Beruflich Dokumente
Kultur Dokumente
M166631
Table 1 shows several methods to produce MMA such as ACH method, modify
ACH methods, Profin methods and direct acid method. This data reveals that the ACH
method is the best method to produce MMA efficiently because of high purity product, use
relatively less equipment e.g column distillation or reactor, and relatively low running cost
materials. However, this method not only produce MMA but also produce side product such
as (NH4)2SO4 that can be overcame by apply this side product for other application e.g
fertilizer. Therefore, in this plant, the MMA production will be conducted by ACH
method.
The Mitsubishi Rayon has competent to produce the MMA as much 107,000 t/year
with MMA purity 99.8%. Therefore, in this plant, we define the target product is around
100,000 t/year with same purity. If we assumed that reactor will be run 24 hour/day for 345
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day ( 20 days allocated for maintenance ) in one year, it means our product target is 12.1
t/h with 99.8% purity.
would like to focus on MMA process part ( MMA 合成反応器 ). Based on literature the
ACH method can be produced the MMA following the chemical reaction :
𝐤𝟏
𝐌𝐀𝐀𝐬 + 𝐌𝐞𝐎𝐇 →
← 𝐌𝐌𝐀 + 𝐍𝐇𝟒 𝐇𝐒𝐎𝟒 ∆𝐇 = −𝟏𝟎. 𝟗 𝒌𝑱/𝒎𝒐𝒍
𝐤𝟐
with MAAs is MAA-H2SO4 solution and MeOH is methanol.
In this part, there are several step to design this process. First, we decided the
Continuous Stir Tank Reactor (CSTR) as reactor because this reactor enable us to control the
solution temperature easly and have high potential to establish large scale production.
Second, we decided the reaction rate formula that originated from literature as
follows :
−𝒓𝑨 = 𝒌𝟏 (𝑪𝑴𝑨𝑨𝒔 − 𝒙)(𝑪𝑴𝒆𝑶𝑯 − 𝒙) − 𝒌𝟐 (𝑪𝑴𝑴𝑨 + 𝒙)(𝑪𝑵𝑯𝟒 𝑯𝑺𝑶𝟒 + 𝒙)
with C is molar concentration of materials (mol/m3), k is reaction constant (m3/mol.s) and x is
molar concentration of reacted materials.
Table 2. temperature dependence of reaction rate constant
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Third, we decided the temperature and pressure of reactor based on calculation with
consider the temperature and reaction time dependence. The calculation was restricted on T
less than 100 oC due to the formation of large amount of side product. Table 2 shows that T=
90 oC gives the highest reaction rate constant. In addition, Figure 1 shows that T= 90 oC
provides high reaction rate on short time. Therefore, we define the temperature of reactor is
90 oC. The pressure of reactor is 101.3 kPa that was originated from previous process. The
MMA reaction is exothermic reaction, that means this reaction will release some heat to the
environmental. Therefore, to maintain the temperature reaction from heat that produced from
reaction, we use water as coolant of tank. Since the temperature is below than boiling point of
water, water is a good coolant due to low cost and easy handling.
Fourth step is calculation of number of tank. The result shows that the residence time
materials on reactor is decrease as increasing the number of tank. However, based on cost
calculation, more tank will consume high cost production. The cost calculation shows that 2
tanks give the lowest cost process. Therefore, we define number of tank is 2.
Last step is material selection. Since the process will be conducted on strong acid
phase (from H2SO4), we should consider the corrosion of reactor wall. Thus, we select the
MC alloys that contains 50% Ni, 45%Cr and 1%Mo as wall reactor materials to prevent the
corrosion due to strong acid.
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VI. Understanding of The Process Flow and The Function of Process Components
The MMA manufacturing process by ACH method is shown in Figure 4. The process
was separate into 4 main process i.e ACH process, MAAs process, MMA process, and MMA
purification.
In the ACH process, we synthesize the ACH by react the cyanide acid (HCN) with
acetone. However, because the HCN was originated from reaction of acrylonitrile (AN), the
HCN still contain some of AN and water. Therefore, firstly the HCN will be distillated by
column distillation. In the reactor, the HCN is mixing with acetone using stirrer. In order to
obtain homogeneous solution, usually the NaOH addition is used as catalyze. Therefore, we
should add a column distillation for remove the water. However, in this plant, we replace the
NaOH with Dietylamine (DEA) as catalyze, thus the column distillation is not needed. Then,
the product is neutralized and then through the column distillation to remove the unreacted
raw materials. Water is used as heat exchanger on all of column distillation.
