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Application instructions of A110-H pre-reduced ammonia synthesis catalyst

时间:2019-04-09 点击: 66 次

        A110-H型预还原氨合成催化剂使用说明
A110-H型氨合成催化剂是山东临朐泰丰环保科技有限公司在A110氨合成催化剂基础上,通过优化原料选择,优化工艺条件,改进产品质量后生产的新型氨合成催化剂,它提高了颗粒的球化系数,通过合理的配比,使催化剂适用范围更宽,耐热前后的活性更忧,抗毒和解毒性能提高,同时由于采用著名的临朐优质磁铁矿为原料,产品的质量实现优质、稳定。特别二氧化硅含量很低,获“国家质量金牌”称号。
Shandong Linqu Taifeng Chemical Co., Ltd A110 - H type ammonia synthesis catalyst is produced on the basis of A110 ammonia synthesis catalyst, It is new type ammonia synthesis catalyst through optimizing raw material selection, optimize the process conditions, improve the quality of the products after production; Through the reasonable matching and  increasing the spheroidizing coefficient of the particles, , the catalyst has got a wider range of application; Before and after the heating , it increase the resistance of poison and detoxifying ; At the same time with the famous Linqu high quality magnetite as raw materials, It achieves the high quality with stable status; Low silica content has help win national gold metal;
众所周知,氧化态的氨合成催化剂使用前必须用氢气进行还原,把三氧化二铁还原成α-Fe,方具有活性。A110-H预还原氨合成催化剂是在催化剂制造厂家中,采用专门的设备,在更符合A110型氨合成催化剂的还原工艺条件下进行还原,使催化剂的使用质量得到更好地保证。还原结束后,为了运输、装填的安全,有控制的对催化剂进行表面钝化处理,使催化剂表面形成一层FeO保护薄膜。
Before use, the oxidation state of ammonia synthesis catalyst must be conducted with hydrogen , ferric oxide reduction into alpha Fe to get activity;A110-h pre-reduced ammonia synthesis catalysts are reduction in catalyst manufacturer , using specialized equipment; There will form a layer of FeO protection film after reducing process; This layer gets through surface passivation and can guarantee the safety during transparent and loading;
  1. A110-H型氨合成催化剂的物化性能和特点
A110 - chemical properties and characteristics of H type ammonia synthesis catalyst
1.1 A110-H型氨合成催化剂的化学性能
A110 -H- ammonia synthesis catalyst chemical properties
A110-H型氨合成催化剂以α-Fe为主要组份,并添加了适量的碱金属氧化物和稀土化合物作为促进剂和稳定剂,主要是三氧化二铝、氧化钾、氧化钙、等。A110 - H type ammonia synthesis catalyst main components is alpha Fe with added certain amount of alkali metal oxide and rare earth compound as accelerator and stabilizer which are main 3 oxidation 2 aluminium potassium hydroxide calcium oxide, etc
 
