CN113908848A - 一种合成气制低碳混合醇的富勒烯负载催化剂制法和应用 - Google Patents
一种合成气制低碳混合醇的富勒烯负载催化剂制法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
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- 229910052700 potassium Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
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- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
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- 125000004429 atom Chemical group 0.000 description 13
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- 229910052698 phosphorus Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
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- 150000002823 nitrates Chemical class 0.000 description 5
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 241000282326 Felis catus Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
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- 239000000446 fuel Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 238000004664 delocalization energy Methods 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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Abstract
本发明涉及合成气制低碳混合醇领域，特别涉及合成气制低碳混合醇的催化剂领域。一种合成气制低碳混合醇的富勒烯负载催化剂，该催化剂按重量百分比计组成为：富勒烯:30‑50%,Cu:20‑35%,Fe:10‑25%,Mn:5‑15%,Zn:5‑15%,Zr:5‑15%,Co:1‑5%,M:0.1‑5%。本发明还涉及该富勒烯负载催化剂的制备方法和应用。本发明的催化剂制备方法简单，易于操作，并且催化剂反应性能重复性比较好，容易实现工业放大。
Description
技术领域
本发明涉及合成气制低碳混合醇领域，特别涉及合成气制低碳混合醇的催化剂领域。
背景技术
低碳混合醇可作为优良的洁净车用燃料，由于醇本身含有氧，具有燃烧充分、效率高且CO、NOx 及烃类排放量少等优点。其本身也是一种良好的洁净燃料，加之近年来经济价格较高的高级醇类的市场需求增加也使得低碳醇的研究受到关注。因此，CO加氢催化合成低碳混合醇反应在化学领域中具有重要应用前景。
由合成气直接合成低碳醇的研究较为广泛，所形成的催化剂体系主要有以下四种：
（1）改性甲醇合成催化剂（Cu/ZnO/Al2O3, ZnO/Cr2O3）：此催化剂由甲醇合成催化剂加入适量的碱金属或碱土金属化合物改性而得，较典型的专利有 EP-0034338-A2 （C.E.Hofstadt等人）及美国专利4513100（Snam公司资助，发明人为Fattore等人）。此类催化剂虽然活性较高，产物中异丁醇含量高，但缺点是反应条件苛刻（压力为14-20MPa，温度为350-450℃），高级醇选择性低(一般小于35％)，产物中含水量高（一般为30-50％）；（2）Rh基催化剂（如US 4014913及4096164 ）：负载型Rh催化剂中加入一到两种过渡金属或金属氧化物助剂后，对低碳醇合成有较高的活性和选择性，特别是对C2+醇的选择性较高，产物以乙醇为主。但Rh化合物价格昂贵，催化剂易被CO2毒化，其活性和选择性一般达不到工业生产的要求。（3）抗硫MoS2催化剂：最值得一提是美国DOW公司开发的钼系硫化物催化剂（主要专利见Stevens等人的US patent 4882360），该催化体系不仅具有抗硫性，产物含水少，而且高级醇含量较高，达30-70%，其中主要是乙醇和正丙醇。此催化剂存在的主要问题是其中的助剂元素极易与一氧化碳之间形成羰基化合物，造成助剂元素的流失，影响催化剂的活性及选择性，致使催化剂稳定性和寿命受到限制。（4）Cu-Co催化剂：法国石油研究所(IFP)首先开发了Cu-Co共沉淀低碳醇催化剂，仅1985前就获得了四个催化剂专利(US Patent 4122110,4291126及GB Patent 2118061, 2158730)，此催化剂合成的产物主要为C1-C6直链正构醇，副产物主要为C1-C6脂肪烃，反应条件温和（与低压甲醇合成催化剂相似）。该催化剂的缺点是稳定性较差。
