CN1116110C - 含钼氧化物流化床催化剂的再生方法 - Google Patents
含钼氧化物流化床催化剂的再生方法 Download PDFInfo
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- CN1116110C CN1116110C CN99806050A CN99806050A CN1116110C CN 1116110 C CN1116110 C CN 1116110C CN 99806050 A CN99806050 A CN 99806050A CN 99806050 A CN99806050 A CN 99806050A CN 1116110 C CN1116110 C CN 1116110C
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- Prior art keywords
- catalyst
- molybdenum
- bismuth
- chromium
- deactivation
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 47
- 239000011733 molybdenum Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000001172 regenerating effect Effects 0.000 title abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 239000011651 chromium Substances 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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Abstract
本发明涉及含钼氧化物流化床催化剂的再生方法,包括将用于丙烯氨氧化生产丙烯腈反应过程的已减活的含钼、铋和铁的金属氧化物流化床催化剂用分别制备的钼化合物溶液和至少一种含至少一种选自铁、铬、镧和铈元素的化合物溶液浸渍或是用预制的上述化合物混合溶液浸渍,然后将所得催化剂干燥并在500-700℃温度下焙烧催化剂。
Description
技术领域
本发明涉及用于丙烯氨氧化反应的已减活的含钼氧化物流化床催化剂的再生方法。
先有工艺
在丙烯的氨氧化反应中使用的含钼氧化物催化剂是我们所熟知的,可举出的实例如US-A-2,904,580所公开的含钼·铋催化剂,US-A-3,226,422所公开的含钼·铋·铁催化剂,GB-A-1,319,190所公开的含钼·铋·铁·钴·镍等的催化剂,和US-A-5,132,269、US-A-5,134,105和US-A-5,663,113所公开的含更多组分的催化剂。但是,已知这些催化剂有时会因长时间反应或所设定的反应条件不合适造成活性衰减。
对在反应中使用而减活的催化剂再生问题已做出了许多努力。例如US-A-4,425,255提出的一种包括将减活的含钼催化剂于200-700℃下在一种还原气体中热处理,然后于500-700℃下在含氧气体中焙烧催化剂的方法;US-A-4,609,635公开的一种包括将减活的含K·Co·Ni·Fe·Bi·P·Mo催化剂用Bi·Mo组分浸渍,然后将所得催化剂焙烧的方法;和US-A-4,052,332公开的一种包括将减活的含Mo·Bi·P·Fe·Co·Ni·碱金属催化剂用钼酸盐水溶液浸渍,然后将所得催化剂干燥并于250-450℃下焙烧的方法。但是,所提出的这些方法再生操作过程复杂,且催化剂性能的恢复不足,因此仍然有许多问题有待解决。这些是工业上要完成的重要任务。