1.2 A110-H型氨合成催化剂的物理性能
1.2 A110-H Physical Properties of H type ammonia synthesis catalyst
外观:无定形固体颗粒,经磨角球化处理,球化率可达0.6以上。
Appearance: amorphous solids,after the processing of grinding corner, the spheroidization rate can reach to more than 0.6
颜色:银灰色带金属光泽。
Color: silver gray metallic luster
颗粒度:常规分为1.5-3.0mm  2.2-3.3mm  3.3-4.7mm  4.7-6.7mm  6.7-9.4mm级别的颗粒,特殊的颗粒可根据用户要求进行加工。
Granularity: conventional divided into 1.5 3.0 mm 2.2 3.3 3.3 4.7 mm to 4.7 mm - 6.7 mm, 6.7 to 9.4 mm level of particles; Granularity can special processing to meet customer requirements;
堆积密度2.3-2.5t/m3
Bulk Density 2.3-2.5t/m3
孔隙率:~46%。
Voil Ratio:~46%
孔容积:0.129cm3/g
Pore Volume:0.129cm3/g
总比表面:13 ~17m2/g(还原态)。
Surface:13 ~17m2/g (The reduced state)
1.3 A110-H型氨合成催化剂的特点
The characteristics of A110 - H type ammonia synthesis catalyst
1.3.1 起始还原还原低,在200℃左右便开始还原反应,250~300℃还原反应已十分明显,300℃以上可进入还原主期。
1.3.1 Lower initial reduction reaction: reduction reaction will begin at around 200℃ ,;The reduction reaction will be apparent when the temperature's around 250℃ ~ 300℃;  When begin entering main phase can reach to more than 300℃
1.3.2 出水少,只有氧化态催化剂的10%左右,因此大大减少稀氨水的排放量,减少稀氨水处理的麻烦,有利于环境的保护。
1.3.2 Less water will be produced; There only about 10% of the catalyst for oxidation state;Thus greatly reduce the dilute of aqua ammonia ;Thus the dilute ammonia treatment will be easy;, Thus will benefit the environment;
1.3.3 提高了整炉催化剂的还原质量,特别是塔底部不容易提温的塔型,如果使用预还原催化剂,由于容易还原,从而提高整炉催化剂的使用质量和使用效果。1.3.3 The quality of reducing will be improved , especially the bottom where the temperature not easy to rise; After using pre-reduced catalyst, it is easy for reduction, thus can improve the whole quality of furnace catalyst and use effect
1.3.4 催化剂质量提高。由于是在制造厂中专用设备和专门工艺条件下进行预还原,还原过程中工艺气净化程度高,减少对催化剂的污染。从而提高催化剂的质量。
1.3.4  Improvement of catalyst quality;  There will be pre-reduction with special equipment and specialized manufacture process, it will be easy to get high degree gas purification; Not only reduce the pollution of the catalysts but also improve the quality of catalyst
1.3.5 大大缩短开车时间,一般约为氧化态催化剂的1/4-1/5,节约开车的费用。
greatly shorten the driving time, generally about 1/4 to 1/5 of oxidation catalyst,saving cost;                  
1.3.6 催化剂床层高度不会发生明显的下降,从而保证使用效果。1.3.6 catalyst bed height will not significant reduction;This can guarantee the using effects
1.3.7 经济效果明显。从减少开车时间的费用和提前投入生产产生的效益,减去催化剂相对增加的成本后,使用厂普遍认为经济效益十分明显。1.3.7 Obviously economic benefits: Economic benefits will be obvious from reducing the cost of time and advancing production schedule;
2、A110-H型氨合成催化剂的用途
2 A110 - H type ammonia synthesis catalyst application
在化肥企业的合成氨装置中,必须把经净化后的在高压下合成NH3,这一过程称之为氨合成反应,而氨合成反应必须依靠氨合成催化剂,方能高效的完成。TA110-4-H型氨合成催化剂的就是促进氨合成反应进行的一种催化剂。The device of synthesis ammonia will high voltage synthetic H2―N2 to NH3 ;This process is called ammonia synthesis reaction which only depend on ammonia synthesis catalyst can efficiently complete the process; TA110-4 - H type NH3 is a kind of catalyst for ammonia synthesis reaction
3 H2+N2=2NH3          △H0298=―45.9kj/mol
它主要用于合成氨厂制氮过程。同时也可用于金属加工工业和电子工业中采用NH3进行裂解制备H2+N2保护气。It is mainly used in nitrogen making process; And at the same time can also be used as a kind of protection in metal processing industry and electronic industry where using NH3 to split for the production of H2 + N2;
 3、A110-H型氨合成催化剂的使用条件
A110 - H type ammonia synthesis catalyst using conditions
3.1使用温度范围:350-530℃
Temperature range:350-530℃
   正常使用温度:350-500℃
Temperature range:350-500℃
3.2使用压力范围:12-40Mpa
Applicable Pressure Range:12-40Mpa
3.3使用空速:6000-30000h-1(根据压力和塔型进行选择
space velocity: 6000-30000h-1( According to the pressure and the tower type to choose)
3.4 还原起始温度:200-250℃
The initial reduction temperature:200-250℃
  1. A110-H型氨合成催化剂的使用
The use of A110 - H type ammonia synthesis catalyst
催化剂的装填和升温还原,必须按工厂的实际情况和催化剂本身性能的要求制定方案,作为催化剂升温还原的指导方针。Catalyst loading and temperature reduction, must make steps according to the actual situation of the factory and the performance of the catalyst itself, as a catalyst reduction guidelines
4.1 催化剂的装填The Loading Process
     氨合成催化剂的装填是一项重要的工作,装填的好坏,直接影响到催化剂的使用效果,因此必须十分重视。装填必须在干燥、通风的环境下进行,应避免阳光的直接照射,避免与水蒸气、水、及油污和有毒有害气体等杂物接触,最好选择在天气晴好,干燥的环境下进行装填。装填前催化剂应进行过筛,除去运输过程中产生的碎片和粉尘。装填过程应均匀的把催化剂撒向催化剂筐各个部位,要求尽可能装填紧密,可以采用小型的手提式电动振荡器或带铜、铝头的铁管均匀地捣实。装填时要严格控制,不要用铁器耙。以免引起催化剂与空气中的氧接触,发生氧化反应,生成热量,可能最终引发催化剂烧坏。建议装填过程“随装随开包装桶”。Ammonia synthesis catalyst installation is an important work which directly affect the effect of catalyst; It should be carried out in a dry and ventilated environment,avoid direct sunlight,water and water vapor, oil and toxic or harmful gases and other sundry contact;It is better choose in sunny weather, dry environment; Before  loading, first sieve catalyst and remove the ebris and dust; loading process should be homogeneous catalyst and to all parts of catalyst basket, request as quick as possible loading closely, can use small portable electric generator or iron pipe with copper and aluminum head evenly compacted fill when we will strictly control;  Do not use the iron rake;Thus to avoid catalyst and oxygen air contact; The oxidation reaction; Best way is load while open the pack;
在催化剂装填前要求现场备有99.5%以上的高纯氮,当装填过程中发现催化剂温度升高时,操作人员应及时离开,对塔内催化剂筐通入氮气,直至温度正常后,方可重新装填。
建议在催化剂制造厂技术人员的参与下进行装填。Before catalyst loading should prepared 99.5% of high purity nitrogen ; Operators should leave in time when found catalyst temperature is rising; And at this time,   catalyst baskets should be filled with nitrogen; Only when the temperature back to normal, can begin load again;
4.2 催化剂的升温还原The reduction by warm-up
A110-H型氨合成催化剂出厂主要以α-Fe形态提供,表面有一层FeO保护膜,使用前只要采用H2―N2把催化剂在一定的条件下把保护膜还原成α-Fe,就可投入使用。A110 - H type ammonia synthesis catalyst protect by alpha Fe with surfaced a layer of FeO film: It can be used only after deduction the film toα-Fe with  H2 N2 before use;
A110-H型氨合成催化剂的还原,一般可分为三个阶段:还原初期、还原主期、还原末期,他们的温度范围为200-300℃、300-440℃、440-500℃,不同的催化剂颗粒度,还原其温度范围和起始还原温度略有差异。表2列出部分催化剂一般的起始还原温度、大量出水温度和最终出水温度的情况。
A110 - reduction of H type ammonia synthesis catalyst can be divided into three stages: At the early reduction and owner period, the late period ; The temperature range of these 3 period range from 200-300, 300-440, 440-300;Different catalyst granularity, Different temperature range and initial temperature; In table 2 general starting final reduction temperature and large water temperature and final water temperature
表2   A110-H型氨合成催化剂各还原阶段温度
Table 2  A110 - H type ammonia synthesis catalyst reduction stage temperature
 
