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TA201-2/TA201-2-H Ammonia Synthesis Catalyst

时间:2019-04-11 点击: 178 次

TA201-2/TA201-2-H型氨合成催化剂技术性能和使用条件

 TA201-2/TA201-2-H Ammonia Synthesis Catalyst
Technical Performance and Usage Conditions
   TA201-2型催化剂是临朐泰丰环保科技有限公司在A201型氨合成催化剂的基础上进行改进研发的一种使用温度较宽、高活性的氨合成催化剂,由于生产厂地处临朐,有我国最为优秀(也是世界上排行第二位)的氨合成催化剂的主要原料—磁铁矿沙这一独特的优势,加上良好的配方和工艺。经精心操作,产品有十分优良的性能,实验室检测结果,比同类催化剂的氨合成催化剂出口氨增加1个百分点。
   TA201-2 is one kind of Ammonia Synthesis Catalyst research and development by Linqu Taifeng Chemical Co., Ltd which is based on A201 . Due to the factory is localed in Linqu city where has the best raw material of Ammonia Synthesis Catalyst --highest great magnetic resource(Top 2 worldly), and together with the great formula and professional team, TA201-2 has high activity and wide temperature range performance. After check, it can produce 1% more Ammonia than the same kind Ammonia Synthesis Catalyst.
TA201-2-H型氨合成催化剂是在TA201-2型催化剂的基础上,在生产厂中采用符合催化剂的最佳还原条件的设备和工艺生产出的预还原型催化剂。
    TA201-2-H is a kind of pre-reduction catalyst based on TA201-2, and produced by the best equipment which has the great reducing condition and excellent technology.
  1. 型号
1.Type
1.1 TA201-2氧化态型氨合成催化剂
1.1 TA201-2 Oxidation State Type Ammonia Synthesis Catalyst
1.2 TA201-2-H预还原型氨合成催化剂
1.2 TA201-2-H Pre-Reduction Type Ammonia Synthesis Catalyst
  1. TA201-2/TA201-2-H型氨合成催化剂的物理性能
2、TA201-2/TA201-2-H Ammonia Synthesis Physical Performance
表1  TA201-2/TA201-2-H型氨合成催化剂的物理性能
Form 1   TA201-2/TA201-2-H    Ammonia Synthesis Physical Performance
Items Units TA201-2 TA201-2-H
Appearance   Black with Metal Luster, Magnetic Solid Particle without fixed shape Silver Gray with Metal Luster, Magnetic Solid Particle without fixed shape
Particle Size mm 1.5~3.0 、2.2~3.3、3.3~4.7、4.7~6.7、6.7~9.4、9.4~13.0 etc.
Bulk density Kg/l 2.8~3.2 2.4~2.6
Particle Density Kg/l 3.8~4.2 2.8~3.2
Skeletal Density Kg/l 7.2~7.6 7.2~7.6
Specific Surface m2/g ~15.18 ~15.18
Porosity
 
