CN111491727A - 氢化反应用催化剂及其制备方法 - Google Patents
氢化反应用催化剂及其制备方法 Download PDFInfo
- Publication number
- CN111491727A CN111491727A CN201880078348.9A CN201880078348A CN111491727A CN 111491727 A CN111491727 A CN 111491727A CN 201880078348 A CN201880078348 A CN 201880078348A CN 111491727 A CN111491727 A CN 111491727A
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- Prior art keywords
- catalyst
- hydrogenation
- nickel
- sulfur
- prepare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 43
- 150000001336 alkenes Chemical group 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 19
- 239000003426 co-catalyst Substances 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 96
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 39
- 239000003208 petroleum Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 241001550224 Apha Species 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000009467 reduction Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 ethylene, propylene, butylene Chemical group 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005180 public health Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002352 steam pyrolysis Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种氢化反应用催化剂及其制备方法,更详细涉及通过包含硫作为助催化剂,当对包含芳基的不饱和烃进行加氢反应时,使烯烃与芳香族的相对氢化速度发生变化,从而对烯烃进行选择性氢化的氢化反应用催化剂及其制备方法。
Description
技术领域
本发明涉及一种氢化反应用催化剂及其制备方法,更详细涉及通过包含硫作为助催化剂,当对包含芳基的不饱和烃进行加氢反应时,使烯烃与芳香族的相对氢化速度发生变化,从而对烯烃进行选择性氢化的氢化反应用催化剂及其制备方法。
背景技术
低级烯烃(即,乙烯、丙烯、丁烯以及丁二烯)及芳香族化合物(即,苯、甲苯以及二甲苯)是广泛用于石油化学及化学工业的基本的中间体。热裂化或蒸汽热解是典型的用于在存在蒸汽且不存在氧气的条件下,形成这些物质的工艺的主要类型。供给原料可包括诸如石脑油、煤油以及瓦斯油等石油气及蒸馏物。此时,能够对石脑油等进行热解,从而生成乙烯、丙烯、包括丁烷及丁二烯的C4馏分、裂化汽油(包括苯、甲苯以及二甲苯)、裂化煤油(C9以上馏分)、裂化重油(乙烯残油(bottom oil))以及氢气等物质,并能够由馏分进行聚合而制备石油树脂。
