CN103205574A - Comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas - Google Patents

Comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas Download PDF

Info

Publication number
CN103205574A
CN103205574A CN201210013483XA CN201210013483A CN103205574A CN 103205574 A CN103205574 A CN 103205574A CN 201210013483X A CN201210013483X A CN 201210013483XA CN 201210013483 A CN201210013483 A CN 201210013483A CN 103205574 A CN103205574 A CN 103205574A
Authority
CN
China
Prior art keywords
waste water
vanadium
flue gas
ammonia
water
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
CN201210013483XA
Other languages
Chinese (zh)
Inventor
徐欣
李自树
叶宏
操卫平
李林峰
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.)
SICHUAN GERUI CHEMICAL ENGINEERING Co Ltd
Original Assignee
SICHUAN GERUI CHEMICAL ENGINEERING 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 SICHUAN GERUI CHEMICAL ENGINEERING Co Ltd filed Critical SICHUAN GERUI CHEMICAL ENGINEERING Co Ltd
Priority to CN201210013483XA priority Critical patent/CN103205574A/en
Publication of CN103205574A publication Critical patent/CN103205574A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y02W30/54—

Abstract

The invention relates to a comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas, and belongs to the technical field of environmental protection. An object of the invention is to change a conventional method of separately treating the waste water and the flue gas in a vanadium oxide factory, vanadium and chromium in the vanadium precipitation waste water are subjected to separate separation and recycle treatment, then waste heat of the kiln and furnace flue gas is directly used as a gas source and an energy source for ammonia nitrogen stripping the waste water; exhaust gas blowing the ammonia is used to prepare ammonia recycled and purified liquid by using ammonium sulfate and sulfuric acid which are produced by coking so as to prepare an ammonium sulfate vanadium precipitation agent; and the treated waste water is used for flue gas desulfurization of a sintering machine or blast furnace slag. The treated water and flue gas fully meet "emission standards of the vanadium industry pollutants" (GB26452-2011), at the same time, vanadium and chromium filter cakes produced by the water treatment process are utilized comprehensively; and the waste is turned in to wealth.

