CN1061163A - 丙烯腈流化床催化剂活性长期稳定的方法 - Google Patents
丙烯腈流化床催化剂活性长期稳定的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 230000000694 effects Effects 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title abstract description 11
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 30
- 239000011733 molybdenum Substances 0.000 claims abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 6
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
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- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
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- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 abstract description 6
- 230000002950 deficient Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract 1
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 229910021529 ammonia Inorganic materials 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
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
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Abstract
本发明是用于保持丙烯氨氧化法制造丙烯腈的
流化床催化剂活性长期稳定的方法，目前任何一种流
化床钼系催化剂在长期运转中，均不可避免发生催化
剂中钼组分的挥发和催化剂的细颗粒损失，使催化剂
活性下降而需再生，或用新催化剂予以更换。本发明
提出一种补加用的催化剂，以弥补流化床中催化剂中
钼组分的挥发和催化剂的细颗粒损失的缺陷。采用
本发明的补加催化剂，可使流化床反应器内催化剂的
使用寿命由原来的1-1.5年延长到4年或4年以
上。
Description
丙烯氨氧化制丙烯腈多数使用含有钼组分的多元催化剂。如美国专利4162234、日本专利特公昭58-2232所报道的均是钼、铋、铁系多组分催化剂;CN86101301A所报道的是钼、铋、铅系多组分催化剂。由于丙烯氨氧化反应在430-470℃的温度条件下进行，且反应过程中产生大量的水蒸气，因此对任何一种含钼催化剂均不可避免地发生钼的挥发损失，从而影响含钼催化剂的寿命。J.Buiten（J.Catal.，1968.10[2].188）对此进行了研究，并提出钼的挥发量与温度和水蒸气分压的定量关系以计算钼的损失量。
由于丙烯腈生产绝大多数采用流化床反应器，除了催化剂中的钼损失使催化剂组成发生变化影响活性外;气固相之间的接触效率，也直接影响到催化剂在流化床反应器中能否发挥其最佳性能。催化剂中细颗粒的含量，特别是小于45微米的细颗粒直接影响到气固相之间的接触效率。如果细颗粒催化剂含量过低，如低于10%（重量），将使丙烯转化率明显下降。
为保持丙烯腈流化床反应器的长期稳定运转，针对上述原因，曾提出过许多改进方法。如日本专利特公昭63-33903提出催化剂使用一定时间后，从反应器放出，补加损失的钼组分后再用;美国专利3882159提出向反应器中加入氧化钼或含有氧化钼的微球惰性物;美国专利4590011提出定期将反应器内催化剂抽出一部分，筛去粗粒催化剂后再放回反应器或加入细颗粒惰性粒子以补充反应器内细颗粒催化剂的损失;日本专利特公昭63-30065提及长期使用后的催化剂用机械粉碎方法使大颗粒催化剂粉碎以增加细颗粒的含量。
上述方法均有一定的缺陷，将催化剂从反应器取出补充钼组分或用过筛、粉碎等方法增加细颗粒含量，必须使反应器停止运转，从而造成经济损失。放出的催化剂除了在处理上麻烦外，粉碎后不再成球形，会影响反应器的流化质量。如用加入氧化钼或含有氧化钼的物料，虽然可以补加流化床中催化剂的钼的损失，但加入物与原有催化剂是机械混合，两者物理性质不同，会造成过多的氧化钼流出反应器，使后面的冷却器易发生堵塞，而需定期清理。
本发明的要点在于不需要使流化床反应器停止运转，使用一种特制的补加用的催化剂，可以同时解决运行中催化剂中钼组分的损失与细颗粒下降的问题，从而保证流化床反应器内的催化剂能较长期稳定运转。
本发明的要点在于采用的补加催化剂的各元素组成与原催化剂的各元素组成相同或接近，但钼含量高于原催化剂，小于45微米的细颗粒要占催化剂的50-60%（重量）。补充用的催化剂中过量的钼组分与其他组分形成固溶体而不是机械混合或存在着游离的氧化钼结构。本发明的补加催化剂是由二氧化硅载体和化学式如下的组合物组成：
AaBbCcDdFefBigMohOx
式中，A是钾、钠、铷、铯、铊、钐或它们的混合物;B是锰、镁、钙、锶、钡、铅或它们的混合物;C是磷、砷、硼、锑、铬、钨或它们的混合物;D是钴、镍或它们的混合物。
a为0.01-1、最佳为0.1-0.6，b为0-10、最佳为1-8，c为0.01-2、最佳为0.05-1.5，d为4-10、最佳为5-8，f为0.1-8、最佳为0.5-5，g为0.01-6、最佳为0.1-4，h为12-16，最佳为13-15。
x为满足催化剂中其它元素化合价所需的氧原子数总和。
