CN106573230A - 高性能多金属氧酸盐催化剂及其制备方法 - Google Patents
高性能多金属氧酸盐催化剂及其制备方法 Download PDFInfo
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- CN106573230A CN106573230A CN201680002204.6A CN201680002204A CN106573230A CN 106573230 A CN106573230 A CN 106573230A CN 201680002204 A CN201680002204 A CN 201680002204A CN 106573230 A CN106573230 A CN 106573230A
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- Prior art keywords
- polyoxometallate
- catalyst
- vanadium
- inert carrier
- metal
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000013460 polyoxometalate Substances 0.000 title abstract 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims description 31
- 238000007254 oxidation reaction Methods 0.000 claims description 31
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- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
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- 239000002243 precursor Substances 0.000 claims description 15
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
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- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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Abstract
本发明涉及一种高性能多金属氧酸盐催化剂及其制备方法。更具体地,本发明提供了一种高性能多金属氧酸盐催化剂及其制备方法等,其中,所述多金属氧酸盐催化剂的活性和选择性可以通过控制钒等的含量来改善,并且其具有卓越的再现性,并且可长时间以高产率由不饱和醛产生不饱和羧酸。
Description
技术领域
[相关申请的交叉引用]
本申请要求于2015年8月11日在韩国知识产权局提交的韩国专利申请第10-2015-0113111的优先权,其公开的内容在此通过引用并入。
本发明涉及一种多金属氧酸盐催化剂及其制备方法,并且更具体地,涉及一种在壳管式热交换器中通过气相部分氧化由不饱和醛气体产生不饱和羧酸的催化剂及其制备方法。
背景技术
由烯烃经不饱和醛制备不饱和脂肪酸的过程是催化气相氧化的典型实例。
在烯烃的部分氧化中,使用氧化钼和过渡金属氧化物来制备催化剂。作为典型工艺,有通过氧化丙烯或异丁烯经异丁烯醛产生(甲基)丙烯酸的工艺,通过氧化萘或邻二甲苯产生邻苯二甲酸酐的工艺,和通过部分氧化苯、丁烯或丁二烯制备马来酐的工艺。
