CN105668755B - A kind of method of the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia- - Google Patents
A kind of method of the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia- Download PDFInfo
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- CN105668755B CN105668755B CN201610226469.6A CN201610226469A CN105668755B CN 105668755 B CN105668755 B CN 105668755B CN 201610226469 A CN201610226469 A CN 201610226469A CN 105668755 B CN105668755 B CN 105668755B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
A kind of method of the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-, includes the following steps: that vanadium extracting waste water is placed in tank or pond by (1), adds aqueous property regulator adjustment pH value to 5.5~11, obtains solution A；(2) using solution A as primary raw material and NOXReducing agent, denitration promotor ingredient together, are by mass percentage solution A 40~90%, NOXThe ratio ingredient of reducing agent 9.9~50%, denitration promotor 0.1~10%, under stiring by NOXReducing agent, denitration promotor be added solution A in be made uniform liquid to get.The present invention is simple and practical, and investment is small, and processing operation energy consumption is very low, can thoroughly solve the technical problem seriously polluted for restricting the vanadium-containing water of vanadium product industrial sustainable development, improve Business Economic Benefit, be conducive to energy-saving and environmental protection.
Description
Technical field
The present invention relates to environmental protection and waste utilization fields, produce dry-process rotary kiln water more particularly, to a kind of resource utilization vanadium extracting waste water
The method of the hydrocarbon denitrfying agent of the industrial ammonia-of mud.
Background technique
Vanadium product purpose is extensive, and the raw material of vanadium extraction includes mineral series containing vanadium such as bone coal, vanadium titano-magnetite, vanadium slag etc.,
Currently, economy is preferably largest for vanadium titano-magnetite metallurgical slag-vanadium slag.The main method of vanadium extraction have sodium roasting,
Calcification baking, saltless roasting etc..The vanadium extracting waste water of sodium roasting occurs mainly with supernatant waste residue and filtering during precipitation
Filtrate in dehydration, the main polluted factors in waste water have PH, V5+、Cr6+、Fe2+、Mn5+、Ti2+、NH4 +、Na+、SO4 2-、Cl-
Deng.The vanadium extracting waste water of calcification baking occurs mainly with the waste water that waste water during filtration washing and acidleach residual washing-out generate,
Main polluted factors in vanadium wastewater have PH, V5+、Cr6+, Fe, Mn, P, Mg and SO4 2- Deng.Sodium and calcification baking vanadium extraction are useless
The maximum difference of water is that sodium roasting uses ammonium salt precipitation, general without the ammonia nitrogen concentration recycled in its disposable waste water
I.e. up to 5400mg/L or higher, and ammonium salt precipitation is not generally used in calcification baking technique, therefore ammonia nitrogen concentration is very in its waste water
It is small.But no matter which kind of the method vanadium extraction of which kind of raw material used, can all generate in vanadium process of producing product largely containing high price vanadium,
The waste water of the heavy metal ion such as chromium, titanium, manganese, and due to vanadium extraction production in, sal-ammoniac or ammonium sulfate, sodium carbonate, sodium chloride and sulphur
The utilization rate of the industrial chemicals such as acid is relatively low, and the pollutant kind of generation is more, toxicity is big, discharge amount is big, harm is heavy.With current domestic
Produce V2O5Or V2O3Main method-Leaching of Vanadium from Vanadium slag for, using Converter Vanadium-bearing Slag as raw material, using vanadium slag grinding-complex salt,
Thick vanadium-piece vanadium-powder the vanadium-of alkali-sodium oxide baking-water logging-acidity ammonia salt precipitation-washing ammonium poly-vanadate-is also primary
Produce V2O5Or V2O3Technique, during precipitation, vanadic acid root is largely combined to form ammonium poly-vanadate or ammonium metavanadate with ammonium ion
Precipitating, chromate or dichromate ion and precipitate others titaniums, manganese etc. under halfway vanadic acid root and acid condition because not precipitating
Water soluble ion or ion cluster stay together enters upper liquid in the solution, part ammonium vanadate and other water-soluble when washing ammonium poly-vanadate
Property metal ion etc. is soluble in water.Therefore, precipitation, contain ammonium chromate ((CH in the waste water generated in water-washing process4)2Cr2O7), sodium chromate (Na2CrO4), ammonium vanadate ((CH4)2V6O16), sodium metavanadate (Na VO3), vanadic acid hydrogen ammonium (sodium) (such as Na
H3V2O7), sodium manganate, titanium sulfate etc. and a large amount of sodium salt, free acid, and because raw material is different, sodium or calcification method it is different and
The part of vanadium-containing water recycles mode and degree is different, the pollutants such as heavy metal component content and ammonia nitrogen in vanadium-containing water
Content etc. has very big difference, and waste component is relatively stable under same materials and process conditions.One ton of V of every production2O5It generates about
30~60m3Vanadium extracting waste water, the main physico-chemical property fluctuation range of all kinds of vanadium-containing waters:
Obviously, the harm of vanadium extracting waste water includes complicated heavy metal pollution, ammonia and nitrogen pollution, high concentration chloride and sulfate radical
Pollution etc., it is necessary for implementing comprehensive harmless treatment.But so far, it is useless to be concentrated mainly on extraction for the processing technique of vanadium extracting waste water
Heavy metal vanadium, chromium in water etc. and processing waste water in ammonia nitrogen in high density the two aspect.