富勒烯具有封闭笼状结构的还可能有C28、C32、C50、C70、C84……C240、C540等，其中最主要的碳60，化学式为C60，是一种碳原子簇。它由60个碳原子构成像足球一样的32面体，包括20个六边形，12个五边形。这60个C原子在空间进行排列时，形成一个化学键最稳定的空间排列位置，恰好与足球表面格的排列一致。属于一种非金属单质。由碳原子结合形成的稳定分子是一种具有半导体性、碱性、高硬度、良好化学稳定性和力学稳定性的材料。富勒烯的碳骨架掺杂氮原子不但产生独特的电子结构和合适的带隙，而且增强了场发射、光催化和碱催化、碳捕获和储能性能。C60分子轨道计算表明，富勒烯烯具有较大的离域能。C60具有金属光泽，有许多优异性能，如超导、强磁性、耐高压、抗化学腐蚀、在光、电、磁等领域有潜在的应用前景。。
C60由碳和氮构成的共价键化合物，具有类似金刚石的四面体结构单元，因而具有非常好的化学稳定性、高的机械强度和硬度，以及良好的导热导电性能。在催化反应过程中可以有效地传递反应热，此外C60不仅具有较大的比表面积和多孔结构，而且具有形状、尺寸均一的孔洞，能够显著增加催化剂活性位点和吸附能力，因此富勒烯尤其适合作为催化剂载体。富勒烯良好的化学稳定性，有利于保持催化剂结构的稳定，从而延长催化剂寿命；高的机械强度和硬度，有利于提高催化剂的强度和耐磨损性能；良好的导热导电性能，有利于催化剂在反应过程中的热传递以及催化剂活性组分与载体间的电子传递。目前，国内外对于由合成气制低碳混合醇的以富勒烯为基体的催化剂研究还相对较少。中国专利CN1736594A 报道了一种钴和钯负载锌铬尖晶石的催化剂及其制备方法，该催化剂可以选择地使合成气转化为低碳混合醇和液态烷烃混合物。该催化剂采用简单的浸渍法制备，但催化剂活性组分为钴和钯，价格昂贵，稳定性较差，致使催化剂的工业应用受到限制。
发明内容
本发明的目的是提供一种选择性高，稳定性好，成本低，在温和反应条件下高选择性的由合成气制低碳混合醇的催化剂及其制备方法和应用。
一种合成气制低碳混合醇的富勒烯负载催化剂，该催化剂按重量百分比计组成为：富勒烯:30-50%,Cu:20-35%, Fe:10-25%, Mn:5-15%, Zn:5-15%, Zr:5-15%, Co:1-5%,M:0.1-5%。
所述的富勒烯为40-60目的，富勒烯为C60和C70中的的一种或者两种任意比混合。
M为碱土金属、碱金属、过渡金属中的一种金属或者几种金属的混合。
碱土金属为Mg、Ca或Ba，碱金属为Na、 K、Li或Cs，过渡金属为Al、Si、Mo、Cr、La或Ce。
一种合成气制低碳混合醇的富勒烯负载催化剂的制备方法，将富勒烯和金属硝酸盐溶液混合成悬浮液，在30-50℃加入在搅拌条件下沉淀剂，保持pH=6-9，生成沉淀，将沉淀经蒸馏水洗涤至中性，在80-110℃下干燥，在450-550℃下焙烧，获得合成气制低碳混合醇的富勒烯负载催化剂。
沉淀剂为碳酸钠，碳酸锂，碳酸铯，碳酸钾和氨水中的一种或多种。
加入沉淀剂时，加入一种沉淀剂形成所有金属的共沉淀。
加入沉淀剂时，加入一种沉淀剂形成部分金属的沉淀，然后依次再加入一种不同的沉淀剂，形成其它金属的分层沉淀。
保持pH=7-8，生成沉淀。
一种合成气制低碳混合醇的富勒烯负载催化剂的应用，在温度为220-280℃，压力为4.5-12.0MPa, 空速为1000-10000h-1, H2和CO体积比为0.5-2.0条件下合成气制低碳混合醇。
本发明的运用沉淀法将Cu、Mn、Zn、Zr元素负载在富勒烯上，再引入具有较强碳链增长能力的VIII族元素Fe和Co，最后添加碱土金属、碱金属、过渡金属中的一种金属或者几种金属的混合，从而提高CO加氢反应的活性，改善C2+醇和C4+烃的选择性，并同时抑制CO2和甲烷等副产物的生成，富勒烯能够提高催化剂反应时传热效率，提高催化剂稳定性。其中碱金属为Na、K、Li或Cs；碱土金属为Mg、Ca或Ba；过渡金属元素为Al、Si、Mo、Cr、La或Ce。
用本发明催化剂进行低碳醇的合成，CO转化率30-60%，总醇选择性为65-80%，总烃选择性15-15%，CO2选择性10-18%。总醇时空产率为0.30-0.60g/h.mL.cat；产物中水含量为10-25%；C2+醇含量为60-80%，C4+烃在总烃中所占百分含量50-85%。
本发明具有如下优点：(a)本发明的催化剂制备方法简单，易于操作，并且催化剂反应性能重复性比较好，容易实现工业放大。(b)本发明的催化剂各组分分布比较均匀，并各组分间存在强相互作用，抗烧结性能比较好。(c)本发明的催化剂干燥后可直接成型，也可加粘结剂压片或挤条成型。并且经焙烧后的催化剂机械强度比较好。(d)本发明的催化剂在还原和反应过程中，不需要添加CO2气体，大大降低了操作费用。
