CN112844400A - 一种Bi基多酸催化剂及在2-甲基丙烯氧化制备2-甲基丙烯醛中的应用 - Google Patents
一种Bi基多酸催化剂及在2-甲基丙烯氧化制备2-甲基丙烯醛中的应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 title abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title description 12
- 230000003647 oxidation Effects 0.000 title description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910016285 MxNy Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 16
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 13
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 13
- 239000011609 ammonium molybdate Substances 0.000 claims description 13
- 229940010552 ammonium molybdate Drugs 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
本发明提供了一种Bi基多酸催化剂及在2‑甲基丙烯氧化制备2‑甲基丙烯醛中的应用。所制备的催化剂主体为MxNyBizOn,其中M为高价态的Mo、W、V中的至少一种,再通过引入其他金属元素N为K、Cs、Fe、Co、Ni、Mn、Ce、Cu中的至少一种,x=0.05‑10,y=0.05‑10,z=1‑25,n=1‑50。制备的催化剂具有高活性和高选择性的双重优点,转化率为60%‑88%,选择性为70%‑89%,其最优活性是转化率88%,选择性89%,可用于实现甲基丙烯醛中间体的工业化生产。
Description
技术领域
本发明属于无机催化剂制备与2-甲基丙烯醛的合成技术领域,具体涉及一种Bi基催化剂及其制备方法与催化2-甲基丙烯氧化反应制备甲基丙烯醛中的应用。
背景技术
2-甲基丙烯催化氧化制甲基丙烯酸甲酯(MMA)为两步反应,第一步为2-甲基丙烯氧化生成甲基丙烯醛(MAL),第二步为甲基丙烯醛氧化酯化生成甲基丙烯酸甲酯。而两步反应中催化剂的研究是2-甲基丙烯氧化法制备甲基丙烯酸甲酯研究的关键所在。
40年代中期,Shell公司最先采用Cu2O催化剂用于2-甲基丙烯选择氧化制MAL反应。60年代初期,Mo-Bi催化剂在2-甲基丙烯选择氧化反应中初露头角,80年代初期,日本将Mo-Bi系多组分复合金属氧化物催化剂应用于2-甲基丙烯氧化制MMA的工业化生产中。目前Mo系催化剂仍是应用最为广泛的催化剂,并通过添加其他元素进行改性研究,以期达到更好的催化效果。但是单一Mo系催化剂选择性和稳定性不尽如人意。
所以通过引入高价态的V等促进形成π-烯丙基中间物种,改善催化剂的催化活性和选择性。王国芳等研究发现BiMoVO复合氧化物催化剂具有较好的催化性能,但是选择性虽然有提高但副产物品种很多,对后续分离带来困难。
因此又通过引入碱金属,其主要目的是为了调节催化剂的酸性活性中心,从而提高目标产物的选择性。张明森等研究发现,将碱金属加入Mo-Bi-Fe能显著提高低温区的反应活性,选择性和收率也有明显提高,但引入碱金属后选择性提高,但很难做到单程反应转化的提高,单位时间转化能力仍有提升空间。
