基于DFSS方法优化52#费托蜡的制备工艺

doi:10.16085/j.issn.1000-6613.2023-0706

摘要/Abstract

摘要：

以煤间接液化的加氢精制减三线油为原料，采用溶剂萃取-结晶的方法制备52^#费托蜡，并通过六西格玛设计对制备工艺进行开发。利用响应曲面设计中的中心复合设计建立响应值含油量、收率、熔点与剂油比、溶剂比、结晶时间、降温速率、结晶温度之间的数学模型，深入分析了各考察因素及其间的交互作用对响应值的影响。通过优化实验结果，验证模型，得到最佳的制备工艺参数组合以及较优的操作窗口，指导100kg/h中试试验顺利进行。研究结果表明：当剂油比为5、溶剂比为2、结晶时间6min、结晶温度5℃、降温速率为5.3℃/min时，实验室小试和中试试验产品蜡的熔点在52~54℃，含油量为0.2%~0.8%（质量分数），收率均大于25%（质量分数），产品符合国标GB/T446—2010《全精炼石蜡》的要求；实验值和模型预测值较为接近，模型的拟合效果好，预测精度高，质量可靠。

关键词: 52^#费托蜡, 萃取结晶, 六西格玛, 响应曲面设计

Abstract:

52^# Fischer-Tropsch wax was prepared by solvent extraction from hydrorefining reduced third-line oil, which was investigated based on the six sigma design. The mathematical models of the oil content, yield, melting point and solvent-oil ratio, solvent ratio, crystallization time, cooling rate, and crystallization temperature were proposed by using the central composite design assigned to response surface design, analyzing the influence of each factor and their interaction on the response value. The optimal combination of preparation process parameters and better operation window were obtained by multi-objective optimizing, which guided the 100kg/h pilot test to proceed smoothly. The results showed that when the solvent-oil ratio was 5, solvent ratio was 2, crystallization time was 6min, crystallization temperature was 5℃, and the cooling rate was 5.3℃/min, the melting point of the wax was 52—54℃, the oil content was 0.2%—0.8%, and the yield was more than 25%, which met the requirement of the refined wax. The experimental value was closed to the predicted value of the model, which indicated that the models had good fitting effect, high prediction accuracy and reliable quality.

Key words: 52^# Fischer-Tropsch wax, extractive crystallization, six sigma, response surface design

中图分类号:

TQ53

蒋晨光, 张胜振, 张翠清, 郭屹, 孙永伟. 基于DFSS方法优化52^#费托蜡的制备工艺[J]. 化工进展, 2024, 43(4): 1742-1753.

JIANG Chenguang, ZHANG Shengzhen, ZHANG Cuiqing, GUO Yi, SUN Yongwei. Optimization of the preparation process of 52^# Fischer-Tropsch wax based on DFSS method[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1742-1753.

图/表 19

表1 实验因子及水平设置

因子	代号	编码和水平
因子	代号	-1	-	0	+	+1
剂油比	X₁	4.45	3.5	6.75	10	9.04
溶剂比	X₂	2.88	2	5	8	7.12
结晶时间/min	X₃	2.19	0	7.5	15	12.80
降温速率/℃·min^-1	X₄	5.48	5.3	5.9	6.5	6.32
结晶温度/℃	X₅	1.47	0	5	10	8.53