在第一个步骤中,丙烯和异丁烯被氧气、稀释的惰性气体、水蒸气和预定量的催化剂氧化,由此主要产生异丁烯醛。在步骤2中,异丁烯醛被氧气、稀释的惰性气体、水蒸气和预定量的催化剂氧化,由此产生(甲基)丙烯酸。可以在一个装置中配置用于该过程的反应器以运行两个过程,或者在不同的装置中运行各个过程。
主要使用与乙醇反应的(甲基)丙烯酸来制备用作油漆、纺织助剂和纸的涂层剂的(甲基)丙烯酸酯。使用高纯度(甲基)丙烯酸作为高度吸湿树脂的原料,近年来对其需求快速增长。
通常,金属氧化物催化剂通过共沉淀反应、热液合成、溶胶-凝胶合成、物理混合反应等而产生。在该反应过程中,所述金属氧化物催化剂以聚阴离子、金属氧化物或金属羟化物形式沉淀。这里,沉淀的物理性能和形态根据水溶液的pH、浓度、反应温度和老化时间而变化,由此影响金属氧化物催化剂的物理状态、粒度和晶体结构。
作为与用于产生不饱和脂肪酸的催化剂中的含氧阴离子和过渡金属前体结合的配体的实例,有-NH4、-NH2、-NOx、-Cl、-F、-N、-OH(羟基)、-SOx、-CO、-COO、-CnHmOx、醇盐(O-金属)等。作为溶解或纯化金属氧化物的必要成分的该配体,可以用作根据适当的控制方法改变催化剂的物理化学特性并且因此控制所述催化剂活性的因素。
在相关技术(日本专利第4295521号中介绍的“用于制备催化剂的技术”)中,催化剂通过粉末涂布和煅烧块状载体来制备。这里,制备的催化剂是丙烯酸催化剂,其特征在于,在空气气氛中在300℃的催化剂干燥温度下其干燥产物的质量减少率是5至40质量%。然而,由于相对高的干燥温度,该制备方法导致所述催化剂的结构改变,从而对所述催化剂的性能有负面影响,并且因此转化率趋于变差。
此外,KR 10-0746971B1介绍了一种催化剂,其包含钼和钒,以及通过离子色谱法测量的含量为10至100ppb的催化剂毒物,进一步包含至少一种易挥发的催化剂毒物成分,并且通过氧和丙烯醛之间的催化气相氧化产生丙烯酸,以及制备丙烯酸的方法,其包括使用所述催化剂在氧和丙烯醛之间进行接触气相氧化的步骤。
通过人工地加入催化剂毒物成分(例如氨水)而制备的催化剂可降低热点温度并抑制伴随劣化的反应效率降低,从而长时间高度稳定地保持丙烯醛转化率。然而,当还原物质(如氨)存在于所述催化剂中时,所述还原物质起到催化剂毒物的作用,从而大大增加反应温度,并且长时间运转后,激活所述催化剂。因此,尽管所述还原物质可以用作控制催化活性的催化剂毒物,在生产所述催化剂的过程中在数量上控制所述还原物质的量仍存在相当大的困难。
与此同时,在催化剂前体中存在的无机盐的处理应当在制备催化剂的过程中降低。然而,额外添加该无机盐,并且因此,缺点在于额外需要去除所述还原物质的过程。因此,需要一种通过升华而简单控制包含在催化剂中的配体的类型及其数量的技术,当煅烧所述催化剂时,同时提供卓越的再现性。
发明内容
技术问题
因此,考虑到上述问题而做出本发明,并且本发明的一个目的是提供一种可控制活性和选择性,具有卓越的再现性,可长时间以高产率由不饱和醛产生不包含羧酸的高性能多金属氧酸盐催化剂及其制备方法等。
上述及其他目的可以通过下述的本发明来实现。
技术方案
根据本发明,上述及其他目的可以通过提供包含由下式1表示的金属氧化物的多金属氧酸盐催化剂来实现:
[式1]
MoaAbVcBdCeDfOg,
其中,A是选自W和Cr的一种或多种元素;B是选自P、As、B(硼)、Sb、Ce、Pb、Mn、Nb和Te的一种或多种元素;C是选自Si、Al、Zr、Rh、Cu、Ni、Ti、Ag、Fe、Co和Sn的一种多种元素;D是选自Na、K、Li、Rb、Cs、Ta、Ca、Mg、Sr和Ba的一种或多种;并且a、b、c、d、e、f和g表示各元素的原子比,其中,当a=12,b是0.01至15;c是0.01至15,d是0至20,e是0至20,f是0至20;并且g根据各成分的氧化态确定,并且其中,V与A(V/A)的摩尔比是0.01至10。
