CN106745212B - 一种合成草酸二甲酯催化剂用载体的制备方法 - Google Patents
一种合成草酸二甲酯催化剂用载体的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000583 acetic acid Drugs 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 6
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Chemical group 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Chemical group 0.000 claims description 2
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- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
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- 229910017676 MgTiO3 Inorganic materials 0.000 description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 238000003795 desorption Methods 0.000 description 2
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- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical group CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFNKLDDSWHOKLQ-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O OFNKLDDSWHOKLQ-UHFFFAOYSA-N 0.000 description 1
- 241000627951 Osteobrama cotio Species 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
本发明公开了一种合成草酸二甲酯催化剂用载体的制备方法。本发明所采用的制备方法是将可溶性M盐(M盐为Zn、Mg、Ca和Co的硝酸盐、氯化物、醋酸盐)加入到钛酸酯的冰醋酸溶液中,再加入大分子量的有机物为致孔剂,于60~90℃水浴中不断搅拌直至形成透明凝胶,将此凝胶烘干、焙烧、挤条成型后制备得到MTiO3载体。采用本方法制备的载体的结晶度高,具有无规则的片状结构。载体的表面具有不同强度的碱性位,但主要以弱碱性为主。所制备载体比表面积为10~35m2/g,其平均孔径为8~25nm。该法制备的载体适用于制备负载型的Pd基催化剂来催化一氧化碳氧化偶联合成草酸二甲酯。
Description
技术领域
本发明涉及一种载体的制备方法,该载体主要用于制备负载型Pd基催化剂催化一氧化碳氧化偶联合成草酸二甲酯,属于草酸二甲酯的制备技术领域。
背景技术
载体是固体催化剂的重要组成部分,是用来担载活性组分和助剂的物质。在催化反应中的载体的作用主要有:(1)增大活性表面和提供适宜的孔结构;(2)改善催化剂的机械强度,保证其具有一定的形状;(3)改善催化剂的导热性和热稳定性,以防局部过热导致催化剂的烧结失活;(4)对主催化剂起分散作用和支撑作用。
一氧化碳气相催化偶联合成草酸二甲酯是煤制乙二醇工艺的一个关键步骤。该反应所需催化剂性能的优劣不仅取决于催化剂的制备方法,而且也取决于对载体的选择。目前已见报道中(104190414B、104190415B、102527377A、102527377A、105597743A、105381799A等)合成草酸二甲酯催化剂是采用α-Al2O3作载体,由于α-Al2O3要经过1300℃高温焙烧,这就会使得α-Al2O3载体的一些孔道在高温焙烧的过程中坍塌,从而导致其比表面积和平均孔径变小。比表面积过小,不利于活性组分的分散,从而不利于催化剂活性的发挥。为了克服α-Al2O3载体的较小的比表面积和较小的孔径,本发明公开了一种合成草酸二甲酯催化剂用MTiO3载体的制备方法,该法制备的载体结晶度高,呈无规则的片状结构,其比表面积和平均孔径可以通过添加合适量的致孔剂来控制。采用该法提供的载体来制备负载型的Pd基催化剂,其在一氧化碳气相偶联合成草酸二甲酯的反应中表现出较好的催化活性。在较低的Pd负载量的情况下(0.3%,以载体质量计),草酸二甲酯的时空收率能够达到1200g/Lcat·h以上,草酸二甲酯的选择性能够达到98%以上。
