CN116832822A - 一种加氢催化剂及其制备方法与应用 - Google Patents
一种加氢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 60
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002283 diesel fuel Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 description 39
- 238000002791 soaking Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 description 3
- -1 amine molybdate Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 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 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
-
- 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
- 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
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种加氢催化剂及其制备方法与应用。所述加氢催化剂包含载体、活性组分和助剂组分,其中,所述活性组分选自VIII族的金属、VIB族的金属中的至少一种金属;所述助剂组分选自元素周期表的IIA族金属、IIB族金属、IVB族金属、稀土金属中的至少一种金属。本发明提供的加氢催化剂具有较高的活性,能够显著降低直馏柴油的硫含量和氮含量,达到提高直馏柴油质量的目的。
Description
技术领域
本发明涉及催化剂技术领域,具体涉及一种加氢催化剂及其制备方法与应用。
背景技术
加氢催化剂一般采用活性金属组分浸渍载体的方法,一般是VIB族和第VIII组金属组分负载于氧化铝载体上,常用的活性组分包括CoMo、NiMo、CoW、NiW,对于主要是脱硫反应的过程,加氢催化剂活性金属组分选择Co-Mo或者Ni-Mo组合,对于主要是芳烃饱和的反应过程,主要选择Ni-Mo或者Ni-W组合,而加氢脱氮过程主要选择Ni-W或Ni-Mo组合。
当前由于环保要求的提高,加工石油馏分的加氢催化剂技术得到了快速的发展,石油馏分中含有较多的含硫化合物、含氮化合物、芳烃、烯烃等,需要进行加氢处理,降低其硫化物、氮化物、芳烃、烯烃等物质的含量,从而达到环保的目的。
CN200310117323.0公开了一种馏分油加氢精制催化剂及其制备方法,该方法使用含钼化合物的溶液浸渍氧化铝载体,然后进行干燥,再用含镍、钨化合物的溶液浸渍,最后进行干燥以及焙烧,得到一种NiMW/Al2O3催化剂。
上述方法,在一定程度上改善了加氢催化剂的活性,但是在柴油加氢精制中,仍存在催化剂活性不高的缺陷。
发明内容
为此,本发明提供一种加氢催化剂及其制备方法,以解决现有催化剂在柴油加氢精制中存在的催化活性较低的问题。
为了实现上述目的,本发明提供如下技术方案:
根据本发明实施例的第一方面,提供了一种加氢催化剂,所述加氢催化剂包含载体、活性组分和助剂组分,其中,所述活性组分选自VIII族的金属、VIB族的金属中的至少一种金属;所述助剂组分选自元素周期表的IIA族金属、IIB族金属、IVB族金属、稀土金属中的至少一种金属。
进一步地,以所述加氢催化剂重量为基准,活性组分以氧化物计含量为1-50%,优选10-30%;助剂组分以氧化物计含量为0.1-10%,优选1-5%。
进一步地,所述活性组分包括镍、钼和钨,以氧化物计,所述镍、钼与钨的质量比为1:0.1-10:0.1-10。
进一步地,所述助剂组分选自Zn、La、Ce、Ga中的至少一种金属。
进一步地,所述载体为氧化铝载体,其比表面积为150-300m2/g,孔体积为0.3-1.1ml/g。
根据本发明实施例的第二方面,提供了一种如上所述的加氢催化剂的制备方法,所述方法包括:
所述载体与活性组分/助剂组分前驱体接触,进行干燥、焙烧,之后与助剂组分/活性组分前驱体接触,再次进行干燥、焙烧。本发明进一步发现,当所述载体先与助剂组分前驱体接触,进行干燥、焙烧后,再与活性组分前驱体接触,之后进行干燥、焙烧,更有利于提高加氢催化剂的活性。
