CN113289599A - 一种硅酸盐/氧化铝复合型再生催化剂及其制备方法和应用 - Google Patents
一种硅酸盐/氧化铝复合型再生催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 29
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
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- 239000001110 calcium chloride Substances 0.000 claims description 4
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 8
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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Abstract
本发明提供了一种硅酸盐/氧化铝复合型再生催化剂,其化学通式为:MxSiyOnH2z/Al2O3,其中MxSiyOnH2z为硅酸盐类,其质量百分含量为30‑60wt%,其中M是Mg2+或Ca2+的一种,Al2O3的晶型为γ型。该催化剂的形状是条形或三叶草形,其直径3‑10mm,长度为10‑50mm。该催化剂的制备方法是,先制备活性组分硅酸盐MxSiyOnH2z粉体,再添加造孔剂、助挤剂和水后进行挤出成型,后经蒸养、干燥、焙烧得到。该催化剂专用于蒽醌法制过氧化氢工作液中蒽醌降解物的再生,用该催化剂再生后蒽醌增量达到7.0‑11.6g·L‑1,远高于目前工业上所使用的蒽醌再生催化剂。
Description
所属领域
本发明涉及一种再生催化剂,具体涉及一种硅酸盐/氧化铝复合催化剂,该催化剂用于蒽醌法制过氧化氢工作液中蒽醌降解物的再生。
背景技术
过氧化氢又名双氧水,是一种绿色无污染的化工产品,被广泛应用于纺织、造纸、军工、电子、污水处理等领域。过氧化氢全球年消耗量超过3000万吨(按照27.5%质量浓度计算),我国年产量已达1350万吨,是世界上最大的生产国和消费国。蒽醌法凭借其自动化程度高、生产效率高和能规模化生产等优点,已成为国际上规模化生产双氧水的唯一方法。然而,在蒽醌法制备过氧化氢的生产工艺中,会生成一些副产物即蒽醌降解物。蒽醌降解物的生成不仅严重影响工艺稳定性,而且极大影响双氧水的品质和存在安全隐患。因此,通常采用催化剂使蒽醌降解物再生即转化为蒽醌,从而降低工作液中降解物的含量,维持稳定正常运转。
目前工业上蒽醌降解物再生催化剂主要成分为碱浸渍的活性氧化铝(碱通常为NaOH或KOH),但是NaOH(或Na2O)或KOH(或K2O)等活性组分易溶于水而随着蒽醌工作液中少量水流失,导致该类再生催化剂使用寿命短,通常为50-60天就要更换,每年需活性氧化铝4万余吨。这一方面导致大量宝贵铝资源浪费,另一方面多孔活性氧化铝载体中吸附有大量价格昂贵的有效蒽醌成分。因此,再生催化剂频繁更换无疑将大幅度增加过氧化氢生产成本,同时也造成环境的污染。因此亟需开发新型高效长寿命持久型蒽醌降解物再生催化剂。
中国专利CN102728338A公开了一种MeO/Al2O3型再生催化剂及其制备方法。该催化剂是利用氧化铝自身的铝源或外加铝源的方式,再与镁盐、沉淀剂、模板剂水热反应,制备出在氧化铝表面或孔道内生长的MeAlCO3-LDH/Al2O3水滑石前体,后经高温焙烧得到MeO/Al2O3型固体碱再生催化剂。该方法能有效地延长催化剂的使用寿命,经过96h的再生性能评价,催化剂的有效蒽醌增量范围为6.0-9.0g·L-1。