% ~45 ~45
Shape Coefficient φs Large Particle Catalyst 0.40~0.50
Small Particle Catalyst 0.50~0.60
3、 TA201-2/TA201-2-H型催化剂的化学组成:
3、 TA201-2/TA201-2-H Ammonia Synthesis Chemical Composition
TA201-2型氨合成催化剂的主要成分为四氧化三铁,并含有适量的氧化钴、氧化铝、氧化钾和氧化钙等助剂。TA201-2-H型氨合成催化剂是在TA201-2型氨合成催化剂的基础上在工厂专门设备上进行预还原成具有活性的α-Fe,为了运输和仓储、装填过程的安全性,在催化剂颗粒的表面(包括催化剂微孔表面,用氧对其进行有控制的钝化,使其表面生成一层FeO薄膜,这层薄膜,不但可以保证催化剂的安全,而且在使用还原时极容易还原。经预还原后的TA201-2-H型氨合成催化剂,其还原度可达90%以上,氧含量一般为2%以下。
 The main ingredient of TA201-2 is ferroferric oxide(Fe3o4), contains moderate Cobalt Oxide/Al2O3/K2O and CaO etc. additives. TA201-2-H is an activity α-Fe which based on and developed from TA201-2 , it has an Feo film packing in its surface for keeping the safety during transfering and loading. This film not only can keep the safety of TA201-2-H, it also could easily reducing action when use it. After Pre-reduction, the TA201-2-H could reducing more than 90%, the content of Oxygen usually under 2%.
表2  TA201-2型氨合成催化剂的化学组成
Form 2 TA201-2 Ammonia Synthesis Chemical Composition
TA201-2 Content
TFe 65~70%
Fe2+/Fe3+ 0.35~0.45
K2O 0.5~1.0%
Al2O3 1.3~2.0%
SiO2 ≤0.40%
CaO 0.5~1.0%
Co3O4 0.8~1.1%
P <0.04%
S <0.01%
  1. TA201-2型氨合成催化剂的结构组成特点
        3、TA201-2  Structure Constitute Features                        
3.1 K2O的含量有所提高
3.1 K2O Content Increased
K2O是电子型助剂,可提高催化剂的比活性。在催化剂制备过程中K2O与磁铁矿或其它类型的助剂生成钾盐,还原后均匀分布在α-Fe表面上,降低了铁表面的电子逸出功,促进了氨的解吸与吸附。TA201-2的 K2O含量比其它类型催化剂提高约20%~30%,这是TA201-2型催化剂活性较高的一个原因。
K2O is one kind of Electrical Additives, it can increase the specific activity of catalyst. In the process of preparing catalyst, K2O and magnetite or other type additives reaction get sylvine, after reduction is evenly distributed on the surface of α-Fe, reduced the electrical work function on the surface of Iron, promoted the desorption and adsorption for ammonia. TA201-2 K2O content about 20% ~ 20% higher than that of other types of catalyst, it is one reason for TA201-2 has higher activity.
3.2 加入氧化钴,提高催化剂活性
3.2 Adding cobalt oxide to improve the catalyst activity
TA201-2型氨合成催化剂是一种铁钴双活性组分的催化剂,在熔融过程中氧化钴与磁铁矿形成固熔体,还原后,钴原子均匀分布在α-Fe中,使α-Fe晶粒明显变小,晶格畸变,促进更多的【111】面暴露,增加了活性中心数目,同时也改善了孔结构,40~70A0微孔增多,这有利于反应物和产物的传递,TA201-2型催化剂含有一定量的CO3O4,使其具有良好的低温活性。
TA201-2 is one kind of double active component of iron cobalt catalyst. In the process of melting, cobalt oxide and magnetite forms solid. After the reduction, cobalt atoms uniformly distributed in the α-Fe, which decreases the α-Fe significantly, lattice distortion, promotes more [111] face to expose, increases the number of active center, and improves the pore structure, increase 40 ~ 70A0 micropore. It is benefit to the transfer of reactants and products. Type TA201-2 ammonia synthesis catalyst contains a certain amount of CO3O4,, which makes it have good low temperature activity.
   3.3适当调整Al2O3与CaO助剂的含量
    3.3 Adjust the content of Al2O3 and CaO additives
Al2O3与CaO为结构性助剂,在熔融过程中与磁铁矿形成固熔体,金属离子进入尖晶石结构的氧离子密堆集的正四面体和正八面体空隙,使它们均匀的分布在磁铁矿当中。还原或使用过程中,这些氧化物不被还原,起了隔离α-Fe作用,使晶粒变小而且稳定,提高了催化剂活性与稳定性。另一方面,氨合成是在熔铁催化剂上进行的多项催化反应。H2、N2分子的吸附、解离和合成反应均在α-Fe 晶粒表面上进行的。表面结构分析表明,铁表面积占催化剂整个表面积的百分之几,绝大部分表面被不能还原的氧化物助剂所占据,因此,有文献认为,在不影响寿命的基础上,可通过减少助剂加量来改善催化性能。TA201-2型催化剂研制过程中,充分考虑了结构性助剂的综合作用,合理的调整了Al2O3与CaO助剂的含量。这对于提高催化剂的活性、改善催化剂的还原性能都是十分有利的。与其它类型催化剂相比TA201-2型催化剂大幅度降低了Al2O3与CaO的含量。
Al2O3 and CaO are structural additives. In the process of melting, they form solid solution with magnetite, metal ions into the spinel structure of oxygen ions of closest packing is tetrahedral and octahedral gap, making them evenly distributed among the magnetite. In the process of reduction and use, these oxide can not be restored with function of isolation of alpha Fe, making the grain size and stability, improving the catalyst activity and stability. on the other hand, ammonia synthesis make a number of catalytic reaction on molten iron catalyst. The dissociation and synthetic reaction of H2N2 molecule adsorption are conducted in alpha Fe grain on the surface. Analysis shows that the surface structure, iron surface area occupy some percent of the entire surface area of catalyst. Most of the surface is occupied by oxide additives without reduction. Therefore, some documents think, on the basis of not affecting lifetime, we can decrease additives to improve the catalytic performance.TA201-2 fully considers the combination of structural auxiliaries, reasonably adjust the content of Al2O3 and CaO additives. It is great to improve the activity of catalyst and to improve the catalyst reduction performance. Compared with other type catalyst, TA201-2 reduce the content of Al2O3 and CaO dramatically.
 