开始出水温度℃
Initial Water Temperature
明显出水温度℃
Clearly Water Temperature
最终出水温度℃
Final Water Temperature
200-300 300-400 470-490
4.2.1催化剂还原过程的影响因素
The factors effect catalyst reduction process
催化剂的还原反应,有热力学和动力学两个方面的问题,也就是还原反应的限度和还原反应的速度问题。氨合成催化剂还原反应是一个吸热可逆反应,提高温度有利于α-Fe的生成,但还原过程生成的少量水汽,又可以把已生成的α-Fe重新氧化成Fe3O4 ,由于催化剂中加入了各种助剂,与Fe3O4生成复杂的固熔体,其还原远比纯Fe3O4  还原成 α-Fe 在热力学的要求难度大的多。催化剂还原影响过程的影响因素主要有温度、压力、空速、水汽浓度、还原气体的成分和杂质含量等。Two aspects of Catalyst reduction reaction: thermodynamics and kinetics ;The catalyst reduction reaction is an endothermic reversible reaction; Which raise the temperature is beneficial to the production of alpha Fe;But a small amount of water vapor generated by the reduction process, can make alpha Fe regenerated into Fe3O4 ; due to the  various additives, Fe3O4 regenerate to complex solid solution;The reduction is far tough than pure Fe3O4 reduction into alpha Fe ; The factor influenced Catalyst reduction process include temperature ,air speed, vapour concentration, gas reducing content and impurity particle;
 
4.2.1.1 还原温度的影响
The influence of reduction temperature
氨合成催化剂的还原是一个吸热过程,提高温度能加速还原的速度,但长时间在高温下还原,会导致还原后铁晶粒的长大。所以在还原的不同阶段要控制不同的升温速率和床层的最高温度(热点温度)。一般来说,还原初期,升温速率视出水浓度可以快一些,但温度不宜太高。当催化剂进入还原主期是,必须放慢升温速率,必要时应进行恒温,以保证塔出口气体中的水汽浓度在指标的范围内。还原的最高温度必须控制在催化剂使用说明书中提出的温度间,过高的还原温度会影响到还原中催化剂的结构,使催化剂的孔隙率、孔容积及平均孔径增大,比表面下降,从而影响到催化剂的活性。但过低的还原温度则会造成催化剂还原不彻底,同样会影响催化剂的最佳使用效果。有人认为催化剂不彻底没有关系,可以在以后的使用中继续还原,实验室和工业试验均证明,这种方法比一次性彻底还原效果差些,建议还原时进行一次性彻底还原的方法,对于A110-H型氨合成催化剂来说,还原的最高温度一般可控制490-510℃.
Reduction of ammonia synthesis catalyst is an endothermic process, which raise the temperature can accelerate the speed of reduction, but reduction at high temperature for a long time, can lead to a reduction of iron grain; In different stage should control the heating rate and the highest temperature and bed temperature (hot);  General, the early reduction, can be quick, but temperature should not be too high when the catalyst is also in the owner state; Slow heating rate, when necessary, to ensure that the tower outlet gas water;The lower temperature will incur deducting not complete; The suggest temperature can control between 490-510℃
4.2.1.2 水汽浓度的影响
The effect of water vapor concentration
水汽是氨合成催化剂还原反应的生成物,同时也是还原后催化剂的毒物。因此,在还原中控制气体中的水汽浓度十分重要。氨合成催化剂的还原是以掘井方式进行,因此当颗粒外部催化剂已经还原时,催化剂颗粒内部正处于还原中,其生成的水汽不可避免地已影响到外部已经还原的催化剂,这就会使α-Fe又重新被氧化,因此,重要的是必须把生成的水汽不断从系统中排除出去,以降低系统中的水汽浓度,减少催化剂被重新氧化。从催化剂的角度要求,水汽浓度越低越好,但控制过低的水汽浓度,做到又能最低限度减少催化剂受水汽的毒害,又能尽量缩短还原的时间。表3列出不同类型的装置催化剂还原时水汽浓度的控制指标。Water vapor is ammonia synthesis catalyst reduction reaction products, is also the poison of catalyst after reduction; Therefore, it is very important to control the water vapor in the gas concentration during reduction of ammonia synthesis catalyst reduction by digging Wells manner; when the external catalyst particles has been reducing, inside the catalyst particles are in the reduction of the water vapor generated has inevitably affect the external reduction catalyst, this makes the alpha Fe again to oxidation:It is important that the water vapor continuously generated from the system out, in order to reduce the water vapor concentration in the system, reduce catalyst oxidation to requirements from the perspective of catalyst, water vapor concentration is lower, the better, but the control of low concentration of water vapor, and the minimum reduce the catalyst poisoning by water vapor, but also try to shorten the time of the reduction
 
表3  不同类型的装置催化剂还原时水汽浓度的控制指标 table 3: Water vapor concentration Control index for  catalyst reduction in Different types of device
装置类型
Type
大型合成塔Large synthetic tower
 