然而,石油树脂的一部分包含不饱和键,因此品质会降低。此时,能够通过加氢的氢化工艺,去除不饱和键,从而使颜色变得明亮,并减少石油树脂特有的气味等,改善品质。另外,去除不饱和键后的石油树脂无色透明,因此被称为水白(water white)树脂,并作为耐热性及紫外线稳定性等突出的高级树脂流通。
由C5馏分、C9馏分以及双环戊二烯(DCPD)等共聚而成的石油树脂具有根据芳香族含量而调节与诸如乙烯-醋酸乙烯(ethylene-vinyl acetate,EVA)、苯乙烯-异戊二烯-苯乙烯(styrene-isoprene-styrene,SIS)、苯乙烯-丁二烯-苯乙烯(styrene-butadiene-styrene,SBS)等苯乙烯(styrene)类高分子的相容性的特征。因此,当石油树脂进行氢化反应时,为了在控制芳香族含量的同时制备水白树脂,需要对树脂的烯烃部分进行选择性氢化。
因此,为了对不饱和的石油树脂供给原料进行氢化,对多种催化剂进行了研究,尤其是,为了对芳香族不饱和烃中的烯烃进行选择性氢化,会使用钯(Pd)、铂(Pt)等贵金属催化剂,并由于钯催化剂与其他金属催化剂相比,活性及选择性更加优秀,因此用作选择性氢化催化剂。然而,当钯类催化剂在液相中进行氢化时,存在的问题在于,发生钯损失,并形成Pd络合物。此外,当使用Ni基催化剂时,存在的问题在于,芳香族一同被加氢,因此难以用于包含芳基的不饱和烃的选择性氢化反应。
为了解决此类问题,美国授权专利第5,223,470号公开了包含担载于氧化铝(Al2O3)的硫的镍催化剂,但其不是用于芳香族/烯烃选择性加氢的催化剂,并且不含铜,因此其构成要素与本发明不同。美国授权专利第4,328,090号公开了包含在γ-Al2O3上担载有硫的Ni-W或包含在γ-Al2O3上担载有硫的Ni-Mo催化剂,涉及对石油树脂进行氢化的催化剂,但不是用于芳香族/烯烃的选择性加氢的催化剂,并且本发明不含钨(W)或钼(Mo),因此与本发明不同。美国授权专利第3,687,989号公开了包含Ni3S2、WS2以及MoS2的催化剂,其用于脂肪(fat)或脂肪酸(fatty acid)加氢,但仅提出了烯烃加氢,其不是用于芳香族/烯烃的选择性加氢,其构成要素与本发明不同。
另外,对将活性金属担载于二氧化硅、氧化铝或活性碳等作为氢化催化剂的形态进行了多种研究。
韩国公开专利第10-2010-0100834号记载了将包含镍和硫的催化剂用于选择性氢化,但没有记载载体的种类和粉末状态,以及将硫用作促进剂。日本公开专利平10-0502865记载了将镍和硫担载到二氧化硅或氧化铝载体的氢化催化剂,但没有记载包含硫作为促进剂和粉末状形态以及芳香族/烯烃的选择性加氢。
对此,本发明的发明人通过研究,开发了包含铜和硫作为助催化剂的构成的镍催化剂,从而解决上述文献未能解决的芳香族/烯烃的选择性氢化的问题,并能够通过简单的工艺制备催化剂,并确立了将所制备的催化剂用于包含芳基的不饱和烃的氢化反应时,芳香族/烯烃加氢选择性高的氢化方法。另外,能够使用以此方式所开发的催化剂,容易地确保水白(water white)树脂。
发明内容
技术问题
本发明的目的在于解决上述所有问题。
本发明的另一目的在于提供一种氢化反应用催化剂及其制备方法,该催化剂包含硫作为助催化剂,当对包含芳基的不饱和烃进行加氢反应时,改变烯烃与芳香族的相对氢化速度,从而对烯烃进行选择性氢化。
本发明的另一目的在于提供一种氢化反应用催化剂及其制备方法,该催化剂能够对烯烃进行选择性加氢,从而调节包含芳基的不饱和烃中的芳香族含量。
本发明的另一目的在于提供一种氢化反应用催化剂及其制备方法,该催化剂能够在对包含芳基的不饱和烃进行氢化反应时,控制芳香族含量,从而容易地制备水白树脂。
技术方案
为了达成如上所述的本发明目的并实现后述的本发明的特征效果,本发明的特征构成如下。