1) processing technique about heavy metal vanadium, chromium, manganese in vanadium extracting waste water etc., researchs and develops for a long time both at home and abroad
Up to more than 20, these methods for solving heavy metal vanadium, chromium, manganese in vanadium extracting waste water etc. are broadly divided into as follows application method
Four major class:
The first kind is physical method: predominantly absorption method, such as kieselguhr adsorption method, Activated Zeolite Adsorption, active carbon adsorption, pine
Sawdust absorption method etc., such method is using relatively simple, but process flow is long, investment is larger, operating cost is higher and brings two
Secondary pollution.
Second class is chemical method: mainly having iron filings or iron sulfate precipitation method, the sulfur dioxide precipitation method, barium salt process (chlorination
Barium method etc.), iron barium salt process (ferric trichloride-barium sulphide method), high vanadium ferroalloy method etc..As Chinese patent CN102337411A provides one
The method that kind recycles vanadium and chromium from the low vanadium vanadium wastewater of high chromium, Chinese patent CN103922454A provide a kind of acid precipitation
The method of removal of manganese from waste water.The application of these methods is mature, but process flow is long, and investment is big mostly, and operating cost is high, and there are waste residues
The secondary pollutions such as processing.
Third class is physical-chemical process: mainly having ion-exchange, solvent extraction, membrane separation process (hyperfiltration, electric osmose
Analysis, membrane extraction, ultrafiltration etc.), electrolysis method and electrolysis+catalysis method etc..Physical-chemical process has gradually formed one in environmentally friendly application aspect
It is the effective method of example, but handles that its process flow is long, investment is big, operating cost is still higher for the heavy metal of vanadium extracting waste water,
And there are secondary pollutions.
4th class is bioanalysis: mainly have anaerobic biological process, aerobe method, if it can select suitable flora can it is low at
This processing, but the breeding of flora is extremely difficult for vanadium chromium waste water, and there are subsequent processings and secondary pollution.
Currently, chemical precipitation method (iron barium salt process, iron are industrially taken mostly for the processing of the heavy metal in vanadium extracting waste water
Bits or iron sulfate precipitation method, the sulfur dioxide precipitation method, high vanadium ferroalloy method) and ion-exchange.Wherein reduction neutralisation is in industry
On be most widely used, reducing agent used has: ferrous sulfate, iron filings, granulated iron, sponge iron, waste fused salt, sulfur dioxide, sulfurous
Sour sodium, sodium pyrosulfite, sodium hydrogensulfite, sodium thiosulfate, vulcanized sodium, Bentiromide.Neutralizer have sodium hydroxide, lime,
Soda ash.
2) processing technique about the ammonia nitrogen in high density in vanadium extracting waste water:
Vanadium-containing water belongs to the highly acid high-concentration ammonia nitrogenous wastewater containing contents of many kinds of heavy metal ion such as vanadium, chromium, titanium, manganese, iron, nitre
The activity and breeding for changing bacterium and denitrifying bacterium are suppressed, therefore mainly use physical method and chemistry for such ammonia nitrogen waste water
Method.
Physical method has reverse osmosis, distillation, and chemical method has ion-exchange, air stripping, chemical precipitation method, breakpoint chlorination
Method, electroosmose process, electrochemical treatment, Coordination Adsorption method, microwave method, catalytic pyrolysis etc..But the process flow length of the above method,
Investment is big, and running cost is high, and will cause certain secondary pollution.
