CN106902892B - 一种SiO2-C改性Al2O3载体及制备方法和应用 - Google Patents
一种SiO2-C改性Al2O3载体及制备方法和应用 Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 45
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
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Abstract
一种SiO2‑C改性Al2O3载体包括SiO2,C,Al2O3,其中SiO2重量与C重量分别是Al2O3重量的0.7wt%~15wt%与0.05wt%~7wt%;孔容0.5mL/g~1.1mL/g,比表面积180m2/g~270m2/g,平均孔径5nm~13nm。本发明具有良好的热稳定性,高的机械强度,适宜的表面酸碱性质,制备简单的优点。
Description
技术领域
本发明属于一种载体及制备方法,具体涉及一种SiO2-C改性Al2O3载体及制备方法和应用。
背景技术
炔醛法合成1,4-丁二醇加氢催化剂一般选用以氧化铝为载体的负载镍催化剂。近年来的研究发现,由于炔醛法合成1,4-丁二醇所采用的1,4-丁炔二醇原料是以水为溶剂,加氢反应过程是一个水热条件下的反应,长期的反应过程中,氧化铝载体易出现水合脱结构问题,最终造成催化剂的不可逆失活。CN101322949报道了通过在Al2O3表面浸渍法引入硅的可溶性前驱物,经干燥、焙烧后制备SiO2改性Al2O3载体及催化剂的方法,该载体及催化剂中SiO2的存在有效提高了载体氧化铝的水热稳定性,延长了催化剂使用寿命;同时,使催化剂的表面酸性得到了有效调控,可有效地将物料中的环状缩醛2-(4′-羟基丁氧基)-四氢呋喃水解、加氢转化,在一定程度上提高了催化剂的加氢活性。然而,该Al2O3载体表面的SiO2呈现聚集状态,使负载的活性组分易于聚集。 CN102145286,进一步在SiO2改性的Al2O3载体中,以浸渍-沉积法,利用载体孔结构中尿素的水解,使镍物种原位沉积到载体的孔内表面,提高了活性组分的分散度,使催化剂的加氢活性进一步提高。但该制备过程较为复杂,催化剂放大过程中许多条件难以控制。
发明内容
本发明的目的在于提供一种良好的水热稳定性,适宜的表面酸碱性质,制备简单的SiO2-C改性Al2O3载体及制备方法和应用。
本发明SiO2-C改性Al2O3载体包括SiO2,C,Al2O3,其中SiO2重量与C 重量分别是Al2O3重量的0.7wt%~15wt%与0.05wt%~7wt%;孔容0.5 mL/g~1.1mL/g,比表面积180m2/g~270m2/g,平均孔径5nm~13nm。
本发明提供的SiO2-C改性Al2O3载体的制备方法,包括以下步骤:
(1)将氧化铝在120℃~200℃条件下,水蒸汽处理0.5h~2h,之后 30℃~50℃抽真空干燥1h~5h;
(2)称取有机炭源及可溶性硅前驱物,溶解于含水体积分数1%~10%的醇-水体系中,配制成混合溶液,并向其中加入有机酸调节溶液pH值在3~ 5;
(3)将步骤(2)配制的混合溶液加入到步骤(1)所述的物料中,密闭静置1h~5h,在温度70℃~200℃下干燥2h~15h;
(4)将步骤(3)所得物料在温度450℃~750℃下,H2/N2混合气氛焙烧1h~8h,得SiO2-C改性Al2O3载体。
所述步骤(2)中所称取的有机炭源的重量、可溶性硅前驱物中SiO2的重量,分别为步骤(1)中所述氧化铝重量的0.1wt%~12wt%与0.7wt%~15 wt%。
所述步骤(2)中所配制混合溶液,按每克步骤(1)中所述氧化铝,配制0.5mL~1.2mL混合溶液计算。
所述步骤(2)中可溶性硅前驱物选自正硅酸甲酯、正硅酸乙酯中的一种。
所述步骤(2)中有机炭源为蔗糖、葡萄糖、聚乙二醇中的一种。
所述步骤(2)中醇为甲醇、乙醇、丙醇、丁醇中的一种。
所述步骤(2)所述的有机酸为甲酸、冰醋酸、柠檬酸中的一种。
所述步骤(4)H2/N2混合气氛中,H2体积分数为5%~55%。
本发明SiO2-C改性Al2O3载体的应用如下:
以可溶性镍盐的水溶液为浸渍液,SiO2-C改性Al2O3为载体,按每100g 载体取43.08g~165.13g六水合硝酸镍的量配制成80mL~110mL水溶液,将溶液浸渍到载体中,经110℃~130℃干燥3h~5h,在氮气、氩气或氦气气氛下,以1℃/分~10℃/分的升温速率升高到500℃~550℃,焙烧3h~5h, 450℃~550℃氢气氛还原3h~5h,得到Ni负载量为8wt%~25wt%的 Ni/SiO2-C/Al2O3催化剂。