Description

Method is administered and utilized to a kind of vanadium wastewater and stove smoke comprehensive
Technical field
The present invention relates to the improvement of a kind of vanadium wastewater and stove smoke comprehensive and utilize technology, belong to environmental technology field.
Background technology
At present domestic and international vanadium oxide factory continues to use waste water and flue gas separates the mode of administering, and the special environment treating facility of a kind of processing unit (or operation) auxiliary construction disperses to administer.The difficult problem that vanadium wastewater conventional process technology exists that vanadium chromium does not separate, vitriol can't qualified discharge in the waste water, and the energy consumption height of evaporating and concentrating process, processing cost height, and high-content activated silica acid group can cause device to stop up or fouling.And only the particulate matter of rotary kiln and smelting furnace flue gas has been formulated clear and definite emission standard in originally " vanadium industrial pollution emission standard ", toxic and harmful has not wherein been explicitly called for.According to the factual survey of vanadium manufacturing enterprise, one ton of V of every production 2O 5To produce 20-53m 3Efflux vanadium wastewater.Except containing toxic heavy metal ions such as vanadium chromium, also contain a large amount of ammonia nitrogens, sodium ion in waste water and the flue gas, sulfate ion and toxic and harmful, be very harmful source of pollution be again the secondary resource with certain value.Therefore, vanadium oxide factory environment protection treating lacks the entire system planning and design, the environmental protection ideas backwardness causes treatment process, backward in technique, and the present situation of reaching advanced world standards with China vanadium oxide production technique and " vanadium emission of industrial pollutants standard " requiring (GB26452-2011) is incompatible.Waste water and flue gas disperse the mode of improvement to invest greatly simultaneously, occupation of land is many, the energy consumption height, the working cost height, waste water is not reused as the process water of smoke gas treatment, Lowlevel thermal energy and source of the gas that flue gas is contained are not utilized effectively, and the by product of recovery can not effectively utilize and form new source of pollution.
It is according to practice and the exploration of vanadium factory environment protection treating both at home and abroad that vanadium wastewater vanadium chromium recovery-flue gas blows the ammonia process technology, vanadium wastewater and flue gas are carried out the system development utilization as the secondary resource of coexistence enrichment, administer vanadium factory's waste water and flue gas comprehensively, make it to reach " vanadium emission of industrial pollutants standard " (GB26452-2011), realized meeting the vanadium of vanadium oxide factory reality, chromium, ammonia, the zero release of water resources and the new model of comprehensive utilization of resources, formed the environment protection treating technology of practicable recycling economy and cleaner production, made vanadium oxide factory realize environmental benefit, the harmony of economic benefit and social benefit.
Summary of the invention
The purpose of present technique invention is that waste water and the flue gas that change vanadium oxide factory continues to use separates the thinking of administering, vanadium in the vanadium wastewater is separated separately respectively with chromium and reclaims improvement, directly utilize the waste heat of stove flue gas as source of the gas and the energy of ammonia nitrogen in waste water stripping then, blow ammonia tail gas and adopt the ammonium sulfate of coking production and sulfuric acid preparation ammonia reclaiming clean liquid to produce ammonium sulfate precipitation agent; Processed waste water is used for flue gas of sintering machine or iron work blast furnace slag flushing.
