CN114160104A - 一种窑炉烟气co2捕集与利用耦合材料及其应用 - Google Patents
一种窑炉烟气co2捕集与利用耦合材料及其应用 Download PDFInfo
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Abstract
本发明公开了一种窑炉烟气CO2捕集与利用耦合材料及其应用，包括以下步骤：以氯化锆(ZrCl4)和对苯二甲酸(H2BDC)为原料，在DMF溶剂进行溶剂热反应，制备UiO‑66；然后以UiO‑66材料为载体，采用真空浸渍法负载K、Cu、Zn和Fe等组分，经干燥、煅烧和H2还原处理，得到高分散的KCuFeZn/UiO‑66耦合材料。本发明具有如下优势：（1）耦合材料由载体、CO2吸附活性位点和催化活性位点构成，具有良好的CO2捕集和催化加氢制甲醇两个功能；（2）CO2吸附活性位点K2CO3对CO2分子具有较高的吸附量和选择性，其吸附产物KHCO3的解吸CO2的温度约为170℃‑350℃，与催化加氢制乙醇的温度窗口重合；（3）耦合材料由载体UiO‑66不仅具有超高的比表面积和孔体积用于分散其他组分，其金属配位中心Zr也是CO2加氢反应的活化中心。
Description
技术领域
本发明属于烟气碳捕集与利用领域，特别涉及一种窑炉烟气CO2捕集与利用耦合材料及其应用。
背景技术
全球气候变暖和环境问题日益严峻，据统计分析，每生产1吨水泥熟料产生的CO2超过0.8吨，我国CO2年排放量多年连续超过100亿吨，水泥行业CO2排放仅次于电力行业，约占全国排放总量的15 %。近年来，随着人类对CO2温室气体的关注，碳捕集与利用技术开发成为研究热点，在石化、火电行业已有较多的研究，但在水泥行业发展缓慢。水泥工业烟气CO2排放来源于碳酸盐分解和燃料燃烧，按照窑炉行业排放标准，经过治理后的烟气SO2、NOx和颗粒物等污染物浓度较火力发电较高，易造成捕集材料和催化剂失效。因此，研发水泥炉窑烟气CO2捕集与利用技术对实现我国碳减排具有重要的现实意义。针对CO2分子特性，将其选择性地捕获与催化加氢，在减少碳排放的同时也将富集的CO2转化为燃料，具有重要的能源、环境和经济效益。
国内外在CO2捕集和CO2利用两个领域均有广泛的研究，主要针对的火力发电和工业生产中排放的CO2。碳捕集技术可以分为溶剂吸收法、吸附法、膜分离法和深冷分离法等。目前CO2减排技术尚处于研究和工业示范阶段，使用最多的是化学吸收法，该法虽技术成熟，吸收率高，但很多运行中的固有问题始终存在，包括设备腐蚀、溶剂降解、需大量外供热能用于溶剂再生等。此外，水泥烟气中颗粒物的成分以CaO、CaCO3和SiO2为主，颗粒物会引起设备结垢、产品不纯等问题。与吸收法相比，吸附法能耗低、操作简单。在CO2利用技术中，催化加氢制化学品是实现CO2资源化利用的有效途径。其中，乙醇是一种理想产品，既可作为清洁燃料，也是燃料添加剂。2017年，十五部委联合印发《关于扩大生物燃料乙醇生产和推广使用车用乙醇汽油的实施方案》，乙醇的需求量大幅度提高，为CO2加氢制乙醇提供了巨大的开发前景。
发明内容
目前尚未开展针对炉窑烟气CO2捕集与利用耦合技术的研究，实现CO2捕集和转化连续生产工艺未见报道。若能制备出一种同时具有CO2吸附和催化加氢转化的耦合材料用于窑炉烟气的CO2捕集与利用，则为工业窑炉行业碳达峰、推进碳中和工作提供一条新思路。同时通过CO2催化加氢制备乙醇，提供了新的再生能源，实现碳的有效循环，势必产生巨大的经济效益和社会效应，成为窑炉烟气CO2减排和利用的主要方向，本发明将对技术创造提供新的研究路径。
