CN105682797B - 树脂氢化的方法与催化剂 - Google Patents
树脂氢化的方法与催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title description 6
- 239000011347 resin Substances 0.000 title description 6
- 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 65
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 43
- 239000010941 cobalt Substances 0.000 claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007868 Raney catalyst Substances 0.000 claims abstract description 14
- 229910000564 Raney nickel Inorganic materials 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
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Abstract
本发明属于催化剂领域。具体而言,本发明有关于催化剂氢化方法和其中所使用的催化剂。依据本发明,提供一种用于烃树脂的氢化的方法、催化剂本身、以及制备该催化剂的方法,特别是使用钴促进的在氧化硅/氧化铝上的镍催化剂,烃树脂进料有相当高的硫含量。
Description
技术领域
本发明涉及催化剂领域。更详细地,本发明涉及催化剂氢化方法和方法中所使用的催化剂。
背景技术
WO-A-01/36093叙述用于烃树脂的氢化的镍-铁-氧化硅-氧化铝催化剂。这些和其他习知的镍氢化催化剂,在烃树脂进料中具有低活性,特别是当在进料中的硫量超过100ppm时。因此,需要提供一种催化剂和方法,对于有较高量硫的烃树脂的氢化,可得到良好的催化剂活性。
因此,本发明的目的为提供用于烃树脂的氢化的催化剂和方法,而得到此优点。另一目的为提供制备此催化剂的方法。本发明的再一目的为,提供适用于烃树脂的氢化的催化剂,而有成本效益。
US-A-4 263 225叙述镍-钴-氧化硅和镍-钴-铜-氧化硅的氢化催化剂,以及使用这些催化剂的氢化单体芳香族化合物的方法。在此文件中没有提到烃树脂的氢化。
US-A-3 945 944叙述一种钴促进的镍催化剂,承载于耐火物质上,以及使用此催化剂以制造含氢或富含甲烷的气体。如US-A-4 263 225一样,此文件中没有提到烃树脂的氢化。
US-A-4 532 351叙述一种氢化方法,系使用包括镍、钴、铜、氧化铝和氧化硅的催化剂以氢化有机化合物例如烯烃。US-A-4 532 351亦叙述此催化剂可适用于加氢脱硫方法。然而,此文件并未提及烃树脂的氢化。
WO-A-2004/035204叙述一种镁促进的镍催化剂,适用于不饱和有机化合物的氢化,特别是具有高硫量的脂肪油。WO-A-2004/035204亦叙述一种包括镍、氧化硅、氧化铝和钴的催化剂,其不适用于该氢化反应。此文件中没有提到烃树脂的氢化。
AU-B-66865/81叙述一种经承载的共沉淀催化剂,系由铝、一种或多种第VIII族非铁金属的盐类、和固体多孔粒子而得,以及制造此催化剂的方法。AU-B-66865/81没有提到烃树脂的氢化,也没有提到具有含硫化合物的烃树脂。
发明内容
本发明的发明人发现,钴促进的承载于氧化硅/氧化铝上的镍催化剂,非常适合于烃树脂的氢化,特别是有相当高硫含量的烃树脂进料。
