CN1520927A - 丁烷氧化制顺丁烯二酸酐V-P-Si复合氧化物催化剂前驱体 - Google Patents
丁烷氧化制顺丁烯二酸酐V-P-Si复合氧化物催化剂前驱体 Download PDFInfo
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 35
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001273 butane Substances 0.000 title claims abstract description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title claims description 40
- 239000002131 composite material Substances 0.000 title claims description 13
- 239000002243 precursor Substances 0.000 title description 6
- 230000001590 oxidative effect Effects 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- -1 alkyl silicide Chemical compound 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 150000003682 vanadium compounds Chemical class 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 1
- 229910021332 silicide Inorganic materials 0.000 abstract 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 24
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 description 1
- AKPIVDFIYMRBMN-UHFFFAOYSA-N [Si]=O.[P].[V] Chemical compound [Si]=O.[P].[V] AKPIVDFIYMRBMN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
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- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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Abstract
本发明提供了一种由丁烷催化氧化制备顺酐的催化剂前驱体。该催化剂前区体是通过在有机溶剂中将V+5至少部分还原成V+4,然后,依次加入磷酸和烷基硅来制备。保证该催化剂前区体在适当的孔径分布情况下有较小的孔容和较大的堆密度。
Description
技术领域
本发明涉及一种制备顺丁烯二酸酐(简称顺酐,俗称马来酐)的催化剂。更具体地说,本发明涉及一种由丁烷经催化氧化制备顺酐的固体催化剂前驱体,特别是涉及制备顺酐的钒-磷-硅复合氧化物固定床或流化床固体催化剂前驱体。
背景技术
顺酐是重要的有机化工原料,大量用于生产热固性树脂、不饱和聚酯树脂、农药和精细化工产品。以前,用苯作原料生产顺酐。由于苯的毒性、不安全性和对环境的危害性,人们采用丁烯代替苯作原料生产顺酐,于60年代建立了由丁烯催化氧化生产顺酐的装置。由于丁烯昂贵,自70年代以来,逐渐转向以价廉且易得到的丁烷取代苯和丁烯作为原料生产顺酐。
对生产顺酐的不同方法进行比较认为,以正丁烷为原料生产顺酐要比用苯和丁烯经济,可采用固定床和/或流化床。
目前,对用丁烷作原料的固定床或流化床法制备顺酐催化剂的研究非常重视,已有许多专利文献报道,对流化床法中的许多问题进行了深入广泛地研究。但是,对流化床法用催化剂的研究集中在钒-磷-氧化物前驱体的组成和制备方法方面,提出了许多催化剂前驱体的制备方法。
CN1059297A公开了一种用于流化床正丁烷氧化制备顺酐的V-P-O系催化剂的制备方法,该方法是以工业级五氧化二钒为和85%磷酸为原料,以异丁醇为还原剂,在加热的条件下进行还原反应,再经热滤、改性处理、添加金属助催化剂、调浆、喷雾干燥得到微球催化剂。该方法要加金属助催化剂和改性处理,制备流程长,催化剂的活性和选择性不高。