进一步地,所述接触为浸渍法,浸渍温度为20-50℃、浸渍时间为1-12h;所述干燥温度为100-300℃,干燥时间为1-24h;所述焙烧温度为300-600℃,焙烧时间为1-12h。
进一步地,所述助剂组分前驱体为金属的硝酸盐、碳酸盐或醋酸盐。
进一步地,所述方法还包括:在所述活性组分前驱体进行接触的步骤时,向反应体系加入添加剂,所述添加剂选自乙二醇、聚乙二醇、乙酸、草酸、柠檬酸中的至少一种。
本发明发现,加入上述添加剂能够调节载体表面的酸性,减弱活性组分与载体间的作用,提高活性组分的分散性能,进而提高加氢催化剂的活性。
进一步地,以所述加氢催化剂重量为基准,所述助剂的添加量为0.1-15%,优选1-10%。
根据本发明实施例的第三方面,提供了一种如上所述的加氢催化剂在柴油精制中的应用。
本发明具有如下优点:
本发明通过提高了催化剂中活性金属组分含量以及在制备过程中采用分步浸渍多次煅烧的制备方式改善催化剂活性。本发明提供的加氢催化剂具有较高的活性,能够显著降低直馏柴油的硫含量和氮含量,达到提高直馏柴油质量的目的。
具体实施方式
以下由特定的具体实施例说明本发明的实施方式,熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明使用的氧化铝载体可以通过商购途径获得,也可以通过氧化铝前驱体压片、挤条、焙烧等方法制得。
以下实施例中,氧化铝载体的制备方法如下:取1000g氢氧化铝干胶粉和1000g拟薄水铝石,挤条成三叶草形状,120℃干燥10h,600℃焙烧5.5h,制成氧化铝载体。
实施例1
本实施例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用含硝酸锌12.3g的水溶液100ml浸渍2h,120℃干燥6h,550℃焙烧6h,降至室温后,用含钼酸胺7.3g的水溶液100ml浸渍2.0h,150℃干燥8h降至室温后,用含硝酸镍18g、偏钨酸铵19.7g的水溶液100ml浸渍2h,160℃干燥8h,500℃焙烧4h,得到催化剂1。
实施例2
本实施例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用含硝酸锌20.5g的水溶液100ml浸渍2h,120℃干燥6h,550℃焙烧6h,降至室温后,用含钼酸胺12.1g的水溶液100ml浸渍2.0h,150℃干燥8h,用含硝酸镍30g、偏钨酸铵32.8g的100ml水溶液浸渍2h,160℃干燥8h,500℃焙烧4h,得到催化剂2。
实施例3
本实施例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用硝酸镧5.0g的水溶液100ml浸渍2h,120℃干燥6h,500℃焙烧6h,降至室温后,用含钼酸胺12.1g、硝酸镍30g、偏钨酸铵32.8g的水溶液100ml浸渍2h,160℃干燥8h,550℃焙烧4h,得到催化剂3。
实施例4
本实施例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用硝酸镧5.0g的水溶液100ml浸渍2h,120℃干燥6h,500℃焙烧6h,降至室温后,用含钼酸胺12.1g、硝酸镍30g、偏钨酸铵32.8g、丙三醇30.6g的水溶液100ml浸渍2h,160℃干燥8h,480℃焙烧4h,得到催化剂4。
实施例5
本实施例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用硝酸镓8.0g的水溶液100ml浸渍2h,120℃干燥6h,500℃焙烧6h,降至室温后,用含钼酸胺7.3g、硝酸镍18g、偏钨酸铵19.7g水溶液100ml浸渍2h,160℃干燥8h,450℃焙烧4h,得到催化剂5。
实施例6
本实施例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用硝酸镓8.0g的100ml水溶液浸渍2h,120℃干燥6h,500℃焙烧6h,降至室温后,用含钼酸胺7.3g、硝酸镍18g、偏钨酸铵19.7g、柠檬酸10.0g的水溶液100ml浸渍2h,160℃干燥8h,500℃焙烧4h,得到催化剂6。
实施例7
本实施例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用含钼酸胺7.3g的水溶液100ml浸渍2.0h,150℃干燥8h降至室温后,用含硝酸镍18g、偏钨酸铵19.7g的水溶液100ml浸渍2h,160℃干燥8h,500℃焙烧4h,降至室温后,用含硝酸锌12.3g的水溶液100ml浸渍2h,120℃干燥6h,550℃焙烧6h,得到催化剂7。
对比例1
本对比例提供一种加氢催化剂,其制备方法如下:
取氧化铝载体100g,用含钼酸胺7.3g的水溶液100ml浸渍2.0h,150℃干燥8h降至室温后,用含硝酸镍18g、偏钨酸铵19.7g的水溶液100ml浸渍2h,160℃干燥8h,500℃焙烧4h,得到催化剂8。
测试例1
采用X荧光法对催化剂1-8的组成进行测定,结果见表1。
表1
测试例2
直馏柴油的性能见表2。
表2
密度,20℃,g/cm3 | 0.8277 |
硫含量,ppm | 3512 |
氮含量,ppm | 110 |
芳烃,m% | 20 |
溴价,gBr/100g | 3.76 |
凝点,℃ | -2 |
馏程,ASTM B86 | |
初馏点 | 208 |
10% | 245 |
50% | 285 |
90% | 328 |
干点 | 339 |
(1)反应条件:
反应压力:6.0MPa;
反应温度:300-350℃;
空速:2.0h-1;
氢油体积比:500。
(2)催化剂反应效果见表3。
表3
结果显示,本发明实施例提供的加氢催化剂具有较高的活性,能够显著降低直馏柴油的硫含量和氮含量,达到提高直馏柴油质量的目的。
虽然,上文中已经用一般性说明及具体实施例对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (10)
1.一种加氢催化剂,其特征在于,所述加氢催化剂包含载体、活性组分和助剂组分,其中,所述活性组分选自VIII族的金属、VIB族的金属中的至少一种金属;所述助剂组分选自元素周期表的IIA族金属、IIB族金属、IVB族金属、稀土金属中的至少一种金属。
2.根据权利要求1所述的加氢催化剂,其特征在于,以所述加氢催化剂重量为基准,活性组分以氧化物计含量为1-50%,优选10-30%;助剂组分以氧化物计含量为0.1-10%,优选1-5%。
3.根据权利要求1所述的加氢催化剂,其特征在于,所述活性组分包括镍、钼和钨,以氧化物计,所述镍、钼与钨的质量比为1:0.1-10:0.1-10。
4.根据权利要求1所述的加氢催化剂,其特征在于,所述助剂组分选自Zn、La、Ce、Ga中的至少一种金属。
5.根据权利要求1所述的加氢催化剂,其特征在于,所述载体为氧化铝载体,其比表面积为150-300m2/g,孔体积为0.3-1.1ml/g。
6.权利要求1所述的加氢催化剂的制备方法,其特征在于,所述方法包括:所述载体与活性组分/助剂组分前驱体溶液接触,进行干燥、焙烧,之后与助剂组分/活性组分前驱体接触,再次进行干燥、焙烧。
7.根据权利要求6所述的加氢催化剂的制备方法,其特征在于,所述接触为浸渍法,浸渍温度为20-50℃、浸渍时间为1-12h;所述干燥温度为100-300℃,干燥时间为1-24h;所述焙烧温度为300-600℃,焙烧时间为1-12h。
8.根据权利要求6所述的加氢催化剂的制备方法,其特征在于,所述助剂组分前驱体为金属的硝酸盐、碳酸盐或醋酸盐。
9.根据权利要求6所述的加氢催化剂的制备方法,其特征在于,所述方法还包括:
在所述活性组分前驱体进行接触的步骤时,向反应体系加入添加剂,所述添加剂选自乙二醇、聚乙二醇、乙酸、草酸、柠檬酸中的至少一种;
以所述加氢催化剂重量为基准,所述助剂的添加量为0.1-15%,优选1-10%。
10.权利要求1所述的加氢催化剂在柴油精制中的应用。
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MX2017015793A (es) * | 2017-12-06 | 2019-06-07 | Mexicano Inst Petrol | Catalizadores metalicos soportados, proceso de obtencion y uso en la produccion de diesel de ultra bajo azufre. |
CN116037178A (zh) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | 加氢脱氮催化剂及其制备方法与应用 |
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CN101722039A (zh) * | 2008-10-21 | 2010-06-09 | 中国石油化工股份有限公司 | 一种加氢催化剂及其制备方法 |
CN103480408A (zh) * | 2012-06-13 | 2014-01-01 | 中国石油天然气股份有限公司 | 一种含稀土的柴油馏分油加氢催化剂及其制备和应用 |
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