CN115121270A - 一种选择性加氢合成2-乙基己醛的催化剂及其应用方法 - Google Patents
一种选择性加氢合成2-乙基己醛的催化剂及其应用方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005751 Copper oxide Substances 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 3
- 239000011787 zinc oxide Substances 0.000 claims abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 3
- PYLMCYQHBRSDND-UHFFFAOYSA-N 2-ethyl-2-hexenal Chemical compound CCCC=C(CC)C=O PYLMCYQHBRSDND-UHFFFAOYSA-N 0.000 claims description 13
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- -1 organic acid salt Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
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- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
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- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- LCEHKIHBHIJPCD-UHFFFAOYSA-N 6-methylheptanal Chemical compound CC(C)CCCCC=O LCEHKIHBHIJPCD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
本发明提供了一种选择性加氢合成2‑乙基己醛的催化剂及其应用方法，所述催化剂组成如下(以催化剂总重量100％计)：(a)1～40％氧化镍；(b)0.5～20％氧化钴、氧化锌、氧化铜或氧化锆中的一种或多种过渡金属氧化物；(c)0.1～10％选自Ce、La、Sm中的一种或多种稀土金属氧化物；(d)0.01～7％选自P、B中的一种或两种氧化物；(e)其余为氧化硅和/或氧化铝。本发明催化剂以非贵金属镍为活性组分，加入过渡金属元素，有利于提高对碳碳双键加氢的选择性；同时，加入稀土金属元素，可提高Ni在载体上的分散度，进而提升催化剂的活性以及稳定性。本发明催化剂具有原料转化率和产物选择性高以及催化剂寿命长的优点，可应用于2‑乙基己醛的工业生产。
Description
技术领域
本发明属于选择性加氢技术领域，具体涉及一种2-乙基己烯醛选择性加氢合成2-乙基己醛的催化剂及其应用方法。
背景技术
2-乙基己醛，又称异辛醛，主要用作香料，合成其他化合物的原料。例如用于合成2-乙基己酸(又称异辛酸)，而异辛酸被广泛应用于医药、香料、染料、杀菌剂、化妆品、树脂、塑料等领域。此外，异辛酸可用来制备异辛酸盐，用作催干剂，与传统环烷酸盐催干剂相比，异辛酸盐催干剂性能优势明显，正在逐步取代环烷酸盐催干剂，需求量不断增长。
目前，2-乙基己醛主要通过2-乙基己烯醛选择性加氢制备而来。工业上大多使用Pd系催化剂，收率可达97％左右。然而，贵金属Pd价格高昂且对原料要求较高，进而导致生产成本高。近年来，较多的研究集中在采用非贵金属如Ni等金属的加氢催化剂领域，如专利GB1102796A公开了一种Ni/硅藻土催化剂，采用硫化物毒化部分Ni催化剂的方式，来提高饱和醛的选择性，在225℃和常压下，2-乙基己醛收率为96％，但该反应为气相加氢反应，反应温度较高，原料易发生裂解等副反应。专利US4018831A通过共沉淀法制备的Ni基催化剂，在120℃和3.4MPa下，2-乙基己烯醛转化率为88％，2-乙基己醛的选择性为94％。CN114471618A公开了一种硫掺杂碳负载的Ni基催化剂，在70℃和10MPa下，2-乙基己烯醛转化率为72.1％，产物选择性为89.1％。上述基于非贵金属的2-乙基己烯醛选择性加氢催化剂，存在着反应压力高、反应温度高等缺陷，且这些催化剂的2-乙基己醛收率都较低。
发明内容