Followed by Biochemical method, in recent years, culture utilization is aerobic or the Study on processing method of anaerobic bacteria is in the ascendant,
The cultivation and exploitation technique of especially Anammox (bacterium) technique has become one important development of vanadium-containing water processing technique and becomes
Gesture, but different kind organism method is objectively still in laboratory stage.
Air stripping method is mostly industrially now used, and chemical precipitation method (is such as precipitated as NH4MgPO4·6H2O crystalline solid)
Effect is limited, there is not yet being used for industrial production.
3) processing technique about the high concentration chloride of vanadium extracting waste water and sulfate pollution
Under laboratory condition, removing for sulfate radical can be used barium salt process (barium chloride, barium hydroxide etc.) and effectively precipitate
Sulfate radical is removed, but is dfficult to apply to vanadium extracting waste water, because pretreatment process is complicated and barium salt cost is high.
Equally, under laboratory condition, removing for chlorine root, resin such as D201 anion exchange resin, which can be used, to be had
Effect removal part chloride ion, but industrial processing complex procedures, operating cost are high-leveled and difficult to bear.
The now industrially disposition for high concentration chloride and sulfate radical concentrating spent liquor, except a small amount of multistage for taking highly energy-consuming
Vacuum distillation, condensing crystallizing recycling are outer, and the disposal options generally taken are to try every possible means directly to put aside as useless.
In fact, being referred to according to the related sewage discharge of " vanadium emission of industrial pollutants standard " (GB26452-2011) control
In mark, vanadium, chromium and PH after the reduction of the higher cost of complex process, neutralisation treatment in waste water are easy to up to standard, but NH4-N
(ammonia nitrogen), COD(COD), SS(suspended matter) be difficult to control, the processing difficulty of especially ammonia nitrogen is very big, it is domestic now also
Have not seen that vanadium-containing water NH_3-N treating problem up to standard is the current country in relation to vanadium-containing water NH_3-N treating objectively report up to standard
The very intractable problem that vanadium products factory wastewater treatment is faced, currently comparatively effective processing method mainly has
" air stripping+oxidation removes ammonia " or " stripping ammonia nitrogen+evaporation and concentration " or " stripping ammonia nitrogen+absorption " two-stage treatment technology and " electricity
Solution+catalysis oxidation " technology, but the process flow of these methods is long, and equipment is more complex, and investment is big, and energy consumption is high, and there are secondary dirts
It contaminates, and still remain a large amount of thick slurry waste liquids after ammonia nitrogen removal to transport outward disposition.
Obviously, although above-mentioned technical method is related to the processing of each pollutant in vanadium extracting waste water, but, one side technique stream
Journey is long, and investment is big, and energy consumption is high, at high cost, and on the other hand, there are still waste residue and concentrate problem to be treated and secondary dirts
Dye, and the recycling of various compositions especially ammonia nitrogen, salt and moisture content resource in vanadium extracting waste water is ignored, it does not meet green, low
Carbon, recycling economy development theory.
In consideration of it, the harmless treatment of vanadium extracting waste water is synchronized and is resolved there is an urgent need to there is a kind of completely new idea and method
In vanadium extracting waste water the problems such as complicated heavy metal pollution, the pollution of phenol cyanogen, ammonia and nitrogen pollution, high concentration chloride and sulfate pollution, energy
Achieve the purpose that resource utilization is turned harm into good.
On the other hand, China is energy consumption big country, and the mainly fossil energy currently consumed, annual Industrial Stoves number
The burning of 1000000000 tons of fossil energies needs to implement environment-friendlydenitration denitration, for solve denitration environmental issue, need to consume a large amount of vanadium, chromium,
Denitration catalyst and denitration reducing agent ammonium hydroxide, urea based on titanium etc., the wherein catalyst of tunnel gas catalytic denitration
It is the elements such as vanadium, chromium, titanium, the denitration of (600~1200 DEG C) denitration is ammonium hydroxide and/or urea with reducing agent in kiln.
