CN113828324A - 一种丙烯腈生产用催化剂 - Google Patents
一种丙烯腈生产用催化剂 Download PDFInfo
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- CN113828324A CN113828324A CN202111206687.0A CN202111206687A CN113828324A CN 113828324 A CN113828324 A CN 113828324A CN 202111206687 A CN202111206687 A CN 202111206687A CN 113828324 A CN113828324 A CN 113828324A
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- catalyst
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- acrylonitrile
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [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 abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 239000010937 tungsten Substances 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011852 carbon nanoparticle Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012824 chemical production Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
- B01J23/8878—Chromium
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- 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
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- 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
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- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J23/889—Manganese, technetium or rhenium
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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
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
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Abstract
本发明公开了一种丙烯腈生产用催化剂,涉及化工生产催化剂技术领域,具体为一种丙烯腈生产用催化剂,其特征在于:包括含有铁、铋、钼、镁、碳的基本体与任选的含有锂、钠、钾、铷、铯、钴、镍、锶、锰、钙、钡、磷、硼、锑、铬、钨、钒中一种或多种元素的催化氧化物的复合物以及催化剂载体,具有以下通式:AaBbMgcFedCeBifMogOx。该丙烯腈生产用催化剂,通过在催化剂中设置铁、铋、钼、镁、碳的基本体之外,在催化剂中加入锂、钠、钾、铷、钡、磷、硼等活泼元素的一种或几种,提高催化剂整体的活性,从而降低催化剂反应时所需的温度与压力,降低了对生产设备的限制,从而降低了制备成本,同时降低反应所需的温度与压力,提高了生产时的安全性。
Description
技术领域
本发明涉及化工生产催化剂技术领域,具体为一种丙烯腈生产用催化剂。
背景技术
目前烯烃氨氧化制备不饱和腈的工业生产仍普遍采用流化床氨氧化工艺,催化剂作为该工艺的核心技术之一,其研究、改进一直得到重视。当前工业丙烯氨氧化制丙烯腈的催化剂主要有两类:Mo-Bi系和Sb系,其中Mo-Bi 系催化剂占主导地位,达到烯烃氧化市场的95%,前人研究和探索也主要集中在Mo-Bi系催化剂上。通过在催化剂中引入具有可变价态的金属组分如Fe、Ce等元素提高催化剂的氧化-还原性能,加快恢复催化剂活性组分的有效状态;通过引入离子半径大于0.8nm和小于0.8nm的金属元素,如Cr、Ni、Mg、 Mn、Zn、Al等元素,起到结构和电子助剂作用,改进催化剂的结构和稳定性能;通过引入稀土元素,提高催化剂的晶格氧数量,改善催化剂的催化性能;通过引入Cs、Rb、P、B、Al等元素,对催化剂进行表面修饰和酸碱性的调节,改善催化剂的选择性和活性。