载体二氧化硅的用量占催化剂的30-70%（重量），最佳为40-60%（重量）。
过量氧化钼的过量值可用“过量氧化钼指数”表示，其定义是催化剂中所有阳离子的正电荷和所有阴离子的负电荷的总和被-2除之。如果某种阳离子有几种价态，则以较低价态计算，例如铁是按+2价计，而不是按+3价计。在阴离子方面，如果是多元酸，则以最高负价数为准，例如磷酸根中的磷则按-3价计算。以组成为Mo12P0.5Fe3Bi1Ni2.5Co4.5K0.1的催化剂为例，它的过量氧化钼的指数计算值如下：
阳离子电荷总数为：3×2+1×3+2.5×2+4.5×2+0.1×1＝23.1
阴离子电荷总数为：12×（-2）+0.5×（-3）＝-25.5
过量氧化钼指数＝ (（-25.5）+23.1)/(（-2）) ＝1.2
过去已发表的钼系催化剂的专利，均未指出其过量氧化钼指数，但根据这些催化剂的组成可以计算出。绝大多数催化剂的过量氧化钼指数均为零或大于零。本发明催化剂的过量氧化钼指数为2-8，最好为2.5-6。
由于用于补加的催化剂中含有过量的钼组分，因此补加用的催化剂的活性低于原催化剂水平。但随着补加催化剂在流化床中的运转钼有所挥发，随之活性会上升到原用的催化剂水平。采用本发明的方法不会引起反应器中催化剂的组成变化。
补加用的催化剂的加入量和时间没有严格限止。补加量等于或大于从反应器被带出的数量。补加时间的间隔应尽可能短一些，而每次补加量应较小。
本发明催化剂只作补加用，不适宜单独用于生产丙烯腈。
[实例]按中国专利87103455.7（CN1005248B）中实例6的方法，但增加钼酸铵用量，使催化剂组成中的钼的原子比由原来的12增到13.8。在浆料喷雾成型过程中，将喷雾机转速增大，并将焙烧温度由原来的670℃提高到690℃，其余操作条件不变。制成的补加用的催化剂化学式如下：
Cs0.1K0.2Ni2.5Co4.5Fe2Mn1Bi1Cr0.5Na0.4Mo13.8Ox+50%SiO2
催化剂中小于45微米的细颗粒占60%（重量），过氧化钼指数为3.0。
长期运转试验按中国专利87103455.7（CN1005248B）中实例9进行。将组成为Cs0.1K0.2Ni2.5Co4.5Fe2Mn1Bi1Cr0.5Na0.4Mo12Ox+50%SiO2的催化剂放在直径2米的大型流化床中进行试验，反应温度为425-430℃，反应压力为0.05兆帕，线速为0.58米/秒，WWH为0.085，丙烯∶氨∶空气＝1∶1.15∶10.6（摩尔比）。
每周补加一次本发明组成为Cs0.1K0.2Ni2.5Co4.5Fe2Mn1Bi1Cr0.5Na0.4Mo13.8Ox+50%SiO2的催化剂。
在开始3个月内，丙烯腈的单程收率由初活性82%降到正常值77-78%，以后连续运转40个月，丙烯腈单程收率均保持在76-78%范围内无变化。补加催化剂的消耗量为0.4-0.5公斤/吨丙烯腈。
如果不采用本发明的补加催化剂方法，连续运转18个月后，丙烯腈单程收率下降到75%以下，必须从反应器放出全部催化剂进行处理或换用新催化剂。
Claims (4)
1、一种用于保持丙烯氨氧化制丙烯腈的流化床反应器内钼系催化剂活性的补加催化剂，由二氧化硅载体和化学式如下的组合物组成：
AaBbCcDdFefBigMohOx
式中A是钾、钠、铷、铯、铊、钐和它们的混合物；B是锰、镁、钙、锶、钡、铅或它们的混合物；C是磷、砷、硼、锑、铬、钨或它们的混合物；D是钴、镍或它们的混合物。
a为0.01-1，b为0-10，c为0.01-2，d为4-10，f为0.1-8，g为0.01-6，h为12-16。
x为满足催化剂中其它元素化合价所需的氧原子数总和。
催化剂中二氧化硅含量为30-70%(重量)。
催化剂的过量氧化钼指数为2-8。
2、根据权利要求1所述的催化剂，其中a为0.1-0.6，b为1-8，c为0.05-1，5，d为5-8，f为0.5-5，9为0.1-4，h为13-15，x为满足催化剂中各元素化合价所需的氧原子数。
催化剂中二氧化硅含量为40-60%（重量）。
3、根据权利要求1所述的催化剂，其特征在于小于45微米的细颗粒要占50-60%（重量）。
4、根据权利要求1所述的催化剂，其特征在于过量氧化钼指数为2.5-6。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90108809.9A CN1025551C (zh) | 1990-11-05 | 1990-11-05 | 保持丙烯腈流化床钼系催化剂活性稳定的补加催化剂 |
| US07/786,790 US5177048A (en) | 1990-11-05 | 1991-11-04 | Supplementary catalyst for ammoxidation catalysts |
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| Application Number | Priority Date | Filing Date | Title |
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| CN90108809.9A CN1025551C (zh) | 1990-11-05 | 1990-11-05 | 保持丙烯腈流化床钼系催化剂活性稳定的补加催化剂 |
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| CN1061163A true CN1061163A (zh) | 1992-05-20 |
| CN1025551C CN1025551C (zh) | 1994-08-03 |
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| CN90108809.9A Expired - Lifetime CN1025551C (zh) | 1990-11-05 | 1990-11-05 | 保持丙烯腈流化床钼系催化剂活性稳定的补加催化剂 |
