CN107774275B - 一种加氢催化剂的制备方法 - Google Patents
一种加氢催化剂的制备方法 Download PDFInfo
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- CN107774275B CN107774275B CN201610767708.9A CN201610767708A CN107774275B CN 107774275 B CN107774275 B CN 107774275B CN 201610767708 A CN201610767708 A CN 201610767708A CN 107774275 B CN107774275 B CN 107774275B
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- alumina powder
- acid
- organic
- modified alumina
- modified
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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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 3
- 150000003839 salts Chemical class 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- 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
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明提供了一种加氢催化剂的制备方法。该方法在载体成型的过程中引入部分活性金属组分和有机酸络合剂,通过一定的焙烧处理程序使载体成型,然后再进行后续的活性金属浸渍步骤,得到加氢催化剂。本发明方法制备的加氢催化剂,活性金属均匀分散,制备方法简单易行,尤其适用于柴油超深度加氢脱硫反应。
Description
技术领域
本发明涉及一种加氢催化剂的制备方法,具体是一种适用于柴油超深度加氢脱硫催化剂的制备方法。
背景技术
由于世界原油生产日趋重质化,而当今对清洁油品的需求量不断增加,因此在生产清洁油品的过程中,石油馏分的加氢脱硫工艺技术起到越来越重要的作用,对加氢催化剂的高活性要求也日益增多。
对于超深度加氢脱硫催化剂,Co-Mo-S和Ni-Mo-S的Ⅱ类活性中心理论已经被各大研发机构广泛接受,并以此开发了新型高活性加氢处理催化剂。主要的改进方案包括载体的选择、添加助剂的应用、浸渍液络合、硫化过程以及金属组分的调整等。同时,催化剂的制备方式也是提高Ⅱ类活性中心有效数目和分散的重要方法。
CN1938087B、US7737071B2 、EP1733787A1 介绍了一种加氢催化剂的制备方法,包括:用包含第VIB 族金属的化合物、含磷成分、第VIII 族金属的化合物以及有机酸的溶液浸渍载体,接着在200℃或更低的温度下进行干燥,得到催化剂。在催化剂中,源于有机酸的C含量为2%~14%。
EP0870003B2 介绍了一种制备加氢催化剂的方法,包括:用包含第VIB 族金属的化合物、第VIII 族金属的化合物以及有机醇和/ 或糖的溶液浸渍载体,接着在200℃或更低的温度下进行干燥,得到催化剂。在催化剂中,源于有机醇和/ 或糖的C含量为2%~10%。
CN201210409660.6公开了一种馏分油加氢处理催化剂。该催化剂是以氧化铝为载体,以至少一种第VIB族金属和至少一种第VIII 族金属为加氢活性金属,第VIII族金属/(第VIB 族金属+第VIII 族金属)以氧化物计的重量比为0.30~0.55,催化剂中含有有机化合物,以C 的重量计,有机化合物在催化剂中的含量为1.0wt%~1.8wt%,所述的有机化合物源于有机酸以及有机醇和/ 或有机糖。该催化剂中加入少量的两种有机化合物,并采用较高VIII/(VIB+VIII)的配比,提高了催化剂的加氢活性。
在上述制备催化剂的方法中,活性金属组分的加入均采用含有机助剂浸渍液的方式在载体成型后加入,由于超深度加氢脱硫催化剂所需活性金属含量较高,导致浸渍液中需要添加的助剂含量也较高,浸渍液粘度较大,不利于活性金属的分散,因而制备难度较大甚至无法工业化制备。同时,大量有机酸的加入会导致载体孔结构损失,催化剂的侧压强度下降的缺陷。
