CN101284232A - 甲烷溴氧化制溴甲烷及其转化制碳氢化合物的催化剂 - Google Patents
甲烷溴氧化制溴甲烷及其转化制碳氢化合物的催化剂 Download PDFInfo
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- CN101284232A CN101284232A CNA2007100347267A CN200710034726A CN101284232A CN 101284232 A CN101284232 A CN 101284232A CN A2007100347267 A CNA2007100347267 A CN A2007100347267A CN 200710034726 A CN200710034726 A CN 200710034726A CN 101284232 A CN101284232 A CN 101284232A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 171
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 25
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 19
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 title abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 8
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- 238000002360 preparation method Methods 0.000 claims abstract description 43
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 39
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 10
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000000376 reactant Substances 0.000 claims abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 71
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- 239000002184 metal Substances 0.000 claims description 17
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical group NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101150101537 Olah gene Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
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- 238000002372 labelling Methods 0.000 description 2
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- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- AGYKGLGUMGTNHK-UHFFFAOYSA-N C.[Br] Chemical compound C.[Br] AGYKGLGUMGTNHK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
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- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 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
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
本发明公开了甲烷经过溴氧化反应转化为溴代烃的催化剂以及由溴代烃进一步制高碳烃的催化剂,属于催化剂及其制备方法的技术领域。使用的第一种催化剂,由可溶解于水的Rh、Ru、Cu、Zn、Ag、Ce、V、W、Cd、Mo、Mn、Cr和La等金属化合物前体和硅前体混合水解、烘干、然后焙烧制得,可使一定量的反应物甲烷、HBr、H2O和氧源(O2、空气或富氧空气)进行催化溴氧化反应,生成目的产物CH3Br和CH2Br2等;使用第二种催化剂,由HZSM-5、HY、Hβ、3A、4A、5A和13X等分子筛负载Zn和Mg金属化合物制得,可使甲烷溴化产物CH3Br和CH2Br2进一步反应生成C3至C13的高碳烃和HBr,其中HBr作为循环反应介质利用。
Description
技术领域
本发明公开一种把天然气中甲烷催化转化成溴代烷烃的催化剂以及进一步把溴代烷烃如溴甲烷转化为高碳烃的催化剂,以及该催化剂的制备方法和应用。属于催化剂及其制备方法的技术领域。是对申请号为200410022850.8、200510031734.7和200610031377.9的中国专利的催化剂部分的扩展与延伸,涉及进一步的研究成果。
背景技术
随着石油资源的日益减少,天然气转化为高附加值的化学品已经受到越来越多的重视。目前已经探明,地球上有丰富的天然气储量,我国的天然气储量高达124万亿m3,占世界天然气储量的第22位,而且还在不断的发现新的天然气田。天然气中含有大量的甲烷,其含量可以从60%到99%间变化,其余主要为乙烷和丙烷。目前油田开采中的大量低级烷烃仍以火炬形式烧掉,不仅浪费了资源,而且增大了大气中二氧化碳的浓度,污染了环境。对天然气有效利用的研究也主要集中在对甲烷的有效利用研究上,因此对甲烷的开发利用具有重大的经济意义。
甲烷(CH4)是一种分子结构类似于惰性气体,本身无任何特征官能团,通过C原子的sp3杂化形成一个对称性很好的正四面体结构,C-H键的平均键能为414kJ/mol,是很难在温和条件下活化的分子,其气相CH4、CH3、CH2和CH的C-H键解离能分别为420kJ/mol、360kJ/mol、520kJ/mol和330kJ/mol。研究其C-H键活化和选择性转化可为其它烃类的活化转化提供借鉴。
天然气转化为液体化工原料,为解决从偏远地区运输低分子量烷烃提供了一种有效的办法。目前采用的利用天然气的方法主要包括将其转化为合成气(氢气和一氧化碳的混合物),随后将合成气转化为液体产品。如采用Fischer-Tropsch(F-T)方法将合成气转化为合成油,进而通过常规精制方法提升为运输燃料(Fischer,F.,and Tropsch,H.,Brennst.Chem.4,276(1923).)。尽管F-T合成方法提供了一种流程可以将天然气转化为更易于运输的液体燃料,但是该方法在制合成气的过程中是一个强吸热反应,需要燃烧大量的甲烷来提供反应所需要的热量。
Periana等人进行了把甲烷转化为甲醇和醋酸的研究(Roy A.Periana,et al,Science 280,560(1998),Roy A.Periana,et al,Science 301,814(2003).),但是在反应中生成了不能循环处理的SO2,而且浓硫酸作为反应物和溶剂在反应后由于水的生成而变稀,不能继续使用,所以经过Periana组和美国公司Catalytica Inc.的多年努力研究也没能实现工业化。
目前我们设计的一种甲烷活化路线已经逐渐得到诸多的科研机构和学者的重视。包括在第一步对甲烷使用溴进行溴氧化反应得到溴代甲烷,进而在第二步中将溴代甲烷转化为有商用价值的化工产品如甲醇、二甲醚、轻质烯烃和较高级烯烃包括汽油。
在这个领域的研究中,我们已经开发出甲烷经过非合成气路线合成醋酸、甲醇、二甲醚和高碳烃的流程(CN200410022850.8、CN200510031734.7、CN200610031377.9),在这些流程中,首先把天然气中的烷烃组分转化为溴代烷烃和一氧化碳,然后再把溴代烷烃转化为相应的产物和回收HBr,HBr再回到第一个反应器中生产溴代烷烃,以实现HBr的循环使用。当第一级反应产物为高选择性的溴代烷烃时,我们可以通过第二级反应得到甲醇、二甲醚或高碳烃;当第一级产物主要为溴代烷烃和一氧化碳混合物时,我们进而可以合成醋酸。对本流程的主要创新点就是通过改变第一级催化剂的性能从而得到适应不同下游产物需求的溴代烷烃和一氧化碳。
目前没有与我们的流程相似的报道。在Olah的研究工作中(G.A.Olah,A.Molnar,HydrocarbonChemistry(Wiley,New York,1995)),是用甲烷与单质溴Br2反应生成CH3Br和HBr,然后再水解CH3Br制二甲醚和甲醇。而且他们报道的甲烷单程转化率低于20%。
