CN107999083B - 一种合成丁炔二醇CuBiMgSi催化剂的制备方法 - Google Patents
一种合成丁炔二醇CuBiMgSi催化剂的制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
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- 238000001556 precipitation Methods 0.000 claims abstract description 6
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
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- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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Abstract
一种合成丁炔二醇Cu Bi Mg Si催化剂的制备方法，其属于催化剂制备的技术领域。该催化剂由Cu、Bi、Si、Mg的氧化物的复合物，采用分步沉淀法制成。本发明的催化剂用于甲醛与乙炔的炔化反应合成1,4‑丁炔二醇，具有催化活性高，稳定性好，甲醛转化率可达到97.5%以上，1,4‑丁炔二醇的选择性可达到98.9%以上，1,4‑丁炔二醇的收率可达到96.5%。
Description
技术领域
本发明涉及一种从甲醛和乙炔合成1,4－丁炔二醇的CuO-Bi2O3-MgO-SiO2催化剂的制备方法，其属于催化剂制备的技术领域。
背景技术
丁炔二醇是制造丁烯二醇、丁二醇、正丁醇、二氢呋喃、四氢呋喃、 γ-丁内酯、吡咯烷酮等一系列重要有机产品的原料，在医药、纺织、人造革、防腐剂及军工等领域有着重要而广泛的用途。近年来,合成聚氨酯弹性纤维、聚四亚甲基乙二醇醚、聚丁二酸丁二醇酯等可生物降解塑料的迅速发展，1,4-丁炔二醇的需求量以每年10%的速度增长。在合成1,4-丁二醇的众多工艺路线中，以甲醛和乙炔为原料的炔醛法工艺是目前采用最多，技术最为成熟，经济效益最为显著。
1975年美国公开了GAF公司铜铋硝酸盐溶液浸渍硅酸镁载体的专利US3920759，随后又公开了以分子筛为载体浸渍法制备催化乙炔和甲醛反应合成丁炔二醇的催化剂专利US4288641，促进1,4丁炔二醇生产技术的发展。但该类催化剂分子筛和硅酸镁载体，存在制备工艺复杂、费用较高的缺点。
2001年，我国山西三维集团从美国引进了以乙炔和甲醛为原料的Reppe法，生产1,4-丁炔二醇的技术，建成2.5万吨/年1,4-丁二醇生产装置，开始大规模生产1,4-丁二醇。但生产丁炔二醇的核心技术，丁炔二醇化催化剂仍然依赖进口，制约我国丁炔二醇及下游产业的发展。
用于炔醛法生产丁炔二醇合成工艺的铜铋催化剂有两种：无载体的孔雀石型催化剂和硅镁氧化物等负载的铜铋氧化物型催化剂。这两种催化剂及使用这两种催化剂合成丁炔二醇的生产工艺，在设备投资和技术经济上各具特色，在工业上同时使用，竞放异彩。
70年代后期，随着催化剂性能的提高，生产工艺由高压固定床转向低压悬浮床和淤浆床工艺，尤其是淤浆床工艺。采用淤浆床，反应可以在 0～100 ℃ 、压力低于0.2MPa的温和条件下运行，选择性和经济指标均优于固定床工艺。
这两种催化剂，以铜作为主活性组分，元素铋作为助剂，控制 Cu+被还原成 Cu0，抑制聚炔的生成，提高丁炔二醇的选择性和稳定性。催化剂的制备工艺对它的性能影响大，研发的难度高，一直由美、德等国家垄断。
我国对丁炔二醇催化剂的研究起步较晚，催化剂的研究水平落后。2011年申请的中国专利CN 102125856 A报道了以高岭土为载体，以沉积沉淀方法把可溶性铜盐和铋盐沉淀到载体上制取催化剂。2012年申请的专利CN 102658158 A将硅酸酯的醇溶液与铜盐、铋盐、镁盐混合溶液反应制取Cu-Bi-Mg-Si 氧化物催化剂。但催化剂的寿命都较短，未能实现工业应用。
发明内容