表3   部分氨合成催化剂中Al2O3与CaO的含量
Form 3    Portion of Al2O3 and CaO content in ammonia synthesis catalyst
 
Type
Content of additives  
TA201-2 A110 A B C
Al2O3% 1.30 2.60 2.25 1.95 2.40
Relatively content 100 200 173 150 185
CaO% 0.80 2.20 1.40 1.78 1.60
Relatively content 100 275 175 225 200
K2O% 0.87 0.60 0.58 0.52 0.70
Relatively content 100 75 72 65 88
注:A、B、C为国内同类型的氨合成催化剂
Noted: A、B、C is the same type ammonia synthesis catalyst in domestic
3.4 加入一种特殊的助剂,提高了催化剂热稳定性
3.4 Adding a special additives to improve the catalyst thermal stability
通常认为,降低Al2O3与CaO的含量虽然有利于催化剂活性提高以及使催化剂容易还原,但其热稳定性将有所降低,为弥补这一缺点,我们通过了大量的筛选工作,加入了一种特殊助剂。这一助剂是一种电子授受型助剂,它可以有效的阻止聚集在催化剂表面的钾离子向催化剂颗粒内部转移,使钾离子在催化剂的表面停留时间更长,从而大大提高了催化剂的热稳定性和使用寿命。同时,由于这一助剂可以首先和毒物(主要是CO和CO2)结合,又能在高H2下解释,因此,在一定程度上可以增强了催化剂的抗毒性能。
It is generally recognized that reducing the content of Al2O3 and CaO can be advantageous to the catalyst activity increase and makes the catalyst easy to restore. But its thermal stability will be reduced. To make up for the shortcomings, we work through a large number of screening, add a special additives. It can effectively prevent gathered in potassium ion transfer to the inside catalyst particles on the surface of the catalyst, making the potassium ions on the surface of catalyst residence time longer. Then it will greatly improve the thermal stability and service life of the catalyst. Using the additives can first combine with poison (mainly CO and CO2)and can release under high H2, therefore, to a certain extent, it can enhance the poison resistance of the catalyst.
3.5 Fe2+/ Fe3的选择
3.5 The choice of Fe2 + / Fe3
Fe2+/Fe3+也是熔铁催化剂的一项关键指标。有关铁比值对催化剂性能的影响,国内外已有不少研究报导,通常认为铁比值控制在0.50~0.60之间,催化活性最好,我们认为,添加不同种类和含量的助剂,最佳铁比值的选择不能一概而论。在TA201-2研制开发过程中,铁比值对于催化剂的还原性能、催化活性、热稳定性能以及机械强度的影响进行了的研究,获得了最佳铁比值。与其它催化剂相比,TA201-2的铁比值是最低的,这有利于Al2O3的金属离子进入到尖晶石结构中,使它们均匀分布于磁铁矿相中,充分发挥Al2O3的结构助剂作用。因而,虽然TA201-2催化剂中Al2O3含量明显降低。但通过调整铁比以及加入一些特殊助剂,使其仍具有良好的热稳定性。实验室性能测试结果以及工厂使用实践也证实了上述看法。
Fe2 / Fe3 + is a key indicator of molten iron catalysts. There are a few research reports at home and abroad about the influence of the ratio of iron for catalytic performance. Usually Think that the ratio of iron has the best catalytic activity controlling the number in 0.50~0.60. We think that, there are different choices for the best ratio of iron as for adding different types and contents of additives. In the process of research and development of Type TA201-2 ammonia synthesis catalyst, we made research on the influence of ratio of iron for the reducing property, catalytic activity, thermal stability, and mechanical strength of catalyst. Compared with other catalyst,ratio of iron of Type TA201-2 ammonia synthesis catalyst is the lowest. This is good for Al2O3 metal ions to enter into the spinel structure, making them evenly distributed in the magnetite phase, giving full play to the structure of Al2O3 fertilizer effect. Therefore, although TA201-2 Al2O3 content in the catalyst decreased obviously, adjusting the ratio and adding some special additives of iron make it still has good thermal stability. Laboratory performance test results and factory usage practice also confirmed the related view.
表4  部分氨合成催化剂中Fe2+/Fe3
 
