CN113101970B - 一种用于生产甲乙酮的复合催化剂及其制备方法 - Google Patents
一种用于生产甲乙酮的复合催化剂及其制备方法 Download PDFInfo
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 24
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 18
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
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- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
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- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 26
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种用于生产甲乙酮的复合催化剂及其制备方法，该复合催化剂是由SO4 2‑/ZrO2‑MCM‑41与Zr基固态离子液体构成；所述Zr基固态离子液体为Zr0.5[MIMPS]PW12O40、Zr0.25[MIMPS]2PW12O40、Zr0.25[MIMPS]HPW12O40中的任意一种。本发明所得复合催化剂是具有新型结构的Brönsted‑Lewis双酸性杂多酸功能化类离子液体有机‑无机杂化催化材料，其具有较强的酸性，从而可以强化甲乙酮的制备过程，并能有效抑制反应过程中催化剂的中毒失活。
Description
技术领域
本发明属于石油化工生产技术领域，具体涉及一种用于2,3-丁二醇脱水制甲乙酮的复合催化剂及其制备方法。
背景技术
甲乙酮是一种重要的有机溶剂，在化工产品生产过程中有着非常广泛的应用。如其可以用作工业溶剂，应用于油墨、涂料、润滑油脱蜡剂等方面，是重要的“三苯”溶剂替代物之一；还可以用于生产医药、染料、洗涤剂以及香料等；此外，其还可以用于制备液体燃料添加剂；同时，甲乙酮还是一种有机合成的中间体，可用于生产丁二酮、过氧化甲乙酮以及抗氧化剂等。目前工业上合成甲乙酮应用较多的方法有正丁烯两步法、正丁烷液相氧化法和异丁苯法，其中正丁烯两步法是最普及的方法。但是其生产工艺路线流程复杂、操作困难且原料来源于不可再生资源。
以生物发酵法制备的2,3-丁二醇作为原料，通过催化剂进行脱水制备甲乙酮的方法是一种极具优势的生产工艺，其与传统的正丁烯两步法相比具有工艺短、设备简单、投资少、生产成本低及操作便捷等优点。但现有技术在反应过程中使用的催化剂不仅易对设备造成腐蚀，反应后需要用强碱对产物进行洗涤处理，容易造成三废，不符合绿色环保的理念。
专利“一种2,3-丁二醇高效脱水制甲乙酮的方法”（CN 101580462B）公开了一种将H型ZSM-5分子筛负载SO4 2-/Fe2O3后得到的分子筛型固体酸催化剂应用于2,3-丁二醇脱水制备甲乙酮的工艺，其2,3-丁二醇转化率为94.2~100%，甲乙酮的选择性可达70.1~94.2%。但是其原料要求的浓度为10%~90%，且在200~300℃条件下反应时需要将一部分水汽化，耗能较高。邵园艳等(2,3-丁二醇液相脱水制备甲乙酮反应研究，化学世界，2013,54(4):227-230)以2,3-丁二醇为原料，以对甲苯磺酸作为催化剂，其最佳收率可以达到78.9%。
