CN105772070A - 一种用于汽油非临氢改质的催化剂及其制备方法 - Google Patents
一种用于汽油非临氢改质的催化剂及其制备方法 Download PDFInfo
- Publication number
- CN105772070A CN105772070A CN201610099508.0A CN201610099508A CN105772070A CN 105772070 A CN105772070 A CN 105772070A CN 201610099508 A CN201610099508 A CN 201610099508A CN 105772070 A CN105772070 A CN 105772070A
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- Prior art keywords
- catalyst
- molecular sieve
- gasoline
- hydrogen
- modification
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
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- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims description 25
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- 238000000034 method Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 25
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- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
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- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
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- 244000275012 Sesbania cannabina Species 0.000 claims 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
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- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
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- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- 239000004411 aluminium Substances 0.000 description 2
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- 238000004090 dissolution Methods 0.000 description 2
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- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 229940084478 ganite Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
本发明提供了一种用于汽油非临氢改质的催化剂及其制备方法。该催化剂包括:主要由分子筛和粘结剂制成的载体;以及负载在所述载体上的非主族金属元素;所述分子筛的晶粒尺寸为300nm‑600nm,所述分子筛在所述载体中的重量百分比为5%‑85%。本发明用于汽油非临氢改质时,具有能同时提高脱硫率和辛烷值、汽油收率高等优点。
Description
技术领域
本发明涉及汽油加工领域,具体而言,涉及一种用于汽油非临氢改质的催化剂及其制备方法。
背景技术
超低硫含量和高辛烷值是评价高质量汽油的两个重要指标。一直以来,我国炼油企业催化重整、烷基化、醚化、异构化等装置的总加工能力较低,汽油组分来源相对单一,主要为催化裂化汽油,而催化裂化汽油中烯烃含量高,其烯烃体积分数为45%~50%,远高于35%的新配方汽油标准。烯烃化学性质活泼,一方面挥发后和大气中的NOx经太阳紫外线照射,会形成以臭氧为主的有毒化学烟雾,对大气造成严重污染;另一方面由于烯烃不稳定,易在发动机及其进气系统形成焦质和积炭,影响发动机的正常运转。然而降低汽油中烯烃的含量会导致汽油辛烷值的降低,因此在降低催化裂化汽油中烯烃含量的同时,保持或提高汽油辛烷值已成为目前汽油生产面临的首要问题。