目前常见的丙烯腈生产用催化剂,在使用时需要在较高温度与压力下才能保持较高活性,满足催化要求,导致丙烯腈生产条件严格,进一步导致生产成本急剧增加,同时在高温高压下对丙烯腈进行制备,具有一定的安全隐患,此外,现有催化剂通常担载在催化剂载体上,如球状硅胶载体,将催化剂包裹在球状载体上,但是在催化剂使用时,只有球状载体最外圈的催化剂可直接与丙烯腈原料接触反应,接触面积较小,导致丙烯腈原料整体反应速率较慢,造成整体生产周期的延长,为此我们提出一种丙烯腈生产用催化剂以解决上述提出的问题。
发明内容
针对现有技术的不足,本发明提供了一种丙烯腈生产用催化剂,解决了上述背景技术中提出的问题。
为实现以上目的,本发明通过以下技术方案予以实现:一种丙烯腈生产用催化剂,包括含有铁、铋、钼、镁、碳的基本体与任选的含有锂、钠、钾、铷、铯、钴、镍、锶、锰、钙、钡、磷、硼、锑、铬、钨、钒中一种或多种元素的催化氧化物的复合物以及催化剂载体,具有以下通式: AaBbMgcFedCeBifMogOx,通过在催化剂中设置铁、铋、钼、镁、碳的基本体之外,在催化剂中加入锂、钠、钾、铷、钡、磷、硼等活泼元素的一种或几种,提高催化剂整体的活性,从而降低催化剂反应时所需的温度与压力,降低了对生产设备的限制,从而降低了制备成本,大大增进该方法的效率和经济性,此外该催化剂可在较低温度下对丙烯腈进行制备,降低反应所需的温度与压力,提高了生产时的安全性,其中:
A是锂、钠、钾、铷、铯、钴、镍、锶、锰、钙、钡中的一种或者多中元素;
B是磷、硼、锑、铬、钨、钒中的一种或者多种元素;
a是大于0小于4之间的数;
b是大于0小于3之间的数;
c是0至0.4之间的数;
d、e、f以及g均为0至8之间的数;
x为满足催化剂中各元素化合价所需的氧原子总数。
优选的,所述a与b之和大于0至7,该催化剂可以在较低温度下对丙烯腈进行制备,同时具有较好的氧化还原稳定性,因此可以采用较低的过程空气/烯烃比例和较高的重量时空速率,该催化剂可有效地利用氨,大大降低了反应器流出物中未反应的氨含量,从而减少了中和流出物中氨所需硫酸用量。
优选的,所述催化剂担载在一种催化剂载体上,该催化剂载体可以为氧化铝、硅胶、碳纳米、二氧化硅中的任意一中或者多种混合。
优选的,所述催化剂载体包括球体骨架以及改性剂,所述催化剂喷涂于骨架载体上,通过将催化剂载体设备为球体骨架结构,在反应时,球状骨架表面以及内部的催化剂均可与丙烯腈接触,使催化剂可以充分与丙烯腈原料接触,提高丙烯腈原料的反应速率,进一步的缩短了生产周期,通过在将催化剂制备完成后,可直接喷涂在催化剂载体上,降低了制备难度。
优选的,所述催化剂载体含量为30-65wt%,所述改性剂含量为0.1-3wt%。
优选的,一种丙烯腈生产用催化剂,包括以下制备方法:
S1、将所需量除Mo外的相应活性组分元素的盐进行溶解,得到溶液1;
S2、将所需量的骨架载体与改性剂溶液混合,得到处理后的催化剂载体;
S3、将所需量含钼的钼酸盐进行溶解,并与溶液1混合,在pH为1~7 (pH优选为4)和温度在30~90℃(温度优选为60℃)下搅拌,得到浆料1;
S4、浆料1经喷雾干燥和在500-650℃(温度优选为600℃)下焙烧活化 0.2-0.5(时间优选为0.35)小时,得到所需催化剂,通过喷涂设备将催化剂喷涂在骨架催化剂载体上,实现对催化剂的生产。
本发明提供了一种丙烯腈生产用催化剂,具备以下有益效果:
1、该丙烯腈生产用催化剂,通过在催化剂中设置铁、铋、钼、镁、碳的基本体之外,在催化剂中加入锂、钠、钾、铷、钡、磷、硼等活泼元素的一种或几种,提高催化剂整体的活性,从而降低催化剂反应时所需的温度与压力,降低了对生产设备的限制,从而降低了制备成本,同时降低反应所需的温度与压力,提高了生产时的安全性。
2、该丙烯腈生产用催化剂,该催化剂可以在较低温度下对丙烯腈进行制备,同时具有较好的氧化还原稳定性,因此可以采用较低的过程空气/烯烃比例和较高的重量时空速率,该催化剂可有效地利用氨,大大降低了反应器流出物中未反应的氨含量,从而减少了中和流出物中氨所需硫酸用量。
3、该丙烯腈生产用催化剂,通过将催化剂载体设备为球体骨架结构,在反应时,球状骨架表面以及内部的催化剂均可与丙烯腈接触,使催化剂可以充分与丙烯腈原料接触,提高丙烯腈原料的反应速率,进一步的缩短了生产周期,通过在将催化剂制备完成后,可直接喷涂在催化剂载体上,降低了制备难度。
具体实施方式
下面将结合本发明的实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
本发明提供一种技术方案:一种丙烯腈生产用催化剂,其特征在于:包括含有铁、铋、钼、镁、碳的基本体与任选的含有锂、钠、钾、铷、铯、钴、镍、锶、锰、钙、钡、磷、硼、锑、铬、钨、钒中一种或多种元素的催化氧化物的复合物以及催化剂载体,具有以下通式:AaBbMgcFedCeBifMogOx,通过在催化剂中设置铁、铋、钼、镁、碳的基本体之外,在催化剂中加入锂、钠、钾、铷、钡、磷、硼等活泼元素的一种或几种,提高催化剂整体的活性,从而降低催化剂反应时所需的温度与压力,降低了对生产设备的限制,从而降低了制备成本,大大增进该方法的效率和经济性,此外该催化剂可在较低温度下对丙烯腈进行制备,降低反应所需的温度与压力,提高了生产时的安全性,其中:
A是锂、钠、钾、铷、铯、钴、镍、锶、锰、钙、钡中的一种或者多中元素;
B是磷、硼、锑、铬、钨、钒中的一种或者多种元素;
a是大于0小于4之间的数;
b是大于0小于3之间的数;
c是0至0.4之间的数;
d、e、f以及g均为0至8之间的数;
x为满足催化剂中各元素化合价所需的氧原子总数。
所述a与b之和大于0至7,该催化剂可以在较低温度下对丙烯腈进行制备,同时具有较好的氧化还原稳定性,因此可以采用较低的过程空气/烯烃比例和较高的重量时空速率,该催化剂可有效地利用氨,大大降低了反应器流出物中未反应的氨含量,从而减少了中和流出物中氨所需硫酸用量。
所述催化剂担载在一种催化剂载体上,该催化剂载体可以为氧化铝、硅胶、碳纳米、二氧化硅中的任意一中或者多种混合,该催化剂可以担载在多种载体上,降低了限制条件,且将该催化剂担载在不同的载体上,通过单一载体或者多种载体的配合使用,使该催化剂可在不同工况下进行使用,增加适用范围,降低局限性,同时使该催化剂可对不同的化工原料进行催化。
所述催化剂载体包括球体骨架以及改性剂,所述催化剂喷涂于骨架载体上,通过将催化剂载体设备为球体骨架结构,在反应时,球状骨架表面以及内部的催化剂均可与丙烯腈接触,使催化剂可以充分与丙烯腈原料接触,提高丙烯腈原料的反应速率,进一步的缩短了生产周期,通过在将催化剂制备完成后,可直接喷涂在催化剂载体上,降低了制备难度。
所述催化剂载体含量为30-65wt%,所述改性剂含量为0.1-3wt%,通过对催化剂含量进行限制,保证球体骨架结构的载体可以担载合适数量的催化剂,从而实现增加催化剂与丙烯腈原料接触面积的目的,提高反应速率。
一种丙烯腈生产用催化剂,包括以下制备方法:
S1、将所需量除Mo外的相应活性组分元素的盐进行溶解,得到溶液1;
S2、将所需量的骨架载体与改性剂溶液混合,得到处理后的催化剂载体;
S3、将所需量含钼的钼酸盐进行溶解,并与溶液1混合,在pH为1~7 (pH优选为4)和温度在30~90℃(温度优选为60℃)下搅拌,得到浆料1;
S4、浆料1经喷雾干燥和在500-650℃(温度优选为600℃)下焙烧活化 0.2-0.5(时间优选为0.35)小时,得到所需催化剂,通过喷涂设备将催化剂喷涂在骨架催化剂载体上,实现对催化剂的生产。
在本发明的描述中,需要说明的是,术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于所示的方位或位置关系,仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明的限制;术语“第一”、“第二”、“第三”仅用于描述目的,而不能理解为指示或暗示相对重要性,此外,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或一体地连接;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通。对于本领域的普通技术人员而言,可以具体情况理解上述术语在本发明中的具体含义。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (6)
1.一种丙烯腈生产用催化剂,其特征在于:包括含有铁、铋、钼、镁、碳的基本体与任选的含有锂、钠、钾、铷、铯、钴、镍、锶、锰、钙、钡、磷、硼、锑、铬、钨、钒中一种或多种元素的催化氧化物的复合物以及催化剂载体,具有以下通式:AaBbMgcFedCeBifMogOx,其中:
A是锂、钠、钾、铷、铯、钴、镍、锶、锰、钙、钡中的一种或者多中元素;
B是磷、硼、锑、铬、钨、钒中的一种或者多种元素;
a是大于0小于4之间的数;
b是大于0小于3之间的数;
c是0至0.4之间的数;
d、e、f以及g均为0至8之间的数;
x为满足催化剂中各元素化合价所需的氧原子总数。
2.根据权利要求1所述的一种丙烯腈生产用催化剂,其特征在于:所述a与b之和大于0至7。
3.根据权利要求1-2中任一项的丙烯腈生产用催化剂,其特征在于:所述催化剂担载在一种催化剂载体上,该催化剂载体可以为氧化铝、硅胶、碳纳米、二氧化硅中的任意一中或者多种混合。
4.根据权利要求3所述的一种丙烯腈生产用催化剂,其特征在于:所述催化剂载体包括球体骨架以及改性剂,所述催化剂喷涂于骨架载体上。
5.根据权利要求4所述的一种丙烯腈生产用催化剂,其特征在于:所述催化剂载体含量为30-65wt%,所述改性剂含量为0.1-3wt%。
6.根据权利要求1-5中任一项的一种丙烯腈生产用催化剂,其特征在于:包括以下制备方法:
S1、将所需量除Mo外的相应活性组分元素的盐进行溶解,得到溶液1;
S2、将所需量的骨架载体与改性剂溶液混合,得到处理后的催化剂载体;
S3、将所需量含钼的钼酸盐进行溶解,并与溶液1混合,在pH为1~7(pH优选为4)和温度在30~90℃(温度优选为60℃)下搅拌,得到浆料1;
S4、浆料1经喷雾干燥和在500-650℃(温度优选为600℃)下焙烧活化0.2-0.5(时间优选为0.35)小时,得到所需催化剂,通过喷涂设备将催化剂喷涂在骨架催化剂载体上,实现对催化剂的生产。
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