In MAAs process, the ACH was reacted with sulfuric acid (H2SO4) in the reactor with
stirring assisted. The product of this process that is MAA will be serve as raw materials in
MMA process.
In MMA process, the MAA was reacted with methanol in CSTR. The water supply
the methanol tank to reduce the concentration of methanol. The reaction was conducted with
stirring assisted resulted MMA, NH4SO4 and other side products.
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Last, in MMA purification, the MAA product will be distillated to purified the MMA
from sulfuric acid excess. The sulfuric acid will be recycled. Then, the MA will be distillated
again to separated MMA from methanol. In this part, we use WINTRAY instead of sieve tray
column. The WINTRAY separated the solution based on the difference of liquid density that
can improve the efficiency of distillation and easy to clean.
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Number 1 2 3 4 5 6
物質名 化学式 分子量[kg/kmol] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%]
MMA C5H8O2 100.117 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
MeOH CH4O 32.042 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
青酸 HCN 27.026 150.53 97.12 4068.11 98.00 0.23 4.82 6.10 6.85 150.30 100.00 4062.01 100.00 0 0 0 0 60.51 23.88 1635.44 9.73 0 0 0 0
アセトン C3H6O 58.08 0 0 0 0 0 0 0 0 0 0 0 0 150.30 98.30 8729.50 99.36 39.95 15.77 2320.50 13.81 0 0 0 0
AN C3H3N 53.064 0.08 0.05 4.15 0.10 0.08 1.67 4.15 4.66 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ジエチルアミン C4H11N 73.138 0 0 0 0 0 0 0 0 0 0 0 0 0.17 0.11 12.09 0.14 0.17 0.07 12.09 0.07 0 0 0 0
ジエチルアミン硫酸塩 C4H11N・H2SO4 171.217 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ACH C4H7NO 85.106 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 150.30 59.32 12791.50 76.12 0 0 0 0
水 H2O 18.015 4.38 2.82 78.87 1.90 4.38 93.51 78.87 88.50 0 0 0 0 2.44 1.59 43.87 0.50 2.44 0.96 43.87 0.26 0.03 10.00 0.50 2.00
硫酸 H2SO4 98.079 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.25 90.00 24.29 98.00
硫酸水素アンモニウム NH4HSO4 115.11 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリルアミド硫酸塩 C4H7NO・H2SO4 183.185 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリル酸 C4H6O2 86.08 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
合計 112.10506 154.98 100.00 4151.13 100.00 4.68 100.00 89.13 100.00 150.30 100.00 4062.01 100.00 152.90 100.00 8785.46 100.00 253.37 100.00 16803.40 100.00 0.28 100.00 24.79 100.00
Number 7 8 9 10 11 12
物質名 化学式 分子量[kg/kmol] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%]
MMA C5H8O2 100.117 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1.58 0.27 157.96 1.00
MeOH CH4O 32.042 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 349.45 58.76 11197.09 71.11
青酸 HCN 27.026 60.51 23.87 1635.44 9.72 60.51 60.23 1635.44 41.34 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
アセトン C3H6O 58.08 39.95 15.76 2320.50 13.79 39.95 39.77 2320.50 58.66 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
AN C3H3N 53.064 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ジエチルアミン C4H11N 73.138 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ジエチルアミン硫酸塩 C4H11N・H2SO4 171.217 0.17 0.07 28.31 0.17 0 0 0 0 0.17 0.11 28.31 0.22 0 0 0 0 0.17 0.05 28.31 0.07 0 0 0 0
ACH C4H7NO 85.106 150.30 59.30 12791.50 76.01 0 0 0 0 150.30 98.23 12791.50 99.37 0 0 0 0 10.52 3.03 895.40 2.08 0 0 0 0
