CN112547114A - 烯烃加氢催化剂及其制备方法和应用 - Google Patents
烯烃加氢催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 68
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000007789 gas Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 45
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 11
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
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- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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Abstract
本发明提供一种烯烃加氢催化剂,该催化剂由镍及助剂负载于具有强吸附效果的载体上制得,催化剂使用时利用烯烃物质与催化剂吸附热及反应热进行自发连续加氢反应,即可在常温下将C2‑C4烯烃与氢气进行加氢反应,气相中烯烃摩尔占比1%‑3%,加氢后气相中烯烃摩尔占比可低至≤0.005%。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种烯烃加氢催化剂,该催化剂可在常温下将气态C2-C4烯烃与氢气反应,将烯烃饱和成对应烷烃。
背景技术
蒸汽裂解制乙烯及炼厂副产大量C4馏分,其产量与组成随裂解原料的种类、裂解深度和裂解工艺的不同而各异,一般含有C2-C4烷烃、烯烃、二烯烃。通常情况下C4馏分水量较高,在其经脱水并进行加氢饱和后制得C4馏分烷烃是优质的裂解原料、汽油添加剂、冷冻剂、重质油加工脱沥青溶剂、油田井管脱蜡剂、树脂发泡剂及烯烃聚合溶剂等。
以铂、钯为主的贵金属催化剂用于饱和加氢反应中,由于不饱和烃中往往含有一定量胶质和硫,容易导致贵金属催化剂失活。
CN200810222182.1中公开了一种以氧化铝为载体,钯为活性组分,Ru和Ag为助剂的加氢催化剂,该催化剂适用于选择性脱除丁二烯,达到得到高纯度1-丁烯的目的。通常,C4馏分选择性加氢多采用Pd为活性组分。
相对于贵金属加氢催化剂而言,以镍为主要活性组分的加氢催化剂由于本身结构特点,从催化剂成本和加氢效果上更具有优势。目前镍催化剂主要的制备方法有浸渍法和共沉淀法。
CN110124670A公开了一种碳四组分选择性加氢催化剂及制备方法,采用共沉淀法制备镍-铜/硅藻土催化剂,镍与铜总量占催化剂总量的40%,使用温度130℃,烯烃转化率87%,该催化剂使用温度较高,烯烃转化率较低。
一般低碳馏分油品会涉及C2-C4加氢,如戊烷脱烯烃,需要脱除C2-C5烯烃,其中涵盖C2-C4组成烯烃。通常采用镍系催化剂,在适当加热汽化后进行烯烃脱除。在适宜的工艺条件下单独加氢饱和C2-C4烯烃的催化剂暂时少有报道。
发明内容
发明目的:本发明提供一种C2-C4烯烃常温加氢催化剂,填补目前专门针对C2-C4烯烃加氢市场的空白。
本发明所要解决的技术问题由以下技术方案来实现:烯烃加氢催化剂,包括负载于强吸附载体上的镍及助剂,其特征在于所述载体比表面积≥250m3/g,总孔容量0.25ml/g~0.35ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量50%以上,其余孔容量为中孔、介孔、大孔的孔容量。
通常地,所述载体采用比表面≥250m3/g,孔容量0.2 ml/g ~0.3ml/g,孔径≤2nm,硅铝原子比为0~100任意比例的硅铝基粉末,成型后经焙烧得到。
所述烯烃加氢催化剂,以质量百分含量计,镍含量为7.5%~15%,助剂含量为0.1%~1%。
所述助剂为第一主族或镧系中的一种或几种。
本发明提供的烯烃加氢催化剂的制备方法,是催化剂活性组分以等体积浸渍的方式浸渍到载体上,经烘干,空气气氛下焙烧,再经氢气预还原后,得到成品催化剂。
优选地,催化剂活性组分以等体积浸渍的方式浸渍到载体上,经过烘干,空气气氛下400℃焙烧8h,再在400℃下进行氢气预还原8h后,得到成品催化剂。
本发明催化剂一种典型的制备方法,包括以下步骤:
(1)选择比表面≥250m3/g,孔容量0.2 ml/g -0.3ml/g,孔径≤2nm 的铝基或硅铝基粉末;
(2)将该粉末添加适量去离子水与粘结剂,经过打片或挤条或滚球等常规方法得到具有固定形状的载体,将该载体在550℃下焙烧8h,得到比表面积≥250m3/g,总孔容量0.25ml/g~0.35ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量50%以上的具有较强吸附功能的载体;
(3)按照镍含量占催化剂总重量7.5%~15%,助剂占催化剂总重量0.1%~1%,将镍和助剂的前驱体配制成溶液,以等体积浸渍的方式浸渍到载体上,烘干,空气气氛下400℃焙烧8h,在400℃下进行氢气预还原8h后,得到成品催化剂。
本发明还提供上述催化剂的应用,所述催化剂用烯烃加氢反应中,利用烯烃物质与催化剂吸附热及反应热进行连续加氢反应。
