CN106861636B - 一种用于燃料油品精制的金属有机配位聚合物吸附剂及再生方法 - Google Patents
一种用于燃料油品精制的金属有机配位聚合物吸附剂及再生方法 Download PDFInfo
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- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
本发明公开了一种用于燃料油品精制的金属有机配位聚合物吸附剂，其中所述的金属有机配位聚合物吸附剂为经过铜离子替换改性的由锌离子和对苯二甲酸分别为中心离子和有机配体，通过八面体形式连接而成的三维立体多孔金属有机配位聚合物材料。该吸附剂用于吸附脱除燃料油品中的非碱性氮化物，该吸附剂吸附饱和后采用氮气热吹扫方式进行再生，与其他吸附剂相比，该吸附剂具有再生温度低，大大降低了能耗，减少了再生设备的投资。该方法可用于燃料油品的深度脱除非碱性氮化物，为清洁油品的生产提供了一种制备简单、易再生，低能耗的清洁环保的油品精制方法。
Description
技术领域
本发明属于石油产品加工技术领域，涉及一种吸附脱除轻质燃料油品中碱性含氮化合物的非加氢脱氮方法，提供了一种制备简单、易再生，低能耗的超清洁低氮含量油品的生产方法。
背景技术
近些年，随着环保要求的日益严格及汽车业的不断发展，人们对油品的清洁度要求越来越高。然而，研究表明，我国原油的密度呈上升趋势，原油日趋重质化、劣质化。这使得原油加工困难重重，首先是轻质油品(汽油、煤油、柴油)收率下降，其次是轻质油品质量变差，成品油颜色加深，安定性变差。造成油品劣质化的主要原因之一是石油产品中含氮化合物的存在。含氮化合物的存在对油品安定性和抗氧化性的影响极为严重，对油品的颜色和胶质的生成也影响很大，是成胶的主要因素之一。含氮化合物还会引起催化剂结焦，导致催化剂失活，主要是通过与含硫化合物在催化剂表面的竞争吸附，强烈抑制深度加氢脱硫催化剂活性，尤其是碱性含氮化合物，不仅影响深度脱氮，还对深度脱硫、脱芳有明显的抑制作用。另外，石油产品中的有机氮化物在燃烧过程中会产生腐蚀性很强的酸性气体，以氮氧化物NOX的形式排入大气，造成空气污染，形成酸雨，给公众健康和生态环境带来严重的威胁。
深度加氢脱氮技术耗氢量大、设备投资大、成本高。随着人们对燃料清洁度要求的不断提高，脱氮工艺越来越向着经济、绿色、环保的方向发展，开发新思路的环保经济的吸附脱氮技术很有必要。
发明内容
本发明公开了一种用于燃料油品精制的金属有机配位聚合物吸附剂，其中所述的金属有机配位聚合物吸附剂为经过铜离子替换改性的由锌离子和对苯二甲酸分别为中心离子和有机配体，通过八面体形式连接而成的三维立体多孔金属有机配位聚合物材料，此吸附剂具有制备简单、不溶于油品、易于使用和再生、再生能耗低等特征。该方法可用于燃料油品的深度脱除非碱性氮化物，为清洁油品的生产提供了一种制备简单、易再生，低能耗的清洁环保的油品精制方法。
本发明的吸附剂可以用于超低氮含量轻质油品，吸附饱和后采用氮气热吹扫方式进行再生，该吸附剂相比其他吸附剂具有再生温度低，大大降低了能耗，减少了再生设备的投资。因此本吸附剂具有较大的工业优势和环境保护意义。
本发明所述的燃料油品脱氮吸附剂制备、使用和再生方法如下：
脱氮吸附剂的制备：
取一定量的六水合硝酸锌和对苯二甲酸溶于一定量的DMF中，在20～40℃搅拌30～60分钟，然后加入一定比例的硝酸铜搅拌至溶解。然后将澄清液倒入水热反应釜中，在烘箱中反应24h，反应温度为130℃。反应完毕后，水热反应釜自然冷却至室温。将沉淀用DMF和CH2Cl2冲洗、浸泡，干燥后即得到脱氮吸附剂。
燃料油品脱氮过程：
(1)将一定质量的脱氮吸附剂加入到一定量的燃料油品中，在一定温度下搅拌一定时间后，过滤分离，回收脱氮剂，循环使用。
(2)步骤(1)脱氮过程中，剂油质量比为4:1～1:40，。
(3)步骤(1)中，搅拌时间为5～300min，温度为20～80℃。
脱氮吸附剂再生方法：