发明公开内容
本发明提供一种能有效将因反应中使用而减活的含钼氧化物催化剂再活化的方法,如上所述,这是工业上要完成的重要任务。
本发明人为解决上述问题进行了深入研究,结果发现当减活的催化剂用钼化合物溶液和特定元素的化合物溶液或是它们的混合溶液浸渍,然后将所得催化剂干燥并在特定温度下焙烧时,催化剂性能可提高到等于或高于新鲜催化剂的性能。从而得以完成本发明。
即,本发明涉及含钼氧化物流化床催化剂的再生方法,包括将用于丙烯氨氧化生产丙烯腈反应过程的已减活的含钼、铋和铁的金属氧化物流化床催化剂用分别制备的钼化合物溶液和至少一种含至少一种选自铁、铬、镧和铈元素的化合物溶液浸渍或是用预制的上述化合物混合溶液浸渍,然后将所得催化剂干燥并在500-700℃温度下焙烧催化剂。
实施本发明的最佳模式
适用于本发明方法的流化床用含钼氧化物催化剂是因反应中使用而减活的含钼、铋和铁的催化剂。
本发明方法特别有效于再生或再活化具有如下组成的流化床用氧化物催化剂:
Mo10BiaFebSbcDdEeFfGgHhOi(SiO2)j
上式中,Mo、Bi、Fe和Sb分别代表钼、铋、铁和锑,D代表至少一种选自镁、钙、锶、钡、铬、锰、钴、镍和锌的元素,E代表至少一种选自铜、银、镉、铝、镓、铟、锗、锡、铅、钛、锆和铪的元素,F代表至少一种选自钒、铌、钽、钨、钇、镧、铈、镨、钕、钐、铕、钆、钍、铀、铼、钌、锇、铑、铱、钯、铂和金的元素,G代表至少一种选自磷、硼和碲的元素,H代表至少一种选自锂、钠、钾、铷和铯的元素,O代表氧且Si代表硅,下标a、b、c、d、f、f、g、h、i和j代表原子比,且当Mo=10时,a=0.1-5,b=0.1-15,c=0-20,d=0-10,e=0-10,f=0-5,g=0-5,h=0-3,i为对应于上述各组分结合生成的氧化物的氧原子数,且j=20-150。
优选再生处理前的催化剂(减活催化剂)、用本发明方法再生处理后的催化剂及刚制成的催化剂全部在上述组成范围内。
按本发明方法对减活催化剂的再生处理实施步骤是将催化剂分别或同时用单独制备的含钼组分溶液和至少一种含至少一种选自铁、铬、镧和铈元素的溶液浸渍或是用预制的上述化合物混合溶液浸渍,然后将所得催化剂焙烧,若需要的话,浸渍步骤可分批多次进行。已发现这样的再生处理方法可使减活催化剂改进成性能比新鲜催化剂更好的催化剂。
当催化剂用钼或其它组分浸渍时,各浸渍元素按原子比的组成为Mo1AaBbCc,其中A为至少一种选自磷、硼、碲和铋的元素,B为至少一种选自铁、铬、锆、镧和铈的元素,且C为至少一种选自镁、锰、镍和钴的元素,a=0-1,b=0.03-1,优选b=0.05-0.8和c=0-1,假定催化剂中钼的原子比为10时,则要浸渍的钼的原子比为0.01-2。若浸渍组分的量超过上述范围,则由于所希望产物的收率降低,催化剂的活性不太好。具体来说,若组分钼的量过高,也会引起催化性能下降,例如,在催化剂制备过程中存在发粘、固化等类似现象,或者在反应时产生钼垢。在单独用钼浸渍时,选择性和反应速度的改进不足。在仅加入B组分时,反而会使选择性和反应速度都下降。将钼和B组分同时加入的方法被认为是能够在改进性能方面表现出协同作用。若B组分与钼的比例小于0.03(原子比),则不足以恢复和提高催化剂性能,若该比例大于1,则会造成催化性能衰减,例如所希望产物的收率反而下降。A和C组分要根据具体目的,例如想要控制反应速度或阻止生成副产物的目的而加入。
若需要,可以在本发明方法所用的浸渍溶液中添加少量非钼和A、B与C的其它组分,如钠、钾、铷、铯、钇、镨、钕、钐、钒、铌、钨、铜、银和锌。