本发明的目的在于提供一种用于合成1,4－丁炔二醇的CuO-Bi2O3-MgO-SiO2催化剂，其制备方法如下：
（1）将可溶性铜盐和铋盐溶解于适量酸性水溶液中，用水溶性的碱中和制得铜铋沉淀物的悬浮液或沉淀物；
（2）将可溶性的镁盐和硅酸钠等可溶性硅源反应，制成镁硅沉淀物的悬浮液或沉淀物；
（3）把含铜铋沉淀物的悬浮液与含硅镁沉淀物的悬浮液混合液在搅拌和适当得温度和搅拌条件下，加热反应2～8小时，过滤、洗涤、干燥，制得到CuO-Bi2O3-MgO-SiO2催化剂的前驱体。
该催化剂是采用分步淀法制备的Cu、Bi、Mg和Si的复合氧化物。让铜和铋的可溶性盐溶液与可溶性碱性物质的溶液反应，制得沉淀物的悬浮或液铜铋的沉淀物；让Mg的可溶性盐水溶液与水溶性硅源（水玻璃，硅溶胶等）的溶液，在碱性条件下加入适量的聚丙烯酰胺作为絮凝剂，制得镁硅沉淀物的悬浮液或镁硅的沉淀物。然后，让上述铜铋沉淀物或沉淀物的悬浮液与硅镁沉淀物或沉淀物的悬浮液混合反应，经过滤、干燥和焙烧制得合成丁炔二醇催化剂的前驱体。
催化剂组成按氧化物计算为(w%)：CuO： 18.0～59.2， Bi2O3： 3.0～3.8， MgO：5.4～6.9， SiO2： 29.4～70.0。
催化剂制备所用的镁、铜和铋的盐是硫酸盐和硝酸盐、醋酸盐和氯化物等可溶性盐，优选为硝酸盐。所用的沉淀剂为碱金属和铵的碳酸盐、碳酸氢盐或氢氧化物。
备铜铋沉淀物或它的的悬浮液的方法是：在30～90℃和搅拌条件下让铜铋可溶性盐溶液与碱性沉淀剂反应，在35～95℃陈化1～10小时制得悬浮液，经过滤而得到它的沉淀物。
水可溶性镁盐与水玻璃等可溶性硅化合物反应，制取镁硅沉淀物的条件是：在室温～95℃和搅拌下反应2～8小时、陈化1～9小时，制得镁硅沉淀物的悬浮液；经过滤得到相应的镁硅沉淀物。
的铜铋沉淀物和镁硅沉淀物，可用不同的方式混合：①沉淀的两种悬浮液直接混合，②沉淀物与沉淀物的悬浮液混合，③两种沉淀物的悬浮液分别过滤后，与水混合打浆或碾压，在50～90℃反应2～8小时，制备铜铋镁硅复合物的前体。
制备的沉淀物的复合物的前体，在干燥后，于300～500℃焙烧 2～8小时，得催化剂的前驱体。
本发明与现有技术相比：该催化剂不需要先前制备硅酸镁或硅镁复合氧化物的干燥焙烧过程，也不需要加入表面活性剂等有机物，无有机物污染废水的处理。制得的催化剂活性、选择性高，稳定性好，制备费用省。现有技术中采用硅酸乙酯等有机硅源，价格高，催化剂的原料费用大。在铜铋镁盐溶液中和沉定洗涤液中加入较多的乙二醇等分散剂，催化剂成本增大。要用醇溶剂，增加溶剂回收和污水处理的设备投资和费用。而本申请中只是使用了少量的聚丙烯酰胺是为了过滤更好些，极大的降低了后处理的成本。
近年，大连瑞克科技有限公司开展合成丁炔二醇孔雀石型催化剂的研发，较快地取得成功。2015年06月，新疆美克化工股份有限公司10万吨/年1,4-丁二醇生产装置，采用大连瑞克公司的RK-15孔雀石型催化剂，成功地运行1年，结束中国丁炔二醇催化剂完全依赖进口的历史。大连瑞克公司，在开发成功孔雀石型丁炔二醇催化剂之后，致力于氧化物型丁炔二醇催化剂的研发，采用分步沉淀法制备的铜铋镁硅氧化物型催化剂，显示出良好的催化活性、选择性和稳定性。
具体实施方式
实施例1
1A：称13.1g Bi(NO3)3.5H2O 和99.7g Cu(NO3)2.3H2O 溶解制成1mol/L的水溶液。用浓度为1 mol /L的碳酸钠与铜铋溶液，在55℃和搅拌条件下并流混合，控制PH=6.5～7.0。继续陈化2～5小时，得到碱式碳酸铜铋沉淀物的蓝色悬浮液。
1B：将106g Mg(NO3)2.6H2O配成1摩尔的水溶液。把硝酸镁溶液和233.5g模数为3.5的水玻璃在80℃和搅拌下并流混合，控制PH值等于8.5～9.5，继续在此温度下陈化2～8小时，加入1.8g分子量为750万的聚丙烯酰胺作为絮凝剂，继续在此温度下陈化2～8小时，得白色沉淀的悬浮液。
1C：将悬浮液1B与1A混合，调节PH=8.5～9.5，在75～80℃和搅拌下陈化2～6小时。过滤，洗涤，在100～140℃干燥后，于450℃焙烧4～6小时，得催化剂的前驱体1。