因此,本发明的一个特征为用于烃树脂进料的氢化的方法,该烃树脂进料包括一种或多种硫化合物,该方法包括在催化剂的存在下将该烃树脂进料与氢接触的步骤,其中该催化剂为以钴促进的承载于氧化硅和氧化铝上的镍催化剂,该催化剂具有45至85wt%的镍含量(以Ni作计算),13.75至45wt%的硅含量(以SiO2作计算),1至15wt%的铝含量(以Al2O3作计算),以及0.25至12wt%的钴含量(优选以Co计算),且该催化剂介于2和60nm之间的孔体积为至少0.35ml/g催化剂,优选为介于10和60nm之间的孔体积为至少0.20ml/g催化剂。
在此使用的有关于催化剂的所有重量百分比,都是以还原的催化剂的基础作计算的。在此使用的所有ppm值,都是以重量为基准,除非另有说明。
本发明更有关于上述催化剂本身,以及使用此催化剂的方法。
具体实施方式
令人惊讶地发现,相较于不含有钴促进剂的那些配方,本发明的催化剂在含有硫化合物的烃树脂进料中提供增进的活性。更令人惊讶的是,发现钴促进剂的量可以非常低。相较于已知的氢化树脂催化剂,这提供了显著的经济费用的节省。
依据本发明,钴含量优选为0.25至12wt%(以Co作计算),更佳为0.25至4.5wt%(以Co作计算),且甚至更佳为0.3至4wt%(以Co作计算)。令人惊讶地,发现相较于非促进的镍催化剂,只有约0.3wt%的钴即可导致催化剂活性有>40%的增加。甚至更令人惊讶地,发现相较于WO-A-01/36093非钴促进的类似物,如此低量的钴,导致催化剂活性有大约300%的增加。
希望不受任何理论拘束,假设经承载的镍催化剂中的钴的促进效果,是源于在Ni结晶晶格中无序(disorder)程度的增加,因此可提供催化剂的硫容限的增进。
因此,本发明亦有关于一种钴促进的承载于氧化硅和氧化铝上的镍催化剂,其中该催化剂的镍含量(以Ni作计算)为45至85wt.%,硅含量(以SiO2作计算)为13.75至45wt.%,铝含量(以Al2O3作计算)为1至15wt.%,以及钴含量(以Co作计算)为0.25至1.5wt.%,且此催化剂优选介于2和60nm之间的孔体积为至少0.35ml/g催化剂,更佳为介于10和60nm之间的孔体积为至少0.20ml/g催化剂。
催化剂的镍含量,一般为45至85wt%之间,且优选为55和75wt%之间。在这些范围内,可得到最佳的活性和选择性。
承载物质是氧化硅和氧化铝的组合。此可为这两种成份的混合物,但是硅和铝离子至少部分在相同结晶晶格中也是可能的。
本发明催化剂的BET表面积,优选为介于200至350m2/g之间。在此所用的BET表面积,系以微晶粒孔径分析仪ASAP 2420测量,催化剂样品在180℃脱气之后,测量在77K之下,P/Po大约0.3之下的氮吸附量,假设氮的截面积为
一般而言,本发明的催化剂介于2和60nm之间的孔体积为至少0.35ml/g催化剂,更佳为介于10和60nm之间的孔体积为至少0.20ml/g催化剂。在此所用的孔体积,系使用排气温度300℃、压力<15μm Hg,在微晶粒孔径分析仪ASAP 2420上测量在孔直径为2和200nm内的N2脱附,且假设孔是圆柱形的,样品系在375℃之下煅烧1.5小时。
S-毒化程度,系以所使用反应介质中的镍毒化的百分比表示。这是测定氢化烃树脂的催化剂的反应速率而得,以催化剂的镍含量wt.%为函数。与x轴的交错处为阈值,在催化剂最低量的镍wt.%系没有氢化活性。一般而言,在此函数中,S-毒化的程度越低,催化剂的S-容限越高。
催化剂氢化烃树脂的反应速率系以反应速率常数表示,系在30%至70%转换之间进行线性回归而得,以1/h表示。
氢化吸附力(HAC;hydrogen adsorption capacity),是测定可用于催化剂作用的镍表面积程度的一般量测。本发明的催化剂一般而言HAC的范围为15至25ml H2/g催化剂。于在在线的与氢的还原反应,10℃/min至375℃的温度坡度之下,在375℃之下停留2小时,接着在-75℃之下氩气下进行脱气45分钟之后,在氩气气氛下以10℃/min的速率由-75℃至700℃的温度坡度,藉由氢的脱附量而测定HAC。
本发明的催化剂可为粉末、粒子、颗粒、和成形体(如球体、挤出物、或锭状)的形式。优选本发明的催化剂为粉末催化剂。
本发明的催化剂可以各种方式制备,例如将活性成份在预成形的含有氧化硅和氧化铝的载体上浸渍或沉淀,或在该载体上沉淀。
