CN111905838A - 一种利用渣油加氢失活催化剂制备加氢脱金属催化剂的方法 - Google Patents
一种利用渣油加氢失活催化剂制备加氢脱金属催化剂的方法 Download PDFInfo
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- CN111905838A CN111905838A CN202010839326.9A CN202010839326A CN111905838A CN 111905838 A CN111905838 A CN 111905838A CN 202010839326 A CN202010839326 A CN 202010839326A CN 111905838 A CN111905838 A CN 111905838A
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- Prior art keywords
- catalyst
- preparing
- hydrodemetallization
- heavy oil
- hydrodemetallization catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003921 oil Substances 0.000 claims abstract description 27
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- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 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 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
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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 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 6
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- -1 nitrogen-containing compound Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
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- 239000002699 waste material Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Classifications
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Abstract
本发明公开了一种利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,该方法包括:(1)将渣油加氢失活催化剂进行热处理;(2)向步骤(1)所得催化剂中加入有机酸溶液,湿法研磨得到浆液;(3)将步骤(2)所得的浆液加入到氧化铝前驱体中,加入助挤剂,混捏、成型、干燥、焙烧得到催化剂。本发明所提供催化剂制备方法可以循环利用失活催化剂,减少环境污染,显著降低催化剂生产成本,制备过程简单,易于工业上应用,同时所制得催化剂的加氢脱金属活性优于常规方法制备的催化剂。
Description
技术领域
本发明属于重质油加氢脱金属技术领域,具体涉及一种利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法。
背景技术
近年来,随着原油资源的重质化,对燃料油消费需求的增长和环保法规的日益严格,采用加氢技术将包括渣油在内的重质油转化为优质的燃料油和化工产品,有助于提高原油利用率、减少环境污染、提高轻质油收率和改善产品质量等。
渣油等重质油中的金属镍、钒等以及易形成积碳的前驱体的存在,导致渣油加氢催化剂容易因金属沉积和积碳等原因失活,催化剂使用寿命较短,大约只有一年。尤其是加氢脱金属催化剂,因孔道沉积大量的镍和钒,催化剂孔道结构及强度等受到严重破坏,不易再生,一般仅使用一次。因此,通常采用冶炼对失活催化剂进行金属回收。CN103290223B提出了一种废催化剂多金属综合回收的方法。首先对废催化剂进行稀硫酸预浸、磨细,预浸渣采用浓硫酸熟化,熟化料用水或者预浸液浸出。提钒残渣经过通过配入合适的熔剂进行火法熔炼,实现了镍、钴、钼等有价金属与铝、硅等杂质的分离。通过加压酸浸进一步分离火法熔炼锍相中的镍钴与钼,钼通过氨浸回收。该工艺虽然回收了大部分有价金属,但工艺流程长,回收条件要求苛刻,能耗高,部分金属浪费,回收利用率不够,经济效益不高。若能够直接利用失活催化剂进行加氢脱金属催化剂的制备,部分替代或完全替代新鲜催化剂使用,不仅能够降低催化剂成本、增加炼厂效益,而且能够减少能耗和环境污染。