铝灰中氟及其浸出毒性的高通量测定方法研究

doi:10.19964/j.issn.1006-4990.2023-0586

Abstract

Abstract:

In order to address the issues of complicated operation and time⁃consuming of current determination standards，X-ray fluorescence spectrometry（XRF） with powder pressing was established to determine the fluorine content in aluminum ash.Meanwhile，the response surface method was used to optimize the liquid⁃solid ratio，leaching time and leaching temperature，and rapid extraction method for fluorine in aluminum ash was proposed.The results revealed that the detection limit of fluorine in aluminum ash by XRF with powder pressing was 0.84 g/kg，relative deviation of sample parallel determination was less than 5%，and the relative error between the measurement results and the reference value was within 5%.There was no statistically significant difference between power pressing XRF method and standard method by t test analysis in SPSS 25.0.Under the conditions of liquid⁃solid ratio of 20∶1 and temperature of （25±5） ℃，the relative deviation of soluble fluorine in aluminium ash was less than 5% after stirring extraction for 40 min by strengthening the solid⁃liquid interface mass transfer.The test results were significantly correlated with the standard extraction method.The absolute value of relative error between rapid extraction method and standard extraction method ranged from 2.25% to 6.29%，which was closed to the predicted value of the response surface model.The results of XRF with powder pressing and rapid extraction method were stable and reliable，which simplified the pretreatment process and expected to achieve high throughput determination of fluorine and leaching toxicity in aluminum ash.

Key words: aluminum ash, fluoride, X-ray fluorescence spectrometry, high throughput, rapid determination

CLC Number:

O613.41

CHEN Can, CAO Jun, ZHANG Yongbo. Research on high throughput determination method of fluorine and leaching toxicity in aluminum ash[J]. Inorganic Chemicals Industry, 2024, 56(8): 104-109.

Figures/Tables 9

Table 1

Fig.1

Table 2

Table 3

Table 4

Table 5

Fig.2

Table 6

Table 7

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样品编号	w （Na₂O）	w （MgO）	w （Al₂O₃）	w （SiO₂）	w （K₂O）	w （CaO）	w （Fe₂O₃）	w （Ti）	w （Ba）
V1	3.69	4.88	46.71	12.31	1.79	0.56	0.31	0.33	0.740
V2	1.98	2.65	63.62	14.62	0.51	0.88	0.61	0.16	0.150
V3	5.26	6.09	79.84	13.30	5.50	0.53	0.25	0.13	0.077
V4	1.72	9.19	80.46	14.34	6.51	1.31	0.55	0.21	0.068
V5	1.30	7.89	52.46	13.01	2.78	0.52	0.95	0.28	0.230
V6	3.21	0.51	59.15	13.45	0.71	0.77	1.01	0.86	0.370
V7	1.68	6.71	49.96	12.35	0.25	1.39	0.57	0.82	2.620
V8	11.22	6.27	44.99	12.27	3.02	1.11	0.58	0.22	0.180
V9	2.17	7.28	54.80	12.61	0.26	2.88	0.72	0.21	0.240
V10	1.07	4.19	51.21	20.73	1.42	1.82	1.87	0.28	0.110
V11	8.13	3.15	61.36	15.66	0.67	0.61	1.16	1.03	1.160
V12	6.25	6.13	45.62	22.31	0.29	1.43	0.58	0.64	0.960

样品编号	测定结果/（g·kg^-1）							相对偏差RSD/%
V2	10.90	11.20	11.30	10.50	11.50	11.10	10.60	3.33
V3	6.27	6.66	6.26	6.19	6.14	6.22	6.56	3.15
V7	3.48	3.42	3.50	3.44	3.22	3.36	3.44	2.77
V10	25.80	23.90	24.30	24.50	26.60	27.10	25.20	4.77

样品编号	XRF法测定结果/ （g·kg^-1）		氟离子选择电极法测定结果/（g·kg^-1）		独立样本t 检验t值	显著性概率p
样品编号	单次测定	平均值	单次测定	平均值	独立样本t 检验t值	显著性概率p
QC1	2.26	2.28	2.14	2.23	1.499	0.160
	2.30		2.26
	2.21		2.18
	2.28		2.19
	2.35		2.29
	2.23		2.21
	2.33		2.35
QC2	48.8	48.1	48.3	47.8	0.567	0.581
	47.6		46.2
	48.2		47.9
	47.2		47.2
	49.5		48.6
	46.6		47.5
	48.9		49.0

实验序号	自变量			响应值 Y/%
实验序号	A	B/min	C/℃	响应值 Y/%
1	17.5∶1	15.0	40.0	10.8
2	30∶1	60.0	27.5	12.3
3	5∶1	15.0	27.5	20.6
4	5∶1	60.0	27.5	19.0
5	30∶1	15.0	27.5	14.2
6	17.5∶1	37.5	27.5	4.2
7	17.5∶1	60.0	15.0	7.6
8	30∶1	37.5	15.0	9.1
9	17.5∶1	37.5	27.5	5.1
10	17.5∶1	37.5	27.5	5.6
11	17.5∶1	37.5	27.5	4.5
12	17.5∶1	15.0	15.0	10.6
13	17.5∶1	60.0	40.0	7.9
14	30∶1	37.5	40.0	12.3
15	5∶1	37.5	15.0	19.4
16	5∶1	37.5	40.0	18.9

方差来源	离差平方和	自由度	均方	F值	p值
模型	473.56	9	52.62	73.42	<0.000 1
A	112.50	1	112.50	156.98	<0.000 1
B	11.05	1	11.05	15.41	0.007 8
C	1.28	1	1.28	1.79	0.229 9
AB	0.02	1	0.02	0.03	0.865 2
AC	3.42	1	3.42	4.78	0.071 5
BC	0.002 5	1	0.002 5	0.003 5	0.954 8
A²	301.89	1	301.89	421.24	<0.000 1
B²	35.70	1	35.70	49.81	0.000 4
C²	7.70	1	7.70	10.75	0.016 9
残差	4.30	6	0.72
失拟	3.13	3	1.04	2.68	0.220 2
误差	1.17	3	0.39
总和	477.86	15

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Inorganic Acid-Base-Salt Committee of CIESC

Research on high throughput determination method of fluorine and leaching toxicity in aluminum ash

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样品编号	测定结果/（mg·L^-1）							相对偏差RSD/%
V2	46.10	44.20	43.60	41.80	46.50	47.60	42.60	4.83
V3	10.20	11.20	10.40	10.70	11.40	10.20	10.60	4.42
V7	2.36	2.49	2.26	2.24	2.54	2.41	2.37	4.63
V10	65.80	67.90	64.30	64.50	66.60	68.10	69.20	2.81

样品编号	测定结果/（mg·L^-1）		相对误差/%	相关性检验		配对t检验t值
样品编号	快速浸提法	标准浸提法	相对误差/%	相关系数	显著性概率p	t值	显著性概率p
V1	11.30	11.80	-4.24	0.998	0	-0.635	0.539
V2	9.89	10.40	-4.90
V3	6.29	6.02	4.49
V4	5.47	5.34	2.43
V5	18.60	17.50	6.29
V6	2.97	2.84	4.58
V7	3.48	3.56	-2.25
V8	14.00	13.40	4.48
V9	20.60	21.40	-3.74
V10	25.80	26.60	-3.01
V11	7.11	6.84	3.95
V12	30.50	31.80	-4.09

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