然而,优选为以共沉淀法制备经承载的催化剂。这包括由溶液中沉淀出催化剂成份(催化剂前驱物),特别是由一种或多种的镍盐、钴盐、铝盐,以及一种或多种硅化合物等各种溶液中,且选择性地为其他成份,例如铁盐、锌盐、和镁盐及其组合,通常藉由加入碱或藉由电化学方式而增加或维持pH到7.0以上。可使用通常的技术,例如将所有溶液同时加到沉淀容器中,或提供一种或多种成份以及加入其他成份至容器中。
本发明亦有关于制备上述类型的承载于氧化硅和氧化铝上的镍催化剂的一种方法,该方法包括在pH值7.0至9.0之下共沉淀催化剂成份,由沉淀液体中回收该共沉淀的物质,清洗它,且更处理它以制造出该催化剂。
在沉淀之后,接着可将沉淀物过滤出,清洗,且更依需要作处理。这可包括煅烧、还原、钝化、或其组合。
在本发明中,可使用烃树脂进料。可使用的烃树脂进料,一般系经由蒸馏、预处理、和聚合,而由C5或C9石油分馏物(petroleum fractions)和副产物,以及其组合物而制得。一般而言,此类烃树脂是低分子量聚合物(介于300至3000道耳顿(Daltons)之间),其包括脂肪族主干和选择的一种或多种芳香族和/或脂肪族侧基团。
一般而言,适用于本发明方法中的烃树脂进料包括一种或多种硫化合物。烃树脂进料的硫化合物含量(以硫作计算)通常为大于40ppm,优选为大于100ppm,依据烃树脂进料的重量为基础。
不希望被理论限制,相信在烃树脂进料中存在的硫化合物是在烃树脂分子中。
本发明的方法,亦包括使用前述的催化剂以氢化烃树脂进料,特别是含有一种或多种硫化物的烃树脂进料。适合的温度和压力是基于树脂的性质、最终产物所需的性质、和催化剂的真实组成和构造。
通常,适合的温度为介于100和350℃之间,优选为介于250和325℃之间。适合的部分氢压力可介于1和150bar(abs)之间。氢化时间主要是依据时间、催化剂量、和树脂所需氢化程度而定。
方法优选为批次进行,其中催化剂是以粉末而分散在烃树脂中。本发明粉末催化剂的适合粒子尺寸为介于1和1000μm之间。在氢化方法中新鲜催化剂的装载为,通常相对于树脂介于0.25和4wt.%之间。
方法可在适用于浆液氢化的不同反应器中进行,例如搅拌槽反应器(选择性梯级(cascaded))或循环反应器。
使用前述的催化剂,造成烃树脂的氢化,而产生具有仔细平衡性质(化学和物理)的产物。同时,氢化造成最终产物杂质含量的减少。
本发明依照以下实施例而加以说明。
实施例1(比较)
依据WO-A-01/36093而制备镍催化剂,系在温度95℃下,将含有镍、铁、和氧化铝等的盐类、硅酸盐、和碳酸钠的各种溶液,在充分搅拌的沉淀容器中混合。所形成的浆液的pH为大约7.5,1小时后沉淀完成。在清洗沉淀物后,将催化剂前驱物过滤,在110℃的炉中干燥。将催化剂以氢活化,在空气存在下钝化。所得催化剂的组成和物理性质,详列于表1。
实施例2(比较)
在温度95℃下,将含有镍和氧化铝的盐类、硅酸盐、和碳酸钠的各种溶液,在充分搅拌的沉淀容器中混合。所形成的浆液的pH为大约7.5,1小时后沉淀完成。在清洗沉淀物后,将催化剂前驱物过滤,在110℃的炉中干燥。将催化剂以氢活化,在空气存在下钝化。所得催化剂的组成和物理性质,详列于表1。
实施例3
在温度95℃下,将含有镍、钴、和氧化铝等的盐类、硅酸盐、和碳酸钠的各种溶液,在充分搅拌的沉淀容器中混合。所形成的浆液的pH为大约7.5,1小时后沉淀完成。在清洗沉淀物后,将催化剂前驱物过滤,在110℃的炉中干燥。将催化剂以氢活化,在空气存在下钝化。所得物质含有64wt.%Ni,25wt.%SiO2,2wt.%Al2O3和0.3wt.%Co。所得催化剂的其他物理性质,详列于表1。
实施例4
依据实施例3而制备催化剂,但使用不同浓度的含有镍、钴、和氧化铝等的盐类、硅酸盐、和钠的各种溶液。所得物质含有61wt.%Ni,25wt.%SiO2,2wt.%Al2O3,和0.6wt.%Co。所得催化剂的其他物理性质,详列于表1。
实施例5
