CN114887627A - 一种用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法 - Google Patents
一种用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 58
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-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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- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims abstract description 4
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- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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Abstract
本发明公开了一种丙烯醛氧化制丙烯酸的涂层催化剂及其制备方法。该催化剂由活性组分和载体构成,载体为活性组分的支撑体,活性组分为外壳。催化剂制备方法包括:在高速搅拌下将硫酸铜溶液加入到偏钨酸铵、偏钒酸铵、七钼酸铵和醋酸锑的混合溶液中共沉淀制得活性前体浆液;将活性前体浆液快速干燥、烧制粉碎后得到复合氧化物粉末;在复合氧化物粉末中混入纤维素和丙烯酰胺,同时依次喷入交联剂和引发剂进行滚涂成型,成型产物用微波处理后进行干燥、焙烧后制得催化剂。本发明采用微波辐射对成型后产品处理使纤维素和丙烯酰胺接枝聚合,生成不溶于水的高吸水性高分子化合物,在催化剂涂层中形成贯通孔道,提高催化剂的反应活性。
Description
技术领域
本发明属于氧化反应催化剂制备领域,涉及丙烯醛氧化制丙烯酸催化剂,主要是一种具有较高活性的丙烯醛氧化制丙烯酸的涂层催化剂的制备方法。
背景技术
目前工业上生产丙烯酸多采用以Mo-V系复合氧化物为催化剂的气-固相氧化法,为保证反应气体的通过性,催化剂粉体大多需要采用挤出或者冲压成柱形或中空柱形颗粒。由于丙烯醛氧化为高空速、强放热反应,较大的气流冲刷速度和较为剧烈的床层温度变化都容易使催化剂粉化、破碎,使床层压降升高,装置控制难度升高。因此,提高催化剂的机械强度是丙烯醛氧化制丙烯酸催化剂制备技术领域的重要课题之一。
为提高催化剂的强度,部分研究者试图将活性组分涂覆于高强度载体表面,利用载体的支撑作用提高催化剂的强度。专利CN112547043A将金属氧化物分散于水相后喷涂于载体表面,使催化剂的强度得到一定程度提高。专利CN1087658C将含钼、钒、钨、锑、铜等金属的复合氧化物粉末在甘油等醇类成型助剂和强度改进剂陶瓷纤维的辅助作用下通过转动成型涂覆于惰性载体表面,通过成型过程的滚动压制作用,得到具有较高强度的催化剂。专利CN102039143B将Mo-V系复合氧化物与微晶纤维素和陶瓷纤维混合滚涂于载体表面,得到一种高强度的蛋壳型催化剂。采用喷涂或滚涂的方式可以提高催化剂的强度,但与常规中空柱形催化剂相比,催化剂暴露的外表面积降低导致催化活性偏低。
发明内容
本发明基于现有技术存在的上述问题,工程人员期望通过对涂层式催化剂进行调变在涂层催化剂高强度的基础上提高催化剂的反应活性,以提高催化剂的工业应用价值,提供了一种用于丙烯醛氧化制丙烯酸的涂层催化剂及其制备方法,该方法通过对成型后催化剂进行微波辐射处理,使成型过程中添加的纤维素与丙烯酰胺在引发剂与交联剂的作用下进行接枝聚合并连续分布于催化剂的堆积孔道中。所得催化剂在后续烧制时,所述有机物交联体发生分解,在催化剂涂层内形成贯通孔道,在反应过程中增大原料与涂层内活性组分的接触机会,进而提高了催化剂的反应活性。
一种用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法,包括如下步骤:
(1)在高速搅拌下将偏钨酸铵、偏钒酸铵和七钼酸铵依次加入到90℃以上的去离子水中,随后加入醋酸锑进一步反应得到混合溶液,将硫酸铜水溶液逐渐加入到所述混合溶液中进行共沉淀反应得到水性浆液;将所述水性浆液进行干燥后得到复合氧化物前驱体,将所述复合氧化物前驱体在300~390℃焙烧后进行粉碎得到复合金属氧化物粉末;在所述复合金属氧化物粉末中加入质量含量2~10%的纤维素和质量含量5~20%的丙烯酰胺,混合均匀后得到活性组分;
