CN1050818C - 一种高活性合成氨催化剂的制备方法 - Google Patents
一种高活性合成氨催化剂的制备方法 Download PDFInfo
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- CN1050818C CN1050818C CN93115769A CN93115769A CN1050818C CN 1050818 C CN1050818 C CN 1050818C CN 93115769 A CN93115769 A CN 93115769A CN 93115769 A CN93115769 A CN 93115769A CN 1050818 C CN1050818 C CN 1050818C
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- synthetic ammonia
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 3
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 238000007712 rapid solidification Methods 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- 238000000889 atomisation Methods 0.000 abstract 1
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种高活性合成氨催化剂的制备方法，以精选的磁铁矿、氧化铝、碳酸钙、硝酸钾为主要原料，或以工业用合成氨混合氧化铁催化剂为原料，其特征在于：将原料熔化后，用大于100开氏温度/秒的速度快速凝固。本发明方法所制备催化剂活性明显高于原催化剂活性。
Description
本发明涉及合成氨催化剂，具体地说就是提供了一种用快速凝固技术制造合成氨催化剂—混合氧化铁的方法。
1904年，哈柏(Fritz，Haber)首先发现将氨氧气体在一定条件下，通过金属催化剂可以合成氨。随后Alwin，Mittasch等人先后做了10,000多次实验，完成了4,000多个不同催化剂体系的研究工作，才发明了“熔铁催化剂”，并通过对氨合成反应的化学平衡与温度、压力的关系的系统研究，找出了高温、高压的反应条件，发明了工业上第一个加压催化过程，实现了合成氨的大规模生产。据估计，近八十年来已研究过的合成氨催化剂的配方超过了100,000个，然而还没有证明能对Mittasch发展的混合氧化铁催化剂做出任何根本的改进。
本发明的目的在于提供一种现有工业氨合成催化剂—混合氧化铁的制备方法，使现有催化剂活性大幅度提高。
本发明提供的高活性合成氨催化剂的制造方法，以精选磁铁矿、氧化铝、碳酸钙、硝酸钾为主要原料，或以工业用合成氨混合氧化铁催化剂为原料，其特征在于：将原料熔化后，用大于100开氏温度/秒的速度快速凝固。
本发明首次采用先进的快速凝固技术应用于传统的氨合成催化剂的制造，彻底改变了传统混合氧化铁的晶体结构、表面结构和孔结构，使活化后的α-Fe晶粒度减小，能增加α-Fe微晶粒子高活性晶面的数量。增大了α-Fe微晶的有效活性比表面积。急冷促使催化剂在活化后形成有利于反应物与产物扩散的孔隙结构。由于熔料快速冷却，助催化剂来不及偏析，使助催化剂分布均匀，造成了较大的总比表面的铁比表面提高了催化活性，并防止微晶长大和烧结。因此制造出的急冷混合氧化铁催化剂的活性明显高于现用的合成氨熔铁催化剂。下面通过实施例详述本发明。
实施例1采用“单辊法”，用BN坩锅，以石墨为加热源，熔化温度为大于1500℃，喷射压力为0.4大气压，喷嘴直径为1.0mm，辊轮直径350mm，辊轮线速度为27.5米/秒。制成急冷混合氧化铁催化剂。化学组成：Al2O3 K2O CaO MgO SiO2 余量
2.85％ 0.65％ 2.9％ ≤1.30％ ≤1.00％ 氧化铁催化活性：在693K，30atm的条件下，1g催化剂，H2∶N2＝3∶1，反应气体流量为40ml/min。反应时间(h)： 8 18 30 40 55 80 101活性(NH3％)：0.304 0.35 0.46 0.60 0.87 1.42 1.58比较例1催化剂为工业用与上述急冷催化剂同成份的混合氧化铁催化剂反应条件同上反应时间(h) 8 3 30 40 55 80 101活性(NH3％) 0.06 0.12 0.22 0.32 0.46 1.05 1.28可以看出急冷混合氧化铁催化剂的催化活性明显高于工业用氧化铁催化剂。
实施例2采用“超声雾化法”，用BN坩锅以石墨为加热源制成急冷混合氧化铁催化剂，催化剂粒度45目。化学组成： Al2O3 K2O CaO SiO2 余量
3.7％ 1.1％ 0.9％ 0.3％ 氧化铁催化活性：在693K，30atm的条件下，2g催化剂，H∶N2＝3∶1，反应气体流量为40ml/min。反应时间(h)： 6 15 30 50 90 110催化活性(NH3％)：0.41 0.53 0.79 1.60 2.30 2.92比较例2：
