CN113262788B - 一种烯烃氢甲酰化高效非均相催化剂及其制备方法 - Google Patents
一种烯烃氢甲酰化高效非均相催化剂及其制备方法 Download PDFInfo
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 51
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000002161 passivation Methods 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 12
- 229910003849 O-Si Inorganic materials 0.000 claims description 10
- 229910003872 O—Si Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
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- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
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- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 9
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- 238000006243 chemical reaction Methods 0.000 description 34
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 10
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- 230000000694 effects Effects 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
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- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001460678 Napo <wasp> Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- 229910002441 CoNi Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
本发明涉及一种烯烃氢甲酰化高效非均相催化剂及其制备方法。其特点是:所述催化剂的活性组分为CoM1xM2y/SiO2,其中x的范围为0.05~15,y的范围为0.01~10,M1为含有非金属元素B或者P的盐,M2为过渡金属元素Ti、Cr、Mn、Fe、Ni、Cu、Zn、Zr、Mo、Ru、Rh、Pd、W和Pt中的任意一种,载体为SiO2。本发明方法在整个催化剂制备过程中,操作简单,人为误差因素少,耗时仅3天左右,大大减少了传统负载型非均相催化剂制备时间。原料简单环保,需要的人力物力少,具有较大的工业应用价值。
Description
技术领域
本发明涉及一种烯烃氢甲酰化高效非均相催化剂及其制备方法。
背景技术
烯烃氢甲酰化反应是指烯烃与合成气(CO和H2)在一定的温度和压力下,在催化剂的催化作用下,生成比原烯烃多一个碳的醛或醇的反应。产物醛是合成羧酸、酯类和胺类等有机化合物的重要合成中间体,广泛运用于表面活性剂、添加剂、洗涤剂、化妆品等行业。在工业上,烯烃氢甲酰化反应主要采用铑(Rh)的均相配合物作为催化剂,然而该类催化剂金属铑价格昂贵,催化剂成本高,分离回收困难以及金属流失严重,循环使用困难等缺点,烯烃氢甲酰化非均相催化剂的研究成为近年来的热点。例如中国专利CN110102334A、CN111359655A采用浸渍-化学还原法将Co负载在SBA-15、MCM-41、ZSM-5、活性炭、石墨烯、碳纳米管、13X等载体上,制备了Co基负载型催化剂。该方法虽然转化率较高,但是制备步骤繁琐,制备时间长。中国专利CN111729687A提供了一种固载化的氢甲酰化催化剂及其制备方法,制备的催化剂催化性能稳定,连续多次套用后,活性仍能得到保持,然而该催化剂制备过程中使用了浓硫酸、浓硝酸等危化品,原料多,原料利用率低,过程复杂,操作麻烦,制备周期长。中国专利CN111097416A提供了一种烯烃氢甲酰化反应的碳材料负载Co基催化剂的制备方法,该方法需自己制备活性炭,然后再将Co负载在活性炭上,原料利用率不高,制备过程复杂且长。