针对现有技术的不足，本发明提供了一种窑炉烟气CO2捕集与利用耦合材料及其应用，以实现在窑炉烟气CO2吸附与催化加氢制乙醇一体化，在碳减排的同时产生能源和经济效益。
为解决现有技术问题，本发明采用的技术方案：
一种窑炉烟气CO2捕集与利用耦合材料，其为KCuFeZn/UiO-66耦合材料， UiO-66:K: Cu: Zn: Fe（质量比）=100: 5-20: 10: 20: 2。
一种窑炉烟气CO2捕集与利用耦合材料的制备方法，包括以下步骤：
步骤1：制备载体UiO-66，氯化锆(ZrCl4)和对苯二甲酸(H2BDC)按1.4: 1（质量）比溶于150mLDMF溶剂中，混合均匀后转移至聚四氟乙烯内衬不锈钢反应釜，放入均相反应器中进行溶剂热反应，反应结束后冷却至室温，倾倒出母液，得到白色沉淀，将白色沉淀用DMF和乙醇反复洗涤3-5次，在真空条件下干燥，得到载体UiO-66；
步骤2：将载体UiO-66材料加入烧杯中，按照质量比为UiO-66: K: Cu: Zn: Fe=100: 5-20: 10: 20: 2，加入K、Cu、Zn和Fe的混合盐溶液，接着真空浸渍并进行干燥，得到耦合材料的前驱体；UiO-66是载体，所以用量较多；Cu作为CO2加氢制乙醇的活性组分，其含量一般小于或等于10%，Zn用于调节组分间的协同作用，含量为20%时催化活性较高；Fe为链增长中心，含量过高会影响产物分布，因此选2%；K为吸附助剂，含量过高会影响活性组分的分散性，过低则效果不明显，因此选5%-20%。
步骤3：将步骤2得到的耦合材料的前驱体在混合气氛中进行还原处理，得到最终产品。
步骤1中所述溶剂热反应条件为120 ℃下反应24 h；均相反应器的转速设置为300r/min；真空干燥温度为150 ℃。
步骤1中真空干燥过程中每隔2 h对干燥箱进行抽真空处理。
步骤2中所述真空浸渍条件为将盛有载体UiO-66材料和混合盐溶液的烧杯放入真空烘箱中进行抽真空处理，让液体充分进入到载体内部的孔道中。
步骤2中的入K、Cu、Zn和Fe的混合盐溶液为K2CO3、Cu（NO3）2、Zn（NO3）2、Fe（NO3）3的混合溶液。
步骤3中所述混合气氛为H2/N2 (20/30, v/v)混合气；还原处理条件为400 °C下处理30-60 min。
一种窑炉烟气CO2捕集与利用耦合材料的应用，用于窑炉烟气CO2捕集与利用。
有益效果：与现有技术相比，本发明一种窑炉烟气CO2捕集与利用耦合材料及其应用，具有如下优势：（1）耦合材料由载体、CO2吸附活性位点和催化活性位点构成，具有良好的CO2捕集和催化加氢制甲醇两个功能。（2）将K盐作为吸附助剂，K2CO3对CO2分子具有较高的吸附量和选择性，其吸附产物KHCO3的解吸CO2的温度约为170 ℃-350 ℃，与催化加氢制乙醇的温度窗口重合；同时将Cu作为活性中心、成醇中心，将CO2加氢转化为甲醇，Zn用于调节组分间的协同作用，Fe为链增长中心，将加氢产物由甲醇转变为乙醇。（3）耦合材料由载体UiO-66不仅具有超高的比表面积和孔体积用于分散其他组分，其金属配位中心Zr也是CO2加氢反应的活化中心。
附图说明
图1为本发明窑炉烟气CO2捕集与利用耦合材料的制备工艺示意图。
具体实施方式
下面结合具体实施例及对比例对本发明做进一步说明。根据下述实施例，可以更好的理解本发明。然而，本领域的技术人员容易理解，实施例所描述的具体的物料配比、工艺条件及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
实施例1
（1）氯化锆(ZrCl4)和对苯二甲酸(H2BDC)按照质量比1.4: 1溶于DMF溶剂中，混合均匀，然后转移至聚四氟乙烯内衬不锈钢反应釜，放入均相反应器中，转速设置为300r/min，升温至120 ℃反应24 h，结束后冷却至室温，倾倒出母液，得到白色沉淀；
