湿法磷酸副产渣酸和萃余酸研究进展与展望

doi:10.19964/j.issn.1006-4990.2023-0389

Abstract

Abstract:

The production of sludge acid and raffinate acid in phosphorus chemical enterprises is increasing day by day in China.However，due to the high content of impurities（anion and cation） and the high viscosity of raffinate，the utilization rate of sludge acid and raffinate acid has a certain upper limit.It has become an urgent problem to realize efficient and incremental utilization of sludge acid and raffinate acid for the healthy development of phosphorus chemical industry.The sources and main properties of sludge acid and raffinate acid were introduced.The research progress of purification of raffinate was described，and the existing purification methods were summarized，including complex purification，acid-base regulation，membrane filtration，etc.And progress of comprehensive utilization of sludge acid and raffinate acid were also reviewed，including preparation of fine phosphorus chemical products，preparation of agricultural fertilizer products and application in other chemical fields.The future research direction and content of the efficient utilization of sludge acid and raffinate acid were prospected，so as to provide reference for improving utilization rate of by-product resources such as sludge acid and raffinate acid，promoting transformation and upgrading of fertilizer industry and green development.

Key words: sludge acid, raffinate acid, purification, fertilizer, green development

CLC Number:

TQ126.35

TAO Longhai, WANG Yongjie, DUAN Jiatang, SHU Yizhou, WAN Banglong, HUANG Chengdong, ZHANG Yueqiang, LU Zhenya. Research progress and prospect of sludge acid and raffinate acid by-product of wet-process phosphoric acid[J]. Inorganic Chemicals Industry, 2024, 56(3): 12-18.