d、e和f各自是,例如,0.01至20。
钒(V)可包含,例如,30%以上的氧化值为4+的钒。
所述多金属氧酸盐催化剂可包含,例如,作为所述金属氧化物的载体的惰性载体。
涂布在所述惰性载体上的金属氧化物的负载量可以是,例如,30至80重量%。
所述多金属氧酸盐催化剂可以是,例如,用于气相部分氧化以由不饱和醛产生不饱和羧酸的催化剂。
根据本发明的另一个方面,提供了一种制备根据权利要求1所述的多金属氧酸盐催化剂的方法,所述方法包括:(A)制备包含金属前体的悬浮液以产生由式1表示的金属氧化物,并且如需要,通过加入酸调节pH到0至7.5,接着通过均化器增加粘度以形成多金属氧酸盐的步骤;(B)将20至50重量%的所形成的多金属氧酸盐负载至惰性载体以制备负载物质的步骤;(C)干燥所述负载物质以获得通过以下等式1计算的配体升华率为0%以上的负载物质的步骤;和(D)煅烧干燥的负载物质以获得多金属氧酸盐催化剂的步骤:
[等式1]
配体升华率(%)=(升华的配体的质量/升华之前配体的质量)X 100。
由式1表示的钒(V)前体可以是,例如,含有氧化值为4+的钒的化合物。
所述含有氧化值为4+的钒的化合物可以是,例如,含有氧钒基的化合物。
在步骤(A)中,所述多金属氧酸盐可具有,例如,1,000至15,000cps或3,000至8,000cps的粘度。
所述在步骤(A)中形成的多金属氧酸盐可以,例如,被干燥然后被过滤并干燥,接着粉碎。
所述步骤(B)的负载可以,例如,通过在所述惰性载体上喷涂所述多金属氧酸盐或在所述惰性载体上喷涂所述多金属氧酸盐和水而进行。
所述金属前体的配体可以是选自-NH4、-NH2、-NOx(其中x是1至4的整数)、-Cl、-F、-N、-OH、-SOx(其中x是1至4的整数)、-CO、-COO、-SCN、-CN、-NCS、-ONO、-NC、-CnHmOx(其中n是1至20的整数,m是1至40的整数并且x是1至10的整数)和C1至C20醇盐的一种或多种。
在步骤(A)中,所述悬浮液的浓度可以是25至45重量%或30至40重量%。
所述步骤(C)的干燥可以是,例如,热空气干燥。
所述步骤(B)的负载可以,例如,通过重复用所述多金属氧酸盐涂布所述惰性载体并且干燥所述涂布的惰性载体的过程一次或多次而进行。
所述步骤(C)的干燥可以,例如,在100至230℃下进行。
在步骤(A)中,所述悬浮液的粘度可以在25至50℃下,例如,通过均化器来增加,从而形成多金属氧酸盐。
所述步骤(D)的煅烧可以,例如,在350至550℃下进行1至10小时。
根据本发明的又一个方面,提供的是一种制备不饱和羧酸的方法,其中,在填充有所述多金属氧酸盐催化剂的固定床催化反应器中在0.1至10atm下在240至450℃下进行气相部分氧化,由不饱和醛气体产生所述不饱和羧酸。
所述固定床催化反应器可以是,例如,壳管式热交换器。
有益效果
从上述明显可见,本发明提供了一种高性能多金属氧酸盐催化剂及其制备方法等,其中,所述多金属氧酸盐催化剂活性和选择性可以通过控制钒等的含量改善,并且其具有卓越的再现性,并且可长时间以高产率由不饱和醛产生不饱和羧酸。
具体实施方式
以下,详细描述本发明。
一种本发明的多金属氧酸盐催化剂包含由下式1表示的金属氧化物:
[式1]
MoaAbVcBdCeDfOg,
其中,A是选自W和Cr的一种或多种元素;B是选自P、As、B(硼)、Sb、Ce、Pb、Mn、Nb和Te的一种或多种元素;C是选自Si、Al、Zr、Rh、Cu、Ni、Ti、Ag、Fe、Co和Sn的一种多种元素;D是选自Na、K、Li、Rb、Cs、Ta、Ca、Mg、Sr和Ba的一种或多种;并且a、b、c、d、e、f和g表示各元素的原子比,其中,当a=12,b是0.01至15;c是0.01至15,d是0至20,e是0至20,f是0至20;并且g根据各成分的氧化态确定,并且其中,V与A(V/A)的摩尔比是0.01至10。