（2）将白色沉淀用DMF和乙醇反复洗涤3-5次，在真空条件下干燥，得到白色晶体UiO-66；作为改进的是，步骤2中，所述真空干燥温度为150 ℃，为深度脱除材料内部的配位水和结合水，每隔2 h对干燥箱进行抽真空处理；
（3）将载体UiO-66材料加入烧杯中，按照质量比UiO-66: K: Cu: Zn: Fe=100: 5:10: 20: 2加入各组分的混合盐溶液，真空烘箱中进行抽真空处理，让液体充分进入到载体内部的孔道中，而后进行干燥，得到耦合材料的前驱体；
（4）将耦合材料的前驱体在H2/N2 (20/30, v/v)混合气氛中升温至400 °C，还原处理30-60 min，得到高分散的耦合材料，标记为KCuFeZn/UiO-66-1。
实施例2
（1）氯化锆(ZrCl4)和对苯二甲酸(H2BDC)按照质量比1.4: 1溶于DMF溶剂中，混合均匀，然后转移至聚四氟乙烯内衬不锈钢反应釜，放入均相反应器中，转速设置为300r/min，升温至120 ℃反应24 h，结束后冷却至室温，倾倒出母液，得到白色沉淀；
（2）将白色沉淀用DMF和乙醇反复洗涤3-5次，在真空条件下干燥，得到白色晶体UiO-66；作为改进的是，步骤2中，所述真空干燥温度为150 ℃，为深度脱除材料内部的配位水和结合水，每隔2 h对干燥箱进行抽真空处理；
（3）将载体UiO-66材料加入烧杯中，按照质量比UiO-66: K: Cu: Zn: Fe=100:10: 10: 20: 2加入各组分的混合盐溶液，真空烘箱中进行抽真空处理，让液体充分进入到载体内部的孔道中，而后进行干燥，得到耦合材料的前驱体；
（4）将耦合材料的前驱体在H2/N2 (20/30, v/v)混合气氛中升温至400 °C，还原处理30-60 min，得到高分散的耦合材料，标记为KCuFeZn/UiO-66-2；
实施例3
（1）氯化锆(ZrCl4)和对苯二甲酸(H2BDC)按照质量比1.4: 1溶于DMF溶剂中，混合均匀，然后转移至聚四氟乙烯内衬不锈钢反应釜，放入均相反应器中，转速设置为300r/min，升温至120 ℃反应24 h，结束后冷却至室温，倾倒出母液，得到白色沉淀；
（2）将白色沉淀用DMF和乙醇反复洗涤3-5次，在真空条件下干燥，得到白色晶体UiO-66；作为改进的是，步骤2中，所述真空干燥温度为150 ℃，为深度脱除材料内部的配位水和结合水，每隔2 h对干燥箱进行抽真空处理；
（3）将载体UiO-66材料加入烧杯中，按照质量比UiO-66: K: Cu: Zn: Fe=100:15: 10: 20: 2加入各组分的混合盐溶液，真空烘箱中进行抽真空处理，让液体充分进入到载体内部的孔道中，而后进行干燥，得到耦合材料的前驱体；
（4）将耦合材料的前驱体在H2/N2 (20/30, v/v)混合气氛中升温至400 °C，还原处理30-60 min，得到高分散的耦合材料，标记为KCuFeZn/UiO-66-3；
实施例4
（1）氯化锆(ZrCl4)和对苯二甲酸(H2BDC)按照质量比1.4: 1溶于DMF溶剂中，混合均匀，然后转移至聚四氟乙烯内衬不锈钢反应釜，放入均相反应器中，转速设置为300r/min，升温至120 ℃反应24 h，结束后冷却至室温，倾倒出母液，得到白色沉淀；
（2）将白色沉淀用DMF和乙醇反复洗涤3-5次，在真空条件下干燥，得到白色晶体UiO-66；作为改进的是，步骤2中，所述真空干燥温度为150 ℃，为深度脱除材料内部的配位水和结合水，每隔2 h对干燥箱进行抽真空处理；