因此,开发一种制备过程简单,操作少,快速经济的氢甲酰化反应非均相催化剂具有重要的实际意义。
发明内容
本发明的目的是提供一种烯烃氢甲酰化反应快速、经济、高活性的烯烃氢甲酰化高效非均相催化剂;
本发明的目的之二是以提供一种上述催化剂的制备方法。
一种烯烃氢甲酰化高效非均相催化剂,其特别之处在于:所述催化剂的活性组分为CoM1xM2y/SiO2,其中x的范围为0.05~15,y的范围为0.01~10,M1为含有非金属元素B或者P的盐,M2为过渡金属元素Ti、Cr、Mn、Fe、Ni、Cu、Zn、Zr、Mo、Ru、Rh、Pd、W和Pt中的任意一种,载体为SiO2。
其中SiO2来源于硅酸四乙酯的水解。
其中载体为不同结构的SiO2,并且不同结构的CoBNi/SiO2催化剂形成Co-O-Si、Ni-O-Si键从而起到高度分散和稳定金属Co、Ni的作用;其中B、Ni、SiO2调节Co的电子性质从而提高催化剂在烯烃氢甲酰化反应中的催化性能。
一种烯烃氢甲酰化高效非均相催化剂的制备方法,其特别之处在于,包括如下步骤:
(1)采用一锅法将Co盐、M1、M2盐、去离子水、配体、分散剂或模板剂、有机硅按照一定比例直接混合,然后搅拌2~24h;
(2)离心洗涤至少2次;
(3)干燥;
(4)焙烧;
(5)氢气还原、钝化气钝化即可。
步骤(1)中一定比例具体是指Co盐:M1:M2盐:去离子水:分散剂或模板剂:配体:有机硅的摩尔比为0.05~15:0.01~10:0.01~10:100~500:20~150:10~100:1。
步骤(1)中分散剂或模板剂采用胺类、醇类和烷烃类;搅拌具体采用磁力搅拌或机械搅拌;步骤(2)中离心洗涤采用去离子水,洗涤标准为上层液体澄清无色或接近中性;步骤(3)中干燥具体是在空气条件下,控制温度60℃~120℃,时间为6~15h。
步骤(4)中焙烧氛围为流动空气,控制温度为350℃~600℃,时间为2h~8h。
步骤(5)中氢气还原中要求5%H2~100%H2,控制还原温度550℃~800℃,还原时间2h~10h;钝化气为1%/99%的O2/N2,钝化时间为3-12h。
步骤(1)中Co盐为Co的氯化盐、硝酸盐、醋酸盐,和Rh的盐中的任意一种;M1为含有非金属元素B或P的盐;M2盐为过渡金属元素Ti、Cr、Mn、Fe、Ni、Cu、Zn、Zr、Mo、Ru、Rh、Pd、W或者Pt的盐;分散剂或模板剂为乙醇、四丙基氢氧化铵、十六烷基三甲基溴化铵、乙二胺四乙酸、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷、乙二胺、三正丙胺、奎宁环、六亚甲基亚胺和异丙醇中的任意一种;配体为氨水、乙二胺、乙二胺四乙酸或者甘氨酸;有机硅为硅酸酯中的任意一种;溶剂为去离子水。
进一步的,其中Co盐为Co的硝酸盐;M1为硼酸钠;M2盐为Ni盐;分散剂或模板剂为乙醇;配体为氨水;有机硅为硅酸四乙酯。
一种烯烃氢甲酰化高效非均相催化剂的制备方法,其特别之处在于:按照摩尔比一锅将H2O:C12H29NO:Na2B4O7:NH3OH:C4H6CoO4·4H2O:Ni(NO3)2·6H2O:C8H20O4Si=208:4:5:0.9:20:0.9:0.9:1的原料加入烧杯中,磁力搅拌10h,转速为1500r.p.m;搅拌结束后,用去离子水离心、洗涤2次;将固体转移到鼓风干燥箱中90℃干燥12h;研成粉末后,置于流动空气的马弗炉中500℃焙烧5h;转移到炭化炉中,用99.999%的高纯氢气650℃还原6h,H2流量为40mL/min,1%/99%的O2/N2钝化气钝化4h;得到具有交联片层状结构的催化剂CoB0.9Ni0.9/SiO2。
本发明方法在整个催化剂制备过程中,操作简单,人为误差因素少,耗时仅3天左右,大大减少了传统负载型非均相催化剂制备时间。原料简单环保,需要的人力物力少,具有较大的工业应用价值。本发明催化剂应用于但不局限于浆态床反应器,催化剂与反应原料产物易分离,便于回收和循环使用。在分散剂或模板剂的作用下,有机硅水解成不同结构的SiO2,SiO2作为载体,与Co,M2之间有键合作用,大大减少了金属的流失。本发明的催化剂在C3~C50烯烃氢甲酰化反应中表现出良好的活性,烯烃转化率接近100%,醛的选择性可超过90%,正异比可达1.6~3.0。