具体实施方式
实施例1
首先将C60用蒸馏水配成wt0.1%悬浮溶液，将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =1.0:1.0:0.5:1.0:0.1:0.2溶于该溶液当中形成wt30%的硝酸盐混合溶液。在50℃下与30wt%碳酸钠溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在450℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中C60:30.0%, Cu:20.5%, Fe:15.9%, Mn:11.8%, Zn:12.6%, Zr:4.0%, Co:4.2%，Na:1.0。还原温度为400℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1,H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=6.0MPa, GHSV=8000h-1, H2/CO（摩尔）=2.0。反应结果见表1。
实施例2
首先将C60用蒸馏水配成wt0.1%悬浮溶液，将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =0.5:1.0:0.5:1.0:0.1:0.2溶于蒸馏水当中形成wt45%的硝酸盐混合溶液。在50℃下与30wt%碳酸钠溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在500℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中C60:35.0%, Cu:20.9%, Fe:15.5%, Mn:10.9%, Zn:9.6%, Zr:4.0%, Co:3.0%，Na:1.1。还原温度为350℃,压力为4.0-12.0MPa,空速为1000-10000h-1,H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=6.0MPa, GHSV=8000h-1, H2/CO（摩尔）=2.0。反应结果见表1。
实施例3
首先将C60用蒸馏水配成wt0.2%悬浮溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe: Mn: Zn：Zr:Co =1.5: 1.0: 0.5: 1:0.1:0.2溶于悬浮溶液中当中形成wt50%的硝酸盐混合溶液。在40℃下与30wt%碳酸镁溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在500℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为。C60:40.0%, Cu:20.5%, Fe:10.9%,Mn:10.3%, Zn:10.6%, Zr:2.0%, Co:3.2%，Mg:0.5。还原温度为300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=6.0MPa, GHSV=8000h-1, H2/CO（摩尔）=2.0。反应结果见表1。
实施例4
首先将C70用蒸馏水配成wt0.25%悬浮溶液，将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =1.0:1.0:1.0:1:0.2:0.2溶于悬浮溶液当中形成wt30%的硝酸盐混合溶液。在30℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经80℃干燥后在550℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C70:45.0%,Cu:20.3%, Fe:11.1%, Mn:6.8%, Zn:7.6%, Zr:3.8%, Co:5.2%，K:0.2。还原温度为450℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO（摩尔）=2.0，反应结果见表1。
实施例5
首先将C70用蒸馏水配成wt0.3%悬浮溶液，将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =1.0:1.0:1.0:1:0.3:0.2溶于悬浮溶液，当中形成wt60%浓度的硝酸盐混合溶液。在50℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在500℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C70:50.0%, Cu:20.9%, Fe:10.5%, Mn:5.7%, Zn:6.2%, Zr:4.0%, Co:2.2%，K:0.5。还原温度为350℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO（摩尔）=2.0，反应结果见表1。