本发明方法中,制备浸渍溶液所用的起始原料可以使用钼酸铵、过钼酸和/或其铵盐、磷钼酸、硅钼酸等作为钼组分的原料。尤其是由钼酸或其盐与过氧化氢制成的过钼酸和/或其盐能与许多化合物生成稳定的混合溶液,因而使用起来很方便。若很难制成稳定的混合溶液,则分别制备各组分元素化合物的溶液,依次用它们来进行反复浸渍操作。可以很方便地使用水溶性化合物作为A、B和C组分的起始原料,如正磷酸作为磷的原料,硼酸作为硼的原料,碲酸作为碲的原料,和硝酸铋、硝酸铁、硝酸铬、硝酸锆和硝酸铯作为铋、铁、铬、锆和铯的原料。也可很方便地使用硝酸盐作为镁、锰、镍和钴的原料。将它们溶解在水中,并调节溶液的量,获得浸渍溶液。
浸渍步骤中,预先测定减活催化剂的孔体积,按孔体积的80-110%,优选90-98%的量制备浸渍溶液,将指定量的钼原料化合物和指定量的B组分原料化合物或是按需要加入的A和/或C组分原料化合物溶解。然后溶液浸渍减活催化剂的孔隙,接着充分混合。浸渍完成后,将催化剂干燥并焙烧。
焙烧步骤优选在催化剂颗粒移动条件下进行。适合采用旋转焙烧炉、流化床焙烧炉等进行焙烧。若催化剂以固定方式焙烧,则成为固定状态,导致不便于用作流化床催化剂,或者其活性不足以提高。在最后焙烧阶段时,尤其优选使用能更严格对焙烧温度进行控制的流化床焙烧炉。
焙烧气氛通常为空气,但除此之外还可使用惰性气体如氮气、二氧化碳和水蒸汽,或是还原气体如各种包含氨、有机化合物或类似物质的含氧气体。
下面的实施例和比较实施例将对本发明作进一步详细具体说明。
实施例1
将50kg组成为Mo10Bi0.8Fe4.4Sb4.2Ni6.5P0.5B0.3Te0.25K0.7O55.4(SiO2)40的催化剂装入内径8英寸的流化床反应器,当丙烯的氨氧化反应进行较长一段时间后,丙烯腈收率下降。用水滴定法测定的此减活催化剂的孔体积为0.22ml/g。在1940g减活催化剂中加入含比例为Mo1Cr0.2Zr0.1(原子比)的钼、铬和锆浸渍溶液(制备方法见下文),加入量为410ml,相当于孔体积的96%,然后用V形混合机充分混合。浸渍减活催化剂所用钼与减活催化剂中钼的比例为1比10(原子比)。浸渍后的催化剂放入陶瓷容器,用干燥器于250℃下干燥2小时,然后在箱式电炉内于400℃下焙烧2小时,最后在流化床焙烧炉内于570℃空气流化条件下焙烧3小时。将得到的催化剂进行下文所述的活性试验。
按下述方式制备浸渍溶液。
将86g过氧化氢水溶液加入到130g纯水中,在其中溶解61.4g仲钼酸铵(溶液A)。
将128g 63%硝酸加入到95g纯水中,在其中溶解27.8g硝酸铬和9.3g氧化硝酸锆(溶液B)。
搅拌下将溶液B加入到溶液A中。
实施例2
按实施例1的方式用钼和铁浸渍减活催化剂,但浸渍组分为钼和铁。硝酸铁用作铁组分的原料,且最后焙烧步骤于565℃下进行3小时。将得到的催化剂进行下文所述的活性试验。
实施例3
按实施例1的方式用钼、铁、铬、镧和钒浸渍减活催化剂,但浸渍组分为上述这些元素。硝酸镧用作镧组分的原料,且最后焙烧步骤于565℃下进行3小时。将得到的催化剂进行下文所述的活性试验。
实施例4
按实施例1的方式用钼、铋、碲和镁浸渍减活催化剂,但浸渍组分为上述这些元素。硝酸铋用作铋组分的原料,硝酸碲用作碲组分的原料且硝酸镁用作镁组分的原料,最后焙烧步骤于560℃下进行3小时。将得到的催化剂进行下文所述的活性试验。
实施例5
按实施例1的方式用钼、铁、铬、铈和钨浸渍减活催化剂,但浸渍组分为上述这些元素。硝酸铈用作铯组分的原料,仲钨酸铵用作钨的原料,且最后焙烧步骤于570℃下进行3小时。将得到的催化剂进行下文所述的活性试验。实施例6
按实施例1的方式用钼、铁、铬、锆和锰浸渍减活催化剂,但浸渍组分为上述这些元素。硝酸锰用作锰组分的原料,且最后焙烧步骤于570℃下进行3小时。将得到的催化剂进行下文所述的活性试验。
实施例7
