CN102515200A - Method for removing heavy metals in by-product of ammonia desulphurization - Google Patents
Method for removing heavy metals in by-product of ammonia desulphurization Download PDFInfo
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- CN102515200A CN102515200A CN2011103800823A CN201110380082A CN102515200A CN 102515200 A CN102515200 A CN 102515200A CN 2011103800823 A CN2011103800823 A CN 2011103800823A CN 201110380082 A CN201110380082 A CN 201110380082A CN 102515200 A CN102515200 A CN 102515200A
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Abstract
The invention relates to a method for removing heavy metals in the by-product of ammonia desulphurization, comprising the following steps: ammonium sulphate solution enters in the settlement box of a reactor at first, and almost all univalent and divalent metals in the solution is removed by organic sulphur TMT-15 reaction; then the ammonium sulphate solution enters in a flocculation box and then is flocculated by a flocculant, i.e., polyacrylamide (PMA); the ammonium sulphate solution is pumped to a filter device via a filter pump and then filtered, and a sludge filter cake containing heavy metals is used as a waste without leached toxicants and then subjected to a deep burying treatment; and a filtrate is stored in an ammonium sulphate solution buffering box and then is pumped to an evaporation system via an ammonium sulphate solution pump to perform follow-up treatment to prepare an ammonium sulphate fertilizer or pumped to a desulphurization tower to be recycled. The method disclosed by the invention can efficiently remove heavy metals in the by-product, i.e., ammonium sulphate chemical fertilizer, of ammonia desulphurization, and satisfy demands on the national standards of agricultural chemical fertilizer. The method disclosed by the invention is suitable for both inter-tower crystallization and outer-tower crystallization.
Description
Technical field
The present invention relates to a kind of method that removes heavy metal, particularly a kind of method that removes heavy metal in the ammonia process of desulfurization sub product that is applicable to.
Background technology
At present, the wet process of FGD technology mainly comprises limestone/lime-gypsum, sodium base method, seawater method, ammonia process, magnesium method, sodalime double alkali method etc.
Limestone-gypsum method is present most widely used wet desulphurization technology, but because sub product is difficult to comprehensive utilization, all takes mostly to stack and handle, and produces new secondary pollution.
Because ammonia process of desulfurization sub product is the ammonium sulfate fertilizer of high added value, therefore more and more came into one's own in the last few years.But, the ammonia process of desulfurization with the calcium method desulfurization have one very big different, that is exactly that calcium method desulfuration byproduct calcium sulfate is insoluble in water, therefore, all is to handle through discharge of wastewater to discharge in the desulphurization system the constantly heavy metal ion of enrichment in the calcium method sulfur removal technology.And the byproduct of ammonium sulfate of the ammonia process of desulfurization is soluble in water, and therefore, waste discharge also just means the ammonium sulfate that has discharged a large amount of high values.So in the prior art, ammonia process of desulfurization ammonium sulfate crystallization mode mainly contains two kinds of the outer crystallizations of crystallization inside tower and tower, no matter any technology does not all have discharge of wastewater, heavy metal is constantly enrichment in system, finally can only be from sub product the discharge system.Like this, heavy metal accumulation can cause the ammonium sulfate crystallization difficulty on the one hand, influences system stable operation; Cause the ammonium sulfate fertilizer quality of by-product to descend on the other hand, the serious heavy metal content that also can cause exceeds standard, and brings heavy metal pollution of soil.
Summary of the invention
The objective of the invention is provides a kind of new method that removes heavy metal in the ammonia process of desulfurization sub product in order to overcome the deficiency that above-mentioned prior art exists.Method of the present invention can effectively be removed the heavy metal in the ammonia process of desulfurization producing ammonium sulfate byproduct chemical fertilizer, satisfies national agrochemical standard-required.Method of the present invention all is suitable for crystallization inside tower and the outer crystallization of tower.