It is well known that Industrial Stoves burning is hydrogen > hydrocarbon (such as first in denitration effect in 600~1200 DEG C of temperature ranges
Alkane, ethane etc.) > ammonia, urea, but the denitration that Industrial Stoves burning at present is used in the denitration of 600~1200 DEG C of temperature ranges is former
Material exactly can industrial-scale production and the ammonium hydroxide or urea that are readily transported.Denitration in the stove with dry-process rotary kilns production line is
Example, the daily denitration of the clinker production line of a 2500t/d with reducing agent ammonium hydroxide (concentration 20~24%) measure generally 15~20 tons/
It, and the actual design production capacity of the cement of current National is 3,500,000,000 tons/year.Obviously, environment-friendlydenitration denitration one is carried out using ammonia or urea
Aspect and agricultural strive fertilizer, on the other hand increase energy consumption and environmental pollution indirectly because the production energy consumption of ammonia, urine is high, pollution is big.
And contain available denitrating catalyst metallic element, available ammonia nitrogen denitrfying agent and the water such as a large amount of vanadium, chromium, titanium in vanadium extracting waste water
How inorganic salts mineralising sintering aid needed for mud production, break through traditional processing pollutant thoughtcast, then turn harm into good
Resource utilization vanadium extracting waste water, there is an urgent need to a kind of completely new technical methods.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of lower-cost recycling
Utilize the method for the vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-.
The present invention is to solve the technical problem of vanadium extracting waste water environmental protection treatment and resource utilization, provide it is a kind of can be easy,
Component in the resource utilization vanadium extracting waste water of low cost, using vanadium extracting waste water as main material production ammonia-hydrocarbon denitrfying agent, i.e., directly
Connect using in vanadium extracting waste water water-soluble vanadium, chromium, titanium plasma as industrial furnace smoke denitrating catalyst, in vanadium extracting waste water
Ammonia nitrogen as available ammonia nitrogen denitrfying agent component, using the moisture in vanadium extracting waste water as safety solvent, in vanadium extracting waste water
Metal ion and sulphur chlorine fluorine phosphorus etc. be converted into the mineralising of clinker production during dry-process rotary kilns production application and help
Agent is burnt, and whole heavy metal ion are melted admittedly effectively with silicon/aluminic acid root ball, prevents secondary pollution.
The technical solution used to solve the technical problems of the present invention is that a kind of resource utilization vanadium extracting waste water produces ammonia-carbon
The method of hydrogen denitrfying agent mainly includes the following steps: using vanadium extracting waste water as main material production ammonia-hydrocarbon denitrfying agent
(1) it adjusts vanadium extracting waste water property: vanadium extracting waste water is placed in tank or pond, add aqueous property regulator adjustment pH value extremely
The preferred PH 6~9 of 5.5~11(), obtain solution A；
The aqueous property regulator is containing-NH2、-NH-、NH4 +Or/and NH3Compound, preferably monoethanolamine, diethyl
At least one of hydramine, triethanolamine, isopropanolamine, (2-hydroxyethyl)methylamine), dimethyl monoethanolamine, ammonia, ammonium carbonate etc..
The dosage of the aqueous property regulator be subject to vanadium extracting waste water pH value to the preferred PH 6~9 of 5.5~11().
(2) the hydrocarbon denitrfying agent of preparing ammonia-: using step (1) resulting solution A as primary raw material and NOXReducing agent, denitration
Promotor ingredient together, is by mass percentage solution A 40~90%, NOXReducing agent 9.9~50%, denitration promotor 0.1
~10% ratio ingredient, (preferred mass percentage is solution A 50~85%, reducing agent 14~45%, promotor 1~5%
Ratio ingredient), under stiring by NOXReducing agent, denitration promotor, which are added in solution A, is made uniform liquid, obtains ammonia-carbon
Hydrogen denitrfying agent.
The NOXReducing agent refers to the (- NH containing amino that denitration reaction can be realized in 600~1200 DEG C of temperature ranges2、-
NH-、、NH4 +And/or NH3) and/or compound containing aldehyde radical and/or phenolic hydroxy group and/or hydroxyl and/or bis- containing C=C
At least one of compound of key, preferred polymeric hydramine, methyl diethanolamine, monoethanolamine, diethanol amine, triethanolamine,
Diisopropanolamine (DIPA), dimethylamine, aniline, hydroxyethyl ethylenediamine, ethylenediamine, Tyrosine, ammonia, urea, ammonium carbonate, ammonium hydrogencarbonate, second
At least one of alkene of sour ammonia, acetaldehyde, propionic aldehyde, glucose, phenol, propyl alcohol, isopropanol, C6~12 etc..