发明内容
本发明针对现有技术存在的缺陷，提出了一种用于2,3-丁二醇脱水制备甲乙酮的新型复合催化剂及其制备方法，其具有较高催化活性，并可有效抑制甲乙酮生产过程中催化剂的中毒失活。
为实现上述目的，本发明采用如下技术方案：
一种用于生产甲乙酮的复合催化剂，其是以具有强酸性的SO4 2-/ZrO2-MCM-41与Zr基固态离子液体相结合构成，其中Zr基固态离子液体所占重量分数为20~45%；所述Zr基固态离子液体为Zr0.5[MIMPS]PW12O40、Zr0.25[MIMPS]2PW12O40、Zr0.25[MIMPS]HPW12O40中的任意一种。
制备方法包括以下步骤：
（1）SO4 2-/ZrO2-MCM-41的制备：
将正硅酸乙酯溶于乙醇水溶液后，向其中加入CTAB、离子液体M和乙酰丙酮锆，搅拌处理60 min，然后向其中加入氨水调节pH为10~12，再将所得混合液转移至水热反应釜中，于100~140℃下晶化处理12~24h，待其自然冷却到室温后，将所得产物经离心、洗涤后于110℃干燥16h，再在500℃、空气气氛中焙烧5h，得到所述SO4 2-/ZrO2-MCM-41；其中所用正硅酸乙酯、乙酰丙酮锆、离子液体M、CTAB、水和乙醇的摩尔比为1.0:(0.2~0.4):0.1:(0.15~0.30):40:40；所述离子液体M的结构式为：
；
（2）Zr基离子液体的原位负载
i)离子液体前驱体MIMPS的合成
将1,3-丙烷磺酸内酯溶于乙酸乙酯，随后将N-甲基咪唑以6~8滴/min的速度缓慢加入，室温下搅拌反应6h，然后将得到的乳白色反应液经过滤后，所得沉淀用乙酸乙酯洗涤三次后，于80℃下干燥4h，即得到MIMPS的白色粉末固体；其中所用1,3-丙烷磺酸内酯与N-甲基咪唑的摩尔比为1:1；
ii)Zr基固态离子液体的原位负载
将制备好的SO4 2-/ZrO2-MCM-41、MIMPS与磷钨酸、Zr(SO4)2共同加入到去离子水中，在室温下搅拌30min使其混匀后转移至反应釜中，于100~150℃下回流处理6~12h，然后依次进行离心、洗涤、干燥，得到所述复合催化剂；其中所用MIMPS、Zr(SO4)2与磷钨酸的摩尔比为(1~2): (0.25~0.50):1。
本发明与现有其他技术相比，具有如下优势：
1）本发明所制备的催化剂引入了介孔分子筛MCM-41，其可以大大提高催化剂的比表面积和活性组分的分散度，从而可提高催化剂的催化活性。
2）本发明所制备的催化剂是具有新型结构的Brönsted-Lewis双酸性杂多酸功能化类离子液体有机-无机杂化催化材料，其具有较强的酸性，从而可以强化甲乙酮的制备过程，并能有效抑制反应过程中催化剂的中毒失活。
3）本发明催化剂中SO4 2-/ZrO2-MCM-41固体超强酸上的SO4 2-可以和Zr基固态离子液体上的Zr物种之间发生相互作用产生一类催化活性位点；同时，MCM-41可以和固态离子液体上的PO4 3-之间可以发生协同效应产生二类超强酸催化活性位点，固体超强酸和固态离子液体之间的协同效应，可以弥补在反应过程中一类活性位点的流失或失活而造成的催化剂反应活性降低。
具体实施方式
为了使本技术领域人员更好地理解本发明的技术方案，并使本发明的上述特征、目的及优点更加清晰易懂，现结合实施例对本发明做进一步解释说明，应当指出的是，在此列出的所有实施例仅仅是说明性的，并不意味着对本发明范围进行限定。
为了更清晰地说明本发明，列举以下实施例，但对本发明的范围无任何限制。
所用离子液体M的结构式为：
。其制备方法参照发明专利ZL 201510923379.8。
催化剂的评价条件如下：