发明内容
为了克服现有技术的不足,本发明提供了一种加氢催化剂的制备方法。该方法在载体成型的过程中引入部分活性金属组分和有机酸络合剂,通过一定的焙烧处理程序使载体成型,然后再进行后续的活性金属浸渍步骤。由于活性金属分次引入,故浸渍液中有机助剂含量适当,浸渍液粘度较低,利于金属的分散,制备方法简单易行,本发明方法制备的加氢催化剂尤其适用于柴油超深度加氢脱硫反应。
本发明的加氢催化剂的制备方法,包括如下内容:
(1)分别配制浸渍溶液I和浸渍溶液II,其中浸渍溶液I是将含第VIII 族金属化合物、有机酸和水配制而成,浸渍溶液II是将含第VIB族金属、有机醇和/或有机糖以及水配制而成;其中有机酸的加入量以碳含量计与第VIII族金属的摩尔比为0.01~2.0,优选0.25~1.75,有机醇和/或有机糖以碳含量计与第VIB族金属的摩尔比为0.01~2.0,优选0.25~1.75;
(2)取一定量的大孔氧化铝粉,饱和浸渍浸渍溶液I后干燥,然后在惰性气氛下焙烧,得到改性大孔氧化铝粉;
(3)将步骤(2)得到的改性大孔氧化铝粉与小孔氧化铝粉按照一定比例混合均匀后,加入助挤剂,胶溶剂和水混成可塑体,经过混捏、成型、干燥、焙烧后,得到氧化铝载体;
(4)用浸渍液II饱和浸渍步骤(3)中制备的氧化铝载体,经过干燥后,得到馏分油加氢催化剂。
本发明方法中,步骤(1)中所述的有机酸选自碳数为2~10 的有机酸中的至少一种,优选为柠檬酸、苹果酸、酒石酸、草酸、琥珀酸、戊二酸、己二酸、苯甲酸、水杨酸、丙二酸和丁二酸中的一种或几种;所述的有机醇选自碳数为2~10的脂肪醇中的一种或几种,优选为乙二醇、乙烯乙二醇、丙烯乙二醇、丙三醇、异丙醇、三甘醇、2,2′-亚氨基双乙醇、氨基三乙醇、二乙烯乙二醇、二丙烯乙二醇、三亚甲基乙二醇、三乙烯乙二醇、三丁烯乙二醇和四乙烯乙二醇中的一种或几种;所述的有机糖选自碳数为2~16的单糖、二糖中的至少一种,优选为蔗糖、葡萄糖、果糖、半乳糖、乳糖和麦芽糖中的一种或几种。
本发明方法中,步骤(2)所述的大孔氧化铝粉可以为市售产品或按照本领域常规方法制备而成,浸渍液I浓度由氧化铝粉吸水率和催化剂金属组成含量所确定。惰性气体为氮气或稀有气体,焙烧温度为200~650℃,优选250~550℃,焙烧时长为1~5h。
本发明方法中,步骤(3)所述的小孔氧化铝粉为以为市售产品或按照本领域常规方法制备而成,小孔氧化铝粉质量占氧化铝粉总质量(大孔氧化铝粉和小孔氧化铝粉之和,下同)的5%~35%。助挤剂为甲基纤维素、田菁粉、淀粉和聚乙烯醇中的一种或几种,加入量为氧化铝粉总质量的1%~5%。胶溶剂为稀硝酸、稀磷酸和硅酸中的一种或几种,加入量为氧化铝粉总质量的1%~5%。其中所述的混捏、成型、干燥和焙烧采用本领域常规方法进行。所述的干燥条件为温度不高于130℃,优选90~120℃,干燥时间为1~24小时,所述的焙烧条件为温度不高于800℃,优选450~750℃,焙烧时间为2~10小时。
本发明方法中,步骤(4)所述的浸渍液II浓度由载体的吸水率和催化剂金属组成含量所确定。干燥温度不高于200℃,优选110~150℃,干燥时长为1~8h。
本发明方法中,所述的催化剂中含至少一种第VIB 族金属和至少一种第VIII 族金属为加氢活性金属,以催化剂的重量为基准,加氢活性金属以氧化物计的重量含量为8%~50%,优选为10% ~40%;其中第VIB族金属优选为Mo和/或W,第VIII族金属优选为Ni和/或Co;第VIII族金属/(第VIB族金属+第VIII族金属)以氧化物计的重量比(本发明中简写为VIII/(VIB +VIII)的重量比)为0.01~0.70。
与现有技术相比,本发明提供的加氢催化剂的制备方法具有以下优点:
(1)采用分次浸渍,将第VIB 族金属盐和第VIII 族金属盐分别制备成浸渍液,与双金属浸渍相比,浸渍液中金属组分和有机助剂含量的降低,有效的降低了浸渍液粘度和酸度,从而在浸渍过程中保证氧化铝载体孔道不被过度破坏。
(2)浸渍液中金属离子浓度的降低以及不同金属分别浸渍,减少了金属间的竞争吸附作用,提高了金属盐分子的扩散效应,有利于活性金属均匀分散。
(3)将大孔氧化铝粉中预浸渍活性金属和有机助剂,通过惰性气体保护焙烧的方式,形成Al-C石墨化碳前驱体,防止焙烧过程中Co/Ni铝尖晶石形成。同时Al-C石墨化碳前驱体能够保证氧化铝大孔道在混捏成型过程中不被胶溶剂酸化破坏,从而使催化剂孔道较大而畅通。