CN108067245A公开了一种加氢从催化剂的回收利用方法。该方法将钼镍系加氢废催化剂进行抽提,焙烧,粉碎,与碱进行混合后,进行微波处理。往滤液中加入酸溶液,得到钼酸。滤渣氧化铝经粉碎后,再次与碱混合、焙烧,热水浸渍,过滤得铝酸盐溶液和氧化镍固体。利用碳化法从铝酸盐溶液制备拟薄水铝石,将拟薄水铝石与胶黏剂混合,成型、干燥、焙烧制备成载体。往氧化镍中加入酸,制备成镍溶液,加入碳酸盐,制备成碱式碳酸镍。将钼酸和碱式碳酸镍配制成钼镍磷溶液,然后浸渍在氧化铝载体上,经干燥、焙烧制备成催化剂。该方法整体工艺流程长、能耗高,生产过程中易产生大量的废水、废气等。为了达到最大化渣油加氢脱金属的性能,要求催化剂不仅有好的反应活性,同时还需要具备优良的扩散性能。因此,作为渣油加氢脱金属的催化剂一般要求孔径双峰分布,同时具有可为含金属的沥青质等大分子的扩散提供通道的大孔(孔径在50 nm以上)和能为反应提供尽可能大的比表面的介孔(孔径在50 nm以下)两种孔道,促进杂质向催化剂的内部孔道快速扩散和沉积,提高催化剂的利用率,从而使加氢催化剂具有高的脱金属活性和高的容杂质能力,有助于延长渣油加氢催化剂的运转周期。为了改良加氢脱金属催化剂的孔道结构,目前普遍采用加入大量的扩孔剂。CN100496738C公开了一种具有双峰孔的氧化铝载体、催化剂及其制备方法。该载体采用氧化铝的前驱体与一种除酸以外的含氮化合物混合、成型干燥,并在750-800 ℃焙烧制得。现有制备脱金属催化剂的方法所用扩孔剂是含氮化合物,包括柠檬酸铵、碳酸氢铵、草酸铵和尿素等,用量高(氧化铝前驱体质量的20-50 %),焙烧过程中产生大量NOx,易对环境造成污染,催化剂生产成本高。同时含氮化合物的热稳定性较低,在干燥过程中易挥发或分解,从而影响扩孔效果和产品的重复性。
发明内容
针对现有技术的不足,本发明目的是提供一种可以循环利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法。该方法不仅解决了失活催化剂的污染问题,而且具有制备过程简单、成本低等优点,易于实现工业应用,催化剂加氢活性高。
为实现上述目的,本发明的技术方案为:
一种利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,该方法包括:
(1)将渣油加氢失活催化剂进行热处理;
(2)向步骤(1)所得催化剂中加入有机酸溶液,湿法研磨得到浆液;
(3)将步骤(2)所得的浆液加入到氧化铝前驱体中,加入助挤剂,混捏、成型、干燥、焙烧得到催化剂。
步骤(1)所述的渣油加氢失活催化剂指的是已经达不到原反应要求的渣油加氢脱金属或加氢脱硫催化剂。所述的热处理温度在含氧气氛中先在250~450 ℃处理1~24小时,再在450~600 ℃处理1~24小时。所述含氧气氛的氧气体积浓度为1~30%。
步骤(2)所述的有机酸溶液为醋酸、草酸、柠檬酸中的一种或多种的溶液,酸溶液的质量浓度为0.5~20%。所述的湿法研磨是将有机酸溶液与步骤(1)所得的渣油加氢失活催化剂混合后球磨处理至100~400目。所述的湿法研磨处理时间为0.5~12小时。所述的浆液固体质量含量为5~50%
步骤(3)所述氧化铝前驱体可以选自三水铝石、拟薄水铝石、薄水铝石和无定形氢氧化铝中的一种或多种的混合物,可以是市售商品或者现有技术中任意一种方法制备的产品。优选为拟薄水铝石。所述的氧化铝前驱体与失活催化剂质量比为1:1~10:1。所述的助挤剂可以是田菁粉、甲基纤维素、淀粉、聚乙烯醇、聚丙烯酰胺中的一种或者几种,加入量为氧化铝质量的1~5 %。所述成型方法可以采用压片、滚球或挤条等。催化剂的形状可根据不同要求制成片状、球型、圆柱型、三叶草型或四叶草型等。所述的干燥温度为80~200 ℃,干燥时间为1~24小时。所述的焙烧温度为500~1000 ℃,焙烧时间为1~8小时。
本发明所得重质油加氢脱金属催化剂同时具有介孔(孔直径小于50 nm)和大孔(孔直径大于50 nm)双峰孔分布的结构。以压汞法测定,催化剂的孔容为0.6~1.4 mL/g,比表面积为50~300 m2/g,孔直径小于50 nm的孔体积占总孔容的40~80 %,孔直径大于50nm的孔体积占总孔容的 20~60 %。该催化剂含有氧化铝载体和活性金属组分。催化剂所含的活性金属组分为至少一种的VB族的金属组分、至少一种的VIB族的金属组分和至少一种的VIII族的金属组分,以金属氧化物计算并以催化剂为基准,所述VB族的金属组分的氧化物含量为0.1~15 wt%,所述VIB族的金属组分的氧化物含量为0.1~5 wt%,所述VIII族的金属组分氧化物含量为0~5 wt%。
有益效果:本发明所提供催化剂制备方法可以循环利用失活催化剂,减少环境污染,显著降低催化剂生产成本,制备过程简单,易于工业上应用,同时所制得催化剂的加氢脱金属活性优于常规方法制备的催化剂。
具体实施方式
下面通过实施例对本发明作进一步的阐述,但是这些实施例不是对本发明的范围进行限制。
实施例1
取100 g工业装置运转后的渣油加氢失活催化剂,在含10 %的氧气气氛中以1℃/h的速率升温至350 ℃处理4 h,继续以1℃/h的速率升温至500 ℃处理4h。将250 mL质量浓度为12 %的柠檬酸溶液和热处理后的失活催化剂加入球磨机,研磨4h,得到浆液A1。