同时,随着人们对环保意识的增强,车用燃料油的清洁化备受关注。各国制定日益严格的汽车尾气排放标准,要求生产更环保的超低硫汽油。我国2014年已执行国Ⅳ标准汽油,并将在2017年起执行小于10μg·g-1的超低硫汽油国Ⅴ标准。国外正在开发或已经应用的汽油脱硫工艺主要有:IRVAD工艺、SARS工艺和S-Zorb工艺。
其中,IRVAD工艺[IRVINE R Process for desulfurizing gasolineand hydrocarbon feedstocks:USP5730860[P].1998-03-24.]由Black&Veatch Pritchard Inc与Alcon Industrial Chemicals联合开发,据称该工艺是从烃类中低成本脱除含硫或其他杂原子化合物的一项突破性技术,该技术采用多级流化床吸附方式,使用氧化铝基质固体吸附剂(粒径为0.4~1.6mm),吸附剂在床层中所占体积分数为8%~16%,该吸附剂经过无机促进剂改性,提高了对极性氮和硫化物,包括硫醇、二硫化物、噻吩和腈类等的吸附容量,其脱硫率达90%以上,含氮化合物几乎全部脱除,该工艺整套装置包括公用工程系统在内的投资估算为10.4美元/(t.a)。
SARS工艺系由美国宾夕法尼亚大学能源研究所开发的选择性吸附脱硫技术,可将液体燃料的硫含量减至1μg/g。这项仍处在实验室放大规模,该技术采用过渡金属或其化合物选择性吸附液体燃料中的硫。吸附在常温、常压下进行,吸附剂用溶剂洗涤法再生。该工艺使用基于过渡金属的吸附剂,负载于诸如MCM-41分子筛等多孔固体载体上。该吸附剂在饱和前,可净化10倍于其体积的燃料,一旦吸附饱和,可用极性溶剂将硫化物洗涤脱除而使吸附剂再生,吸附剂可以重复使用[MA Xiaoliang,SUN Lu,SONG Chunshan.Anew approach to deep desulfurization of gasoline,diesel fuel and jetfuel by selective adsorption for ultra-clean fuels and for fuel cellapplications[J].Catalysis Today,2002,77(1/2):107-116.]。
催化汽油吸附脱硫(S-Zorb)技术,是美国康菲公司(COP)在气相脱硫(Z-Sorb)技术基础上,研究开发的一种催化汽油或柴油脱硫工艺技术,也是第一种投入工业应用的吸附脱硫技术。该技术采用吸附反应工艺技术原理,可在辛烷值损失较小情况下,使汽油产品硫含量降至10μg/g以下。它组合了流化床反应器和连续再生技术,是目前工业化推广较好的吸附脱硫技术。S-Zorb工艺使用Phillips公司开发的专利吸附剂。2007年,中国石化独家买断了康菲公司的S-Zorb专利技术,从此开始全面负责该技术的后续研发、工程设计、面向全球的技术转让和技术服务等工作。S-Zorb技术与其他吸附脱硫技术相比具有以下特点:①辛烷值损失低;②体积损失少;③硫可脱到10μg/g以下;④无需传统加氢所消耗的氢气量,且氢气纯度要求不高,70%的氢气纯度也可运转;⑤运转费用少,运转周期长。
综上可知,以上几种工艺虽然可以实现深度脱硫,但是或多或少会降低辛烷值。由此可见,迫切需要开发一种兼顾深度脱硫和提高辛烷值的技术。
有鉴于此,特提出本发明。
发明内容
本发明的第一目的在于提供一种用于汽油非临氢改质的催化剂,所述催化剂用于汽油非临氢改质时,具有能同时提高脱硫率和辛烷值、汽油收率高等优点。
本发明的第二目的在于提供一种所述的用于汽油非临氢改质的催化剂的制备方法,所述的制备方法具有流程简单、金属利用率高、更易推广等优点。
为了实现本发明的上述目的,特采用以下技术方案:
一种用于汽油非临氢改质的催化剂,包括:主要由分子筛和粘结剂制成的载体;以及负载在所述载体上的非主族金属元素;
所述分子筛的晶粒尺寸为300nm-600nm,所述分子筛在所述载体中的重量百分比为5%-85%。
与现有技术相比,本发明的区别在于采用中尺寸纳米的分子筛作为载体。分子筛为结晶态的硅酸盐或硅铝酸盐,是由硅氧四面体或铝氧四面体通过氧桥键相连而形成分子2nm以下的孔道和空腔体系,其以5%-85%的比例制成载体,并负载非主族金属元素后可以获得优异的催化性能,即用于汽油的非临氢改质时,在实现深度脱硫的情况下还能提高辛烷值,打破现有技术的局限性,实现了技术突破。更重要的是,本发明用于非临氢改质时汽油损失率仅在10%以下,工艺成本没有增加,甚至低于现有技术。经统计,上述催化剂用于固定床非临氢改质时,脱硫率可达到95%以上,辛烷值提高值可达到15以上。