实施例6
首先将C60和C70按1:1比例，用蒸馏水配成wt0.35%悬浮溶液，将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0: 1.0:0.1:0.3溶于悬浮溶液当中形成wt50%浓度的硝酸盐混合溶液。在40℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:15.0%,C70:15%，Cu:20.9%, Fe:15.5%, Mn:11.6%, Zn:12.8%, Zr:4.3%, Co:3.9%，K:1.0。还原温度为300℃,压力为4.0-12.0MPa,空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO（摩尔）=2.0，反应结果见表1。
实施例7
首先将C60和C70按1:1.5比例，用蒸馏水配成wt0.4%悬浮溶液，将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe: Mn: Zn：Zr:Co=1.0:1.0:1.0:0.5:0.1:0.4溶于悬浮溶液当中形成wt55%浓度的硝酸盐混合溶液。在30℃下与20%wt碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:15.0%,C70:20%, Cu:25.5%, Fe:13.9%, Mn:9.8%, Zn:7.6%, Zr:,3.8%, Co:5.2%，K:0.2。还原温度为260℃, 压力为4.0-12.0MPa,空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=6.0MPa, GHSV=6000h-1, H2/CO=2.0（摩尔），反应结果见表1。
实施例8
首先将C60和C70按2:1比例，用蒸馏水配成wt0.5%悬浮溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe:Mn:Zn:Zr:Co =1.0:1.0:0.5:1:0.1:0.2溶于悬浮溶液当中形成wt50%浓度的硝酸盐混合溶液。在40℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:25.0%,C70:12%,Cu:28.5%, Fe:10.9%, Mn:5.8%, Zn:8.1%, Zr:4.2%, Co:5.0%，K:0.5。还原温度为210℃,压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=10MPa, GHSV=6000h-1, H2/CO=2.0（摩尔），反应结果见表1。
实施例9
首先将C60和石墨相C70按2:1比例，用蒸馏水配成wt0.6%悬浮溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =1.0:1.0:0.5:1:0.1:0.2溶于悬浮溶液当中形成wt45%浓度的硝酸盐混合溶液。在70℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经120℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:30.0%,C70:11%, Cu:29.5%, Fe:10.9%, Mn:4.8%, Zn:6.6%, Zr:3.8%, Co:3.2%，K:0.2。还原温度为280℃, 压力为4.0-12.0MPa,空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=4000h-1, H2/CO（摩尔）=2.0，反应结果见表1。
实施例10
将首先将C60和立方C70按2:1比例混合，用蒸馏水配成wt0.7%悬浮溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2溶于悬浮溶液当中形成wt50%浓度的硝酸盐混合溶液。在40℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:33.0%,C70:15%, Cu:20.5%, Fe:10.9%, Mn:5.8%, Zn:5.6%, Zr:4.2%, Co:4.7%，K:0.3。还原温度为300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=8000h-1, H2/CO=2.0（摩尔），反应结果见表1。
实施例11