本发明制备的催化剂用于炔醛法合成1,4-丁二醇加氢,(1)适用于固定床反应器,原料为1,4-丁炔二醇水溶液经低温、低压预加氢后含25wt%~30 wt%的1,4-丁二醇的水溶液(该溶液羰基值在7mg(KOH)/g~20mg(KOH)/g,含1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)- 四氢呋喃等杂质),进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h。(2)也可适用于原料为含 25wt%~35wt%的1,4-丁炔二醇的水溶液的直接加氢转化,采用外循环加氢反应工艺,进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h,循环比18~22:1。两种工艺加氢后的物料有机相中1,4-丁二醇含量≥96wt%,副产物丁醇含量≤1.2wt%,不饱和生色物质1,4-丁炔二醇、1,4-丁炔二醇、4-羟基丁醛、半缩醛及缩醛2-(4′- 羟基丁氧基)-四氢呋喃等总含量≤0.2wt%,其余为大分子聚合物,该物料羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。经精馏可得到产品纯度:99.6wt%~99.8 wt%;羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g;色度:≤5APHA。加氢催化剂的使用寿命达15-18个月。
本发明所具有的优点是:
1、在所述载体的制备方法中,首先对氧化铝载体进行水蒸汽处理,使氧化铝表面具有发达的表面羟基;同时,严格控制了含硅前驱物溶液的水含量以及pH,可以显著调变硅前驱物的水解速率。在初始的硅前驱物溶液中,硅前驱物以单分子形式存在,具有较小的分子尺寸,该溶液与氧化铝载体接触,硅前驱物分子可容易的扩散进入氧化铝的孔道结构。在孔道中,少量水的存在以及酸的催化作用下,硅前驱物开始水解,并可优先与氧化铝表面的羟基发生发应,与Al2O3形成Si-O-Al键。氧化铝表面丰富的羟基中心成为硅水解优先发生的位点,孔道中的硅逐渐水解,在氧化铝孔道的内表面形成均一的氧化硅层。这样的结构不仅使Al2O3的抗水合性能大幅提高,使其具有了优异的水热稳定性,起到了延长催化剂使用寿命的作用;同时,使载体具有了适宜的表面酸性质,该酸性质在负载活性组分后的催化剂中得到有效保持,与加氢活性中心的协同作用促进了缩醛类物质的水解、加氢转化,有效提高了加氢产品的品质。
2、在上述引入SiO2的溶液中含有有机炭源,如蔗糖、葡萄糖、聚乙二醇,经干燥处理后这些有机炭存在于载体的孔道结构中,之后采用H2/N2混合气氛焙烧时,有机物分解后在孔道内表面残留炭物种。这些炭物种主要存在于载体表面的缺陷结构中,一方面有效调变了载体的亲疏水性,使反应物在孔道内表面优先吸附,加快了反应速率,同时抑制了水对氧化铝的进攻,进一步提高了其抗水合性能;另一方面,炭物种提高了活性组分的分散度、降低了催化剂的还原温度,并起到了稳定活性组分的作用。
3、由于本发明所制备的SiO2-C改性Al2O3载体具有独特的表面性质,能够在保证活性组分具有较高分散度的前提下有效地降低活性组分和载体之间的相互作用,促进活性组分的还原,从而使催化剂中的活性组分具有较高的加氢活性。载体同时表现为适宜的表面酸性质,可与高分散的金属活性中心协同作用,使催化剂具有优异的水解、加氢活性。使其在用于炔醛法合成1,4- 丁二醇加氢催化剂载体时表现出高的活性、选择性及好的使用稳定性。
具体实施方式
实施例1
取100g氧化铝载体,在120℃条件下水蒸汽处理0.5h,后30℃抽真空干燥1h;称取1.79g正硅酸甲酯(含SiO2重量0.7g),及0.1g的蔗糖,溶解于含水体积分数1%的甲醇-水体系中,配制成50mL的混合溶液,并向其中加入甲酸调节溶液pH值在3;将配制的混合溶液加入到经水蒸汽处理的100g 氧化铝载体中,密闭静置1h,在温度70℃下干燥2h;在温度450℃下,H2体积分数为5%的H2/N2混合气氛焙烧1h,得SiO2-C改性Al2O3载体,该载体中含氧化铝重量100g,SiO2质量0.7g,C质量0.05g,孔容1.1mL/g,比表面积270m2/g,平均孔径13nm。
