CN112479171A - 一种金属磷酸盐及其制备方法与用于催化酯化反应的应用 - Google Patents
一种金属磷酸盐及其制备方法与用于催化酯化反应的应用 Download PDFInfo
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- 229910001463 metal phosphate Inorganic materials 0.000 title claims abstract description 42
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 230000003197 catalytic effect Effects 0.000 title abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 6
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 150000002148 esters Chemical class 0.000 claims abstract description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 6
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 6
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
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- 229910008651 TiZr Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 24
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 10
- 238000007036 catalytic synthesis reaction Methods 0.000 description 9
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- 230000015572 biosynthetic process Effects 0.000 description 8
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- 238000010521 absorption reaction Methods 0.000 description 6
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 4
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- 229940090181 propyl acetate Drugs 0.000 description 4
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- 229910003091 WCl6 Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N benzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 3
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
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- 238000001354 calcination Methods 0.000 description 2
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- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
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- UPIJOAFHOIWPLT-UHFFFAOYSA-N methyl 4-tert-butylbenzoate Chemical compound COC(=O)C1=CC=C(C(C)(C)C)C=C1 UPIJOAFHOIWPLT-UHFFFAOYSA-N 0.000 description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 2
- 229940073769 methyl oleate Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/265—General methods for obtaining phosphates