中型合成塔Medium synthetic tower
 
小型合成塔Small synthetic tower
 
容许最高水汽浓度,Highest concentration of water vaporg/Nm3 ≤5.0 ≤3.0 ≤2.0
最佳控制水汽浓度,Best concentration of water vaporg/Nm3 ≤3.0 ≤2.5 ≤1.5
水汽浓度的控制,还应根据还原的不同阶段分别对待,在催化剂还原初期,应控制低一点,特别是上部使用预还原催化剂的工厂,一般应控制在1 g/Nm3下,当催化剂进入还原主期,这一指标可以适当放宽,达到容许的最高值。Water vapor concentration control,  should according to the different stage of reduction;Respectively, at the beginning of the catalyst reduction, should be controlled lower, especially the factory which use pre-reduced catalyst , generally should be controlled under 1 g/Nm3,; while catalyst into the main deduction phrase , the concentration may be extended appropriately, to allow reach the highest level
在这里,还要特别提醒,要严格控制入塔气体中的水汽浓度,一般这一指标应100ppm。
Special remind, we should strictly control the water vapor concentration in the gas.Generally it should ≤l100 PPM
4.2.1.3 空速的影响The effect of airspeed
提高空速,对还原有利。因为提高空速将可以把气相中的水汽浓度降低,还有利于催化剂颗粒孔内水气的溢出,从而降低水汽对已还原催化剂的毒害。实验证明,对于A110-H型氨合成催化剂,还原过程空速越高,水汽浓度越低,还原后的催化剂活性就越好,这是因为提高空速,可以使还原后的催化剂孔分布集中、大孔减少,小孔增加,比表面积也增大,从而催化剂活性和比活性提高。但提高空速受到开工加热(电)炉加热能力的限制,同时必须符合催化剂还原温度的要求,因此,在还原初期采用较低的空速,而到还原进入主期时,可以利用上部已还原的催化剂氨合成反应生成热,逐渐加大空速。
Improve airspeed will benefit reduction; Improved airspeed will be able to reduce the water vapor concentration in the gas phase and also help water overflow from catalyst particles hole ; Lower water vapor for the reduction of catalyst poisoning in experiments show that for A110 - H type ammonia synthesis catalyst, the higher the reduction process speed, the lower the concentration of water vapor, the catalyst activity after reduction is better; This is because the improved airspeed, can make the reduction catalyst concentration distribution after the big hole, hole increases, the specific surface area is also increasing, thus improving catalyst activity and specific activity ; But improve the airspeed under the restriction of  heating capacity of the heating (electric) furnace, And also must accordance with the requirement of catalyst reduction temperature at the same time; As a result, at the beginning of the reduction of the lower space velocity, and to restore into the main stage, the upper reduction catalyst ammonia can be used;
 