The master operation of present technique invention is as follows: (1) waste water vanadium chromium separates respectively and reclaims improvement; (2) the waste water solid ammonium-salt decomposes and except hardness; (3) utilize the stove flue gas to carry out the ammonia nitrogen in waste water stripping and treating tail gas prepares ammonium sulfate precipitation agent; (4) handle water up to standard (containing sodium salt) comprehensive recycling in flue gas desulfurization or blast furnace slag flushing; (5) vanadium, the comprehensive utilization of chromium filter cake.
The present technique invention has following characteristics:
(1) vanadium wastewater is handled and is reached " vanadium emission of industrial pollutants standard " (GB26452-2011), the water yield≤10m of unit product base platoon comprehensively 3/ t (V 2O 5Or V 2O 3), corresponding emission limit is Cr 6+＜0.5mg/l, total vanadium＜1mg/l, total chromium＜1.5mg/l.
(2) vanadium dirt, vanadium steam, the Cl of severe toxicity in the stove flue gas 2, HCl, harmful dust, SO 2/ SO 3, NH 3, NO XDeng obnoxious flavour, reach " vanadium emission of industrial pollutants standard " (GB26452-2011) comprehensively.Blow in the technological process of ammonia at flue gas, at first flue gas is carried out denitration and fall chlorine, removing oxynitride (NO X) time finishes chlorine (Cl in the flue gas 2) degraded.
(3) take full advantage of the stove flue gas and blow ammonia and reclaim ammonia, realize that synchronously coking agricultural grade ammonium sulfate prepares ammonium salt precipitation agent.
(4) vanadium chromium separately separates, and the ferric vandate resource regeneration in the filter residue is in producing APV, elementary chromium hydroxide as raw material, the calcium sulfate making cement additive of producing basic chromium sulfate.
(5) blow whole process waters that ammonia waste water is used as stove smoke gas treatment, realized that vanadium wastewater is multiplexing in the one-level of vanadium factory; Blow ammonia waste water processing up to standard back all for flue gas desulfurization or ironmaking flushing cinder, realized that the secondary of waste water is multiplexing.
Description of drawings
Fig. 1 is that technical process is administered and utilized to vanadium wastewater and stove smoke comprehensive.
Embodiment
(1) waste water vanadium chromium separates and reclaims
Between under the pH=2-6 condition, add ferric sulfate, Fe 3+With VO 3-, VO 4 3-In conjunction with forming Fe (VO 3) precipitation, reaction formula is as follows: 3VO 3 -+ Fe 3+=Fe (VO 3) ↓
3VO 4 3-+Fe 3++6H +＝Fe(VO 3)↓+3H 2O
Regulate pH to 8-9, make Fe (VO 3) 3And excessive Fe 3+And the Cr in the waste water 3+Form precipitation of hydroxide, add and carry out filtering separation after PAM flocculates.Contain Cr after the separation 6+Add sulfuric acid and S-WAT in the waste water again, utilize SO 3 2-Ion is with Cr 2O 7 2-Or CrO 4 2-Middle hexavalent chrome reduction becomes Cr 3+, add NaOH then and regulate pH to 8-9, generate Cr (OH) 3Precipitation, filtering separation.
2H 2Cr 2O 7+3Na 2S 2O 5+3H 2SO 4→2Cr 2(SO 4) 3+3Na 2SO 4+5H 2O
2CrO 4 2-+3HSO 3 -+7H +＝3SO 4 2-+2Cr 3++5H 2O
Cr 3++3OH -＝Cr(OH) 3↓
(2) the waste water solid ammonium-salt decomposes and except hardness
Remove in the waste water behind the vanadium chromium and add lime, make that ammonia nitrogen all exists with volatility ammonium salt (ammonium hydroxide) form in the waste water, when solid ammonium-salt decomposed, the sodium sulfate in the waste water was partly changed into sodium hydroxide and calcium sulfate precipitation; Add the bicarbonate of ammonia dissolving again and remove hardness, ammonia treating tail gas tower is blown in the ammonia-contaminated gas suction of generation.