同成份的工业催化剂(反应条件同上)反应时间(h) 6 15 30 50 90 110催化活性(NH3％) 0.11 0.23 0.41 0.80 1.90 2.03
实施例3采用“单辊法”，用BN坩锅，以石墨为加热源制成急冷混合氧化铁催化剂，催化剂粒度45目化学组成：Al2O3 K2O CaO MgO SiO2 余量
4.32％ 0.26％ 3.40％ 4.11％ 0.33％ 氧化铁催化活性：测定条件同实施例1反应时间(h)： 4 10 18 32 41 50 85 100 110活性(NH3％)：0.16 0.31 0.40 0.51 0.67 0.80 1.71 1.80比较例3：
化学组成同上，反应条件同上。反应时间(h) 4 10 18 32 41 50 85 100 110催化活性(NH3％)0.02 0.10 0.16 0.25 0.40 0.49 1.01 1.20 1.22
Claims (1)
1.一种高活性合成氨催化剂的制备方法，以精选的磁铁矿、氧化铝、碳酸钙、硝酸钾为主要原料，或以工业用合成氨混合氧化铁催化剂为原料，其特征在于：将原料熔化后，用大于100开氏温度/秒的速度快速凝固。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115769A CN1050818C (zh) | 1993-08-27 | 1993-08-27 | 一种高活性合成氨催化剂的制备方法 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115769A CN1050818C (zh) | 1993-08-27 | 1993-08-27 | 一种高活性合成氨催化剂的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1099353A CN1099353A (zh) | 1995-03-01 |
| CN1050818C true CN1050818C (zh) | 2000-03-29 |
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| CN93115769A Expired - Fee Related CN1050818C (zh) | 1993-08-27 | 1993-08-27 | 一种高活性合成氨催化剂的制备方法 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103933986A (zh) * | 2013-01-18 | 2014-07-23 | 济南大学 | 一种高炉除尘灰制备的用于工业合成氨的熔铁催化剂 |
| CN103933985A (zh) * | 2013-01-18 | 2014-07-23 | 济南大学 | 一种硫酸渣制备的用于工业合成氨的熔铁催化剂 |
| CN105733728B (zh) * | 2016-02-24 | 2018-11-06 | 太原理工大学 | 降低民用焦炭着火温度的磁铁矿复合添加剂及制法和应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4430254A (en) * | 1979-02-07 | 1984-02-07 | Ammonia Casale S.A. | Spherical cerium-activated catalyst for ammonia synthesis and process for its manufacture |
| CN85101605A (zh) * | 1985-04-01 | 1986-09-17 | 郑州大学 | 低温高活性氨合成球形催化剂 |
| CN1043272A (zh) * | 1988-12-17 | 1990-06-27 | 浙江工学院 | 旋转造粒喷头喷洒制备球形氨合成催化剂的方法 |
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1993
- 1993-08-27 CN CN93115769A patent/CN1050818C/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4430254A (en) * | 1979-02-07 | 1984-02-07 | Ammonia Casale S.A. | Spherical cerium-activated catalyst for ammonia synthesis and process for its manufacture |
| CN85101605A (zh) * | 1985-04-01 | 1986-09-17 | 郑州大学 | 低温高活性氨合成球形催化剂 |
| CN1043272A (zh) * | 1988-12-17 | 1990-06-27 | 浙江工学院 | 旋转造粒喷头喷洒制备球形氨合成催化剂的方法 |
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| CN1099353A (zh) | 1995-03-01 |
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