美国的GRT Inc公司Xiao Ping Zhou等设计了以Br2为媒介把天然气中的烷烃转化为二甲醚和甲醇的流程(CN02827498.9,US6472572,US6462243),这一流程与Olah报道的不同之处是在于用烷烃与溴反应生成溴代烃和HBr,然后进一步与一种金属氧化物反应生成目的产物和金属溴化物,最后金属溴化物与氧气反应再生出Br2和金属氧化物,完成溴的循环。以上流程都涉及单质溴的使用和需要额外的步骤再生单质溴,而且大量使用和储藏单质溴是非常危险的。由于反应不是催化反应,而是计量化学反应,所以需要在反应系统中传输化学计量的金属氧化物,使流程复杂化,并且增加了能耗。
美国Dow环球公司报道了使用单质氯或氯化氢为媒介制备甲醇/二甲醚,轻质烯烃如乙烯、丙烯和丁烯、较高级烯烃包括汽油,卤乙烯单体和醋酸(CN02813796.5)。但是这一流程使用氯化氢制备氯甲烷作为反应中间产物。在该专利中使用金属卤氧化物作为催化剂,并没有使用载体,催化剂不稳定,并且所使用的金属主要为稀土金属,价格相对较高,而且甲烷的单程转化率最高只达到13.3%。
本发明是对天然气中甲烷等低碳烃溴氧化制溴代烷催化剂以及进一步把溴代烷烃转化为高碳烃的催化剂的进一步改进。
发明内容
本发明的一个目的就是优化一种把天然气中甲烷转化为溴代烷烃的催化剂,是由可溶解于水的金属化合物前体和硅前体混合水解、烘干、然后焙烧制备的金属或金属化合物分散在SiO2物相中形成的复合型催化剂。
具体的讲,第一种催化剂是使用二氧化硅作为载体,金属化合物前体是Ru、Rh、Pd、Pt、Ni、Cu、Zn、Ag、Ce、V、W、Cd、Mo、Mn、Cr和La的氯化物、溴化物或硝酸盐等可溶性盐。
催化剂用于如下反应:
本发明是将甲烷经过溴氧化反应转化为溴代烃的催化剂,在反应中以甲烷、HBr、H2O和氧源(O2、空气或富氧空气)为反应物,在一定的反应温度下,在固定床反应器中与催化剂接触发生催化反应,生成目的产物CH3Br和CH2Br2以及副产物CO和CO2。这一反应的产物CH3Br和CH2Br2的用途是合成高碳烃。其中由CH3Br和CH2Br2合成高碳烃的方法我们已经在申请号为200610031377.9的中国专利中描述。
本发明的溴氧化催化剂是由金属或金属化合物分散在SiO2物相中形成的复合型化合物催化。具体的方法是在本发明的催化剂制备中,以Ru、Rh、Pd、Pt、Ni、Cu、Zn、Ag、Ce、V、W、Cd、Mo、Mn、Cr和La的氯化物、溴化物和硝酸盐为原料配制相应的金属盐水溶液;以SiCl4、硅元酸酯为原料水解配制硅溶胶溶液或直接用商品硅溶胶溶液。把金属盐水溶液与硅溶胶水溶液混合、烘干、然后焙烧制成用于甲烷溴氧化反应的催化剂。
在Ru、Rh、Pd、Pt、Ni、Cu、Zn、Ag、Ce、V、W、Cd、Mo、Mn、Cr和La的氯化物、溴化物和硝酸盐中,Ru和Rh的氯化物、溴化物和硝酸盐与硅前体制备的催化剂的催化性能最好,Ru和Rh的氯化物、溴化物和硝酸盐是我们优先选择的催化剂前体。一般Ru在SiO2中的重量百分含量选择在0.10%至2.0%,较好的Ru浓度范围是0.40%至1.40%,最好的Ru浓度范围是0.60%至1.20%。对于含Rh的催化剂,一般Rh在SiO2中的重量百分含量选择在0.10%至0.80%之间,较好的Rh浓度范围是0.20%至0.50%之间,最好的Rh浓度范围是在0.30%至0.50%之间。催化剂的烧制温度选择在500到1200℃,较好的焙烧温度是700到1000℃,最佳的催化剂焙烧温度是700到900℃。甲烷、HBr、H2O与O2在催化剂上的反应温度一般是在500至750℃之间,较好的反应温度范围是在600至680℃之间,最好的反应温度是在620至670℃之间。
本发明的另一个目的是优化一种用于将溴代烃进一步转化为高碳烃的催化剂,溴代烃CH3Br和CH2Br2在催化剂上脱HBr制碳三以上的高碳烃的反应如下:
本反应的催化剂是分子筛HZSM-5、HY、Hβ、3A、4A、5A和13X负载的金属化合物催化剂,其中优选的载体是HZSM-5。催化剂的制备方法是把活性金属化合物前体——Zn或Mg的氯化物、溴化物和硝酸盐等水溶性盐配成水溶液,然后加入需要量的分子筛,在室温下浸泡一段时间,然后烘干,最后焙烧制成相应催化剂。Zn在分子筛中以ZnO的重量百分数计算含量范围是0.10%至18%,较好的ZnO含量范围是0.50%至15.0%,最好的含量范围是1.0%至8.0%;Mg在分子筛中以MgO的重量百分数计算含量范围是0.10%至20.0%,较好的MgO含量范围是0.50%至18.0%,最好的含量范围是1.0%至15.0%。溴代烃CH3Br和CH2Br2在催化剂上脱HBr制碳三以上的高碳烃的反应一般在200至450℃之间进行,较好的反应温度是在220至400℃之间,最好的反应温度是在240至360℃之间。
