CN102131578B - 包含在多孔硅玻璃上的钯的新颖选择性氢化催化剂及其用途 - Google Patents
包含在多孔硅玻璃上的钯的新颖选择性氢化催化剂及其用途 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 235000013311 vegetables Nutrition 0.000 claims description 16
- 150000001345 alkine derivatives Chemical class 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 10
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
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- 239000005977 Ethylene Substances 0.000 claims description 4
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- QDLPJHIEFRSZJK-UHFFFAOYSA-N 2-methylbut-3-yn-1-ol Chemical compound OCC(C)C#C QDLPJHIEFRSZJK-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- RLOISEUPMPOJMI-UHFFFAOYSA-N 2-methylbut-1-en-1-ol Chemical class CCC(C)=CO RLOISEUPMPOJMI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000001337 aliphatic alkines Chemical class 0.000 abstract 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 8
- -1 2,4,6-trimethylphenyl Chemical group 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002769 thiazolinyl group Chemical group 0.000 description 4
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 229930007744 linalool Natural products 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
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- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 1
- WPWWHXPRJFDTTJ-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzamide Chemical compound NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F WPWWHXPRJFDTTJ-UHFFFAOYSA-N 0.000 description 1
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VBPSVYDSYVJIPX-UHFFFAOYSA-N methylbutenol Natural products CCC=C(C)O VBPSVYDSYVJIPX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
本发明涉及包含在作为载体的多孔硅玻璃上的钯的催化剂，还涉及该催化剂用于使炔烃选择性氢化为烯烃的用途。
Description
本发明涉及包含在作为载体的多孔硅玻璃(Silica glass)上的钯的催化剂，还涉及该催化剂用于使炔烃选择性氢化为烯烃的用途。
本发明的催化剂包含在多孔硅玻璃上的钯。
优选地，本发明的催化剂是在多孔硅玻璃上的钯。
优选地，多孔硅玻璃具有下述特性：
a)粒径范围为20到500μm，优选范围为50到400μm，更优选范围为80到300μm，最优选范围为100到200μm；和/或
b)孔径大小范围为10到400nm，优选范围为30到250nm，更优选范围为40到150nm，最优选范围为50到60nm；和/或
c)孔体积范围为100到5000mm3/g，优选范围为250到2500mm3/g；更优选范围为500到2000mm3/g，最优选范围为1000到1500mm3/g；和/或
d)比表面积范围为5到500m2/g，优选范围为25到300m2/g，更优选范围为40到250m2/g，最优选范围为50到200m2/g。
