CN104342201A - 一种重整生成油加氢脱烯烃的方法 - Google Patents
一种重整生成油加氢脱烯烃的方法 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 210000003278 egg shell Anatomy 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- -1 olefin hydrocarbon Chemical class 0.000 claims description 9
- 239000010970 precious metal Substances 0.000 claims description 8
- 102000002322 Egg Proteins Human genes 0.000 claims description 6
- 108010000912 Egg Proteins Proteins 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 3
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- 150000003568 thioethers Chemical class 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000007598 dipping method Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
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- 230000008569 process Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- 208000012826 adjustment disease Diseases 0.000 description 5
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- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- 239000012876 carrier material Substances 0.000 description 2
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- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 238000002407 reforming Methods 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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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
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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Abstract
本发明涉及一种重整生成油选择性加氢脱烯烃的方法；催化剂催化剂活性组分为Pt、Pd中的至少一种，助剂为Sn、Pb中的一种或两种，载体为Al2O3，贵金属在载体上呈薄蛋壳型分布，蛋壳厚度为0.05-1mm；催化剂的比表面积为50-400m2/g；孔体积为0.2-1.2cm3/g，其中孔径在5-50nm的孔占催化剂总孔道的50-80%；活性组分的质量百分含量为0.05-0.5wt%，助剂的质量百分含量为0.5-10wt%，其余为载体；本方法催化剂降低了贵金属的用量，提高了贵金属的利用率，通过添加无机金属助剂抑制催化剂初始活性，有效避免了有机硫化物对操作人员的毒害和对环境的污染。
Description
技术领域
本发明涉及一种重整生成油选择性加氢脱烯烃的方法。
背景技术
贵金属催化剂由于其活性高，处理量大，选择性好，因此被广泛应用于重整生成油选择性加氢脱烯烃中。例如，中国专利CN85100215A介绍了一种用于重整抽余油加氢精制的催化剂，它由0.02-0.2wt%的Pt或Pd担载在γ-Al2O3上构成，该专利申请在说明书中提到：“在常压和200℃左右对苯和甲苯有加氢活性”。因此，该催化剂加氢选择性需进一步提高，否则必将导致芳烃过量加氢而损失。
中国专利CN85100760A介绍了一种烯烃加氢精制催化剂及其制法。这种用于石油产品烯烃加氢的催化剂由0.2～lwt％的Pt或Pd或Pd和Pt以及0.05～2wt％的Sn或Pb担载于纤维状氧化铝上所制成。然而由于目前纤维状Al2O3的成型技术尚未实现，纤维状Al2O3很难成型为具有一定机械强度的工业催化剂载体，所以该发明的催化剂要实现工业应用还有许多工作要做。
