CN112371079A - 一种劣化油再生处理吸附剂及其制备方法 - Google Patents
一种劣化油再生处理吸附剂及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种劣化油再生处理吸附剂及其制备方法,以偏铝酸钠、硅溶胶、氧化稀土、硫酸和高岭土为主原料,先用偏铝酸钠和硅溶胶搅拌形成凝胶,然后缓慢滴入硫酸和氧化稀土的混合溶液,调节凝胶的PH值,将凝胶转入到不锈钢反应釜中动态晶化,出料后充分洗涤、过滤、烘干,研磨,过200目筛,得多孔吸附剂。称取一定质量的高岭土,通过硫酸进行酸化改性得到改性高岭土。将多孔吸附剂和改性高岭土混合均匀后焙烧得到吸附剂。本发明原料来源广泛且价格便宜,制备方法工艺简单、操作方便、成品率高。球形吸附剂的抗压强度可以达到10~12N/mm,劣化油的脱酸率可以达到80~90%,去除油泥效果明显。
Description
技术领域
本发明涉及电力用油再生处理吸附剂领域,具体涉及一种劣化油再生处理吸附剂及其制备方法。
背景技术
电力用油主要有变压器油、汽轮机润滑油和抗燃油等,是保障电力设备安全稳定运行的“血液”。油品在运行过程中受温度、氧气、水分、电场等多种因素的共同作用下会老化生成醛类、酮类、酚类、羧酸、低分子有机酸等溶于油中的氧化产物,一方面导致油品理化性能下降,进而降低电力设备的绝缘性能,增大设备的磨损;另一方面这些酸类物质会腐蚀电力设备的材料,严重危害设备的使用寿命。当油品劣化时需要进行再生处理,而吸附再生处理技术由于操作工艺简单,处理效果好,设备投资少、运行成本低等诸多优势,不仅能有效延长油品的使用周期,还可以实现资源的回收利用,节约生产成本,带来显著的经济效益和社会效益,被广泛应用于电力用油的处理中。吸附剂作为吸附处理技术的关键和核心,一直是研究的重点。
目前劣化油再生常用的吸附剂有活性白土、801吸附剂、活性氧化铝和硅胶等,这些吸附剂因不是劣化变压器油专用再生吸附剂,均存在使用量大、降介损、脱酸、脱色效果差等问题。随着新型吸附材料的不断涌现,使得替代型吸附剂的开发和应用成为油处理领域迫切需要解决的问题和未来发展的趋势。西安热工研究院研制的电力用油再生吸附剂(CN102908989A一种电力用油再生处理高性能微孔吸附剂及其制备方法)和(专利号CN103432983A一种电力用油再生处理微孔极性诱导吸附剂及其制备方法),处理效果好,但是生产工艺复杂,难以工业化生产,价格昂贵。孝感供电公司研制的变压器废油再生吸附剂(专利号CN101406824A一种处理变压器废油的吸附剂及其生产方法)生产工艺简单,处理效果较好,但形状为不规则块状,坚硬度较差,易破碎成粉末状,反而会污染油***。专利号CN101992059A公开了一种对废变压器油进行精制脱色的吸附剂,该发明使用硝酸银、硫酸铜、氯化铝做为还原体系,其使用比例需要根据废变压器油的污染情况进行调整,推广应用受限。专利号CN110465261A公开了一种对废变压器油进行回收再生吸附剂的制作工艺及应用,使用天然黏土为原料,通过配浆、分散、除杂后再加入碱性造孔剂形成纳米孔道,该发明生产工艺较难控制,尤其是碱性造孔剂的加入量较难掌握,容易造成孔道失效。
综上所述,目前劣化油再生常用的吸附剂均存在使用量大,吸附性能弱等缺点,需要一种结构稳定,粒度均匀,吸附能力强,脱酸、脱色效果明显的吸附剂,原料来源广泛且价格便宜,制备方法工艺简单、操作方便、结构稳定,能够大规模生产。
发明内容
为了解决上述技术存在的不足,本发明提供了一种劣化油再生处理吸附剂及其制备方法,本发明的吸附剂能够有效去除油品劣化产生的醛类、酮类、酚类、羧酸、低分子有机酸等溶于油中的氧化产物,降低变压器油的酸值,有效脱色和去除油泥沉淀物,从而全面恢复油品的各项理化指标。其制备方法简便、原料来源广泛、易于操作、成本费用低,成品率高,特别适合于工业化生产。
本发明还提供了使用上述制备方法制备得到的吸附剂,其具有粒径均匀、结构稳定、吸附效果好等优点。
为实现上述目的,本发明提供的技术方案是:
一种劣化油再生处理吸附剂,吸附剂的组成粒径尺寸分布在0.7~0.9μm,孔容为0.6~0.8ml/g;混合成型后为直径为1-2mm的颗粒形状,抗压强度为10~12N/mm;该吸附剂对劣化油的脱酸率达到80~90%,能够高效去除油泥。