依据实施例3而制备催化剂,但使用不同浓度的含有镍、钴、和氧化铝等的盐类、硅酸盐、和碳酸钠的各种溶液。所得物质含有59wt.%Ni,25wt.%SiO2,2wt.%Al2O3,和1.5wt.%Co。所得催化剂的其他物理性质,详列于表1。
实施例6
依据实施例3而制备催化剂,但使用不同浓度的含有镍、钴、和氧化铝等的盐类、硅酸盐、和碳酸钠的各种溶液。所得物质含有61wt.%Ni,25wt.%SiO2,2wt.%Al2O3,和2.4wt.%Co。所得催化剂的其他物理性质,详列于表1。
实施例7
依据实施例3而制备催化剂,但使用不同浓度的含有镍、钴、和氧化铝等的盐类、硅酸盐、和碳酸钠的各种溶液。所得物质含有59wt.%Ni,25wt.%SiO2,2wt.%Al2O3,和3.7wt.%Co。所得催化剂的其他物理性质,详列于表1。
实施例8
依据实施例3而制备催化剂,但使用不同浓度的含有镍、钴、和氧化铝等的盐类、硅酸盐、和碳酸钠的各种溶液。所得物质含有56wt.%Ni,25wt.%SiO2,2wt.%Al2O3,和9.2wt.%Co。所得催化剂的其他物理性质,详列于表1。
实施例9-催化剂的测试
75克的50wt.%烃树脂(含有140ppm的硫化合物,依据烃树脂的重量以硫作计算)在Shellsol D40中的溶液,与0.75克的镍催化剂混合,在20bars氢气下,在高压反应器中加热,以1400rpm搅拌。当温度达到270℃时,将氢压力增加到80bar。接下来的氢化方法系由记录氢消耗来监控。氢化烃树脂的催化剂的反应速率,系以反应速率常数来表示,系在30%和70%的转化进行线性回归而得,且以1/h表示。2小时后,完成氢化方法。将实施例1-8中所述的催化剂进行上述的活性测试。这些测试结果,列于表1。实施例表1中的总重量百分比并没有加到100wt.%,因为催化剂中的金属被部分氧化,因此含有另外的氧原子。此氧含量并没有列于以下的表1中。
表1
表1显示,相较于实施例2中非促进的催化剂和实施例1中铁促进的催化剂,实施例3-8中本发明的催化剂具有改良的氢化反应速率和改良的对于S-毒化的容限。表1亦显示,使用非常低的钴含量(只有0.3wt%)(见表1,实施例3),可得到改良的S-容限。
图1亦显示,相较于实施例2中非促进的催化剂,实施例3-8中本发明的催化剂具有改良的氢化反应速率。
Claims (10)
1.一种用于烃树脂进料的氢化的方法,该烃树脂进料包括一种或多种硫化合物,该方法包括在催化剂的存在下将该烃树脂进料与氢接触的步骤,其中该催化剂为以钴促进的承载于氧化硅和氧化铝上的镍催化剂,基于还原的催化剂的重量,该以钴促进的催化剂具有以Co作计算0.25至4wt%的钴含量,以Ni作计算45至85wt%的镍含量,以SiO2作计算13.75至45wt%的硅含量,以及以Al2O3作计算1至15wt%的铝含量,且其中该催化剂介于2nm和60nm之间的孔体积为至少0.35mL /g催化剂。
2.如权利要求1所述的方法,其中该催化剂介于10nm和60nm之间的孔体积为至少0.20mL /g催化剂。
3.如权利要求1至2中任一项所述的方法,其中,基于烃树脂进料的重量,该烃树脂以硫作计算的硫化合物含量为大于40ppm。
4.如权利要求3所述的方法,其中,基于烃树脂进料的重量,该烃树脂以硫作计算的硫化合物含量为大于100ppm。
5.一种以钴促进的承载于氧化硅和氧化铝上的镍催化剂,其中,基于还原的催化剂的重量,该催化剂具有以Ni作计算45至85wt%的镍含量,以SiO2作计算13.75至45wt%的硅含量,以Al2O3作计算1至15wt%的铝含量,以及以Co作计算0.25至1.5wt%的钴含量,且其中该催化剂介于2nm和60nm之间的孔体积为至少0.35mL /g催化剂。
6.如权利要求5所述的催化剂,其中该催化剂介于10nm和60nm之间的孔体积为至少0.20mL /g催化剂。
7.制备以钴促进的承载于氧化硅和氧化铝上的镍催化剂的方法,其中,基于还原的催化剂的重量,该催化剂具有以Ni作计算45至85wt%的镍含量,以SiO2作计算13.75至45wt%的硅含量,以Al2O3作计算1至15wt%的铝含量,以及以Co作计算0.25至4wt%的钴含量,且其中该催化剂介于2nm和60nm之间的孔体积为至少0.35mL /g催化剂,该方法包括在pH值为7.0至9.0之下共沉淀一种或多种镍盐、钴盐、铝盐、和一种或多种硅化合物,接着由沉淀液体中回收该共沉淀物质,将其清洗、并进一步处理的步骤而制造该催化剂。