（3）将载体UiO-66材料加入烧杯中，按照质量比UiO-66: K: Cu: Zn: Fe=100:20: 10: 20: 2加入各组分的混合盐溶液，真空烘箱中进行抽真空处理，让液体充分进入到载体内部的孔道中，而后进行干燥，得到耦合材料的前驱体；
（4）将耦合材料的前驱体在H2/N2 (20/30, v/v)混合气氛中升温至400 °C，还原处理30-60 min，得到高分散的耦合材料，标记为KCuFeZn/UiO-66-4；
上述耦合材料的CO2吸附性能测试在热重分析仪中进行，将耦合材料称重后装入坩埚中，坩埚置于热天平上，在CO2气氛下升温至250℃，持续一段时间至热重曲线基本持平，而后得到耦合材料在250℃下的CO2吸附量；上述耦合材料的CO2催化加氢制甲醇性能测试在固定床反应器上进行（不锈钢反应管内径10mm），催化剂装填量为0.5g，与0.5g石英砂混合，在催化剂反应前，用H2/N2体积比为10%～50%的气体中常压活化4h。还原温度略高于反应温度，待冷却制反应温度250℃时，通入H2:CO2:N2=72:24:4体积比的混合气，反应压力为2MPa，反应后产物用气相色谱进行分析，而后得到耦合材料在250℃下CO2催化加氢制甲醇反应中的CO2转化率和甲醇选择性。测试结果如表1所示。
表1耦合材料CO2吸附与催化加氢制甲醇性能测试结果
Q(CO2)表示二氧化碳吸附量，X(CO2) 表示二氧化碳转化率，S(CH3OH) 表示甲醇选择性，Y(CH3OH) 表示甲醇收率；反应条件：P=2MPa, T=250℃, H2/CO2=3/1, GHSV=12,000ml/(g h)。
Claims (7)
1.一种窑炉烟气CO2捕集与利用耦合材料，其特征在于其为KCuFeZn/UiO-66耦合材料，UiO-66: K: Cu: Zn: Fe的质量比=100: 5-20: 10: 20: 2。
2.一种如权利要求1所述的窑炉烟气CO2捕集与利用耦合材料的制备方法，其特征在于包括以下步骤：
步骤1：制备载体UiO-66，将氯化锆(ZrCl4)和对苯二甲酸(H2BDC)按质量比1.4: 1的溶于150 mLDMF溶剂中，混合均匀后转移至聚四氟乙烯内衬不锈钢反应釜，放入均相反应器中进行溶剂热反应，反应结束后冷却至室温，倾倒出母液，得到白色沉淀，将白色沉淀用DMF和乙醇反复洗涤3-5次，在真空条件下干燥，得到载体UiO-66；
步骤2：将载体UiO-66加入烧杯中，按照质量比为UiO-66: K: Cu: Zn: Fe=100: 5-20:10: 20: 2，加入K、Cu、Zn和Fe的混合盐溶液，接着真空浸渍并进行干燥，得到耦合材料的前驱体；
步骤3：将步骤2得到的耦合材料的前驱体在混合气氛中进行还原处理，得到最终产品。
3.根据权利要求2所述的窑炉烟气CO2捕集与利用耦合材料的制备方法，其特征在于步骤1中所述溶剂热反应条件为120 ℃下反应24 h；均相反应器的转速设置为300r/min；真空干燥温度为150 ℃。
4.根据权利要求3所述的窑炉烟气CO2捕集与利用耦合材料的制备方法，其特征在于步骤1中真空干燥过程中每隔2 h对干燥箱进行抽真空处理。
5.根据权利要求2所述的窑炉烟气CO2捕集与利用耦合材料的制备方法，其特征在于步骤2中所述真空浸渍条件为将载体UiO-66和混合盐溶液放入真空烘箱中进行抽真空处理。
6.根据权利要求2所述的窑炉烟气CO2捕集与利用耦合材料的制备方法，其特征在于步骤3中所述混合气氛为H2/N2 (20/30, v/v)混合气；还原处理条件为400 °C下处理30-60min。
7.一种如权利要求1所述的窑炉烟气CO2捕集与利用耦合材料的应用，用于窑炉烟气CO2捕集与利用。
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