本发明的加氢催化剂适用于液化气、汽油、煤油、柴油、蜡油等馏分的加氢处理,尤其适用于柴油超深度加氢工艺。
具体实施方式
下面通过实施例进一步说明本发明方案及效果,但并不构成对本发明的限制。实施例中所用的大孔氧化铝粉为市用418粉,小孔氧化铝粉为市用SB粉。实施例1
将100g大孔氧化铝粉(干基85)置于滚锅中,在转动条件下,向滚锅中的大孔氧化铝粉以雾化方式喷入80ml含有18.5g硝酸钴,1.1g 柠檬酸的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在110℃下干燥3小时后,放入气氛炉中焙烧2h,保护气体为氮气,焙烧温度300℃。
取出改性大孔氧化铝粉与20g小孔氧化铝粉(干基75)混合均匀,再然后加入田菁粉2g、10%磷酸25g和90ml去离子水,混捏、成型、110℃干燥4h后,550℃焙烧3h,获得氧化铝载体。
将得到的氧化铝载体置于滚锅中,在转动条件下,向滚锅中再以雾化方式喷入60ml含有25.4g七钼酸铵,3.2g丙三醇的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在130℃下干燥4小时,制得成品催化剂A。
实施例2
将100g大孔氧化铝粉(干基85)置于滚锅中,在转动条件下,向滚锅中的大孔氧化铝粉以雾化方式喷入80ml含有18.5g硝酸钴,3.0g草酸的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在110℃下干燥3小时后,放入气氛炉中焙烧2h,保护气体为氮气,焙烧温度350℃。
取出改性大孔氧化铝粉与20g小孔氧化铝粉(干基75)混合均匀,再然后加入田菁粉2g、10%硝酸20g和90ml去离子水,混捏、成型、110℃干燥4h后,550℃焙烧3h,获得氧化铝载体。
将得到的氧化铝载体置于滚锅中,在转动条件下,向滚锅中再以雾化方式喷入60ml 含有25.4g七钼酸铵,4.5g乙二醇的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在130℃下干燥4小时,制得成品催化剂B。
实施例3
将100g大孔氧化铝粉(干基85)置于滚锅中,在转动条件下,向滚锅中的大孔氧化铝粉以雾化方式喷入80ml含有18.5g硝酸镍,3.5g酒石酸的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在110℃下干燥3小时后,放入气氛炉中焙烧2h,保护气体为氮气,焙烧温度400℃。
取出改性大孔氧化铝粉与20g小孔氧化铝粉(干基75)混合均匀,再然后加入田菁粉2g、10%硝酸20g和90ml去离子水,混捏、成型、110℃干燥4h后,550℃焙烧3h,获得氧化铝载体。
将得到的氧化铝载体置于滚锅中,在转动条件下,向滚锅中再以雾化方式喷入60ml 含有25.4g七钼酸铵,3g三甘醇的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在130℃下干燥4小时,制得成品催化剂C。
实施例4
将100g大孔氧化铝粉(干基85)置于滚锅中,在转动条件下,向滚锅中的大孔氧化铝粉以雾化方式喷入80ml含有18.5g硝酸镍,2.0g戊二酸的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在110℃下干燥3小时后,放入气氛炉中焙烧2h,保护气体为氮气,焙烧温度400℃。
取出改性大孔氧化铝粉与20g小孔氧化铝粉(干基75)混合均匀,然后再加入田菁粉2g、10%硝酸20g和90ml去离子水,混捏、成型、110℃干燥4h后,550℃焙烧3h,获得氧化铝载体。
将得到的氧化铝载体置于滚锅中,在转动条件下,向滚锅中再以雾化方式喷入60ml含有,2.5g七钼酸铵,20.5g偏钨酸铵,4.2g葡萄糖的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在120℃下干燥4小时,制得成品催化剂D。
比较例1
将100g大孔氧化铝粉(干基85)与20g小孔氧化铝粉(干基75)混合均匀,然后再加入田菁粉2g、10%硝酸20g和90ml去离子水,混捏、成型、110℃干燥4h后,550℃焙烧3h,获得氧化铝载体。
将100g按上述方法制备的氧化铝载体置于滚锅中,在转动条件下,向滚锅中的氧化铝载体以雾化方式喷入80ml含有25.4g七钼酸铵,18.5g硝酸钴,3g三甘醇的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在120℃下干燥5小时,制得成品催化剂E。