The denitration promotor, which refers to, can generate ionic hydrogen, the substance of hydrogen and/or the substance that has denitration catalyst to act on, preferably city
Hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine nitrate, carbohydrazide, acethydrazide, diformylhydrazine, the dihydro sold are bis- (2- methoxy ethoxy)
At least one of sodium aluminate, ammonium metavanadate, ammonium chromate etc..
Further, above-mentioned vanadium extracting waste water, aqueous property regulator, NOXReducing agent, denitration promotor each raw material composition
Selection need to consider mutual Antagonism and concertedness.
Further, in step (1), the vanadium extracting waste water is the vanadium-containing water generated in all kinds of vanadium extraction production processes,
Or vanadium-containing water recycles the high concentration vanadium-containing water or preprocessed (such as through chemical precipitation method or ion-exchange of generation
Processing) after the high ammonia nitrogen vanadium extracting waste water of high chlorine.
Technical principle of the invention:
1) it is directed to the feature of vanadium extracting waste water, especially in sodium roasting-water logging-acidity ammonia salt precipitation art production process
The physicochemical properties feature for the high concentration vanadium-containing water that the vanadium-containing water or cycling utilization of wastewater of generation generate, according to vanadium extracting waste water
In each material composition feature, from can functionally be considered as three big material components, the first big functional raw material component is objectively
It can be used as elements and the denitrification reducing agent ammonia nitrogen compounds such as the denitrating catalyst component vanadium, chromium, titanium of catalytic denitration；The second largest function
Energy property material component is in fact that can improve cement slurry burn-ability, reduce sinter leaching heat consumption, improve sinter leaching quality
Mineralising sintering aid, including suitable vanadium Cr-Mn-Ti potassium sodium thion chloride fluoride element；The third-largest material component is water, and current is common de-
Ammonia used in nitre reducing agent, urea are all made of aqueous solution, and wherein ammonia is generally tuned into 20~24% aqueous solution of concentration, and urea generally adds
Water is dissolved into the aqueous solution of concentration about 40%.The three big raw materials that all material in resource utilization vanadium extracting waste water of the present invention is constituted
Component is directly restored using elements such as water-soluble vanadium, chromium, titaniums in vanadium extracting waste water as denitrating catalyst and ammonia nitrogen as denitration
Agent；Using the moisture in vanadium extracting waste water as safety solvent.I.e. using vanadium extracting waste water as primary raw material, adjustment vanadium extracting waste water
Matter, the insufficient NO of supplementXReducing agent component is aided with NOXDenitration promotor, for producing industrial kiln denitrfying agent-ammonia-carbon
Hydrogen denitrfying agent.
2) big for industrial furnace coal fines dosage, the grey quantity of slag is big, utilizes the limited amount vanadium Cr-Mn-Ti potassium in vanadium extracting waste water
The hydraulicity vivacity of the raising coal ash lime-ash such as the metal ions such as sodium and sulphur chlorine fluorine phosphorus.It is raw in particular for dry-process rotary kilns
Production feature, it is raw equal to cement produced with the dry method using the metal ions such as limited amount vanadium Cr-Mn-Ti potassium sodium in vanadium extracting waste water and sulphur chlorine fluorine phosphorus
The mineralising sintering aid that clinker production is converted into application is produced, caning be controlled in chloride ion in cement content will not be exceeded.
3) it is industrialness grinding (having a certain amount of compared with rough coal grain) for coal dust used in Industrial Stoves, and is big flow
Coal dust firing (is difficult to obtain sufficient oxygen in pulverized coal flow, always has certain reducing atmosphere, kiln space are limited always to have on a small quantity
Coal grain not in time after-flame and fall into coal ash lime-ash or kiln and to generate reduction in material) the characteristics of, by high price toxic vanadium, chromium etc.
It is reduced to the nontoxic metal ion of lower valency, and with dynamics caused by pulverized coal flame high temperature and thermodynamic condition, is promoted
Silicic acid root ball or aluminic acid root ball or aluminosilicate root ball lattice in lime-ash or clinker melt admittedly or the admittedly molten whole heavy metals of package
Ion such as forms aluminosilicate chromium sodium calcium or the stable complicated ion exchange type mineral of aluminosilicate vanadium sodium calcium, thoroughly eliminates vanadium extraction
The possible heavy metal pollution of waste water.
4) with aqueous property regulator leniently solve the problems, such as vanadium extracting waste water deep-etching and with NOx reducing agent, out of stock rush
Fused and synergistic effect function problem can be simply compounded into each raw material composition of agent.