所述活性前体浆液的干燥方式优选为喷雾干燥;
(2)将球形载体放入转鼓造粒机中,喷入浓度为0.05~0.5%的N,N’-亚甲基双丙烯酰胺水溶液,同时将所述活性组分分批加入到成型机中成型,粉体加入完毕后向成型机内球体喷入0.2~1%引发剂的水溶液;将得到的球体用微波处理5~30min,在流动气氛下烘干后在350~390℃焙烧2~10h,得到用于丙烯醛氧化制丙烯酸的涂层催化剂;
所述的用于丙烯醛氧化制丙烯酸的涂层催化剂由活性组分和球形载体形成核壳式结构,其中活性组分包覆于催化剂载体表面,活性组分涂层内有贯通孔道,活性组分与载体的质量比为1:3~3:1;
所述活性组分可用以下通式表示:
Mo12VaWbSbcCudOx
以Mo原子数取值12为基准,其中:
a的取值范围为1~5;
b的取值范围为0.5~2;
c的取值范围为0.2~1;
d的取值范围为0.5~2;
x的取值取决于其他各元素取值。
本发明上述用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法中,所述的纤维素优选为非水溶性的木质纤维素、微晶纤维素和水溶性的甲基纤维素、羧甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素的一种或几种。
所述引发剂优选为过硫酸铵、过硫酸钾、硝酸铈铵的一种或几种。
所述焙烧温度优选为360~390℃,所述焙烧时间优选为2~5h。
本发明还进一步提供了一种由上述制备方法制备得到的用于丙烯醛氧化制丙烯酸的涂层催化剂。
更进一步,本发明还提供了一种上述涂层催化剂在丙烯醛氧化制丙烯酸中的应用。
本发明提供的涂层催化剂的制备方法利用成型液体助剂丙烯酰胺成型时在粉体内分布较均匀,成型后的催化剂在微波辅助下与纤维素进行交联聚合,随后丙烯酰胺固化为网状孔道结构。所述催化剂烧制后在涂层内形成网状贯通孔道,有效提高活性组分利用率,改善催化剂活性。本发明用于丙烯醛氧化制丙烯酸的涂层催化剂具有较高的催化活性和催化剂强度。
具体实施方式
下面结合具体实施例对本发明技术方案作进一步说明。
实施例1
(1)于反应釜中加入6L去离子水并加热至95℃,在搅拌下依次加入162.6g偏钨酸铵、182g偏钒酸铵和1100g七钼酸铵,上述溶液搅拌30min后加入78g醋酸锑并持续搅拌1h使之反应完全得到混合溶液;取960mL去离子水加入155.6g硫酸铜搅拌使之溶解,在95℃保温条件下将硫酸铜溶液加入到所述混合溶液中进行共沉淀,反应结束后继续恒温95℃老化1h得到活性前体浆液。把上述前驱体浆液进行喷雾干燥,控制入口温度为360℃,调节加料速度使得出口温度保持在105℃。经喷雾干燥得到的干燥物在370℃的空气气氛下焙烧3小时,得到复合氧化物粉末。将上述复合氧化物粉末粉碎后过100目筛并取出400g与20g微晶纤维素、40g丙烯酰胺混合均匀后制成活性组分;
(2)将600g球形载体放入转鼓造粒机中,喷入0.1%N,N’-亚甲基双丙烯酰胺水溶液,同时将步骤(1)得到的活性组分分批加入到成型机中,粉体加入完毕后向成型机内喷入20g的0.5%过硫酸铵水溶液完成成型。成型结束后将球体取出并用微波处理15min,在烘箱中120℃烘干5h后干燥产品于390℃焙烧3h得到丙烯醛氧化制丙烯酸涂层催化剂。
实施例2
将实施例1步骤(1)中“取出400g与20g微晶纤维素、40g丙烯酰胺”替换成“取出400g与30g微晶纤维素、40g丙烯酰胺”;
将实施例1步骤(2)中“0.1%N,N’-亚甲基双丙烯酰胺水溶液”替换成“0.2%N,N’-亚甲基双丙烯酰胺水溶液”,“喷入20g的0.5%过硫酸铵水溶液”替换成“喷入20g的1%硝酸铈铵水溶液”,其他同实施例1。
实施例3
将实施例1步骤(1)中“取出400g与20g微晶纤维素、40g丙烯酰胺”替换成“取出400g与10g羟乙基纤维素、20g丙烯酰胺”;
将实施例1步骤(2)中“喷入20g的0.5%过硫酸铵水溶液”替换为“喷入20g的0.5%过硫酸钾水溶液”,其他同实施例1。
对比例1
(1)将实施例1步骤(1)中“取出400g与20g微晶纤维素、40g丙烯酰胺”替换成“取出400g与20g微晶纤维素”;
(2)将600g球形载体放入转鼓造粒机中,喷入30%甘油水溶液,同时将混有微晶纤维素的复合氧化物粉末分批加入到成型机中。成型结束后将球体取出晾置20h后,在烘箱中120℃烘干5h后干燥产品于390℃焙烧3h得到丙烯醛氧化制丙烯酸涂层催化剂。
对比例2
(1)同实施例1步骤(1);
(2)将600g球形载体放入转鼓造粒机中,喷入去离子水,同时将混有微晶纤维素和丙烯酰胺的复合氧化物粉末分批加入到成型机中。成型结束后将球体取出晾置20h后,在烘箱中120℃烘干5h后干燥产品于390℃焙烧3h得到丙烯醛氧化制丙烯酸涂层催化剂。