中国专利CN106179427A公开了一种再生催化剂及其制备方法。该催化剂以活性氧化铝为原料,以金属氧化物、金属氯化物为活性组分,经过高速混合机混合均匀后,向体系中加入胶溶剂,进行液压挤出成型,再经养生、高温焙烧等工序制备出再生催化剂。催化剂的有效蒽醌增量为9.0g·L-1左右。
中国专利CN110327907 A公开了一种MeO/Al2O3型再生催化剂及其制备方法。该催化剂金属氧化物或金属氢氧化物为活性物质,氧化铝为载体,经胶体磨混合均匀后转入高温高压晶化釜,水热反应后得到层状水滑石包裹的活性氧化铝粉体,后经挤条成型、焙烧制备出MeO/Al2O3型再生催化剂。该方法制备的催化剂的有效蒽醌增量为9.0g·L-1左右。。
发明内容
本发明的目的在于提供一种硅酸盐/氧化铝复合再生催化剂及其制备方法,该催化剂专用于蒽醌法制过氧化氢工作液中蒽醌降解物的再生。
本发明中的硅酸盐/氧化铝复合催化剂的化学通式为:
MxSiyOnH2z/Al2O3
其中x=1-3,y=0.5-4,n=x+2y+z,1.0≤x:y≤2.0,M为Mg2+或Ca2+,其中MxSiyOnH2z的质量百分含量为30-60wt%,较优的为40-50wt%;MxSiyOnH2z为硅酸盐类,M是Mg2+、Ca2+的任意一种,Al2O3的晶型为γ型;催化剂的形状是条形或三叶草形,其直径3-10mm,长度为10-50mm,较佳的长度为10-30mm。
上述硅酸盐/氧化铝复合催化剂的具体制备步骤如下:
步骤A:将可溶性金属M盐加入混合溶剂中,超声使其充分溶解,配制浓度为0.15-0.5mol/L的M盐溶液;再将硅酸盐加入去离子水中,超声使其完全溶解,配制浓度为0.15-2.0mol/L硅酸盐溶液。
所述的可溶性金属M盐为MgCl2、MgSO4、Mg(NO3)2、CaCl2、Ca(NO3)2的任意一种,所述硅酸盐为硅酸钠或硅酸钾,所述混合溶剂为有机醇与水的混合物,其中有机醇的体积比为10-90%,所述有机醇为乙醇、丙醇、乙二醇、丙三醇、丁醇中的任意一种,优选乙醇或丙醇。
步骤B:将步骤A中M盐溶液加入带磁力搅拌的容器,以700-900rpm转速下搅拌,再将硅酸盐溶液逐滴加入M盐溶液中,滴毕继续磁力搅拌4-8min得到混合盐溶液;其中硅酸盐溶液的滴加量按照滴完后溶液中M/硅比为1.0-2.0定量。
步骤C:将步骤B的混合盐浆液转入高压反应釜中,120-200℃反应12-24h,离心分离、水洗和醇洗滤出的固体物,于50-60℃的烘箱中干燥8-12h,研磨成粉即得所需的硅酸盐,其化学式为MxSiyOnH2z;其比表面积为100-500m2·g-1,孔容为0.3-1.0cm3·g-1。
步骤D:将MxSiyOnH2z粉末、快脱粉、造孔剂和助挤剂按下列百分数混合均匀
向上述混合粉体中加入占粉体质量50-60%的去离子水,继续搅拌均匀制成挤条湿粉,将挤条湿粉通过挤条机混捏3-4次后,挤出成型,后经蒸养、干燥、于450-550℃焙烧3-5h得到催化剂,表示为MxSiyOnH2z/Al2O3。
所述造孔剂为纤维素或淀粉,淀粉与其他物料混合前,需要进行糊化;所述助挤剂为田菁粉、多元羟酸、无机酸中的一种;所述的脱粉是市售的晶型为ρ型氧化铝。
制备的MxSiyOnH2z/γ-Al2O3催化剂比表面积为100-480m2·g-1,孔容为0.3-1.0cm3·g-1,压碎强度为50-100N/颗。
将该催化剂用于蒽醌降解物再生反应,再生后催化剂的有效蒽醌增量为7.0-11.6g·L-1。