将1.0g的催化剂样品装入常压固定床反应器中，在N2保护下将催化剂床层升高到一定温度，将一定浓度的2,3-丁二醇溶液注入到反应器，经预热气化后进入催化剂床层进行催化脱水反应，反应器出口物料经气液分离后获得甲乙酮。其中2,3-丁二醇的浓度适用范围：70wt%~100wt%; 2,3-丁二醇的质量空速6.0~8.0h-1；原料及所得产物用气相色谱仪进行分析。
实施例1
（1）SO4 2-/ZrO2-MCM-41的制备
将正硅酸乙酯溶于乙醇水溶液后，向其中加入CTAB、离子液体M和乙酰丙酮锆，搅拌处理60 min，然后向其中加入氨水调节pH为11，将所得混合液转移至水热反应釜中，于120℃下晶化处理18h，待其自然冷却到室温后，将所得产物经离心、洗涤后于110℃干燥16h，再在500℃、空气气氛中焙烧处理5h，即可得到SO4 2-/ZrO2-MCM-41；其中各原料的摩尔比为：nSiO2:nZrC20H28O8:n离子液体M:nCTAB:nH2O:n乙醇=1.0:0.3:0.1:0.25:40:40；
(2)Zr基离子液体的原位负载
i)离子液体前驱体MIMPS的合成
称取0.10 moL 1,3-丙烷磺酸内酯，加入三口烧瓶中，然后向其中加入100mL乙酸乙酯使其溶解，随后将0.10 moL N-甲基咪唑以6滴/min的速度缓慢加入，室温下搅拌反应6h，所得乳白色反应液经过滤后，所得沉淀用乙酸乙酯洗涤三次，再于80℃下干燥4h，得到的白色粉末固体即为MIMPS；
ii)Zr基固态离子液体的原位负载
将SO4 2-/ZrO2-MCM-41、磷钨酸、Zr(SO4)2、MIMPS加入到去离子水中得到混合物，在室温下搅拌30min使其混匀后转移至反应釜中，于120℃下回流处理10 h，然后依次进行离心、洗涤、干燥，得到SO4 2-/ZrO2-MCM-41与Zr基固态离子液体Zr0.5[MIMPS]PW12O40构成的复合催化剂；其中MIMPS与磷钨酸的物质的量之比为1:1，Zr(SO4)2与磷钨酸的物质的量之比为0.50:1，复合催化剂中Zr基固态离子液体所占质量分数为35wt%。
该催化剂在反应温度250℃，2,3-丁二醇的浓度为99.8wt%，2,3-丁二醇的质量空速为6.0h-1时反应48h后，2,3-丁二醇的转化率达到99.5%，甲乙酮的选择性达到98.2%。
实施例2
（1）SO4 2-/ZrO2-MCM-41的制备
将正硅酸乙酯溶于乙醇水溶液后，向其中加入CTAB、离子液体M和乙酰丙酮锆，搅拌处理60 min，然后向其中加入氨水调节pH为12，将所得混合液转移至水热反应釜中，于100℃下晶化处理24h，待其自然冷却到室温后，将所得产物经离心、洗涤后于110℃干燥16h，再在500℃、空气气氛中焙烧处理5h，即可得到SO4 2-/ZrO2-MCM-41；其中各原料的摩尔比为：nSiO2:nZrC20H28O8:n离子液体M:nCTAB:nH2O:n乙醇=1.0:0.4:0.1:0.3:40:40；
(2)Zr基离子液体的原位负载
i)离子液体前驱体MIMPS的合成
称取0.10 moL 1,3-丙烷磺酸内酯，加入三口烧瓶中，然后向其中加入100mL乙酸乙酯使其溶解，随后将0.10 moL N-甲基咪唑以6滴/min的速度缓慢加入，室温下搅拌反应6h，所得乳白色反应液经过滤后，所得沉淀用乙酸乙酯洗涤三次，再于80℃下干燥4h，得到的白色粉末固体即为MIMPS；
ii)Zr基固态离子液体的原位负载