比较例2
将100g按比较例1方法制备的氧化铝载体置于滚锅中,在转动条件下,向滚锅中的氧化铝载体以雾化方式喷入80ml含有25.4g七钼酸铵,18.5g硝酸钴,1.1g柠檬酸,4.5g乙二醇的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在120℃下干燥5小时,制得成品催化剂F。
比较例3
将100g大孔氧化铝粉(干基85)和20g小孔氧化铝粉(干基75)置于滚锅中混合均匀,在转动条件下,向滚锅中的氧化铝粉以雾化方式喷入80ml含有18.5g硝酸钴,1.1g柠檬酸的水溶液,溶液喷完后,然后放置3小时,在110℃下干燥3小时后,400℃焙烧2h。
将2g田菁粉、10%硝酸20g和90ml去离子水加入上述步骤制得的混合氧化铝粉后,混捏、成型、110℃干燥4h后,550℃焙烧3h,获得氧化铝载体。
将得到的氧化铝载体置于滚锅中,在转动条件下,向滚锅中再以雾化方式喷入60ml 含有25.4g七钼酸铵,3.2g丙三醇的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在130℃下干燥4小时,制得成品催化剂G。
比较例4
将100g大孔氧化铝粉(干基85)置于滚锅中,在转动条件下,向滚锅中的大孔氧化铝粉以雾化方式喷入80ml含有18.5g硝酸镍,3.5g酒石酸的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在110℃下干燥3小时后,放入马弗炉中400℃焙烧2h。
取出改性大孔氧化铝粉与20g小孔氧化铝粉(干基75)混合均匀,再然后加入田菁粉2g、10%硝酸20g和90ml去离子水,混捏、成型、110℃干燥4h后,550℃焙烧3h,获得氧化铝载体。
将得到的氧化铝载体置于滚锅中,在转动条件下,向滚锅中再以雾化方式喷入60ml 含有25.4g七钼酸铵,4.2g葡萄糖的水溶液,溶液喷完后,在滚锅中继续转动30分钟,然后放置3小时,在130℃下干燥4小时,制得成品催化剂H。
各催化剂的物化性质见表1。
表1 催化剂的主要物化性质
催化剂评价在100ml小型加氢装置上进行,活性评价前先对催化剂进行预硫化。催化剂评价工艺条件为压力4.0 MPa,液时体积空速2.0h-1,氢油体积比300:1,反应温度为360℃。活性评价原料油性质见表2,活性评价结果见表3。
表2 原料油性质。
表3 活性评价结果。
从评价结果来看,使用本发明方法制备的催化剂具有更好的脱硫和脱氮活性。
Claims (9)
1.一种加氢催化剂的制备方法,其特征在于包括如下内容:(1)分别配制浸渍溶液I和浸渍溶液II,其中浸渍溶液I是将含第VIII 族金属化合物、有机酸和水配制而成,浸渍溶液II是将含第VIB族金属、有机醇和有机糖中的至少一种以及水配制而成;其中有机酸的加入量以碳含量计与第VIII族金属的摩尔比为0.01~2.0;有机醇和/或有机糖以碳含量计与第VIB族金属的摩尔比为0.01~2.0;所述的有机酸选自碳数为2~10 的有机酸中的至少一种;所述的有机醇选自碳数为2~10的脂肪醇中的一种或几种;所述的有机糖选自碳数为2~16的单糖、二糖中的至少一种;(2)取一定量的大孔氧化铝粉,饱和浸渍浸渍溶液I后干燥,然后在惰性气氛下焙烧,得到改性大孔氧化铝粉;(3)将步骤(2)得到的改性大孔氧化铝粉与小孔氧化铝粉按照一定比例混合均匀后,加入助挤剂,胶溶剂和水混成可塑体,经过混捏、成型、干燥、焙烧后,得到氧化铝载体;(4)用浸渍液II饱和浸渍步骤(3)中制备的氧化铝载体,经过干燥后,得到加氢催化剂;步骤(2)所述的惰性气氛为氮气或稀有气体,焙烧温度为200~650℃,焙烧时长为1~5h。
2.按照权利要求1所述的方法,其特征在于:步骤(1)中所述的有机酸为柠檬酸、苹果酸、酒石酸、草酸、琥珀酸、戊二酸、己二酸、苯甲酸、水杨酸、丙二酸和丁二酸中的一种或几种。
3.按照权利要求1所述的方法,其特征在于:步骤(1)中所述的有机醇为乙二醇、乙烯乙二醇、丙烯乙二醇、丙三醇、异丙醇、三甘醇、2,2′-亚氨基双乙醇、氨基三乙醇和四乙烯乙二醇中的一种或几种。
4.按照权利要求1所述的方法,其特征在于:步骤(1)中所述的有机糖为蔗糖、葡萄糖、果糖、半乳糖、乳糖和麦芽糖中的一种或几种。