表2 DOE 设计矩阵及实验结果

序号	X₁	X₂	X₃/min	X₄/℃·min^-1	X₅/℃	熔点/℃	含油量（质量分数）/%	收率（质量分数）/%
1	6.75	5	12.80	5.9	5	51.75	0.606	18.48
2	9.04	5	7.5	5.9	5	53.08	0.6	18.12
3	10	8	15	5.3	10	52.47	2.2	21.04
4	3.5	2	0	6.5	10	58.85	0	2.24
5	10	8	0	5.3	0	49.14	1.388	38.96
6	3.5	8	15	6.5	10	50.92	3.565	23.66
7	3.5	8	0	6.5	0	50.51	1.912	27.28
8	3.5	8	0	5.3	10	50.56	2.165	28
9	6.75	7.12	7.5	5.9	5	50.49	1.123	26.06
10	6.75	5	7.5	5.48	5	51.39	0.993	26.4
11	3.5	2	15	5.3	10	54.82	0.847	11.5
12	3.5	2	15	6.5	0	52.11	0.898	22.94
13	6.75	5	7.5	5.9	5	52.03	0.548	24.86
14	4.45	5	7.5	5.9	5	51.29	0.77	27.82
15	6.75	5	7.5	5.9	1.47	50.65	0.615	30.64
16	6.75	5	7.5	6.32	5	52.63	0.877	25.56
17	10	2	0	5.3	10	60.01	0.678	3.6
18	6.75	5	2.19	5.9	5	53.35	0.545	19.56
19	6.75	5	7.5	5.9	5	51.71	0.546	22.78
20	10	2	15	5.3	0	52.87	0.384	19.68
21	6.75	5	7.5	5.9	5	52.17	0.656	24.22
22	10	8	15	6.5	0	50.21	0.1	33.74
23	10	8	0	6.5	10	57.04	1.558	7.18
24	6.75	5	7.5	5.9	8.53	53.53	0.89	20.76
25	10	2	0	6.5	0	57.27	0.91	6.06
26	3.5	2	0	5.3	0	51.85	0.576	24.6
27	10	2	15	6.5	10	60.94	0.067	2.5
28	6.75	2.88	7.5	5.9	5	53.46	0.255	15.1
29	3.5	8	15	5.3	0	46.83	1.424	46.44

表3 熔点回归模型的方差分析

方差来源	平方和	自由度	均方	F值	P值
模型	285.795	11	25.981	587.799	<0.0001
X₁	36.079	1	36.079	816.245	0.00000
X₂	109.475	1	109.475	2476.746	0.00000
X₃	13.575	1	13.575	307.121	0.00000
X₄	23.947	1	23.947	541.782	0.00000
X₅	79.906	1	79.906	1807.780	0.00000
X₁X₂	0.731	1	0.731	16.539	0.00080
$X 32$	14.547	1	14.547	329.109	0.00000
X₁X₄	0.436	1	0.436	9.855	0.00598
X₃X₄	1.513	1	1.513	34.227	0.00002
X₁X₅	3.168	1	3.168	71.681	0.00000
X₂X₅	2.418	1	2.418	54.705	0.00000
残差	0.751	17	0.044	—	—
失拟项	0.640	15	0.043	0.767	0.6992
纯误差	0.111	2	0.055	—	—
R²=0.997378
$R A d j 2$ =0.995681
W=0.1803>0.05

表3 熔点回归模型的方差分析

方差来源	平方和	自由度	均方	F值	P值
模型	285.795	11	25.981	587.799	<0.0001
X₁	36.079	1	36.079	816.245	0.00000
X₂	109.475	1	109.475	2476.746	0.00000
X₃	13.575	1	13.575	307.121	0.00000
X₄	23.947	1	23.947	541.782	0.00000
X₅	79.906	1	79.906	1807.780	0.00000
X₁X₂	0.731	1	0.731	16.539	0.00080
$X 32$	14.547	1	14.547	329.109	0.00000
X₁X₄	0.436	1	0.436	9.855	0.00598
X₃X₄	1.513	1	1.513	34.227	0.00002
X₁X₅	3.168	1	3.168	71.681	0.00000
X₂X₅	2.418	1	2.418	54.705	0.00000
残差	0.751	17	0.044	—	—
失拟项	0.640	15	0.043	0.767	0.6992
纯误差	0.111	2	0.055	—	—
R²=0.997378
$R A d j 2$ =0.995681
W=0.1803>0.05

表4 含油量模型的方差分析

方差来源	平方和	自由度	均方	F值	P值
模型	15.971	15	1.065	252.213	<0.0001
X₁	1.049	1	1.049	248.401	0.00000
X₂	6.567	1	6.567	1555.510	0.00000
X₃	0.007	1	0.007	1.622	0.22518
X₄	0.032	1	0.032	7.507	0.01689
X₅	0.798	1	0.798	188.949	0.00000
X₁X₂	0.782	1	0.782	185.317	0.00000
X₁X₃	0.933	1	0.933	221.041	0.00000
$X 32$	0.026	1	0.026	6.078	0.02838
X₁X₄	0.713	1	0.713	168.934	0.00000
X₂X₄	0.020	1	0.020	4.776	0.04775
$X 42$	0.210	1	0.210	49.762	0.00001
X₂X₅	2.132	1	2.132	504.923	0.00000
X₃X₅	1.133	1	1.133	268.417	0.00000
X₄X₅	0.035	1	0.035	8.283	0.01294
$X 52$	0.021	1	0.021	4.935	0.04469
残差	0.055	13	0.004	—	—
失拟项	0.047	11	0.004	1.078	0.5758
纯误差	0.008	2	0.004	—	—
R²=0.996
R²_Adj=0.992
W=0.4765>0.05