称取上述SiO2-C/Al2O3载体100g,称43.08g六水合硝酸镍,配制成80mL 浸渍液,加入到载体中,110℃干燥5h,氮气气氛下,以2℃/min的升温速率升到500℃,焙烧3h,后在氢气气氛下500℃还原3h,得到Ni负载量为 8wt%的Ni/SiO2-C/Al2O3催化剂。
实施例2
取100g氧化铝载体,在200℃条件下水蒸汽处理2h,后50℃抽真空干燥5h;称取53.57g正硅酸乙酯(含SiO2重量15g),及12g的葡萄糖,溶解于含水体积分数10%的乙醇-水体系中,配制成120mL的混合溶液,并向其中加入冰醋酸调节溶液pH值在5;将配制的混合溶液加入到经水蒸汽处理的 100g氧化铝载体中,密闭静置5h,在温度200℃下干燥15h;在温度750℃下,H2体积分数为55%的H2/N2混合气氛焙烧8h,得SiO2-C改性Al2O3载体,该载体中含氧化铝重量100g,SiO2质量15g,C质量7g,孔容0.5mL/g,比表面积180m2/g,平均孔径5nm。
称取上述SiO2-C/Al2O3载体100g,称67.55g六水合硝酸镍,配制成90mL 浸渍液,加入到载体中,120℃干燥5h,氦气气氛下,以10℃/min的升温速率升到550℃,焙烧3h,后在氢气气氛下450℃还原3h,得到Ni负载量为 12wt%的Ni/SiO2-C/Al2O3催化剂。
实施例3
取100g氧化铝载体,在160℃条件下水蒸汽处理1h,后40℃抽真空干燥3h;称取17.86g正硅酸乙酯(含SiO2重量5g),及3g的聚乙二醇,溶解于含水体积分数5%的丙醇-水体系中,配制成80mL的混合溶液,并向其中加入柠檬酸调节溶液pH值在4;将配制的混合溶液加入到经水蒸汽处理的100 g氧化铝载体中,密闭静置3h,在温度140℃下干燥10h;在温度600℃下, H2体积分数为40%的H2/N2混合气氛焙烧5h,得SiO2-C改性Al2O3载体,该载体中含氧化铝重量100g,SiO2质量5g,C质量1.5g,孔容0.8mL/g,比表面积220m2/g,平均孔径9nm。
称取上述SiO2-C/Al2O3载体100g,称108.75g六水合硝酸镍,配制成100 mL浸渍液,加入到载体中,130℃干燥3h,氩气气氛下,以1℃/min的升温速率升到500℃,焙烧5h,后在氢气气氛下550℃还原3h,得到Ni负载量为18wt%的Ni/SiO2-C/Al2O3催化剂。
实施例4
取100g氧化铝载体,在180℃条件下水蒸汽处理1.5h,后50℃抽真空干燥5h;称取35.71g正硅酸乙酯(含SiO2重量10g),及8g的蔗糖,溶解于含水体积分数8%的丁醇-水体系中,配制成100mL的混合溶液,并向其中加入冰醋酸调节溶液pH值在4.5;将配制的混合溶液加入到经水蒸汽处理的 100g氧化铝载体中,密闭静置5h,在温度180℃下干燥10h;在温度550℃下,H2体积分数为15%的H2/N2混合气氛焙烧5h,得SiO2-C改性Al2O3载体,该载体中含氧化铝重量100g,SiO2质量10g,C质量4.1g,孔容0.7mL/g,比表面积200m2/g,平均孔径7nm。
称取上述SiO2-C/Al2O3载体100g,称165.13g六水合硝酸镍,配制成110 mL浸渍液,加入到载体中,120℃干燥3h,氮气气氛下,以5℃/min的升温速率升到530℃,焙烧4h,后在氢气气氛下530℃还原5h,得到Ni负载量为25wt%的Ni/SiO2-C/Al2O3催化剂。
实施例5
取100g氧化铝载体,在130℃条件下水蒸汽处理1h,后40℃抽真空干燥4h;称取20.51g正硅酸甲酯(含SiO2重量8g),及6g的葡萄糖,溶解于含水体积分数6%的甲醇-水体系中,配制成80mL的混合溶液,并向其中加入甲酸调节溶液pH值在4;将配制的混合溶液加入到经水蒸汽处理的100g 氧化铝载体中,密闭静置4h,在温度130℃下干燥7h;在温度700℃下, H2体积分数为35%的H2/N2混合气氛焙烧6h,得SiO2-C改性Al2O3载体,该载体中含氧化铝重量100g,SiO2质量8g,C质量3g,孔容0.9mL/g,比表面积260m2/g,平均孔径9nm。
称取上述SiO2-C/Al2O3载体100g,称43.08g六水合硝酸镍,配制成100 mL浸渍液,加入到载体中,110℃干燥4h,氩气气氛下,以7℃/min的升温速率升到520℃,焙烧5h,后在氢气气氛下480℃还原4h,得到Ni负载量为8wt%的Ni/SiO2-C/Al2O3催化剂。
