CN107983381A - 磷酸氧钒催化剂的制备方法及其在催化氧化反应中的应用 - Google Patents
磷酸氧钒催化剂的制备方法及其在催化氧化反应中的应用 Download PDFInfo
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- -1 vanadyl phosphate Chemical compound 0.000 title claims abstract description 37
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 35
- 239000010452 phosphate Substances 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 title description 8
- 230000003647 oxidation Effects 0.000 title description 5
- 238000007254 oxidation reaction Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
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- 150000002500 ions Chemical class 0.000 claims abstract description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 4
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- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 6
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- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
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- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
磷酸氧钒催化剂的制备方法，本发明采用次亚磷酸钠、次亚磷酸铵等磷源与五氧化二钒、偏钒酸铵的一种或多种钒源在多种离子液体和低共熔混合物中进行材料合成反应，在反应过程中辅以微波加热手段，制备得到磷酸氧钒前驱体VOHPO4·1/2H2O，磷酸氧钒前驱体在含1.5％丁烷的空气中焙烧得到最终的催化剂磷酸氧钒。本发明采用离子液体热合成法具有操作简便(常压)、制备的材料比表面积高等优势。采用还原性较强的次亚磷酸盐(H2PO2‑，磷为+1价态)为还原剂和磷源，可以大大降低反应温度，降低能耗。
Description
技术领域
本发明具体涉及一种磷酸氧钒催化剂的制备方法及其在催化氧化反应中的应用。
背景技术
磷酸氧钒催化剂的合成研究主要集中在前驱体的制备，前驱体磷酸氢盐半水化合物通常用五氧化二钒和磷酸在还原剂下生成，通过良好的还原剂将V5+有效的还原为V4+，继而和磷酸根形成具有明确晶相的磷酸氧钒前驱体(比如VOHPO4·1/2H2O)。大致包括以下几种路线：
(1)VPA路线。该法以水为溶剂、盐酸为还原剂制备VOHPO4·1/2H2O。后来人们开始改变还原剂，比如，乳酸和草酸等。此路线合成的前驱体磷酸氢盐半水化合物为大块状不规则形貌，比表面积很低(3m2/g)，且产生大量杂质VO(H2PO4)2。
(2)VPO路线。该法以醇类做溶剂及还原剂，一锅法制得VOHPO4·1/2H2O。该前驱体比VPA路线制备的片层薄，表面积也有所增加，但依然很低(10m2/g)。
(3)VPD路线。该法以水为溶剂，以磷酸和五氧化二钒为原料先制得VOPO4·2H2O，然后在醇溶液中回流，得到VOHPO4·1/2H2O。该路线制备的前驱体比表面积有所增加(30m2/g)，但步骤复杂，为两步法合成。
(4)其他方法。通过添加有机模板剂的方法，将NaVO3、V、H3PO4、H2O及模板剂哌嗪混合后在170℃下晶化7天，得到介孔磷酸氧钒，缺点是反应温度过高，且时间很长，对设备要求高；采用加晶种磷酸氢盐半水化合物的方法大幅提高合成材料的产率，减少杂质VO(H2PO4)2的生成，缺点是没有改变催化剂本身的性质，比表面积依然很低，且合成步骤复杂。
然而目前磷酸氧钒材料几乎全部由以水或醇作溶剂而制备，这些方法所合成的催化剂比表面积低(<30m2/g)，制备过程对设备要求高(密闭，高压)等。鉴于此，寻求一种操作简便、安全，且催化剂具有高表面积的制备方法显得尤为重要。用亚磷酸(H3PO3)为还原剂在水溶液中成功制备了磷酸氧钒前驱体。由于亚磷酸的还原性相对偏弱(磷为+3价态)，该反应需要较高的反应温度(145℃以上)和较长的反应时间(72h以上)才能与V2O5完成氧化还原反应。离子液体中以五氧化二钒或偏钒酸胺和磷酸为原料制备磷酸氧钒催化剂，体系内没有有效的还原剂，从而只能得到无定形物质，不能得到明确晶相的磷酸氧钒前驱体。
甲氧基丙酮是一种重要的精细化工产品，被作为中间体广泛应用于医药、农药的生产。目前工业上多以1-甲氧基-2-丙醇为原料，通过催化脱氢制得甲氧基丙酮，继而作为中间体生产农药异丙甲草胺。1-甲氧基-2-丙醇中的甲氧基诱导效应使1-甲氧基-2-丙醇难以氧化，目前工业生产中1-甲氧基-2-丙醇的转化率只有20％左右，大量的原料需要精馏分离回收使用，造成了巨大的能耗浪费。