按实施例1的方式用钼、铁、铬和锆浸渍减活催化剂,但浸渍组分为上述这些元素。最后焙烧步骤于570℃下进行。将得到的催化剂进行下文所述的活性试验。
实施例8
按实施例1的方式用钼、磷、碲、铁、铬、锆、镍和钴浸渍减活催化剂,但浸渍组分为上述这些元素。正磷酸用作磷组分原料,且硝酸镍和硝酸钴分别用作镍和钴组分原料,最后焙烧步骤于565℃下进行3小时。将得到的催化剂进行下文所述的活性试验。
实施例9
按实施例1的方式用钼、铁、铬、锆和镧浸渍减活催化剂,但浸渍组分为上述这些元素。最后焙烧步骤于570℃下进行3小时。将得到的催化剂进行下文所述的活性试验。
实施例10
按实施例1的方式用钼、硼和铁浸渍减活催化剂,但浸渍组分为上述这些元素。硼酸用作硼组分的原料,且最后焙烧步骤于570℃下进行3小时。将得到的催化剂进行下文所述的活性试验。比较实施例1
因长时间丙烯氨氧化反应而减活的催化剂进行下文所述的活性试验。比较实施例2
将2kg比较实施例1的减活催化剂于565℃下在流化床焙烧炉内空气流化条件下焙烧3小时。得到的催化剂进行下文所述的活性试验。比较实施例3
实施例1的催化剂用于长时间反应之前进行下文所述的活性试验。比较实施例4
按实施例1相同的方式进行再生处理,但不加钼组分。得到的催化剂进行下文所述的活性试验。比较实施例5
按实施例1相同的方式进行再生处理,但不加铬和锆组分。得到的催化剂进行下文所述的活性试验。活性试验
对上述实施例和比较实施例中的催化剂进行活性试验。活性试验按下文所例举的丙烯氨氧化反应的方式进行。
将催化剂装入催化剂流化部分为400mm高和25mm内径的流化床反应器内,将组成为丙烯/氨/空气/水蒸汽=1/1.2/10/0.5(摩尔比)的混合气体送入反应器中,气体的线速度为4.5cm/秒,反应压力为200kPa。
催化时间、丙烯腈收率、选择性和丙烯转化率的定义如下。
催化时间(秒)=根据表观松密度计算的催化剂体积(ml)/不同条件下计算的气体流速(ml/秒)。
丙烯腈收率(%)=生成的丙烯腈摩尔数/送入的丙烯摩尔数×100
丙烯腈选择性(%)=生成的丙烯腈摩尔数/已反应的丙烯摩尔数×100
丙烯转化率(%)=已反应的丙烯摩尔数/送入的丙烯摩尔数×100
活性试验的结果示于表1。
表1
注:1)丙烯腈 2)丙烯
浸渍组分(在Mo为1时的原子比) | Mo*1的浸渍量 | 最后焙烧温度(℃) | 表观松密度(g/ml) | 反应条件 | 反应结果 | ||||||
A | B | C | 其它组分 | 反应温度(℃) | 催化时间(秒) | AN1)收率(%) | C3 2)转化率(%) | ||||
实施例12345678910 | ---Bi0.2Te0.2---P0.1Te0.1-B0.1 | Cr0.2Zr0.1Fe0.2Fe0.1Cr0.2La0.1Fe0.2Fe0.1Cr0.1Ce0.05Fe0.1Cr0.4Zr0.1Fe0.05Cr0.2Zr0.1Fe0.1Cr0.2Zr0.1Fe0.1Cr0.3Zr0.1La0.1Fe0.2 | ---Mg0.05-Mn0.1-N0.1Co0.1-- | --V0.05-W0.05----- | 10.61.5110.60.521.51.5 | 570565570560570570570565570570 | 1.051.031.071.041.051.041.041.071.061.05 | 440440440440440440440440440440 | 2.252.502.002.502.252.252.252.002.002.00 | 84.582.384.382.583.883.183.083.583.682.5 | 98.398.098.797.798.798.098.298.198.298.2 |