优选地，多孔硅玻璃显示了a)到d)所有特性，其中本发明包括优选的/更优选的/最优选的特性的任何可能组合。
此类多孔硅玻璃可商购。由Schuller GmbH，Wertheim，Germany销售的商标为
的是特别优选的一种。
是具有范围为100到200μm的平均颗粒大小，54.47nm的平均孔径大小，93.72m2/g的比表面积和1255.5mm3/g的平均孔体积的多孔硅玻璃。
根据本发明的催化剂可在下述官能团的存在下用于使末端C≡C三键选择性氢化为末端C＝C双键：
◇烷基：直链C1-50烷基、支化的C3-50烷基、C3-20环烷基以及有1到50个C原子的烷基环烷基或环烷基烷基；优选是C1-20烷基——其可以是直链的(C1-20)、支化的(C3-20)或环状的(C3-20)或烷基环烷基(C4-20)或环烷基烷基(C4-20)；
◇烯基：直链C2-50烯基、支化的C3-50烯基；优选是C2-20烯基——其可以是直链的(C2-20)或支化的(C3-20)；
◇杂烷基：即非芳香碳氢基，优选包含一个或多个杂原子氮和/或氧且有3到50个C原子(优选3到30个C原子)的饱和碳氢基，例如醚类，例如四氢呋喃和四氢吡喃。
◇烷基芳基和芳基：例如苯基、甲苯基、二甲苯基、2，4，6-三甲苯基、萘基等等，优选有6-17个C原子；
◇杂芳基：优选具有5-17个C原子，其中杂原子是氧或氮；杂芳基还可含有多个杂原子(杂原子数目≥1)，所以也包括含有O原子和N原子的杂芳基；例子有吡啶基、吲哚基、呋喃基。
◇羟基(-OH)；
◇硝基氧(-NO2)；
◇氨基(-NH2)；
◇-SiR 1 R 2 R 3 ，其中R1、R2和R3彼此独立地是烷基(直链的或支化的C1-C6)或芳基或烷基芳基；优选R1＝R2＝R3。
这表示炔烃RC≡CH被氢化为烯烃RHC＝CH2，其中R是碳氢基，可选地具有杂原子O和/或N或它们中的多个和/或如上定义的下述官能团：-OH、-NO2、-NH2和-SiR3。优选地，R选自由如上定义的烷基、烯基、芳基、烷基芳基、杂芳基组成的组，所有烷基、烯基、芳基、烷基芳基、杂芳基还可具有一个或多个杂原子O和/或N，或还具有例如-OH、-NO2、-NH2和-SiR3官能团。优选地，炔烃是类异戊二烯构建单元(buildingblock)的前体。
从而，本发明还涉及在上述定义的催化剂的存在下用于烯烃的制造的这样的用途和方法，所述方法包括使炔烃氢化的步骤。
一般而言，氢化可在范围为0℃到150℃的温度下和/或在范围为1bar到150bar的压力下进行。
此类炔烃和相应的烯烃的优选的例子给出在下表中：
| 炔烃 | 烯烃 | 图1 |
| 2-甲基丁炔醇 | 2-甲基丁烯醇 | (1) |
| 脱氢芳樟醇 | 芳樟醇 | (2) |
| 脱氢异植物醇 | 异植物醇 | (3) |
| 3，7-二甲基-1-辛炔-3-醇 | 3，7-二甲基-1-辛烯-3-醇 | (4) |
本发明的优选的实施方式
使脱氢异植物醇氢化为异植物醇
在本发明的优选的实施方式中，炔烃3，7，11，15-四甲基-1-十六碳炔-3-醇(脱氢异植物醇)被氢化为烯烃3，7，11，15-四甲基-1-十六碳烯-3-醇(异植物醇)。
一般而言，该氢化可在范围为0℃到150℃的温度下，优选在范围为10℃到100℃的温度下，更优选在范围为15℃到95℃的温度下，最优选在最高达到75℃的温度下进行。
氢压力可在范围为1到50bar，优选范围为1.1到10bar，更优选范围为1.2到8bar，最优选在6bar左右变化。
优选地，该氢化在溶剂不存在下进行。
使2-甲基丁炔醇氢化为2-甲基丁烯醇
在本发明的另一优选实施方式中，炔烃2-甲基丁炔醇被氢化为烯烃2-甲基丁烯醇。
一般而言，该氢化可在范围为0℃到150℃的温度下，优选在范围为15℃到80℃的温度下，更优选在范围为20℃到75℃的温度下，最优选在60℃左右的温度下进行。
氢压力可在范围为1到50bar，优选范围为1.2到15bar，更优选范围为1.5到10bar，最优选在6bar左右变化。
有利地，使用毒化催化剂的化合物，从而降低其活性。该化合物通常是含硫或磷的有机化合物。优选地，催化剂毒物选自由磷烷(特别是三烷基膦)、硫醚、硫醇和二硫化物组成的组。特别优选硫醚，例如二丙硫醚、羟基二乙硫醚(ethyl-2-hydroxyethyl sulfide)、四氢噻吩、噻吩和2，2’-(亚乙基二硫代)-二乙醇；硫醇，例如2，2’-(乙烯二氧)-二乙硫醇；以及二硫化物例如丙基二硫醚和异丙基二硫醚。最优选2，2’-(亚乙基二硫代)-二乙醇。催化剂毒物也可用在上述的使脱氢异植物醇氢化为异植物醇中。
使脱氢芳樟醇氢化为芳樟醇
在本发明的进一步优选的实施方式中，炔烃脱氢芳樟醇被氢化为烯烃芳樟醇。
一般而言，该氢化可在范围为0℃到120℃的温度下，优选在范围为10℃到100℃的温度下，更优选在范围为20℃到90℃的温度下进行。
氢压力可在范围为1bar到50bar，优选范围为1.2到15bar，更优选在范围为1.5到10bar，最优选在3bar左右变化。
使3，7-二甲基-1-辛炔-3-醇氢化为3，7-二甲基-1-辛烯-3-醇