由实施例 1制备的催化剂10g 置于 250mL 三口烧瓶中，加入150mL 质量分数为37% 的甲醛水溶液和2g乙酸钠，在 85℃下，通入乙炔与氮气的混合气体(C2H2 3.5L/h，N21.5L/h)，在搅拌条件下活化催化剂10小时，然后进行甲醛炔化反应7 小时，采用气相色谱法分析样品的组成。甲醛转化率 97.5％，1,4-丁炔二醇选择性 96.8％
实施例2
2A：称取12.0g Bi(NO3)3.5H2O 和102.8g Cu(NO3)2.3H2O，用水溶解成2mol/L的水溶液。用浓度为1 mol/L的碳酸钠溶液与2mol/L的硝酸铜铋溶液，在50℃和搅拌条件下并流混合，控制PH=6.5～7.0。继续陈化2～5小时，得到蓝色的碱式碳酸铜铋沉淀物的悬浮液。
2B：将106g Mg(NO3)2.6H2O配成1mol/L的水溶液。把硝酸镁溶液和236.4g模数为3.5的水玻璃在80℃和搅拌下并流混合，控制PH值等于8.5～9.2，继续在此温度下陈化2～8小时，加入1.6g分子量为750万的聚丙烯酰胺作为絮凝剂，得白色悬浮液。
2C：将上述的悬浮液A和B混合，调节PH=8.5～9.2，在75～80℃和搅拌下反应2～7小时。过滤，洗涤，在120～140℃干燥后，于450℃焙烧4～6小时，得催化剂的前驱体2。
由实施例2制备的催化剂前驱体，用实施例1同样的方法活化和进行甲醛炔化反应及产物分析。甲醛转化率95.4％，1,4- 丁炔二醇选择性 95.8％。
实施例3
3A：称取14.0g Bi(NO3)3.5H2O 和96.7gCu(NO3)2.3H2O，溶解制成1mol/L水溶液。用浓度为1mol/L的碳酸钠溶液与铜铋溶液，在65℃和搅拌条件下并流混合，控制PH=6.5～7.0制得蓝色的碱式碳酸铜铋沉淀物的悬浮液。
3B：将106gMg(NO3)2.6H2O配成1mol/L的水溶液。把硝酸镁溶液231.8g模数为3.5的水玻璃在50℃和搅拌下并流混合，控制PH值等于8.5～9.3。然后，继续在此温度下陈化2～8小时，加入1.6g分子量为750万的聚丙烯酰胺作为絮凝剂，生成白色沉淀的悬浮液。
3C：将悬浮液3A和3B混合，调节PH=8.5～9.5，在75～80℃和搅拌下反应6～10小时。过滤，洗涤，在120～140℃干燥后，于500℃焙烧4～6小时，得催化化剂的前驱体3。
由实施例3制备的催化剂前驱体，用与实施例1同样的方法活化和进行甲醛炔化反应及产物分析。甲醛转化率为 95.7％，1,4- 丁炔二醇选择性 96.5％。
Claims (1)
1.一种合成丁炔二醇Cu Bi Mg Si催化剂的制备方法，其特征在于：该催化剂是采用分步淀法制备的Cu、Bi、Mg和Si的复合氧化物；铜的可溶性盐溶液和铋的可溶性盐溶液与碱性沉淀剂溶液反应，制得铜铋沉淀物的悬浮液；让镁的可溶性盐溶液与水溶性硅源的溶液，在碱性条件下加入聚丙烯酰胺作为絮凝剂，制得镁硅沉淀物的悬浮液；铜铋沉淀物的悬浮液与硅镁沉淀物或硅镁沉淀物的悬浮液混合反应，得到铜铋镁硅复合物的前体；经过滤、干燥和焙烧制得合成丁炔二醇催化剂的前驱体；
所述铜铋沉淀物的悬浮液的制备方法为：称13.1g Bi(NO3)3.5H2O 和99.7g Cu(NO3)2.3H2O 溶解制成1mol/L的水溶液；用浓度为1 mol /L的碳酸钠与铜铋溶液，在55℃和搅拌条件下并流混合，控制pH=6.5～7.0；继续陈化2～5小时，得到碱式碳酸铜铋沉淀物的蓝色悬浮液；
所述镁硅沉淀物的悬浮液的制备方法为：将106g Mg(NO3)2.6H2O配成1mol/L的水溶液；把硝酸镁溶液和233.5g模数为3.5的水玻璃在80℃和搅拌下并流混合，控制pH=8.5～9.5，继续在此温度下陈化2～8小时，加入1.8g分子量为750万的聚丙烯酰胺作为絮凝剂，继续在此温度下陈化2～8小时，得白色沉淀的悬浮液；
铜铋沉淀物悬浮液与硅镁沉淀物的悬浮液混合反应，调节pH=8.5～9.5，在75～80℃反应2～6小时，过滤，洗涤，在100～140℃干燥后，于450℃焙烧 4～6小时，得催化剂的前驱体。
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