在本公开中,除非另有说明,否则术语“多金属氧酸盐”具有一般定义的含义。
在本公开中,术语“配体”指结合金属前体中金属阳离子的阴离子基团,并且除非另有说明,否则具有一般定义的含义。
在另一个实施方式中,V与A的摩尔比可以是0.05至5,优选0.5至4,更优选0.5至3。在该范围中,影响钒的氧化态,从而所述催化剂具有卓越的活性和选择性。尤其是,钨(W)在所述催化剂中起到结构促进剂的作用,并且因此增加催化剂中的V4+的量,从而增加催化活性。
钒(V)可包含,例如,30(mol)%以上,40%以上或50%以上的氧化值为4+的钒。在此范围内,所述催化剂的活性和选择性增加,显示出卓越的再现性,并且可以长时间以高产率产生不饱和羧酸。
在所述金属氧化物中,V4+与钒(V)的总含量的摩尔比(V4+/(V4++V5+))是,例如,0.3至1、0.4至0.8或0.5至0.8。在此范围内,所述催化剂的活性和选择性增加,提供了卓越的再现性,并且长时间以高产率产生不饱和羧酸。
b可以是,例如,0.1至10、1.0至6.0或1.5至5.0。在此范围内,所述催化剂的活性、选择性和使用期限大大改善。
c可以是,例如,0.5至10、1.0至5.0或2.0至3.0。在此范围内,所述催化剂的活性、选择性和使用期限大大改善。
d、e和f各自可以是,例如,0.01至20或0.05至10。
在另一个实施方式中,d可以是0.01至0.5、0.05至0.4或0.1至0.3,e可以是0.1至8.0、0.5至7.0或1.0至5.5,并且f可以是0.1至5.0、0.5至2或0.8至1.3。在此范围内,所述催化剂显示出卓越的活性和选择性。
A可以是例如W,B可以是例如Nb或Mn或其组合,C可以是例如选自Cu、Fe和Co的一种或多种,D可以是例如Sr。在此情况下,所述催化剂的活性和选择性增加,提供了卓越的再现性,并且长时间以高产率产生不饱和的羧酸。
所述多金属氧酸盐催化剂可包含,例如,惰性载体作为所述金属氧化物的载体。
所述惰性载体可以是选自,例如,多孔硅铝酸盐、碳化硅氧化铝和二氧化硅的一种或多种。
涂布在所述惰性载体上的金属氧化物的负载量可以是,例如,30至80重量%、40至70重量%或50至60重量%。在此范围内,所述催化剂具有卓越的活性和选择性。
所述多金属氧酸盐催化剂可以是,例如,用于气相部分氧化以由不饱和醛产生不饱和羧酸的催化剂。
一种制备本发明的多金属氧酸盐催化剂的方法包括(A)制备包含金属前体的悬浮液以产生由式1表示的金属氧化物,并且,如果需要,通过加入酸调节pH到0至7.5,接着通过均化器增加粘度以形成多金属氧酸盐的步骤;(B)将20至50重量%的所形成的多金属氧酸盐负载至惰性载体以制备负载物质的步骤;(C)干燥所述负载物质以获得通过以下等式1计算的配体升华率为0%以上的负载物质的步骤;和(D)煅烧干燥的负载物质以获得多金属氧酸盐催化剂的步骤:
[等式1]
配体升华率(%)=(升华的配体的质量/升华之前配体的质量)X 100。
由式1表示的钒(V)前体可以是,例如,含有氧化值为4+的钒的化合物,优选含有氧钒基的化合物。在此范围内,所述催化剂的活性和选择性增加,提供了卓越的再现性,并且长时间以高产率产生不饱和的羧酸。
所述含有氧钒基的化合物可以是,例如,乙酰丙酮氧钒、硫酸氧钒等。
在步骤(A)中,所述多金属氧酸盐可具有,例如,1,000至15,000cps或3,000至8,000cps的粘度。在此范围内,所述催化剂显示出卓越的活性和选择性。
步骤(A)中调节的pH可以是,例如,3至5,优选4至5。在此范围内,所述催化剂显示出卓越的活性、选择性和使用寿命,并且干燥时间和温度减小。