本发明的氢化反应用催化剂包含镍、助催化剂以及载体,所述助催化剂包含铜和硫,所述载体为选自二氧化硅及氧化铝中的一种以上,所述镍的平均结晶尺寸为1~10nm,所述氢化反应用催化剂具有1~20μm的平均粒径。
以100重量份的总组合物为基准,可包含40~80重量份的所述镍,并包含0.1~5重量份的所述铜。所述硫与所述镍的摩尔比(mole ratio)为1∶0.02~0.2。
每单位重量的所述镍的氢吸附量为0.01~0.5mmol-H2/g-Ni。
本发明的氢化反应用催化剂的制备方法包括如下步骤:将镍化合物、铜化合物及载体粉末添加于蒸馏水中溶解,以制备第一溶液;将所述第一溶液放入沉淀容器中,搅拌并升温至50~120℃;在30分钟~2小时内向经升温的所述第一溶液中注入包含pH调节剂及硫的溶液,以制备第二溶液,并通过沉淀,形成担载有镍(Ni)的沉淀物;将所述沉淀物洗涤并过滤之后,在100~200℃下加热5~24小时,以制备干燥物;以及在氢气氛围下,以200~500℃的温度对所述干燥物进行还原,以制备还原物。
可进一步包括在氢气氛围下进行还原之前,在空气氛围下,以200~500℃的温度对所述干燥物进行烧制的步骤。
可进一步包括利用包含0.1%~20%的氧气的氧氮混合气体对所述还原物进行钝化,以制备粉末催化剂的步骤。
所述沉淀在pH值7~9下进行。
选择性氢化方法利用根据本发明制备的氢化反应用催化剂,对包含芳基的不饱和烃的烯烃进行选择性加氢。
根据所述选择性氢化方法制备的被加氢的石油树脂具有30以下的APHA值。
有益效果
本发明的氢化反应用催化剂及其制备方法通过包含硫作为助催化剂,当对包含芳基的不饱和烃进行加氢反应时,使芳香族加氢速度与烯烃相比大幅减小,从而对烯烃进行选择性氢化。
并且,本发明能够对烯烃进行选择性加氢,从而调节包含芳基的不饱和烃的芳香族含量。
另外,本发明能够在石油树脂进行氢化反应时,控制芳香族含量,从而容易地制备水白树脂。
附图说明
图1是示出实施例及比较例的芳香族/烯烃加氢选择度的图。
图2是示出实施例及比较例的被加氢后的APHA值的图。
具体实施方式
对后述的本发明详细说明将参照作为示例示出的能够实施本发明的特定实施例的附图。详细说明这些实施例,以使本领域技术人员能够实施本发明。本发明的多种实施例彼此不同,但不必彼此排斥。例如,记载于此的特定形状、结构以及特性与一实施例相关联,在不脱离本发明的精神及范围内,能够以其他实施例实现。另外,各个公开的实施例内的各个构成要素的位置或配置可以在不脱离本发明的精神及范围内进行变更。因此,后述的详细说明不是限定性的,本发明的范围仅由所附的权利要求及其等同范围限定。在附图中,相似的附图标记在多个方面指代相同或相似的功能。
以下,参照附图对本发明的多个优选实施例进行详细说明,以使本领域技术人员能够容易地实施本发明。
本发明的氢化反应用催化剂包含镍、助催化剂以及载体,所述助催化剂包含铜和硫,所述载体为选自二氧化硅及氧化铝中的一种以上,所述镍的平均结晶尺寸为1~10nm,更优选为3~7nm。当所述镍的平均结晶尺寸脱离上述范围时,会存在催化剂活性降低的问题。另外,本发明的催化剂的平均粒径为1~20μm,更优选为3~10μm。当催化剂的平均粒径小于上述范围时,会存在催化剂的过滤性不足的可能性,当大于上述范围时,会存在催化剂的活性降低的问题。
以100重量份的总催化剂组合物为基准,可包含40~80重量份的所述镍。可以优选包含50~70重量份,更优选包含55~65重量份。当镍含量小于上述范围时,催化剂活性会降低,当大于上述范围时,存在的问题在于分散性降低,导致催化剂活性会降低。
以100重量份的总催化剂组合物为基准,可包含0.1~5重量份的所述铜。可以优选包含0.2~2重量份,更优选包含0.5~1重量份。当铜含量小于上述范围时,因镍的还原度减小,会导致催化剂活性降低,当大于所述范围时,因活性金属表面的镍比例减小,会导致活性降低。
