CN100497187C - Method for extracting cobalt-manganese metal compound from active sludge - Google Patents
Method for extracting cobalt-manganese metal compound from active sludge Download PDFInfo
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- CN100497187C CN100497187C CNB2007100204776A CN200710020477A CN100497187C CN 100497187 C CN100497187 C CN 100497187C CN B2007100204776 A CNB2007100204776 A CN B2007100204776A CN 200710020477 A CN200710020477 A CN 200710020477A CN 100497187 C CN100497187 C CN 100497187C
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- cobalt
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- active sludge
- pta
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
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- Treatment Of Sludge (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a method of extracting metallic compound of cobalt and manganese from activated sludge, which belongs to the technique field of environmental protection comprehensive treatment and utilization. In the present invention, the activated sludge is subjected to drying, incinerating, acid-dissolution and relative adsorption, and extraction technology so as to obtain cobaltous sulfate and manganess sulfate. The rate of recovery of cobalt and manganese is more than 90%; the cost is low, the processing cost of metallic cobalt is only 50 thousand yuan per tone; the purity is high, the purity of cobaltous sulfate and manganese sulfate can meet the relative standard. The present invention has obvious economic benefits and social benefits, which can not only solve the sludge pollution caused by chemical fiber industry, but also obtain economic interest during the harnesing of sludge pollution.
Description
Technical field
The present invention relates to a kind of method of from the PTA active sludge, extracting cobalt and manganese metal compound, belong to comprehensive management of environmental protection and utilize technical field.
Background technology
Development along with China's chemical fibre industry, the existing PTA device yearly capacity of China reaches more than 8,000,000 tons, the processing of Chemical Manufacture waste water and mud is the difficult problem of efforts at environmental protection always, in the PTA production process, contain organic compound beyond the region of objective existences such as a large amount of phenylformic acid, terephthalic acid, m-phthalic acid in the waste water that is produced, also contain mineral compound such as cobalt, manganese salt.Wherein Cobaltous diacetate, manganese acetate are the catalyzer in the Production of Terephthalic Acid, and after catalyzer used for some time, its catalytic activity weakened, along with making beating waste water is discharged.Through wastewater treatment, cobalt, manganese sink in the mud, and after the filtration, mud is transported to special-purpose refuse tip.And resource but also its stench serious environment pollution are not only wasted in the stacking of active sludge.The more than one hundred million units of value of the product such as cobalt, manganese salt and phenylformic acid in the waste material of annual discharging because the limitation of traditional recovery technology can't realize that cobalt manganese separates, have therefore caused a large amount of precious resources wastes.
Summary of the invention
The purpose of this invention is to provide a kind of method of from the PTA active sludge, extracting cobalt and manganese metal compound, solve existing PTA produce in a large amount of waste materials of discharging can't handle and stack the pollution that causes with its foul gas, realize resource regeneration, help environmental protection and increase economic efficiency.
The objective of the invention is to be achieved through the following technical solutions, a kind of method of from the PTA active sludge, extracting cobalt and manganese metal compound, it is characterized in that described method is with after PTA active sludge drying, the burning, molten through acid again, resin absorption, extracting and separating are produced rose vitriol and manganous sulfate, extracting and separating is that solution is through nine grades of extracting and separating cobalt manganese, after manganese is stripped with sulfuric acid in the organic phase, condensing crystal becomes manganese sulfate monohydrate, the aqueous phase cobalt is again through three grades of extraction process extraction cobalts, three grades of sulfuric acid reextraction cobalts, the condensing crystal heptahydrate.
The present invention passes through PTA active sludge drying, burning, and molten and relevant absorption, extraction process are produced rose vitriol and manganous sulfate through acid again, and cobalt manganese recovery ratio height reaches more than 90%; Production cost is low, and the tooling cost of cobalt metal per ton only needs about 50,000 yuan; The product purity height, rose vitriol and manganese sulfate product can both reach products standards, and the present invention is turned waste into wealth, and have not only solved the mud pollution that chemical fibre industry production brings, and in the governance process that mud pollutes, having obtained economic interests, the present invention has remarkable economic efficiency and social benefit.
Embodiment
Further specify the present invention in conjunction with the embodiments, the advanced rotary kiln drying technology of the present invention, 300 ℃ of drying and dewaterings slough 80% with water in the PTA mud, make mud be dried to moisture about 10% particle by original colloidal.Contain great number of organic matters in the mud, when temperature reaches 500 ℃, organic can spontaneous combustion, the spontaneous combustion liberated heat material that can ignite does not need fire coal substantially, can save a large amount of energy like this, has reduced processing cost.Utilize this characteristics, we voluntarily design-build suitable incinerator, at present every day can be dry, burn about 100 tons of mud.In the ash after burning, cobalt manganese content appoints 0.2% by former, is enriched to about 10%, add the acid dissolving then, merge together with removing benzoic making beating waste water, through resin absorption, desorb, further enriched in cobalt manganese, remove organism such as phenylformic acid, obtain the solution that contains cobalt-manganese salt of relative clean.