水 H2O 18.015 2.46 0.97 44.36 0.26 0 0 0 0 2.46 1.61 44.36 0.34 33.40 10.00 601.69 2.00 35.86 10.33 646.05 1.50 243.70 40.98 4390.23 27.88
硫酸 H2SO4 98.079 0.08 0.03 8.08 0.05 0 0 0 0 0.08 0.05 8.08 0.06 300.60 90.00 29482.80 98.00 160.90 46.34 15781.38 36.74 0 0 0 0
硫酸水素アンモニウム NH4HSO4 115.11 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリルアミド硫酸塩 C4H7NO・H2SO4 183.185 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 139.78 40.26 25605.60 59.61 0 0 0 0
メタクリル酸 C4H6O2 86.08 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
合計 253.48 100.00 16828.18 100.00 100.47 100.00 3955.94 100.00 153.01 100.00 12872.24 100.00 334.00 100.00 30084.49 100.00 347.23 100.00 42956.74 100.00 594.73 100.00 15745.28 100.00
Number 13 14 15 16 17 18
物質名 化学式 分子量[kg/kmol] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%]
MMA C5H8O2 100.117 0 0 0 0 0 0 0 0 132.97 14.12 13312.67 22.68 0 0 0 0 132.97 20.74 13312.67 49.66 0 0 0 0
MeOH CH4O 32.042 136.64 95.00 4378 97.13 0 0 0 0 218.06 23.15 6986.99 11.90 0 0 0 0 218.06 34.01 6986.99 26.06 0 0 0 0
青酸 HCN 27.026 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
アセトン C3H6O 58.08 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
AN C3H3N 53.064 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ジエチルアミン C4H11N 73.138 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ジエチルアミン硫酸塩 C4H11N・H2SO4 171.217 0 0 0 0 0 0 0 0 0.17 0.02 28.31 0.05 0.17 0.05 28.31 0.09 0 0 0 0 0 0 0 0
ACH C4H7NO 85.106 0 0 0 0 0 0 0 0 10.52 1.12 895.40 1.53 0 0 0 0 10.52 1.64 895.40 3.34 0 0 0 0
水 H2O 18.015 7.19 5.00 129.56 2.87 143.92 100.00 2592.76 100.00 271.17 28.79 4885.19 8.32 0 0 0 0 271.17 42.29 4885.19 18.22 500.00 100.00 9007.50 100.00
硫酸 H2SO4 98.079 0 0 0 0 0 0 0 0 160.90 17.08 15781.38 26.88 160.83 53.47 15774.34 49.46 0.07 0.01 7.03 0.03 0 0 0 0
硫酸水素アンモニウム NH4HSO4 115.11 0 0 0 0 0 0 0 0 139.78 14.84 16090.14 27.41 139.78 46.47 16090.14 50.45 0 0 0 0 0 0 0 0
メタクリルアミド硫酸塩 C4H7NO・H2SO4 183.185 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリル酸 C4H6O2 86.08 0 0 0 0 0 0 0 0 8.39 0.89 721.94 1.23 0 0 0 0 8.39 1.31 721.94 2.69 0 0 0 0
合計 143.83 100.00 4507.86 100.00 143.92 100.00 2592.76 100.00 941.96 100.00 58702.02 100.00 300.78 100.00 31892.79 100.00 641.18 100.00 26809.23 100.00 500.00 100.00 9007.50 100.00
35816.73
Number 19 20 21 22 23 24
物質名 化学式 分子量[kg/kmol] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%]
MMA C5H8O2 100.117 11.77 1.18 1178.86 5.20 1.58 0.51 157.96 1.83 10.20 1.47 1020.90 7.27 121.20 86.07 12133.81 92.36 11.19 48.68 1120.66 82.47 0.05 0.53 5.40 2.68
MeOH CH4O 32.042 216.97 21.69 6952.16 30.66 212.81 69.33 6818.80 78.88 4.16 0.60 133.36 0.95 1.09 0.77 34.83 0.27 1.83 7.95 58.59 4.31 1.07 10.59 34.25 17.01
青酸 HCN 27.026 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0
アセトン C3H6O 58.08 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0
AN C3H3N 53.064 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0
ジエチルアミン C4H11N 73.138 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0
ジエチルアミン硫酸塩 C4H11N・H2SO4 171.217 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0
ACH C4H7NO 85.106 8.76 0.88 745.47 3.29 0 0 0 0 8.76 1.26 745.47 5.31 1.76 1.25 149.94 1.14 0 0 0 0 0 0 0.00 0
水 H2O 18.015 762.01 76.17 13727.52 60.53 92.58 30.16 1667.91 19.29 669.42 96.54 12059.61 85.93 9.17 6.51 165.17 1.26 9.97 43.37 179.67 13.22 8.98 88.88 161.69 80.31