优选地,所述催化剂用于烯烃加氢反应中时,烯烃存在于气相中,与H2进行混合,烯烃的总摩尔占比不高于10%,H2总摩尔占比不低于60%,其余为不参与加氢的气相物质。
优选地,所述催化剂用于烯烃加氢反应中时,所述烯烃为C2-C4烯烃。
优选地,所述催化剂用于烯烃加氢反应中时,将催化剂置于固定床反应器中,在压力0.1MPa~6MPa下,以空速1500h-1~6000 h-1通入与H2混合后的烯烃,投料温度-5℃~40℃,反应后气体中烯烃总摩尔占比≤0.005%。
本发明的有益效果:
(1)本催化剂可将气相中C2-C4烯烃加氢饱和,反应温度-5℃-40℃,反应压力0.1MPa-6MPa,通常情况下不需加热,压力保持在正压,反应即可自发进行;
(2)气相中烯烃摩尔占比1%-3%,加氢后气相中烯烃摩尔占比可低至≤0.005%。
具体实施方式
下面结合实施例对本发明加以详细描述。
实施例1
载体1制备:取硅铝比25,比表面=250m3/g,孔容量0.2 ml/g,孔径0.5nm的ZSM-5氢型分子筛160g,加入去离子水40ml,羧甲基纤维素钠0.04g,搅匀,造粒,烘干,打片,550℃焙烧8h,得到载体1。载体1比表面积=250m3/g,总孔容量0.25ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量50%。
实施例2
载体2制备:取硅铝比38,比表面=300m3/g,孔容量0.3 ml/g,孔径0.5nm的ZSM-5氢型分子筛160g,加入去离子水40ml,羧甲基纤维素钠0.04g,搅匀,滚球,烘干,550℃焙烧8h,得到载体2。载体2比表面积=300m3/g,总孔容量0.35ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量55%。
实施例3
载体3制备:取硅铝比70,比表面=260m3/g,孔容量0.25 ml/g,孔径0.5nm的ZSM-5氢型分子筛160g,加入去离子水40ml,羧甲基纤维素钠0.04g,搅匀,挤条,烘干,550℃焙烧8h,得到载体3。载体3比表面积=260m3/g,总孔容量0.30ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量50%。
实施例4
载体4制备:取比表面=250m3/g,孔容量0.30 ml/g,平均孔径2nm的氧化铝铝粉160g,加入去离子水40ml,羧甲基纤维素钠0.04g,搅匀,造粒,烘干,打片,550℃焙烧8h,得到载体4。载体4比表面积=260m3/g,总孔容量0.30ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量50%。
实施例5
载体5制备:取比表面=260m3/g,孔容量0.30 ml/g,平均孔径2nm的硅粉160g,加入去离子水40ml,羧甲基纤维素钠0.04g,搅匀,造粒,烘干,打片,550℃焙烧8h,得到载体5。载体5比表面积=250m3/g,总孔容量0.25ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量50%。
实施例6
催化剂1制备:取80g六水合硝酸镍,1.5g硝酸钾,加热至自溶解,加入去离子水调至30ml。将该溶液喷淋于100g载体1上,浸渍均匀,静置60min后,120℃烘干8h,再在空气气氛下400℃焙烧8h,最后经氢气气氛下400℃还原8小时后得到催化剂1。
实施例7
催化剂2制备:取40g六水合硝酸镍,0.15g硝酸钾,加热至自溶解,加入去离子水调至25ml。将该溶液喷淋于100g载体2上,浸渍均匀,静置60min后,120℃烘干8h,再在空气气氛下400℃焙烧8h,最后经氢气气氛下400℃还原8小时后得到催化剂2。
实施例8
催化剂3制备:取60g六水合硝酸镍,1g硝酸钾,加热至自溶解,加入去离子水调至25ml。将该溶液喷淋于100g载体3上,浸渍均匀,静置60min后,120℃烘干8h,再在空气气氛下400℃焙烧8h,最后经氢气气氛下400℃还原8小时后得到催化剂3。
实施例9
催化剂4制备:取60g六水合硝酸镍,1.5g硝酸镧,加热至自溶解,加入去离子水调至25ml。将该溶液喷淋于100g载体4上,浸渍均匀,静置60min后,120℃烘干8h,再在空气气氛下400℃焙烧8h,最后经氢气气氛下400℃还原8小时后得到催化剂4。
实施例10
催化剂5制备:取60g六水合硝酸镍,1.5g硝酸镧,加热至自溶解,加入去离子水调至25ml。将该溶液喷淋于100g载体5上,浸渍均匀,静置60min后,120℃烘干8h,再在空气气氛下400℃焙烧8h,最后经氢气气氛下400℃还原8小时后得到催化剂5。
实施例11
取50ml催化剂1,装入固定床反应器,400℃下通入纯氢还原8h后降温至40℃,将系统压力升至0.1MPa,以体积空速6000 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为1%。加氢后结果如表1所示。
实施例12
取50ml催化剂1,装入固定床反应器,400℃下通入纯氢还原8h后降温至25℃,将系统压力升至1.5MPa,以体积空速3000 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为5%。加氢后结果如表1所示。