5.按照权利要求1所述的方法,其特征在于:步骤(3)所述的小孔氧化铝粉质量占氧化铝粉总质量的5%~35%;助挤剂为甲基纤维素、田菁粉、淀粉和聚乙烯醇中的一种或几种,加入量为氧化铝粉总质量的1%~5%;胶溶剂为稀硝酸、稀磷酸和硅酸中的一种或几种,加入量为氧化铝粉总质量的1%~5%。
6.按照权利要求1所述的方法,其特征在于:步骤(3)所述的干燥温度为90~120℃,干燥时间为1~24小时;所述的焙烧温度450~750℃,焙烧时间为2~10小时。
7.按照权利要求1所述的方法,其特征在于:步骤(4)所述的浸渍液II浓度由载体的吸水率和催化剂金属组成含量所确定;干燥温度不高于200℃,干燥时长为1~8h。
8.按照权利要求1~7任一项所述的方法制备的加氢催化剂,其特征在于:所述的催化剂中含至少一种第VIB 族金属和至少一种第VIII 族金属为加氢活性金属,以催化剂的重量为基准,加氢活性金属以氧化物计的重量含量为8%~50%;其中第VIB族金属为Mo和/或W,第VIII族金属为Ni和/或Co;第VIII族金属/(第VIB族金属+第VIII族金属)以氧化物计的重量比为0.01~0.70。
9.按照权利要求1~7任一项所述的方法制备的加氢催化剂在液化气、汽油、煤油、柴油、蜡油馏分的加氢处理中的应用。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101439293A (zh) * | 2007-11-19 | 2009-05-27 | 中国石油天然气集团公司 | 含有介孔分子筛的选择性加氢脱硫催化剂及其制备方法 |
CN102806088A (zh) * | 2012-08-13 | 2012-12-05 | 中国海洋石油总公司 | 一种重整原料加氢预精制催化剂的制备方法 |
CN102847541A (zh) * | 2012-08-27 | 2013-01-02 | 王小英 | 煤焦油加氢脱金属催化剂及其制备方法 |
CN103769221A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 馏分油加氢处理催化剂的制备方法 |
CN103769222A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种馏分油加氢处理催化剂 |
CN103785400A (zh) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | 一种高活性渣油加氢脱金属催化剂的制备方法 |
CN104549333A (zh) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | 一种渣油加氢脱金属催化剂的制备方法 |
-
2016
- 2016-08-31 CN CN201610767708.9A patent/CN107774275B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101439293A (zh) * | 2007-11-19 | 2009-05-27 | 中国石油天然气集团公司 | 含有介孔分子筛的选择性加氢脱硫催化剂及其制备方法 |
CN102806088A (zh) * | 2012-08-13 | 2012-12-05 | 中国海洋石油总公司 | 一种重整原料加氢预精制催化剂的制备方法 |
CN102847541A (zh) * | 2012-08-27 | 2013-01-02 | 王小英 | 煤焦油加氢脱金属催化剂及其制备方法 |
CN103769221A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 馏分油加氢处理催化剂的制备方法 |
CN103769222A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种馏分油加氢处理催化剂 |
CN103785400A (zh) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | 一种高活性渣油加氢脱金属催化剂的制备方法 |
CN104549333A (zh) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | 一种渣油加氢脱金属催化剂的制备方法 |
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