本发明对分子筛的孔道结构和组成没有任何限制,可以含有硅、铝元素中的任一种及组合或不含硅、铝成分,对分子筛的孔径也不做任何限定,而且分子筛本身具有均匀的微孔,孔径与一般分子大小相当。一般分子大小中所说的分子,包括所有已知的有机物和无机物,也包括这些有机物或无机物的聚集体。分子大小可以采用X射线衍射法测定,也可以采用计算机模拟的方式计算或估算。
本发明提到的载体,其外形可以是条状、球状、锭状,也可以是环状、三叶状、蜂窝状、纤维状,甚至是微球状,对载体的外形,本发明不做任何限定。
本发明提到的非主族元素包括元素周期表中副族元素和VIII族元素,包括常见的钛、铬、锰、铜、锌、铁、钴、镍、镓、镉等,也包括铂、铑、钯、钌、银、金等贵金属元素,本发明对非主族元素不做任何限定。可以是单独的一种,也可以是两种或多种元素同时存在,本发明对各元素在催化剂上的用量不做任何限定,对多种元素的之间的用量比例也不做任何限定。金属元素的负载量一方面受制备工艺的限制,一方面应实际需求而定,理论上,其负载量越高催化剂活性越高。
另外,上述催化剂还可以进一步改进:
优选地,所述分子筛为硅铝型分子筛,并且含有10元环或扭曲(即非平面)12元环,具有三维孔道结构。
具备以上结构特征的分子筛的特点是:具有合适的孔径范围、三维孔道结构,孔容、比表面积、活性都较高。更优选为Pentasil分子筛、MFI族分子筛ZSM-5、MEL族分子筛ZSM-11、含有扭曲12元环的BEA族分子筛beta中的一种或多种。
优选地,所述粘结剂为拟薄水铝石、田菁粉、高岭土、凹凸棒中的一种或多种,优选为拟薄水铝石。
以上粘结剂除了具有粘结作用外,还可以提高载体的强度,并且具有耐热性,也不会过多降低分子筛的催化活性,而且干燥后的载体稳定性高。
优选地,所述非主族金属元素为VIII族或IIB族元素,优选为铁、钴、镍、锌、镓、镉中的一种或多种,更优选为镍、锌、镓、镉中的一种或多种。
相比之下,这几种金属元素的成本低,且具有不同的价态变化、d电子的数量和电子形态,催化性能更优异。在负载金属元素时,其前驱态可以是任意可用的化合物,比较常见的是金属盐,本发明对此不作限制。
优选地,所述载体的原料还包括耐热无机氧化物、成型助剂、增强剂中的一种或多种。
在实际制备载体时,为了降低载体的成型难度或者提高载体的强度、耐热等物化性能,可以适当加入耐热无机氧化物、成型助剂、增强剂等助剂,这些助剂既可以采用常规的种类,也可以采用新型的化合物或其它原料,助剂的添加量应实际需要而定,本发明均不作限定。
优选地,所述分子筛与所述粘结剂的重量比为5-85:15-95,优选为30-80:20-70,更优选40-75:25-60,更优选2.7-3.6:1。
分子筛与粘结剂的比例不同时,脱硫率、辛烷值提高量、汽油收率均会有相应变化。总体而言,分子筛占主要部分时,以上三个指标能取得最佳组合水平。
优选地,所述分子筛的晶粒尺寸为300nm-450nm,更优选350-380nm;所述非主族金属元素的前驱态的粒径优选在100nm以下。
同样,分子筛的晶粒尺寸对脱硫率、辛烷值提高量、汽油收率也有重要影响,当其尺寸为300nm-450nm时,脱硫率和辛烷值都较高,尤其以350-380nm的尺寸为最佳。
另外,金属元素的前驱态粒径越小,其活性态含量越高,催化剂的活性也就越高。
本发明的上述催化剂可以采用任意能实现的方法制成,例如以滚球法、压片法、混捏挤条法或者喷雾法制造载体,以浸渍法、喷淋法、再分散法、嫁接法负载金属,或者在载体成型过程中直接添加进去金属元素而一步制成催化剂。下文仅提供其中一种性价较高的制备方法,包括下列步骤:
步骤A:按照配方,取所述载体的所有原料混合,并加入溶剂溶解,再采用混捏挤条法挤条,再依次经过烘干、焙烧,得到载体;
步骤B:取含所述非主族金属元素的化合物,将其制成溶液,然后采用孔饱和法浸渍在所述载体上,再依次经过烘干、焙烧,得到催化剂。
由于目前汽油加工领域所用的催化剂主要采用混捏挤条设备,因此本发明采用混捏挤条法,企业无需更换制造设备,极容易推广本发明的产品。
另外,孔饱和法对金属的利用率高,且容易形成合适的活性相,制得的催化剂质量更高。
综上可知,以上制备方法具有流程简单、金属利用率高、更易推广等优点。
该制备方法也可以进一步优化:
优选地,所述步骤A中烘干的条件为:在120-150℃下烘干5-6h,焙烧的条件为:在550-620℃下焙烧2.5-4h。
烘干和焙烧对载体的晶体形态非常重要,采用以上条件可以获得孔容大、比表面积大、微孔更均匀规则的载体。
同样,为了获得更好物理形态的载体,所述步骤B中焙烧的条件优选为:在350-450℃下焙烧3-4h。
另外,本发明的催化剂可用于多种改质工艺,尤其用于固定床非临氢改质时催化效果较好。当然,针对不同原料以及所需的目标产物,反应条件有所不同。
与现有技术相比,本发明的有益效果为:
(1)脱硫率高;
(2)可以提高辛烷值;