发明内容
本发明的目的是提供一种用于合成草酸二甲酯用催化剂的载体。本方法提供的载体主要用来制备负载型的Pd基催化剂来催化CO偶联合成草酸二甲酯反应。
本发明提供的用于合成草酸二甲酯催化剂用MTiO3载体的制备方法,其制备步骤为:
A.将钛酸酯溶于冰醋酸中形成0.5mol/L~1.5mol/L的溶液;所述钛酸酯为钛酸四正丁酯、钛酸四异丁酯、钛酸四正丙酯、钛酸四异丙酯中的任意一种;
B.将可溶性M盐溶于水中形成0.5mol/L~1.5mol/L的盐溶液;其中M代表Mg2+、Ca2 +、Zn2+、Co2+、Ni2+中的任意一种,盐溶液中的阴离子为硝酸根、醋酸根、氯离子中的任意一种,较佳的M盐是硝酸镁、硝酸钙或硝酸钴;
C.将步骤B得到的溶液加入到步骤A的溶液中,同时加入致孔剂于60~90℃水浴中不断搅拌,直至形成透明凝胶;其中致孔剂的加入量为溶液种钛质量的1~10%;
所述的致孔剂为葡萄糖、P123、环糊精、聚乙二醇、聚乙烯醇、聚环氧乙烷、壳聚糖中的任意一种,较佳的是环糊精、壳聚糖或聚乙二醇;
D.将上述凝胶置于烘箱中在60~80℃干燥12h,再升温至100~120℃干燥12h,最后置于马弗炉中450~600℃焙烧4~6h后得到块状白色粉体;
E.将上述块状白色粉体进行球磨,然后加入聚乙烯醇的水溶液作为粘合剂,经过挤条成型后,在700℃高温焙烧后获得所需的载体。
所制备的载体化学式为MTiO3,其中M代表Mg2+、Ca2+、Zn2+、Co2+、Ni2+中的任意一种,其比表面积为10~35m2/g,均孔径为8~25nm。
对得到的载体进行表征结果见图1-5,由图1可以看出,所制备的载体主要组分为MgTiO3,但含有少量的MgO和TiO2。由图2可见,所制备的MgTiO3载体为无规则的片状结构。图3的N2的吸脱附曲线表明,所制备的载体的孔主要为狭缝型。图4的CO2的程序升温脱附曲线表明所制备的载体表面具有不同的强度的碱性位,但是以弱碱性为主,这种弱碱性可以有效抑制亚硝酸甲酯的催化分解。
从表1催化剂的评价结果可以看出,以本方法制备的MTiO3为载体制备的催化剂,在Pd的负载量低至0.3%时,草酸二甲酯的选择性高于98%,草酸二甲酯的收率能够达到1200g/Lcat·h以上。
本发明的有益效果:所采用的制备工艺独特,未见文献报道,所制备的MTiO3载体呈无规则的片状结构,载体的结晶度高,载体表面呈现弱碱性,载体的比表面积和平均孔径可以通过添加不同量的致孔剂来控制。采用该发明方法制备的MTiO3载体来制备草酸二甲酯合成催化剂,其催化活性好,活性组分Pd的分散度高,同时草酸二甲酯的具有较高的选择性和时空收率。
附图说明
图1实施例1制备的载体的XRD图。
图2实施例1制备的载体的SEM图。
图3实施例1制备的载体的N2吸脱附曲线图。
图4实施例1制备的载体的CO2程序升温脱附曲线图。
图5采用实施例1得到的载体制备的草酸二甲酯合成催化剂的TEM谱图。
具体实施方式
下面通过具体实施例对本发明的合成气制草酸二甲酯催化剂用MTiO3载体的制备方法进行详细的描述,但是本发明并不限于以下具体实施例。
实施例1
称取0.02mol钛酸四正酯溶于冰醋酸,形成0.5mol/L的溶液。称取0.02mol硝酸镁溶于去离子水中形成0.4mol/L的溶液,在不断搅拌的条件下加入到已配置好的钛酸四正丁酯的醋酸溶液中,同时加入0.02g环糊精作为致孔剂。将上述混合溶液置于80℃的水浴中,获得透明凝胶。将上述凝胶在60℃的烘箱干燥12h,再将温度升至100℃干燥12h后,转移至刚玉坩埚中置于马弗炉中600℃焙烧2h,得到块状白色粉体。将上述白色粉体球磨后,加入5mL 1mol/L的聚乙烯醇水溶液作为胶黏剂,充分混合后进行挤条成型,最后置于700℃马弗炉中焙烧2h后,即获得MgTiO3载体。
对得到的MgTiO3载体表征结果见图1-4
实施例2
称取0.04mol钛酸四异丁酯溶于冰醋酸,形成1mol/L的溶液。称取0.04mol硝酸钙溶于去离子水中形成0.8mol/L的溶液,在不断搅拌的条件下加入到已配置好的钛酸四异丁酯的醋酸溶液中,同时加入0.04g环糊精作为致孔剂。将上述混合溶液置于85℃的水浴中,获得透明凝胶。将上述凝胶在70℃的烘箱干燥12h,再将温度升至110℃干燥12h后,转移至刚玉坩埚中置于马弗炉中500℃焙烧4h,得到块状白色粉体。将上述白色粉体球磨后,加入5mL 1.5mol/L的聚乙烯醇水溶液作为胶黏剂,充分混合后进行挤条成型,最后置于700℃马弗炉中焙烧4h后,即获得CaTiO3载体。