Technical scheme of the present invention is:
Remove the method for heavy metal in the ammonia process of desulfurization sub product, it is characterized in that carrying out according to the following steps:
(1), the outer crystallization ammonia desulfurizing process of tower is from thionizer slurries pond or the tower external oxidation jar ammonia process of desulfurization byproduct of ammonium sulfate solution of discharging; At first get into the heavy metal reactor drum; Crystallization inside tower technology is then with getting into the heavy metal reactor drum behind the swirler-overflowing liquid adding suitable quantity of water dissolving small amount of ammonium sulfate crystal; Heavy metal reactor drum inner-use clapboard is divided into two reaction boxs that interconnect: sludge box and flocculation tanks, play heavy metal precipitation, flocculation respectively; The sludge box of heavy metal reactor drum and flocculation tanks all are provided with the jacking-type whisking appliance respectively;
(2), ammoniumsulphate soln at first gets into sludge box, adding mass concentration in the sludge box is organosulfur (TMT-15) solution of 10-20%, adding organosulfur TMT-15 in every cube of ammoniumsulphate soln is 30-50mg/m
3TMT-15 is a kind of triazines component; Can precipitate nearly all unit price and divalent metal; With the reaction rapidly of various heavy metal ion (mercury, lead, copper, cadmium, nickel, manganese, zinc, chromium etc.) in the ammoniumsulphate soln, generate water insoluble, and inner complex with good chemicalstability; Equally, also can remove the heavy metal that has been transformed into complex compound, and nontoxic, and safety can not produce secondary pollution, below with Cd
2+And Hg
2+Be example, TMT-15 precipitin reaction principle of work be described:
3Cd
2++2(TMT-15)
3-→Cd
3(TMT-15)
2↓
3Hg
2++2(TMT-15)
3-→Hg
3(TMT-15)
2↓；
(3), ammoniumsulphate soln gets into flocculation tanks through dividing plate after in sludge box, stopping 30-60min; Adding mass concentration in the flocculation tanks is the flocculation agent SEPIGEL 305 (PMA) of 0.05-0.15%, and adding flocculation agent SEPIGEL 305 (PMA) in every cube of ammoniumsulphate soln is 2.5-7.5mg/m
3Flocculation agent can produce absorption, bridge formation, the net effect of catching and the less solid subparticle that separates out connected together become the bigger deposition of volume, be beneficial to filter;
(4), ammoniumsulphate soln stops 30-60min in flocculation tanks after, through filtration pump ammoniumsulphate soln is got to filtration unit and filter, filtration unit can be the on-line continuous strainer, also can be plate-and-frame filter press; The sludge filter cake that contains heavy metal is as there not being the buried processing of refuse of leaching poisonous substance;
(5), filtrating gets into the ammoniumsulphate soln baffle-box, removed the ammoniumsulphate soln of the cleaning of heavy metal and stored at the ammoniumsulphate soln baffle-box; If the outer crystallization ammonia desulfurizing process of tower is got to vapo(u)rization system through the ammoniumsulphate soln pump and is carried out subsequent disposal; The sub product after-treatment system adopts general sophisticated technology and device at present; If crystallization inside tower technology is got to thionizer through the ammoniumsulphate soln pump.
The present invention has following positively effect:
Through heavy metal precipitation, flocculation, filtration, can dust, heavy metal content in the desulfurization producing ammonium sulfate byproduct be dropped to minimumly, thoroughly avoid by-product chemical fertilizer quality low, heavy metal content exceeds standard.Simultaneously, owing to, make desulphurization system dust and heavy metal accumulative total concentration lower, with ammonium sulfate crystallization positive influence is arranged all to desulfurizer is stable constantly with outside heavy metal and the dust discharge system.
The present invention is suitable for the outer crystallization of ammonia process of desulfurization tower and two kinds of different production technologies of crystallization inside tower, and different is that process unit of the present invention can accomplish that heavy metal basically all removes on the technical process main line to the outer crystallization of tower; For crystallization inside tower, process unit of the present invention can only accomplish that in the technical process bypass heavy metal partly removes.
According to test, adopt technology of the present invention, the desulfuration byproduct heavy metal content declines to a great extent, and sees the following form:
Table one: adopt the outer crystallization of tower
Table two: adopt crystallization inside tower
Description of drawings
Fig. 1 is that heavy metal is removed process flow sheet in the outer crystallization flow process of tower of the present invention.
Fig. 2 is that heavy metal is removed process flow sheet in the crystallization inside tower flow process of the present invention.
Embodiment
Embodiment one:
As shown in Figure 1, from the ammoniumsulphate soln of the outer crystallization ammonia process of desulfurization absorption system of tower, flow is 20m
3/ hr.This solution at first gets into heavy metal reactor drum 1.Heavy metal reactor drum 1 inner-use clapboard is divided into two reaction boxs that interconnect: sludge box 2 and flocculation tanks 3, play heavy metal precipitation, flocculation respectively, and all be provided with jacking-type whisking appliance 8 respectively;
Ammoniumsulphate soln at first gets into sludge box 2; The adding mass concentration is 15% organosulfur (TMT-15) solution in the sludge box; With various heavy metal ion (mercury, lead, copper, cadmium, nickel, manganese, zinc, the chromium etc.) reaction rapidly in the ammoniumsulphate soln; Generate water insoluble, and inner complex with good chemicalstability.The organosulfur add-on is 30-50mg/m
3Ammoniumsulphate soln.