(1)将吸附剂取出，离心去除残留油品，置于再生器中。
(2)使用氮气吹扫进行再生，再生气体空速为2-50h-1。
(3)将再生器升温，再生器温度为120-280℃，再生时间为30-180min。
本发明的优点：
本发明的吸附剂用于生产超低氮含量清洁燃料油品，吸附剂充分利用金属有机配位聚合物材料的高比表面和空隙的性质，在保留由锌离子和对苯二甲酸构成的金属有机配位聚合物材料较好的稳定性的基础上，通过铜离子部分替换改性得到的多孔金属有机框架材料具有更高的空隙率和提高氮化物吸附位点，因此该吸附剂具有制备简单、脱氮效果好的特点。
吸附饱和后采用氮气热吹扫方式进行再生，该吸附剂相比其他吸附剂具有再生温度低，大大降低了能耗，降低了再生设备的投资。因此本吸附剂具有较大的工业优势，为生产清洁油品提供一种新颖、低成本、操作简单、易再生、再生能耗低的吸附剂。
附图说明
图1为以混合氮化物(吡咯、吲哚和咔唑)的正庚烷溶液(氮含量为122μg·g-1)为模型化合物，在同一条件下(剂油质量比为1：10、25℃恒温搅拌60min)对比含10％铜离子的金属有机配位聚合物材料吸附剂和不含金属铜离子的金属有机配位聚合物材料吸附剂的脱除效果。1为铜离子改性的金属有机配位聚合物吸附剂，2为未经铜离子改性的金属有机配位聚合物吸附剂。
具体实施方案：
实施例1：
在含吡咯氮为120μg·g-1的油品中，按照剂油质量比为1：20的比例加入含铜离子10％的吸附脱氮剂，25℃恒温搅拌40min后，含氮化合物脱除率为74.8％。吸附饱和后经过氮气140℃吹扫60min再生后，进行吸附脱除氮化物实验，氮化物脱除率为67.2％。
实施例2：
在含吲哚氮为110μg·g-1的油品中，按照剂油质量比为1：10的比例加入含铜离子8％的吸附脱氮剂，35℃恒温搅拌30min后，含氮化合物脱除率为70.5％。吸附饱和后经过氮气200℃吹扫80min再生后，进行吸附脱除氮化物实验，氮化物脱除率为65.2％。
实施例3：
对某石化企业的石脑油进行碱性氮脱除之后的油品进行非碱性氮吸附脱除实验。非碱性氮含量为63.3μg·g-1，按照剂油质量比为1：10的比例加入含铜离子6％的吸附脱氮剂，25℃恒温搅拌60min后，含氮化合物氮脱除率为77.8％。吸附饱和后经过氮气180℃吹扫100min再生后，进行吸附脱除氮化物实验，氮化物脱除率为70.2％，再生效果良好。
对比实施例1：
以混合氮化物(吡咯、吲哚和咔唑)的正庚烷溶液(氮含量为122μg·g-1)为模型化合物，在同一条件下(剂油质量比为1：10、25℃恒温搅拌60min)对比含铜离子10％的金属有机配位聚合物材料吸附剂和不含金属铜离子的金属有机配位聚合物材料吸附剂的脱除效果，结果见图1。
从图1可以看出，本发明的离子替换改性金属有机配位聚合物吸附脱氮剂相比没有改性的金属有机配位聚合物材料具有更好的脱氮效果。
显然，上述的实施例仅仅是为了清楚的说明所作的举例，而非对吸附剂全部使用和再生方法。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或变动。这里无需与无法对所用的实施方式予以穷举。而由此所引伸出的显而易见的的变化或变动仍处于本发明创造的保护范围之中。
Claims (2)
1.一种用于燃料油品精制的金属有机配位聚合物吸附剂的制备方法，其特征在于： 取一定量的六水合硝酸锌和对苯二甲酸溶于一定量的 DMF 中，在20～40℃搅拌30~60分钟，然后加入一定比例的硝酸铜搅拌至溶解，然后将澄清液倒入水热反应釜中，在烘箱中反应24h，反应温度为130℃，反应完毕后，自然冷却至室温，将沉淀用DMF 和CH2Cl2 冲洗、浸泡，干燥后即得到经过铜离子替换改性的三维立体多孔金属有机配位聚合物吸附剂。
2.根据权利要求1所述的金属有机配位聚合物吸附剂的制备方法，其特征在于所述的铜离子替换改性中离子添加量为2%-30%。
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