步骤(A)中形成的所述多金属氧酸盐可以,例如,被干燥,然后被过滤并干燥,接着粉碎。
所述过滤器可以用来,例如,通过过滤器和/或压滤机从浆状多金属氧酸盐中除去无机盐。
所述金属前体的配体可以是选自,例如,-NH4、-NH2、-NOx(其中x是1至4的整数)、-Cl、-F、-N、-OH、-SOx(其中x是1至4的整数)、-CO、-COO、-SCN、-CN、-NCS、-ONO、-NC、-CnHmOx(其中n是1至20的整数,m是1至40的整数并且x是1至10的整数)和C1至C20醇盐的一种或多种。在此情况下,影响所述过渡金属和过渡金属氧化物的氧化态和形态,从而改善所述催化剂的活性和选择性。
在步骤(A)中,所述悬浮液的浓度是25至45重量%或30至40重量%。在此范围内,所述催化剂显示出卓越的活性和选择性。
在实施方式中,在步骤(A)中,所述悬浮液的粘度在25至50℃,优选20至40℃下通过均化器增加,从而形成多金属氧酸盐。在此范围内,所述催化剂显示出卓越的活性和选择性。这里,所述多金属氧酸盐可相当于本公开所述的多金属氧酸盐催化剂的前体。
所述多金属氧酸盐的粘度可以是,例如,1,000至15,000cps或3,000至8,000cps。在此范围内,所述催化剂显示出卓越的活性和选择性。
步骤(A)中的多金属氧酸盐可进一步包含,例如,表面活性剂。在此情况下,可以减轻共沉淀溶液中的分层现象。
所述表面活性剂可以是,例如,非离子型表面活性剂或中性表面活性剂。
所述非离子型表面活性剂可以是,例如,CH3(CH2)15(EO)nOH,其中,n是2至20的整数。
所述中性表面活性剂可以是,例如,CH3(CH2)n-1NH2,其中,n是12至16的整数。
基于浆液的总重,可以,例如,以0.1重量%以下、0.001至0.1重量%或0.01至0.05重量%的量包含所述表面活性剂。在此范围内,可以减轻共沉淀溶液中的分层现象。
在步骤(A)中,除非另有说明,否则形成多金属氧酸盐的方法可以是一般的多金属氧酸盐形成方法,如热液反应、共沉淀等,而没有任何特殊限制。
步骤(B)的涂布可以,例如,通过在所述惰性载体上喷涂多金属氧酸盐或在所述惰性载体上喷涂多金属氧酸盐和水而进行。
用多金属氧酸盐的喷涂可以,例如,通过使用喷嘴在所述惰性载体上喷涂未经过滤或干燥的浆状多金属氧酸盐来进行,以在所述惰性载体上涂布所述浆状多金属氧酸盐。
用多金属氧酸盐和水的喷涂可以,例如,通过在所述惰性载体上喷涂未经过滤和/或干燥的多金属氧酸盐和水来进行,以在所述惰性载体上涂布所述浆状多金属氧酸盐。
在步骤(B)的负载物质中,由以下等式2计算的多金属氧酸盐的负载量可以是,例如,15至50%、20至50%、20至40%或20至30%。在此范围内,所述催化剂显示出卓越的活性和选择性。
[等式2]
负载量(%)=(催化剂前体的总质量/负载物质的总质量)X 100
步骤(B)的负载可以,例如,通过重复在所述惰性载体上涂布多金属氧酸盐并干燥涂布的多金属氧酸盐的过程一次或多次、一至十次、一至八次或五次至八次而进行。在此范围内,所述催化剂显示出卓越的活性和选择性。
步骤(C)的干燥可以是,例如,热空气干燥。
所述干燥可以,例如,在金刚砂(SiC)容器、氧化铝容器、不锈钢容器、金属容器或由具有传热能力的不可燃材料制成的容器中进行。
步骤(C)的干燥可以,例如,在100至230℃、110至200℃或120至150℃下进行3至10小时或5至8小时。
步骤(C)的配体升华率可以是,例如,1.7%以上或1.7至4%。在此范围内,所述催化剂的活性、选择性和使用寿命大大改善。
步骤(D)的煅烧可以,例如,在350至550℃或400至500℃下进行1至10小时或3至5小时。
在步骤(A)至步骤(D)中,由以下等式3计算的总重量减少率(%)可以是,例如,30至50%、35至45%或40至45%。在此范围内,所述催化剂显示出卓越的活性和选择性。