8.如权利要求7所述的方法,其中,基于还原的催化剂的重量,该催化剂以Co作计算的钴含量为0.25至1.5wt%。
9.如权利要求7至8中任一项所述的方法,其中该催化剂介于10nm和60nm之间的孔体积为至少0.20mL /g催化剂。
10.根据权利要求5或6所述的催化剂在烃树脂的氢化中的用途。
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EP4091711A1 (en) | 2021-05-21 | 2022-11-23 | BASF Corporation | A hydrogenation catalyst and its precursor comprising ni, al, and a support material comprising sio2 |
CN114225940A (zh) * | 2021-12-27 | 2022-03-25 | 中国科学院兰州化学物理研究所 | 一种用于苯乙烯系热塑性弹性体加氢的非均相催化剂 |
EP4215269A1 (en) | 2022-01-19 | 2023-07-26 | BASF Corporation | Packaged hydrogenation catalyst |
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2014
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CN1237117A (zh) * | 1996-11-22 | 1999-12-01 | 埃克森化学专利公司 | 不饱和烃的加氢方法 |
CN1322217A (zh) * | 1999-01-15 | 2001-11-14 | 埃克森美孚化学专利公司 | 烃类树脂的氢化方法 |
CN1705514A (zh) * | 2002-10-18 | 2005-12-07 | 英格哈得公司 | 用于氢化反应的镍催化剂 |
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ZA201600529B (en) | 2017-05-31 |
DK3021967T3 (da) | 2019-08-26 |
CN105682797A (zh) | 2016-06-15 |
AR096953A1 (es) | 2016-02-10 |
TW201509971A (zh) | 2015-03-16 |
WO2015008247A3 (en) | 2015-04-16 |
US20160159941A1 (en) | 2016-06-09 |
JP6250156B2 (ja) | 2017-12-20 |
CA2918454C (en) | 2019-02-12 |
JP2016531977A (ja) | 2016-10-13 |
WO2015008247A2 (en) | 2015-01-22 |
US9644044B2 (en) | 2017-05-09 |
BR112016000768B1 (pt) | 2021-03-23 |
TWI637001B (zh) | 2018-10-01 |
EP3021967B1 (en) | 2018-11-21 |
KR101797406B1 (ko) | 2017-11-13 |
EP3021967A2 (en) | 2016-05-25 |
CA2918454A1 (en) | 2015-01-22 |
KR20160040177A (ko) | 2016-04-12 |
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