The making beating wastewater temperature of discharging during PTA produces is up to 90 ℃, be dissolved with a large amount of organism such as phenylformic acid in the hot water, and terephthalic acid solubleness is very little at this moment, take advantage of heat filtering, realize terephthalic acid and benzoic initial gross separation, adopt the method for nature cooling then, the phenylformic acid crystallisation by cooling, filter, at this moment organic content about 5% in the solution.
Owing to adopt P204 (two (2-ethylhexyl) phosphonic acids) extracting and separating cobalt manganese, if organic compound removes untotally, a large amount of organism can be dissolved in the extraction agent, causes the extracting power of extraction agent to descend, and making cobalt manganese separate can't realize.Therefore, also need organism is further separated.Solution is heated, adopt positively charged ions such as resin cation (R.C.) adsorption of cobalt manganese, containing a spot of phenylformic acid in the PTA active sludge discharges with hot water, the reusable heat water washing resin, with resin bed residual organic washes clean, through the sodium sulfate desorb, obtain containing cobalt, the manganese liquid of the high density of micro-content organism, send extraction plant.
The P204 organic extractant under different pH, has different extracting powers to metal ion.When pH was 4.5, the percentage extraction of mn ion reached 99%, and the percentage extraction of cobalt ion is 80%, its separation factor is 1.68, utilizes cobalt and manganese different partition ratio in P204, through multi-stage solvent extraction, realize the separation of cobalt manganese, obtain rose vitriol and manganese sulfate product respectively.Calculate and do McCabe_Thiele figure, reaching the separation of cobalt manganese needs with 6 grades, small-scale test and medium-sized test adopt 9 grades of extracting and separating, manganese content is less than 5ppm in the cobalt liquid, cobalt concentration can reach 70g/L, manganese concentration can reach 50g/L, obtains rose vitriol and manganous sulfate respectively through condensing crystal, and its quality product all reaches respective standard.
The method that adopts ion-exchange and extracting and separating to combine just can make cobalt, manganese obtain separating and purifying, produces products such as qualified rose vitriol and manganous sulfate.This is unique strip adoption ion-exchange of China and extraction phase reclaim cobalt manganese from PTA making beating waste water in conjunction with way a production line.
Major technique and performance index
A: 300 ℃ of drying and dewaterings of mud, 800 ℃ of burnings, burning back ash amount has only 3% of primary sludge, and that cobalt manganese content is enriched to is about 10%, is the high quality raw material that reclaim cobalt manganese.
B: waste water cools and isolates terephthalic acid (PTA) and phenylformic acid after filtration, and cobalt manganese content reaches more than the 10g/L respectively in the stripping liquid, and organism such as phenylformic acid are less than 0.1%.Cobalt, manganese yield reach 98% respectively.
C: solution through nine grades of extracting and separating cobalt manganese, after the separation, is contained the about 10g/L of manganese in the extracted organic phase; Aqueous phase contains the about 10g/L of cobalt.After manganese is stripped with sulfuric acid in the organic phase, can the condensing crystal manganese sulfate monohydrate, manganese content is greater than 31% in the product; The aqueous phase cobalt extracts cobalts through three grades of extraction processs again, three grades of sulfuric acid reextraction cobalts, and the condensing crystal heptahydrate, cobalt contents is greater than 20% in the product.Product purity all reaches the relevant product index of country.
D: the cobalt manganese element is removed after GOLD FROM PLATING SOLUTION belongs to impurity through chemical method behind sulfuric acid dissolution in the lime-ash, the rose vitriol that obtains, manganous sulfate mixture, and foreign matter content is less than 100ppm in the product.
E: the cobalt manganese whole process rate of recovery is greater than 90%.
Claims (4)
1, a kind of method of from the PTA active sludge, extracting cobalt and manganese metal compound, it is characterized in that described method is with after PTA active sludge drying, the burning, molten through acid again, resin absorption, extracting and separating are produced rose vitriol and manganous sulfate, extracting and separating is that solution is through nine grades of extracting and separating cobalt manganese, after manganese was stripped with sulfuric acid in the organic phase, condensing crystal became manganese sulfate monohydrate, and the aqueous phase cobalt is again through three grades of extraction process extraction cobalts, three grades of sulfuric acid reextraction cobalts, the condensing crystal heptahydrate.