Ammoniumsulphate soln gets into flocculation tanks 3 through dividing plate after in sludge box 2, stopping 30min, and adding mass concentration in the flocculation tanks 3 is 0.1% flocculation agent SEPIGEL 305 (PMA), and add-on is 5mg/m
3Ammoniumsulphate soln, flocculation agent can produce absorption, bridge formation, the net effect of catching and the less solid subparticle that separates out connected together become the bigger deposition of volume, be beneficial to filter.
Ammoniumsulphate soln is got to filtration unit 5 through filtration pump 4 with ammoniumsulphate soln and is filtered after in flocculation tanks 3, stopping 30, and filtration unit uses pocket type on-line continuous strainer.The sludge filter cake that contains heavy metal is as there not being the buried processing of refuse of leaching poisonous substance.
Filtrating gets into ammoniumsulphate soln baffle-box 6, has removed the ammoniumsulphate soln of the cleaning of heavy metal and has stored at ammoniumsulphate soln baffle-box 6.Get to vapo(u)rization system through ammoniumsulphate soln pump 7 and carry out subsequent disposal.The sub product after-treatment system adopts general sophisticated technology and device at present.
Embodiment two:
As shown in Figure 2, from the ammoniumsulphate soln of crystallization inside tower ammonia process of desulfurization absorption system swirler-overflow, flow is 50m
3/ hr contains the small amount of ammonium sulfate crystalline particle in the solution, the SS mass concentration is about 1.7%, therefore, adds 1.5m
3/ hr water; With this part ammonium sulfate crystallization dissolving, this solution at first gets into heavy metal reactor drum 1, and heavy metal reactor drum 1 inner-use clapboard is divided into two reaction boxs that interconnect: sludge box 2 and flocculation tanks 3; Play heavy metal precipitation, flocculation respectively, and all be provided with jacking-type whisking appliance 8 respectively.
Ammoniumsulphate soln at first gets into sludge box 2; The adding mass concentration is 15% organosulfur (TMT-15) solution in the sludge box; With various heavy metal ion (mercury, lead, copper, cadmium, nickel, manganese, zinc, the chromium etc.) reaction rapidly in the ammoniumsulphate soln; Generate water insoluble, and inner complex with good chemicalstability, the organosulfur add-on is 30-50mg/m
3Ammoniumsulphate soln.
Ammoniumsulphate soln gets into flocculation tanks 3 through dividing plate after in sludge box 2, stopping 30min, and the adding mass concentration is 0.1% flocculation agent non-ionic polyacrylamide (PMA) in the flocculation tanks 3, and add-on is 5mg/m
3Ammoniumsulphate soln, flocculation agent can produce absorption, bridge formation, the net effect of catching and the less solid subparticle that separates out connected together become the bigger deposition of volume.
Ammoniumsulphate soln is got to filtration unit 5 through filtration pump 4 with ammoniumsulphate soln and is filtered after in flocculation tanks 3, stopping 30, and filtration unit uses pocket type on-line continuous strainer.The sludge filter cake that contains heavy metal is as there not being the buried processing of refuse of leaching poisonous substance.
Filtrating gets into ammoniumsulphate soln baffle-box 6, has removed the ammoniumsulphate soln of the cleaning of heavy metal and has stored at ammoniumsulphate soln baffle-box 6.Get to thionizer through ammoniumsulphate soln pump 7.
Claims (2)
1. remove the method for heavy metal in the ammonia process of desulfurization sub product, it is characterized in that carrying out according to the following steps:
(1), the outer crystallization ammonia desulfurizing process of tower is from thionizer slurries pond or the tower external oxidation jar ammonia process of desulfurization byproduct of ammonium sulfate solution of discharging, and at first gets into the sludge box of heavy metal reactor drum; Crystallization inside tower technology is then with the sludge box that gets into the heavy metal reactor drum behind the swirler-overflowing liquid adding suitable quantity of water dissolving small amount of ammonium sulfate crystal; Heavy metal reactor drum inner-use clapboard is divided into two sludge boxs that interconnect and flocculation tanks;
(2), ammoniumsulphate soln at first gets into the sludge box of reactor drum, adding mass concentration in the sludge box is organosulfur (TMT-15) solution of 10-20%, adding organosulfur TMT-15 in every cube of ammoniumsulphate soln is 30-50mg/m
3
(3), ammoniumsulphate soln gets into flocculation tanks through dividing plate after in sludge box, stopping 30-60min; Adding mass concentration in the flocculation tanks is the flocculation agent SEPIGEL 305 (PMA) of 0.05-0.15%, and adding flocculation agent SEPIGEL 305 (PMA) in every cube of ammoniumsulphate soln is 2.5-7.5mg/m
3
(4), ammoniumsulphate soln stops 30-60min in flocculation tanks after, through filtration pump ammoniumsulphate soln is got to filtration unit and filter, filtration unit is on-line continuous strainer or plate-and-frame filter press; The sludge filter cake that contains heavy metal is as there not being the buried processing of refuse of leaching poisonous substance;
(5), filtrating gets into the ammoniumsulphate soln baffle-box, removed the ammoniumsulphate soln of the cleaning of heavy metal and stored at the ammoniumsulphate soln baffle-box; If the outer crystallization ammonia desulfurizing process of tower, get to vapo(u)rization system through the ammoniumsulphate soln pump and carry out subsequent disposal and make ammonium sulfate fertilizer; If getting to thionizer through the ammoniumsulphate soln pump, crystallization inside tower technology recycles.