CaO+H 2O→Ca(OH) 2↓
NH 4 ++OH -→NH 3↑+H 2O
(NH 4) 2SO 4+Ca(OH) 2+2H 2O→2NH 3·H 2O+CaSO 4·2H 2O↓
Na 2SO 4+Ca(OH) 2+2H 2O→2NaOH+CaSO 4·2H 2O↓
MgSO 4+Ca(OH) 2+2H 2O→Mg(OH) 2↓+CaSO 4·2H 2O↓
MnSO 4+Ca(OH) 2+2H 2O→Mn(OH) 2↓+CaSO 4·2H 2O↓
FeSO 4+Ca(OH) 2+2H 2O→Fe(OH) 2↓+CaSO 4·2H 2O↓
R 2O·nSiO 2+CaX 2+mH 2O→2CaO·3SiO 2·mH 2O↓+RX
Wherein, R is Na +, K +, X is Cl -, NO 3 -And OH -Negatively charged ion in energy and Ca generation salt and alkali.N, m are positive number, and n is 0.1～10.
Ca(OH) 2+2NH 4HCO 3→CaCO 3↓+2NH 3·H 2O+H 2O
Figure BSA00000659010000031
(3) utilize the stove flue gas to carry out the ammonia nitrogen in waste water stripping and treating tail gas prepares ammonium sulfate precipitation agent
Directly utilize the stove fume afterheat to blow ammonia and realize that flue gas managing technique comprises three parts of carrying out successively: chlorine (chlorine) and dedusting again fall in the denitration that at first is flue gas; Next is up to standard as the ammonia-nitrogen desorption that thermal source and source of the gas carry out in the waste water with flue gas, and the ammonia nitrogen in the after-blow ammonia flue gas reclaims to administer produces qualified discharge behind the ammonium sulfate.The NOx about 95% that vanadium factory rotary kiln and smelting furnace adopt gas-fired to produce is NO, and all the other 5% mainly are NO 2, substantially exceed NO owing to exist in the flue gas 2The SO of content 2And CO, NO 2All by SO 2Become NO with the CO Restore All.
SO 2+NO 2→SO 3+NO
CO+NO 2→CO 2+NO
Be full of in syllogic smelting furnace and the flue and contain certain density V 2O 5Steam, vanadium powder dirt and the huge ammonia of change in concentration are at catalyzer (V 2O 5) and the oxygen existence condition under, in lower temperature range (180～420 ℃), reductive agent ammonia selectively is generated as the NOx in the flue gas reduction N 2And water, realize denitration.
In the SCR denitrator, spray into and contain NH 3About 8%～10% weak ammonia makes the flue gas among the SCR be in about 180 ℃ of states that contain a large amount of water vapour.Since the existence of a large amount of water vapour, the Cl of strong oxidizing property 2NH with reductibility 3Instantaneous reaction realizes falling chlorine.3Cl 2+ 8NH 3=N 2+ 6NH 4Cl (white cigarette)
Cl 2+SO 2+2H 2O＝H 2SO 4+2HCl
Cl 2+2NO＝2NOCl
NH 4Cl+NaOH＝NH 4OH+NaCl
NH 4OH＝NH 3↑+H 2O
Under the condition of flue gas as source of the gas and thermal source behind the denitration dechlorination gas, alkaline ammonia waste water and the flue gas of blowing carries out the three stage countercurrents direct mass-and heat-transfer process of connecting, make in the waste water ammonia nitrogen by stripping in flue gas, enter the ammonia recovery tower then and produce thiamines.
2NH 3+H 2SO 4→(NH 4) 2SO 4，ΔH＝-275014J/mol
NH 3+H 2SO 4→NH 4HSO 4，ΔH＝-165017J/mol
NH 4HSO 4+NH 3→(NH 4) 2SO 4
(4) handle water up to standard (containing sodium salt) comprehensive utilization.
Stripping is handled water up to standard in the make up water as sintering desulfuration technology, improves desulfuration efficiency, and liquid slurry back mixing iron blast furnace flushing cinder does not influence the blast furnace slag flushing circulating water quality after the desulfurization.
(5) vanadium, the comprehensive utilization of chromium filter cake
Waste water is except filter cake (the butt V behind the vanadium 2O 5Content average 10%) add sulfuric acid dissolution with washing water, filter and remove acid insolubles impurity, after filtrate is adjusted pH value with sodium hydroxide, be steam heated to and boil, add sulphur ammonium precipitation and produce thick APV, the filtrate of separating thick APV is ferric sulfate of polymerized silica solution, as coking chemical waste water pre-treatment special efficient coagulating agent.Filter cake behind the dechromisation is elementary chromium hydroxide, as the raw material of producing basic chromium sulfate.