CN106807394B中提到Mo2BiaFebXcOh组成催化剂用于异丁烯氧化,其催化剂制备缺少酸性调控不利于发挥催化剂氧化优势。并且在反应中有水参与,不利于后续提纯。
CN 101385978 A中提到一种用于合成甲基丙烯醛的催化剂,所述催化剂由活性组分和载体组成,活性组分是一种含Mo、Bi、Fe、Co等组分的复合氧化物,除此之外,还含有碱金属或其他过渡金属的一种或几种,载体是石墨、硼、硅或锗粉中的至少一种。将其用于叔丁醇或异丁烯气相选择氧化合成甲基丙烯醛,但该催化剂需要其他载体负载增加了生产工艺,催化剂选择性较低,资源的利用率也相应较低。
CN109433221A中提到制备过程是将至少包括钼盐、铋盐和铁盐的金属盐与结构调控剂混合溶解,然后加入沉淀剂,得到共沉淀物作为主要催化剂成分。但其中加入了石墨烯,这可能会带来中低温原料气转化积碳严重的问题。
CN109513446A中提到所述催化剂在制备过程中添加一种或多种表面活性剂作为模板剂,与其它组分反应。但模板剂通常难以绝对去除干净,这将对于原料气的转化带来污染,引入新的杂质影响反应结果。
CN103769159A、CN1647853A都提到通过制备负载型催化剂的方式提高催化剂活性组分分布,用于异丁烯或叔丁醇氧化合成甲基丙烯醛的反应,但催化剂的活性仍然较低。
CN105413702B提到一种多层催化剂及其制备方法。所述多层催化剂从外层、中间层到内层由不同催化剂组分构成。多层催化剂由多种元素化合物组成,高温状态下容易引发催化剂产生裂纹,从而减弱催化剂强度,造成催化剂粉碎。
发明内容
基于以上背景技术,本发明以Bi基催化剂为出发点,通过碱金属和过渡金属的结构组成和比例调控,实现对于催化产物的分布、生产能耗、单程转化能力的提高。获得微观与宏观结构的高度统一催化剂。
本发明则采用上述所述M为高价态Mo、W、V中至少一种,再通过引入其他金属元素N为K、Cs、Fe、Co、Ni、Mn、Ce、Cu中至少一种,通过原位原子级掺杂合成通式为M-N-Bi的系列催化剂,催化2-甲基丙烯氧化制2-甲基丙烯醛的反应,良好的催化活性和选择性是催化剂的双重优点。
本发明一方面提供一种Bi基复合多酸催化剂,所述催化剂通式为MxNyBizOn,M为Mo、W、V中的至少一种,N为K、Cs、Fe、Co、Ni、Mn、Ce、Cu中的至少一种;x=0.05-10,y=0.05-10,z=1-25,n=1-50。
本发明还提供一种上述的Bi基复合多酸催化剂的制备方法,包括如下步骤:
(1)将M金属前驱体溶解于蒸馏水中,制得溶液A;所述溶液A中,M金属前驱体的质量浓度为1%-50%;
(2)将金属Bi前驱体溶于HNO3溶液中,得到溶液B’,向溶液B’加入N金属前驱体,最终制得溶液B;所述M金属前驱体和N金属前驱体中的M和N金属的摩尔比为0.01~10:0.01~10;HNO3溶液浓度为0.05wt%-20wt%;所述溶液B’中,金属Bi前驱体的质量浓度为1%-50%;
(3)将A溶液滴加到B溶液中,制得溶液C,控制溶液C的pH<1;溶液C的pH是通过步骤(2)中硝酸溶液的加入量控制的。
(4)将磷酸加入到C溶液中,得到溶液D;于20-80℃下搅拌溶液1-5h后,用氨水调节pH为3-6,继续搅拌20min-2h,蒸发干燥,得到固体粉末;
(5)将固体粉末于200-400℃下煅烧2-12h,得到所述Bi基复合多酸催化剂。
基于以上技术方案,优选的,所述M金属前驱体中,Mo前驱体为钼酸铵、钼酸钠、氧化钼,W前驱体为钨酸钠、钨酸铵、钨酸铁,V前驱体为钒酸钠、偏钒酸铵、草酸氧钒。