附图说明
图1是实施例1催化剂的广角XRD物相图;
图2是实施例2催化剂的广角XRD物相图;
图3是实施例3催化剂的广角XRD物相图;
图4是实施例4催化剂的广角XRD物相图。
具体实施方式
本发明公开了一种烯烃氢甲酰化反应的高效非均相催化剂及其制备方法,其特征在于所述催化剂含有Co、非金属元素M1、过渡金属M2和SiO2形成的非均相体系,以CoM1xM2y/SiO2表示,x、y的范围均为0.01~10,通过调节x、y的比例,调节烯烃氢甲酰化催化性能。所述催化剂制备过程中,在分散剂或模板剂的作用下,有机硅水解成具有不同形貌结构的SiO2,这些不同结构的SiO2都具有多孔和较高比表面积的特点。有机硅水解生成的SiO2作为Co、M1、M2的载体,并可以与Co和M2结合,形成Co-O-Si键、M2-O-Si键,对M1和M2起到高度分散和稳定的作用,同时M1、M2和SiO2都可以调节Co的电子性质,从而提高了在烯烃氢甲酰化反应中的催化性能,烯烃转化率达到99%以上,醛选择性达到90%以上,且主要为正构醛;其制备方法简单,特征在于催化剂制备方法包括如下主要步骤:
(1)将Co盐、M1盐、M2盐、有机硅、分散剂或模板剂、配体等按比例直接混合搅拌均匀;
(2)经洗涤、干燥、焙烧后,进行还原和钝化,得到催化剂。
该方法将Co盐、M1盐、M2盐、分散剂或模板剂、配体、有机硅直接混合搅拌,通过离心洗涤、干燥、焙烧、还原、钝化得到CoM1xM2y/SiO2烯烃氢甲酰化反应非均相催化剂。本方法操作过程简单,耗时少,原料利用率高,有重要的工业应用前景。该催化剂价格低廉,性能优良,易保存,抗烧结能力强,活性组分的分散性好。在烯烃氢甲酰化反应中表现出优异的催化性能,烯烃转化率和醛的选择性高,产物和催化剂易分离,显著提高了烯烃氢甲酰化反应工艺的经济性。
进一步的,一种烯烃氢甲酰化反应的高效非均相催化剂及其制备方法,所述催化剂为含有Co、非金属元素M1、过渡金属M2和SiO2形成的不同结构的固体催化剂,以CoM1xM2y/SiO2表示,x、y分别表示M1和M2与SiO2的摩尔比。所述催化剂制备过程中,在分散剂或模板剂的作用下,有机硅水解并形成不同的结构的SiO2,作为Co、M1和M2的载体,并可以与Co和M2结合,形成Co-O-Si键、M2-O-Si键,对Co和M2起到高度分散和稳定的作用,同时M1、M2和SiO2都可以调节Co的电子性质,从而提高在烯烃氢甲酰化反应中的催化性能,烯烃转化率达到99%以上,醛选择性达到90%以上。其制备方法简单,特征在于催化剂制备方法包括如下主要步骤:通过添加不同分散剂或模板剂,调节x、y的比例,制成不同结构的非均相催化剂CoM1xM2y/SiO2,可以调节烯烃氢甲酰化催化性能。
所述催化剂应用于浆态床,非均相催化剂便于与产物分离回收和循环使用,同时也可以应用于其他合适的反应器,如固定床。
所述方法中Co盐为Co的氯化盐、硝酸盐、醋酸盐,以及Rh的盐中的一种,优选为Co的硝酸盐;M1盐为含有非金属元素B或P的B盐、P盐,优选为硼酸钠;M2盐为过渡金属元素Ti、Cr、Mn、Fe、Ni、Cu、Zn、Zr、Mo、Ru、Rh、Pd、W、Pt其中至少一种,优选为Ni;分散剂或模板剂为乙醇(C2H5OH)、四丙基氢氧化铵(C12H29NO)、十六烷基三甲基溴化铵(C16H33(CH3)3NBr)、乙二胺四乙酸(C10H16N2O8)、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷(P123)、乙二胺(C2H8N2)、三正丙胺(C9H21N)、奎宁环(C7H13N)、六亚甲基亚胺(C6H12N4)、异丙醇(C3H8O)等;配体为氨水(NH4OH)、乙二胺(C2H8N2)、乙二胺四乙酸(C10H16N2O8)、甘氨酸(C2H5NO2)等,优选为氨水(NH4OH);有机硅为硅酸酯中的一种,优选为硅酸四乙酯(C8H20O4Si);溶剂为去离子水(H2O)。
所述步骤中,Co:M1:M2:H2O:分散剂或模板剂:配体:有机硅=0.05~15:0.01~10:0.01~10:100~500:20~150:10~100:1(摩尔比);混合没有先后顺序,搅拌为磁力搅拌或机械搅拌;洗涤用去离子水,洗涤标准为上层液体澄清无色或接近中性;干燥为空气条件下,温度为60℃~120℃,时间为6~15h;焙烧氛围为流动空气,温度为350℃~600℃,时间为2h~8h;采用氢气(5%H2~100%H2)还原,温度550℃~800℃,还原时间2h~10h;钝化气为1%/99%的O2/N2,钝化时间为3-12h。