图1-3是对实施例1步骤C制备的样品的表征,图1的XRD谱图中2θ=22°、35°、60°处出现了硅酸镁的特征衍射峰。图2显示样品为花状结构。图3中,3680cm-1和464cm-1的吸收峰分别归因于Mg-OH的伸缩振动峰和Mg-O的弯曲振动峰,663cm-1处的峰归属于Si-O-Si的弯曲振动峰,906cm-1和1030cm-1处为Si-O-Si的伸缩振动峰,均属硅酸镁的红外特征峰。图1-3说明实施例1步骤C成功制备出花状结构硅酸镁材料。
图4和图5分别为实施例2制备的催化剂的XRD谱图和FT-IR谱图,图4中2θ=22°、35°、60°处出现了硅酸镁的特征衍射峰,在2θ=37°、45°和66°处出现了γ-Al2O3的特征衍射峰。图5中即出现了硅酸镁的红外特征吸收峰,又在500cm-1-900cm-1出现了宽且光滑的氧化铝的红外特征峰。图4-5实施例2制备的催化剂为硅酸镁/γ-Al2O3催化剂。
本发明的有益效果是:
本发明所制备的硅酸盐/氧化铝复合催化剂,具有较大的比表面积、丰富的孔道、而且还同时具有酸碱活性位点、化学性质稳定,该催化剂专用于蒽醌工作液中降解物的再生,应用结果显示其再生活性高、使用寿命长。
附图说明:
图1实施例1中步骤C制备的粉体硅酸盐的XRD谱图;
图2实施例1中步骤C制备的粉体硅酸盐的形貌图;
图3实施例1中步骤C制备的粉体硅酸盐的FT-IR谱图;
图4实施例2制备的催化剂的XRD谱图;
图5实施例2制备的催化剂的FT-IR谱图。
具体实施方式:
以下实施例仅用于说明本发明而非用于限制本发明的范围。
实施例1
步骤A:称取4.87g的MgCl2·6H2O于烧杯中,加入120mL的乙醇和10mL的去离子水,超声使其完全溶解得到MgCl2溶液。
称取6.82g的Na2SiO3·9H2O于烧杯中,加入30mL的去离子水,超声使其完全溶解得到Na2SiO3溶液。
步骤B:将步骤A的MgCl2溶液在磁力搅拌台上以700rpm转速搅拌;将步骤A的Na2SiO3溶液转移至常压滴液漏斗中,以0.05mL/s滴入到MgCl2溶液中,滴毕继续磁力搅拌5min得到混合盐溶液
步骤C:将步骤B得到的混合盐溶液转入高压反应釜中,于170℃反应12h,自然冷却至室温,离心分离,用水洗和乙醇交替洗涤至无杂质,于60℃的烘箱中干燥12h,研磨成粉即得硅酸镁MgSiO4·H2样品。表征结果见图1-3。
步骤D:将20.0g的快脱粉、2.2g的硅酸镁和0.67g的田菁粉于容器中混合均匀;称取1.3g的淀粉于烧杯中,加入去离子水12.6g,置于加热台上,加热使其形成糊状(俗称糊化),冷却至室温后,向烧杯中补加由于加热蒸发而损失的水量,搅拌均匀,将上述混合物料和糊化的淀粉搅拌均匀,转入挤条机中混捏3-4次后,挤条成型,后经蒸养、干燥、于500℃焙烧4h得到条形催化剂,表示为MgSiO4·H2/γ-Al2O3。
测得该催化剂比表面为:244.56m2·g-1,孔容为0.38cm3·g-1。
取5.0g的MxSiyOnH2z/γ-Al2O3催化剂样品和50mL的蒽醌工作液(取自鲁西化工蒽醌法制过氧化氢使用后的工作液)于100mL的锥形瓶中,待气泡消失后,将锥形瓶密封并置于恒温振荡器中进行再生反应,分别在0h、12h、24h、48h、72h时间点取样,经色谱甲醇稀释后,使用依利特W1100型高效液相色谱仪测定工作液中2-乙基蒽醌和四氢2-乙基蒽醌的浓度变化。实验结果如表1所示。
实施例2
步骤A:称取7.69g的Mg(NO3)2·6H2O于烧杯中,然后向烧杯中加入120mL的乙醇和10mL的去离子水,超声使其完全溶解得到Mg(NO3)2溶液。
称取6.82g的Na2SiO3·9H2O于烧杯中,然后加入30mL的去离子水,超声使其完全溶解Na2SiO3溶液。
步骤B:将步骤A的Mg(NO3)2溶液在磁力搅拌台上以700rpm转速搅拌;将步骤A的Na2SiO3溶液转移至常压滴液漏斗中,以0.05mL/s滴入到Mg(NO3)2溶液中,滴毕继续磁力搅拌5min得到混合盐溶液
