不锈钢老化着色液预还原草酸沉淀除杂过程研究

doi:10.19964/j.issn.1006-4990.2022-0189

Abstract

Abstract:

In order to realize the separation and recovery of impurity ions in stainless steel aging coloring liquid，the impurity removal process of iron，nickel and manganese in aging liquid was studied by a prereduction-oxalic acid precipitation method.The precipitation efficiency of iron，nickel and manganese ions was investigated by the solution chemistry calculation and condition optimization test.The morphology feature and phase structure of oxalate precipitate were analyzed by X-ray diffraction，scanning electron microscope and energy spectrum analysis，respectively.The results showed that Fe²⁺，Mn²⁺，Ni²⁺ in the solution could readily complex with C₂O₄^2- to form oxalate precipitate by controlling the solution pH and the oxalic acid dosage，which would realize the separation with Cr³⁺.The precipitation order of impurity ions was Mn²⁺，Ni²⁺，Fe²⁺.After prereduction of the aging solution，the precipitation reaction was carried out for 2 h under the conditions that the oxalic acid excess coefficient was 1.2，the solution pH was 2，and the reaction temperature was 25 ℃.The precipitation efficiency of iron，manganese and nickel ions could reach 98.12%，99.35% and 87.26%，respectively.The precipitate was mainly composed of ferrous oxalate dihydrate，a small amount of nickel oxalate and manganese oxalate.

Key words: stainless steel coloring liquid, ageing liquid, oxalate precipitation method, impurity removal, ferrous oxalate

CLC Number:

TQ110.3

WU Hao,LI Xi,ZHANG Jun,DUAN Siyu. Study on impurity removal process of prereduction-oxalic acid precipitation in stainless steel coloring ageing liquid[J]. Inorganic Chemicals Industry, 2023, 55(2): 119-125.

Figures/Tables 21

Table 1

Fig.1

Table 2

Fig.2

Fig.3

Fig.4

Table 3

Fig.5

Fig.6

Table 4

Fig.7

Fig.8

Table 5

Fig.9

Fig.10

Fig.11

Fig.12

Fig.13

Fig.14

Fig.15

Fig.16

References 13

1	王海人，王宜民，屈钧娥，等.不锈钢着色方法及表征技术[J].材料保护，2012，45（12）：38-41，45，1.
	WANG Hairen， WANG Yimin， QU June，et al.Research progresses in coloring methods of stainless steel and characterization techniques of coloring films[J].Materials Protection，2012，45（12）：38-41，45，1.
2	王玥，满瑞林，赵鹏飞，等.电化学氧化法再生不锈钢着色老化液的研究[J].表面技术，2012，41（5）：114-118.
	WANG Yue， MAN Ruilin， ZHAO Pengfei，et al.Study on regeneration of ageing liquid for stainless steel coloring by electrochemical oxidation[J].Surface Technology，2012，41（5）：114-118.
3	LI Wenwei， QU Jun'e， CAO Zhiyong，et al.Effects of NiSO₄ concentration on the coloring performance and corrosion resistance of the colored film on 304 stainless steel[J].Coatings，2020，10（6）.Doi：10.3390/coatings10060598 . doi: 10.3390/coatings10060598
4	王海人，李文维，屈钧娥，等.Cr³⁺和Fe³⁺对不锈钢着色液老化进程的协同影响[J].表面技术，2011，40（2）：29-32.
	WANG Hairen， LI Wenwei， QU June，et al.Synergy effect of Cr³⁺ and Fe³⁺ on the aging process of coloring liquid for stainless st-eel[J].Surface Technology，2011，40（2）：29-32.
5	汤芝平，薛永强，程作慧，等.Cr³⁺，Fe³⁺和Ni²⁺对不锈钢着色的影响[J].材料保护，2008，41（9）：24-27，85.
	TANG Zhiping， XUE Yongqiang， CHENG Zuohui，et al.Effect of metallic ion impurities on coloring of stainless steel[J].Materials Protection，2008，41（9）：24-27，85.
6	张晓丽，鞠洪斌，薛永强，等.不锈钢化学着色老化液处理的新技术[J].电镀与环保，2013，33（3）：39-41.
	ZHANG Xiaoli， JU Hongbin， XUE Yongqiang，et al.A new technology for treating deteriorated stainless steel chemical coloring liquid[J].Electroplating ＆ Pollution Control，2013，33（3）：39-41.
7	秦险峰，全学军，叶鹏，等.铬铁矿酸浸过程强化及铬铁分离研究进展[J].无机盐工业，2020，52（6）：13-19.
	QIN Xianfeng， QUAN Xuejun， YE Peng，et al.Research progress of process intensification of acid leaching technology from chromite ore and separation of chromium-iron[J].Inorganic Chemicals Industry，2020，52（6）：13-19.
8	邵武俊，刘春燕，贺宁，等.草酸溶液处理对SAPO-34分子筛物性和催化性能的影响[J].无机盐工业，2020，52（2）：84-90.
	SHAO Wujun， LIU Chunyan， HE Ning，et al.Effect of oxalic acid solution treatment on physiochemical properties and catalytic performance of SAPO-34 molecular sieve[J].Inorganic Chemicals Industry，2020，52（2）：84-90.
9	LI Wang， YAN Xudong， NIU Zeping，et al.Selective recovery of vanadium from red mud by leaching with using oxalic acid and sodium sulfite[J].Journal of Environmental Chemical Engineering，2021，9（4）.Doi：10.1016/j.jece.2021.105669 . doi: 10.1016/j.jece.2021.105669
10	刘继军，林红梅，胡国荣，等.利用铬铁合金生产铬盐的新工艺研究[J].无机盐工业，2021，53（6）：156-159.
	LIU Jijun， LIN Hongmei， HU Guorong，et al.Study on new process of producing chromium salt with ferrochrome alloy[J].Inorganic Chemicals Industry，2021，53（6）：156-159.
11	苏玉长，陈宏艳，胡泽星，等.不同维度草酸亚铁的合成及其组织结构[J].中南大学学报：自然科学版，2013，44（6）：2237-2243.
	SU Yuchang， CHEN Hongyan， HU Zexing，et al.Synthesis and microstructure of ferrous oxalate dehydrate of different dimensionalities[J].Journal of Central South University：Science and Technology，2013，44（6）：2237-2243.
12	柯望，贾艳梅，余学峰，等.多方法制备草酸亚铁对其结构和形貌影响条件的探究[J].湖北大学学报：自然科学版，2020，42（2）：222-227，232.
	KE Wang， JIA Yanmei， YU Xuefeng，et al.Study on the effects of multiple methods to prepare ferrous oxalate on its structure and morphology[J].Journal of Hubei University：Natural Science，2020，42（2）：222-227，232.
13	HU Pengcheng， ZHANG Yimin， LIU Tao，et al.Separation and recovery of iron impurity from a vanadium-bearing stone coal via an oxalic acid leaching-reduction precipitation process[J].Separation and Purification Technology，2017，180：99-106.