Beneficial effects of the present invention:
1) the technology of the present invention method is simple and practical, and investment is small, and processing operation energy consumption is very low, can thoroughly solve to restrict vanadium
The technical problem of the vanadium-containing water of product industrial sustainable development seriously polluted improves Business Economic Benefit.
2) it is conducive to solve the problems, such as the with high investment of vanadium extracting waste water processing for a long time, high energy consumption, high cost and secondary pollution, benefit
In energy-saving and environmental protection.
3) all material component of energy recycling innoxious use vanadium extracting waste water, can save resource, be conducive to built environment
Friendly conservation-minded society.
4) coal-fired industrial furnace to have a large capacity and a wide range provides a kind of new environmental emission reduction new material and technology, is conducive to promote section
Energy and emission reduction.
5) present invention is green, low-carbon, recycling economy development technology, conducive to implementing industrial transformation and making new growth
Point.
Specific embodiment
Below in conjunction with specific embodiment resource utilization vanadium extracting waste water ammonia-hydrocarbon denitrfying agent that the present invention is further explained
Method.
Embodiment 1
Vanadium extracting waste water selects certain with the vanadium wastewater of vanadium slag sodium roasting, and aqueous property regulator selects a commercially available ethyl alcohol
Amine, NOXReducing agent selects triethanolamine, and denitration promotor selects hydrazine hydrate.It with vanadium extracting waste water is directly according to the following steps main
Waste ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent):
(1) it adjusts vanadium extracting waste water property: vanadium extracting waste water being placed in agitator tank, aqueous property regulator monoethanolamine tune is added
Whole pH value obtains solution A to 6.1；
(2) the hydrocarbon denitrfying agent of preparing ammonia-: using resulting solution A as primary raw material and NOXReducing agent triethanolamine takes off
Nitre promotor hydrazine hydrate ingredient together is by mass percentage solution A 81%, the hydration of reducing agent triethanolamine 17%, promotor
The ratio ingredient of hydrazine 2% will be made uniform molten in reducing agent triethanolamine, promotor hydrazine hydrate addition solution A under stiring
Liquid obtains the hydrocarbon denitrfying agent of ammonia-.
Embodiment 2
Vanadium extracting waste water selects certain with the vanadium wastewater of Rock coal containing alum sodium roasting, and aqueous property regulator selects commercially available N-
Methyl monoethanolamine, NOXReducing agent selects commercially available carbonic acid ammonia and isopropanol, and denitration promotor selects carbohydrazide.According to the following steps
Directly with vanadium extracting waste water for main waste ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent):
(1) it adjusts vanadium extracting waste water property: vanadium extracting waste water being placed in agitator tank, aqueous property regulator N- methyl list second is added
Hydramine adjusts pH value to 6.3, obtains solution A；
(2) the hydrocarbon denitrfying agent of preparing ammonia-: using resulting solution A as primary raw material and NOXReducing agent carbonic acid ammonia and isopropyl
Alcohol, denitration promotor carbohydrazide ingredient together are by mass percentage solution A 75%, reducing agent 21%(wherein carbonic acid ammonia 15%+
Isopropanol 6%), the ratio ingredient of denitration promotor carbohydrazide 4%, under stiring by reducing agent carbonic acid ammonia and isopropanol, promotor
Carbohydrazide is added in solution A and uniform solution is made, and obtains the hydrocarbon denitrfying agent of ammonia-.
Embodiment 3
Vanadium extracting waste water selects vanadium wastewater of certain factory with fluidized bed furnace to Rock coal containing alum progress saltless roasting, the adjustment of aqueous property
Commercially available ammonium carbonate, NO are selected in agentXReducing agent selects commercially available ammonium hydroxide (mass concentration 27%) and glucose (waste liquid), and denitration promotes
Hydrazine hydrate is selected in agent.According to the following steps directly with vanadium extracting waste water for main waste ammonia-hydrocarbon denitrfying agent:
(1) it adjusts vanadium extracting waste water property: vanadium extracting waste water is placed in agitator tank, aqueous property regulator ammonium carbonate is added to adjust
PH value obtains solution A to 7.8；
(2) it the hydrocarbon denitrfying agent of preparing ammonia-: using resulting solution A as primary raw material and reducing agent ammonium hydroxide and glucose, takes off
Nitre promotor hydrazine hydrate ingredient together, is by mass percentage solution A 60%, NOXReducing agent 39%(wherein ammonium hydroxide 35%+ grape
Sugar 4%), the ratio ingredient of promotor hydrazine hydrate 1%, reducing agent ammonium hydroxide and glucose, promotor hydrazine hydrate are added under stiring
Enter and uniform solution is made in solution A, obtains the hydrocarbon denitrfying agent of ammonia-.