Form 4  Portion Ammonia Synthesis Catalyst Fe2+/Fe3
Type
Iron Proportion
 
TA201-2
 
A110
 
A
 
B
 
C
Fe2+/Fe3+ 0.35~0.45 0.50~0.60 0.68 0.45~0.60 0.50~0.60
注:A、B、C为国内同类型的氨合成催化剂
Noted: A、B、C is the same type ammonia synthesis catalyst in domestic
  1. TA201-2/TA201-2-H型催化剂质量标准
  2. TA201-2/TA201-2-H Quality Standard
我公司生产的TA201-2、TA201-2-H型氨合成催化剂产品已通过ISO9002国际质量体系认证,所生产的产品严格按行业标准进行,发出的产品均为经检验符合质量要求的合格品。
Our TA201-2、TA201-2 - H passed ISO9002 authentication, products strictly in accordance with industry standards, the products we sent out are all conform to the requirements of the quality.
TA201-2型氨合成催化剂产品质量执行企业标准,标准号为Q/LQCJ002-2010。
TA201-2 implement enterprise standards, Standard NO. Is :Q/LQCJ002-2010.
 
TA201-2-H型氨合成催化剂产品质量参照Q/HG-1551-85标准执行。
 TA201-2 - H product quality reference standards Q/HG - 1551-1551 execution.
 
4.1TA201-2型氨合成催化剂
4.1TA201-2
活性:(按Q/LQCJ002-2010氨合成催化剂试验方法)
Activity:(according to Q/LQCJ002-2010 test method)
在实验室条件下,当催化剂粒度为1.0~1.4mm,装量2ml,压力15.0Mpa、空速3×104hr-1、温度415℃(在500℃耐热20h后)时,出口氨不小于14.2%。
Under laboratory conditions, when the catalyst particle size was 1.0 ~ 1.4 mm, loading 2 ml, pressure 15.0 Mpa, airspeed 3 x 104 hr - 1, temperature 415 ℃(500 ℃ heat after 20 h), got ammonia is not less than 14.2% .
 
4.2、 TA201-2-H型氨合成催化剂
4.2、 TA201-2-H
   活性:(参照Q/HG-1551-85标准执行)
   Activity: (refer to Q/HG - 1551-85 standard)
在实验室条件下,当催化剂粒度为1.0~1.4mm,装量2ml,压力15.0Mpa、空速3×104hr-1、温度415℃(在500℃耐热20h后)时,出口氨仍不小于14.2%。
Under laboratory conditions, when the catalyst particle size was 1.0 ~ 1.4 mm, loading 2 ml, pressure 15.0 Mpa, airspeed 3 x 104 hr - 1, temperature 415 ℃(500 ℃ heat after 20 h), ammonia still not less than 14.2%.
 