基于以上技术方案,优选的,所述N金属前驱体为所述金属的硝酸盐,硝酸钾、硝酸铯、硝酸铁、硝酸钴、硝酸镍、硝酸锰、硝酸铈、硝酸铜等。
基于以上技术方案,优选的,所述金属Bi前驱体为硝酸铋、硫酸铋、醋酸铋。
基于以上技术方案,优选的,步骤(4)所述催化剂的蒸发干燥温度为50-250℃,时间为8-12h。
基于以上技术方案,优选的,步骤(5)所述焙烧的初始温度为20-40℃,所述焙烧为程序升温焙烧,程序升温的升温速率为2-5℃/min。
基于以上技术方案,优选的,步骤(5)所述的煅烧为200-380℃下1-5h,380-400℃下1-5h。
本发明还提供一种上述Bi基复合多酸催化剂的应用,所述Bi基复合多酸催化剂用于2-甲基丙烯合成甲基丙烯醛的反应中,所述反应以2-甲基丙烯和氧气为原料,氮气为稀释气体;所述2-甲基丙烯与氧气的摩尔比为1:1~1:16,氮气组分占总气体的体积分数1%-90%;反应温度为300-400℃;空速为2500-10000h-1。
基于以上技术方案,优选的,2-甲基丙烯转化率为88%,对于甲基丙烯醛选择性为89%。
具体的制备步骤如下:
(1)将0.01-10mol的钼酸铵、0.01-10mol的钨酸钠、0.01-10mol的钒酸钠的至少一种溶解于25mL-10000mL蒸馏水中,制得溶液A;质量浓度为1%-50%;
(2)将0.01-100mol的硝酸铋溶于HNO3溶液中,制备溶B’,HNO3溶液浓度为0.05%-20%,HNO3溶液体积为0.1mL-500mL,再依次在溶液B’中引入其他金属元素N为K、Cs、Fe、Co、Ni、Mn、Ce、Cu中至少一种的盐0.01-10mol,最终制得溶液B;
(3)将A溶液滴加到B溶液中,制得溶液C,控制溶液pH<1;
(4)将0.0-0.5g的磷酸缓慢滴加到C溶液中,得到溶液D;
(5)将D溶液中不断搅拌,直至出现相应的沉淀,继续搅拌20min。
(6)取0.5-5mL的氨水调节pH=3-6,继续搅拌20min;
(7)在50-150℃烘箱中干燥8-12h,直至得到固体粉末;
(8)将固体粉末在200-400℃下置于马弗炉里焙烧,初始温度20-40℃,以2-5℃/min的升温速率,达到焙烧温度时保持2-10h,焙烧后自然降温,得到所述复合金属催化剂。
有益效果
(1)本发明中的M-N-Bi基多酸催化剂的制备方法简单,一锅制备方法即可得到催化剂,催化剂结构统一利于在催化反应中均匀发挥作用。
(2)在催化剂制备过程中加入酸,目的达到调控催化剂表面酸性效果,从而实现催化剂活性调控。
(3)催化剂中加入两种以上多酸类金属盐,使催化剂体相和表面存在大量氧缺陷,实现增强活性目的。
附图说明
图1为对比例1的催化氧化活性测试图。
图2为对比例1制备的催化剂XRD图。
图3为实施例2制备的催化剂的XRD图。
具体实施方式
对比例1
将9.8g钼酸铵溶于50mL的水中,搅拌溶解,量取10mLHNO3溶于25mL水中,2.4g硝酸铋进行溶解形成溶液,再将钼酸铵溶液滴加到硝酸铋盐溶液中,搅拌,缓慢加入0.1g磷酸,待沉淀生成后加入氨水调节pH=4,80℃烘箱中干燥12h,待水分蒸干后,加入蒸馏水进行洗涤抽滤,再放入80℃烘箱中干燥,得到的固体粉末。
将固体粉末置于马弗炉里200℃下焙烧1h,380℃下焙烧2h,初始温度20℃,以2℃/min的升温速率,焙烧后自然降温,得到所述复合金属催化剂Mo5Bi2O18。