本发明的目的在于提供一种成本低廉且具有较高2-乙基己醛收率的选择性加氢催化剂及其应用方法。所制备的催化剂具有比表面积高、活性组分分散度好的特点，在较温和的液相加氢条件下，实现了原料2-乙基己烯醛的高转化率、2-乙基己醛的高选择性。
本发明通过以下技术方案实现上述目的：一种选择性加氢合成2-乙基己醛的催化剂及其应用方法，以催化剂总重量100％计，包括以下组分：
(a)1～40％氧化镍；
(b)0.5～20％氧化钴、氧化锌、氧化铜或氧化锆中的一种或多种过渡金属氧化物；
(c)0.1～10％选自Ce、La、Sm中的一种或多种稀土金属氧化物；
(d)0.01～7％选自P、B中的一种或两种非金属氧化物；
(e)其余为氧化硅和/或氧化铝。
本发明催化剂具有的比表面积为150～400m2/g。
催化剂活性组分Ni的前驱体选自硝酸镍、碱式碳酸镍、氯化镍或醋酸镍；活性组分Co、Zn、Cu或Zr的前驱体选自其相对应的硫酸盐、盐酸盐、硝酸盐或有机酸盐。
本发明同时提供了一种选择性加氢合成2-乙基己醛的催化剂应用方法，该方法采用本发明催化剂，以2-乙基己烯醛和溶剂为原料，与H2反应得到加氢产物；加氢产物再经脱除轻、重杂质，得到高纯度2-乙基己醛。
溶剂选自甲醇、乙醇、正丁醇、环己醇、2-乙基己醇或2-乙基己醛，优选为2-乙基己醛；溶剂与原料2-乙基己烯醛的混合比例为(质量)0.5～50。
选择性加氢反应器可设计为鼓泡床、滴流床或固定床反应器。
选择性加氢反应的反应压力为0.5～5.0MPa，反应温度为30～300℃，氢气与原料的比例为(摩尔)1.01～20，原料体积空速为0.1～20.0h-1。
本发明催化剂以Ni为活性组分，显著降低了催化剂的生产成本；同时，本发明催化剂中添加了Co、Zn、Cu或Zr过渡金属元素，有利于提高对碳碳双键加氢的选择性，减少副产物的生成。另外，本发明通过在载体中添加P、B等非金属元素以及少量的稀土金属元素，获得了具有适宜酸性和比表面积的载体，其中稀土元素的添加有利于提高Ni在载体上的分散度，进而提高了催化剂的活性中心数量、延长了催化剂的使用寿命以及提高了原料的转化率。
下面通过实施例对本发明作进一步阐述。但不能对本发明的实施范围构成任何限定。
具体实施方式
实施例1
首先，称取300g的拟薄水铝石，12g的田菁粉和30g的炭黑，将其混合均匀后，加入300g含6.6g的硅溶胶(质量分数40％)、4.3g的磷酸(85％质量浓度)、26.3g的硝酸镧、15g的硝酸铈和12g硝酸(65％质量浓度)的水溶液，混捏，挤成
的三叶草条状，并经110℃干燥12h，650℃焙烧5h，制得载体Z1。然后，称取3.2g的硝酸钴，并溶于10g的水后，将上述硝酸钴溶液与148g硝酸镍溶液(14％Ni)配成浸渍液。最后，将载体Z1在浸渍液中浸渍12h，经120℃干燥，450℃焙烧6h，制得催化剂C1。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
实施例2
首先，称取300g的拟薄水铝石，12g的田菁粉和20g的炭黑，将其混合均匀后，加入300g含36.2g的硅溶胶(质量分数40％)、5.88g的磷酸(85％质量浓度)、12.86g的硼酸、20.6g的硝酸铈、14g的硝酸钐和10g硝酸(65％质量浓度)的水溶液，混捏，挤成
的三叶草条状，并经110℃干燥12h，850℃焙烧5h，制得载体Z2。然后，称取84.2g的硝酸锌，并溶于100g的水后，将上述硝酸锌溶液与406.5g醋酸镍溶液(14％Ni)配成浸渍液。最后，将载体Z2在浸渍液中浸渍12h，经120℃干燥，500℃焙烧6h，制得催化剂C2。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
实施例3
首先，称取300g的氧化铝，10g的田菁粉和25g的炭黑，将其混合均匀后，加入300g含59.1g的硅溶胶(质量分数40％)、59g的硝酸镧、5.7g的硝酸钐和13g硝酸(65％质量浓度)的水溶液，混捏，挤成
的三叶草条状，并经110℃干燥12h，680℃焙烧5h，制得载体Z3。然后，称取153.8g的氯化钴，并溶于150g的水后，将上述氯化钴溶液与1328g醋酸镍溶液(14％Ni)配成浸渍液。最后，将载体Z3在浸渍液中浸渍12h，经120℃干燥，400℃焙烧6h，制得催化剂C3。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
实施例4
首先，称取300g的拟薄水铝石，15g的田菁粉和25g的炭黑，将其混合均匀后，加入300g含13.4g的磷酸(85％质量浓度)、2.7g的硝酸镧和3g硝酸(65％质量浓度)的水溶液，混捏，挤成