比较实1施例2345 | 减活催化剂 | ----1 | -570-570570 | 1.031.021.031.031.04 | 440440440440440 | 3.503.252.503.002.75 | 78.580.581.779.681.0 | 98.198.098.398.298.5 | |||
空气中焙烧的减活催化剂 | |||||||||||
新鲜催化剂 | |||||||||||
-- | Cr0.2Zr0.1- | -- | -- |
减活的含钼氧化物流化床催化剂可通过本发明方法有效进行再生。再生的催化剂未显示物理性能退化,此外,还可使反应结果优于新鲜催化剂所得到的结果。
Claims (5)
1.一种含钼氧化物流化床催化剂的再生方法,包括将用于丙烯氨氧化生产丙烯腈反应过程的已减活的含钼、铋和铁的金属氧化物流化床催化剂用分别制备的钼化合物溶液和至少一种含至少一种选自铁、铬、镧和铈元素的化合物溶液浸渍或是用预制的上述化合物混合溶液浸渍,然后将所得催化剂干燥并在500-700℃温度下焙烧催化剂。
2.一种含钼氧化物流化床催化剂的再生方法,包括将用于丙烯氨氧化生产丙烯腈反应过程的已减活的含钼、铋和铁的金属氧化物流化床催化剂用分别制备的钼化合物溶液和至少一种含至少一种选自铁、铬、镧和铈元素的化合物溶液浸渍或是用预制的上述化合物混合溶液浸渍,然后将所得催化剂干燥并在500-700℃温度下焙烧催化剂,附带条件是各浸渍组分元素按原子比的组成为Mo1AaBbCc,其中A为至少一种选自磷、硼、碲和铋的元素,B为至少一种选自铁、铬、锆、镧和铈的元素,且C为至少一种选自镁、锰、镍和钴的元素,a=0-1,b=0.03-1,和c=0-1,假定催化剂中钼的原子比为10时,则要浸渍的钼的原子比为0.01-2。
3.按权利要求1或2的方法,其中过钼酸或其盐用作钼化合物。
4.按权利要求1或2的方法,其中最后焙烧步骤采用流化床焙烧炉进行。
5.按权利要求1-4任一项的方法,其中含钼氧化物流化床催化剂具有如下组成:
Mo10BiaFebSbcDdEeFfGgHhOi(SiO2)j上式中,Mo、Bi、Fe和Sb分别代表钼、铋、铁和锑,D代表至少一种选自镁、钙、锶、钡、铬、锰、钴、镍和锌的元素,E代表至少一种选自铜、银、镉、铝、镓、铟、锗、锡、铅、钛、锆和铪的元素,F代表至少一种选自钒、铌、钽、钨、钇、镧、铈、镨、钕、钐、铕、钆、钍、铀、铼、钌、锇、铑、铱、钯、铂和金的元素,G代表至少一种选自磷、硼和碲的元素,H代表至少一种选自锂、钠、钾、铷和铯的元素,O代表氧且Si代表硅,下标a、b、c、d、f、f、g、h、i和j代表原子比,且当Mo=10时,a=0.1-5,b=0.1-15,c=0-20,d=0-10,e=0-10,f=0-5,g=0-5,h=0-3,i为对应于上述各组分结合生成的氧化物的氧原子数,且j=20-150。
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US6919295B2 (en) * | 2002-05-01 | 2005-07-19 | Rohm And Haas Company | Supported mixed metal oxide catalyst |
US20040024071A1 (en) * | 2002-08-01 | 2004-02-05 | Meier Paul F. | Perovskite compositions and method of making and process of using such compositions |
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