Simulation and analysis of reactive dividing-wall column for methylal production process

doi:10.11949/j.issn.0438-1157.20180623

Abstract

Abstract:

Methylal is an important raw material used for the production of chemical intermediates, solvents, paints and fuel additives, etc. At present, reactive distillation technology is the main method for preparing methylal from methanol and formaldehyde. In this work, the reactive distillation with a dividing-wall column for producing methylal was proposed and simulated. The results show that the preparation of methylal by such a process can avoid the back mixing effect of the middle component in the column and reduce the total cost by 8.09% annually, then significantly improve the economics of the process.

Key words: methylal, reactive distillation, reactive dividing-wall column, optimal design, process analysis

摘要：

甲缩醛（methylal）是一种重要的化工基本原料，广泛应用于化工中间体、溶剂、涂料及燃料添加剂等的生产中。目前，反应精馏技术是用于以甲醇和甲醛为原料制取甲缩醛的主要方法。利用Aspen Plus过程模拟软件模拟了常规的双进料甲缩醛反应精馏工艺流程，同时提出并模拟了反应精馏隔壁塔（RDWC）工艺制备甲缩醛的流程，通过对比来探究RDWC流程的优越性。结果表明，采用RDWC制备甲缩醛可避免中间组分在塔内的返混效应，同时可使年度总费用降低8.09%，显著提高过程的经济性。

关键词: 甲缩醛, 反应精馏, 反应精馏隔壁塔, 优化设计, 过程分析

CLC Number:

TQ 224.1

Jie YANG, Jiangyu QI, Yong SHA. Simulation and analysis of reactive dividing-wall column for methylal production process[J]. CIESC Journal, 2019, 70(3): 960-968.

杨杰, 祁江羽, 沙勇. 反应精馏隔壁塔制甲缩醛过程模拟与分析[J]. 化工学报, 2019, 70(3): 960-968.

Figures/Tables 9

Table 1 Reaction equilibrium constants

平衡常数	A	B
$K M G 1, g$	-16.984	5233.2
$K M G 1, l$	-8.145	3991
$K M G 2, g$	4.980×10^-3	869.5
$K M G n$ , n>2	1.908×10^-2	544.5
$K H F 1$ _,g	-14.755	5969.4
$K H F 1$ _, _l	-5.851	4463
$K H F n$ , n>2	-4.966×10^-1	-491.3

Table 1 Reaction equilibrium constants

平衡常数	A	B
$K M G 1, g$	-16.984	5233.2
$K M G 1, l$	-8.145	3991
$K M G 2, g$	4.980×10^-3	869.5
$K M G n$ , n>2	1.908×10^-2	544.5
$K H F 1$ _,g	-14.755	5969.4
$K H F 1$ _, _l	-5.851	4463
$K H F n$ , n>2	-4.966×10^-1	-491.3

Table 2 Parameters of reactive kinetic model of methylal formation

k _f(T ⁰)/(mol/(g·s))	k _b(T ⁰)/(mol/(g·s))	E _f/(kJ/mol)	E _b/(kJ/mol)	T ⁰/K
1.571×10^-3	6.1×10^-5	54.65	54.74	333.15

Fig.1 Schematic of optimization procedure

Table 3 Formulas of TAC calculation

项目		计算关联关系^[25]	备注^[26,27]
设备投资费用(CI)/USD	塔壳	$M & S 280 × 937.64 × D 1.066 H 0.802 × (2.18 + F c)$ , $H = 1.4 × H E T P × (N T - 1)$ ， $F c = F m × F p$	M&S=1497.73 F _m=F _p=1.0
	填料	$∑ i = 1 n C p, n V n$ , $V n = 14 π D 2 × H E T P n × N T, n$	C_{p, n} =3000 USD/m³
	换热器	$M & S 280 × 474.67 × A 0.65 × (2.29 + F c)$ , $A = Q / (U × Δ T)$ ， $F c = (F d × F p) × F m$	U _C=852 W/(m²·K) U _R=568 W/ (m²·K) F _d,C=0.85 F _d,R=1.35
操作费用(OC)/(USD/a)	蒸汽	$C s × Q r λ v × 7200 × 3600$	C _s=0.028 USD/kg λ _v=2762.9 kJ/kg
	冷水	$C w × Q c Δ T c p × 7200 × 3600$	C _w=1.48×10^-5USD/kg ?T=10 K c_p =4.18 kJ/(kg·K)
	催化剂	$4 × m c a t × C c a t$	C _cat=7.7 USD/kg

Table 3 Formulas of TAC calculation

项目		计算关联关系^[25]	备注^[26,27]
设备投资费用(CI)/USD	塔壳	$M & S 280 × 937.64 × D 1.066 H 0.802 × (2.18 + F c)$ , $H = 1.4 × H E T P × (N T - 1)$ ， $F c = F m × F p$	M&S=1497.73 F _m=F _p=1.0
	填料	$∑ i = 1 n C p, n V n$ , $V n = 14 π D 2 × H E T P n × N T, n$	C_{p, n} =3000 USD/m³
	换热器	$M & S 280 × 474.67 × A 0.65 × (2.29 + F c)$ , $A = Q / (U × Δ T)$ ， $F c = (F d × F p) × F m$	U _C=852 W/(m²·K) U _R=568 W/ (m²·K) F _d,C=0.85 F _d,R=1.35
操作费用(OC)/(USD/a)	蒸汽	$C s × Q r λ v × 7200 × 3600$	C _s=0.028 USD/kg λ _v=2762.9 kJ/kg
	冷水	$C w × Q c Δ T c p × 7200 × 3600$	C _w=1.48×10^-5USD/kg ?T=10 K c_p =4.18 kJ/(kg·K)
	催化剂	$4 × m c a t × C c a t$	C _cat=7.7 USD/kg

Fig.2 Relationships between FR and methylal yield and reboiler duty of RE-C

Fig.3 Optimized configurations of double-feed reactive distillation process

Fig.4 Schematic of double-feed RDWC process

Fig.5 Methanol concentration profiles in RD and RDWC process

Table 4 Configurations and costs of two processes

Item	RD		RDWC
Item	RD-C	RE-C	RD-C
column parameters
pressure/kPa	101.3	101.3	101.3
number of theoretical stages	29	19	40, 5
column diameter/m	0.8	0.4	0.8
mole reflux ratio	3.48	1.20	3.48
distillate rate/(kg/h)	1381	333.1	1381, 333.1
total catalyst mass/kg	290		290
capacity cost×10^-3/(USD/a)
column	90.0	22.3	126.3
heat exchanger	177.6	65.3	217.2
operating cost×10^-3/(USD/a)
energy	187.8	72.8	233.1
catalyst	8.93		8.93
TAC×10^-3/(USD/a)	285.9	102.0	356.5
total TAC×10^-3/(USD/a)	387.9		356.5

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