热解法脱除工业废盐中总有机碳的工艺研究

doi:10.19964/j.issn.1006-4990.2024-0128

Abstract

Abstract:

Highly efficient and low⁃cost removal of total organic carbon（TOC） from waste salt is an important pretreatment method in achieving salt resource utilization.This study focused on the high⁃temperature pyrolysis process of two representative industrial waste salts（sodium chloride and sodium sulfate）.The results showed that under the condition of 350 ℃ and a stacking thickness of 12.5 mm，sodium chloride underwent pyrolysis for 60 min，the TOC removal rate was 94%.Under the condition of 450 ℃ and a stacking thickness of 18.5 mm，the pyrolysis time of high sodium sulfate was 40 min，the TOC removal rate was 94.2%.Before pyrolysis，7.5 mL/kg hydrogen peroxide was added to high sodium chloride.The TOC removal rate during 250 ℃ pyrolysis was comparable to that at 350 ℃ without hydrogen peroxide.After adding 10 mL/kg hydrogen peroxide to high sodium sulfate，the TOC removal rate during 350 ℃ pyrolysis was comparable to that at 450 ℃ without hydrogen peroxide.The pyrolysis temperature of both waste salts was reduced by 100 ℃ after using advanced oxidation synergistic pyrolysis，and the energy⁃saving effect was significant.A stepwise crystallization experiment was conducted and the recovered salt was tested.The results showed that under the condition of a recovery rate of 90%，the TOC content of the recovered sodium chloride and sodium sulfate were 22.7 mg/kg and 26.5 mg/kg，respectively.The purity of sodium chloride was 93.2%，which met the secondary standard of sun industrial salt in the national industrial salt standard.Sodium sulfate had a purity of 93.0% and met the Class Ⅲ qualified products standard in the national industrial anhydrous sodium sulfate standard.

Key words: waste salt, sodium chloride, sodium sulfate, pyrolysis, total organic carbon, crystallization

CLC Number:

X705

LI Hongyuan, ZHANG Jianhua. Study on removal process of total organic carbon from industrial waste salts by pyrolysis[J]. Inorganic Chemicals Industry, 2024, 56(10): 95-102.

Figures/Tables 16

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样品	w（Na）	w（Mg）	w（Al）	w（Si）	w（S）	w（Cl）	w（K）	w（Ca）
高氯化钠	36.0±0.1	0.03±0.01	0.14±0.02	0.19±0.01	0.5±0.1	49.20±0.30	0.20±0.05	0.20±0.01
高硫酸钠	30.8±0.2	0.02±0.01	0.16±0.05	0.21±0.04	22.8±0.2	0.31±0.06	0.20±0.04	0.19±0.01

保留时间/min	有机组分	峰面积占比/%	沸点/ ℃	匹配度/ %
5.02	乙酸异丙烯酯	3.81	98.0	91.30
25.42	乙酸	11.45	117.9	82.10
31.81	环己酮	26.67	155.0	92.30
36.36	4-甲氧基环己醇	17.76	102.4	94.65
39.83	3-甲基苯甲醇	4.12	215.0	52.83
45.2	4-甲氧基苯酚	2.87	243.0	75.41

保留时间/min	有机组分	峰面积占比/%	沸点/ ℃	匹配度/%
5.02	八甲基环四硅氧烷	2.36	175.0	91.45
25.42	N-丁基甲基硫醚	5.54	122.6	64.72
30.25	2，4-二叔丁基酚	9.01	265.5	61.68
40.94	4-（乙酰氧甲基）苯甲酸	27.55	327.4	72.40
41.05	3-甲基-5-硝基-1，2-苯二酚	13.23	364.9	62.30
43.63	5-溴吲哚-3-甲醛	4.76	395.6	48.40

方差来源	平方和	自由度	均方	F值	Prob>F	显著性
模型	72.75	9	8.08	1 593.83	<0.000 1	显著
A-温度	45.13	1	45.13	8 897.89	<0.000 1	显著
B-时间	3.00	1	3.00	591.80	<0.000 1	显著
C-堆积厚度	0.66	1	0.66	130.39	<0.000 1	显著
AB	0.49	1	0.49	96.62	<0.000 1	显著
AC	0.090	1	0.090	17.75	0.004 0	显著
BC	0.20	1	0.20	39.93	0.000 4	显著
A²	22.23	1	22.23	4 382.45	<0.000 1	显著
B²	0.31	1	0.31	61.65	0.000 1	显著
C²	0.063	1	0.063	12.46	0.009 6	显著
残差	0.035	7	5.07
失拟性	7.50	3	2.50	0.36	0.788 0	不显著
纯误差	0.028	4	7.00
总和	72.78	16

方差来源	平方和	自由度	均方	F值	Prob>F	显著性
模型	71.72	9	7.97	1 412.17	<0.000 1	显著
A-温度	44.65	1	44.65	7 912.88	<0.000 1	显著
B-时间	2.65	1	2.65	468.73	<0.000 1	显著
C-堆积厚度	0.66	1	0.66	117.18	<0.000 1	显著
AB	0.36	1	0.36	63.80	<0.000 1	显著
AC	0.063	1	0.063	11.08	0.012 6	显著
BC	0.16	1	0.16	28.35	0.001 1	显著
A²	22.13	1	22.13	3 921.53	<0.000 1	显著
B²	0.42	1	0.42	75.22	<0.000 1	显著
C²	0.036	1	0.036	6.38	0.039 4	显著
残差	0.039	7	5.64
失拟性	0.028	3	9.16	3.06	0.154 4	不显著
纯误差	0.012	4	3.00
总和	71.76	16

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Inorganic Acid-Base-Salt Committee of CIESC

Study on removal process of total organic carbon from industrial waste salts by pyrolysis

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项目日晒工业盐		氯化钠含量	水分含量	水不溶物含量	钙镁离子总量	硫酸根含量
GB/T 5462—2015 《工业盐》	优级	≥96.2	≤2.80	≤0.20	≤0.30	≤0.50
	一级	≥94.8	≤3.80	≤0.30	≤0.40	≤0.70
	二级	≥92.0	≤6.00	≤0.40	≤0.60	≤1.00
40%回收率产品		99.2±0.2	0.74±0.20	0.01±0.01	0.02±0.01	0.01±0.01
90%回收率产品		93.2±0.2	2.72±0.02	2.38±0.02	0.47±0.01	1.33±0.02

项目		硫酸钠含量	钙和镁含量	氯化物含量	水分含量
GB/T 6009—2014	Ⅲ类一等品	≥95.0	≤0.60	≤2.00	≤1.50
GB/T 6009—2014	Ⅲ类合格品	≥92.0	—		—
55%回收率产品		96.9±0.2	0.01±0.01	1.46±0.01	1.53±0.01
90%回收率产品		93.0±0.1	—	—	—

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