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| CN (1) | CN1025551C (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086152C (zh) * | 1997-09-03 | 2002-06-12 | 中国石油化工总公司 | 烯烃氨氧化生产丙烯腈催化剂 |
| CN100358629C (zh) * | 2004-09-24 | 2008-01-02 | 中国石油化工股份有限公司 | 制备乙腈的流化床催化剂 |
| CN101992128B (zh) * | 2009-08-31 | 2012-09-05 | 中国石油化工股份有限公司 | 氨氧化流化床催化剂的再生方法 |
| CN103418405A (zh) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | 维持丙烯腈装置稳定生产的补加催化剂 |
| CN111744493A (zh) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | 一种氨氧化催化剂颗粒、其制造方法及其应用 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR960003792B1 (ko) * | 1992-12-31 | 1996-03-22 | 한국과학기술원 | 신규한 다성분계 혼합산화물 촉매 조성물 및 그의 제조방법 |
| EP0889027B1 (en) * | 1996-03-12 | 2002-11-20 | Asahi Kasei Kabushiki Kaisha | Process for preparing unsaturated nitrile |
| US5854172A (en) * | 1997-01-17 | 1998-12-29 | The Standard Oil Company | Preparation of vanadium antimonate based catalysts using SnO2 ·xH2 O |
| US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
| CN1108865C (zh) * | 1997-09-03 | 2003-05-21 | 中国石油化工集团公司 | 生产丙烯腈的催化剂 |
| CN104144910B (zh) | 2012-02-29 | 2016-08-17 | 三菱丽阳株式会社 | 丙烯腈的制造方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3882159A (en) * | 1973-08-20 | 1975-05-06 | Standard Oil Co | Reactivation of molybdenum containing oxidation catalysts in fluid bed reactors |
| US4162234A (en) * | 1974-07-22 | 1979-07-24 | The Standard Oil Company | Oxidation catalysts |
| JPS5976544A (ja) * | 1982-10-26 | 1984-05-01 | Nitto Chem Ind Co Ltd | 鉄・アンチモン系金属酸化物触媒の再生方法 |
| IT1176080B (it) * | 1984-04-18 | 1987-08-12 | Enichimica Secondaria | Procedimento per la rigenerazione di catalizzatori di ammonoossidazione |
| US4855275A (en) * | 1988-02-18 | 1989-08-08 | The Standard Oil Company | Catalyst performance improvement via separate boron addition |
-
1990
- 1990-11-05 CN CN90108809.9A patent/CN1025551C/zh not_active Expired - Lifetime
-
1991
- 1991-11-04 US US07/786,790 patent/US5177048A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086152C (zh) * | 1997-09-03 | 2002-06-12 | 中国石油化工总公司 | 烯烃氨氧化生产丙烯腈催化剂 |
| CN100358629C (zh) * | 2004-09-24 | 2008-01-02 | 中国石油化工股份有限公司 | 制备乙腈的流化床催化剂 |
| CN101992128B (zh) * | 2009-08-31 | 2012-09-05 | 中国石油化工股份有限公司 | 氨氧化流化床催化剂的再生方法 |
| CN103418405A (zh) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | 维持丙烯腈装置稳定生产的补加催化剂 |
| CN111744493A (zh) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | 一种氨氧化催化剂颗粒、其制造方法及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1025551C (zh) | 1994-08-03 |
| US5177048A (en) | 1993-01-05 |
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