该劣化油再生处理吸附剂的制备方法包括以下步骤:
步骤(1):制备多孔吸附剂
将偏铝酸钠溶于水中配制成50g/L的溶液,然后将其缓慢加入浓度为25%~30%硅溶胶中,搅拌2~3小时,浆液沉淀;然后缓慢滴入硫酸和氧化稀土的混合溶液,形成凝胶;调节凝胶的PH值,并搅拌均匀后,将凝胶转入到不锈钢反应釜中进行动态合成,其中转速:300r/min,晶化条件:50~80℃晶化24小时;出料后充分洗涤、过滤、烘干,研磨,过200目筛,得多孔吸附剂原粉;
步骤(2):制备改性高岭土
称取一定质量的高岭土于烧杯中,按液固质量比为5∶1加入浓度为8%的硫酸进行酸改性,在室温下搅拌2h,然后过滤、洗涤至中性;将酸改性后的高岭土在105℃烘干,研磨,过200目筛,得到改性高岭土;
步骤(3):制备成品吸附剂
将多孔吸附剂原粉与高岭土混合搅拌均匀,放在滚球机中,运转过程中喷淋硅溶胶溶液,成型过程中用直径1-2mm的双层筛子筛分球形颗粒,得到球形吸附剂,将其置于焙烧炉中200~400℃焙烧3小时,得到成品吸附剂。
步骤(1)中,调节凝胶的PH值为6-7。
步骤(1)中所述的氧化稀土为氧化镧、氧化铈、氧化镨、氧化钕、氧化钷、氧化钐、氧化铕中的一种或多种混合。
步骤(1)中配制1升氧化稀土和硫酸混合溶液的方法为:称取0.5g氧化稀土于烧杯中,缓慢加入10mL浓硫酸中,搅拌至氧化稀土完全溶解,然后缓慢加入到1升水中。
步骤(3)多孔吸附剂原粉与高岭土的混合物中,多孔吸附剂原粉与高岭土质量比为(7-8):(2-3)。
步骤(3)中喷淋浓度为10%~20%的硅溶胶溶液。
得到的球形吸附剂的直径为2mm。
与现有技术相比,本发明的有益效果是:
本发明的吸附剂中因引入了少量稀土,稀土元素的原子半径大又极易失掉外层的6s电子和5d或4f电子,在不等价离子取代中将会产生空位等缺陷,使内晶表面高度极化,从而提高了晶间的库伦力和静电吸附力,极大地改善了吸附剂的稳定性和吸附性能。
高岭土具有层链状结构,有较强的吸附能力和粘结力,且亲水疏油,本发明经过酸活化改性处理后,可疏通微孔,去除杂质,提高其活性基团的种类和数量,可很好地与有机物相容,能有效地吸附油品中的色素等杂质,吸附饱和后不容易破碎,是一种性能优异的吸附剂和脱色剂。
本发明的吸附剂的原料来源广泛且价格便宜,制备方法工艺简单、操作方便、结构稳定,能够大规模生产。本发明制备的球形吸附剂的抗压强度可以达到10~12N/mm,变压器油脱酸率可以达到80~90%,脱色、降介损效果明显。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某些实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。
图1为实施例2制备吸附剂的X射线衍射图。
图2为实施例2制备吸附剂的电镜照片。
具体实施方式
下面结合具体实施例对本发明作进一步详细的说明。以下实施例仅用于说明本发明而不用于限制本发明的范围。
本发明提供了上述吸附剂与801吸附剂、硅胶、活性氧化铝和13X分子筛再生变压器油性能对比试验,该吸附剂脱酸、脱色、降介损效果明显优于801吸附剂、硅胶、活性氧化铝和13X分子筛。
实施例1
多孔吸附剂的制备:
步骤1:将偏铝酸钠溶于水中配成50g/L的溶液,然后缓慢加入浓度25%~30%硅溶胶中,搅拌2~3小时浆液沉淀。
步骤2:称取0.5g氧化稀土于烧杯中,缓慢加入10mL浓硫酸中,搅拌至氧化稀土完全溶解,然后缓慢加入到1升水中,配制成氧化稀土和硫酸混合溶液,用其调节步骤1制得的凝胶的PH为6~7。
步骤3:将步骤2制得的凝胶放入不锈钢反应釜中,转速为300r/min,80℃下晶化24小时。出料后充分洗涤、过滤、烘干,研磨,过200目筛,得到多孔吸附剂。
改性高岭土的制备:
称取20g高岭土于烧杯中,加入200mL浓度为8%的硫酸,室温下搅拌2h,然后过滤、洗涤至中性,将酸改性后的高岭土在105℃烘干,研磨,过200目筛,即得到改性高岭土。
吸附剂成品的制备:
按照重量比9:1分别称取多孔吸附剂和改性高岭土,混合均匀后放入滚球机中,运转过程中喷淋10%~20%硅溶胶溶液,成型过程中用直径1-2mm的双层筛子筛分球形颗粒,最终得到直径2mm的球形吸附剂,将其置于焙烧炉200~400℃焙烧3小时得到成品,即为本发明的球形吸附剂。
实施例2
多孔吸附剂的制备:
步骤1:将偏铝酸钠溶于水中配成50g/L的溶液,然后缓慢加入浓度25%~30%硅溶胶中,搅拌2~3小时浆液沉淀。
步骤2:称取0.5g氧化稀土于烧杯中,缓慢加入10mL浓硫酸中,搅拌至氧化稀土完全溶解,然后缓慢加入到1升水中,配制成氧化稀土和硫酸混合溶液,用其调节步骤1制得的凝胶的PH为6~7。
步骤3:将步骤2制得的凝胶放入不锈钢反应釜中,转速为300r/min,80℃下晶化24小时。出料后充分洗涤、过滤、烘干,研磨,过200目筛,得多孔吸附剂。
改性高岭土的制备:
称取20g高岭土于烧杯中,加入200mL浓度为8%的硫酸,室温下搅拌2h,然后过滤、洗涤至中性,将酸改性后的高岭土在105℃烘干,研磨,过200目筛,即得到改性高岭土。
吸附剂成品的制备:
按重量比8:1称取多孔吸附剂和改性高岭土,混合均匀后放入滚球机中,运转过程中喷淋10%~20%硅溶胶溶液,成型过程中用直径1-2mm的双层筛子筛分球形颗粒,最终得到直径2mm的球形吸附剂,将其置于焙烧炉200~400℃焙烧3小时得到成品,即为本发明的球形吸附剂。
实施例3
多孔吸附剂的制备:
步骤1:将偏铝酸钠溶于水中配成50g/L的溶液,然后缓慢加入浓度25%~30%硅溶胶中,搅拌2~3小时浆液沉淀。
步骤2:称取0.5g氧化稀土于烧杯中,缓慢加入10mL浓硫酸,搅拌至氧化稀土完全溶解,然后缓慢加入到1升水中,配制成氧化稀土和硫酸混合溶液,用其调节步骤1制得的凝胶的PH为6~7。
步骤3:将步骤2制得的凝胶放入不锈钢反应釜中,转速为300r/min,80℃下晶化24小时。出料后充分洗涤、过滤、烘干,研磨,过200目筛,得多孔吸附剂。
改性高岭土的制备:
称取20g高岭土于烧杯中,加入200mL浓度为8%的硫酸,室温下搅拌2h,然后过滤、洗涤至中性,将酸改性后的高岭土在105℃烘干,研磨,过200目筛,即得到改性高岭土。
吸附剂成品的制备:
按照重量比7:1称取多孔吸附剂和改性高岭土,混合均匀后放入滚球机中,运转过程中喷淋10%~20%硅溶胶溶液,成型过程中用直径1-2mm的双层筛子筛分球形颗粒,最终得到直径2mm的球形吸附剂,将其置于焙烧炉200~400℃焙烧3小时得到成品,即为本发明的球形吸附剂。
吸附剂再生油品性能检测
选用801吸附剂、硅胶、活性氧化铝和13X分子筛与本发明实施例2的吸附剂进行劣化变压器油再生比对试验。油液再生试验采用接触法,即分别称取2克吸附剂加入500克劣化变压器油中,在55℃恒温水浴下搅拌1h,使吸附剂与油液充分接触以达到最佳吸附效果,吸附完成后将油液与吸附剂的混合物过滤分离,按照《GB/T 14542-2017变压器油维护管理导则》中规定的检测方法测定劣化变压器油和再生后油液的外状、水溶性酸、酸值、界面张力、介质损耗因数和体积电阻率。
表1劣化变压器油再生性能比对试验
选用801吸附剂、硅胶、活性氧化铝和13X分子筛与本发明实施例2的吸附剂进行劣化汽轮机油再生比对试验。油液再生试验采用接触法,即分别称取2克吸附剂加入500克劣化汽轮机油中,在55℃恒温水浴下搅拌1h,使吸附剂与油液充分接触以达到最佳吸附效果,吸附完成后将油液与吸附剂的混合物过滤分离,按照《GB/T 14541-2017电厂用矿物涡轮机油维护管理导则》中规定的检测方法测定劣化汽轮机油和再生后油液的外状、酸值、破乳化度。
表2劣化汽轮机油再生性能比对试验
选用801吸附剂、硅胶、活性氧化铝和13X分子筛与本发明实施例2的吸附剂进行劣化抗燃油再生比对试验。油液再生试验采用接触法,即分别称取2克吸附剂加入500克劣化抗燃油中,在55℃恒温水浴下搅拌1h,使吸附剂与油液充分接触以达到最佳吸附效果,吸附完成后将油液与吸附剂的混合物过滤分离,按照《DLT 571-2014电厂用磷酸酯抗燃油运行维护导则》中规定的检测方法测定劣化抗燃油和再生后油液的外状、酸值、体积电阻率。
表3劣化抗燃油再生性能比对试验