步骤C:将步骤B得到的混合盐溶液转入高压反应釜中,于170℃反应12h,自然冷却至室温,离心分离,用水洗和乙醇交替洗涤至无杂质,于60℃的烘箱中干燥12h,研磨成粉即得硅酸镁Mg3Si2O8·H2样品
步骤D:将20.0g的快脱粉、20.0g的硅酸镁和1.20g的田菁粉于容器中混合均匀;称取2.4g的淀粉(6%wt)于烧杯中,加入水粉比为55%的去离子水22.6g,置于加热台上,加热使其形成糊状(俗称糊化),冷却至室温后,向烧杯中补加由于加热蒸发而损失的水量,搅拌均匀后待用;将上述混合物料和糊化的淀粉搅拌均匀,转入挤条机中混捏3-4次后,挤条成型,后经蒸养、干燥、于550℃焙烧3h得到条形催化剂,表示为Mg3Si2O8·H2/γ-Al2O3。
测得该催化剂比表面为:324.1m2·g-1,孔容为0.35cm3·g-1。
按实施例1相同的方法对于实施例2制备催化剂进行应用性能评价,实验结果如表1所示。
实施例3
步骤A:称取7.88g的CaCl2·6H2O于烧杯中,然后向烧杯中加入120mL的乙醇和10mL的去离子水,超声使其完全溶解得到CaCl2溶液。
称取6.82g的Na2SiO3·9H2O于烧杯中,然后加入30mL的去离子水,超声使其完全溶解得到Na2SiO3溶液。
步骤B:将步骤A的CaCl2溶液在磁力搅拌台上以700rpm转速搅拌;将步骤A的Na2SiO3溶液转移至常压滴液漏斗中,以0.05mL/s滴入到CaCl2溶液中,滴毕继续磁力搅拌5min得到混合盐溶液
步骤C:将步骤B得到的混合盐溶液转入高压反应釜中,于170℃反应12h,自然冷却至室温,离心分离,用水洗和乙醇交替洗涤至无杂质,于60℃的烘箱中干燥12h,研磨成粉即得硅酸钙Ca3Si2O8·H2样品。
步骤D:将20.0g的快脱粉、2.22g的硅酸钙和0.67g的田菁粉于容器中混合均匀;称取1.33g的淀粉(6%wt)于烧杯中,加入水粉比为55%的去离子水12.59g,置于加热台上,加热使其形成糊状(俗称糊化),向烧杯中补加由于加热蒸发而损失的水量,搅拌均匀后待用;将上述混合物料和糊化的淀粉搅拌均匀,转入挤条机中混捏3-4次后,挤条成型,后经蒸养、干燥、于480℃焙烧5h得到条形催化剂,表示为Ca3Si2O8·H2/γ-Al2O3。
测得该催化剂比表面为:318.75m2·g-1,孔容为0.25cm3·g-1。
按实施例1相同的方法对于实施例3制备催化剂进行应用性能评价,实验结果如表1所示。
实施例4
步骤A:称取5.67g的Ca(NO3)2·4H2O于烧杯中,然后向烧杯中加入120mL的乙醇和10mL的去离子水,超声使其完全溶解得到Ca(NO3)2溶液。
称取6.82g的Na2SiO3·9H2O于烧杯中,然后加入30mL的去离子水,超声使其完全溶解得到Na2SiO3溶液。
步骤B:将步骤A的Ca(NO3)2溶液在磁力搅拌台上以700rpm转速搅拌;将步骤A的Na2SiO3溶液转移至常压滴液漏斗中,以0.05mL/s滴入到Ca(NO3)2溶液中,滴毕继续磁力搅拌5min得到混合盐溶液。
步骤C:将步骤B得到的混合盐溶液转入高压反应釜中,于170℃反应12h,自然冷却至室温,离心分离,用水洗和乙醇交替洗涤至无杂质,于60℃的烘箱中干燥12h,研磨成粉即得硅酸钙CaSiO4·H2样品。
步骤D:将20.0g的快脱粉、8.57g的硅酸钙和0.86g的田菁粉于容器中混合均匀;称取1.33g的淀粉(6%wt)于烧杯中,加入水粉比为55%的去离子水16.45g,置于加热台上,加热使其形成糊状(俗称糊化),冷却至室温后,向烧杯中补加由于加热蒸发而损失的水量,搅拌均匀后待用;将上述混合物料和糊化的淀粉搅拌均匀,转入挤条机中混捏3-4次后,挤条成型,后经蒸养、干燥、于500℃焙烧4h得到出条形催化剂,表示为CaSiO4·H2/γ-Al2O3。