具体实施例
甲烷制溴甲烷
实例1
催化剂的制备:
称量6.300g草酸固体溶解于100mL去离子水中得到溶液A,称量负载Rh金属质量分数为0.40%的相应RhCl3·nH2O计量重量0.10224g溶解于50mL去离子水中得到溶液B,称量34.5831g四乙氧基硅烷液体加入到溶液A中形成两相互不相溶的液体。密封搅拌1小时后溶液变成均匀无色透明的一相溶液,加入溶液B,继续搅拌0.5小时,然后将该混合溶液放入120℃烘箱烘干至胶状固体,随后将该胶状固体置入马弗炉中以200℃/h的升温速度加热至900℃,维持该温度10小时后降温,等温度降至室温后取出催化剂,筛分至20-60目,最终得到0.40%Rh/SiO2-900-10催化剂(“0.40%”表示负载相应金属的质量分数,“-900-10”表示900℃焙烧10小时制得的催化剂,标记方法下同)。
催化剂的测试:
采用固定床流动反应器,反应在常压下进行。反应器为内径为14mm的石英玻璃管,催化剂用量5.00g,在自制的管式炉中进行反应。反应气为CH4、O2、N2(内标用),流量分别为20.0mL/min、5.0mL/min、5.0mL/min。反应液为氢溴酸水溶液(HBr/H2O),浓度为≥40wt%。催化剂在反应气体通入半小时后开始升温至660℃,期间在温度升至400℃以上时开始以6.5mL/h速度通入HBr/H2O溶液。反应稳定2小时后,开始取样分析尾气的成分含量,收集数据。
实验得出:甲烷的转化率为35.8%,产物主要为溴甲烷,以及少量的二溴甲烷、一氧化碳、二氧化碳和痕量的三溴甲烷(质谱可以检测到其存在,但在色谱中不能准确检测到)、四溴甲烷。其中溴甲烷的选择性为90.8%,二溴甲烷的选择性为2.1%,一氧化碳选择性为5.8%,二氧化碳选择性为1.3%。
在上述催化剂制备过程中,可以用Ru、Rh、Pd、Pt、Ni、Cu、Zn、Ag、Ce、V、W、Cd、Mo、Mn、Cr和La的氯化物、溴化物和硝酸盐等水溶性盐为原料配制相应的金属盐水溶液,用SiCl4、其它硅元酸酯为原料水解配制硅溶胶溶液或直接用商品硅溶胶溶液,制得的此类催化剂,经测试均表现出了对甲烷溴氧化反应有催化活性,只是转化率和选择性有差异,并不改变反应产物,实施例2-59仅列出了小部分催化剂实验结果。
实例2至实例6
催化剂的制备:
按照实例1中催化剂的制备方法,使用不同浓度的RhCl3·nH2O溶液50.0mL去离子水中得到溶液B,其中RhCl3·nH2O溶液的浓度为所需负载不同质量分数Rh的折算量。最终得到0.10%Rh/SiO2-900-10(实例2)、0.20%Rh/SiO2-900-10(实例3)、0.30%Rh/SiO2-900-10(实例4)、0.50%Rh/SiO2-900-10(实例5)、0.60%Rh/SiO2-900-10(实例6)催化剂。
催化剂的测试:
按照实例1中催化剂的测试条件,在相同的反应条件下进行反应。实验结果列于表1。
表1实例1至实例6的实验结果(金属Rh负载量的影响)
实例7至实例12
催化剂的制备:
按照实例1中催化剂的制备方法,在马弗炉中使用不同的焙烧温度和时间。最终得到具有不同比表面积的催化剂。即0.40%Rh/SiO2-900-6(实例7)、0.40%Rh/SiO2-900-2(实例8)、0.40%Rh/SiO2-800-6(实例9)、0.40%Rh/SiO2-800-2(实例10)、0.40%Rh/SiO2-700-10(实例11)、0.40%Rh/SiO2-700-6(实例12)催化剂。
催化剂的测试:
按照实例1中催化剂的测试方法,在相同的反应条件下进行反应。实验结果列于表2。
表2实例1、实例7至实例12的实验结果(催化剂制备过程中焙烧温度的影响,催化剂组成0.40%Rh/SiO2)
实例13至实例16
催化剂的制备:
按照实例1中催化剂的制备方法得到0.40%Rh/SiO2-900-10催化剂。
催化剂的测试:
按照实例1中催化剂的测试方法,在不同的反应温度(600℃(实例13)、620℃(实例14)、640℃(实例15)、680℃(实例16))下进行反应。实验结果列于表3。
表3实例1、实例13至实例16的实验结果(反应温度的影响)
实例17至实例22
催化剂的制备:
按照实例1中催化剂的制备方法得到0.40%Rh/SiO2-900-10催化剂。
催化剂的测试:
按照实例1中催化剂的测试方法,在不同的HBr/H2O溶液的进料情况(3.0mL/h(实例17)、4.0mL/h(实例18)、5.0mL/h(实例19)、6.0mL/h(实例20)、7.0mL/h(实例21)、8.0mL/h(实例22))下进行反应。实验结果列于表4。
表4实例1、实例17至实例22的实验结果(反应温度的影响)
实例23至实例25
催化剂的制备:
按照实例1中催化剂的制备方法得到0.40%Rh/SiO2-900-10催化剂。
催化剂的测试:
按照实例1中催化剂的测试方法,催化剂用量为10.00g,反应进料气CH4、O2、N2(内标用)的流量分别为40.0mL/min、10.0mL/min、10.0mL/min,在HBr/H2O溶液的进料速率为13.0mL/h(实例23)、12.0mL/h(实例24)、10.0mL/h(实例25)下进行反应。实验结果列于表5。
表5实例23至实例25的实验结果(催化剂用量10.00g时不同HBr/H2O进料的影响)
实例26至实例28
催化剂的制备:
按照实例1中催化剂的制备方法得到0.40%Rh/SiO2-900-10催化剂。
催化剂的测试:
按照实例1中催化剂的测试方法,催化剂用量为10.00g,CH4和N2流量为40.0mL/min和10.0mL/min,HBr/H2O溶液进料速率为10.0mL/h。O2流量分别为9.0mL/min(实例26)、8.0mL/min(实例27)、7.0mL/min(实例28)进行反应。实验结果列于表6。
表6实例25、实例26至实例28的实验结果(不同CH4/O2进料的影响)
实例29至实例39
催化剂的制备:
按照实例1中催化剂的制备方法,在溶解相同量的RhCl3·nH2O的基础上,同时溶解金属质量分数为2.0%的其他相应计量的金属硝酸盐制得溶液B,最终得到2.0%Cu0.40%Rh/SiO2-900-10(实例29)、2.0%Zn0.40%Rh/SiO2-900-10(实例30)、2.0%Ag0.40%Rh/SiO2-900-10(实例31)、2.0%Ce0.40%Rh/SiO2-900-10(实例32)、2.0%V0.40%Rh/SiO2-900-10(实例33)、2.0%W0.40%Rh/SiO2900-10(实例34)、2.0%Cd0.40%Rh/SiO2-900-10(实例35)、2.0%Mo0.40%Rh/SiO2-900-10(实例36)、2.0%Mn0.40%Rh/SiO2-900-10(实例37)、2.0%Cr0.40%Rh/SiO2-900-10(实例38)、2.0%La0.40%Rh/SiO2-900-10(实例39)催化剂、2.5%Ni0.40%Rh/SiO2-900-10(实例40)催化剂。
催化剂的测试:
按照实例1中催化剂的测试方法,在相同的反应条件下进行反应,实验结果列于表7。
表7实例1、实例29至实例39的实验结果(Rh基双组分金属负载催化剂)
实例41至实例46
催化剂的制备:
按照实例11中催化剂的制备方法得到0.40%Rh/SiO2-700-10催化剂。
催化剂的测试:
按照实例1中催化剂的测试方法,反应进料气CH4、O2、N2(内标用)的流量分别为20.0mL/min、10.0mL/min、5.0mL/min,HBr/H2O溶液的进料速率为8.0mL/h,在不同的反应温度(560℃(实例40)、580℃(实例41)、600℃(实例42)、620℃(实例43)、640℃(实例44)、660℃(实例45))下进行反应。
实验结果列于表8。
表8实例41至实例46的实验结果(反应温度的影响)
实例47至实例56
催化剂的制备:
称量6.300g草酸固体溶解于100mL去离子水中得到溶液A,称量负载不同Ru金属质量分数相应RuCl3·nH2O计量重量溶解于50mL去离子水中得到溶液B,称量34.583g四乙氧基硅烷液体加入到溶液A中形成两相互不相溶的液体。密封搅拌1小时后溶液变成均匀无色透明的一相溶液,加入溶液B,继续搅拌0.5小时,然后将该混合溶液放入120℃烘箱烘干至胶状固体,随后将该胶状固体置入马弗炉中以200℃/h的升温速度加热至900℃,维持该温度10小时,等温度降至室温后取出催化剂,筛分至20-60目,最终得到催化剂0.10%Ru/SiO2-900-10(实例46)、0.20%Ru/SiO2-900-10(实例47)、0.30%Ru/SiO2-900-10(实例48)、0.40%Ru/SiO2-900-10(实例49)、0.50%Ru/SiO2-900-10(实例50)、0.60%Ru/SiO2-900-10(实例51)、0.80%Ru/SiO2-900-10(实例52)、1.0%Ru/SiO2-900-10(实例53)、1.20%Ru/SiO2-900-10(实例54)、1.40%Ru/SiO2-900-10(实例55)。