将制备得到催化剂在常压连续流动床中进行测试,管径6mm,催化剂用量1g,GHSV=2500h-1,2-甲基丙烯与氧气摩尔含量比7%,在320-400℃间反应,催化性能在图1中。图2为对比例1制备的催化剂XRD图,从图中可以看出,所有出现的峰说明是Mo和Bi的多酸化合物结构,衍射峰锐利催化剂结晶程度高对于耐高温具有结构优势。
实施例1
将9.8钼酸铵溶于50mL的水中,搅拌溶解,量取10mLHNO3溶于25mL水中,0.51g硝酸钾,2.43g硝酸铋,0.97g硝酸铯,2.02g硝酸铁,1.46g硝酸钴进行溶解形成溶液,再将钼酸铵溶液滴加到硝酸铋盐溶液中,搅拌,待沉淀生成后加入氨水调节pH=7,80℃烘箱中干燥12h,待水分蒸干后,加入蒸馏水进行洗涤抽滤,再放入80℃烘箱中干燥,得到的固体粉末。
将固体粉末置于马弗炉里200℃下焙烧1h,380℃下焙烧2h,初始温度20℃,以2℃/min的升温速率,焙烧后自然降温,得到所述复合金属催化剂Mo5(Cs0.05Fe0.8Co0.5)Bi2O20。
将制备得到催化剂在常压连续流动床中进行测试,管径6mm,催化剂用量1g,GHSV=2500h-1,2-甲基丙烯与氧气摩尔含量比7%,在320-400℃间反应。
反应结果如表1:给出了不同反应温度下2-甲基丙烯转化率和甲基丙烯醛选择性。
实施例2
将9.8钼酸铵溶于50mL的水中,搅拌溶解,量取10mLHNO3溶于25mL水中,0.51g硝酸钾,2.43g硝酸铋,0.97g硝酸铯,2.02g硝酸铁,1.46g硝酸钴,0.85g硫酸锰进行溶解形成溶液,再将钼酸铵溶液滴加到硝酸铋盐溶液中,搅拌,待沉淀生成后加入氨水调节pH=7,80℃烘箱中干燥12h,待水分蒸干后,加入蒸馏水进行洗涤抽滤,再放入80℃烘箱中干燥,得到的固体粉末。
对比对比例1和实施例2的XRD图,说明本发明掺杂其他金属后,没有衍射峰,原子级别分散,说明掺杂的金属是原子级分散对于Mo-Bi基催化剂的XRD衍射峰没有影响。
将固体粉末置于马弗炉里200℃下焙烧1h,380℃下焙烧2h,初始温度20℃,以2℃/min的升温速率,焙烧后自然降温,得到所述复合金属催化剂Mo5(Cs0.05Fe0.8Co0.5Mn0.05)Bi2O21。
将制备得到催化剂在常压连续流动床中进行测试,管径6mm,催化剂用量1g,GHSV=2500h-1,2-甲基丙烯与氧气摩尔含量比7%,在320-400℃间反应。
反应结果如表1:给出了不同反应温度下2-甲基丙烯转化率和甲基丙烯醛选择性。
实施例3
将9.8g钼酸铵,0.68g钨酸钠溶于100mL的水中,搅拌溶解,量取10mLHNO3溶于100mL水中,1.6g硝酸铋,5.1g硝酸铁,0.6g硝酸钴,0.97g硝酸铯,0.6g硝酸锌进行溶解形成溶液,再将钼酸铵溶液滴加到硝酸铋盐溶液中,搅拌,待沉淀生成后加入氨水调节pH=3,80℃烘箱中干燥12h,待水分蒸干后,加入蒸馏水进行洗涤抽滤,再放入80℃烘箱中干燥,得到的固体粉末。
将固体粉末置于马弗炉里200℃下焙烧1h,380℃下焙烧2h,初始温度20℃,以2℃/min的升温速率,焙烧后自然降温,得到所述复合金属催化剂(Mo3W0.05)(Cs0.05Fe1.6Co0.25Zn0.1)Bi2O23。
将制备得到催化剂在常压连续流动床中进行测试,管径6mm,催化剂用量1g,GHSV=2500h-1,2-甲基丙烯与氧气摩尔含量比7%,在320-400℃间反应。
反应结果如表1:给出了不同反应温度下2-甲基丙烯转化率和甲基丙烯醛选择性。
实施例4