(3)汽油收率高。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
取颗粒大小为300nm的分子筛纳米beta(中国石化催化剂建长分公司产)185.1g,加入SASOL的干胶粉SB粉134.2g,混合均匀后,添加2.5%的稀硝酸溶液260mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于550℃下焙烧3h,取出,取硝酸镍20.5g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于420℃下焙烧3h。
实施例2
取颗粒大小为380nm的分子筛纳米ZSM-5239.5g,加入SASOL的干胶粉SB粉67.1g,混合均匀后,添加2.5%的稀硝酸溶液275mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于600℃下焙烧2.5h,取出,取硝酸镓6.96g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于400℃下焙烧3.5h。
实施例3
取颗粒大小为450nm的分子筛纳米ZSM-5136.3g,加入SASOL的干胶粉SB粉184.5g,混合均匀后,添加2.5%的稀硝酸溶液250mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于580℃下焙烧3h,取出,取六水硝酸锌17.5g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于450℃下焙烧3h。
实施例4
取颗粒大小为350nm的分子筛纳米ZSM-5228.6g,加入SASOL的干胶粉SB粉83.8g,混合均匀后,添加2.5%的稀硝酸溶液275mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于580℃下焙烧3h,取出,取硝酸镉8.7g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于400℃下焙烧3h。
实施例5
取颗粒大小为300nm的分子筛纳米ZSM-5106.7g,加入SASOL的干胶粉SB粉218.1g,混合均匀后,添加2.5%的稀硝酸溶液240mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于620℃下焙烧3h,取出,取六水硝酸锌17.5g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于420℃下焙烧3h。
实施例6
取颗粒大小为350nm的分子筛纳米ZSM-5227.2g,加入SASOL的干胶粉SB粉83.8g,混合均匀后,添加2.5%的稀硝酸溶液275mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于600℃下焙烧3h,取出,取乙酸锌11.5g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于400℃下焙烧3h。
实施例7
取颗粒大小为380nm的分子筛纳米ZSM-5240.9g,加入SASOL的干胶粉SB粉67.1g,混合均匀后,添加2.5%的稀硝酸溶液275mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于580℃下焙烧3.5h,取出。取氧化锌(AR,含量99.5%)6.45g,碳酸氢铵(AR,含量99.0%)7.6g,加入15%的氨水35mL,搅拌、加热下溶解完毕,加去离子水稀释,按照孔饱和法浸渍,烘干后,于380℃下焙烧3.5h。
实施例8
取颗粒大小为500nm的分子筛纳米ZSM-515.8g,加入SASOL的干胶粉SB粉300g,混合均匀后,添加2.5%的稀硝酸溶液250mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,150℃下烘干6h后,于580℃下焙烧3.5h,取出。取氧化锌(AR,含量99.5%)6.45g,碳酸氢铵(AR,含量99.0%)7.6g,加入15%的氨水35mL,搅拌、加热下溶解完毕,加去离子水稀释,按照孔饱和法浸渍,烘干后,于400℃下焙烧4h。
实施例9
取颗粒大小为600nm的分子筛纳米ZSM-5250g,加入田菁粉44.1g,混合均匀后,添加2.5%的稀硝酸溶液250mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于600℃下焙烧4h,取出。取氧化锌(AR,含量99.5%)6.45g,碳酸氢铵(AR,含量99.0%)7.6g,加入15%的氨水35mL,搅拌、加热下溶解完毕,加去离子水稀释,按照孔饱和法浸渍,烘干后,于380℃下焙烧3.5h。
