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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
heavy metal
ammoniumsulphate soln
tower
box
crystallization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011103800823A
Other languages
Chinese (zh)
Inventor
殷兴华
殷茵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WUHAN XINGNENG ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
Original Assignee
WUHAN XINGNENG ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by WUHAN XINGNENG ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd filed Critical WUHAN XINGNENG ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
Priority to CN2011103800823A priority Critical patent/CN102515200A/en
Publication of CN102515200A publication Critical patent/CN102515200A/en
Pending legal-status Critical Current

Links

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

Remove the method for heavy metal in the ammonia process of desulfurization sub product
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.
CN2011103800823A 2011-11-25 2011-11-25 Method for removing heavy metals in by-product of ammonia desulphurization Pending CN102515200A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011103800823A CN102515200A (en) 2011-11-25 2011-11-25 Method for removing heavy metals in by-product of ammonia desulphurization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011103800823A CN102515200A (en) 2011-11-25 2011-11-25 Method for removing heavy metals in by-product of ammonia desulphurization

Publications (1)

Publication Number Publication Date
CN102515200A true CN102515200A (en) 2012-06-27

Family

ID=46286352

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011103800823A Pending CN102515200A (en) 2011-11-25 2011-11-25 Method for removing heavy metals in by-product of ammonia desulphurization

Country Status (1)

Country Link
CN (1) CN102515200A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (4)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
CN101746874B (en) Processing method of wastewater desulfurized by fume wet method
CN102503015A (en) Method for treating wastewater generated by ammonia process desulfurization
CN105271436B (en) The method that poly ferric chloride flocculant agent is prepared using steel wire rope sludge and waste hydrochloric acid
CN101817575B (en) Electric flocculation method and device for recovering and processing desulfurized wastewater
CN201762204U (en) Wastewater treatment system of power plant
CN101244831A (en) Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor
CN102642953B (en) Treatment method for high-salinity heavy-metal-containing production sewage
CN102936070A (en) Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process
CN204874164U (en) Zero release processing system of desulfurization waste water
CN103011439A (en) Cadmium-containing wastewater treatment method
CN202322537U (en) Ammonia desulphurization waste water treatment equipment
CN102515200A (en) Method for removing heavy metals in by-product of ammonia desulphurization
CN105198122A (en) Resource utilization method of waste hydrochloric acid containing heavy metal lead and iron
CN103570159A (en) Device for treating high-concentration ammonia nitrogen in coal chemical wastewater in vortex mixing dispersion way by using surfactant
CN102910760A (en) Treatment process of contaminated acid containing heavy metals
JP4954131B2 (en) Treatment method of water containing borofluoride
CN106215863B (en) A kind of heavy metal absorbent of purification diluted sulfric acid and its application
CN103725883A (en) Method for preparing zinc sulfate solution de-fluorination agent
CN110342710A (en) High chlorine low-sulfur acid group waste water treatment system and its technique
CN202322400U (en) Device for desulfurizing heavy metals in by-products by ammonia removal method
CN102247742A (en) Purification process for sintering flue gas desulfurization solution
CN101165058B (en) 2,4,6- trithione-s-triazine alkali metal salt preparation method
CN102092869A (en) Processing method of waste acid in acid producing system
CN101898824A (en) Sulfide heavy metal chelating trapping agent and preparation method thereof
CN106882884A (en) A kind of method of chlorion in recycling waste water

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20120627

C02 Deemed withdrawal of patent application after publication (patent law 2001)