催化剂的测试:
采用固定床流动反应器,反应在常压下进行。反应器为内径为14mm的石英管,催化剂用量5.00g,在自制的管式炉中进行反应。反应气为CH4、O2、N2(内标用),流量分别为20.0mL/min、5.0mL/min、5.0mL/min。反应液体为氢溴酸水溶液(HBr/H2O),浓度为≥40wt%。催化剂在反应气体通入半小时后开始升温至660℃,期间在温度升至400℃以上时开始以6.5mL/h速度通入HBr/H2O溶液。反应稳定2小时后,开始取样分析尾气的成分含量,收集数据。
实例57
催化剂的制备:
称量6.300g草酸固体溶解于100mL去离子水中得到溶液A,称量负载0.1%Pt金属质量分数相应RuCl4计量重量溶解于50mL去离子水中得到溶液B,称量34.6872g四乙氧基硅烷液体加入到溶液A中形成两相互不相溶的液体。密封搅拌1小时后溶液变成均匀无色透明的一相溶液,加入溶液B,继续搅拌0.5小时,然后将该混合溶液放入120℃烘箱烘干至胶状固体,随后将该胶状固体置入马弗炉中以200℃/h的升温速度加热至900℃,维持该温度10小时,等温度降至室温后取出催化剂,筛分至20-60目,最终得到催化剂0.10%Pt/SiO2-900-10(实例57)
催化剂的测试:
采用固定床流动反应器,反应在常压下进行。反应器为内径为14mm的石英管,催化剂用量5.00g,在自制的管式炉中进行反应。反应气为CH4、O2、N2(内标用),流量分别为20.0mL/min、5.0mL/min、5.0mL/min。反应液体为氢溴酸水溶液(HBr/H2O),浓度为≥40wt%。催化剂在反应气体通入半小时后开始升温至660℃,期间在温度升至400℃以上时开始以6.5mL/h速度通入HBr/H2O溶液。反应稳定2小时后,开始取样分析尾气的成分含量,收集数据。
实例58至实例59
催化剂的制备(采用浸渍法制备):
称量6.300g草酸固体溶解于100mL去离子水中得到溶液A,称量34.5831g四乙氧基硅烷液体加入到溶液A中形成两相互不相溶的液体。密封搅拌1小时后溶液变成均匀无色透明的一相溶液,然后将该混合溶液放入120℃烘箱烘干至胶状固体,随后将该胶状固体置入马弗炉中以200℃/h的升温速度加热至1000℃,维持该温度5小时,等温度降至300℃以下后取出催化剂,筛分至20-60目,最终得到催化剂载体SiO2
称量负载不同Pd或Pt金属质量分数相应水合氯化物计量重量溶解于50mL去离子水中得到溶液B。称取10.0g已制备的SiO2载体加入到溶液B中搅拌0.5小时,静置3小时候后将该溶液放入120℃烘箱烘干,随后将样品置入马弗炉中在450℃温度下恒温8小时,等温度降至室温后取出催化剂,最终得到催化剂0.10%Pd/SiO2-1000-5(实例58)、0.10%Pt/SiO2-1000-5(实例59)。
催化剂的测试:
采用固定床流动反应器,反应在常压下进行。反应器为内径为14mm的石英管,催化剂用量5.00g,在自制的管式炉中进行反应。反应气为CH4、O2,流量分别为20.0mL/min、5.0mL/min。反应液体为氢溴酸水溶液(HBr/H2O),浓度为≥40wt%。催化剂在反应气体通入半小时后开始升温至660℃,期间在温度升至400℃以上时开始以6.0mL/h速度通入HBr/H2O溶液。反应稳定2小时后,开始取样分析尾气的成分含量,收集数据。实验结果列于表9。
表9实例47至实例59的实验结果(负载金属Ru、Pt、Pd的影响)
甲烷溴制高碳烃反应具体实施方式
实例60
催化剂的制备:
称量负载ZnO质量分数为5.0%的相应Zn(NO3)2·6H2O 2.8856g溶解于100mL去离子水中用玻璃棒搅拌得到澄清溶液,称量15.00g的HZSM-5载体加入到溶液中,密封搅拌40-60min,静置浸泡12h后90℃水浴4h,再放入120℃烘箱烘干,随后将样品置入马弗炉中在450℃下恒温8h,等温度降至室温后取出催化剂,压片筛分至20-60目即得到催化剂5.0%Zn/HZSM-5-450-8(“5.0%”表示负载相应金属氧化物的质量分数,“-450-8”表示450℃焙烧8小时制得的催化剂,标记方法下同)。
催化剂的测试:
采用固定床反应器,反应在常压下进行。反应器为内径14mm的玻璃管,催化剂用量为8.00g,在铝制加热套中进行反应。利用流量为5.0mL/min的N2作为内标和载气,反应气为CH3Br,流量为7.76mL/min。催化剂在N2通入半小时后开始升温至300℃。反应稳定2小时后开始取样分析尾气的成分含量,收集数据。