本发明催化剂包含金属组分Co、M2和非金属组分M1、SiO2,形成催化活性组分CoM1xM2y/SiO2,x、y的范围分别为0.05~15,0.01~10。M1为含有非金属元素B或P的B盐、P盐,M2为过渡金属元素Ti、Cr、Mn、Fe、Ni、Cu、Zn、Zr、Mo、Ru、Rh、Pd、W、Pt,SiO2来源于有机硅的水解。Co、M2和SiO2之间形成较强的Co-O-Si键、M2-O-Si键,SiO2作为Co、M1、M2的载体,对Co、M1和M2起到高度分散和稳定的作用,M1、M2和SiO2都可以调节Co的电子性质,从而提高烯烃氢甲酰化反应的反应速率,大大提高原料烯烃的转化率。
本发明中催化剂的制备方法主要包括以下几个主要步骤:
(1)本发明采用一锅法将Co盐、M1盐、M2盐、去离子水(H2O)、配体、分散剂或模板剂、有机硅按照一定比例直接混合,搅拌2~24h;
(2)离心洗涤至少2次;
(3)干燥;
(4)焙烧;
(5)氢气还原、钝化气钝化。
本发明上述制备步骤中,步骤(1)中Co盐为Co的氯化盐、硝酸盐或醋酸盐中的一种;M1盐为含有非金属元素B或P的B盐、P盐;M2盐为过渡金属元素Ti、Cr、Mn、Fe、Ni、Cu、Zn、Zr、Mo、Ru、Rh、Pd、W、Pt其中至少一种;Co盐:M1盐:M2盐:H2O:分散剂或模板剂:配体:有机硅=0.05~15:0.01~10:0.01~10:100~500:20~150:10~100:1(摩尔比);混合没有先后顺序,搅拌为磁力搅拌或机械搅拌。步骤(2)中离心洗涤用去离子水,洗涤标准为上层液体澄清无色或接近中性。步骤(3)中干燥为空气条件下,温度为60℃~120℃,时间为6~15h。步骤(4)中焙烧氛围为流动空气,温度为350℃~600℃,时间为2h~8h。步骤(5)中氢气(5%H2~100%H2)还原温度550℃~800℃,还原时间2h~10h,钝化气为1%/99%的O2/N2,钝化时间为3-12h。
下面通过实施例对本发明作进一步阐述,但本发明的保护范围不限于以下实施例。
实施例1:
称取300.0000g的去离子H2O,80.0000g C2H5OH,36.0000g NH4OH,23.2824g Co(NO3)2·6H2O,23.2632g Ni(NO3)2·6H2O,16.6664g C8H20O4Si于烧杯中,磁力搅拌12h,转速为1200r.p.m;用去离子水离心洗涤4次;转移到烘箱中80℃干燥过夜(12h);马弗炉中550℃流动空气中焙烧5h;转移到炭化炉中用高纯H2(99.999%)在750℃下还原6h,H2流量为40mL/min;再用1%/99%的O2/N2钝化4h,得到目标交联片层状催化剂CoNi/SiO2。1-己烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例2:
称取120.0000g的去离子H2O,32.0000g C12H29NO,6.4384g Na2B4O7,22.000gNH4OH,7.9706g C4H6CoO4·4H2O,7.8053g Ni(NO3)2·6H2O,6.6666g C8H20O4Si于烧杯中,磁力搅拌10h,转速为1500r.p.m;用去离子水离心洗涤4次;转移到烘箱中90℃干燥过夜(12h);马弗炉中500℃流动空气中焙烧5h;转移到炭化炉中用高纯H2(99.999%)在650℃下还原6h,H2流量为40mL/min;1%/99%的O2/N2钝化4h,得到目标催化剂CoB0.9Ni0.9/SiO2。1-辛烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例3:
称取180.0000g的去离子H2O,48.0000g P123,13.0756g Na2B4O7,14.4000g NH4OH,13.8000g CoCl2·6H2O,10.3500g FeCl2·6H2O,10.0000g C8H20O4Si于烧杯中,磁力搅拌10h,转速为1500r.p.m;用去离子水离心洗涤4次;转移到烘箱中100℃干燥过夜(12h);马弗炉中500℃流动空气中焙烧6h;转移到炭化炉中用高纯H2(99.999%)在650℃下还原6h,H2流量为40mL/min;1%/99%的O2/N2钝化4h,得到目标催化剂CoB1.4Fe0.9/SiO2。1-癸烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例4:
称取150g的去离子H2O,20g C9H21N,13g NaPO3,20g C2H5NO2,12g Co(NO3)2·6H2O,6g Ni(NO3)2·6H2O,8g C8H20O4Si于烧杯中,磁力搅拌8h,转速为1000r.p.m;用去离子水离心洗涤5次;转移到烘箱中100℃干燥过夜(11h);马弗炉中450℃流动空气中焙烧6h;转移到炭化炉中用高纯H2(99.999%)在700℃下还原4h,H2流量为40mL/min;1%/99%的O2/N2钝化4h,得到目标催化剂CoP3.3Ni0.5/SiO2。1-十二烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例5:
称取240g的去离子H2O,70g C10H16N2O8,16g NaPO3,32g NH4OH,20g CoCl2·6H2O,0.5g RhCl2·6H2O,15g C8H20O4Si于烧杯中,磁力搅拌10h,转速为1500r.p.m;用去离子水离心洗涤6次;转移到烘箱中120℃干燥过夜(12h);马弗炉中500℃流动空气中焙烧6h;转移到炭化炉中用高纯H2(99.999%)在750℃下还原5h,H2流量为40mL/min;1%/99%的O2/N2钝化6h,得到目标催化剂CoP2.2Rh0.02/SiO2。1-己烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例6:
称取150g的去离子H2O,50g C7H13N,12g Na3PO4,15g C10H16N2O8,12g Co(NO3)2·6H2O,10g FeCl3·6H2O,10g C8H20O4Si于烧杯中,磁力搅拌13h,转速为1000r.p.m;用去离子水离心洗涤4次;转移到烘箱中80℃干燥过夜(12h);马弗炉中550℃流动空气中焙烧5h;转移到炭化炉中用高纯H2(99.999%)在800℃下还原5h,H2流量为40mL/min;1%/99%的O2/N2钝化6h,得到目标催化剂CoP1.5Fe0.8/SiO2。1-己烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例7:
称取200g的去离子H2O,50g C3H8O,16gNa2B4O7,25g C2H8N2,15g Co(NO3)2·6H2O,10g Cu(NO3)2·6H2O,12g C8H20O4Si于烧杯中,磁力搅拌8h,转速为1500r.p.m;用去离子水离心洗涤5次;转移到烘箱中100℃干燥过夜(10h);马弗炉中500℃流动空气中焙烧6h;转移到炭化炉中用高纯H2(99.999%)在800℃下还原6h,H2流量为40mL/min;1%/99%的O2/N2钝化6h,得到目标催化剂CoB1.4Cu0.6/SiO2。1-十六烯烃氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为130℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例8:
称取200g的去离子H2O,50g C6H12N4,13gNaH2PO2,25g NH4OH,16g C4H6CoO4·4H2O,10g Ni(NO3)2·6H2O,15g C8H20O4Si于烧杯中,磁力搅拌10h,转速为1500r.p.m;用去离子水离心洗涤4次;转移到烘箱中90℃干燥过夜(12h);马弗炉中500℃流动空气中焙烧6h;转移到炭化炉中用高纯H2(99.999%)在650℃下还原6h,H2流量为40mL/min;1%/99%的O2/N2钝化5h,得到目标催化剂CoP2.1Ni0.5/SiO2。1-己烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例9:
称取200g的去离子H2O,50g C12H29NO,16g Na2B4O7,25g C2H5NO,15g CoCl2·6H2O,10g ZnCl2·6H2O,15g C8H20O4Si于烧杯中,磁力搅拌8h,转速为1500r.p.m;用去离子水离心洗涤4次;转移到烘箱中80℃干燥过夜(12h);马弗炉中500℃流动空气中焙烧5h;转移到炭化炉中用高纯H2(99.999%)在750℃下还原6h,H2流量为40mL/min;1%/99%的O2/N2钝化6h,得到目标催化剂CoB1.1Zn0.6/SiO2。1-辛氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