目前工业上多采用Cu-Zn/Al2O3多相催化体系及直接脱氢工艺。直接脱氢工艺虽然操作简单，但由于Cu-Zn/Al2O3催化剂同时也具有加氢活性，故该反应为可逆反应，受热力学平衡控制，存在平衡转化率，限制了转化率的提升空间。
发明内容
针对目前磷酸氧钒材料几乎全部由以水或醇作溶剂而制备，这些方法所合成的催化剂比表面积低(<30m2/g)，制备过程对设备要求高(密闭，高压)，本发明旨在提供一种操作简便、安全，且催化剂具有高表面积的磷酸氧钒催化剂的制备方法及其在催化氧化反应中的应用。
为此，本发明采用以下技术方案：磷酸氧钒催化剂的制备方法，其特征在于：采用次亚磷酸钠、次亚磷酸铵等磷源与五氧化二钒、偏钒酸铵的一种或多种钒源在多种离子液体和低共熔混合物中进行材料合成反应，在反应过程中辅以微波加热手段，制备得到磷酸氧钒前驱体VOHPO4·1/2H2O，磷酸氧钒前驱体在含1.5％丁烷的空气中焙烧得到最终的催化剂磷酸氧钒。
优选地，上述材料合成反应温度90～150℃，反应时间5～144h，常压，钒与离子液体比值1：5～1：80，磷与钒的摩尔比5～0.5。
优选地，上述多种离子液体为[Bmim]+及[Emim]+正离子和Br-、PF6 -、BF4 -、Tf2N-、CF3SO3 -等负离子组成的化合物，低共熔混合物为氯化胆碱/丁二酸体系、氯化胆碱/草酸体系中的一种或多种混合形成。
一种甲氧基丙醇制备甲氧基丙酮催化反应中的应用，其特征在于：在反应过程中采用上述所述的磷酸氧钒作为催化剂。采用微型固定床催化反应器评价磷酸氧钒催化剂对于1-甲氧基-2-丙醇氧化脱氢制备甲氧基丙酮的反应性能，考察不同的催化剂及反应工艺条件对氧化脱氢反应的影响，获得较高的1-甲氧基-2-丙醇转化率和甲氧基丙酮的收率。(1-甲氧基-2-丙醇转化率可达80％以上，甲氧基丙酮的选择性90％以上。反应条件：反应压力0.1～1MPa,温度150～250℃，空速0.3～10h-1。
使用本发明可以达到以下有益效果：本专利采用离子液体热合成法具有操作简便(常压)、制备的材料比表面积高等优势。采用还原性较强的次亚磷酸盐(H2PO2-，磷为+1价态)为还原剂和磷源，可以大大降低反应温度，降低能耗；因此，该方法不需后续还原步骤，同时又不引入其他物种，从而使反应过程更加简单易研究。本发明在离子液体中制备，可以辅助微波合成等手段，显著缩短其反应时间；离子液体同时作为溶剂和模板剂，可以有效提高合成材料的表面积或制备出可调控的特定形貌。本发明磷酸氧钒催化剂用于甲氧基丙醇氧化脱氢制备甲氧基丙酮的反应，消除了热力学平衡限制，反应物的转化率可以达到较高水平，可以显著提高甲氧基丙醇的转化率和甲氧基丙酮的收率。
具体实施方式
本专利采用次亚磷酸钠、次亚磷酸铵等磷源与五氧化二钒、偏钒酸铵等钒源在多种离子液体和低共熔混合物([Bmim]Br，[Bmim]PF6，[Bmim]BF4，[Bmim]Tf2N，[Bmim]CF3SO3，[Emim]Br，[Emim]PF6，[Emim]BF4，[Emim]Tf2N，[Emim]CF3SO3以及氯化胆碱/丁二酸体系，氯化胆碱/草酸体系等)中进行材料合成反应，辅以微波加热手段，考察反应物浓度、反应温度、反应时间等对于制备材料质构性质的影响，最终得到优化条件，制备出高表面积(50～300m2/g)、高结晶度(VOHPO4·1/2H2O晶态)的磷酸氧钒前驱体VOHPO4·1/2H2O。反应温度90～150℃，反应时间5～144h，常压，钒与离子液体比值1：5～1：80，磷与钒的摩尔比5～0.5。
磷酸氧钒前驱体在含1.5％丁烷的空气中焙烧得到最终的催化剂焦磷酸氧钒。
采用微型固定床催化反应器评价磷酸氧钒催化剂对于1-甲氧基-2-丙醇氧化脱氢制备甲氧基丙酮的反应性能，考察不同的催化剂及反应工艺条件对氧化脱氢反应的影响，获得较高的1-甲氧基-2-丙醇转化率和甲氧基丙酮的收率。(1-甲氧基-2-丙醇转化率可达80％以上，甲氧基丙酮的选择性90％以上。反应条件：反应压力0.1～1MPa,温度150～250℃，空速0.3～10h-1。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (4)
1.磷酸氧钒催化剂的制备方法，其特征在于：采用次亚磷酸钠、次亚磷酸铵等磷源与五氧化二钒、偏钒酸铵的一种或多种钒源在多种离子液体和低共熔混合物中进行材料合成反应，在反应过程中辅以微波加热手段，制备得到磷酸氧钒前驱体，磷酸氧钒前驱体在含1.5％丁烷的空气中焙烧得到最终的催化剂磷酸氧钒。
2.根据权利要求1所述的磷酸氧钒催化剂的制备方法，其特征在于：上述材料合成反应温度90～150℃，反应时间5～144h，常压，钒与离子液体比值1：5～1：80，磷与钒的摩尔比5～0.5。
3.根据权利要求1或2所述的磷酸氧钒催化剂的制备方法，其特征在于：上述多种离子液体为[Bmim]+及[Emim]+正离子和Br-、PF6 -、BF4 -、Tf2N-、CF3SO3 -等负离子组成的化合物，低共熔混合物为氯化胆碱/丁二酸体系、氯化胆碱/草酸体系中的一种或多种混合形成。
4.一种甲氧基丙醇制备甲氧基丙酮催化反应中的应用，其特征在于：在反应过程中采用权利要求1所述的的磷酸氧钒作为催化剂。
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