对比例3
(1)同实施例1步骤(1);
(2)同实施例1,仅将步骤(2)中“成型结束后将球体取出并用微波处理15min”替换为“成型结束后将球体取出晾置20h”。
催化剂性能评价方法
催化剂性能评价于固定床管式反应器中进行,反应管内径为20mm,反应管长为2000mm,催化剂装于反应管恒温区内,装填体积为30ml,反应压力为常压,反应温度为250℃,气体总空速为1800h-1,反应原料中丙烯醛气体占比6.5%,氧气占比8.5%,水蒸气占比33%,氮气占比52%,采用气相色谱法分析反应转化率及收率结果。
以下各表给出实施例及对比例催化剂的物性情况。
表1催化剂反应性能结果
催化剂 | 丙烯醛转化率/% | 丙烯酸选择性/% | 丙烯酸收率/% |
实施例1 | 98.7 | 98.1 | 96.8 |
实施例2 | 99.1 | 98.2 | 97.3 |
实施例3 | 98.3 | 98.5 | 96.8 |
对比例1 | 95.3 | 98.1 | 93.5 |
对比例2 | 96.1 | 97.7 | 93.9 |
对比例3 | 96.5 | 97.2 | 93.8 |
表1给出按本发明方法制备的涂层催化剂与采用常规滚动涂覆工艺制备的涂层催化剂的反应性能情况对比,可以看出,采用本发明方法制备的催化剂具有更高的丙烯醛转化率和更高的丙烯酸收率,催化反应性能更加优良。对比例1采用常规涂覆工艺,甘油在涂层内自由移动,扩孔效果不明显;对比例2未加引发剂,对比例3未用微波处理成型后产品,丙烯酰胺基本未发生交联,未能达到更优的反应性能。
Claims (7)
1.一种用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法,其特征在于,制备过程包含以下步骤:
(1)在高速搅拌下将偏钨酸铵、偏钒酸铵和七钼酸铵依次加入到90℃以上的去离子水中,随后加入醋酸锑进一步反应得到混合溶液,将硫酸铜水溶液逐渐加入到所述混合溶液中进行共沉淀反应得到水性浆液;将所述水性浆液进行干燥后得到复合氧化物前驱体,将所述复合氧化物前驱体在300~390℃焙烧后进行粉碎得到复合金属氧化物粉末;在所述复合金属氧化物粉末中加入质量含量2~10%的纤维素和质量含量5~20%的丙烯酰胺,混合均匀后得到活性组分;
(2)将球形载体放入转鼓造粒机中,喷入浓度为0.05~0.5%的N,N’-亚甲基双丙烯酰胺水溶液,同时将所述活性组分分批加入到成型机中成型,粉体加入完毕后向成型机内球体喷入0.2~1%引发剂的水溶液;将得到的球体用微波处理5~30min,在流动气氛下烘干后在350~390℃焙烧2~10h,得到用于丙烯醛氧化制丙烯酸的涂层催化剂;
所述的用于丙烯醛氧化制丙烯酸的涂层催化剂由活性组分和球形载体形成核壳式结构,其中活性组分包覆于催化剂载体表面,活性组分涂层内有贯通孔道,活性组分与载体的质量比为1:3~3:1;
所述活性组分可用以下通式表示:
Mo12VaWbSbcCudOx
以Mo原子数取值12为基准,其中:
a的取值范围为1~5;
b的取值范围为0.5~2;
c的取值范围为0.2~1;
d的取值范围为0.5~2;
x的取值取决于其他各元素取值。
2.根据权利要求1所述的用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法,其特征在于,步骤(1)中所述活性前体浆液的干燥方式为喷雾干燥。
3.根据权利要求1所述的用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法,其特征在于,步骤(1)中所述纤维素为非水溶性的木质纤维素、微晶纤维素和水溶性的甲基纤维素、羧甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素的一种或几种。
4.根据权利要求1所述的用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法,其特征在于,步骤(2)中所述引发剂为过硫酸铵、过硫酸钾、硝酸铈铵的一种或几种。
5.根据权利要求1所述的用于丙烯醛氧化制丙烯酸的涂层催化剂的制备方法,其特征在于,步骤(2)中所述焙烧温度为360~390℃,所述焙烧时间为2~5h。
6.一种权利要求1~5任一项权利要求所述的制备方法制备得到的用于丙烯醛氧化制丙烯酸的涂层催化剂。
7.一种权利要求6所述的涂层催化剂在丙烯醛氧化制丙烯酸中的应用。
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