表4 含油量模型的方差分析

方差来源	平方和	自由度	均方	F值	P值
模型	15.971	15	1.065	252.213	<0.0001
X₁	1.049	1	1.049	248.401	0.00000
X₂	6.567	1	6.567	1555.510	0.00000
X₃	0.007	1	0.007	1.622	0.22518
X₄	0.032	1	0.032	7.507	0.01689
X₅	0.798	1	0.798	188.949	0.00000
X₁X₂	0.782	1	0.782	185.317	0.00000
X₁X₃	0.933	1	0.933	221.041	0.00000
$X 32$	0.026	1	0.026	6.078	0.02838
X₁X₄	0.713	1	0.713	168.934	0.00000
X₂X₄	0.020	1	0.020	4.776	0.04775
$X 42$	0.210	1	0.210	49.762	0.00001
X₂X₅	2.132	1	2.132	504.923	0.00000
X₃X₅	1.133	1	1.133	268.417	0.00000
X₄X₅	0.035	1	0.035	8.283	0.01294
$X 52$	0.021	1	0.021	4.935	0.04469
残差	0.055	13	0.004	—	—
失拟项	0.047	11	0.004	1.078	0.5758
纯误差	0.008	2	0.004	—	—
R²=0.996
R²_Adj=0.992
W=0.4765>0.05

表5 收率模型的方差分析

方差来源	平方和	自由度	均方	F值	P值
模型	2925.057	8	365.632	64.488	<0.0001
X₁	217.152	1	217.152	38.300	0.0000
X₂	1168.309	1	1168.309	206.059	0.0000
X₃	107.840	1	107.840	19.020	0.0000
X₄	278.555	1	278.555	49.129	0.0000
X₅	948.261	1	948.261	167.248	0.0003
$X 32$	72.162	1	72.162	12.727	0.00102
X₃X₄	83.631	1	83.631	14.750	0.00193
$X 42$	26.589	1	26.589	4.689	0.04261
残差	113.395	20	5.669	—	—
失拟项	111.126	18	6.174	5.439	0.1664
纯误差	2.270	2	1.135	—	—
R²=0.962
R²_Adj=0.947
W=0.1532>0.05

表5 收率模型的方差分析

方差来源	平方和	自由度	均方	F值	P值
模型	2925.057	8	365.632	64.488	<0.0001
X₁	217.152	1	217.152	38.300	0.0000
X₂	1168.309	1	1168.309	206.059	0.0000
X₃	107.840	1	107.840	19.020	0.0000
X₄	278.555	1	278.555	49.129	0.0000
X₅	948.261	1	948.261	167.248	0.0003
$X 32$	72.162	1	72.162	12.727	0.00102
X₃X₄	83.631	1	83.631	14.750	0.00193
$X 42$	26.589	1	26.589	4.689	0.04261
残差	113.395	20	5.669	—	—
失拟项	111.126	18	6.174	5.439	0.1664
纯误差	2.270	2	1.135	—	—
R²=0.962
R²_Adj=0.947
W=0.1532>0.05

图1 各考察因素及其间的标准化效应对Y熔点的影响

图2 Y熔点的因子交互作用图

图3 Y熔点=fX3,X4的响应曲面图

图4 各考察因素及其间的标准化效应对Y含油量的影响

图5 Y含油量=fX2, X5的响应曲面图

图6 Y含油量=fX3, X5的响应曲面图

图7 Y含油量=fX1, X3的响应曲面图

图8 Y含油量的因子交互作用图

图9 各考察因素及其间的标准化效应对Y收率的影响

图10 Y收率的因子交互作用图

图11 Y收率=fX3, X4的响应曲面图

图12 加氢精制减三线油在复配溶剂中的结晶过程

图13 Y=fX1, X3的可行域和Y=fX1, X5的可行域

图14 实验室小试与中试试验结果对比（操作条件：剂油比5，溶剂比为2，结晶时间6min，结晶温度5℃，降温速率为5.3℃/min）

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