离子	浓度/（mol·L^-1）	离子	浓度/（mol·L^-1）
Cr³⁺	2.491	Fe³⁺	1.397
Cr⁶⁺	1.183	Ni²⁺	0.016
Mn²⁺	0.148	SO₄^2-	5.946

反应方程式	平衡常数对数值log K
Fe³⁺+3H₂O=3H⁺+Fe（OH）₃（s）（4）	-4.89
Fe³⁺+3C₂O₄^2-=Fe（C₂O₄）₃^3-（5）	20.43
Fe³⁺+2C₂O₄^2-=Fe（C₂O₄）₂^- （6）	16.25
Fe²⁺+2H₂O=2H⁺+Fe（OH）₂（s）（7）	-12.996
Fe²⁺+C₂O₄^2-=FeC₂O₄（s）（8）	4.27
Fe²⁺+2C₂O₄^2-=Fe（C₂O₄）₂^2- （9）	6.3

反应方程式	平衡常数对数值log K
2H⁺+2CrO₄^2-=Cr₂O₇^2-+H₂O （10）	14.69
2H⁺+CrO₄^2-=H₂CrO₄（11）	6.35
H⁺+CrO₄^2-=HCrO₄^-（12）	6.55
Cr³⁺+3H₂O=3H⁺+Cr（OH）₃（13）	16.17
2Cr³⁺+2H₂O=2H⁺+Cr₂（OH）₂⁴⁺（14）	-5.06
3Cr³⁺+4H₂O=4H⁺+Cr₃（OH）₄⁵⁺（15）	-8.15

反应方程式	平衡常数对数值log K
Mn²⁺+2H₂O=2H⁺+Mn（OH）₂（s）（16）	-15.2
Mn²⁺+C₂O₄^2-=MnC₂O₄（s）（17）	6.715
Mn²⁺+2C₂O₄^2-=Mn（C₂O₄）₂^2-（18）	5.25

反应方程式	平衡常数对数值log K
Ni²⁺+2H₂O=2H⁺+Ni（OH）₂（s）（19）	-10.5
Ni²⁺+C₂O₄^2-=NiC₂O₄（s）（20）	5.16
Ni²⁺+2C₂O₄^2-=Ni（C₂O₄）₂^2-（21）	8.48

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on impurity removal process of prereduction-oxalic acid precipitation in stainless steel coloring ageing liquid

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 21

References 13

Related Articles 6

Metrics

Comments

Recommended 0

[1]	LI Shuqi, LI Xinqian, FENG Haitao, LI Bo, NIU Zhengrong, DONG Yaping. Study on separation of iron from chromium trichloride solution [J]. Inorganic Chemicals Industry, 2023, 55(8): 91-94.
[2]	GU Qingshan,LIN Xihua,Zhao Shihao,YUAN Yijin. Effect of different pretreatment processes on properties of phosphogypsum [J]. Inorganic Chemicals Industry, 2022, 54(4): 17-23.
[3]	LIU Qiu-Bin, CHEN Yi, WU Bo-Rong, CHEN Fei-Biao. Study on preparing high purity manganese chloride from electrolytic manganese powder [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(6): 20-.
[4]	JING Yan-Wei, NAI Xue-Ying, DANG Li, LI Wu, 吕Zhi-Hui . Research on purifying of calcium carbonate whiskers [J]. INORGANICCHEMICALSINDUSTRY, 2015, 47(7): 35-.
[5]	PENG Ai-Guo, HE Zhou-Chu, YU Chang-Yan, XIAO Wei, ZHUANG Xin-Juan, LIU Yan. Research on preparation of battery-grade ferrous oxalate from by-product ferrous sulfate [J]. INORGANICCHEMICALSINDUSTRY, 2012, 44(8): 60-.
[6]	Tian Weijun;Lai Naibin. Process research and production practice of recovering calcium oxide from carbide slag [J]. INORGANICCHEMICALSINDUSTRY, 2010, 0(8): 0-0.