的三叶草条状，并经110℃干燥12h，650℃焙烧5h，制得载体Z4。然后，称取31.9g的硝酸锌，并溶于30g的水后，将上述硝酸锌溶液与231.1g硝酸镍溶液(14％Ni)配成浸渍液。最后，将载体Z4在浸渍液中浸渍12h，经110℃干燥，500℃焙烧6h，制得催化剂C4。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
实施例5
首先，称取300g的氧化铝，12g的田菁粉和20g的炭黑，将其混合均匀后，加入300g含38.4g的硅溶胶(质量分数40％)、48.5g的硝酸铈、9.9g的硝酸钐和14g硝酸(65％质量浓度)的水溶液，混捏，挤成
的三叶草条状，并经110℃干燥12h，700℃焙烧5h，制得载体Z5。然后，称取177.5g的氯化钴，并溶于200g的水后，将上述氯化钴溶液与862.5g硝酸镍溶液(14％Ni)配成浸渍液。最后，将载体Z5在浸渍液中浸渍12h，经120℃干燥，450℃焙烧6h，制得催化剂C5。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
实施例6
首先，称取300g的拟薄水铝石，12g的田菁粉和30g的炭黑，将其混合均匀后，加入300g含17.2g的硅溶胶(质量分数40％)、11.2g的磷酸(85％质量浓度)、34.33g的硝酸镧和5g硝酸(65％质量浓度)的水溶液，混捏，挤成
的三叶草条状，并经110℃干燥12h，650℃焙烧5h，制得载体Z6。然后，称取84g的硝酸钴，并溶于80g的水后，将上述硝酸钴溶液与386.5g硝酸镍溶液(14％Ni)配成浸渍液。最后，将载体Z6在浸渍液中浸渍12h，经120℃干燥，480℃焙烧6h，制得催化剂C6。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
对比实施例1
采用实施例6中载体和催化剂相同的制备步骤和条件，制得不含过渡金属的催化剂D1。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
对比实施例2
采用实施例6中载体和催化剂相同的制备步骤和条件，制得不含稀土金属的催化剂D2。催化剂组成及物化性质见表1，其中各组分含量均以催化剂总重量计。
表1催化剂组成及物化性质
将实施例1-6和对比例1-2所得催化剂样品C1、C2、C3、C4、C5、C6、D1和D2分别置于鼓泡床反应器中，以2-乙基己烯醛为原料，进行催化剂选择性加氢的性能评价。
使用前用氢气对催化剂进行众所周知的活化处理，催化剂评价条件为：
反应温度：80℃；
反应压力：2.0MPa；
催化剂装填量：100g；
氢气/2-乙基己烯醛(摩尔)：5。
催化剂加氢活性及选择性见表2。
表2催化剂加氢活性及选择性
从表2中可以得出本发明催化剂的选择性加氢性能优异，原料2-乙基己烯醛的转化率大于99.5％，产品2-乙基己醛的选择性大于99％。
Claims (7)
1.一种选择性加氢合成2-乙基己醛的催化剂及其应用方法，以催化剂总重量100％计，包括以下组分：
(a)1～40％氧化镍；
(b)0.5～20％氧化钴、氧化锌、氧化铜或氧化锆中的一种或多种过渡金属氧化物；
(c)0.1～10％选自Ce、La、Sm中的一种或多种稀土金属氧化物；
(d)0.01～7％选自P、B中的一种或两种非金属氧化物；
(e)其余为氧化硅和/或氧化铝。
2.根据权利要求1所述催化剂，其特征在于所述催化剂具有的比表面积为150～400m2/g。
3.根据权利要求1所述催化剂，其特征在于所述活性组分Ni的前驱体选自硝酸镍、碱式碳酸镍、氯化镍或醋酸镍；活性组分Co、Zn、Cu或Zr的前驱体选自其相对应的硫酸盐、盐酸盐、硝酸盐或有机酸盐。
4.一种选择性加氢合成2-乙基己醛的催化剂应用方法，其特征在于采用权利要求1～3所述的催化剂，以2-乙基己烯醛和溶剂为原料，与H2反应得到加氢产物；加氢产物再经脱除轻、重杂质，得到高纯度2-乙基己醛。
5.根据权利要求4所述催化剂应用方法，其特征在于所述溶剂选自甲醇、乙醇、正丁醇、环己醇、2-乙基己醇或2-乙基己醛，优选为2-乙基己醛；溶剂与原料2-乙基己烯醛的混合比例为(质量)0.5～50。
6.根据权利要求4所述催化剂应用方法，其特征在于选择性加氢反应器可设计为鼓泡床、滴流床或固定床反应器。
7.根据权利要求4所述催化剂应用方法，其特征在于选择性加氢反应的反应压力为0.5～5.0MPa，反应温度为30～300℃，氢气与原料的比例为(摩尔)1.01～20，原料体积空速为0.1～20.0h-1。
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