4.2.1.4 压力的影响The effects of stress
还原过程一般要求在较低的压力下进行,过高的压力,将会使催化剂孔内部的水气不容易被逸出,增加了催化剂彻底还原的难度。但是工厂实际操作时压力与空速存在一定的关系。加大空速必然会引起压力的提高,因此应区分不同还原阶段。制定操作压力指标,一般来说,还原初期应保持在低压条件下进行,还原主期的压力也不能高,应尽可能控制在10MPa以下,还原末期可适当提高到10-12MPa。
Reduction process general requires under lower pressure environment; The high pressure make the internal moisture inside the catalyst not easy to escape;Which make it difficulty for catalyst reduction thoroughly; But in practical there is a certain relationship between pressure and space velocity; Increasing airspeed will inevitably cause a pressure increase, therefore different reduction stage operating pressure  should be distinguished; Generally, the reduction in early stage should maintain in low pressure conditions, during owner of pressure should not control in under 10 mpa; In the final stage  can be appropriately increased to 10 to 12 mpa;
4.2.1.5 其他因素的影响Other factors
还原气体中含有一定量的氨,可以避免催化剂还原水的冷冻,造成堵塞。因此工业上均采用3:1的氢氮气作为还原气体。但为了更好地促进下部催化剂的还原,一般要求在还原主期应提高其气体中的氢浓度。在升温和还原初期,可控制气体中的氢≥68%,还原进入主期应提高氢的浓度≥70%,尽可能达到75%。这一方面可以促进上部已还原的催化剂进行氨合成反应,以提供氨合成反应热辅助开工加热炉的热量,另一方面产出的氨可以防止水分冻结;另方面也为下部的催化剂的还原提供更多的氢,促进还原的速度。Reducing gas contains a certain amount of ammonia, which can avoid catalyst and raw water from frozen, In industry adopt 3:1 hydrogen nitrogen as reducing gas but in order to better promote the reduction of the lower catalyst, During owner period should improve hydrogen concentration on; In the early warming and reduction period, can be controlled to 68% of the hydrogen gas, hydrogen reduction into the main period should increase the concentration of 70%, to 75% as much as possible this aspect can promote upside reduction catalyst for ammonia synthesis reaction, heat of heating furnace for ammonia synthesis reaction heat auxiliary construction,:On the other hand, output of ammonia can prevent the water from freezing. Also it can provide more hydrogen to the lower catalyst reduction to promote the speed of reduction
CO、CO2等含氧化合物它们会在催化剂上,加氢生成有害的水,因而要严格控制,要求总量应小于30ppm,现代化工业的严格要求是小于10ppm.
Harmful water will be generated when CO, CO2 and oxygen compounds mixed; The dosage should be strictly used; Normally it should be less than 30ppm;In the modern industry, it should be less than10ppm;
4.2.2推荐升温还原方案Recommended heating reduction scheme
氨合成催化剂的升温还原操作与氨合成塔的结构和工艺条件有关,编写升温还原方案时,应结合工厂的具体情况,也可与我公司的技术服务人员合作,共同编制。对于轴向结构的中、小塔型,一般可参考下列的方案:The process of Ammonia synthesis deducting of operation related to the structure and process condition of  Ammonia converter; It should consider the factory own condition when draft the temperature rising reduction; Please reference the below program for the axial structure tower shape  ;
Period Time(h) Level catalyst℃ Heating-up rate℃/h Moisture density
g/m3
Pressure
Mpa
IntoH2,% NH3 LOW℃℃
Phase Total
Heating-up 3-4 3-3 Room ℃-250 40-60 3-5 >75 0-5
Initial reduction -3 6-7 250-300 20-30 ≤1.5 5-7 >75 -5~-10
Main reduction 20 26-27 300-440 5-10 ≤2.5 7-8 70-75 ~-15
End reduction 10 36-37 440-500 2-3 ≤1.0 9-12 >70 ~-15
Light Load 24 60-61 460-470 15-18 Normal -5
其它塔型的还原,可向催化剂生产厂的技术人员进行咨询。Other tower model reduction, can consult factory technical stuff.
4.2.3 催化剂的还原终点Catalyst reduction destination
催化剂的还原终点是以催化剂的还原度来判断。在工厂的还原操作中还原度又是以累计出水量来间接量度。一般要求还原终点的累计出水量应达到理论值的95%以上。在实际操作中,对于A110-H型氨合成催化剂我们希望把最终还原温度升高一些,可达到500℃,并稳定保持1-2小时,这是因为这样的操作可以把催化剂更为彻底的还原,将有利于催化剂活性性能的充分发挥。Catalyst reduction destination is catalyst reduction degree to determine the degree of reduction in the operation of reduction in plant and accumulative water yield to indirectly measure the cumulative water yield at the end of general demand reduction should reach more than 95% of the theoretical value in practice, for A110 - H type ammonia synthesis catalyst we hope to eventually reduction temperature, can be up to 500, and held steady 1-2 hours, this is because such operations can be the catalyst for more radical reduction, will be conducive to give full play to the performance of catalyst activity
4.2.4 还原过程中不正常情况的处理Abnormal condition in the process of reduction
催化剂还原过程中有可能会碰到各种不正常的情况发生,主要有以下情况:Catalyst reduction process likely to encounter all sorts of abnormal happens, basically has the following situation
4.24.1 电加热炉,开工加热炉故障Electric heating furnace, starts heating furnace fault
电加热炉或开工加热炉是催化剂升温还原所需热量的主要来源,由于断电、断气或其他原因造成还原过程中断而处理不及时,往往会使合成塔内水汽浓度上升,从而使催化剂反复氧化还原的机会,许多操作者在这种情况下往往会采用停塔保温的措施,这一处理方法是不够正确的。正确的措施应先将催化剂床层温度降低一些,若循环处仍能运转,可运转一会后再作停塔处理。若系统全部停车,则应通过塔后放空适当降低压力,并使塔内温度下降来降低催化剂床层中的水汽浓度。Electric furnace or start heating furnace is the catalyst reduction, the major source of calories, due to power cuts to snuff out or for other reasons in reduction process interrupt processing is not timely, tend to make synthetic tower water vapor concentration increased, so that the chance of repeated REDOX catalyst, many operators in such a case will often use tower heat preservation measures, the processing method is not enough to correct the right measures should be to reduce the catalyst bed temperature, if the cycle can still work, but after a operation to stop tower processing if all parking system, should be through the tower after emptying appropriate to reduce the pressure, temperature drop and the tower to reduce the water vapor concentration in the catalyst bed
4.2.4.2 温度计失灵The thermometer failure
当催化剂升温至100℃左右时,有些温度计套管内因水分蒸发,蒸汽上升至套管顶部后又冷凝回流,当凝结在热电偶上时会造成短路,使温度发生失灵,在一定的温区间上下波动。此时应打开套管上盖,拉出热电偶进行干燥处理。热电偶安装前进行干燥、校正是避免发生这一现象的措施。When catalyst heat up to about 100, some thermometer casing internal moisture evaporation, the steam rose to again after casing at the top of the condenser, when the condensation on the thermocouple will cause short circuit, make temperature failure occurs, fluctuates up and down in a certain temperature range at this time should be opened on the casing cover, pull the thermocouple to dry processing thermocouple before installation to dry calibration is avoiding the phenomenon of measure
4.2.4.3 催化剂床层平面温差大Catalyst bed surface temperature difference is bi
引起催化剂床层平面温差大的原因很多,如装填密度不均匀、气体分布不均匀是主要原因,一般采用降低压力,适当调整循环量,维持热点温度对高温侧压力下降使氨合成反应减弱,温度升高势头减缓,而低温侧还原落后于高温侧,所以压力降低对这一侧催化剂的氨合成反应的抑制不甚明显,采用这一方法可以缩小同平面温差。当同平面温差一时消除不了时,应将整个升温还原过程速度放慢,且以高温侧的热点温度座位个阶段温度控制点,这样才能保证不会发生超温过热现象。Cause catalyst bed layer surface temperature difference for many reasons, such as uneven loading density of uneven distribution of gas is the main reason, commonly used to reduce the pressure, adjust circulation, to maintain hot spot temperature on the high side pressure drop decreased, the ammonia synthesis reaction temperature increase momentum slowed, and low side reduction lags behind that of the high temperature side, so the pressure to reduce on this side of the inhibition of catalyst for ammonia synthesis reaction was not obvious, when using this method can shrink with planar temperature difference with the surface temperature difference can not eliminate the slowing down of the whole process of temperature reduction should be, and in high temperature hot seat phase temperature control points in the side, which ensures that overtemperature overheating phenomenon will not occur
4.3 正常使用条件Regular service condition
4.3.1 使用温度Service temperature
氨合成反应中,提高反应温度能够加快反应速度的进行,但提高反应温度,不利于反应的平衡,在现代氨合成生产中,往往采用较低的反应温度来进行操作,以确保氨合成生产能耗的降低和催化剂正常使用寿命。A110-H型氨合成催化剂具有良好的低温活性性能,可以在较低的操作温度下获得较高的氨合成率,而且具有良好的耐热性能,以保证其使用寿命。Ammonia synthesis reaction, improve the reaction temperature can accelerate the reaction rate, but increase the temperature of reaction, does not favor the reaction balance, in the modern ammonia synthesis production, often used at low reaction temperature, to ensure that the energy consumption of ammonia synthesis production and normal service life of the catalyst A110 - H type ammonia synthesis catalyst has good activity at low temperature performance, can be operated at lower temperature and higher rate of ammonia synthesis, and it has good heat resistance, to ensure that its service life
A110-H型氨合成催化剂使用温度范围为:350-530℃,推荐最佳使用温度为350-500℃.短暂超温(小于550℃)不会对催化剂的活性造成大的影响,但为了更好地发挥催化剂的低温活性性能和尽可能延长催化剂的使用寿命,催化剂使用初期,应尽可能把热点的温度控制低一些,最好在470-490℃,以后随着使用时间的伸延,可以逐步提高热点的温度。A110 - H type ammonia synthesis catalyst using temperature range is: 350-530, recommend the best temperature is 350-500. A brief overtemperature (less than 550) will not have big impact on the activity of catalyst, but in order to better play to the catalyst activity at low temperature performance and prolong the service life of catalyst as far as possible temperature.
4.3.2 使用压力Service Pressure
氨合成反应是一个体积缩小的化学反应,提高压力,有利于氨合成反应的进行,但过高的压力,将会增加动力的消耗,增大了氨合成生产的成本。现代的氨合成生产工艺均向低压方向发展,因而选择适当的压力进行操作,将可以确保能耗处于较低的水平。A110-H型氨合成催化剂有较宽的操作压力范围,可以在10-40Mpa范围内,根据氨合成工艺和设备的要求选择合适的操作压力。Ammonia synthesis reaction is a smaller chemical reaction, improve the pressure, is advantageous to the ammonia synthesis reaction, but high pressure will increase power consumption, increasing the ammonia synthesis of ammonia synthesis production, the cost of modern production technology to develop in the direction of low pressure, and select the appropriate pressure, will be able to ensure that the standard of low energy consumption of A110 - H type ammonia synthesis catalyst has a wide range of operating pressure, can be between 10 and 40 mpa range, according to the requirement of the ammonia synthesis technology and equipment to choose the appropriate operating pressure
4.3.3 操作空速  Service Air speed
A110-H型氨合成催化剂操作空速范围为6000-30000h-1,工厂可以根据设备、气体净化情况和操作压力等工艺条件选择合适的空速,一般来说,小型的氨合成塔(φ800mm)以下15000~25000h-1为宜,中型塔以10000~20000 h-1,大型塔可以采用较低的空速进行操作。A110 - H type ammonia synthesis catalyst operating space velocity range of 6000-30000 - H - 1, the factory can according to the situation of gas purification equipment operation and process conditions such as pressure to choose the right airspeed, in general, small ammonia synthetic tower (800 mm) under 15000 ~ 25000 H - 1 advisable, medium-sized tower at 10000 ~ 20000 H - 1, lower space velocity may be used for large tower operation
4.3.4 气体的质量 Gas Mass
CO、CO2、H2O等含氧化合物均是催化剂的毒物,少量可以引起催化剂的暂时中毒,使催化剂暂时失去活性,在采用合格氢氮气经过一段时间的操作后,其活性可以得到绝大部分的恢复,但经常或高浓度的含氧化物会是催化剂活性下降,因此要求气体中的CO、CO2总量最大不得大于30ppm,应尽可能低于10ppm,而且越低越好。Oxygen-containing compounds such as CO, CO2 H2O is the catalyst poison, a small amount can cause catalyst poisoning, temporarily make catalysts losing activity, for the time being in the qualified hydrogen nitrogen over a period of time after operation, the active can get most of the recovery, but often or high levels of oxide will be the catalyst activity decreased, so the demand amount of CO, CO2 gas maximum shall not be greater than 30 PPM, should as far as possible below 10 PPM, and the lower the better
硫、砷、磷及其化合物,能引起催化剂的永久性中毒,因此要求气体中应尽量避免存在这些问题或尽可能低,以免影响催化剂的使用寿命。Sulfur, phosphorus and arsenic compounds, can cause permanent catalyst poisoning, so should try to avoid these problems in gas or as low as possible, lest affect the service life of catalyst.
润滑油的进入则可以使催化剂的孔道受到堵塞,降低催化剂的活性,因此,应尽可能避免压缩机和循环机的润滑油进入合成塔。Lubricating oil into the can make the catalyst pore jams, reduce the activity of the catalyst, therefore, should as far as possible to avoid compressor and circulation machine oil into synthetic tower
此外,升温还原时要注意把塔底部的温度尽可能提上来,使底部的催化剂得到充分的还原,这有利于整炉催化剂的作用得到充分发挥。In addition, the reduction in pay attention to the temperature of the bottom as much as possible to be brought, makes the bottom of the catalyst are fully restore, this is good for the whole furnace catalyst role into full play
 