实施例6
取上述1-5号载体制备的催化剂分别标记为1-5#及现有的商品催化剂 (生产厂家:Degussa OctolystTM 1003)(标记为6#),(1)在固定床反应器上,以1,4-丁炔二醇水溶液经低温、低压预加氢后含25wt%~30wt%的1,4-丁二醇水溶液(该溶液羰基值在7mg(KOH)/g~20mg(KOH)/g,含1,4-丁炔二醇、 1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等杂质) 为原料,进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h。具体的反应条件及结果见表1。
(2)或以含25wt%~35wt%的1,4-丁炔二醇水溶液为原料,采用外循环加氢反应工艺,进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h,循环比18~22:1。具体的反应条件及结果见表2。
两种工艺加氢后的物料有机相中1,4-丁二醇含量≥96wt%,副产物丁醇含量≤1.2wt%,不饱和生色物质1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等总含量≤0.2wt%,其余为大分子聚合物,该物料羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。经精馏可得到产品纯度:99.6wt%~99.8wt%;羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g;色度:≤5APHA。加氢催化剂的使用寿命达15-18个月。
表1
表2
Claims (8)
1.一种SiO2-C改性Al2O3载体的制备方法,该SiO2-C改性Al2O3载体包括SiO2,C,Al2O3,其中SiO2重量与C重量分别是Al2O3重量的0.7wt%~15wt%与0.05wt%~7wt%;孔容0.5mL/g~1.1mL/g,比表面积180m2/g~270m2/g,平均孔径5nm~13nm,其特征在于包括以下步骤:
(1)将氧化铝在120℃~200℃条件下,水蒸汽处理0.5h~2h,之后30℃~50℃抽真空干燥1h~5h;
(2)称取有机炭源及可溶性硅前驱物,溶解于含水体积分数1%~10%的醇-水体系中,配制成混合溶液,并向其中加入有机酸调节溶液pH值在3~5;
(3)将步骤(2)配制的混合溶液加入到步骤(1)的物料中,密闭静置1h~5h,在温度70℃~200℃下干燥2h~15h;
(4)将步骤(3)所得物料在温度450℃~750℃下,H2/N2混合气氛焙烧1h~8h,得SiO2-C改性Al2O3载体。
2.如权利要求1所述的一种SiO2-C改性Al2O3载体的制备方法,其特征在于步骤(2)中所称取的有机炭源的重量、可溶性硅前驱物中SiO2的重量,分别为步骤(1)中所述氧化铝重量的0.1wt%~12wt%与0.7wt%~15wt%。
3.如权利要求1所述的一种SiO2-C改性Al2O3载体的制备方法,其特征在于步骤(2)中所配制混合溶液,按每克步骤(1)中所述氧化铝,配制0.5mL~1.2mL混合溶液计算。
4.如权利要求1所述的一种SiO2-C改性Al2O3载体的制备方法,其特征在于步骤(2)中可溶性硅前驱物选自正硅酸甲酯、正硅酸乙酯中的一种。
5.如权利要求1所述的一种SiO2-C改性Al2O3载体的制备方法,其特征在于步骤(2)中有机炭源为蔗糖、葡萄糖、聚乙二醇中的一种。
6.如权利要求1所述的一种SiO2-C改性Al2O3载体的制备方法,其特征在于步骤(2)中醇为甲醇、乙醇、丙醇、丁醇中的一种。
7.如权利要求1所述的一种SiO2-C改性Al2O3载体的制备方法,其特征在于步骤(2)所述的有机酸为甲酸、冰醋酸、柠檬酸中的一种。
8.如权利要求1所述的一种SiO2-C改性Al2O3载体的制备方法,其特征在于步骤(4)H2/N2混合气氛中,H2体积分数为5%~55%。
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CN102049270A (zh) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | 一种汽油选择性加氢催化剂及其制备方法 |
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