1. 104DA 104DA 2. R R3004 R3004 R3004 II

Transcription

1 湖南大学硕士学位论文高中温变换炉及加氢反应器的腐蚀与防护研究姓名 : 陈鹏申请学位级别 : 硕士专业 :@ 指导教师 : 旷亚非 ; 李海根

2 1. 104DA 104DA 2. R R3004 R3004 R3004 II

3 Abstract Metal corrosion does harm for many fields of civil economy, including metallurgy, transportation, petroleum chemical engineering aerospace, power source, communication etc. Corrosion and protection of materials are very important and elaborate work in chemistry industry because of the complicated working environment and strict production conditions. Ammonia synthesis is an important process in caprolactam production of Baling petrochemical company. In this paper, corrosion and protection measurements of several key devices in ammonia synthesis were discussed in detail. The results are as follows: 1. The corrosion invalidation reasons of 104DA high temperature shift furnace were analyzed and discussed in detail. Macroscopical check, metallography analyses, magnetic power and ultrasonic wave detection, material components analyses and mechanical performance measurement were used to study the corrosion of 104DA device. The results show that the hydrogen corrosion cracking of 104DA device is caused by wrong selection of materials. Restoring and running administration methods were proposed according to the corrosion and running state of the device. After 4 years production running, abnormal running of super-temperature and super-pressure of the device didn t occur. It brings good social and economic benefit. 2. The corrosion cracking reasons of the gland of R3002 caprolactam-cyclohexanone hydrogenation reactor were researched. The appearance, wall thickness, micro-hardness and mechanical performance of the corrosion sites were measured. And chemical elements analyses metallogrsphy microscope rupture scanning electron microscope were also used to study the corrosion of the device The results indicate that the corrosion cracking is caused by the following reasons Firstly the mechanical performance of the device didn t meet the design demand because of the wrong selection of lower head material Secondly the phenomenon of super-temperature during the device running is the direct and main reason In order to avoid the similar accident effective inspection measures and corresponding running monitor methods of the device were proposed 3. Metallogrsphy analyses, magnetic power and ultrasonic wave detection methods were used to investigate the reason of hydrogen corrosion of R3004 medium temperature shift furnace The results present that the hydrogen corrosion of R3004 is III

4 caused by the high running temperature, which is higher than the designed wall temperature The corrosion of the devise is not serious at present Through adopting strict safe running measures and corresponding process conditions the R3004 device can run a production period Key words: high temperature shift furnace; medium temperature shift furnace; hydrogenation reactor; corrosion; protection IV

5 1 2 I

6 % 10% SO 2 30 / 100 [1] 20 [2]

7 [3] (1) (2) (3) [4,5,6] (1) (2) (3) (4) (1) ph (2) lo 1 3 (3) (4) % - 2 -

8 [7-9] No8020 No5024 No % 30 35% %

9 [10,11] (1) [12,13] (2) (3) (4) (5)

10 1.3.3 [14,15] Cl

11 [16,17] [18,19] (1) (2) (3) (4) (5) T U (6)

12 (1) (2) (3) (1) (2) (3) (4) (1) (2) (3) (4) (5) - 7 -

13 ,,,,, 20, :, (CO 2 ) 1, 90% [20],, N 2 +3H 2 = 2 NH 3 + Q

14 ( ) [21] Cr Ti Mo V W MPa, NH 3 3[H] + [N]

15 Al V Ti Mo [22-24] 1 H + H 2 S CO 2 H 2 O 1Cr18Ni9Ti 15 CrMo TH

16 H 2 S CO 2 H 2 O SO 2 Cl - SO Fe Fe + 2e O 2 + 2H 2 O + 4e 4OH - Fe 2+,Fe 3+ FeO Fe 3 O 4 nh 2 O, Fe 2 O 3 ( ) A.D.A. Na 2 CO 3 10H 2 O

17 / 14 / Shell , 104DA E R3002 [39] 3

18 2 104DA 104DA DA M.K.W SA204B 3886mm 20951mm 81mm MPa 2.865MPa MPa H 2 CO N 2 CO CO MPa 2.805MPa CO 2 H