实施例10:
称取200g的去离子H2O,50g C2H5OH,16gNa2B4O7,25g NH4OH,15g Co(NO3)2·6H2O,18g Cr(NO3)3·9H2O,15g C8H20O4Si于烧杯中,磁力搅拌8h,转速为1500r.p.m;用去离子水离心洗涤4次;转移到烘箱中80℃干燥过夜(12h);马弗炉中550℃流动空气中焙烧5h;转移到炭化炉中用高纯H2(99.999%)在750℃下还原4h,H2流量为40mL/min;1%/99%的O2/N2钝化6h,得到目标催化剂CoB0.6Cr0.6/SiO2。1-癸烯氢甲酰化反应活性评价:浆态床反应器,苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h,结果见表1。
图1为实施例1催化剂的广角XRD图,图2为实施例2催化剂的广角XRD图,图3为实施例3催化剂的广角XRD图,图4为实施例4催化剂的广角XRD图。可看出即使在高负载量,高温还原条件下,活性组分Co没有明显的特征峰,表明Co在SiO2载体上分散均匀,抗烧结能力强。
表1为催化剂的烯烃氢甲酰化反应活性。
表1烯烃氢甲酰化反应活性
实施例 | 烯烃转化率 | 醛的选择性 |
1 | 99.5% | 86.4% |
2 | 99.8% | 94.5% |
3 | 96.9% | 82.6% |
4 | 98.7% | 86.9% |
5 | 99.9% | 93.1% |
6 | 99.4% | 82.6% |
7 | 97.8% | 84.6% |
8 | 98.6% | 85.7% |
9 | 96.7% | 85.9% |
10 | 97.8% | 84.8% |
从表中可以看出本发明的催化剂CoM1xM2y/SiO2在烯烃氢甲酰化反应中表现出高效的性能,具有较高的烯烃转化率(96%以上)和较高的醛选择性(82%以上);催化剂CoB0.9Ni0.9/SiO2尤为突出,其转化率接近100%,醛选择性94.5%。
本发明催化剂的活性测定步骤:在间歇浆态床反应器中进行,以甲苯为溶剂,甲苯45mL,烯烃15mL,催化剂1g,原料气CO:H2=1:1,反应温度为120℃,搅拌速率为700r.p.m,反应压力为5MPa,反应时间为4h。
Claims (3)
1.一种烯烃氢甲酰化高效非均相催化剂,其特征在于:所述催化剂的活性组分为CoM1xM2y/SiO2,其中x的范围为0.05~15,y的范围为0.01~10,M1为含有非金属元素B或者P的盐,M2为过渡金属元素Cr、Fe、Ni、Cu、Zn、Rh中的任意一种,载体为SiO2 ;
所述催化剂的制备方法包括如下步骤:
(1)采用一锅法将Co盐、M1、M2盐、去离子水、配体、分散剂或模板剂、有机硅按照一定比例直接混合,然后搅拌2~24h;
(2)离心洗涤至少2次;
(3)干燥;
(4)焙烧;
(5)氢气还原、钝化气钝化即可;
步骤(1)中分散剂或模板剂采用胺类、醇类和烷烃类;搅拌具体采用磁力搅拌或机械搅拌;步骤(2)中离心洗涤采用去离子水,洗涤标准为上层液体澄清无色或接近中性;步骤(3)中干燥具体是在空气条件下,控制温度60℃~120℃,时间为6~15h;
步骤(5)中氢气还原中要求5%H2~100%H2,控制还原温度550℃~800℃,还原时间2h~10h;钝化气为1%/99%的O2/N2,钝化时间为3-12h;
步骤(1)中Co盐为Co的氯化盐、硝酸盐和醋酸盐中的任意一种;M1为含有非金属元素B或P的盐;M2盐为过渡金属元素Cr、Fe、Ni、Cu、Zn或者Rh的盐;分散剂或模板剂为乙醇、四丙基氢氧化铵、十六烷基三甲基溴化铵、乙二胺四乙酸、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷、乙二胺、三正丙胺、奎宁环、六亚甲基亚胺和异丙醇中的任意一种;配体为氨水、乙二胺、乙二胺四乙酸或者甘氨酸;有机硅为硅酸酯中的任意一种;溶剂为去离子水。
2.如权利要求1所述的一种烯烃氢甲酰化高效非均相催化剂,其特征在于:其中SiO2来源于硅酸四乙酯的水解。
3.如权利要求1所述的一种烯烃氢甲酰化高效非均相催化剂,其特征在于:其中载体为不同结构的SiO2,并且不同结构的CoBNi/SiO2催化剂形成Co-O-Si、Ni-O-Si键从而起到高度分散和稳定金属Co、Ni的作用;其中B、Ni、SiO2调节Co的电子性质从而提高催化剂在烯烃氢甲酰化反应中的催化性能。
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