20nm的孔径占20%以上,48~53nm的孔径占15%以上,比表面积为480~520m2/g,孔容为1.5~1.8cm3/g。
8.根据权利要求7所述的催化裂化汽油加氢脱硫催化剂,其特征在于,所述催化剂的复合载体中SBA-15含量为28~44wt%、MCFs含量为26~44wt%以及氧化铝含量为6~19wt%。
9.根据权利要求7所述的催化裂化汽油加氢脱硫催化剂,其特征在于,所述催化剂的复合载体比表面积为400~600m2/g,孔容为1.0~2.0cm3/g,15~20nm的孔径占20%以上,48~53nm的孔径占15%以上。
10.根据权利要求7所述的催化裂化汽油加氢脱硫催化剂,其特征在于,所述活性组分为钴盐和钼盐,钴盐为碱式碳酸钴、硝酸钴、氧化钴和乙酸钴中的至少一种,所述钼盐为钼酸铵和氧化钼中的至少一种。
11.根据权利要求10所述的催化裂化汽油加氢脱硫催化剂,其特征在于,所述钼盐为氧化钼MoO3,含量为10~20wt%;所述钴盐为氧化钴CoO,含量为2~5wt%。
12.一种催化裂化汽油加氢脱硫催化剂的应用,其特征在于,选用权利要求7-11任一所述的催化裂化汽油加氢脱硫催化剂用于催化裂化汽油或催化裂化重汽油加氢脱硫反应,催化裂化重汽油由催化裂化汽油按照切割比3:7切割所得,切割温度为52℃,所述加氢脱硫反应条件为氢气压力1.5-2.5MPa、温度200-280℃、空速2.0-4.0h-1以及氢油比200:1-500:1。
13.根据权利要求12所述的催化裂化汽油加氢脱硫催化剂的应用,其特征在于,所述催化裂化汽油或催化裂化重汽油的硫含量小于1000mg/kg,烯烃含量小于45v%,将切割出的轻汽油与重汽油产品按照比例调合,调和组分硫含量小于15mg/kg,烯烃含量降低小于10v%,辛烷值损失小于2.0。
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