在本发明的另一优选的实施方式中，炔烃3，7-二甲基-1-辛炔-3-醇被氢化为烯烃3，7-二甲基-1-辛烯-3-醇。
本发明将在下述非限制性实施例中阐述。
实施例
用于实施例中的载体是由Schuller GmbH，Wertheim，Germany销售的
是有在100到200μm之间的平均颗粒大小，54.47nm的平均孔径大小，93.72m2/g的比表面积和1255.5mm3/g的平均孔体积的多孔硅玻璃。
实施例1：催化剂的制备
将21mg Pd(OAc)2(0.09mmol)悬浮在50mL二氯甲烷中。加入1g
并除去溶剂(浴温度：40℃/压力：950mbar)。将掺杂有Pd(OAc)2的载体在烘炉中在300℃下煅烧2小时(烘炉1000W预热20分钟至300℃)。在载体上的催化剂的负载量从而为约1重量％Pd，即10mg Pd在1g载体上。
实施例2：在高压釜中使2-甲基-3-丁炔-2醇(MBI)氢化为2-甲基-3-丁烯
-2醇(MBE)
在根据实施例1制备的200mg催化剂的存在下，将3.2mol MBI在60℃和2.8bara下搅拌(2000rpm)280分钟氢化。转化率为98％，产率为94％。
实施例3-4：在无溶剂情况下使脱氢异植物醇(DIP)氢化为异植物醇
(IP)
在根据实施例1制备的100mg催化剂的存在下，使3.75mmol DIP氢化。进行氢化的温度和压力给出在下表中。3小时反应时间后取样，用气相色谱测定产率和选择性。
b)反应时间：3小时
| 实施例 | 压力[bara] | 温度[℃] | 基于DIP的转化率[％] | 基于IP的选择性[％] |
| 3 | 21 | 50 | 88 | 86 |
| 4 | 41 | 50 | 95 | 85 |
实施例5：在无溶剂较大规模下使脱氢异植物醇(DIP)氢化为异植物醇
(IP)
在500ml高压釜中，在根据实施例1制备的106mg催化剂和23mg2，2’-(亚乙基二硫代)-二乙醇的存在下，使265g(0.9mol)DIP在80℃和2bar下氢化。反应混合物在2000rpm下搅拌4小时。基于DIP的转化率为99％，产率为89.6％。
实施例6：在溶剂中使脱氢异植物醇(DIP)氢化为异植物醇(IP)
将3.75mmol DIP溶于0.5ml乙酸乙酯，并在根据实施例1制备的100mg催化剂的存在下，在50℃和21bara下将DIP氢化。1小时反应时间后取样，用气相色谱测定产率和选择性。基于DIP的转化率为93％，基于IP的选择性为91％。
Claims (14)
1.包含在作为载体的多孔硅玻璃上的钯的催化剂用于使C≡C三键选择性氢化为C=C双键的用途。
2.根据权利要求1的用途，其中所述载体具有范围为20到500μm的粒径。
3.根据权利要求1的用途，其中所述载体具有范围为50到400μm的粒径。
4.根据权利要求1至3中任意一项的用途，其中所述载体具有范围为10到400nm的孔径大小。
5.根据权利要求1至3中任意一项的用途，其中所述载体具有范围为30到250nm的孔径大小。
6.根据权利要求1至3中任何一项的用途，其中所述载体具有范围为100到5000mm3/g的孔体积。
7.根据权利要求1至3中任何一项的用途，其中所述载体具有范围为250到2500mm3/g的孔体积。
8.根据权利要求1至3中任何一项的用途，其中所述载体具有范围为5到500m2/g的比表面积。
9.根据权利要求1至3中任何一项的用途，其中所述载体具有范围为25到300m2/g的比表面积。
10.用于制造烯烃的方法，所述方法包括在包含作为载体的多孔硅玻璃上的钯的催化剂的存在下使炔烃氢化的步骤。
11.根据权利要求10的方法，其中所述炔烃是3,7,11,15-四甲基-1-十六碳炔-3-醇(脱氢异植物醇)且所述烯烃是3,7,11,15-四甲基-1-十六碳烯-3-醇(异植物醇)。
12.根据权利要求10的方法，其中所述炔烃是2-甲基丁炔醇且所述烯烃是2-甲基丁烯醇。
13.根据权利要求11或12的方法，其中所述氢化在含硫化合物的存在下进行。
14.根据权利要求13的方法，其中所述含硫化合物是2，2’-(亚乙基二硫代)-二乙醇。
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| PCT/EP2009/060764 WO2010020671A1 (en) | 2008-08-20 | 2009-08-20 | Novel selective hydrogenation catalyst comprising palladium on porous silica glass and the use thereof |
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| CN107262112A (zh) * | 2010-07-01 | 2017-10-20 | 帝斯曼知识产权资产管理有限公司 | 新的结构化催化剂 |
| WO2012121156A1 (ja) * | 2011-03-09 | 2012-09-13 | 和光純薬工業株式会社 | アルキン誘導体の部分水素化反応 |