[等式3]
T总重量减少率(%)=(去除材料的质量/包含溶剂的添加材料的总质量)X 100
在步骤(A)至(D)中,由以下等式4计算的总配体升华率(%)可以是,例如,0.1至20%、1至10%或2至5%。在此范围内,所述催化剂显示出卓越的活性和选择性。
[等式4]
总配体升华率(%)=(去除配体的质量/包含溶剂的添加材料的总质量)X100
所述多金属氧酸盐催化剂可具有,例如,圆柱形,中空圆柱形或球形。
所述多金属氧酸盐催化剂的外径可以是,例如,3至10mm或5至8mm。
圆筒型催化剂的长度与直径(外径)的比可以是,例如,1以下、0.1至1或1.0至1.3。
一种制备本发明所述的不饱和羧酸的方法,其特征在于,由不饱和醛气体产生不饱和羧酸的气相部分氧化在填充有所述多金属氧酸盐催化剂的固定床催化反应器中在0.1至10atm下在240至450℃下进行。
所述不饱和醛可以是例如异丁烯醛。
所述不饱和羧酸可以是例如不饱和脂肪酸。在另一个实施方式中,所述不饱和羧酸可以是(甲基)丙烯酸等。
所述固定床催化反应器可以是,例如,使用通过其减少催化剂的占有体积的方法用催化剂填充的固定床催化反应器。
例如,不饱和醛气体可以连同不饱和脂肪酸一起加入。
所述气相部分氧化可以,例如,在240至370℃和0.4至3atm下进行。在另一个实施方式中,所述气相部分氧化可以在250至310℃和1至3atm下进行。
所述气相部分氧化可以,例如,通过在所述反应器中以80至100hr-1的空速、20体积%以下的氧(不包括0体积%)、50体积%以下的水蒸汽(不包括0体积%)和20至80体积%以下的惰性气体引入不饱和醛来进行。
在另一个实施方式中,所述气相部分氧化可以,例如,通过在所述反应器中以500至3000hr-1的空速引入包含不饱和醛、氧、蒸汽和氮气的原料气体来进行。
所述固定床催化反应器可以是,例如,壳管式热交换器。
所述壳管式热交换器的材料可以是,例如,金刚砂(SiC)、不锈钢、金属或具有卓越的传热能力的材料。
提供以上描述仅用来说明根据本发明的实施方式。本领域的那些技术人员将理解的是,在不脱离本发明的范围和精神的情况下,各种修改、添加和替代是可能的。因此,显而易见的是,修改、添加和替代包括在本发明的范围中。
实施例1
搅拌3000ml的100℃的蒸馏水时,加入246g的钨酸铵、1,000g的钼酸铵和12g的草酸铌(NbC2O4),从而制备由式1的Mo、A和B成分组成的溶液(1)。将276g的硫酸氧钒单独溶解在1000ml的蒸馏水中,从而制备溶液(2)。
将溶液(1)与溶液(2)混合,然后加入570g的Cu(CH3COO)2·H2O、99g的硝酸锶、23g的硝酸锰和95g的硝酸铁作为式1的C和D成分,从而制备悬浮液。所述悬浮液的pH使用稀释的硫酸调整到4至5,然后运转均化器直到多金属氧酸盐形成其中粘度充分增加的淤浆。
随后,通过喷嘴在球形载体,外径为4.0mm至8.0mm的硅铝酸盐(Saint Gobain,SA5218),上涂布所述浆状多金属氧酸盐,并且在120℃下充分干燥。重复该过程八次。由此制备以25重量%的量负载的负载物质。
随后,在500℃下煅烧所述负载物质5小时以上,从而制备最终外径为4.7mm、5.4mm或7.8mm的球形多金属氧酸盐催化剂,其比所述载体的外径略大,具体略大0.2至0.4mm。在此情况下,除氧以外,产生的多金属氧酸盐的元素的组成如下:
Mo12V5.0W2.0Nb0.1Cu5.0Sr1.0Mn0.2Fe0.5
实施例2
除使用123g的量的钨酸铵之外,以与实施例1相同的方式制备多金属氧酸盐催化剂。除氧以外,产生的催化剂成分的元素的组成如下:
Mo12V5.0W5.0Nb0.1Cu5.0Sr1.0Mn0.2Fe0.5
对比实施例1
除不使用硫酸氧钒之外,以与实施例1相同的方式制备多金属氧酸盐催化剂。除氧以外,产生的催化剂成分的元素的组成如下:
Mo12W5.0Nb0.1Cu5.0Sr1.0Mn0.2Fe0.5
对比实施例2
除不使用钨酸铵之外,以与实施例1相同的方式制备多金属氧酸盐催化剂。除氧以外,产生的催化剂成分的元素的组成如下:
Mo12V5.0Nb0.1Cu5.0Sr1.0Mn0.2Fe0.5
参考实施例1
除使用钒酸铵代替硫酸氧钒之外,以与实施例1相同的方式制备多金属氧酸盐催化剂。除氧以外,产生的催化剂成分的元素的组成如下:
Mo12V5.0W2.0Nb0.1Cu5.0Sr1.0Mn0.2Fe0.5
[试验实施例]
通过以下方法测量根据实施例1和2、对比实施例1和2以及参考实施例1各自制备的多金属氧酸盐催化剂的性能。结果在下表1中汇总。
*V4+和V5+的比例:通过XPS(ESCA)(设备名称:X射线光电子能谱,型号名称:UK-Multilab 2000,制造商:Thermos VG)使用制备的催化剂测量。这里,未检测氧化值为2+或3+的钒。
*配体升华率:测量升华的配体的质量并根据以下等式1计算:
[等式1]
配体升华率(%)=(升华的配体的质量/升华前的配体的质量)X 100
*粘度(cps):通过布氏粘度计测量,#63转子,2RPM和室温(阻抗(resistance):5至6%)。
<催化剂活性试验>
使用填充有根据实施例1至2、对比实施例1和2以及参考实施例1各自获得的催化剂的不锈钢反应器作为固定床,在100hr-1的空速和240至310℃下在1至3atm下引入醛与由氧、水蒸气和惰性气体组成的混合气体,从而发生气相部分氧化。反应物的转化率、选择性和产率分别根据以下等式5至7计算。结果在下表1中汇总。
[等式5]
丙烯醛的转化率(%)=[反应的丙烯醛的摩尔数/提供的丙烯醛的摩尔数]X 100
[等式6]
丙烯醛的选择性(%)=[产生的丙烯酸的摩尔数/反应的丙烯醛的摩尔数]X 100
[等式7]
产率(%)=[产生的丙烯酸的摩尔数/提供的丙烯醛的摩尔数]X 100
[表1]
如表1所示,可以确认的是,与在本发明的V/A范围之外的常规技术与对比实施例1和2相比,根据本发明所述的调节V/A值的多金属氧酸盐催化剂(实施例1至2)显示出卓越的转化率、选择性、产率等。
此外,可以确认的是,与使用含有V5+的前体比较,当含有V4+的前体的作为钒前体使用时,选择性和产率大大增加。
此外,可以确认的是,所述配体升华率、所述悬浮液的pH等对催化活性、选择性和产率有一定影响。
此外,可以确认的是,本发明所述的多金属氧酸盐催化剂(实施例1和2)可以在比常规技术的反应温度范围(即,270至310℃)宽的反应温度范围内(即,250至310℃)反应,并且因此,与常规情况相比,可以反应较长时间。
Claims (20)
1.一种多金属氧酸盐催化剂,其包含由下式1表示的金属氧化物:
[式1]
MoaAbVcBdCeDfOg,
其中,A是选自W和Cr的一种或多种元素;B是选自P、As、B(硼)、Sb、Ce、Pb、Mn、Nb和Te的一种或多种元素;C是选自Si、Al、Zr、Rh、Cu、Ni、Ti、Ag、Fe、Co和Sn的一种多种元素;D是选自Na、K、Li、Rb、Cs、Ta、Ca、Mg、Sr和Ba的一种或多种;并且a、b、c、d、e、f和g表示各元素的原子比,
其中,当a=12,b是0.01至15;c是0.01至15,d是0至20,e是0至20,f是0至20;并且g根据各成分的氧化态确定,并且
其中,V与A(V/A)的摩尔比是0.01至10。
2.根据权利要求1所述的多金属氧酸盐催化剂,其中,d、e和f各自是0.01至20。
3.根据权利要求1所述的多金属氧酸盐催化剂,其中,钒(V)包含30%以上的氧化值为4+的钒。
4.根据权利要求1所述的多金属氧酸盐催化剂,其中,所述多金属氧酸盐催化剂包含惰性载体,作为所述金属氧化物的载体。