所述硫与所述镍的摩尔比(mole ratio)可以是1∶0.02~0.2。可以优选为1∶0.04~0.15,更优选为1∶0.05~0.1。当硫的含量小于上述范围时,氢化催化剂的选择性会降低,当大于上述范围时,会存在催化剂活性降低的问题。
所述镍的供给源包括诸如硝酸盐、醋酸盐、硫酸盐、氯化物等金属盐,最优选包含氯化物的氯化镍前体。
另外,铜前体可使用选自硝酸盐、醋酸盐、硫酸盐、氯化物以及氢氧化物中的至少一种以上的形态,硫前体可使用选自碱金属硫化物、噻吩以及硫醇中的至少一种。
在本发明的氢化反应用催化剂中,催化剂所包含的单位重量的镍的氢吸附量为0.01~0.5mmol-H2/g-Ni。
通常,在进行加氢反应时,包含芳基的不饱和烃中所包含的烯烃和芳香族都会通过催化剂反应而被氢化,因此,需要能够对烯烃进行选择性氢化的催化剂,以调节石油树脂中的芳香族含量。当使用镍基催化剂时,树脂中的芳香族会一同被加氢,因此,难以调节石油树脂中的芳香族含量。
然而,本发明的一实施例的选择性氢化催化剂通过包含硫作为助催化剂(promoter),当对包含芳基的不饱和烃进行加氢反应时,能够使芳香族加氢速度与烯烃相比大幅减小,从而对烯烃进行选择性氢化。
本发明的一实施例的氢化反应用催化剂是在将镍化合物及助催化剂混合到溶剂中之后,使固体载体悬浮于其中,从而使镍化合物及助催化剂形成沉淀体并沉积到所述载体上。所述载体可以是选自多孔性二氧化硅(SiO2)及氧化铝(Al2O3)中的一种以上。
另外,本发明的一实施例的氢化反应用催化剂能够通过蒸馏、前处理以及聚合,对由C5或C9石油馏分和副产物以及它们的组合物组成的石油树脂进行氢化。
当对包含芳基的不饱和烃进行氢化反应时,温度可以是100~400℃,优选为200~300℃,压力可以是1~200bar,优选为30~100bar。氢化时间主要可以根据温度、催化剂的量以及氢化程度而改变。并且,氢化反应可在多种反应器中进行,优选地,可根据混合方式,在连续搅拌反应器(CSTR)、环流(loop)反应器、高压釜(autoclave)反应器等中进行。
本发明的氢化反应用催化剂的制备方法包括如下步骤:将镍化合物、铜化合物及载体粉末添加于蒸馏水中溶解,以制备第一溶液;将所述第一溶液放入沉淀容器中,搅拌并升温至50~120℃;在30分钟~2小时内向经升温的所述第一溶液中注入包含pH调节剂及硫的溶液,以制备第二溶液,并通过沉淀,形成担载有Ni的沉淀物;以及将所述沉淀物洗涤并过滤之后,在100~200℃下加热5~24小时,以制备干燥物;以及在氢气氛围下,以200~500℃的温度对所述干燥物进行还原,以制备还原物。
可以有选择地进一步包括在氢气氛围下对所述干燥物进行还原以制备还原物之前,在空气氛围下以200~500℃的温度对所述干燥物进行烧制的步骤。
可进一步包括利用包含0.1%~20%的氧气的氧氮混合气体对所述还原物进行钝化,以制备粉末催化剂的步骤。
另外,如上所述,当还原温度为200~500℃,优选为300~450℃,更优选为370~430℃时,能够表现出最优的活性。
另外,所述沉淀可通过加碱或以电化学方式在pH值为7以上的环境中进行,可以优选pH值为7~9。此时,为了加碱,可添加碱性化合物,碱性添加剂可包括碳酸钠、氢氧化钠、碳酸氢钠或其水合物,但不限于此,可以优选包括碳酸钠或其水合物。
本发明的催化剂可以是粉末、粒子、颗粒的形态,优选为粉末的形态。
本发明的氢化反应用催化剂的制备方法能够根据载体来优化表面积、气孔结构及尺寸,由于镍的含量高,能够在低温下进行还原,而且活性优秀并能够均匀地分散,进而能够抑制镍与载体的副反应。
另外,选择性氢化方法能够利用根据本发明制备的包含铜和硫作为助催化剂的担载有镍的催化剂,使包含芳基的不饱和烃中的芳香族加氢速度与烯烃相比大幅减小,从而对烯烃进行选择性的加氢。
根据所述选择性氢化方法制备的被加氢的石油树脂具有30以下的APHA值。