  1. TA201-2/TA201-2-H型氨合成催化剂的使用条件
  1. TA201-2/TA201-2-H Use Condition
 
5.1、TA201-2/TA201-2-H型氨合成催化剂的还原条件
5.1、TA201-2/TA201-2-H Reduction Condition
 
 
TA201-2型氨合成催化剂为氧化态催化剂,使用前必须用氢气进行还原,一般还原气体使用氢氮混合气。用其上的氢气把催化剂中的Fe3O4还原成α-Fe,方具有活性;TA201-2-H型氨合成催化剂,在工厂经还原后,又进行表面钝化,使用前也必须把表面的氧化膜破坏,方可投入使用。
TA201-2 is one kind of oxidation catalyst, before use must be conducted with hydrogen reduction, reducing gas commonly use hydrogen nitrogen mixture. The catalyst with its hydrogen reduction of Fe3O4 into α-Fe, then it has activity; TA201-2 - H after reduction and surface passivation, before use must be demage the film which on the surface of it.
Fe3O4+4H2=3Fe+4H2O
升温时采用经净化后的纯氮气进行,还原时采用纯净的氢氮混合气,条件如下表:
Warms up with the purification of pure nitrogen, reduction when using pure nitrogen mixture, condition in the following table:
    表5  TA201-2/TA201-2-H型氨合成催化剂还原性能和条件要求
Form 5 TA201-2/TA201-2-H Reduction Performance and Qualification
Catalyst type TA201-2-H TA201-2  
Initial reduction temperature ℃ 200±20 270  
Obvious out of water Temperature 300~380 320~410  
A large number of water temperature 400~440 420~460  
The final reduction temperature ℃ 490~500 490~500  
Reducing gas Hydrogen and nitrogen Hydrogen and nitrogen  
Reducing the amount of CO + CO2 gas ≤10ppm ≤10ppm  
When reducing tower into the water vapor content <100ppm <100ppm  
Reducing pressure 8~12MPa 8~12MPa According to the requirements of different reduction level
Cl content in reducing gas <0.01ppm    
Reduction of H2S content in gas <0.1ppm    
Other requirements in the reducing gas harmful material such as arsenic, dust, oil, should be strictly controlled, the lower the better  
 