CN1133755A披露了一种用于流化床正丁烷催化氧化制备顺酐催化剂的制备方法,该方法包括催化剂前驱体的制备和后处理加工过程。前驱体的制备以五氧化二钒和磷酸为原料,以水合肼为还原剂,以苯甲醇和异丁醇为混合液为溶剂,在反应过程中加入铁离子或锆离子,得到的前体与硅溶胶和胶凝剂制成负载型催化剂浆液,再经干燥脱水,在一定的气氛和温度下活化,最后成型筛分得到催化剂成品。该方法同样具有流程长和活化工艺复杂的缺点。
CN1282631A提示了一种钒-磷-氧催化剂的制备方法,该方法是将五氧化二钒与浓盐酸加热回流后,再加入磷酸继续回流,,冷却后加入硝酸锆、钼酸铵和乙酸锌。这种催化剂成分复杂,而催化活性和选择性不高。
CN1303741A描述了一种正丁烷氧化制顺酐的复合钒-磷-氧催化剂的制备方法,该方法是通过向VPO催化剂添加储氧体二氧化铈基复合氧化物来增加催化剂体系可用氧量,该方法制备的催化剂成分复杂,添加昂贵的稀土氧化物。
US5108974公开了一种钒-磷-氧化物催化剂前体的制备方法,该方法是通过在正硅酸烷基酯和磷酸混合物存在下,在醇溶剂中将五氧化二钒加热还原成四氧化二钒(V2O4),在正硅酸烷基酯的存在下,产物与其余的磷酸生成沉淀。
US4294722公开了一种含钒磷混合氧化物催化剂的对正丁烷的氧化特别有效的氧化催化剂的制备方法,该方法是将五氧化二钒溶于异丁醇中,回流加热约16小时;将磷酸溶于异丁醇中并加入上述的滤液中,得到的混合物加热回流8小时;冷却收集沉淀物得到催化剂前体。顺酐的选择性和收率均较低。
US4062873提示了一种钒-磷-硅-氧化物的制备方法,该方法是在有机介质中,共沉淀钒氧化物和正硅酸烷基酯,生成钒氧化物和氧化硅的的共沉淀物前体;磷与钒氧化物和正硅酸烷基酯的共沉淀物同时或其后共沉淀得到催化剂前驱体;煅烧该催化剂前驱体,得到含氧化硅的催化剂。
如上所述,现有技术中制备方法制备的生产顺酐的催化剂还存在顺酐产率和选择性不高、制备过程长等缺点。为克服这些不足,本发明人经过长期而深入地研究发现,将五价钒化合物在有机介质中还原后,使还原产物与磷酸在加热条件下进行反应,其生成物再与烷基硅在加热条件下进行反应生成催化剂前驱体,这种催化剂前驱体孔径分布适宜,孔容小,堆密度大。因此,由这种催化剂前驱体制备的催化剂比上述现有催化剂单位体积上具有更多的催化活性组分,对顺酐具有高的转化率,能够进一步提高顺酐基于正丁烷的收率,从而完成了本发明。
发明内容
因此,本发明的目的是提供一种由丁烷催化氧化制备顺酐的钒-磷-硅复合氧化物催化剂前驱体,特别是固定床或流化床用的钒-磷-硅复合氧化物催化剂前驱体。
本发明的另一目的是提供丁烷催化氧化制备顺酐的钒-磷-硅复合氧化物催化剂前驱体,特别是固定床或流化床催化剂前驱体的制备方法。
本发明的第三个目的是提供一种由丁烷催化氧化制备顺酐的改进方法。
本发明的丁烷催化氧化制备顺酐的钒-磷-硅复合氧化物催化剂前驱体,特别是固定床或流化床催化剂前驱体是由钒、磷和硅的复合氧化物组成,钒∶磷∶硅(摩尔比)=0.77-1.1∶1∶0.1-1;由ASAP2405吸附仪检测孔径分布为:孔径大于100的孔占90%以上,孔径小于100的孔占10%以下,平均孔径为130-180。孔容为0.03-0.10毫升/克,优选为孔容为0.02-0.06毫升/克。堆密度为0.80-1.00克/厘米3,优选为0.85-0.90克/厘米3。
如上所述,本发明的催化剂前体具有适宜的孔径分布,致使催化剂的孔容比现有技术中催化剂的孔容小,堆密度高,因而单位催化剂中的催化氧化有效活性位高。因此,本发明催化剂顺酐基于丁烷的摩尔收率在固定床和流化床上比现有技术中的催化剂分别高5摩尔%和10摩尔%以上。
本发明的催化剂前体的制备方法包括:
(1)将五氧化二钒加入混合醇[异丁醇/苯甲醇(体积比=2.5-5.0)]中,回流加热0.5-2小时;
(2)在回流加热条件下,向(1)中的生成物中以1.0-10克/分的速率加入85重量%磷酸,继续回流加热0.5-5小时;
(3)在回流加热的条件下,向(2)中的生成物中以0.5-5克/分的速率加入烷基硅,继续回流加热6-12小时;
(4)冷却、过滤、用有机溶剂洗涤滤饼、干燥得到催化剂前驱体。
本发明的催化剂前驱体的制备方法的特征在于,原料分步加入,还原反应分步进行。即先将钒化合物加入混合醇中,回流加热,使V+5至少部分还原成V+4,然后在回流状态下加完磷酸后再滴加烷基硅。
本发明的另一特征是磷酸和烷基硅是以不同的速率滴加的,使反应缓慢进行,晶体以一定的速度生长,从而使催化剂前驱体有适宜的孔径、孔容和堆密度。
本发明中所使用的有机溶剂是异丁醇和/或苯甲醇。如果用苯甲醇和异丁醇的混合溶液,则异丁醇∶苯甲醇=2.5-5.0(体积比)
本发明中所使用的五价钒化合物没有特别限制,但是优选五氧化二钒。为了加速反应,优选五氧化二钒研磨成粒径小于100微米,更优选小于30微米。
本发明中所使用的磷含氧酸同样没有特别限制,但是优选磷酸。