-
- 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
- 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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
-
- 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
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
本发明公开了一种金属磷酸盐及其制备方法与用于催化酯化反应的应用,所述金属磷酸盐包括单金属磷酸盐或双金属磷酸盐,所述单金属磷酸盐的金属元素是Fe、Cr、Sn、Zr、Ti、Nb中的一种,所述双金属磷酸盐的金属元素是Fe、Cr、Sn、Zr、Ti、Al、Mo、Co、Cu、Nb、Ge、W中的两种,且两种金属元素的摩尔比为1:1。金属磷酸盐用于催化有机羧酸与醇反应生成酯,所述有机羧酸为乙酸、乙酰丙酸、己酸、己二酸、月桂酸、棕榈酸、油酸、苯甲酸、对叔丁基苯甲酸中的一种,所述醇为甲醇、乙醇、丙醇、丁醇中的一种,反应物转化率和产物选择性可达到99%以上,且反应条件温和、反应时间短。
Description
技术领域
本发明涉及固体催化剂技术领域,具体涉及一种金属磷酸盐及其制备方法与用于催化酯化反应的应用。
背景技术
酯化反应是一类重要的有机化学反应,通常是指醇和饱和及不饱和的脂肪族酸(如乙酸、乙酰丙酸、己酸、己二酸、月桂酸、棕榈酸、油酸)及芳香酸(如苯甲酸、对叔丁基苯甲酸)间的反应。其生成的酯是重要的精细有机化工产品,广泛用于溶剂、增塑剂、树脂、涂料、香料、化妆品、医药、表面活性剂及有机合成等工业。
酯化反应可以在气相或液相中进行,反应一般都是可逆的,但通常受平衡限制,反应非常缓慢。尤其是在液相反应中,必须不断地将产生的水去除或者在某一反应过剩的情况下操作,这样才可能得到更高的酯产率。因此,酯化反应一般都需要加入催化剂来提高反应速率和酯产率。工业上低炭酯的合成一般采用传统的液体酸作催化剂,如H2SO4、HCl、H3PO4、HF,它们因以分子形态参与化学反应,因此在较低的温度下就有相当高的催化活性,但使用传统的液体酸催化剂时也存在一系列问题,如产生大量的废液废渣、设备腐蚀严重及催化剂与原料和产物不易分离、在工艺上难以实现连续生产,对操作人员危险大。因此,近年来固体酸催化酯化反应受到广泛研究。
CN1323655A公开了一种酯化反应用高选择性、高活性固体酸催化剂SO4 2-/Fe2O3-ZrO2-SiO2,采用共沉淀-浸渍法制备,其固体催化剂体系及制备较为复杂。CN1957070A公开了一种包含金属磷酸盐粘合剂和沸石的催化剂组合物,用于提高烃裂化工艺过程中的烯烃收率。CN101492458A公开了一种采用四价金属磷酸盐作催化剂,脱水反应制备异山梨醇的方法。但对于金属磷酸盐在酯化反应中的应用还少有报道。
发明内容
本发明的目的在于提供一种金属磷酸盐及其制备方法与用于催化酯化反应的应用,将金属磷酸盐用于催化酯化反应,提高酯化反应物转化率和产物选择性,且反应条件温和、反应时间短。
本发明的目的通过以下技术方案实现:一种金属磷酸盐,所述金属磷酸盐包括单金属磷酸盐或双金属磷酸盐,所述单金属磷酸盐的金属元素是Fe、Cr、Sn、Zr、Ti、Nb中的一种;所述双金属磷酸盐的金属元素是Fe、Cr、Sn、Zr、Ti、Al、Mo、Co、Cu、Nb、Ge、W中的两种,且两种金属元素的摩尔比为1:1。
优选的,所述金属磷酸盐中的金属元素包括Sn、Zr、Ti、Nb、W中的一种,催化酯化反应的转化率达到60%以上,选择性达到97%以上。
优选的,所述金属磷酸盐中的金属元素为SnNb、TiZr或TiW,催化酯化反应的转化率达到85%以上,选择性达到99%以上。
一种金属磷酸盐的制备方法,包括如下步骤:
步骤一:用蒸馏水分别配置磷酸二氢钠溶液和金属可溶性盐溶液。
步骤二:在40~80℃条件下,用磷酸二氢钠溶液滴定金属可溶性盐溶液,并持续搅拌2~3h。
步骤三:在室温条件下持续搅拌6~24h,过滤得到固体,干燥、焙烧,即得金属磷酸盐。
优选的,所述步骤一中磷酸二氢钠的摩尔浓度与金属可溶性盐溶液中金属元素的总摩尔浓度相等。
优选的,所述步骤三的干燥条件为60~120℃下干燥10h,焙烧条件为200~700℃焙烧4h。
一种金属磷酸盐用于催化酯化反应的应用,包括在以醇为溶剂条件下,将有机羧酸和金属磷酸盐混合,在常压下反应生成酯。
优选的,所述有机羧酸为乙酸、乙酰丙酸、己酸、己二酸、月桂酸、棕榈酸、油酸、苯甲酸、对叔丁基苯甲酸中的一种;所述醇为甲醇、乙醇、丙醇、丁醇中的一种。
优选的,所述金属磷酸盐与有机羧酸的质量比为1:(8~18),所述有机羧酸与醇的摩尔比为1:(2~10)。