实验得出:溴甲烷的转化率为99.63%,气相产物为C2-C5的烷烃、烯烃以及剩余的溴甲烷;液相产物主要为C5-C13的烷烃、烯烃及芳烃。
活性金属化合物前体也可以用Zn或Mg的氯化物和溴化物等水溶性盐,去配制水溶液。
实例61至实例65
催化剂的制备:
按照实例59中催化剂的制备方法得到5.0%Zn/HZSM-5-450-8催化剂。
催化剂的测试:
按照实例59中催化剂的测试方法,在不同的反应温度(280℃(实例61)、260℃(实例62)、240℃(实例63)、220℃(实例64)、200℃(实例65))下进行反应。实验结果列于表10。
表10实例60、实例61至实例65的实验结果(反应温度的影响)
实例66至实例71
催化剂的制备:
按照实例59中催化剂的制备方法,使用不同量的Zn(NO3)2·6H2O与100mL去离子水配制的溶液,其中Zn(NO3)2·6H2O溶液的浓度为所需负载不同质量分数ZnO的折算量。最终得到1.0%Zn/HZSM-5-450-8(实例66、3.0%Zn/HZSM-5-450-8(实例67)、8.0%Zn/HZSM-5-450-8(实例68)、10.0%Zn/HZSM-5-450-8(实例69)、12.0%Zn/HZSM-5-450-8(实例70)、15.0%Zn/HZSM-5-450-8(实例71)催化剂。
催化剂的测试:
按照实例59中催化剂的测试条件,催化剂先在300℃活化4h,然后在260℃时进行反应。实验结果列于表11。
表11实例62、实例65至实例70的实验结果(ZnO负载量的影响)
实例72至实例77
催化剂的制备:
按照实例59中催化剂的制备方法,使用不同的分子筛载体(HY、Hβ、、、、13X)制备(3.0%Zn/HY-450-8(实例72)、3.0%Zn/H β-450-8(实例73)、3.0%Zn/3A-450-8(实例74)、3.0%Zn/4A-450-8(实例75)、3.0%Zn/5A-450-8(实例76)、3.0%Zn/13X-450-8(实例77))催化剂。
催化剂的测试:
按照实例59中催化剂的测试条件,催化剂先在300℃活化4h,然后在260℃时进行反应。实验结果列于表12。
表12实例72至实例77的实验结果(不同载体的影响)
实例78至实例84
催化剂的制备:
称量负载不同MgO质量分数的相应Mg(NO3)2·6H2O计量重量溶解于100mL去离子水中用玻璃棒搅拌得到澄清溶液,称量15.00g的HZSM-5(Si/Al=360)载体加入到溶液中,密封搅拌40-60min,静置浸泡12h后90℃水浴4h,再放入120℃烘箱烘干,随后将样品置入马弗炉中在450℃下恒温8h,等温度降至室温后取出催化剂,压片筛分至20-60目即得到催化剂(1.0%Mg/HZSM-5-450-8(实例78)、3.0%Mg/HZSM-5-450-8(实例79)、5.0%Mg/HZSM-5-450-8(实例80)、8.0%Mg/HZSM-5-450-8(实例81)、10.0%Mg/HZSM-5-450-8(实例82)、15.0%Mg/HZSM-5-450-8(实例83)、18.0%Mg/HZSM-5-450-8(实例84)。
催化剂的测试:
按照实例59中催化剂的测试条件,催化剂先在300℃活化4h,然后在260℃时进行反应。实验结果列于表13。
表13实例78至实例84的实验结果(MgO负载量的影响)
Claims (14)
1、本发明公开了甲烷经过溴氧化反应转化为溴代烃的催化剂以及由溴代烃进一步制高碳烃的催化剂:
使用第一种催化剂,使反应物甲烷、HBr、H2O和氧源(O2、空气或富氧空气)进行催化溴氧化反应,生成目的产物CH3Br和CH2Br2以及副产物CO和CO2;
使用第二种催化剂,使甲烷溴化产物CH3Br和CH2Br2进一步反应生成C3至C13的高碳烃和HBr,其中HBr作为循环反应介质利用。
2、根据权利要求1所说的第一种催化剂,其特征在于它是由可溶解于水的金属化合物前体和硅前体混合水解、烘干、然后焙烧制备的金属或金属化合物分散在SiO2物相中形成的复合型催化剂。
3、根据权利要求2所说的复合型催化剂,其特征在于所说的金属化合物前体是Ru、Rh、Pd、Pt、Ni、Cu、Zn、Ag、Ce、V、W、Cd、Mo、Mn、Cr和La的氯化物、溴化物和硝酸盐,优选的金属化合物前体是Ru或Rh的氯化物、溴化物和硝酸盐。
4、根据权利要求2所说的复合型催化剂,其特征在于所说的硅前体是SiCl4、硅元酸酯和硅溶胶溶液。
5、根据权利要求2、3所说的复合型催化剂,其特征在于Ru在SiO2中的重量百分含量在0.10%至2.0%,较好的含量范围是0.40%至1.40%,最好的含量范围是0.60%至1.20%。