APHA色度(color)也被称作Hazen标度(scale)或铂-钴(Platinum-Cobalt,Pt/Co)标度(scale),作为名称源于美国公共卫生协会(American Public Health Association)的颜色标准分析方法(ASTM D1209),通过APHA值,分析加氢石油树脂的颜色。
作为基准的是铂钴储备溶液(Platinum-Cobalt Stock Solution),其相当于APHA500。利用将其定量稀释而成的标准溶液(Standard Solution),细分为1~500的阶段的数值后,以该数值来表示颜色。其中,用作稀释剂的去离子水(D.Iwater)对应于APHA0。APHA色度(Color)尤其与黄度指数(Yellowness Index)具有相关关系,因此,能够利用关于黄度(Yellowness)的标准溶液(Standard Solution)的APHA色度(Color)标准曲线(StandardCurve)来获得待测试样的APHA色度(Color)值。
根据本发明的选择性氢化方法被加氢的石油树脂的APHA值为30以下,芳香族/烯烃加氢比例为0.1~1.0,并且是被加氢的石油树脂的颜色及气味几乎消失的水白树脂。
实施方式
以下,通过本发明的优选实施例对本发明的构成及作用进行更加详细说明。这只是本发明优选示例,无论以任何含义进行解释,本发明也不限于此。
未记载于此的内容为本领域技术人员能够从技术上充分类推的部分,因此省略其说明。
<实施例>
实施例1
将1g的具有200m2/g的比表面积和28nm的气孔尺寸的多孔性二氧化硅粉末和50mL的氯化镍(243g/L的镍)及氯化铜(2.2g/L的铜)溶解于蒸馏水中而成的溶液投入到沉淀容器中,搅拌并升温至80℃。达到80℃之后,利用注射泵(syringe pump),将40mL的包含碳酸钠(175g/L)及硫化钠(15g/L)的溶液在1小时内全部注入,以使硫/镍摩尔比达到0.09。沉淀完毕之后,浆液的pH值为7.7,将其用约1.5L的蒸馏水洗涤并过滤之后,利用干燥炉在120℃下干燥12小时以上。将其分成小份之后,在氢气氛围中,以400℃的温度进行还原。还原之后,利用包含1%氧气的氧氮混合气体对粉末进行钝化,以制备氢化催化剂。
经测量,以催化剂的重量为基准,钝化后的催化剂的镍含量为63.8%,铜含量为0.87%,硫含量为2.8%,镍结晶的平均尺寸为5.1nm。用于测试催化剂的活性的加氢反应在230℃的温度下进行。
实施例2
利用注射泵(syringe pump),将40mL的包含作为沉淀剂的碳酸钠(175g/L)及硫化钠(12.5g/L)的溶液在1小时内全部注入,以使加氢催化剂的硫/镍摩尔比达到0.075。沉淀完毕之后,浆液的pH值为7.6。洗涤及过滤、干燥等其余方法与实施例1相同。
经测量,以催化剂的重量为基准,钝化后的催化剂的镍含量为62.1%,铜含量为0.84%,硫含量为2.5%,镍结晶的平均尺寸为5.0nm。用于测试催化剂的活性的加氢反应在230℃的温度下进行。
实施例3
利用注射泵(syringe pump),将40mL的包含作为沉淀剂的碳酸钠(175g/L)及硫化钠(10g/L)的溶液在1小时内全部注入,以使加氢催化剂中的硫/镍的摩尔比达到0.06。沉淀完毕之后,浆液的pH值为7.7。洗涤及过滤、干燥等其余方法与实施例1相同。
经测量,以催化剂的重量为基准,钝化后的催化剂的镍含量为62.1%,铜含量为0.86%,硫含量为2.2%,镍结晶的平均尺寸为4.1nm。用于测试催化剂的活性的加氢反应在230℃的温度下进行。
实施例4
除了变更为包括在氢气氛围中进行还原之前的烧制步骤以外,以与实施例1相同的方法制备氢化催化剂。在马弗炉中进行烧制,在将干燥的粉末分成小份之后,在空气流量(air flow)为1000ml/min、升温速率(heating rate)为5℃/min的条件下,升温至400℃之后,保持3小时。烧制完毕后的粉末的回收率为80%。接下来,在将经过烧制的粉末分成小份之后,在氢气氛围中,以400℃的温度进行还原。还原之后,利用包含1%氧气的氧氮混合气体对粉末进行钝化,以制备氢化催化剂。经测量,以催化剂的重量为基准,钝化后的催化剂的镍含量为62.4%,铜含量为0.85%,硫含量为2.9%,镍结晶的平均尺寸为4.2nm。用于测试催化剂的活性的加氢反应在230℃的温度下进行。