2. the method that removes heavy metal in the ammonia process of desulfurization sub product according to claim 1 is characterized in that: the sludge box of described heavy metal reactor drum and flocculation tanks all are provided with the jacking-type whisking appliance respectively.
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| CN2011103800823A CN102515200A (en) | 2011-11-25 | 2011-11-25 | Method for removing heavy metals in by-product of ammonia desulphurization |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103405961A (en) * | 2013-08-22 | 2013-11-27 | 武汉钢铁(集团)公司 | Process and equipment for efficiently removing ash in ammonia process desulfurization slurry by adopting membrane filtration |
| CN103555340A (en) * | 2013-10-29 | 2014-02-05 | 廖清琳 | Novel environment-friendly reagent for reducing leaching concentration of various heavy metals |
| CN109399667A (en) * | 2018-12-14 | 2019-03-01 | 湖南江冶机电科技股份有限公司 | A kind of method and equipment of lead plaster ammonium method desulfurizing byproduct-ammonium sulfate deep purifying |
| CN114656064A (en) * | 2022-04-11 | 2022-06-24 | 河北中科同创科技发展有限公司 | Method for removing ferric ions and ferrous ions in ammonium sulfate solution |
| CN115490315A (en) * | 2022-08-31 | 2022-12-20 | 中国环境科学研究院 | Method for removing heavy metals and/or arsenic in water body |
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| CN101597070A (en) * | 2009-07-03 | 2009-12-09 | 中钢集团天澄环保科技股份有限公司 | Sintering, pelletizing and stove purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process and method |
| CN201433144Y (en) * | 2009-04-09 | 2010-03-31 | 宇星科技发展(深圳)有限公司 | Desulfurization waste water treatment recycling device |
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2011
- 2011-11-25 CN CN2011103800823A patent/CN102515200A/en active Pending
Patent Citations (3)
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| CN101003412A (en) * | 2006-12-31 | 2007-07-25 | 湖南华迪电力环保工程技术有限公司 | Method and system unit for flue gas desulfurization and wastewater treatment |
| CN201433144Y (en) * | 2009-04-09 | 2010-03-31 | 宇星科技发展(深圳)有限公司 | Desulfurization waste water treatment recycling device |
| CN101597070A (en) * | 2009-07-03 | 2009-12-09 | 中钢集团天澄环保科技股份有限公司 | Sintering, pelletizing and stove purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process and method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103405961A (en) * | 2013-08-22 | 2013-11-27 | 武汉钢铁(集团)公司 | Process and equipment for efficiently removing ash in ammonia process desulfurization slurry by adopting membrane filtration |
| CN103405961B (en) * | 2013-08-22 | 2015-05-27 | 武汉钢铁(集团)公司 | Process and equipment for efficiently removing ash in ammonia process desulfurization slurry by adopting membrane filtration |
| CN103555340A (en) * | 2013-10-29 | 2014-02-05 | 廖清琳 | Novel environment-friendly reagent for reducing leaching concentration of various heavy metals |
| CN109399667A (en) * | 2018-12-14 | 2019-03-01 | 湖南江冶机电科技股份有限公司 | A kind of method and equipment of lead plaster ammonium method desulfurizing byproduct-ammonium sulfate deep purifying |
| CN114656064A (en) * | 2022-04-11 | 2022-06-24 | 河北中科同创科技发展有限公司 | Method for removing ferric ions and ferrous ions in ammonium sulfate solution |
| CN115490315A (en) * | 2022-08-31 | 2022-12-20 | 中国环境科学研究院 | Method for removing heavy metals and/or arsenic in water body |
| CN115490315B (en) * | 2022-08-31 | 2023-10-13 | 中国环境科学研究院 | Method for removing heavy metals and/or arsenic in water body |
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Application publication date: 20120627 |