Figures/Tables 3

References 52

1	冉瑞泉，金央，刘辉，等.溶剂萃取法净化盐酸法湿法磷酸的研究进展［J］.无机盐工业，2021，53（7）：18-22.
	RAN Ruiquan， JIN Yang， LIU Hui，et al.Research progress purification of solvent extraction of wet-process phosphoric acid by hydrochloric acid route［J］.Inorganic Chemicals Industry，2021，53（7）：18-22.
2	陈芝清，张沂圭.昆阳磷肥厂湿法磷酸工程磷酸淤渣分离技术［J］.磷肥与复肥，2001，16（5）：26-28.
	CHEN Zhiqing， ZHANG Yigui.Technology for separation of sludge in WPA unit of kunyang phosphate fertilizer factory［J］.Phosphate & Compound Fertilizer，2001，16（5）：26-28.
3	王波，周志鑫，许德华，等.渣酸制饲料级磷酸氢钙工艺研究［J］.无机盐工业，2022，54（4）：141-144，151.
	WANG Bo， ZHOU Zhixin， XU Dehua，et al.Study on preparation process of feed grade DCP from sludge acid［J］.Inorganic Chemicals Industry，2022，54（4）：141-144，151.
4	和彦.降低湿法磷酸淤渣产生量的措施［J］.磷肥与复肥，2017，32（5）：31-33.
	HE Yan.Measures for reducing sludge discharge of wet-process phosphoric acid production［J］.Phosphate & Compound Fertilizer，2017，32（5）：31-33.
5	王玉训.磷化工园区萃余酸资源化利用及工艺控制［J］.磷肥与复肥，2021，36（4）：31-33，38.
	WANG Yuxun.Resource utilization and process control of raffinate acid in phosphorus chemical industry park［J］.Phosphate & Compound Fertilizer，2021，36（4）：31-33，38.
6	杨金会.卧式螺旋卸料沉降离心机在湿法磷酸渣酸处理上的应用［J］.磷肥与复肥，2019，34（8）：49-50.
	YANG Jinhui.Application of horizontal spiral discharge settling centrifuge in sludge acid treatment from WPA［J］.Phosphate & Compound Fertilizer，2019，34（8）：49-50.
7	张华，黄云凡，李海兵，等.磷酸渣酸作为磷矿浮选调整剂实验研究［J］.磷肥与复肥，2020，35（9）：30-32.
	ZHANG Hua， HUANG Yunfan， LI Haibing，et al.Experimental study on phosphoric acid sludge acid as flotation regulator of phosphate rock［J］.Phosphate & Compound Fertilizer，2020，35（9）：30-32.
8	常青.用浓密渣酸制重过磷酸钙的实验与探索［J］.硫磷设计与粉体工程，2002（6）：16-18，1.
	CHANG Qing.The experiment and exploration of TSP production with thick acid sludge［J］.Sulphur Phosphorus & Bulk Materials Handling Related Engineering，2002（6）：16-18，1.
9	卢秀君.以浓缩磷酸的浓密渣酸制取富过磷酸钙的实验研究［J］.磷肥与复肥，2003，18（1）：18-20.
	LU Xiujun.Experimental study on production of enriched superphosphate with thickened sludge acid from concentrated WPA［J］.Phosphate & Compound Fertilizer，2003，18（1）：18-20.
10	傅英，刘文彪，王静明，等.渣酸、萃余酸作磷矿选矿调整剂试验研究［J］.化工矿物与加工，2021，50（6）：20-24.
	FU Ying， LIU Wenbiao， WANG Jingming，et al.Experimental study on beneficiation of phosphate rock using sludge acid and raffinate as regulators［J］.Industrial Minerals & Processing，2021，50（6）：20-24.
11	舒艺周，马航，杨先，等.湿法磷酸淤渣酸制备微粒磷肥可行性研究［J］.磷肥与复肥，2021，36（8）：12-14.
	SHU Yizhou， MA Hang， YANG Xian，et al.Feasibility on preparation of micro-granular fertilizer from WPA sludge acid［J］.Phosphate & Compound Fertilizer，2021，36（8）：12-14.
12	齐亚兵，张思敬.湿法磷酸净化技术研究新进展及应用现状［J］.应用化工，2022，51（9）：2798-2804.
	QI Yabing， ZHANG Sijing.New research progress and present application situation of purification technology for wet-process pho-sphoric acid［J］.Applied Chemical Industry，2022，51（9）：2798-2804.
13	张团慧，向鹏，李国斌，等.湿法磷酸净化技术的研究进展［J］.材料导报，2015，29（15）：113-117.