本发明中所使用的有机硅化合物也没有特别限制,但是优选四甲氧基硅烷和四乙基硅烷。
在本发明中,五氧化二钒与有机介质即醇类的还原反应是在回流加热下进行,反应时间通常为0.5-2小时,优选1-2小时。搅拌速度为100-1000转/分,优选为300-800转/分。
在本发明中,对磷酸的加入速率没有特别限制,通常为1.0-10克/分,优选为1-9克/分,更优选为3-8克/分。
在本发明中,对烷基硅的加入速率也没有特别限制,通常为0.5-5.0克/分,优选为1.0-5.0克/分,更优选为1.0-4.5克/分。
在本发明中,磷酸和烷基硅是单独分开添加,两者的添加速率可相同,也可不相同,优选磷酸的添加速率大于烷基硅的添加速率,只要使(VO)2H4P2O9晶体以所希望的速度成长即可。
在按本发明的方法得到催化剂前驱体后,可通过本技术领域内技术人员公知的知识和本技术领域内通用的成型方法,添加本技术领域内常用的粘结剂成型,制成片状、柱状、丸状、环状、球形、颗粒状等任何适宜的形状。
下面通过实施例更详细地描述本发明,但是,本发明不受这些实施例的限制。本发明的范围在附属的权利要求书中提出。
实施例1
在一个2升的设置加热器、机械搅拌器和冷凝器的玻璃反应釜内,在搅拌下,加入980毫升异丁醇和200毫升苯甲醇,然后加入60克五氧化二钒,回流加热1小时。此后,以2.3克/分的速率滴加95克85%的磷酸。此后,继续以3克/分的速率滴加50克四甲氧基硅烷,继续回流12小时后,冷却到室温,真空过滤收集沉淀物。滤饼用500毫升异丁醇洗涤后,于150℃温度下干燥2小时,得到约110克左右产品。制备条件和性能评价结果列于表1。
实施例2
除不加苯甲醇外,其它与实施例1相同,得到约110克产品。制备条件和性能评价结果列于表1。
实施例3
除不加烷基硅外,其它与实施例1相同,得到约110克产品。制备条件和性能评价结果列于表1。
实施例4
除五氧化二钒与醇及部分磷酸(约30克)和烷基硅(20克)的混合溶液进行还原反应后,再滴加剩余的磷酸和烷基硅外,其它与实施例1相同,得到约110克产品。制备条件和性能评价结果列于表1。
实施例5
除五氧化二钒与醇和全部烷基硅的混合液进行还原反应后再滴加磷酸外,其它与实施例1相同,得到约110克产品。制备条件和性能评价结果列于表1。
实施例6
除烷基硅采用倒入反应器不控制加料速率外,其它与实施例1相同,得到约110克产品。制备条件和性能评价结果列于表1。
实施例7
除磷酸采用倒入反应器不控制加料速率外,其它与实施例1相同,得到约110克产品。制备条件和性能评价结果列于表1。
实施例8
除五氧化二钒与醇和全部磷酸的混合溶液进行还原反应后再滴加烷基硅外,其它与实施例1相同,得到约110克产品。制备条件和性能评价结果列于表1。
表1
实施例 | 原料总量 | 磷酸烷基硅分步加料 | 控制加料速率 | 催化剂前驱体 | 催化剂固定床评价收率% | ||
平均孔径 | 孔容毫升/克 | 堆密度克/毫升 | |||||
1 | 是 | 是 | 是 | 148 | 0.03 | 0.94 | 62 |
2 | 否 | 是 | 是 | 147 | 0.045 | 0.80 | 45 |
3 | 否 | 是 | 是 | 129 | 0.04 | 0.82 | 50 |
4 | 是 | 否 | 是 | 154 | 0.07 | 0.79 | 57 |
5 | 是 | 否 | 是 | 179 | 0.09 | 0.52 | 48 |
6 | 是 | 是 | 否 | 160 | 0.075 | 0.75 | 54 |
7 | 是 | 是 | 否 | 172 | 0.08 | 0.6 | 50 |
8 | 是 | 否 | 是 | 185 | 0.10 | 0.48 | 45 |
表1的结果表明,在总的原料组成相同的情况下,采用将原料分步加入混合醇中,回流加热,使V+5至少部分还原成V+4。然后,在回流条件下,依次滴加磷酸和烷基硅,并控制其反应速度,使反应缓慢进行,从而得到孔径分布适宜,孔容小,堆密度高的钒-磷-硅复合氧化物催化剂前驱体。该钒-磷-硅复合氧化物催化剂前驱体经用本技术领域内众所周知的成型技术成型后,可用作由丁烷催化氧化制顺酐的催化剂,特别是用作由丁烷催化氧化制顺酐的固定床或流化床催化剂。该催化剂的催化活性评价表明,活性高,选择性好,与本技术领域内的传统催化剂相比,顺酐产率要高10摩尔%以上。
如上所述,本发明提供了一种由丁烷经催化氧化制备顺酐的钒-磷-硅复合氧化物催化剂前驱体及其制备方法和该催化剂前驱体在丁烷催化氧化制备顺酐中的应用。十分清楚,本领域内技术人员还可以对本发明做出修改和改进,这些修改和改进在不背离本发明精神的情况下,都在本发明的范围内。本发明的范围由附属的权利要求书提出。
Claims (11)