硫酸 H2SO4 98.079 0.07 0.01 7.03 0.03 0 0 0 0 0.07 0.01 7.03 0.05 0 0 0 0 0 0 0 0 0 0 0 0
硫酸水素アンモニウム NH4HSO4 115.11 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリルアミド硫酸塩 C4H7NO・H2SO4 183.185 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリル酸 C4H6O2 86.08 0.79 0.08 67.62 0.30 0 0 0 0 0.79 0.11 67.62 0.48 7.60 5.40 654.32 4.98 0 0 0 0 0 0 0 0
合計 1000.37 100.00 22678.66 100.00 306.97 100.00 8644.67 100.00 693.40 100.00 14033.99 100.00 140.81 100.00 13138.07 100.00 23.00 100.00 1358.92 100.00 10.10 100.00 201.34 100.00
Number 25 26 27 28
物質名 化学式 分子量[kg/kmol] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%] [kmol/h] [mol%] [kg/h] [wt%]
MMA C5H8O2 100.117 11.14 86.37 1115.26 96.34 121.14 92.68 12128.42 93.75 0.02 0.17 1.61 0.20 121.13 99.83 12126.81 99.97
MeOH CH4O 32.042 0.76 5.89 24.34 2.10 0.02 0.01 0.58 0.00 0 0 0 0 0.02 0.01 0.58 0.00
青酸 HCN 27.026 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
アセトン C3H6O 58.08 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
AN C3H3N 53.064 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ジエチルアミン C4H11N 73.138 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ジエチルアミン硫酸塩 C4H11N・H2SO4 171.217 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
ACH C4H7NO 85.106 0 0 0 0 1.76 1.35 149.94 1.16 1.76 18.78 149.94 18.61 0 0 0 0
水 H2O 18.015 1.00 7.74 17.98 1.55 0.19 0.15 3.48 0.03 0 0 0 0 0.19 0.16 3.48 0.03
硫酸 H2SO4 98.079 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
硫酸水素アンモニウム NH4HSO4 115.11 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリルアミド硫酸塩 C4H7NO・H2SO4 183.185 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
メタクリル酸 C4H6O2 86.08 0 0 0 0 7.60 5.82 654.32 5.06 7.60 81.04 654.32 81.19 0 0 0 0
合計 12.90 100.00 1157.58 100.00 130.72 100.00 12936.72 100.00 9.38 100.00 805.86 100.00 121.34 100.00 12130.86 100.00
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番号 1 2 3 4 5 6 7 8 9 10 11
温度 [K] 298.2 354.0 298.8 293.2 298.2 293.2 273.2 298.2 273.2 293.6 274.1
状態 l l g l l l l l l l g
Q [kJ/h] 1.49.E+07 2.78.E+05 2.03.E+07 1.59.E+07 -6.10.E+07 -6.35.E+07 -4.80.E+07 -3.97.E+06 -4.96.E+07 -3.66.E+07 -6.20.E+05
番号 12 13 14 15 16 17 18 19 20 21 22
温度 [K] 274.1 293.2 327.9 383.2 298.2 383.2 383.2 363.2 320.5 363.2 298.2
状態 l l l l l l l l l l l
Q [kJ/h] -2.15.E+07 -1.02.E+07 -2.55.E+07 -2.48.E+07 -4.81.E+09 -2.72.E+09 -1.61.E+09 -1.85.E+09 -2.41.E+09 -1.99.E+09 -5.30.E+07
番号 23 24 25 26 27 28 29 30 31 32 33
温度 [K] 298.2 338.1 688 355.7 298.2 298.2 298.2 298.2 338.1 372.0 347.9
状態 l l l g l l l l g l g
Q [kJ/h] -5.81.E+07 -6.05.E+07 -1.82.E+09 -5.41.E+07 -3.97.E+09 -1.65.E+08 -3.47.E+09 -6.71.E+08 -2.98.E+07 5.60.E+07 -2.82.E+06
番号 34 35 36 37 38 39 40
温度 [K] 347.9 347.9 347.9 375.1 430.2 372.6 372.6
状態 l l l l l g l
Q [kJ/h] -4.06.E+07 -4.05.E+07 -4.65.E+04 -5.12.E+07 -3.61.E+06 -4.09.E+07 -4.67.E+07
VIII. Optimization of The Chemical Process Based on The Economic Efficiency and
Safety
This process provides the MMA as 10.000 t/year, purity 99.97% for 345 day/year.
The rate of production MMA is 80.7%, indicating the process is conducted efficiently.
Moreover, in this process we use DEA that improve the efficiency due to less column
distillation and WINTRAY to replace sieve column that provide easy cleaning.
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