硫磺流化法还原钛白石膏工艺模拟研究

doi:10.19964/j.issn.1006-4990.2021-0027

Abstract

Abstract:

Reducing titanium dioxide gypsum of by-product of titanium dioxide production by sulfuric acid method with sulfur and carbon is one of the methods to deal with the stacking problem of titanium dioxide gypsum.Aiming at the problems of long time,large amount of sulfur and low output of calcium sulfide in the process of decomposing titanium dioxide gypsum to sulfuric acid and calcium oxide in rotary kiln.It was pointed out that using titanium dioxide gypsum as raw material,after removing iron impurities by acid leaching,gypsum was calcined in gas-solid vertical reactor with sulfur as reducing agent to produce calcium sulfide and sulfur dioxide.The former was calcined with calcium sulfate to obtain calcium oxide and sulfur dioxide.The obtained calcium oxide could neutralize waste acid and wastewater,and the generated sulfur dioxide was used to prepare sulfuric acid.The experimental scheme was determined by reaction thermodynamics analysis by HSC software.After fluidization experiment（800 ℃,40 min for heat preservation） and calcination experiment（1 100 ℃,1.5 h for heat preservation）,the conversion rate of calcium sulfide and purity of calcium oxide were both about 90%.Then the process flow was simulated by using Aspen software,the volume fraction of SO₂ could reach 12.09%,which could meet the requirement of sulfuric acid production.The production cost of sulfuric acid was estimated to be 263.9 CNY/t,which had a great market prospect.

Key words: titanium gypsum, sulfur, calcium oxide, fluidization

CLC Number:

TQ132.32

Meng Hua,Zhao Jingyi,Nie Chaoyang,Wang Ye. Study on simulation process of reducing titanium dioxide gypsum by sulfur fluidization[J]. Inorganic Chemicals Industry, 2021, 53(9): 61-66.

Figures/Tables 11

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References 9

[1]	曾小星, 郭中坚, 徐昕. 钛石膏在水泥与混凝土中的应用研究[J]. 广东建材, 2014, 30(9):27-28.
[2]	黄绪泉, 刘立明, 别双桥, 等. 钛石膏改性胶凝材料制备及水化机理[J]. 三峡大学学报:自然科学版, 2016, 38(1):45-50.
[3]	郝建璋. 钛石膏墙体砌块的研制[J]. 砖瓦, 2011(8):41-44.
[4]	孙家瑛, 郑京彪, 周震雷. 钛石膏-粉煤灰复合制备路基回填材料试验研究[J]. 公路, 2001(6):107-110.
[5]	黄佳乐, 武斌, 陈葵, 等. 钛石膏作土壤镉污染改良剂的可行性分析[J]. 无机盐工业, 2016, 48(10):68-72.
[6]	张雨露, 王烨, 杨林, 等. 硫磺分解氟石膏制高纯氧化钙联产硫酸的研究[J]. 无机盐工业, 2020, 52(7):70-73.
[7]	杨秀山, 张志业, 王辛龙, 等. 一种用硫磺还原分解磷石膏的方法:中国, 101708826A[P]. 2010-05-19.
[8]	刘立文, 刘珍如, 宁爱民, 等. 一种石膏分解生产硫酸和氧化钙的方法:中国, 102838153A[P]. 2012-12-26.
[9]	蒋美雪, 孙红娟, 彭同江. 钛石膏硫酸浸取法提取铁质氧化物及石膏的物相变化[J]. 化工进展, 2019, 38(4):441-447.

气氛	熔融液质量/g
气氛	1 400 ℃	1 450 ℃	1 500 ℃	1 550 ℃	1 600 ℃
空气	0	6.78	23.70	23.61	23.36
N₂气	0	21.41	20.33	18.88	16.94
混合气	0	17.53	15.98	13.98	11.45

t/min	w（CaS）/%	t/min	w（CaS）/%
20	30.21	40	89.59
30	72.33	50	91.31

实验编号	第二阶段产物质量（90%CaS）/g	纯CaSO₄质量/g	w（CaO）/%
1	1.343 3	3.298 5	86.61
2	1.504 6	5.404 6	89.78

反应编号	单位	转换分数	硫磺相变
1	kmol/h	0.953 7	2S（固态）→S₂（混合气态）
2	kmol/h	0.042 3	3S（固态）→S₃（混合气态）
3	kmol/h	0.001 1	4S（固态）→S₄（混合气态）
4	kmol/h	0.002 7	5S（固态）→S₅（混合气态）
5	kmol/h	0.000 2	6S（固态）→S₆（混合气态）

项目		消耗定额	单价	金额/元	合计金额/元
1.原材料	钛白石膏（干基）	0.93 t	0元/t	0.0	182.2
	硫磺（99%）	0.12 t	1 500元/t	180.0
	水	5.5 t	0.40元/t	2.2
2.燃料和动力	电	136 kW·h	0.7元/（kW·h）	95.2	315.2
2.燃料和动力	标煤（煅烧）	0.22 t	1 000.0元/t	220.0	315.2
3.其他（副产品回收等）	氧化钙渣（90%CaO）	-0.40 t	500元/t	-200.0	-285.0
3.其他（副产品回收等）	蒸汽（98 N）	-0.85 t	100元/t	-85.0	-285.0
4.工资和福利费用					31.5
5.制造费用					20.0
6.生产成本					263.9

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on simulation process of reducing titanium dioxide gypsum by sulfur fluidization

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