首先将将C60和C70按1:2比例混合，用蒸馏水配成wt0.8%悬浮溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =1.0:1.0:0.5:1:0.1:0.2溶于悬浮溶液当中形成wt30%浓度的硝酸盐混合溶液。在70℃下与20wt%碳酸铝溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经120℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:11.0%,C70:20%, Cu:30.5%, Fe:10.9%, Mn:5.8%, Zn:12.1%, Zr:4.7%, Co:4.5%，AL:0.5。还原温度为300℃, 压力为4.0-12.0MPa,空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO=2.0（摩尔），反应结果见表1。
实施例12
首先将将C60和C70按1:2比例混合，用蒸馏水配成0.9 wt %悬浮溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe: Mn:Zn:Zr:Co =1.0: 1.0: 0.5: 1:0.1:0.2溶于悬浮溶液当中形成wt40%浓度的硝酸盐混合溶液。在30℃下与20wt%碳酸锂溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:10.0%,C70:20%, Cu:30.0%, Fe:16.2%, Mn:5.8%, Zn:6.6%, Zr:3.0%, Co:3.2%，Li:0.2。还原温度为450℃,压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO=2.0（摩尔），反应结果见表1。
实施例13
首先将C60和C70按2:1比例混合，用蒸馏水配成wt1.0%悬浮溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe: Mn: Zn:Zr:Co =0.5:1.0:0.5:1:0.1:0.2溶于悬浮溶液当中形成wt60%浓度的硝酸盐混合溶液。在40℃下与20wt%碳酸锂溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经110℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为C60:20.0%,C70:10%，Cu:20.5%, Fe:20.9%, Mn:11.2%, Zn:6.7%, Zr:2.0%, Co:3.2%，Li:0.5。还原温度为450℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO=2.0（摩尔），反应结果见表1。
表1
表1可以看出，总醇时空产率为0.31-0.60g/h.mL.cat，C2+醇含量为60.6-70.8%，C4+烃在总烃中所占百分含量50.3-68.7%。
Claims (10)
1.一种合成气制低碳混合醇的富勒烯负载催化剂，其特征在于：该催化剂按重量百分比计组成为：富勒烯:30-50%,Cu:20-35%, Fe:10-25%, Mn:5-15%, Zn:5-15%, Zr:5-15%,Co:1-5%, M:0.1-5%。
2.如权利要求1所述的一种合成气制低碳混合醇的富勒烯负载催化剂，其特征在于：所述的富勒烯为40-60目的，富勒烯为C60和C70中的的一种或者两种任意比混合。
3.如权利要求1所述的一种合成气制低碳混合醇的富勒烯负载催化剂，其特征在于：M为碱土金属、碱金属、过渡金属中的一种金属或者几种金属的混合。
4.如权利要求3所述的一种合成气制低碳混合醇的富勒烯负载催化剂，其特征在于：碱土金属为Mg、Ca或Ba，碱金属为Na、 K、Li或Cs，过渡金属为Al、Si、Mo、Cr、La或Ce。
5.如权利要求1所述的一种合成气制低碳混合醇的富勒烯负载催化剂的制备方法，其特征在于：将富勒烯和金属硝酸盐溶液混合成悬浮液，在30-50℃加入在搅拌条件下沉淀剂，保持pH=6-9，生成沉淀，将沉淀经蒸馏水洗涤至中性，在80-110℃下干燥，在450-550℃下焙烧，获得合成气制低碳混合醇的富勒烯负载催化剂。
6.如权利要求5所述的一种合成气制低碳混合醇的富勒烯负载催化剂的制备方法，其特征在于：沉淀剂为碳酸钠，碳酸锂，碳酸铯，碳酸钾和氨水中的一种或多种。
7.如权利要求6所述的一种合成气制低碳混合醇的富勒烯负载催化剂的制备方法，其特征在于：加入沉淀剂时，加入一种沉淀剂形成所有金属的共沉淀。
8.如权利要求6所述的一种合成气制低碳混合醇的富勒烯负载催化剂的制备方法，其特征在于：加入沉淀剂时，加入一种沉淀剂形成部分金属的沉淀，然后依次再加入一种不同的沉淀剂，形成其它金属的分层沉淀。
9.如权利要求5所述的一种合成气制低碳混合醇的富勒烯负载催化剂的制备方法，其特征在于：保持pH=7-8，生成沉淀。
10.如权利要求1所述的一种合成气制低碳混合醇的富勒烯负载催化剂的应用，其特征在于：在温度为220-280℃，压力为4.5-12.0MPa, 空速为1000-10000h-1, H2和CO体积比为0.5-2.0条件下合成气制低碳混合醇。
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