比较例1
仅使用沉淀剂中除硫化钠以外的碳酸钠溶液,以与实施例1相同的方法依次进行沉淀/洗涤/过滤/干燥/还原,以制备不含硫的催化剂。
将1g的具有200m2/g的比表面积和28nm的气孔尺寸的多孔性二氧化硅粉末和50mL的将氯化镍(243g/L的镍)及氯化铜(2.2g/L的铜)溶解于蒸馏水中而成的溶液投入到沉淀容器中,搅拌并升温至80℃。达到80℃之后,利用注射泵(syringe pump),将40mL的包含碳酸钠(175g/L)的溶液在1小时内全部注入。沉淀完毕之后,浆液的pH值为7.8,将其用约1.5L的蒸馏水洗涤并过滤之后,利用干燥炉在120℃下干燥12小时以上。将其分成小份之后,在氢气氛围中,以400℃的温度进行还原之后,利用包含1%氧气的氧氮混合气体进行钝化,以制备氢化催化剂。
经测量,以催化剂的重量为基准,钝化后的催化剂的镍含量为63.2%,铜含量为0.89%,镍结晶的平均尺寸为5.7nm。用于测试催化剂的活性的加氢反应在230℃的温度下进行。
比较例2
购买碳载体上担载有5重量%的钯的粉末形态的商用催化剂,并将其用于选择性加氢。催化剂为具有10μm的平均尺寸、1,190m2/g的BET比表面积、1.1cm3/g的总气孔体积的粉末形态。用于测试催化剂的活性的加氢反应在230℃的温度下进行。
比较例3
利用比较例2所使用的催化剂,测试催化剂的活性。用于测试活性的加氢反应在270℃的温度下进行。
下表1示出实施例1至4以及比较例1至3的催化剂组合物中镍(Ni)的含量、助催化剂的种类和含量。
表1
Ni/Si摩尔比 | S/Ni摩尔比 | Pd/C重量比 | 氢吸附量(mmol-H<sub>2</sub>/g-Ni) | |
实施例1 | 3.2 | 0.09 | - | 0.020 |
实施例2 | 3.2 | 0.075 | - | 0.041 |
实施例3 | 3.1 | 0.06 | - | 0.087 |
实施例4 | 3.1 | 0.09 | - | 0.023 |
比较例1 | 3.2 | 0.00 | - | 0.982 |
比较例2 | - | 0.00 | 0.05 | - |
比较例3 | - | 0.00 | 0.05 | - |
<实验例>催化剂的活性测试(Activity Test)
利用了300mL高压釜,该高压釜包括中空轴(Hollow shaft)搅拌器且具有1600rpm的搅拌速度。
将非加氢石油树脂以30重量%溶解于ExxsolTMD40,以形成溶液,在230℃、90bar下,向75g的该溶液中添加0.5%~2%(基于石油树脂质量)的催化剂,进行氢化,并通过ASTM D1209测量颜色。与石油树脂内烯烃含量成正比的石油树脂的加氢前的颜色(APHA值)为750,当石油树脂的颜色为30以下时,会成为石油树脂的颜色及气味几乎消失的水白树脂,此时残留的烯烃含量(NMR%area)小于0.1%。
即,当氢化反应进行至APHA值为30以下时,几乎没有残留的烯烃,并且能够通过测量加氢至此时的芳香族的量来比较芳香族/烯烃加氢选择度,通过测量该值,对催化剂活性进行比较,并示于下表2。
表2
参照所述表2及图1和2,确认了在依照本发明包含硫作为助催化剂的实施例1至4中,芳香族/烯烃加氢选择性与比较例1相比显著地优秀。另外,确认了能够通过所添加的硫的含量来调节芳香族/烯烃加氢选择度。
另外,确认了依照本发明制备的实施例1至4与比较例2及3的钯催化剂相比,在芳香族/烯烃加氢选择度方面表现出同等以上的水平,尤其是,与比较例3相比,在低温下也能够很好地实现活化。
本发明的氢化反应用催化剂及其制备方法通过包含硫作为助催化剂,当对包含芳基的不饱和烃进行加氢反应时,能够使芳香族加氢速度与烯烃相比大幅减小,从而对烯烃进行选择性加氢。