由表1-3可见,本发明的吸附剂具有优良的脱色、脱酸、去除油泥的吸附能力,可以大幅提升劣化油的理化性能,其吸附性能优于801吸附剂、硅胶、活性氧化铝和13X分子筛。
以上所述,仅是本发明的较佳实施例,并非对本发明作任何形式上的限制,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,依据本发明的技术实质,对以上实施例所作的任何简单的修改、等同替换与改进等,均仍属于本发明技术方案的保护范围之内。
Claims (8)
1.一种劣化油再生处理吸附剂,其特征在于:吸附剂的组成粒径尺寸分布在0.7~0.9μm,孔容为0.6~0.8ml/g;混合成型后为直径为1-2mm的颗粒形状,抗压强度为10~12N/mm;该吸附剂对劣化油的脱酸率达到80~90%,能够高效去除油泥。
2.权利要求1所述的劣化油再生处理吸附剂的制备方法,其特征在于:包括以下步骤:
步骤(1):制备多孔吸附剂
将偏铝酸钠溶于水中配制成50g/L的溶液,然后将其缓慢加入浓度为25%~30%硅溶胶中,搅拌2~3小时,浆液沉淀;然后缓慢滴入硫酸和氧化稀土的混合溶液,形成凝胶;调节凝胶的PH值,并搅拌均匀后,将凝胶转入到不锈钢反应釜中进行动态合成,其中转速:300r/min,晶化条件:50~80℃晶化24小时;出料后充分洗涤、过滤、烘干,研磨,过200目筛,得多孔吸附剂原粉;
步骤(2):制备改性高岭土
称取一定质量的高岭土于烧杯中,按液固质量比为5∶1加入浓度为8%的硫酸进行酸改性,在室温下搅拌2h,然后过滤、洗涤至中性;将酸改性后的高岭土在105℃烘干,研磨,过200目筛,得到改性高岭土;
步骤(3):制备成品吸附剂
将多孔吸附剂原粉与高岭土混合搅拌均匀,放在滚球机中,运转过程中喷淋硅溶胶溶液,成型过程中用直径1-2mm的双层筛子筛分球形颗粒,得到球形吸附剂,将其置于焙烧炉中200~400℃焙烧3小时,得到成品吸附剂。
3.根据权利要求2所述的劣化油再生处理吸附剂的制备方法,其特征在于:步骤(1)中,调节凝胶的PH值为6-7。
4.根据权利要求2所述的劣化油再生处理吸附剂的制备方法,其特征在于:步骤(1)中所述的氧化稀土为氧化镧、氧化铈、氧化镨、氧化钕、氧化钷、氧化钐、氧化铕中的一种或多种混合。
5.根据权利要求2所述的劣化油再生处理吸附剂的制备方法,其特征在于:步骤(1)中配制1升氧化稀土和硫酸混合溶液的方法为:称取0.5g氧化稀土于烧杯中,缓慢加入10mL浓硫酸中,搅拌至氧化稀土完全溶解,然后缓慢加入到1升水中。
6.根据权利要求2所述的劣化油再生处理吸附剂的制备方法,其特征在于:步骤(3)多孔吸附剂原粉与高岭土的混合物中,多孔吸附剂原粉与高岭土质量比为(7-8):(2-3)。
7.根据权利要求2所述的劣化油再生处理吸附剂的制备方法,其特征在于:步骤(3)中喷淋浓度为10%~20%的硅溶胶溶液。
8.根据权利要求2所述的劣化油再生处理吸附剂的制备方法,其特征在于:得到的球形吸附剂的直径为2mm。
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Cited By (4)
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CN114700029A (zh) * | 2022-05-19 | 2022-07-05 | 青岛惠城环保科技股份有限公司 | 一种抗燃油吸附再生剂的制备方法 |
CN114700030A (zh) * | 2022-05-19 | 2022-07-05 | 青岛惠城环保科技股份有限公司 | 一种抗燃油吸附再生剂的制备方法 |
CN114700029B (zh) * | 2022-05-19 | 2023-12-12 | 青岛惠城环保科技集团股份有限公司 | 一种抗燃油吸附再生剂的制备方法 |
CN114700030B (zh) * | 2022-05-19 | 2024-05-28 | 青岛惠城环保科技集团股份有限公司 | 一种抗燃油吸附再生剂的制备方法 |
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