1.一种用于生产顺酐催化剂的V-P-Si复合氧化物催化剂前驱体,其特征是该催化剂前驱体的孔径分布为:孔径大于100的孔占90%以上,孔径小于100的孔占10%以下,孔容为0.01-1.00毫升/克。
2.按权利要求1所述的催化剂前驱体,其特征是孔容为0.02-0.06毫升/克。
3.按权利要求1或2所述的催化剂前驱体,其特征是堆密度为0.80-1.00厘米3/克。
4.权利要求1所述的催化剂前驱体,其特征是V∶P∶Si(摩尔比)=0.77-1.1∶1∶0.1-1。
5.权利要求1-4所述催化剂前驱体的制备方法,其特征是该方法包括如下步骤:
(1)将五价钒化合物加入混合醇中,回流加热0.5-2小时;
(2)在回流加热条件下,向(1)中的生成物中以1.0-10克/分的速率加入85重量%磷酸;
(3)在回流加热的条件下,向(2)中的生成物中以0.5-5克/分的速率加入烷基硅,继续回流加热6-12小时;
(4)冷却、过滤、用有机溶剂洗涤滤饼、干燥得到催化剂前驱体。
6.按权利要求5所述的方法,其特征是步骤(2)和(3)分两次进行。
7.按权利要求5所述的方法,其特征是五价钒化合物与混合醇进行还原反应后,再滴加磷酸。
8.按权利要求5所述的方法,其特征是磷酸的滴加速率为1-10克/分。
9.按权利要求5所述的方法,其特征是烷基硅的滴加速率为0.5-5.0克/分。
10.按权利要求5所述的方法,其特征是烷基硅为四甲氧基硅烷或四乙氧基硅烷。
11.权利要求1-4所述催化剂前驱体在丁烷催化氧化制备顺酐中的应用。
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CN1147359C (zh) | 2000-05-17 | 2004-04-28 | 中国石油化工集团公司 | 一种用正丁烷选择氧化制顺酐的钒磷氧催化剂及其制法 |
DE10211449A1 (de) * | 2002-03-15 | 2003-09-25 | Basf Ag | Katalysator-Precursor für die Herstellung von Maleinsäureanhydrid und Verfahren zu dessen Herstellung |
-
2003
- 2003-01-30 CN CNA031019374A patent/CN1520927A/zh active Pending
-
2004
- 2004-01-30 US US10/543,807 patent/US7547655B2/en not_active Expired - Fee Related
- 2004-01-30 WO PCT/CN2004/000085 patent/WO2004067170A1/zh active Application Filing
- 2004-01-30 CN CNB2004800028707A patent/CN100341620C/zh not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104056647A (zh) * | 2014-06-13 | 2014-09-24 | 大连拓润化工科技有限公司 | 可用于正丁烷氧化的催化剂制备方法 |
CN104028288A (zh) * | 2014-06-27 | 2014-09-10 | 大连龙泰科技发展有限公司 | 一种用于正丁烷氧化制备顺酐的催化剂 |
CN104028288B (zh) * | 2014-06-27 | 2016-08-24 | 大连龙缘化学有限公司 | 一种用于正丁烷氧化制备顺酐的催化剂 |
CN106622315A (zh) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | 一种钒磷氧化物及其制备方法 |
CN109926078A (zh) * | 2017-12-15 | 2019-06-25 | 北京淮颖顺酐科技有限公司 | V-P-In复合氧化物催化剂前驱体及其制备方法和应用 |
Also Published As
Publication number | Publication date |
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CN1741847A (zh) | 2006-03-01 |
WO2004067170A1 (fr) | 2004-08-12 |
US20060241310A1 (en) | 2006-10-26 |
CN100341620C (zh) | 2007-10-10 |
US7547655B2 (en) | 2009-06-16 |
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