当在升温还原或使用过程中。对催化剂床层进行提压或降压时,必须注意升降压的速率,要求升降压速率应小于0.3Mpa/min为好。以防止因压力激烈波动,引起催化剂强度破坏,粉化。When in the process of reduction or use of the catalyst bed layer for pressure or step-down, must pay attention to lift the rate of pressure for lifting pressure rate should be less than 0.3 Mpa/min as well to prevent because of the intense fluctuation pressure, cause catalyst strength damage, pulverization
5、停车Stop
5.1 短暂停车 Temporary Stop
使用过程,当碰到短时停电、停气、或因气体质量不合格,设备短期故障等原因,必须对合成塔进行短暂停车,可以适当降低操作压力,保持气体循环,等一切恢复正常后,可逐渐恢复正常条件进行操作,也可在短时间内适当降压后,封闭合成塔。Use process, when encounter a short outage stopping air or gas quality is unqualified, equipment such as short-term failure reason, must carry on the temporary parking on synthesis tower, can decrease the operating pressure, keep the gas cycle, after everything is back to normal, can be gradually returned to normal operating conditions, can also be appropriate in a short time after decompression, closed synthetic tower
5.2 长期停车Long-term Stop
长期停车可对催化剂进行钝化处理,也可降压及适当降温,采用冲钝氮置换后,封闭合成塔,使其自然降至室温。Long-term parking for catalyst passivation treatment, can also be step-down and proper cooling, using blunt blunt after nitrogen replacement, closed synthetic tower, make its natural down to room temperature
催化剂的钝化时必须先循环冷却至50℃以下,再用氮气置换后,在0.3~0.5 Mpa压力下,开始氮气循环,直到氢气含量小于4%,在通入干燥的压缩空气,空气的通入量必须保证催化剂床层的最高温度不超过100℃。当分析塔进出口气体的氧含量相同时,在再加大空气量后催化剂床层温度没有变化,可以认为钝化结束,封存闭合成塔。Catalyst passivation must first circulating cooling below 50, reoccupy after nitrogen replacement, under pressure from 0.3 ~ 0.5 Mpa, start the nitrogen cycle, until the hydrogen content is less than 4%, the dry compressed air is piped in, the on air intake must ensure that the highest temperature of catalyst bed layer is not more than 100 when analyzing tower import and export of the oxygen content of the gas phase at the same time, increase the air again in catalyst bed temperature did not change after volume, can think the end of the passivation, sealed closed into a tower.
没有氮气的条件下,则必须进行氢氮气循环降温,降压,同时改变造气操Under the condition of no nitrogen, hydrogen nitrogen cycle must be carried out in the cool, step-down, change the gasification operating at the same time,
作,使氢含量降至40%以下,通入空气,这是要特别小心,注意床层的温度,不得超过100℃,最好在80℃以下。
To make hydrogen content drops below 40%, pass into the air, which is to be especially careful attention to the temperature of the bed, does not exceed 100 ℃, preferably below 80 ℃.
6. 贮藏和运输注意事项 Storage and transport considerations
6.1 催化剂采用铁桶、内衬塑料袋密封包装,每桶净重80Kg。未使用时,请不要打开桶盖,以免受污染。
Catalysts used iron, lined with plastic sealed packaging, net weight 80Kg. When not in use, do not open the lid, to protect against contamination.
6.2贮存及运输过程中要防止受潮,避免摔滚冲撞。Storage and transportation process to prevent moisture, avoid throwing roll collision.