6、根据权利要求2、3所说的复合型催化剂,其特征在于Rh在SiO2中的重量百分含量在0.10%至0.80%,较好的含量范围是0.20%至0.50%,最好的含量范围是0.30%至0.50%。
7、根据权利要求2所说的复合型催化剂,其特征在于催化剂的焙烧温度是500到1200℃,较好的焙烧温度是700到1000℃,最佳焙烧温度是700到900℃。
8、根据权利要求1所说的第一种催化剂,其特征在于它的活性反应温度是在500至750℃之间,较好的反应温度是在600至680℃之间,最好的反应温度是在620至670℃之间。
9、根据权利要求1所说的第二种催化剂,其特征在于它是由活性金属化合物前体负载于载体上,经过烘干、然后焙烧制成的用于溴代烃脱HBr制高碳烃反应的催化剂。
10、根据权利要求9所说的用于溴代烃脱HBr制高碳烃反应的催化剂,其特征在于所说的活性金属化合物前体是Zn或Mg的氯化物、溴化物和硝酸盐。
11、根据权利要求9所说的用于溴代烃脱HBr制高碳烃反应的催化剂,其特征在于所说的载体是HZSM-5、HY、Hβ、3A、4A、5A和13X分子筛,优选的载体是HZSM-5。
12、根据权利要求9、10所说的用于溴代烃脱HBr制高碳烃反应的催化剂,其特征在于Zn在分子筛中以ZnO的重量百分数计算含量范围是0.10%至18%,较好的ZnO含量范围是0.50%至15.0%,最好的含量范围是1.0%至8.0%。
13、根据权利要求9、10所说的用于溴代烃脱HBr制高碳烃反应的催化剂,其特征在于Mg在分子筛中以MgO的重量百分数计算含量范围是0.10%至20.0%,较好的MgO含量范围是0.50%至18.0%,最好的含量范围是1.0%至15.0%。
14、根据权利要求1所说的第二种催化剂,其特征在于它的活性反应温度是在180至500℃之间,较好的反应温度是在220至400℃之间,最好的反应温度是在240至360℃之间。
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CN2007100347267A CN101284232B (zh) | 2007-04-13 | 2007-04-13 | 甲烷溴氧化制溴甲烷及其转化制碳氢化合物的催化剂 |
US12/595,797 US20110136658A1 (en) | 2007-04-13 | 2008-04-14 | The catalyst used in the reaction of brominating oxidation of methane and the catalyst used in the farther reaction of producing higher hydrocarbon |
PCT/CN2008/000771 WO2008125017A1 (fr) | 2007-04-13 | 2008-04-14 | Catalyseur utilisé dans la réaction de bromation oxydante du méthane et catalyseur utilisé dans la réaction ultérieure de production d'hydrocarbures supérieurs |
EP08733969A EP2147719A4 (en) | 2007-04-13 | 2008-04-14 | CATALYST USED IN THE REACTION OF METHANE OXIDIZING BROMATION AND CATALYST USED IN THE FUTURE REACTION OF UPPER HYDROCARBON PRODUCTION |
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Also Published As
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US20110136658A1 (en) | 2011-06-09 |
CN101284232B (zh) | 2013-01-16 |
EP2147719A4 (en) | 2012-05-02 |
EP2147719A1 (en) | 2010-01-27 |
WO2008125017A1 (fr) | 2008-10-23 |
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