实施例13
取50ml催化剂1,装入固定床反应器,400℃下通入纯氢还原8h后降温至-5℃,将系统压力升至6.0MPa,以体积空速1500 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为10%。加氢后结果如表1所示。
实施例14
取50ml催化剂2,装入固定床反应器,400℃下通入纯氢还原8h后降温至25℃,将系统压力升至1.5MPa,以体积空速3000 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为5%。加氢后结果如表1所示。
实施例15
取50ml催化剂3,装入固定床反应器,400℃下通入纯氢还原8h后降温至25℃,将系统压力升至1.5MPa,以体积空速3000 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为5%。加氢后结果如表1所示。
实施例16
取50ml催化剂4,装入固定床反应器,400℃下通入纯氢还原8h后降温至25℃,将系统压力升至1.5MPa,以体积空速3000 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为5%。加氢后结果如表1所示。
实施例17
取50ml催化剂5,装入固定床反应器,400℃下通入纯氢还原8h后降温至25℃,将系统压力升至1.5MPa,以体积空速3000 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为5%。加氢后结果如表1所示。
实施例18
取50ml催化剂1,装入固定床反应器,400℃下通入纯氢还原8h后降温至25℃,将系统压力升至1.5MPa,以体积空速3000 h-1通入原料气,原料气中C2-C4混合烯烃摩尔含量为5%。反应时间500h,500h后加氢后结果如表1所示。
表1 催化剂使用结果
原料中烯烃摩尔含量百分比,% | 加氢后烯烃摩尔含量百分比,% | 入口温度,℃ | 反应压力,MPa | 空速,h<sup>-1</sup> | |
实施例11 | 1 | 0.002 | 40 | 0.1 | 6000 |
实施例12 | 5 | 0.001 | 25 | 1.5 | 3000 |
实施例13 | 10 | 0.005 | -5 | 6 | 1500 |
实施例14 | 5 | 0.002 | 25 | 1.5 | 3000 |
实施例15 | 5 | 0.002 | 25 | 1.5 | 3000 |
实施例16 | 5 | 0.005 | 25 | 1.5 | 3000 |
实施例17 | 5 | 0.005 | 25 | 1.5 | 3000 |
实施例18 | 5 | 0.003 | 25 | 1.5 | 3000 |
从表1数据可以看出,选定孔结构范围的不同硅铝比粉末制备的载体,在制备成催化剂后,在-5℃~40℃时均可自发进行加氢脱烯烃效果。加氢后残烯烃摩尔百分含量≤0.005%。
如上所述,尽管参照特定的优选实施例已经表示和表述了本发明,但其不得解释为对本发明自身的限制。在不脱离所附权利要求定义的本发明的精神和范围前提下,可对其在形式上和细节上作出各种变化。
Claims (10)
1.一种烯烃加氢催化剂,包括负载于强吸附载体上的镍及助剂,其特征在于所述载体比表面积≥250m3/g,总孔容量0.25ml/g~0.35ml/g,其中直径≤2nm微孔总孔容量占载体总孔容量50%以上,其余孔容量为中孔、介孔、大孔的孔容量。
2.根据权利要求1中所述烯烃加氢催化剂,其特征在于所述载体采用比表面≥250m3/g,孔容量0.2 ml/g ~0.3ml/g,孔径≤2nm ,硅铝原子比为0~100任意比例的硅铝基粉末,成型后经焙烧得到。
3.根据权利要求1中所述烯烃加氢催化剂,其特征在于以质量百分含量计,镍含量为7.5%~15%,助剂含量为0.1%~1%。
4.根据权利要求1或4所述烯烃加氢催化剂,其特征在于所述助剂为第一主族或镧系中的一种或几种。
5.根据权利要求1所述烯烃加氢催化剂的制备方法,其特征在于催化剂活性组分以等体积浸渍的方式浸渍到载体上,经烘干,空气气氛下焙烧,再经氢气预还原后,得到成品催化剂。
6.根据权利要求5所述烯烃加氢催化剂的制备方法,其特征在于催化剂活性组分以等体积浸渍的方式浸渍到载体上,经过烘干,空气气氛下400℃焙烧8h,再在400℃下进行氢气预还原8h后,得到成品催化剂。
7.根据权利要求1所述烯烃加氢催化剂的应用,其特征在于所述催化剂用于烯烃加氢反应中,烯烃存在于气相中,与H2进行混合。
8.根据权利要求7所述烯烃加氢催化剂的应用,其特征在于烯烃存在于气相中,与H2进行混合,烯烃的总摩尔占比不高于10%,H2总摩尔占比不低于60%,其余为不参与加氢的气相物质。
9.根据权利要求7所述加烯烃加氢催化剂的应用,其特征在于所述烯烃为C2-C4烯烃。
10.根据权利要求7所述加烯烃加氢催化剂的应用,其特征在于将催化剂置于固定床反应器中,在压力0.1MPa~6MPa下,以空速1500h-1~6000 h-1通入与H2混合后的烯烃,投料温度-5℃~40℃,反应后气体中烯烃总摩尔占比≤0.005%。
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