6.3贮存运输过程中应严防油污、灰尘及其他化学品的污染。
Storage and transportation process should prevent oil pollution, dust and other chemicals.
6.4运输中要注意包装标志,保持完整、清楚、以便核对产品的型号、规格等和有关查询。
 
 
 A110-H型氨合成催化剂的预还原方案
Transport packaging should pay attention to signs, intact, clearly, in order to check the product numbers and specifications and related queries
Pre-reduction program A110-H ammonia synthesis catalyst.
A110-H型氨合成催化剂是氧化态氨合成催化剂,其主要主要组分为Fe3O4,在合成氨反应中,Fe3O4是不具有活性的,必须还原成α-Fe方具有活性。
A110-H ammonia synthesis catalyst is ammonia synthesis catalyst oxidation state, whose main component is mainly Fe3O4, the ammonia reaction, Fe3O4 is not active, you must restore the α-Fe parties active.
Fe3O4+4H2=3Fe+H2O
在催化剂生产厂中,采用专门的设备,在符合催化剂特性的工艺条件下,对催化剂进行预还原,使其生成具有活性的α-Fe,为了运输、仑储和装填的安全,在一定的条件下,有控制地对催化剂表面进行钝化,使其表面生成一层FeO薄膜,这一产品通常称之为预还原催化剂。采用A110型氨合成催化剂进行预还原,生成了A110-H型预还原氨合成催化剂。
In the catalyst production plant, the use of specialized equipment in compliance with performance of the catalyst under process conditions, prereduced catalyst, having activity to generate the α-Fe, for transport, storage and filling security under certain conditions Next, the controlled passivation of the catalyst surface, so the surface layer of FeO film, the product is commonly referred to prereduced catalyst. Using A110 ammonia synthesis catalyst pre-reduction, generated synthesis catalyst A110-H-type pre-reduced ammonia.
A110-H型预还原催化剂的生产方案如下:
A110-H-type pre-reduction catalyst production program are as follows:
  1. 生产工艺:本产品生产经过两道工序即还原和钝化。
The production process: the product through two processes that’s reduction and passivation.
1.1还原工序
Process of Reduction
本工序是整个生产中的主导工序,任务是把来自工厂生产的氧化态A110型催化剂还原成为具有活性的还原态催化剂,本工序利用H2作为还原剂,在0.8~1.0Mpa的压力下把A110中的Fe3O4还原成为α-Fe使其具有催化活性的还原态催化剂以便使用。
This step is the step of producing the dominant task is the oxidation state of the A110 type reduction catalyst from the plant into a reduced state of activity of the catalyst, the step of using H2 as a reducing agent, in the A110 at a pressure 0.8 ~ 1.0Mpa reduction of Fe3O4 becomes reducible to α-Fe catalyst having catalytic activity for use.
反应方程式:         Fe3O4+H2→α-Fe+H2O-Q
Reaction equation:     Fe3O4+H2→α-Fe+H2O-Q
 
本反应中生成的水如不能及时除去,将会造成铁的再次氧化而降低其活性(Fe+H2O→FeO+H2),因此生产中采取高空速带走水份,并利用冷冻及分子筛除去生成的水,以利反应的进行。
If the water formed in the reaction can not be removed in time, it will cause oxidation of the iron and reducing its activity (Fe + H2O → FeO + H2), and therefore the production adopts high speed to take away the water, and using the freezing and removing the formed zeolite water, to facilitate the reaction.
1.2钝化工序Passivation processes
由于还原后的催化剂具有较高的活性,如与空气接触就会迅速氧化,放出大量热造成催化剂烧结而失去活性,因此必须经过钝化处理。使其便于存贮和运输。本工序的主要任务是对还原态催化剂进行钝化处理。
As the catalyst after reduction with high activity, such as contact with air will be oxidized rapidly and emit a lot of heat caused by sintering and loss of activity of catalyst, it must go through passivation. Making it easy to store and transport. The main task of this process is to restore the state of the catalyst passivation.
2Fe+O2→2FeO+Q  [反应在低温进行]
2Fe+O2→2FeO+Q  < Reaction at low temperatures>
生产中利用控制反应气中氧含量的方法,使单质Fe和氧发生缓慢反应,在催化剂颗粒表面生成一层约占催化剂重量2%的钝化层即保护膜,以防止催化剂在空气中发生深度氧化,便于运输和贮藏。
Active oxygen content of the reaction gas by the control method that elemental Fe reacts slowly with oxygen, the catalyst particles in the surface layer of approximately 2% by weight of the catalyst layer or passivation protective film to prevent the occurrence of the depth of the catalyst in air oxidation, easy to transport and storage.
2、还原系统 Reduction systerm
2.1还原系统Reduction systerm
 
 
 
 

 
 
  
 
 

1.heat exchanger2.reduction furnace3.water cooler
4. Water separator A5. Ammonia cooler6.water separator B;
7. Zeolite
2、2再生系统:Regeneration System

Water separatorB---Renewable electric furnace—Zeolite- Renewable Water Coolers
2、3钝化系统:Passivation Systems