5.根据权利要求4所述的多金属氧酸盐催化剂,其中,涂布在所述惰性载体上的金属氧化物的负载量是30至80重量%。
6.根据权利要求1所述的多金属氧酸盐催化剂,其中,所述多金属氧酸盐催化剂是用于气相部分氧化以由不饱和醛产生不饱和羧酸的催化剂。
7.一种制备根据权利要求1所述的多金属氧酸盐催化剂的方法,所述方法包括:(A)制备包含金属前体的悬浮液以产生由式1表示的金属氧化物,并且如果需要,通过加入酸调节pH到0至7.5,接着通过均化器增加粘度以形成多金属氧酸盐的步骤;(B)将20至50重量%的所形成的多金属氧酸盐负载至惰性载体以制备负载物质的步骤;(C)干燥所述负载物质以获得通过以下等式1计算的配体升华率为0%以上的负载物质的步骤;和(D)煅烧干燥的负载物质以获得多金属氧酸盐催化剂的步骤:
[等式1]
配体升华率(%)=(升华的配体的质量/升华之前配体的质量)X 100。
8.根据权利要求7所述的方法,其中,由式1表示的钒(V)前体是含有氧化值为4+的钒的化合物。
9.根据权利要求8所述的方法,其中,所述含有氧化值为4+的钒的化合物是含有氧钒基的化合物。
10.根据权利要求7所述的方法,其中,在步骤(A)中,所述多金属氧酸盐具有5,000至20,000cps的粘度。
11.根据权利要求7所述的方法,其中,在步骤(A)中,所述多金属氧酸盐被干燥,然后被过滤并干燥,接着粉碎。
12.根据权利要求7所述的方法,其中,所述步骤(B)的负载通过在所述惰性载体上喷涂所述多金属氧酸盐或在所述惰性载体上喷涂所述多金属氧酸盐和水而进行。
13.根据权利要求7所述的方法,其中,所述金属前体的配体是选自-NH4、-NH2、-NOx(其中x是1至3的整数)、-Cl、-F、-N、-OH、-SOx(其中x是3至4的整数)、-CO、-COO、-SCN、-CN、-NCS、-ONO、-NC、-CnHmOx(其中n是1至20的整数,m是1至40的整数并且x是1至10的整数)和C1至C20醇盐的一种或多种。
14.根据权利要求7所述的方法,其中,在步骤(A)中,所述悬浮液的浓度是25至45重量%。
15.根据权利要求7所述的方法,其中,所述步骤(C)的干燥是热空气干燥。
16.根据权利要求7所述的方法,其中,所述步骤(B)的负载通过重复用所述多金属氧酸盐涂布所述惰性载体并且干燥所述涂布的惰性载体的过程一次或多次而进行。
17.根据权利要求7所述的方法,其中,所述步骤(C)的干燥在100至230℃下进行。
18.根据权利要求7所述的方法,其中,在步骤(A)中,所述悬浮液的粘度在25至50℃下通过均化器来增加,从而形成多金属氧酸盐。
19.根据权利要求7所述的方法,其中,所述步骤(D)的煅烧在350至550℃下进行1至10小时。
20.一种制备不饱和羧酸的方法,其中,由不饱和醛气体产生所述不饱和羧酸的气相部分氧化在填充有根据权利要求1所述的多金属氧酸盐催化剂的固定床催化反应器中在0.1至10atm下在240至450℃下进行。
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US20170225154A1 (en) | 2017-08-10 |
US9919295B2 (en) | 2018-03-20 |
EP3213816B1 (en) | 2022-11-16 |
EP3213816A1 (en) | 2017-09-06 |
WO2017026649A1 (ko) | 2017-02-16 |
KR101960919B1 (ko) | 2019-03-22 |
KR20170019128A (ko) | 2017-02-21 |
EP3213816A4 (en) | 2018-08-01 |
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