| CN102503772A (zh) * | 2011-10-11 | 2012-06-20 | 上海博鹤企业发展有限公司 | 一种生产2-甲基-3-丁烯-2-醇的方法 |
| ES2689754T3 (es) | 2012-08-20 | 2018-11-15 | Evonik Degussa Gmbh | Procedimiento para la preparación fermentativa de L-aminoácidos utilizando cepas mejoradas de la familia Enterobacteriaceae |
| WO2015044410A1 (en) * | 2013-09-30 | 2015-04-02 | Dsm Ip Assets B.V. | Pd on ceria catalytic system for selective hydrogenations of triple bonds |
| WO2015091816A2 (en) * | 2013-12-20 | 2015-06-25 | Dsm Ip Assets B. V. | New catalytic system |
| EP3618961A1 (en) * | 2017-05-01 | 2020-03-11 | DSM IP Assets B.V. | Improved process to deposit pd- nanoparticles |
| CN107876107B (zh) * | 2017-09-29 | 2020-08-14 | 海南汉地阳光石油化工有限公司 | 一种石油加氢催化剂及其制备方法 |
| KR20220011721A (ko) * | 2019-05-27 | 2022-01-28 | 디에스엠 아이피 어셋츠 비.브이. | 인 화합물 및 유기 황 화합물의 존재 하에서의 알킨의 알켄으로의 선택적 수소화 |
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| US3715404A (en) * | 1964-06-03 | 1973-02-06 | Hoffmann La Roche | Process for selective hydrogenation |
| US6002047A (en) * | 1996-11-11 | 1999-12-14 | Roche Vitamins Inc. | Catalytic hydrogenation using amorphous metal alloy and a solvent under near-critical or super-critical conditions |
| WO2008060972A2 (en) * | 2006-11-11 | 2008-05-22 | Uop Llc | Hydrogenation processes using functional surface catalyst composition |
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| US3715404A (en) * | 1964-06-03 | 1973-02-06 | Hoffmann La Roche | Process for selective hydrogenation |
| US6002047A (en) * | 1996-11-11 | 1999-12-14 | Roche Vitamins Inc. | Catalytic hydrogenation using amorphous metal alloy and a solvent under near-critical or super-critical conditions |
| WO2008060972A2 (en) * | 2006-11-11 | 2008-05-22 | Uop Llc | Hydrogenation processes using functional surface catalyst composition |
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| WO2010020671A1 (en) | 2010-02-25 |
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| US8530707B2 (en) | 2013-09-10 |
| CN102131578A (zh) | 2011-07-20 |
| EP2328679A1 (en) | 2011-06-08 |
| JP5584906B2 (ja) | 2014-09-10 |
| JP2012500112A (ja) | 2012-01-05 |
| TW201016317A (en) | 2010-05-01 |
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