 

冷风:cold wind;
1.Heater;2.Passivation furnace;3.fans;4.Water cooler;
每次还原氧化态~8吨,得还原态催化剂~5.36吨,收率约67%。包装净重每桶80Kg,铁桶,衬塑料袋密封包装。
Each time deoxidizing 8 tons, then get reduced catalyst ~ 5.36 tons, the yield of about 67%. Packing net weight 80Kg/ barrel, iron, lined plastic bags, sealed packaging.
2、4  A110型催化剂的还原条件:A110 type catalyst reduction conditions:
 
Bed layer℃ Heatingup℃/h Time
h
Total time/h Notes
Room ~400 ~40 10 10 control
400~460 1~5 16 26 Control moisture strictly
460 0 2 28 Control moisture
460~485 1 10 38  
485 0 10 56  
485~490 1 5 61  
490 0 10 71  
490~500 1 10 81  
500 0 10 91  
500~50 ≤50 15 105 moisture<0.2g/m3decrease temp.
 
2、5  A110-H型催化剂的钝化条件
A110-H Passivation conditions Catalysts
还原后的催化剂的钝化是一个关键问题,困为产品的钝化是一个强放热反应
Deactivation of the catalyst after reduction is a key issue, because the product of passivation is a highly exothermic reaction
2Fe+O2=2FeO             (1)
4Fe+3O2=2Fe2O3           (2)
在钝化过程中,我们希望发生的是反应(1),不希望反应(2)产生,或尽可能少产生,因为FeO已能很好地起保护作用,而且FeO还原速度相对快,可以更好地发挥预还原催化剂使用前再还原速度快的特点,因此,如何控制钝化学是关键,如果控制不好,一是会使钝化程度加深大量发生反应(2),产品将会失去预还原的意义,另一个方面,可能会因放热过大,催化剂温度很高,也加深了氧化,甚至有可能把催化剂过热烧坏,使产品活性丧失。
In the passivation process, we want is the reaction (1), do not want the reaction (2), or produce as little as possible, as well FeO has been able to play a protective role, and FeO reduction rate is relatively fast, can be more good to play again before the pre-reduction catalyst reduction characteristics of speed, therefore, how to control the blunt chemistry is the key, if the control is not good, one would deepen a large degree of passivation reaction (2) occurs, the product will lose the pre-reduction meaning, another aspect may be due to excessive heat, high catalyst temperature, but also deepened the oxidation catalyst overheating may even be burned, so that the loss of the product activity.
钝化时采用的介质是纯N2,其纯度必须达到99.8%以上,钝化采用经净化后的空气作为氧的来源。当催化剂层温度(最高点)达到≤46℃时,方可通入空气,通入的气量由温度上升进行控制,严格控制催化剂床层温度最高点在50±2℃,也就是说,通入的空气量开始要求低,一般从0.1%开始,随着钝化的进行,可根据温升情况,逐渐加大空气量,同时减少氮气量,直到最后通往的空气占20.5%以上,且催化剂层床不再发生温升,并适当提高1~2℃进行操作,催化剂床仍没有温升,循环2~4h后,钝化结束,降温后过筛包装。
Passivation medium used pure N2, which must have a purity of more than 99.8%, the passivation is used by the purified air as the oxygen source. When the catalyst layer temperature (the highest point) reaches ≤ 46 ℃, before they pass into the air introduced into the gas by the temperature rise control, the catalyst bed temperature is strictly controlled at the highest point of 50 ± 2 ℃, ie, access the request to start the low air amount, generally from 0.1% starting with the passivation carried out according to the temperature rise, and gradually increase the amount of air, while reducing the amount of nitrogen, leading to the air until the end of more than 20.5%, and the catalyst layer the bed temperature no longer occur, and appropriately increase 1 ~ 2 ℃ operation, still no catalyst bed temperature, cycle 2 ~ 4h after passivation end, after cooling sifting packaging.
控制指标:Control indicators:
  1. N2纯度:≥99.8%,O2含量:≤0.2%
N2  purity:≥99.8% ,   O2 content:≤0.2%
  1.  循环气入口温度:45±1℃
Recycle gas inlet temperature:45±1℃
  1. 钝化炉气体出口温度:50±2℃
passivation of the furnace gas outlet temperature:50±2℃
  1. 空气中P、S、Cl总含量:≤0.1%
Total content of P,S,Cl in air:≤0.1%
 
  1. SV:~1000h-1.
  2. 还原后催化剂中的氧化铁含量:≤2%
the content of iron oxide in catalyst after reduction:≤2%
 
  1. 一般钝化时间为100~120小时
Average passivation time from 100 to 120 hours.
分析控制一览表/ Analysis Control List
控制项目 控制指标 取样点 分析周期 分析方法
还原前置换 氧含量≤2% 热交换后 每次置换 奥氏仪
还原后放料置换 氢含量<2% 热交换后 每次置换 氢分析仪
系统水汽浓度 ≤3g/m3 热交换后 400℃后每小时一次 碱石棉法
钝化开始前置换 氧含量微量 钝化炉后 每次置换 奥氏仪
钝化系统氧含量 ≥20.5% 钝化炉后 当冷风达50m3/h时每小时一次 奥氏仪
氨系统置换 NH3≥99.5% 系统放空口 每次置换时 碱吸收法
 
Control Project Control targets Sampling points Analysis cycle Analysis
Replacement before reduction O2≤2% After heat exchange Replacement every time Orsat gas analyzer
Feeding replacement after reduction H2<2% After heat exchange Replacement every time

  • hydrogenanalyzer
System water vapor concentration ≤3g/m3 After heat exchange Each/H after 400℃ Alkali asbestos method
replacement before Passivation  oxygen trace Passivation after furnace Replacement every time Orsat gas analyzer
O2 in Passivation systerm ≥20.5% Passivation after furnace Each/H after after cold wind 50m3/h Orsat gas analyzer
Ammonia system replacement NH3≥99.5% The vent system When every replacement alkali absorption process