	ZHANG Tuanhui， XIANG Peng， LI Guobin，et al.Researches of purification technology for wet-process phosphoric acid［J］.Materials Review，2015，29（15）：113-117.
14	徐春.净化湿法磷酸的萃余酸用于DAP生产［J］.磷肥与复肥，2010，25（3）：37-39.
	XU Chun.Production of DAP with the raffinate from purified WPA［J］.Phosphate & Compound Fertilizer，2010，25（3）：37-39.
15	杜怀明，罗容珍，刘兴勇，等.氟硅酸化学沉淀法净化萃余酸中的镁［J］.数理统计与管理，2013，32（3）：391-400.
	DU Huaiming， LUO Rongzhen， LIU Xingyong，et al.Using H₂SiF₆ to precipitate magnesium from raffinate of wet-process phospho-ric acid purification by chemical precipitation［J］.Journal of Applied Statistics and Management，2013，32（3）：391-400.
16	汤德元，杨三可，王邵东，等.一种净化萃余酸的方法：中国，101704518A［P］.2010-05-12.
17	刘兵兵，郑光明，邹学勇，等.一种降低萃余酸中金属离子的方法：中国，110482507A［P］.2019-11-22.
18	吴邦文，蒋世国，田仁道，等.湿法磷酸净化副产萃余酸脱镁技术研究［J］.磷肥与复肥，2021，36（4）：28-30.
	WU Bangwen， JIANG Shiguo， TIAN Rendao，et al.Study on removal of magnesium in raffinate acid produced in WPA purification process［J］.Phosphate & Compound Fertilizer，2021，36（4）：28-30.
19	陈遵逵，丁一刚，龙秉文，等.萃余酸制备工业级磷酸一铵的工艺优化［J］.化学与生物工程，2015，32（8）：63-66.
	CHEN Zunkui， DING Yigang， LONG Bingwen，et al.Optimization on preparation process of industrial-grade monoammonium phosphate using raffinate acid as material［J］.Chemistry & Bioengineering，2015，32（8）：63-66.
20	钟雪莲，尤彩霞，李富兰，等.萃余酸净化制三聚磷酸钠研究［J］.无机盐工业，2013，45（3）：28-30.
	ZHONG Xuelian， YOU Caixia， LI Fulan，et al.Preparation of sodium tripolyphosphate by purification of raffinate［J］.Inorganic Chemicals Industry，2013，45（3）：28-30.
21	张一敏，刘红，黄晶，刘涛.一种基于磷酸萃余酸的磷酸二铵的制备方法：中国，110371939A［P］.2022-08-16.
22	张一敏，刘红，黄晶，刘涛.一种净化磷酸萃余酸和回收六水合磷酸铵镁的方法：中国，110371944A［P］.2022-08-16.
23	刘飞，解田.利用萃余酸微波加热生产高浓度磷酸的方法：中国，102730656A［P］.2012-10-17.
24	罗建洪，屈吉艳，刘端，等.一种萃余酸净化的方法：中国，111115595B［P］.2022-11-04.
25	纪镁铃，黄春梅，李燕玲.一种基于离子交换膜的湿法磷酸萃余酸净化工艺：中国，111204725A［P］.2020-05-29.
26	黄春梅，陈泽恩，张峰，等.扩散渗析法分离纯化萃余酸技术研究［J］.磷肥与复肥，2020，35（5）：11-14.
	HUANG Chunmei， CHEN Zeen， ZHANG Feng，et al.Study on the technology of separation and purification of extraction residual acid by diffusion dialysis［J］.Phosphate & Compound Fertilizer，2020，35（5）：11-14.
27	刘辉，张俊，邓信立，等.一种萃余酸净化工艺：中国，110917717A［P］.2020-03-27.
28	李耀基，张晖，方世祥，等.利用渣酸与黄磷炉渣制备饲料级磷酸氢钙联产水玻璃的方法：中国，103950911A［P］.2014-07-30.
29	周永祥，周桂民，曾润国，等.湿法磷酸有机萃取净化萃余液制备饲料级磷酸氢钙的方法：中国，102807201A［P］.2012-12-05.
30	罗建洪，舒爱桦.一种利用萃余酸制备MCP、MDCP的方法：中国，111086977B［P］.2021-07-06.
31	周静，周骏宏，柏任流，等.萃余酸萃取法制高纯磷酸二氢钾研究［J］.化学研究与应用，2015，27（3）：378-383.
	ZHOU Jing， ZHOU Junhong， BAI Renliu，et al.Study on the extraction raffinate acid of high purity potassium dihydrogen phosphate［J］.Chemical Research and Application，2015，27（3）：378-383.
32	钟林，钟国林，韩科.一种利用磷酸萃余酸制备磷酸二氢钾的方法：中国，103879981A［P］.2016-02-17.
33	王邵东，张红映，李军.湿法磷酸净化的萃余酸联产磷酸二氢铵和磷酸氢二钠［J］.无机盐工业，2008，40（4）：39-40.
	WANG Shaodong， ZHANG Hongying， LI Jun.Study on the joint production of ammonium dihydrogen phosphate and disodium hydrogen phosphate with the raffinate from phosphoric acid purification apparatus［J］.Inorganic Chemicals Industry，2008，40（4）：39-40.
34	罗珍.湿法磷酸溶剂萃取副产萃余酸制磷酸脲和磷镁肥实验研究［D］.昆明：昆明理工大学，2015.