Claims (7)

1. method is administered and utilized to a vanadium wastewater and stove smoke comprehensive, carries out system's utilization with vanadium wastewater and stove flue gas as the secondary resource of coexistence enrichment, administers vanadium factory waste water and flue gas comprehensively, it is characterized in that:
(1) waste water vanadium chromium separates separately and reclaims and administer;
(2) the waste water solid ammonium-salt decomposes and except hardness;
(3) utilize the stove flue gas to carry out the ammonia nitrogen in waste water stripping and treating tail gas prepares ammonium sulfate precipitation agent;
(4) handle water up to standard (containing sodium salt) comprehensive utilization;
(5) vanadium, the comprehensive utilization of chromium filter cake.
2. in accordance with the method for claim 1, it is characterized in that adding ferric sulfate except vanadium under the PH=2-6 condition, re-adjustment pH to 8-9 makes Fe (VO 3) 3And excessive Fe 3+And the Cr in the waste water 3+Form precipitation of hydroxide, add and carry out filtering separation after PAM flocculates.Contain Cr after the separation 6+Add sulfuric acid and S-WAT in the waste water again, utilize SO 3 2-Ion is with Cr 2O 7 2-Or CrO 4 2-Middle hexavalent chrome reduction becomes Cr 3+, add NaOH then and regulate pH to 8-9, generate Cr (OH) 3Precipitation, filtering separation.
3. in accordance with the method for claim 1, it is characterized in that adding lime in the waste water after removing vanadium chromium, make that ammonia nitrogen all exists with volatility ammonium salt (ammonium hydroxide) form in the waste water, when solid ammonium-salt decomposed, the sodium sulfate in the waste water was partly changed into sodium hydroxide and calcium sulfate precipitation; Add the bicarbonate of ammonia dissolving again and remove hardness, ammonia treating tail gas tower is blown in the ammonia-contaminated gas suction of generation.
4. in accordance with the method for claim 1, it is characterized in that directly utilizing the stove flue gas to carry out the ammonia nitrogen in waste water stripping, and tail gas recycle is administered, preparation ammonium sulfate precipitation agent.
5. in accordance with the method for claim 4, it is characterized in that at first the stove flue gas being carried out denitration falls chlorine (chlorine) and dedusting again; Next utilizes flue gas up to standard as the ammonia-nitrogen desorption that thermal source and source of the gas carry out in the waste water, at last the ammonia nitrogen that blows in the ammonia flue gas is reclaimed improvement, produces ammonium sulfate.
6. in accordance with the method for claim 1, it is characterized in that the water up to standard after stripping is handled is used as the make up water of sintering desulfuration technology, improve desulfuration efficiency, liquid slurry back mixing iron blast furnace flushing cinder after the desulfurization.
7. it is characterized in that except filter cake (the butt V behind the vanadium in accordance with the method for claim 2, 2O 5Content average 10%) add sulfuric acid dissolution with washing water, filter and remove acid insolubles impurity, after filtrate is adjusted pH value with sodium hydroxide, be steam heated to and boil, add sulphur ammonium precipitation and produce thick APV, the filtrate of separating thick APV is ferric sulfate of polymerized silica solution, as coking chemical waste water pre-treatment special efficient coagulating agent.Filter cake behind the dechromisation is elementary chromium hydroxide, as the raw material of producing basic chromium sulfate.
CN201210013483XA 2012-01-17 2012-01-17 Comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas Pending CN103205574A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210013483XA CN103205574A (en) 2012-01-17 2012-01-17 Comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210013483XA CN103205574A (en) 2012-01-17 2012-01-17 Comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas

Publications (1)

Publication Number Publication Date
CN103205574A true CN103205574A (en) 2013-07-17

Family

ID=48752977

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210013483XA Pending CN103205574A (en) 2012-01-17 2012-01-17 Comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas

Country Status (1)

Country Link
CN (1) CN103205574A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105800648A (en) * 2016-03-07 2016-07-27 攀钢集团攀枝花钢钒有限公司 Application method of ammonium sulfate prepared from smelting offgas
CN110642430A (en) * 2019-10-31 2020-01-03 重庆雅丽洁环保产业发展有限公司 Treatment process of chromium-containing wastewater
CN112079507A (en) * 2020-08-27 2020-12-15 河钢承德钒钛新材料有限公司 Method for producing anhydrous sodium sulphate from vanadium extraction wastewater