将SO4 2-/ZrO2-MCM-41、磷钨酸、Zr(SO4)2、MIMPS加入到去离子水中得到混合物，在室温下搅拌30min使其混匀后转移至反应釜中，于100℃下回流处理12 h，然后依次进行离心、洗涤、干燥，得到SO4 2-/ZrO2-MCM-41与Zr基固态离子液体Zr0.25[MIMPS]2PW12O40构成的复合催化剂；其中MIMPS与磷钨酸的物质的量之比为2:1，Zr(SO4)2与磷钨酸的物质的量之比为0.25:1，复合催化剂中Zr基固态离子液体所占质量分数为45wt%。
该催化剂在反应温度250℃，2,3-丁二醇的浓度为72.4 wt%，2,3-丁二醇的质量空速为8.0h-1时反应36h后，2,3-丁二醇的转化率达到98.5%，甲乙酮的选择性达到96.4%。
实施例3
（1）SO4 2-/ZrO2-MCM-41的制备
将正硅酸乙酯溶于乙醇水溶液后，向其中加入CTAB、离子液体M和乙酰丙酮锆，搅拌处理60 min，然后向其中加入氨水调节pH为10，将所得混合液转移至水热反应釜中，于100℃下晶化处理24h，待其自然冷却到室温后，将所得产物经离心、洗涤后于110℃干燥16h，再在500℃、空气气氛中焙烧处理5h，即可得到SO4 2-/ZrO2-MCM-41；其中各原料的摩尔比为：nSiO2:nZrC20H28O8:n离子液体M:nCTAB:nH2O:n乙醇=1.0:0.2:0.1:0.15:40:40；
(2)Zr基离子液体的原位负载
i)离子液体前驱体MIMPS的合成
称取0.10 moL 1,3-丙烷磺酸内酯，加入三口烧瓶中，然后向其中加入100mL乙酸乙酯使其溶解，随后将0.10 moL N-甲基咪唑以8滴/min的速度缓慢加入，室温下搅拌反应6h，所得乳白色反应液经过滤后，所得沉淀用乙酸乙酯洗涤三次，再于80℃下干燥4h，得到的白色粉末固体即为MIMPS；
ii)Zr基固态离子液体的原位负载
将SO4 2-/ZrO2-MCM-41、磷钨酸、Zr(SO4)2、MIMPS加入到去离子水中得到混合物，在室温下搅拌30min使其混匀后转移至反应釜中，于150℃下回流处理6 h，然后依次进行离心、洗涤、干燥，得到SO4 2-/ZrO2-MCM-41与Zr基固态离子液体Zr0.25[MIMPS]2PW12O40构成的复合催化剂；其中MIMPS与磷钨酸的物质的量之比为1:1，Zr(SO4)2与磷钨酸的物质的量之比为0.25:1，复合催化剂中Zr基固态离子液体所占质量分数为20wt%。
该催化剂在反应温度250℃，2,3-丁二醇的浓度为85.6wt%，2,3-丁二醇的质量空速为7.0h-1时反应36h后，2,3-丁二醇的转化率达到96.8%，甲乙酮的选择性达到95.1%。
对比例1
SO4 2-/ZrO2-MCM-41的制备
将正硅酸乙酯溶于乙醇水溶液后，向其中加入CTAB、离子液体M和乙酰丙酮锆，搅拌处理60 min，然后向其中加入氨水调节pH为11，将所得混合液转移至水热反应釜中，于120℃下晶化处理18h，待其自然冷却到室温后，将所得产物经离心、洗涤后于110℃干燥16h，再在500℃、空气气氛中焙烧处理5h，即可得到SO4 2-/ZrO2-MCM-41；其中各原料的物质的量之比为：nSiO2:nZrC20H28O8:n离子液体M:nCTAB:nH2O:n乙醇=1.0:0.3:0.1:0.25:40:40；
所制备的SO4 2-/ZrO2-MCM-41在反应温度250℃，2,3-丁二醇的浓度为99.8wt%，2,3-丁二醇的质量空速为6.0h-1时反应48h后，2,3-丁二醇的转化率达到76.5%，甲乙酮的选择性达到80.2%。
对比例2
Zr基离子液体的合成
i)离子液体前驱体MIMPS的合成