	LUO Zhen.Experimental study on preparation of urea phosphate and phosphorus magnesium fertilizer from by-product raffinate by wet phosphoric acid solvent extraction［D］.Kunming：Kunming University of Science and Technology，2015.
35	杨心师，匡家灵，杨欢，等.湿法磷酸净化萃余酸制备磷酸脲工艺研究［J］.磷肥与复肥，2023，38（7）：17-20.
	YANG Xinshi， KUANG Jialing， YANG Huan，et al.Preparation of urea phosphate with raffinate acid from wet-process phosphoric acid purification apparatus［J］.Phosphate & Compound Fertilizer，2023，38（7）：17-20.
36	王丁丁，李长东，王皓，等.一种湿法磷酸萃余酸制备多聚磷酸的方法及其应用：中国，202211179218.9［P］.2022-12-06.
37	饶轶晟，张瑞，张晓迁，等.利用萃余酸生产粒状磷酸一铵的方法：中国，201010236496.4［P］.2010-11-24.
38	马健，李庆.用湿法浓缩磷酸渣酸生产磷酸一铵及磷酸铵镁的方法：中国，201410325000.9［P］.2014-09-24.
39	何浩明，王邵东，李红林，等.用萃余酸生产工业磷酸一铵联产肥料级磷酸一铵的方法：中国，201210203327.X［P］.2012-09-19.
40	曹宇，王永红，张启万，等.萃余酸生产工业级磷酸一铵、磷酸二氢钾和肥料级磷酸一铵的方法：中国，202011636619.3［P］.2021-04-09.
41	黄进，杨毅，张胜，等.用净化磷酸的萃余酸生产磷酸二铵的方法：中国，200910102694.9［P］.2009-12-30.
42	孙天桥.一种萃余酸改性生产过磷酸钙的方法：中国，202010584390.7［P］.2021-12-24.
43	胡宏，解田，李艳，等.用净化磷酸的萃余酸生产重过磷酸钙的方法：中国，201210029255.1［P］.2012-07-18.
44	张克峰，刘春，何兵兵，等.利用萃余磷酸制取重过磷酸钙的工艺条件研究［J］.无机盐工业，2015，47（7）：38-41.
	ZHANG Kefeng， LIU Chun， HE Bingbing，et al.Research on preparation process of tripe superphosphate from raffinate phosphoric acid［J］.Inorganic Chemicals Industry，2015，47（7）：38-41.
45	王权顶，胡家勇，潘志云，等.一种利用A层磷矿石和萃余酸为原料生产重钙的方法：中国，202011374994.5［P］.2021-02-19.
46	盛勇，周佩，韦莎，等.一种湿法磷酸净化淤渣生产多元硝基复合肥的方法：中国，201310069651.1［P］.2013-05-22.
47	解田，胡宏，高晓明，等.利用萃余酸和高镁磷尾矿渣制备磷镁复合肥料的方法：中国，201010608653.X［P］.2011-08-24.
48	张波，王静明，郑永兴.萃余酸在磷矿浮选中的应用［J］.矿产保护与利用，2021，41（1）：61-65.
	ZHANG Bo， WANG Jingming， ZHENG Yongxing.Application of raffinate acid to flotation of phosphate ore［J］.Conservation and Utilization of Mineral Resources，2021，41（1）：61-65.
49	董继发，康鹏鹏，卢昌，等.湿法磷酸净化萃余酸在磷矿反浮选中的应用研究［J］.磷肥与复肥，2023，38（4）：31-32，39.
	DONG Jifa， KANG Pengpeng， LU Chang，et al.Application of raffinate acid from wet-process phosphoric acid purification apparatus in reverse flotation of phosphate rock［J］.Phosphate & Compound Fertilizer，2023，38（4）：31-32，39.
50	李文飞，郭举，张丹，等.一种利用萃余磷酸制备铝合金表面化学抛光液的方法：中国，201410074130.X［P］.2014-06-11.
51	韦昌桃，王智娟，赵彤.精制磷酸副产萃余酸的应用现状及建议［J］.云南化工，2023，50（3）：8-13.
	WEI Changtao， WANG Zhijuan， ZHAO Tong.Application situation and suggestion for raffinate acid by-product in the process of phosphoric acid extraction［J］.Yunnan Chemical Technology，2023，50（3）：8-13.
52	舒艺周，马航，匡家灵，等.湿法磷酸萃余酸用于肥料制备的研究综述［J］.磷肥与复肥，2022，37（11）：19-21，24.
	SHU Yizhou， MA Hang， KAUANG Jialing，et al.Review on application of raffinate acid from WPA purification in fertilizer preparation［J］.Phosphate & Compound Fertilizer，2022，37（11）：19-21，24.

研究方向	主要产品
精细磷化工	磷酸氢钙、磷酸二氢钾、磷酸氢二钠、磷酸脲、三聚磷酸钠、多聚磷酸
农用肥料	磷酸一铵、磷酸二铵、过磷酸钙、磷复肥
其他化工领域	磷矿浮选调整剂、铝合金化学抛光液

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Research progress and prospect of sludge acid and raffinate acid by-product of wet-process phosphoric acid

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