称取500 g商业拟薄水铝石(干基为70 %质量),12 g田菁粉,搅拌混合均匀。加入浆液A1和400mL去离子水,混捏成可塑体,在挤条机上挤成直径为1.3 mm的四叶草型的条状物。将条状物于120 ℃干燥12 h,于焙烧炉中750℃恒温2 h,得到催化剂C1。催化剂C1性质见表1。
实施例2
取100 g工业装置运转后的渣油加氢失活催化剂,在含5 %的氧气气氛中以1℃/h的速率升温至350 ℃处理8 h,继续以1℃/h的速率升温至500 ℃处理8h。将400 mL质量浓度为8%的柠檬酸溶液和热处理后的失活催化剂加入球磨机,研磨4h,得到浆液A2。
称取600 g商业拟薄水铝石(干基为70 %质量),15 g田菁粉,搅拌混合均匀。加入浆液A2和400mL去离子水,混捏成可塑体,在挤条机上挤成直径为1.3 mm的四叶草型的条状物。将条状物于120℃干燥12 h,于焙烧炉中760℃恒温2 h,得到催化剂C2。催化剂C2性质见表1。
实施例3
取100 g工业装置运转后的渣油加氢失活催化剂,在含15 %的氧气气氛中以1℃/h的速率升温至350 ℃处理4 h,继续以1℃/h的速率升温至500 ℃处理4h。将250 mL质量浓度为12 %的柠檬酸溶液和热处理后的失活催化剂加入球磨机,研磨3h,得到浆液A3。
称取400 g商业拟薄水铝石(干基为70 %质量),10 g田菁粉,搅拌混合均匀。加入浆液A3和300mL去离子水,混捏成可塑体,在挤条机上挤成直径为1.3 mm的四叶草型的条状物。将条状物于120℃干燥12 h,于焙烧炉中700 ℃恒温2 h,得到催化剂C3。催化剂C3性质见表1。
对比例1
称取500 g商业拟薄水铝石(干基为70 %质量),10 g田菁粉,搅拌混合均匀。加入600mL含4g硝酸的水溶液,碾压成可塑体,在挤条机上挤成直径为1.3 mm的四叶草型的条状物。将条状物于120 oC干燥12 h,于焙烧炉中750 oC恒温2 h,得到载体B1。
将350 mL含5.0 g NiO,23.0 g MoO3,12 g柠檬酸的Ni-Mo溶液喷浸到300g载体B1。经120℃干燥12 h,焙烧炉中750 ℃恒温2 h后,得到催化剂D1。催化剂D1性质见表1。
表1
应用实施例
以镍含量为24 ppm、钒含量为77 ppm、硫含量为4.54 wt%、氮含量为3220 ppm的渣油为原料。催化剂装填体积为100 mL。评价前采用湿法预硫化对催化剂进行硫化处理。评价实施例1-3和对比例1催化剂采用的工艺条件均相同。反应条件为:反应温度380 ℃,氢分压15MPa,液时空速为1.0 h-1,氢油体积比为760,反应300小时后取样。采用电感耦合等离子体发射光谱仪(ICP-AES)测定加氢处理前后油中镍和钒的含量(具体方法参见GB/T 37160)。按照下列公式计算金属脱除率,评价结果列于表2。
表2
由表1可知,利用渣油加氢失活催化剂制得的加氢脱金属催化剂,具有孔径双峰分布的催化剂。表2给出的结果为评价反应进行300小时后的结果,比较可以看出,本发明提供的重质油加氢脱金属催化剂的脱金属活性高于现有常规方法制备的加氢脱金属催化剂的活性。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (10)
1.一种利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:包括以下步骤:
(1)将渣油加氢失活催化剂进行热处理;
(2)向步骤(1)所得催化剂中加入有机酸溶液,湿法研磨得到浆液;
(3)将步骤(2)所得的浆液加入到氧化铝前驱体中,加入助挤剂,混捏、成型、干燥、焙烧得到重质油加氢脱金属催化剂。
2.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(1)所述的失活催化剂为已经达不到原反应要求的渣油加氢脱金属或加氢脱硫催化剂。
3.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(1)所述热处理具体为:在含氧气氛中先在250~450 ℃处理1~24h,再在450~600 ℃处理1~24小时;所述含氧气氛的氧气体积浓度为1~30%。
4.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(2)所述有机酸溶液为醋酸、草酸、柠檬酸中的一种或多种的水溶液,有机酸溶液中有机酸的质量浓度为0.5~20%。
5.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(2)所述湿法研磨是将有机酸溶液与步骤(1)所得的失活催化剂混合后球磨处理至100~400目。
6.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于,步骤(2)所述的湿法研磨处理时间为0.5~12h,所述浆液中失活催化剂含量为5~50wt%。
7.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(3)所述氧化铝前驱体选自三水铝石、拟薄水铝石、薄水铝石和无定形氢氧化铝中的一种或多种的混合物。
8.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(3)所述氧化铝前驱体与浆液中失活催化剂质量比为1:1~10:1。