将9.8钼酸铵,0.68g钨酸钠,0.7g钒酸钠溶于100mL的水中,搅拌溶解,量取10mLHNO3溶于100mL水中,1.6g硝酸铋,5.1g硝酸铁,0.6g硝酸钴,0.6g硝酸铯,0.6g硝酸锌进行溶解形成溶液,再将钼酸铵溶液滴加到硝酸铋盐溶液中,搅拌,缓慢加入0.5g磷酸,待沉淀生成后加入氨水调节pH=3,80℃烘箱中干燥12h,待水分蒸干后,加入蒸馏水进行洗涤抽滤,再放入80℃烘箱中干燥,得到的固体粉末。
将固体粉末置于马弗炉里200℃下焙烧1h,380℃下焙烧2h,初始温度20℃,以2℃/min的升温速率,焙烧后自然降温,得到所述复合金属催化剂(Mo3W0.05V0.06)(Cs0.05Fe1.6Co0.25Zn0.1)Bi2O25。
将制备得到催化剂在常压连续流动床中进行测试,管径6mm,催化剂用量1g,GHSV=2500h-1,2-甲基丙烯与氧气摩尔含量比7%,在320-400℃间反应。
反应结果如表1:给出了不同反应温度下2-甲基丙烯转化率和甲基丙烯醛选择性。
表1
Claims (10)
1.一种Bi基复合多酸催化剂,其特征在于,所述催化剂通式为MxNyBizOn,M为Mo、W、V中的至少一种,N为K、Cs、Fe、Co、Ni、Mn、Ce、Cu中的至少一种;x=0.05-10,y=0.05-10,z=1-25,n=1-50。
2.一种权利要求1所述的Bi基复合多酸催化剂的制备方法,其特征在于,包括如下步骤:
(1)将M金属前驱体溶解于蒸馏水中,制得溶液A;所述溶液A中,M金属前驱体的质量浓度为1%-50%;
(2)将金属Bi前驱体溶于HNO3溶液中,得到溶液B’,向溶液B’加入N金属前驱体,最终制得溶液B;所述M金属前驱体和N金属前驱体中的M和N金属的摩尔比为0.01~10:0.01~10;HNO3溶液浓度为0.05wt%-20wt%;所述溶液B’中,金属Bi前驱体的质量浓度为1%-50%;
(3)将A溶液滴加到B溶液中,制得溶液C,控制溶液C的pH<1;
(4)将磷酸加入到C溶液中,得到溶液D;于20-80℃下搅拌溶液1-5h后,用氨水调节pH为3-6,继续搅拌20min-2h,蒸发干燥,得到固体粉末;
(5)将固体粉末于200-400℃下煅烧2-12h,得到所述Bi基复合多酸催化剂。
3.根据权利要求2所述的制备方法,其特征在于,所述M金属前驱体中,Mo前驱体为钼酸铵、钼酸钠、氧化钼,W前驱体为钨酸钠、钨酸铵、钨酸铁,V前驱体为钒酸钠、偏钒酸铵、草酸氧钒。
4.根据权利要求2所述的制备方法,其特征在于,所述N金属前驱体为所述金属的硝酸盐。
5.根据权利要求2所述的制备方法,其特征在于,所述金属Bi前驱体为硝酸铋、硫酸铋、醋酸铋。
6.根据权利要求2所述的制备方法,其特征在于,步骤(4)所述催化剂的蒸发干燥温度为50-250℃,时间为8-12h。
7.根据权利要求2所述的制备方法,其特征在于,步骤(5)所述焙烧的初始温度为20-40℃,所述焙烧为程序升温焙烧,程序升温的升温速率为2-5℃/min。
8.根据权利要求2所述的制备方法,其特征在于,步骤(5)所述的煅烧为200-380℃下1-5h,380-400℃下1-5h。
9.一种权利要求1所述的Bi基复合多酸催化剂的应用,其特征在于,所述Bi基复合多酸催化剂用于2-甲基丙烯合成甲基丙烯醛的反应中,所述反应以2-甲基丙烯和氧气为原料,氮气为稀释气体;所述2-甲基丙烯与氧气的摩尔比为1:1~1:16,氮气组分占总气体的体积分数1%-90%;反应温度为300-400℃;空速为2500-10000h-1。
10.根据权利要求9所述的应用,其特征在于,2-甲基丙烯转化率为88%,对于甲基丙烯醛选择性为89%。
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