Embodiment 4
Vanadium extracting waste water select certain with the pretreated vanadium wastewater of Rock coal containing alum sodium roasting technique (through iron reduction,
In sodium carbonate and filtration treatment) i.e. with chemical precipitation method treated the high dense salt waste water of the high ammonia nitrogen of chlorine, the choosing of aqueous property regulator
With commercially available (2-hydroxyethyl)methylamine), NOXReducing agent selects commercially available ammonium hydroxide (mass concentration 27%) and polyalcohol amine, and denitration promotes
Hydrazine hydrate is selected in agent.According to the following steps directly with vanadium extracting waste water for main waste ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent):
1) it adjusts vanadium extracting waste water property: vanadium extracting waste water (the dense salt waste water of high-content ammonia nitrogen) being placed in agitator tank, aqueous is added
Property regulator (2-hydroxyethyl)methylamine) adjusts pH value to 8, obtains solution A；
(2) the hydrocarbon denitrfying agent of preparing ammonia-: using resulting solution A as primary raw material and NOXReducing agent ammonium hydroxide, polymeric alcohol
Amine and denitration promotor hydrazine hydrate ingredient together are by mass percentage solution A 57%, reducing agent 41%(wherein ammonium hydroxide 31%+
Polyalcohol amine 10%), the ratio ingredient of promotor hydrazine hydrate 2%, under stiring by reducing agent ammonium hydroxide, polyalcohol amine and promotor
Hydrazine hydrate is added in solution A and uniform solution is made, and obtains denitrfying agent.
Embodiment 5
Vanadium extracting waste water selects certain (containing the vanadium) vanadium wastewater of bone coal power plant to Rock coal containing alum saltless roasting, aqueous property tune
Whole dose is selected commercially available ammonium hydroxide, NOXReducing agent selects commercial urea and isopropanol, and denitration promotor selects ammonium metavanadate and chromic acid
Ammonium.According to the following steps directly with vanadium extracting waste water for main waste ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent):
(1) it adjusts vanadium extracting waste water property: vanadium extracting waste water is placed in agitator tank, aqueous property regulator ammonium hydroxide is added to adjust PH
Value obtains solution A to 7.1；
(2) the hydrocarbon denitrfying agent of preparing ammonia-: using resulting solution A as primary raw material and NOXReducing agent, denitration promotor
Ingredient together is by mass percentage solution A 60%, NOXReducing agent 39%(wherein urea 25%+ isopropanol 14%), promotor
1%(wherein ammonium metavanadate 0.5%+ ammonium chromate 0.5%) ratio ingredient, under stiring by reducing agent urea and isopropanol and promotion
Agent ammonium metavanadate and ammonium chromate, which are added in solution A, is made uniform solution, obtains the hydrocarbon denitrfying agent of ammonia one.
Embodiment 6
Amount to the hydrocarbon denitrfying agent of ammonia-(abbreviation denitrfying agent) each 5 of 5 kinds of component differences with 1~embodiment of above-described embodiment 5
Ton, until certain Φ 4x64m dry-process rotary kiln production line, carries out pilot scale comparative test with ammonium hydroxide denitration, which normally produces denitration and adopt
Make denitrfying agent, NO with the ammonium hydroxide of mass concentration 21%X(< 200mg/Nm up to standard3) discharge when ammonia volume average out to 0.76t/h.
Pilot plant test is shown:
1) 5 kinds of hydrocarbon denitrfying agents of ammonia-of embodiment 1 to embodiment 5 have a good denitration effect, and dosage 0.51~
NO when 0.67t/hXOn-line checking < 200mg/Nm3, environment-friendlydenitration denitration index can be up to standard, and denitration effect is better than traditional ammonium hydroxide denitration
Agent.
2) resulting clinker carries out weight by standard GB/T 5086.2-1997 " solid waste Leaching leaching method "
Vanadium, chromium is not detected in metal leaching toxicity test, illustrates that the sial acid group hot setting of heavy metal element is very thoroughly very stable.
3) resulting clinker carries out chloride test, right with blank clinker (clinker for not adding catalytic combustion adjuvant for coal)
Than chloride ion content increases (chloride ion content changes in the error range of detection) without obvious in clinker.