有关升温还原详细情况见升温还原方案(讨论稿)。
The reduction details see reduction plan (discussion)
5.2、 工厂使用条件:
5.2、 Factory using conditions:
5.2.1 该催化剂暴露在空气中时,易受潮而引起可溶性钾盐向表面析出,造成活性下降,尤其是低温活性下降。同时也容易受空气中的毒物毒害,特别是预还原的催化剂,因此要求在装填前不要打开桶盖,如需开桶,应立刻重新进行密闭。
5.2.1 When this catalyst is exposed to air, it easy to be affected with damp result in the soluble potassium precipitation on the surface , lead to activity decreased, especially the low temperature activity decline. Is also susceptible to poison poison in the air, especially the prereduced catalyst, so do not open the lid before packing, if you want to open barrels, should be closed immediately.
5.2.2仓储时应放置在干燥通风的仑库中、并应经常检查包装的情况。
  5.2.2 Storage should be placed in dry ventilated shimron repository, and should always check the status of packaging.
5.3、催化剂的使用条件
5.3、Catalyst using conditions
5.3.1使用温度:
5.3.1 Using temperature:
由于TA201-2型氨合成催化剂良好的低温活性和较强的热稳定性使其具有较宽的操作温区。操作温区为340~530℃,正常操作温度为350~500℃,为了保持催化剂的低温活性,一般初期热点温度应尽可能低些。
Because TA201-2 has good low temperature activity and strong thermal stability make it has a wide operating temperature range. Operating temperature range is 340 ~ 530 ℃, the normal operating temperature is 350 ~ 500 ℃, in order to keep low temperature activity, generally more hot spot temperature should be as low as possible.
5.3.2使用压力:
5.3.2 Pressure using:
TA201-2型氨合成催化剂低压操作条件下具有良好的活性。它不仅可适于低压氨合成,也适于中高压氨合成,TA201-2型催化剂操作压力可控制在:8.0~31.4Mpa
 TA201-2 under the condition of low pressure operation has good activity. It not only can be suitable for low pressure ammonia synthesis, also suitable for high pressure ammonia synthesis, TA201-2 operating pressure can be controlled in: 8.0 ~ 31.4 Mpa
5.3.3空速:
  5.3.3 airspeed:
   TA201-2型氨合成催化剂操作空速根据操作压力的不同,可控制 5000~40000hr-1之间。压力高,空速可以加大,对于操作压力在14~16MPa之间,一般操作空速为6000~10000h-1
TA201-2 according to different operating pressure, the operating speed can be controlled between 5000 ~ 40000-1 hr. High pressure, space velocity can be increased, for operating pressure between 14 ~ 16 mpa, general operating speed is 6000 ~ 10000 h - 1.
5.3.4进塔气体的成份控制:
  5.3.4 Feed gas composition control:
    氢氮比:TA201-2型氨合成催化剂氢氮比使用范围1.5~4.0,适宜氢氮比在2.2~3.0 。
Hydrogen Nitrogen proportion: TA201-2 Hydrogen Nitrogen proportion using range is 1.5 ~ 4.0, suitable for Hydrogen Nitrogen proportion is 2.2 ~ 2.2.
惰性气体:
  Inert gas:
反应气中隋性气(CH4+Ar)操作范围可在8~24%之间,较适宜应控制在≤10%比较经济。
 In the reaction of the Inert gas (CH4 + Ar) operating range is between 8 ~ 24%, suitable controlled in 10% more or less.
5.3.5催化剂使用寿命
  5.3.5 catalyst service life
    在正常使用条件下,催化剂使用寿命保证值为10年以上。
  Under the condition of normal use, the service life of the catalyst to ensure value for more than 10 years.
 
  1. 其它注意事项
 6、Other Matters need attention:
6.1催化剂装填时避免受潮,以防止可溶性钾盐析出,影响活性
  6.1 When catalyst loading to avoid be affected with damp, to prevent the soluble potassium precipitation, affect the activity
 
6.2搬运过程中要防潮、避免摔滚撞击,以免损坏包装桶及造成催化剂磨损。                     6.2 In the process of transfer,it has to dampproof , avoid casting roll strike. so as to avoid damage the packaging barrels and wearing catalyst .
6.3装填前催化剂必须过筛。
6.3 Catalyst must be sieving before loading.
6.4在装填前将合成塔内外筒均清理干净,中心管、温度计套管、主线气体入口端、导气管、内外筒环隙均用棉纱堵好。具备装填条件后,再进行装填。
  6.4 Before loading the synthetic tower tube inside and outside have been  cleaned, center pipe, thermometer casing, the main gas inlet end, airway tube, inside and outside the cylinder clearance have to block up in cotton. Have the loading conditions, and then reload.
 
6.5在装填中严格按催化剂的装填方法和注意事项进行操作,向塔内加入催化剂时,应分散平铺,不允许倾倒在一点上或堆积成斜面。装填应紧密均匀,可采用分层多次均匀振动的方式,将催化剂摊平捣实,防止催化剂床层阻力不一,容易产生气体偏流。实际装填堆积密度TA201-2型氨合成催化剂应达到3.0Kg/l以上:TA201-2-H应达到2.4Kg/l以上。
6.5 During filling,be strictly operation in accordance with the catalyst loading method and the notes, when add catalyst into the tower, it should be decentralized tile, not allowed to dump or slant piles in point. Uniform loading should be closely, can adopt the layered homogeneous vibration way for many times, made the catalyst flat and tamping, prevent the catalyst bed layer resistance, easy to produce gas flow deviation. The actual loading bulk density  of TA201-2  should be reached more than 3.0 Kg/l: TA201-2 - H should be reached more than 2.4 Kg/l.