优选的,所述反应温度为60~115℃,反应时间10~12h。
与现有技术相比,本发明的有益技术效果如下:
1)本发明中的金属磷酸盐用于催化酯化反应,反应物转化率和产物选择性均显著提高,可达到99%以上;且反应条件温和、反应时间短。
2)本发明中的金属磷酸盐的制备方法适用于单金属磷酸盐和双金属磷酸盐的制备,且制备过程简单。
附图说明
图1为实施例1、2所得TiP和TiWP的红外表征图(横坐标为波长,纵坐标为吸收强度);
图2为实施例1、2所得TiP和TiWP的TPD表征图(横坐标为温度,纵坐标为信号强度)。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细描述,所述的实施例有助于对本发明的理解和实施,并非构成对本发明的限制。
实施例1
TiP的制备:将0.01mol的磷酸二氢钠和0.01mol的TiCl4分别置于100ml蒸馏水中,完全溶解。50℃下用磷酸二氢钠溶液滴定TiCl4溶液并持续搅拌2h。再在室温下搅拌12h,过滤得到固体,将固体置于鼓风干燥箱中于110℃下干燥10h,然后在600℃下焙烧4h,升温速率为2℃‧min-1,即得单金属磷酸盐TiP。
用红外光谱表征TiP的结构,用程序升温脱附(TPD)技术表征TiP的酸点。
如图1所示,TiP对应的a曲线在1070 cm-1、568 cm-1出现广泛和密集的吸收峰,分别对应于PO4 3-的不对称振动和Ti-O的伸缩振动。
如图2所示,TiP对应的a曲线在100℃附近、200~450℃、450~550℃出现吸收峰,分别对应于弱酸性位点、中强酸性位点和强酸性位点。
TiP催化合成乙酸丁酯:在25ml的圆底烧瓶中分别加入TiP 0.05g,乙酸0.86g,丁醇6.86ml,恒温油浴锅115℃加热,磁力搅拌500r/min,反应10h。乙酸转化率为68.5%,乙酸丁酯选择性为100%。
实施例2
TiWP的制备:将0.01mol的磷酸二氢钠置于100ml蒸馏水中,完全溶解。将0.005mol的TiCl4和0.005mol的WCl6置于100ml蒸馏水中,完全溶解。50℃下用磷酸二氢钠溶液滴定TiCl4、WCl6混合溶液并持续搅拌2h。再在室温下搅拌12h,过滤得到固体,接着将固体置于鼓风干燥箱中于110℃下干燥10h,最后在600℃下焙烧4h,升温速率为2℃‧min-1,即得双金属磷酸盐TiWP。
用红外光谱表征TiWP的结构,用TPD技术表征TiWP的酸点。
如图1所示,TiWP对应的b曲线在1070 cm-1、568 cm-1出现广泛和密集的吸收峰,在755 cm-1出现较弱的吸收峰,分别对应于PO4 3-的不对称振动、Ti-O的伸缩振动和W-O的伸缩振动。
如图2所示,TiWP对应的b曲线也在100℃附近、200~450℃、450~550℃出现吸收峰,与TiP对应的a曲线相比,磷酸盐弱酸和中强酸含量没有明显变化,但强酸含量明显增加。
TiWP催化合成油酸甲酯:在25ml的圆底烧瓶中分别加入TiWP 0.15g,油酸2.38ml,甲醇3.03ml,恒温油浴锅60℃加热,磁力搅拌500r/min,反应10h。油酸转化率为99.5%,油酸甲酯选择性为99.6%。
实施例3~16中单金属磷酸盐的制备方法与实施例1中的制备方法的区别在于:将TiCl4替换为Fe、Cr、Sn、Zr、Nb中任意一种金属的可溶性盐(如氯化物、硝酸盐、硫酸盐等);双金属磷酸盐的制备方法与实施例2中的制备方法的区别在于:将TiCl4和WCl6替换为Fe、Cr、Sn、Zr、Al、Mo、Co、Cu、Nb、Ge中任意两种金属的可溶性盐如氯化物、硝酸盐、硫酸盐等),且两种金属元素的摩尔比为1:1。例如:两种金属元素为Fe和Al、Fe和Mo、Cr和Co、Cr和Cu、Sn和Nb、Sn和Ge、Zr和W、Ti和Zr、Nb和Zr。
具体催化合成反应如下:
实施例3 TiZrP催化合成己二酸单甲酯
在25ml的圆底烧瓶中分别加入TiZrP 0.05g,己二酸0.73g,甲醇3.03ml,恒温油浴锅60℃加热,磁力搅拌600r/min,反应12h。己二酸转化率为95.1%,己二酸单甲酯选择性为99.4%。
实施例4 FeP催化合成乙酸丁酯
在25ml的圆底烧瓶中分别加入FeP 0.05g,乙酸0.86ml,丁醇6.86ml,恒温油浴锅115℃加热,磁力搅拌500r/min,反应10h。乙酸转化率为26.1%,乙酸丁酯选择性为98.4%。
实施例5 FeAlP催化合成己酸乙酯
在25ml的圆底烧瓶中分别加入FeAlP 0.1g,己酸1.87ml,乙醇4.38ml,恒温油浴锅75℃加热,磁力搅拌500r/min,反应10h。己酸转化率为23.7%,己酸乙酯选择性为99.2%。
实施例6 FeMoP催化合成月桂酸甲酯
在25ml的圆底烧瓶中分别加入FeMoP 0.1g,月桂酸1.0g,甲醇3.03ml,恒温油浴锅60℃加热,磁力搅拌600r/min,反应12h。月桂酸转化率为27.1%,月桂酸甲酯选择性为98.1%。
实施例7 CrP催化合成乙酸丁酯