The test result of five groups of pilot scales may validate that the resource utilization vanadium extracting waste water production hydrocarbon denitration of ammonia-of the invention
The method of agent is feasible.The technology of the present invention method is simple and practical, and investment is small, and processing operation energy consumption is very low, can thoroughly solve to make
The about technical problem of the vanadium-containing water of vanadium product industrial sustainable development seriously polluted improves Business Economic Benefit.Conducive to solution
Certainly the with high investment of vanadium extracting waste water processing for a long time, high energy consumption, high cost and secondary pollution problem, are conducive to environmental protection.
Claims (6)
1. a kind of method of the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-, which comprises the steps of:
(1) it adjusts vanadium extracting waste water property: vanadium extracting waste water is placed in tank or pond, aqueous property regulator is added to adjust pH value to 5.5
~11, obtain solution A；
The aqueous property regulator is containing-NH2、-NH-、NH4 +Or/and NH3Compound；
(2) the hydrocarbon denitrfying agent of preparing ammonia-: using step (1) resulting solution A as primary raw material and NOXReducing agent, denitration promote
Agent ingredient together, is by mass percentage solution A 40~90%, NOXReducing agent 9.9~50%, denitration promotor 0.1~10%
Ratio ingredient, under stiring by NOXReducing agent, denitration promotor, which are added in solution A, is made uniform liquid, obtains ammonia-
Hydrocarbon denitrfying agent；
The NOXReducing agent is polyalcohol amine, methyl diethanolamine, monoethanolamine, diethanol amine, triethanolamine, diisopropanol
Amine, dimethylamine, aniline, hydroxyethyl ethylenediamine, ethylenediamine, Tyrosine, ammonia, urea, ammonium carbonate, acetic acid ammonia, glucose, phenol,
At least one of propyl alcohol, isopropanol；
The denitration promotor is hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine nitrate, carbohydrazide, acethydrazide, diformylhydrazine, metavanadic acid
At least one of ammonium, ammonium chromate.
2. the method for the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-according to claim 1, feature exist
In adding aqueous property regulator to adjust vanadium extracting waste water pH value to 6~9 in step (1).
3. the method for the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-according to claim 1 or 2, feature
It is, in step (1), the aqueous property regulator is monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, N- methyl
At least one of monoethanolamine, dimethyl monoethanolamine, ammonia, ammonium carbonate.
4. the method for the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-according to claim 1 or 2, feature
It is, in step (2), each quality of material percentage is solution A 50~85%, NOXReducing agent 14~45%, denitration promotor 1
~5%.
5. the method for the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-according to claim 1 or 2, feature
It is, in step (1), the vanadium extracting waste water, for the vanadium-containing water generated in all kinds of vanadium extraction production processes.
6. the method for the resource utilization vanadium extracting waste water production hydrocarbon denitrfying agent of ammonia-according to claim 1 or 2, feature
It is, in step (1), the vanadium extracting waste water is the high high ammonia nitrogen vanadium extracting waste water of chlorine after pretreatment.
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| CN101412539A (en) * | 2008-11-18 | 2009-04-22 | 攀钢集团研究院有限公司 | Clean production process for vanadium oxide |
| CN101509070A (en) * | 2009-03-27 | 2009-08-19 | 攀钢集团研究院有限公司 | Method for acid leaching extraction of vanadium from vanadium-containing raw material |
| CN101709390A (en) * | 2009-12-15 | 2010-05-19 | 武汉科技大学 | On-line circulation method for process for extracting vanadium from stone coal |
| CN103816789A (en) * | 2014-02-14 | 2014-05-28 | 山东紫晶光电新材料有限公司 | Alkaline denitration absorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412539A (en) * | 2008-11-18 | 2009-04-22 | 攀钢集团研究院有限公司 | Clean production process for vanadium oxide |
| CN101509070A (en) * | 2009-03-27 | 2009-08-19 | 攀钢集团研究院有限公司 | Method for acid leaching extraction of vanadium from vanadium-containing raw material |
| CN101709390A (en) * | 2009-12-15 | 2010-05-19 | 武汉科技大学 | On-line circulation method for process for extracting vanadium from stone coal |
| CN103816789A (en) * | 2014-02-14 | 2014-05-28 | 山东紫晶光电新材料有限公司 | Alkaline denitration absorbent |
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