测得该催化剂比表面为:318.75m2·g-1,孔容为0.25cm3·g-1。
按实施例1相同的方法对于实施例4制备催化剂进行应用性能评价,实验结果如表1所示。
对比例1
目前市售活性氧化铝再生催化剂,比表面为:210.25m2·g-1,孔容为0.31cm3·g-1。按实施例1相同的方法对其进行再生性能评价,实验结果见表1。
表1
由表1可见:相较于市售的氧化铝催化剂,四组催化剂的有效蒽醌再生量明显高于市售的氧化铝的再生量。其中实例2中的有效蒽醌增量达到11.59g·L-1,相较于对比例,有效蒽醌再生量提高了65.34%。结合实际使用情况,本发明所制备的催化剂的使用寿命相较于对比例明显延长,使用寿命为6-12月。
Claims (3)
1.一种硅酸盐/氧化铝复合型再生催化剂,其特征是该催化剂的化学通式为:
MxSiyOnH2z/Al2O3
其中x=1-3,y=0.5-4,n=x+2y+z,1.0≤x:y≤2.0,M为Mg2+或Ca2+,其中MxSiyOnH2z的质量百分含量为30-60wt%,MxSiyOnH2z为硅酸盐类;M为Mg2+或Ca2+;Al2O3的晶型为γ型;催化剂的形状是条形或三叶草形,其直径为3-10mm,长度为10-50mm,;该催化剂的比表面积为100-480m2·g-1,孔容为0.3-1.0cm3·g-1,压碎强度为50-100N/颗;
该催化剂采用如下方法制备:
步骤A:将可溶性金属M盐加入混合溶剂中,超声使其充分溶解,配制浓度为0.15-0.5mol/L的M盐溶液;再将硅酸盐加入去离子水中,超声使其完全溶解,配制浓度为0.15-2.0mol/L硅酸盐溶液;
所述的可溶性金属M盐为MgCl2、MgSO4、Mg(NO3)2、CaCl2、Ca(NO3)2的任意一种,所述硅酸盐为硅酸钠或硅酸钾,所述混合溶剂为有机醇与水的混合物,其中有机醇的体积含量为10-90%,所述有机醇为乙醇或丙醇。
步骤B:将步骤A中M盐溶液加入带磁力搅拌的容器,以700-900rpm转速下搅拌,再将硅酸盐溶液逐滴加入M盐溶液中,滴毕继续磁力搅拌4-8min得到混合盐溶液;其中硅酸盐溶液的滴加量按照滴完后溶液中M/硅比为1.0-2.0定量;
步骤C:将步骤B的混合盐浆液转入高压反应釜中,120-200℃反应12-24h,离心分离、水洗和醇洗滤出的固体物,于50-60℃的烘箱中干燥8-12h,研磨成粉即得所需的硅酸盐,其化学式为MxSiyOnH2z;其比表面积为100-500m2·g-1,孔容为0.3-1.0cm3·g-1;
步骤D:将MxSiyOnH2z粉末、快脱粉、造孔剂和助挤剂按下列百分数混合均匀
向上述混合粉体中加入占粉体质量50-60%的去离子水,继续搅拌均匀制成挤条湿粉,将挤条湿粉通过挤条机混捏3-4次后,挤出成型,后经蒸养、干燥、于450-550℃焙烧3-5h得到催化剂,表示为MxSiyOnH2z/γ-Al2O3;
所述造孔剂为纤维素、淀粉中的一种,粉与其他物料混合前,需要进行糊化;所述助挤剂为田菁粉、多元羟酸、无机酸中的一种;所述的脱粉是市售的晶型为ρ型氧化铝。
2.一种根据权利要求1所述的硅酸盐/氧化铝复合型再生催化剂,其特征是,催化剂中MxSiyOnH2z的质量百分含量为40-50wt%,催化剂的长度为10-30mm。
3.一种权利要求1所述的硅酸盐/氧化铝复合型再生催化剂的应用,该催化剂用于蒽醌法制过氧化氢生产过程工作液中蒽醌降解物的再生。
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