9.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(3)所述助挤剂为田菁粉、甲基纤维素、淀粉、聚乙烯醇、聚丙烯酰胺中的一种或者几种,加入量为氧化铝质量的1~5 %。
10.根据权利要求1所述的利用渣油加氢失活催化剂制备重质油加氢脱金属催化剂的方法,其特征在于:步骤(3)所述干燥的温度为80~200 ℃,干燥时间为1~24h;所述焙烧的温度为500~1000 ℃,焙烧时间为1~8h。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005254083A (ja) * | 2004-03-10 | 2005-09-22 | Petroleum Energy Center | 重質油水素化処理触媒及びその製造方法 |
CN102451774A (zh) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | 一种失活加氢处理催化剂的再生方法 |
US20140076781A1 (en) * | 2011-05-02 | 2014-03-20 | Hea Kyung Park | Regeneration or remanufacturing catalyst for hydrogenation processing heavy oil, and method for manufacturing same |
CN103769136A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种丙烷氧化脱氢催化剂的制备方法 |
CN108067242A (zh) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | 一种加氢催化剂废弃料的回收再利用方法 |
CN108745392A (zh) * | 2018-05-28 | 2018-11-06 | 中化泉州石化有限公司 | 一种加氢脱金属催化剂及其制备方法 |
CN110227481A (zh) * | 2019-06-25 | 2019-09-13 | 中化泉州石化有限公司 | 一种重质油加氢处理催化剂及其制备方法 |
CN111097433A (zh) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | 失活渣油加氢处理催化剂的再生方法 |
CN111097440A (zh) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | 一种失活渣油加氢处理催化剂的再生方法 |
-
2020
- 2020-08-19 CN CN202010839326.9A patent/CN111905838A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005254083A (ja) * | 2004-03-10 | 2005-09-22 | Petroleum Energy Center | 重質油水素化処理触媒及びその製造方法 |
CN102451774A (zh) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | 一种失活加氢处理催化剂的再生方法 |
US20140076781A1 (en) * | 2011-05-02 | 2014-03-20 | Hea Kyung Park | Regeneration or remanufacturing catalyst for hydrogenation processing heavy oil, and method for manufacturing same |
CN103769136A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种丙烷氧化脱氢催化剂的制备方法 |
CN108067242A (zh) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | 一种加氢催化剂废弃料的回收再利用方法 |
CN108745392A (zh) * | 2018-05-28 | 2018-11-06 | 中化泉州石化有限公司 | 一种加氢脱金属催化剂及其制备方法 |
CN111097433A (zh) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | 失活渣油加氢处理催化剂的再生方法 |
CN111097440A (zh) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | 一种失活渣油加氢处理催化剂的再生方法 |
CN110227481A (zh) * | 2019-06-25 | 2019-09-13 | 中化泉州石化有限公司 | 一种重质油加氢处理催化剂及其制备方法 |
Non-Patent Citations (1)
Title |
---|
徐景东等: "渣油加氢失活催化剂回收与再利用的研究进展", 《工业催化》 * |
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