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3136002A1 (en) * 1981-09-11 1983-03-31 GfE Gesellschaft für Elektrometallurgie mbH, 4000 Düsseldorf Process for recovering vanadium and chromium from the effluent of vanadium production
RU2003112715A (en) * 2003-02-03 2005-01-10 НПО "Ванадий-катализатор" (KZ) METHOD FOR PROCESSING CONVERTER VANADIUM CONTAINING SLAGS
CN101054630A (en) * 2007-05-28 2007-10-17 德物华经济信息研究院有限公司 Integrated treatment method for the three wastes generated form method of extracting vanadium pentoxide from stone-like coal navajoite
CN101716457A (en) * 2009-12-30 2010-06-02 湖北郧西隆昌钒业有限公司 Method for treating calcination fume and vanadium-deposition waste water in vanadium extracting production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3136002A1 (en) * 1981-09-11 1983-03-31 GfE Gesellschaft für Elektrometallurgie mbH, 4000 Düsseldorf Process for recovering vanadium and chromium from the effluent of vanadium production
RU2003112715A (en) * 2003-02-03 2005-01-10 НПО "Ванадий-катализатор" (KZ) METHOD FOR PROCESSING CONVERTER VANADIUM CONTAINING SLAGS
CN101054630A (en) * 2007-05-28 2007-10-17 德物华经济信息研究院有限公司 Integrated treatment method for the three wastes generated form method of extracting vanadium pentoxide from stone-like coal navajoite
CN101716457A (en) * 2009-12-30 2010-06-02 湖北郧西隆昌钒业有限公司 Method for treating calcination fume and vanadium-deposition waste water in vanadium extracting production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘莎等: "五氧化二钒生产中的污染问题及治理研究", 《环境科学与管理》, vol. 33, no. 9, 30 September 2008 (2008-09-30) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105800648A (en) * 2016-03-07 2016-07-27 攀钢集团攀枝花钢钒有限公司 Application method of ammonium sulfate prepared from smelting offgas
CN105800648B (en) * 2016-03-07 2018-02-02 攀钢集团攀枝花钢钒有限公司 The Application way for the ammonium sulfate that flue gas during smelting is produced
CN110642430A (en) * 2019-10-31 2020-01-03 重庆雅丽洁环保产业发展有限公司 Treatment process of chromium-containing wastewater
CN112079507A (en) * 2020-08-27 2020-12-15 河钢承德钒钛新材料有限公司 Method for producing anhydrous sodium sulphate from vanadium extraction wastewater

Similar Documents

Publication Publication Date Title
CN108480360B (en) Method for recycling fly ash resources and discharging tail gas in ultra-clean mode by melting method of rotary kiln
CN101709390B (en) On-line circulation method for process for extracting vanadium from stone coal
CN102603098B (en) Circular processing method of stainless steel acid washing waste liquid
CN102534187B (en) Method for treating pyrite cinder by combining acidic leaching with alkaline dissolving
CN101554561B (en) Technical method for combining deamination and desulfurization
CN113149263B (en) Method for treating acidic wastewater by resource utilization of sodium-based desulfurized fly ash
CN104862485A (en) Vanadium and tungsten separating and purifying method for spent vanadium and tungsten SCR (selective catalytic reduction) catalysts
CN108159862A (en) The technique that a kind of composite assistants strengthen low-temperature flue gas simultaneous SO_2 and NO removal
CN113909260A (en) Manganese product clean production and resource recycling treatment process
CN103585869A (en) Flue gas purifying method with recyclable alkali absorption liquid
CN101301560B (en) Comprehensive utilization method of sintered pollutant
CN101983751A (en) Device and method for removing smoke pollutants of sintering machine
CN103205574A (en) Comprehensive control and utilization method of vanadium precipitation waste water and kiln and furnace flue gas
CN112403186A (en) Method for cooperatively treating multi-pollutant flue gas and recovering ammonium ferrous sulfite
CN101862590A (en) Desulfuration process for sintering flue gas
CN112403184B (en) Method for recovering various sulfur resources by using sintering flue gas
CN201832542U (en) Selective flue gas desulfuration and denitration apparatus for sintering machines
CN102825059A (en) Safe pretreatment method for resource utilization of incinerated fly ash
CN105080317A (en) Method for simultaneously reclaiming sulfur and nitrate
CN209968029U (en) Waste gas treatment system for recycling metal surface treatment waste
CN104353351B (en) A kind of by converting waste caustic soda for the industrialized process for preparing of sodium bicarbonate in gas cleaning
CN103351076B (en) Comprehensive industrial wastewater processing method
CN108105760B (en) A kind of method of fire coal circulating fluid bed boiler exhaust gas phosphate ore pulp desulfurization co-production ammonium magnesium phosphate
CN103143251B (en) Purification method for industrial emission gas
CN105668755A (en) Method for resourcefully using vanadium extracting wastewater for producing ammonia-hydrocarbon denitrifying agent

Legal Events

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

Application publication date: 20130717

WD01 Invention patent application deemed withdrawn after publication