另外,本发明能够对烯烃进行选择性加氢,从而调节包含芳基的不饱和烃中的芳香族含量。
另外,本发明能够在对包含芳基的不饱和烃进行氢化反应时,控制芳香族含量,从而容易地制备水白树脂。
以上,通过诸如具体的构成要素等特定事项及经限定的实施例及附图对本发明进行了说明,但其仅用于帮助更全面地理解本发明,本发明不限于多个所述实施例,本领域技术人员能够根据这种记载进行多种修改和变更。
因此,本发明的思想不限于以上说明的实施例,所附的权利要求书及与其等同的所有变形均属于本发明的思想范畴。
Claims (11)
1.一种氢化反应用催化剂,包含镍、助催化剂以及载体,其特征在于,
所述助催化剂包含铜和硫,
所述载体为选自二氧化硅及氧化铝中的一种以上,
所述镍的平均结晶尺寸为1~10nm,所述氢化反应用催化剂具有1~20μm的平均粒径。
2.根据权利要求1所述的氢化反应用催化剂,其特征在于,
以100重量份的总组合物为基准,包含40~80重量份的所述镍,并包含0.1~5重量份的所述铜,
所述硫与所述镍的摩尔比(mole ratio)为1∶0.02~0.2。
3.根据权利要求1所述的氢化反应用催化剂,其特征在于,
每单位重量的所述镍的氢吸附量为0.01~0.5mmol-H2/g-Ni。
4.一种氢化反应用催化剂的制备方法,其特征在于,包括如下步骤:
(a)将镍化合物、铜化合物及载体粉末添加于蒸馏水中溶解,以制备第一溶液;
(b)将所述第一溶液放入沉淀容器中,搅拌并升温至50~120℃;
(c)在30分钟~2小时内向经升温的所述第一溶液中注入包含pH调节剂及硫的溶液,以制备第二溶液,并通过沉淀,形成担载有Ni的沉淀物;
(d)将所述沉淀物洗涤并过滤之后,在100~200℃下加热5~24小时,以制备干燥物;以及
(e)在氢气氛围下,以200~500℃的温度对所述干燥物进行还原,以制备还原物。
5.根据权利要求4所述的氢化反应用催化剂的制备方法,其特征在于,
所述步骤(d)进一步包括在空气氛围下,以200~500℃的温度对干燥物进行烧制的步骤。
6.根据权利要求4所述的氢化反应用催化剂的制备方法,其特征在于,
所述步骤(e)进一步包括利用包含0.1%~20%的氧气的氧氮混合气体对还原物进行钝化,以制备粉末催化剂的步骤。
7.根据权利要求4所述的氢化反应用催化剂的制备方法,其特征在于,
所述沉淀在pH值7~9下进行。
8.一种氢化方法,其特征在于,
利用根据权利要求4至7中任一项的氢化反应用催化剂的制备方法制备的氢化反应用催化剂,对包含芳基的不饱和烃中的烯烃进行选择性的加氢。
9.一种选择性加氢的石油树脂,其特征在于,
根据权利要求8的氢化方法进行制备。
10.根据权利要求9所述的选择性加氢的石油树脂,其特征在于,
所述石油树脂具有30以下的APHA值。
11.根据权利要求9所述的选择性加氢的石油树脂,其特征在于,
所述石油树脂的芳香族/烯烃加氢比例为0.1~1.0。
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KR102300823B1 (ko) | 2021-09-09 |
KR20190081127A (ko) | 2019-07-09 |
CN111491727B (zh) | 2023-12-15 |
WO2019132407A1 (ko) | 2019-07-04 |
US20210002403A1 (en) | 2021-01-07 |
EP3733288A4 (en) | 2021-08-25 |
US11987659B2 (en) | 2024-05-21 |
EP3733288A1 (en) | 2020-11-04 |
JP2021505385A (ja) | 2021-02-18 |
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