CN105668755A - Method for resourcefully using vanadium extracting wastewater for producing ammonia-hydrocarbon denitrifying agent - Google Patents
Method for resourcefully using vanadium extracting wastewater for producing ammonia-hydrocarbon denitrifying agent Download PDFInfo
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- CN105668755A CN105668755A CN201610226469.6A CN201610226469A CN105668755A CN 105668755 A CN105668755 A CN 105668755A CN 201610226469 A CN201610226469 A CN 201610226469A CN 105668755 A CN105668755 A CN 105668755A
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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 method for resourcefully using vanadium extracting wastewater for producing an ammonia-hydrocarbon denitrifying agent includes the following steps of firstly, putting vanadium extracting wastewater in a stirring tank or pool, and adding a liquid property adjusting agent to adjust the pH value to be 5.5-11 to obtain a solution A; secondly, preparing a material from, by mass, 40-90% of solution A as the main raw material, 9.9-50% of NOX reducing agent and 0.1-10% of denitrifying accelerant, and adding the NOX reducing agent and the denitrifying accelerant to the solution A over stirring to prepare uniform liquid, namely, the ammonia-hydrocarbon denitrifying agent.The method is simple and practical, small in investment and quite low in treatment operating energy consumption, the technical problem of severe pollution of vanadium-containing wastewater for restraining the sustainable development of the vanadium product industry can be thoroughly solved, the economic benefits are improved for enterprises, and energy conservation, consumption reduction and environment protection are facilitated.
Description
Technical field
The present invention relates to environmental protection and waste utilization field, especially relate to a kind of method that recycling vanadium extracting waste water produces the industrial ammonia of dry-process rotary kilns-hydrocarbon denitrfying agent.
Background technology
Vanadium end-use is extensive, and the raw material of vanadium extraction comprises the mineral series containing vanadium such as bone coal, vanadium titano-magnetite, vanadium slag etc., and currently, economy is preferably largest is vanadium titano-magnetite metallurgical slag-vanadium slag. The main method of vanadium extraction has sodium roasting, calcification baking, saltless roasting etc. The vanadium extracting waste water of sodium roasting mainly results from the supernatant waste residue in precipitation process and the filtrate in filter dehydration, and the main polluted factors in waste water has PH, V5+、Cr6+、Fe2+、Mn5+、Ti2+、NH4 +、Na+、SO4 2-、Cl-Deng. The vanadium extracting waste water of calcification baking mainly results from the waste water in filtration washing process and the waste water of acidleach residual washing-out generation, and the main polluted factors in vanadium wastewater has PH, V5+、Cr6+, Fe, Mn, P, Mg and SO4 2-Deng. The maximum difference of sodium and calcification baking vanadium extracting waste water is that sodium roasting adopts ammonium salt precipitation, 5400mg/L or higher generally can be reached without the ammonia nitrogen concentration in its disposable waste water of recycle, and generally do not adopt ammonium salt precipitation in calcification baking technique, therefore in its waste water, ammonia nitrogen concentration is very little. But no matter adopt which kind of the method vanadium extraction of which kind of raw material, vanadium process of producing product all can produce a large amount of waste water containing heavy metal ion such as high price vanadium, chromium, titanium, manganese, and due in vanadium extraction production, the utilization ratio of the industrial chemicals such as ammonia chloride or ammonium sulfate, sodium carbonate, sodium-chlor and sulfuric acid is on the low side, and the pollutant kind of generation is many, toxicity is big, quantity discharged is big, harm is heavy. With current domestic production V2O5Or V2O3Main method Leaching of Vanadium from Vanadium slag be example, taking converter vanadium slag as raw material, adopt the acid ammonia salt precipitation washing ammonium poly-vanadate thick vanadium sheet vanadium powder vanadium also original production V of vanadium slag powder grinding-in salt, alkali sodium oxide baking water logging2O5Or V2O3Technique, in its precipitation process, vanadic acid root is combined in a large number with ammonium radical ion and forms ammonium poly-vanadate or ammonium metavanadate precipitate, chromate or dichromate ion be not because precipitating, with precipitation not vanadic acid root thoroughly, and under acidic conditions other titanium, the water soluble ion such as manganese or ionic group stay together and enter upper liquid in the solution, during washing ammonium poly-vanadate, part ammonium vanadate and other water-soluble metal ion etc. are dissolved in water. Therefore, containing ammonium chromate ((CH in the waste water produced in its precipitation, water washing process4)2Cr2O7), Sodium chromate (Na2CrO4), ammonium vanadate ((CH4)2V6O16), sodium metavanadate (NaVO3), vanadic acid hydrogen ammonium (sodium) is (such as NaH3V2O7), sodium manganate, titanium sulfate etc. and a large amount of sodium salts, free acid, and because raw material is different, sodium or calcification method is different and the part recycle mode of vanadium-containing water and degree different, the pollutant load etc. such as heavy metal component content and ammonia nitrogen in vanadium-containing water has very big difference, and under same materials and processing condition, waste water composition is relatively stable.Often produce one ton of V2O5Produce about 30～60m3Vanadium extracting waste water, the main physico-chemical property fluctuation range of all kinds of vanadium-containing water:
Obviously, the harm of vanadium extracting waste water includes complicated heavy metal contamination, ammonia and nitrogen pollution, high concentration chloride and sulfate pollution etc., and it is necessary for implementing comprehensive harmless treatment. So far, but the process technology of vanadium extracting waste water mainly concentrates on the heavy metal vanadium in extraction waste water, chromium etc. and these two aspects of ammonia nitrogen in high density in process waste water.