在25ml的圆底烧瓶中分别加入CrP 0.05g,乙酸0.86ml,丁醇6.86ml,恒温油浴锅115℃加热,磁力搅拌500r/min,反应10h。乙酸转化率为45.1%,乙酸丁酯选择性为99.2%。
实施例8 CrCoP催化合成己酸乙酯
在25ml的圆底烧瓶中分别加入CrCoP 0.1g,己酸1.87ml,乙醇4.38ml,恒温油浴锅75℃加热,磁力搅拌500r/min,反应10h。己酸转化率为47.1%,己酸乙酯选择性为97.4%。
实施例9 CrCuP催化合成对苯甲酸乙酯
在25ml的圆底烧瓶中分别加入CrCuP 0.05g,苯甲酸0.46g,乙醇4.38ml,恒温油浴锅75℃加热,磁力搅拌600r/min,反应12h。苯甲酸转化率为36.1%,苯甲酸乙酯选择性为99.3%。
实施例10 SnP催化合成乙酸丙酯
在25ml的圆底烧瓶中分别加入SnP 0.05g,乙酸0.86g,丙醇5.63ml,恒温油浴锅95℃加热,磁力搅拌500r/min,反应10h。乙酸转化率为63.1%,乙酸丙酯选择性为98.4%。
实施例11 SnNbP催化合成己二酸单甲酯
在25ml的圆底烧瓶中分别加入SnNbP 0.05g,己二酸0.73g,甲醇3.03ml,恒温油浴锅60℃加热,磁力搅拌600r/min,反应12h。己二酸转化率为85.1%,己二酸单甲酯选择性为99.2%。
实施例12 SnGeP催化合成棕榈酸乙酯
在25ml的圆底烧瓶中分别加入SnGeP 0.15g,棕榈酸1.28g,乙醇4.38ml,恒温油浴锅60℃加热,磁力搅拌500r/min,反应10h。棕榈酸转化率为75.8%,棕榈酸乙酯选择性为98.1%。
实施例13 ZrP催化合成乙酰丙酸甲酯
在25ml的圆底烧瓶中分别加入ZrP 0.05g,乙酰丙酸0.87g,甲醇3.03ml,恒温油浴锅60℃加热,磁力搅拌600r/min,反应12h。乙酰丙酸转化率为65.1%,乙酰丙酸甲酯选择性为99.3%。
实施例14 ZrWP催化合成对叔丁基苯甲酸甲酯
在25ml的圆底烧瓶中分别加入ZrWP 0.05g,对叔丁基苯甲酸0.67g,甲醇3.03ml,恒温油浴锅60℃加热,磁力搅拌600r/min,反应12h。对叔丁基苯甲酸转化率为76.8%,对叔丁基苯甲酸甲酯选择性为98.1%。
实施例15 NbP催化合成乙酸丙酯
在25ml的圆底烧瓶中分别加入NbP 0.05g,乙酸0.86g,丙醇5.63ml,恒温油浴锅95℃加热,磁力搅拌500r/min,反应10h。乙酸转化率为61.8%,乙酸丙酯选择性为98.4%。
实施例16 NbZrP催化合成己酸乙酯
在25ml的圆底烧瓶中分别加入NbZrP 0.1g,己酸1.87ml,乙醇4.38ml,恒温油浴锅75℃加热,磁力搅拌500r/min,反应10h。己酸转化率为77.1%,己酸乙酯选择性为97.4%。
Claims (10)
1.一种金属磷酸盐,其特征在于,所述金属磷酸盐包括单金属磷酸盐或双金属磷酸盐,所述单金属磷酸盐的金属元素是Fe、Cr、Sn、Zr、Ti、Nb中的一种,所述双金属磷酸盐的金属元素是Fe、Cr、Sn、Zr、Ti、Al、Mo、Co、Cu、Nb、Ge、W中的两种,且两种金属元素的摩尔比为1:1。
2.如权利要求1所述的金属磷酸盐,其特征在于,所述金属磷酸盐中的金属元素包括Sn、Zr、Ti、Nb、W中的一种。
3.如权利要求1所述的金属磷酸盐,其特征在于,所述金属磷酸盐中的金属元素为SnNb、TiZr或TiW。
4.权利要求1所述的金属磷酸盐的制备方法,包括如下步骤:
步骤一:用蒸馏水分别配置磷酸二氢钠溶液和金属可溶性盐溶液;
步骤二:在40~80℃条件下,用磷酸二氢钠溶液滴定金属可溶性盐溶液,并持续搅拌2~3h;
步骤三:在室温条件下持续搅拌6~24h,过滤得到固体,干燥、焙烧,即得金属磷酸盐。
5.如权利要求4所述的金属磷酸盐的制备方法,其特征在于,所述步骤一中磷酸二氢钠的摩尔浓度与金属可溶性盐溶液中金属元素的总摩尔浓度相等。
6.如权利要求4所述的金属磷酸盐的制备方法,其特征在于,所述步骤三的干燥条件为60~120℃下干燥10h,焙烧条件为200~700℃焙烧4h。
7.权利要求1所述的金属磷酸盐用于催化酯化反应的应用,包括在以醇为溶剂条件下,将有机羧酸和金属磷酸盐混合,在常压下反应生成酯。
8.如权利要求7所述的金属磷酸盐用于催化酯化反应的应用,其特征在于,所述有机羧酸为乙酸、乙酰丙酸、己酸、己二酸、月桂酸、棕榈酸、油酸、苯甲酸、对叔丁基苯甲酸中的一种;所述醇为甲醇、乙醇、丙醇、丁醇中的一种。
9.如权利要求7所述的金属磷酸盐用于催化酯化反应的应用,其特征在于,所述金属磷酸盐与有机羧酸的质量比为1:(8~18),所述有机羧酸与醇的摩尔比为1:(2~10)。
10.如权利要求7所述的金属磷酸盐用于催化酯化反应的应用,其特征在于,所述反应温度为60~115℃,反应时间10~12h。
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