19 mm 0 55mm mm

20 C-0.5Mo ASME SA204B DA C Si Mn P S Mo Cr M.K.W Mpa Mpa Nelson C-0.5Mo C-0.5Mo 1997 API RP941 Nelson 27 C-0.5Mo SA204B mm mm 85.0mm % 3 1~2mm P13 13K1 2.5P13 13LK1 50% 2 2Z20 500mm 500mm 0~55mm 3 25~55mm

21 DA HB 1 137~ ~ ~ ~ ~

22 mm 500mm [25]

23 - 104DA CH 4 CH 4 CH 4 C-0.5Mo

24 DA [26] Nelson 104DA SA204B C-0.5Mo 2.865MPa 436 Nelson MPa 430 SA204B 0.5Mo Nelson 90 Nelson 0.5Mo SA204B Nelson 3.6MPa 3.6MPa

25 2.9MPa DA SA-204B C-0.5Mo MPa mm mm CH mm mm 0.5mm DA

26 DA C-0.5Mo SA204B 0.5Mo Neison

27 3 R3002 R CrMoR R MPa CrMoR mm 36~38mm JB % # 760mm 20mm

28 mm 700mm 6010mm 30mm #2 #1 #2 #1 3mm 3.1 2# 750mm 40mm 3.4 1#

29 3.2 R R R3002 1# 2#

30 S10 S2 S1 S3 S5 S4 S6 S8 S7 S R3002 mm mm mm S S S S S S S S S S mm CrMoR

31 3.2 R3002 % C Si Mn S P Cr Mo GB CrMoR GB R / / CrMoR CrMoR CrMoR R CrMoR Cr Mo 15CrMoR 20R , 3.3 Y1 Y2 Y3 Y4 Y5 Y

32 3.3 R3002 HB Y Y Y Y Y Y # # mm mm mm mm MPa / MPa % MPa %

33 GB mm 15CrMoR MPa 295MPa 5 19% 15CrMoR 15CrMoR # 2# mm

34 R

35 3.5 R3002 Hv , Cr Mo

36 Cr Mo 15CrMoR Cr Mo 411.9MPa MPa 15CrMoR 450~590MPa 295 MPa [27,28,29] 2 CH 4 [30 31]

37

38 4 R3004 R R MPa 2.51~2.54MPa ~395 CO CO 2 H 2 CH 4 H m ~ mm mm =150mm JZ

39 mm MPa ~ ~ mm 42.3mm 43.0mm 38.3mm 40.3mm R mm

40 mm % JB mm 150mm HB HB MnR R , 1 2~

41 R ~ ~ MPa 3 Nelson 16MnR

42 0.76MPa CVDA-1984 COD 16M R SPV36 m 1 Di=2600mm t=42mm 16MnR Pw 2.4MPa Tw 250 cr=0.06mm y=285mpa =119mPa 300 E= MPa 2 1= m=pwpi/2t= / 2 42 =74.29MPa 2=0 3=0.6 y= =171MPa = =245.29MPa 3 m= cr/ e+ey =E cr/ + y = / =7.56mm m=7.56 2/3 =5.04mm=5.0mm 4mm Pw 2.4MPa Tw = / 1 tf-ts/ts-ta mm kcal/m.h. 1 kcal/m.h. tf ts ta R mm 260 ts-ta 15~

43 / = tf-ts / tf-ts = tf-ts / tf-ts = tf-40 / mm tf ~110mm F C Nelson MPa MPa R MnR 15CrMoR R MPa 210~ R R3004 Pw 2.4MPa Tm

44 [32 33]

45 DA Nelson MPa 430 SA204B 0.5Mo Nelson SA204B 250 Nelson 2.9MPa 1 3mm mm CH X600mm mm 0.5mm 2 R3002 Cr Mo 15CrMoR Cr Mo 411.9MPa MPa 15CrMoR 450~590MPa 295 MPa

46 CH 4 3 R3004 Pw 2.4MPa Tm

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49 - 44 -

50 A [1]., (4):