对比例1
取颗粒大小为1500nm的分子筛ZSM-5(山东齐创化工科技有限公司产)184.0g,加入山东铝厂的干胶粉SD粉144.0g,混合均匀后,添加2.5%的稀硝酸溶液245mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于620℃下焙烧2h,取出,取六水硝酸锌20.1g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于410℃下焙烧3h。
对比例2
取颗粒大小为350nm的分子筛纳米ZSM-5210.8g,加入山东铝厂的干胶粉SD粉108.0g,混合均匀后,添加2.5%的稀硝酸溶液240mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于580℃下焙烧3h。
对比例3
取颗粒大小为300nm的分子筛纳米ZSM-5236.4g,加入SASOL的干胶粉SB粉67.1g,混合均匀后,添加2.5%的稀硝酸溶液280mL,反复揉捏,采用小型挤条机挤出直径3mm的圆柱形条,120℃下烘干5h后,于600℃下焙烧3h,取出,取磷酸二氢铵12.5g,加去离子水溶解,按照孔饱和法浸渍,烘干后,于350℃下焙烧3h。
实验例
选取以上实施例和对比例的催化剂用于石脑油的非临氢改质,评价其效果,具体方法如下:
油品一次通过固定床试验装置,催化剂装填量为60mL。以直馏石脑油为原料,在反应温度300℃、压力0.5MPa、体积空速1.0h-1的操作条件下反应。
石脑油性质为:20℃密度,0.693g/cm3;硫含量,195μg/g;辛烷值RON为46,IBP 75℃,50%119℃,FBP 172℃。
改质结果显示,本发明所有的催化剂脱硫率可达到95%以上,辛烷值提高值可达到15以上,汽油收率在90%以上,而三个对比例均不能达到以上效果。表1仅列举了部分实施例的结果。
表1评价结果
由表1可见,与对比例相比,采用本发明提供的催化剂,脱硫率、辛烷值提高值、产品收率具有明显优势,由此可以说明本发明的先进性。
尽管已用具体实施例来说明和描述了本发明,然而应意识到,在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此,这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。
Claims (10)
1.一种用于汽油非临氢改质的催化剂,其特征在于,包括:主要由分子筛和粘结剂制成的载体;以及负载在所述载体上的非主族金属元素;
所述分子筛的晶粒尺寸为300nm-600nm,所述分子筛在所述载体中的重量百分比为5%-85%。
2.根据权利要求1所述的用于汽油非临氢改质的催化剂,其特征在于,所述分子筛为硅铝型分子筛,并且含有10元环或扭曲12元环,并且具有三维孔道结构;所述分子筛优选为Pentasil分子筛、MFI族分子筛ZSM-5、MEL族分子筛ZSM-11、含有扭曲12元环的BEA族分子筛beta中的一种或多种。
3.根据权利要求1所述的用于汽油非临氢改质的催化剂,其特征在于,所述粘结剂为拟薄水铝石、田菁粉、高岭土、凹凸棒中的一种或多种,优选为拟薄水铝石。
4.根据权利要求1所述的用于汽油非临氢改质的催化剂,其特征在于,所述非主族金属元素为VIII族或IIB族元素,优选为铁、钴、镍、锌、镓、镉中的一种或多种,更优选为镍、锌、镓、镉中的一种。
5.根据权利要求1所述的用于汽油非临氢改质的催化剂,其特征在于,所述载体的原料还包括耐热无机氧化物、成型助剂、增强剂中的一种或多种。
6.根据权利要求1-3任一项所述的用于汽油非临氢改质的催化剂,其特征在于,所述分子筛与所述粘结剂的重量比为5-85:15-95,优选为30-80:20-70,更优选40-75:25-60,更优选2.7-3.6:1。
7.根据权利要求1所述的用于汽油非临氢改质的催化剂,其特征在于,所述分子筛的晶粒尺寸为300nm-450nm,更优选350-380nm。
8.权利要求1-7任一项所述的用于汽油非临氢改质的催化剂的制备方法,其特征在于,包括下列步骤:
步骤A:按照配方,取所述载体的所有原料混合,并加入溶剂溶解,再采用混捏挤条法挤条,再依次经过烘干、焙烧,得到载体;
步骤B:取含所述非主族金属元素的化合物,将其制成溶液,然后采用孔饱和法浸渍在所述载体上,再依次经过烘干、焙烧,得到催化剂。
9.根据权利要求8所述的用于汽油非临氢改质的催化剂的制备方法,其特征在于,所述步骤A中烘干的条件为:在120-150℃下烘干5-6h,焙烧的条件为:在550-620℃下焙烧2.5-4h。
10.根据权利要求8所述的用于汽油非临氢改质的催化剂的制备方法,其特征在于,所述步骤B中焙烧的条件为:在350-450℃下焙烧3-4h。
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