CN1448474A公开了一种重整生成油选择性加氢脱烯烃催化剂。该催化剂含0.1～1.0wt％的贵金属，为活性组分，0.05～0.50wt％的碱金属或碱土金属为助剂，催化剂载体为耐熔无机氧化物。催化剂的表面积为150～250m2/g，孔容积为0.3～0.8ml/g。在反应温度150～250℃，压力1.5～3.0MPa，体积空速2.0～4.0h-1条件下，产品的溴指数小于100mgBr/100g油，芳烃损失小于0.5wt％。
CN101260320A公开了一种连续重整汽油选择性加氢脱烯烃催化剂及制备方法。该催化剂的显著特点是贵金属活性组分在载体上呈蛋壳型分布，其优点在于一方面显著提高了贵金属活性组分的利用率，降低了贵金属活性组分的含量和催化剂成本；另一方面显著降低了芳烃加氢的活性，提高了烯烃加氢的选择性，降低了芳烃加氢损失。
国内有些连续重整装置，在重整反应系统的最后一个反应器后面串联一个加氢反应器，采用常规的硫化态Co、Mo、Ni、W加氢精制催化剂，在较高的温度（300-330℃）和较低的空速（2-3h-1）下操作。例如中国专利CN1394937A采用W-Mo、Ni-Co催化剂在200-320℃，压力不小于0.7MPa，液时空速1-8h-1，氢油体积比不下于30。该方法很难达到深度脱烯烃（溴价小于200mgBr/100g油）和保证芳烃在加氢过程中不损失（芳烃损失小于0.5wt%）的要求。另外，由于重整汽油和重整副产氢气中不含硫，硫化态Co-Mo或Ni-Mo加氢精制催化剂很容易失硫而导致失活；同时，这种催化剂再生时析出的硫会严重污染重整反应器中的铂系催化剂。
非晶态合金是一种原子在三维空间呈拓扑无序状排列，不存在长程周期性，但在几个原子间距的范围内，原子的排列仍有一定的规律，这一结构特征使其具有晶态合金不具备的催化性能。非晶态合金催化剂应用于重整生成油选择性加氢脱除烯烃也有报道，例如，CN1152605A公开了一种从重整生成油中除去烯烃的选择性加氢工艺，是在磁稳定床反应器中，使液态重整生成油和氢气与一种铁磁性加氢催化剂接触。其反应条件为：反应温度50～220℃，反应压力0.1～3MPa，反应空速2～40h-1，氢/油比40～150。
CN1250799A公开了一种重整生成油烯烃饱和加氢方法，包括在催化剂存在下，将重整生成油与氢气接触，接触的条件为温度50～200℃，压力大于0.1MPa，液时空速0.1～20h-1，氢/油比大于30；所述催化剂含有一种多孔载体材料、一种第Ⅷ族金属和选自硼、磷中的一种或两种的元素，所述第Ⅷ族金属以非晶态合金的形式存在并负载于多孔载体材料中，第Ⅷ族金属及硼和/或磷的含量为0.1～60wt％，第Ⅷ族金属元素与硼和/或磷的原子比为0.5～10。
贵金属催化剂由于其活性高，处理量大，催化剂稳定性好，使用寿命长，操作简便等优点，因此比其它催化剂更适用于选择性脱除重整生成油中的烯烃。但其也存在催化剂的价格昂贵，反应初期催化剂活性过高，芳烃损失严重等问题。因此，催化剂在开工时需要用有机硫化物进行钝化处理。
发明内容
本发明的目的是提供一种重整生成油加氢脱烯烃方法。开发一种活性高，选择性好，寿命长的加氢催化剂。贵金属在该催化剂上呈薄蛋壳型分布，有效降低贵金属的用量，提高贵金属利用率，同时薄蛋壳型这一结构特征也有利于在脱除烯烃时，尽量降低芳烃的损失。为了进一步抑制芳烃加氢，本发明用助剂对催化剂进行改性，使其初活性降低，因此不需要用具有恶臭味的有机硫进行钝化，有效避免了钝化过程对操作人员和环境的危害，缩短开工时间，节约成本。
本专利经过大量试验，从众多催化剂配方中筛选出适合重整生成油选择性加氢脱烯烃的催化剂，按照本发明提供的方法制备出来的催化剂具有以下特征，以适应重整生成油选择性加氢脱烯烃这一反应：贵金属在载体上呈薄蛋壳型分布，蛋壳厚度为0.05-1mm；催化剂的比表面积为50-400m2/g；孔体积为0.2-1.2cm3/g，其中孔径在5-50nm的孔占催化剂总孔道的50-80%。
本发明催化剂由活性组分、助剂、载体三部分组成，其中，活性组分的质量百分含量为0.05-0.5wt%，助剂的质量百分含量为0.5-10wt%，其余为载体。活性组分为贵金属Pt、Pd中的至少一种，助剂为Sn、Pb中的一种或两种，载体为Al2O3。
本发明催化剂采用浸渍法，为了得到特定织构及性能的催化剂，须用有机酸或无机酸调节浸渍液pH值，使其在1.0-4.0之间。具体制备方法如下：
1)将活性组分可溶性前驱物用去离子水溶解，将助剂可溶性前驱物用含10-20wt%HCl的稀盐酸溶液溶解，将二者混合并加热，使得混合溶液温度在15-80℃之间；
2)用有机酸或无机酸调节步骤1)所得混合溶液，使其pH在1.0-4.0之间；
3)将载体置于2)所得溶液中，浸渍2-24h，浸渍过程中不断搅拌，以使活性组分和助剂在载体上以特定结构特征分布；
4)将步骤3)所得催化剂在100-150℃下干燥6-24h，升温速率为10-20℃/h；
5)将步骤4)所得催化剂在400-600℃下焙烧即得所需催化剂。