称取0.10 moL 1,3-丙烷磺酸内酯，加入三口烧瓶中，然后向其中加入100mL乙酸乙酯使其溶解，随后将0.10 moL N-甲基咪唑以6滴/min的速度缓慢加入，室温下搅拌反应6h，所得乳白色反应液用乙酸乙酯洗涤三次，所得沉淀于80℃下干燥4h，得到的白色粉末固体即为MIMPS；
ii)Zr基固态离子液体的原位负载
将磷钨酸、Zr(SO4)2、MIMPS加入到去离子水中得到混合物，在室温下搅拌30min使其混匀后转移至反应釜中，于120℃下回流处理10 h，然后依次进行离心、洗涤、干燥，得到Zr基固态离子液体Zr0.5[MIMPS]PW12O40；其中MIMPS与磷钨酸的物质的量之比为1:1，Zr(SO4)2与磷钨酸的物质的量之比为0.50:1。
所制备的Zr0.5[MIMPS]PW12O40在反应温度250℃，2,3-丁二醇的浓度为99.8wt%，2,3-丁二醇的质量空速为6.0h-1时反应48h后，2,3-丁二醇的转化率达到63.8%，甲乙酮的选择性达到86.3%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (5)
1.一种用于生产甲乙酮的复合催化剂的制备方法，其特征在于：所述复合催化剂是由SO4 2-/ZrO2-MCM-41与Zr基固态离子液体构成；所述Zr基固态离子液体为Zr0.5[MIMPS]PW12O40、Zr0.25[MIMPS]2PW12O40、Zr0.25[MIMPS]HPW12O40中的任意一种；
其制备包括以下步骤：
（1）SO4 2-/ZrO2-MCM-41的制备：
将正硅酸乙酯溶于乙醇水溶液后，向其中加入CTAB、离子液体M和乙酰丙酮锆，搅拌处理60 min，然后向其中加入氨水调节pH为10~12，再将所得混合液转移至水热反应釜中，于100~140℃下晶化处理12~24h，待其自然冷却到室温后，将所得产物经离心、洗涤、干燥后，再在500℃、空气气氛中焙烧5h，得到所述SO4 2-/ZrO2-MCM-41；
其中所述离子液体M的结构式为：
；
（2）Zr基离子液体的原位负载
i)离子液体前驱体MIMPS的合成
将1,3-丙烷磺酸内酯溶于乙酸乙酯，随后将N-甲基咪唑以6~8滴/min的速度缓慢加入，室温下搅拌反应6h，然后将得到的乳白色反应液经过滤后，所得沉淀用乙酸乙酯洗涤三次，经干燥，即得到MIMPS的白色粉末固体；
ii)Zr基固态离子液体的原位负载
将制备好的SO4 2-/ZrO2-MCM-41、MIMPS与磷钨酸、Zr(SO4)2共同加入到去离子水中，在室温下搅拌30min使其混匀后转移至反应釜中，于100~150℃下回流处理6~12h，然后依次进行离心、洗涤、干燥，得到所述复合催化剂。
2.根据权利要求1所述的用于生产甲乙酮的复合催化剂的制备方法，其特征在于：所述复合催化剂中Zr基固态离子液体所占重量分数为20~45%。
3.根据权利要求1所述的用于生产甲乙酮的复合催化剂的制备方法，其特征在于：步骤（1）中所用正硅酸乙酯、乙酰丙酮锆、离子液体M、CTAB、水和乙醇的摩尔比为1.0:(0.2~0.4):0.1:(0.15~0.30):40:40。
4.根据权利要求1所述的用于生产甲乙酮的复合催化剂的制备方法，其特征在于：步骤（2）中所用1,3-丙烷磺酸内酯与N-甲基咪唑的摩尔比为1:1。
5.根据权利要求1所述的用于生产甲乙酮的复合催化剂的制备方法，其特征在于：步骤（3）中所用MIMPS、Zr(SO4)2与磷钨酸的摩尔比为(1~2):(0.25~0.50):1。
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