实施例3
称取0.02mol钛酸四正丙酯溶于冰醋酸,形成0.5mol/L的溶液。称取0.02mol硝酸钴溶于去离子水中形成0.4mol/L的溶液,在不断搅拌的条件下加入到已配置好的钛酸四正丙酯的醋酸溶液中,同时加入0.02g壳聚糖作为致孔剂。将上述混合溶液置于75℃的水浴中,获得透明凝胶。将上述凝胶在80℃的烘箱干燥12h,再将温度升至120℃干燥12h后,转移至刚玉坩埚中置于马弗炉中600℃焙烧6h,得到块状黑色粉体。将上述黑色粉体球磨后,加入5mL 2mol/L的聚乙烯醇水溶液作为胶黏剂,充分混合后进行挤条成型,最后置于700℃马弗炉中焙烧5h后,即获得本发明的CoTiO3载体。
实施例4
称取0.03mol钛酸四正酯溶于冰醋酸,形成1.5mol/L的溶液。称取0.03mol硝酸镁溶于去离子水中形成0.6mol/L的溶液,在不断搅拌的条件下加入到已配置好的钛酸四正丁酯的醋酸溶液中,同时加入0.03g聚乙二醇作为致孔剂。将上述混合溶液置于80℃的水浴中,获得透明凝胶。将上述凝胶在80℃的烘箱干燥12h,再将温度升至110℃干燥12h后,转移至刚玉坩埚中置于马弗炉中600℃焙烧4h,得到块状白色粉体。将上述白色粉体球磨后,加入5mL 1.5mol/L的聚乙烯醇水溶液作为胶黏剂,充分混合后进行挤条成型,最后置于700℃马弗炉中焙烧2h后,即获得本发明的ZnTiO3载体。
应用例
(1)催化剂的制备:称取5g实施例1-4制备的载体分别加入到30mL 0.005mol/L的氯钯酸钠的溶液中,然后加入0.3g聚乙烯吡咯烷酮和0.3g柠檬酸,搅拌1h后,再加入0.2g抗坏血酸,室温下继续搅拌12小时,然后过滤,分别用蒸馏水和乙醇洗涤数次,过滤后置于60℃的真空干燥箱中干燥12小时,即得到所需的催化剂样品,分别编号为M-1、M-2、M-3、M-4。
对催化剂样品M-1进行透射电镜表征结果见图5,由图5可见,活性组分Pd粒子(图中的白色亮点)均匀分散在载体上,其平均粒径为3.5nm左右。
(2)催化剂样品性能评价:用量筒量取2mL 10-20目的催化剂样品,装入内径为10mm的反应管中,通入50mL/min N2,30mL/min H2,350℃条件下还原6h。待温度下降到130℃时,再开始通入50mL/min N2,30mL/min CO,20mL/min亚硝酸甲酯进行反应,空速为3000h-1,催化剂样品的评价结果列于表1中。
表1实施例催化剂样品的评价结果。
从表1可以看出,采用该发明方法制备的MTiO3作为载体来制备催化剂,在Pd的负载量低至0.3%时,草酸二甲酯的选择性高于98%,草酸二甲酯的收率能够达到1200g/Lcat·h以上。
Claims (2)
1.一种合成草酸二甲酯催化剂用载体的制备方法,具体步骤为:
A.将钛酸酯溶于冰醋酸中配制成0.5~1.5mol/L的溶液;所述钛酸酯为钛酸四正丁酯、钛酸四异丁酯、钛酸四正丙酯、钛酸四异丙酯中的任意一种;
B.将可溶性M盐溶于水中形成0.5~1.5mol/L的盐溶液;其中M代表Mg2+、Ca2+、Zn2+、Co2+、Ni2+中的任意一种,盐溶液中的阴离子为NO3 -、CH3COO-、Cl-中的任意一种;
C.将步骤B得到的溶液加入到步骤A的溶液中,同时加入致孔剂于60~90℃水浴中不断搅拌,直至形成透明凝胶;其中致孔剂的加入量为溶液中钛质量的1~10%;
所述的致孔剂为葡萄糖、P123、环糊精、聚乙二醇、聚乙烯醇、聚环氧乙烷、壳聚糖中的任意一种;
D.将上述凝胶置于烘箱中在60~80℃干燥12h,再升温至100~120℃干燥12h,然后置于马弗炉中450~600℃焙烧4~6h,得到块状白色粉体;
E.将上述块状白色粉体进行球磨,然后加入聚乙烯醇的水溶液作为粘合剂,经过挤条成型后,在700℃高温焙烧后获得载体;所制备的载体的化学式为MTiO3,其中M代表Mg2+、Ca2 +、Zn2+、Co2+、Ni2+中的任意一种,其比表面积为10~35m2/g,均孔径为8~25nm。
2.根据权利要求1所述的合成草酸二甲酯催化剂用载体的制备方法,其特征是:
步骤B所述的M盐是硝酸镁、硝酸钙或硝酸钴;
步骤C所述的致孔剂是环糊精、壳聚糖或聚乙二醇;
步骤E得到的载体MTiO3中M为Mg2+、Ca2+、Co2+中的任意一种。
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