步骤1)所述活性组分可溶性前驱物为氯铂酸、硝酸铂、氯化铂、氯化钯、硝酸钯等。助剂可溶性前驱体为氯化亚锡、硝酸铅、醋酸铅。步骤2)所述有机酸或无机酸为盐酸、硝酸、硫酸、草酸、醋酸、柠檬酸。
本发明采用助剂对催化剂进行钝化，降低其初始活性，避免其在开工初期由于活性过高导致芳烃损失严重。使用前需在氢气氛下还原活化，所需活化温度为150-350℃，压力为1.0-3.0MPa，氢气体积空速为500-2000h-1。经活化后催化剂直接进料反应，反应条件为：温度150-250℃，压力为1.0-3.0MPa，空速为1.0-6.0h-1，氢油体积比为100-1000。本发明催化剂不需用有机硫化物钝化，避免了有机硫化物对操作人员的毒害和对环境污染。
本发明的优点
本发明提供的一种用于重整生成油选择性加氢脱烯烃的方法，按照本发明所用的催化剂，活性组分在载体上呈蛋壳型分布，这一结构特征既能有效降低了贵金属的用量，提高贵金属的利用率，降低催化剂成本，又能在脱除烯烃时，有效降低芳烃的损失。而且本发明催化剂经活化后直接进料反应，不需要用具有恶臭味的有机硫进行钝化，有效避免了钝化过程对操作人员和环境的危害，缩短开工时间，节约成本。
具体实施方式
实施例1：
称取0.133g六水氯铂酸用去离子水溶解，取0.95g氯化亚锡，用含10%HCl的稀盐酸溶解，将二者混合并加热到50℃，向混合溶液中缓慢添加盐酸，使其pH为1.0，溶液总体积为90ml，将溶液搅拌均匀，加入99.45g氧化铝载体浸渍，浸渍的过程中不断搅拌，2h后将浸渍好的催化剂滤出干燥，从室温缓慢升高到110℃，升温速率为20℃/h，在110℃下恒温干燥6h。将干燥好的催化剂在420℃下焙烧3h焙烧，即得所需催化剂。
称取20g催化剂在固定床反应器中程序升温还原活化，活化条件为：氢气压力为1MPa，体积空速为500h-1，在150℃下还原2h，升温速率为10℃/h。还原结束后直接进料反应，其中原料含芳烃70wt%，溴价为6.2gBr/100g油，质量空速为2h-1，H2/油体积比为100，结果如表1所示。
实施例2
称取8.33g氯化钯用去离子水溶解，取15.99g硝酸铅用15%HCl的稀盐酸溶解，将二者混合并加热到30℃，向混合溶液中缓慢添加硝酸，使其pH为2.0，溶液总体积为90ml，将溶液搅拌均匀，加入85g氧化铝载体浸渍，浸渍的过程中不断搅拌，24h后将浸渍好的催化剂滤出干燥，从室温缓慢升高到100℃，升温速率为10℃/h，在100℃下恒温干燥8h。将干燥好的催化剂在400℃下焙烧5h焙烧，即得所需催化剂。
称取20g催化剂在固定床反应器中程序升温还原活化，活化条件为：氢气压力为3.0MPa，体积空速为2000h-1，在350℃下还原5h，升温速率为10℃/h。还原结束后，将温度降到160℃，压力降到2.0MPa，进料反应，调整反应质量空速为2h-1，H2/油体积比为200，原料含芳烃60wt%，溴价为5.5gBr/100g油，结果如表1所示。
实施例3
称取0.17g四氯化铂，0.43g硝酸钯用去离子水溶解，,1.57g醋酸铅用20%HCl的稀盐酸溶解，将二者混合并加热到15℃，向混合溶液中缓慢添加草酸，使其pH为4.0，溶液总体积为100ml，将溶液搅拌均匀，加入98.7g氧化铝载体浸渍，浸渍的过程中不断搅拌，12h后将浸渍好的催化剂滤出干燥，从室温缓慢升高到120℃，升温速率为10℃/h，在120℃下恒温干燥18h。将干燥好的催化剂在500℃下焙烧5h焙烧，即得所需催化剂。
称取20g催化剂在固定床反应器中程序升温还原活化，活化条件为：氢气压力为2.0MPa，体积空速为1500h-1，在250℃下还原5h，升温速率为10℃/h。还原结束后，在温度为250℃，压力为2.0MPa下进料反应，调整反应质量空速为6.0h-1，H2/油体积比为1000，原料含芳烃80wt%，溴价为4.5gBr/100g油，结果如表1所示。
实施例4
称取0.27g硝酸铂用去离子水溶解，取1.90g氯化亚锡，3.14g醋酸铅，用含13%HCl的稀盐酸溶解，将两个溶液混合并加热到70℃，向混合溶液中缓慢添加醋酸，使其pH为3.0，溶液总体积为98ml，将溶液搅拌均匀，加入96.8g氧化铝载体浸渍，浸渍的过程中不断搅拌，18h后将浸渍好的催化剂滤出干燥，从室温缓慢升高到130℃，升温速率为10℃/h，在130℃下恒温干燥10h。将干燥好的催化剂在450℃下焙烧6h焙烧，即得所需催化剂。
称取20g催化剂在固定床反应器中程序升温还原活化，活化条件为：氢气压力为2.5MPa，体积空速为800h-1，在180℃下还原3h，升温速率为10℃/h。还原结束后，在温度为180℃，压力为2.5MPa下进料反应，调整反应质量空速为5.0h-1，H2/油体积比为300，原料含芳烃75wt%，溴价为6.5gBr/100g油，结果如表1所示。
实施例5
称取0.65g硝酸钯用去离子水溶解，取9.59g氯化亚锡，用含HCl12%的稀盐酸溶解，将两个溶液混合并加热到80℃，向混合溶液中缓慢添加柠檬酸，使其pH为2.5，溶液总体积为90ml，将溶液搅拌均匀，加入94.7g氧化铝载体浸渍，浸渍的过程中不断搅拌，11h后将浸渍好的催化剂滤出干燥，从室温缓慢升高到150℃，升温速率为10℃/h，在150℃下恒温干燥8h。将干燥好的催化剂在550℃下焙烧7h焙烧，即得所需催化剂。