2, the method for from the PTA active sludge, extracting cobalt and manganese metal compound according to claim 1, it is characterized in that described drying, burn to be, burn active sludge through 300 ℃ of drying and dewatering dryings of incinerator, make active sludge be dried to moisture about 10% particle by colloidal, when temperature reached 500-800 ℃, organic meeting spontaneous combustion become ash.
3, the method for from the PTA active sludge, extracting cobalt and manganese metal compound according to claim 1, it is characterized in that described acid molten be that the ash after the spontaneous combustion of PTA active sludge is added sulfuric acid dissolution, remove GOLD FROM PLATING SOLUTION through chemical method and belong to impurity.
4, the method for from the PTA active sludge, extracting cobalt and manganese metal compound according to claim 1, it is characterized in that described resin absorption heats solution, adopt resin cation (R.C.) adsorption of cobalt manganese positively charged ion, the phenylformic acid that contains in the PTA active sludge is discharged with hot water, the reusable heat water washing resin, with resin bed residual organic washes clean, through the sodium sulfate desorb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100204776A CN100497187C (en) | 2007-03-05 | 2007-03-05 | Method for extracting cobalt-manganese metal compound from active sludge |
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| CNB2007100204776A CN100497187C (en) | 2007-03-05 | 2007-03-05 | Method for extracting cobalt-manganese metal compound from active sludge |
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| CN101037235A CN101037235A (en) | 2007-09-19 |
| CN100497187C true CN100497187C (en) | 2009-06-10 |
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| CNB2007100204776A Expired - Fee Related CN100497187C (en) | 2007-03-05 | 2007-03-05 | Method for extracting cobalt-manganese metal compound from active sludge |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994778A (en) * | 2012-12-10 | 2013-03-27 | 金川集团股份有限公司 | Method for separating and enriching cobalt from leach liquor used for pickling and vulcanizing tailing |
| CN103771526B (en) * | 2014-01-10 | 2015-11-18 | 湖南邦普循环科技有限公司 | A kind of take industrial manganic sulfate as the method that high purity manganese sulfate prepared by raw material |
| CN110255845B (en) * | 2019-07-09 | 2020-08-21 | 中国科学院城市环境研究所 | Resource utilization method of sludge pyrolytic biochar |
| CN112851503A (en) * | 2021-01-20 | 2021-05-28 | 江苏福昌环保科技集团有限公司 | Comprehensive utilization process of PTA oxidation residues |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058383A (en) * | 1991-04-26 | 1992-02-05 | 黄永忠 | Utilize the pharmaceutical industry waste manganese slag to produce the method for activated manganese dioxide |
| AU5077496A (en) * | 1995-05-01 | 1996-11-14 | Chemix Pty Ltd | A process for the manufacture of manganese sulphate |
| CN1184858A (en) * | 1996-12-13 | 1998-06-17 | 抚顺石油化工公司洗涤剂化工厂 | Method for recovering cobalt from cobalt contg. waste catalyst used is carbonylation syntehsizing process |
| CN1226550A (en) * | 1998-02-16 | 1999-08-25 | 中国石化辽阳石油化纤公司 | Process for recovering cobalt and manganese catalysts from production of terephthalic acid |
-
2007
- 2007-03-05 CN CNB2007100204776A patent/CN100497187C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058383A (en) * | 1991-04-26 | 1992-02-05 | 黄永忠 | Utilize the pharmaceutical industry waste manganese slag to produce the method for activated manganese dioxide |
| AU5077496A (en) * | 1995-05-01 | 1996-11-14 | Chemix Pty Ltd | A process for the manufacture of manganese sulphate |
| CN1184858A (en) * | 1996-12-13 | 1998-06-17 | 抚顺石油化工公司洗涤剂化工厂 | Method for recovering cobalt from cobalt contg. waste catalyst used is carbonylation syntehsizing process |
| CN1226550A (en) * | 1998-02-16 | 1999-08-25 | 中国石化辽阳石油化纤公司 | Process for recovering cobalt and manganese catalysts from production of terephthalic acid |
Non-Patent Citations (4)
| Title |
|---|
| PTA装置氧化残渣的回收利用. 韦士平.PTA装置氧化残渣的回收利用,Vol.17 No.3. 2004 |
| PTA装置氧化残渣的回收利用. 韦士平.PTA装置氧化残渣的回收利用,Vol.17 No.3. 2004 * |
| 粗对苯二甲酸母液中的催化剂回收再利用. 时在国，黄亮.现代化工，第25卷第1期. 2005 |
| 粗对苯二甲酸母液中的催化剂回收再利用. 时在国，黄亮.现代化工，第25卷第1期. 2005 * |
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| CN101037235A (en) | 2007-09-19 |
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