称取20g催化剂在固定床反应器中程序升温还原活化，活化条件为：氢气压力为1.8MPa，体积空速为900h-1，在280℃下还原3h，升温速率为10℃/h。还原结束后，将温度降为170℃，压力为1.8MPa下进料反应，调整反应质量空速为4.0h-1，H2/油体积比为400，原料含芳烃78wt%，溴价为6.8gBr/100g油，结果如表1所示。
实施例6
催化剂稳定性试验，称取100g实施例5催化剂在固定床反应器中程序升温还原活化，活化条件为：氢气压力为2.0MPa，体积空速为800h-1，在180℃下还原3h，升温速率为10℃/h。还原结束后，在温度为180℃，压力为2.0MPa下进料反应，调整反应质量空速为4.0h-1，H2/油体积比为800，原料含芳烃72wt%，溴价为5.2gBr/100g油，结果如表2所示。由表2可以看出，催化剂经2200h运转，产品溴价始终≤0.03gBr/100g油，而芳烃基本不损失。因此，本发明催化剂适合用于重整生成油选择性加氢脱烯烃，能满足工业长期运转的需要。
表1催化剂技术特征及反应结果
表2催化剂稳定性实验结果
| 反应时间/h | 溴价/gBr/100g油 | 芳烃损失/% |
| 0-10 | 0.01 | 0.5 |
| 10-20 | 0.02 | 0.3 |
| 20-100 | 0.02 | 0.2 |
| 100-200 | 0.03 | 0.1 |
| 200-500 | 0.03 | 0.04 |
| 500-900 | 0.03 | 0.05 |
| 900-1500 | 0.02 | 0.06 |
| 1500-2200 | 0.03 | 0.03 |
Claims (1)
1.一种重整生成油选择性加氢脱烯烃的方法，其特征在于：直接进料反应，反应条件为：温度150-250℃，压力为1.0-3.0MPa，空速为1.0-6.0h-1，氢油体积比为100-1000；
所用的催化剂活性组分为Pt、Pd中的至少一种，助剂为Sn、Pb中的一种或两种，载体为Al2O3，催化剂具有以下特征：贵金属在载体上呈薄蛋壳型分布，蛋壳厚度为0.05-1mm；催化剂的比表面积为50-400m2/g；孔体积为0.2-1.2cm3/g，其中孔径在5-50nm的孔占催化剂总孔道的50-80%；
所述的活性组分的质量百分含量为0.05-0.5wt%，助剂的质量百分含量为0.5-10wt%，其余为载体；
催化剂在使用前在氢气氛下还原活化，所需活化温度为150-350℃，压力为0.1-3.0MPa，氢气体积空速为500-2000h-1。
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| CN105601463A (zh) * | 2015-12-31 | 2016-05-25 | 浙江工业大学 | 一种直链烷基苯催化加氢精制的方法 |
| CN105601463B (zh) * | 2015-12-31 | 2017-12-05 | 浙江工业大学 | 一种直链烷基苯催化加氢精制的方法 |
| CN110961124A (zh) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | 一种重整生成油加氢脱烯烃催化剂及制备方法与应用 |
| CN110841650A (zh) * | 2019-11-20 | 2020-02-28 | 湖南长岭石化科技开发有限公司 | 一种重整生成油选择性加氢脱烯烃的非贵金属催化剂及其制备方法和应用 |
| CN110841650B (zh) * | 2019-11-20 | 2022-08-09 | 湖南长岭石化科技开发有限公司 | 一种重整生成油选择性加氢脱烯烃的非贵金属催化剂及其制备方法和应用 |
| CN112892612A (zh) * | 2019-12-03 | 2021-06-04 | 中国石化集团金陵石油化工有限责任公司 | 一种用于烃类转化反应的催化剂 |
| CN112892612B (zh) * | 2019-12-03 | 2023-01-17 | 中国石化集团金陵石油化工有限责任公司 | 一种用于烃类转化反应的催化剂 |
| CN114471619A (zh) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | 一种重整生成油加氢脱烯烃催化剂及其制备方法 |
| CN114471619B (zh) * | 2020-10-26 | 2023-09-01 | 中国石油化工股份有限公司 | 一种重整生成油加氢脱烯烃催化剂及其制备方法 |
| CN114950418A (zh) * | 2021-02-25 | 2022-08-30 | 中国石油化工股份有限公司 | 催化剂及其制备方法以及共轭双烯烃选择性加氢方法 |
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