1) about the process technology of the heavy metal vanadium in vanadium extracting waste water, chromium, manganese etc., the application method researched and developed for a long time both at home and abroad has reached more than 20 kinds, and these methods solving the heavy metal vanadium in vanadium extracting waste water, chromium, manganese etc. are broadly divided into following four big classes:
The first kind is physics method: be mainly absorption method, and such as diatomite adsorption method, Activated Zeolite Adsorption, active carbon adsorption, pine sawdust absorption method etc., the application of such method is comparatively simple, but technical process length, investment are relatively big, running cost is higher and brings secondary pollution.
2nd class is chemical method: mainly contain iron filings or the ferrous sulfate precipitator method, the sulfurous gas precipitator method, barium salt method (barium chloride method etc.), iron barium salt method (iron trichloride-barium sulphide method), high vanadium ferroalloy method etc. As Chinese patent CN102337411A provides a kind of method reclaiming vanadium and chromium from the low vanadium vanadium wastewater of high chromium, Chinese patent CN103922454A provides the method for a kind of acid waste water for depositing vanadium except manganese. The application of these methods is ripe, but technical process is long, and investment is big mostly, running cost height, and there is the secondary pollutions such as Solid state fermentation.
3rd class is physico-chemical processes: mainly contain ion exchange method, solvent extration, membrane separation process (reverse osmosis method, electrodialysis, membrane extraction, ultrafiltration etc.), electrolytic process and electrolysis+catalysis method etc. It is the effective method of example that physico-chemical processes progressively forms one in environmental protection application aspect, but for vanadium extracting waste water heavy metal processes its technical process length, investment is big, working cost is still higher, and there is secondary pollution.
4th class is biological process: mainly contain anaerobic biological process, aerobe method, if suitable bacterium group can be selected, can the process of low cost, but extremely difficult for the seed selection of bacterium group vanadium chrome waste water, and there is subsequent disposal and secondary pollution.
Currently, chemical precipitation method (iron barium salt method, iron filings or the ferrous sulfate precipitator method, the sulfurous gas precipitator method, high vanadium ferroalloy method) and ion exchange method are taked in the industrial process for the heavy metal in vanadium extracting waste water mostly. Neutralisation of wherein reducing industrially is most widely used, and reductive agent used has: ferrous sulfate, iron filings, granulated iron, sponge iron, waste fused salt, sulfurous gas, S-WAT, Sodium Pyrosulfite, sodium bisulfite, Sulfothiorine, sodium sulphite, bentiromide. Neutralizing agent has sodium hydroxide, lime, soda ash.
2) about the process technology of the ammonia nitrogen in high density in vanadium extracting waste water:
Vanadium-containing water belongs to the strongly-acid high-concentration ammonia nitrogenous wastewater containing contents of many kinds of heavy metal ion such as vanadium, chromium, titanium, manganese, iron, and activity and the breeding of nitrifier and denitrifying bacteria are suppressed, and therefore this type of ammonia nitrogen waste water are mainly adopted to physics method and chemical method.
Physics method has reverse osmosis, distillation, and its chemical method has ion exchange method, air stripping, chemical precipitation method, breakpoint chlorination method, electroosmose process, electrochemical treatment method, coordination absorption method, microwave method, catalytic pyrolysis etc. But the technical process length of aforesaid method, investment are greatly, running cost height, and can cause certain secondary pollution.
Next is Biochemical method, in recent years, culture utilization Study on processing method that is aerobic or anaerobic bacterium is in the ascendant, especially the cultivation and exploitation technique of Anammox (bacterium) technique has become vanadium-containing water process technology important development trend, but all kinds of biological process is objectively still in laboratory stage.
Existing industrial mostly adopt air stripping method, and chemical precipitation method (as it is precipitated as NH4MgPO4·6H2O xln) limited efficiency, there is not yet for industrial production.
3) about the high concentration chloride of vanadium extracting waste water and the process technology of sulfate pollution
Under laboratory condition, for the removing of sulfate radical, barium salt method (bariumchloride, hydrated barta etc.) effectively precipitation removing sulfate radical can be adopted, but it is difficult to be applied to vanadium extracting waste water, because pretreatment process is complicated and barium salt cost is extremely high.
Equally, under laboratory condition, for the removing of chlorine root, resin such as D201 anionite-exchange resin can be adopted can effectively to remove part chlorion, but industrial treatment process is complicated, working cost is high-leveled and difficult to bear.
The existing industrial disposal for the concentrated waste liquid of high concentration chloride and sulfate radical, except a small amount of taking that the multi-stage negative pressure of highly energy-consuming distill, except condensing crystal recovery, the disposal options generally taked tries every possible means directly to put aside as useless.
In fact, in relevant sewage discharge Con trolling index according to " vanadium emission of industrial pollutants standard " (GB26452 2011), through the reduction of the relatively high cost of complex process, vanadium in waste water after neutralizing treatment, chromium and PH are easy to up to standard, but NH4-N(ammonia nitrogen), COD(chemical oxygen demand (COD)), SS(suspended substance) it is difficult to control, especially the process difficulty of ammonia nitrogen is very big, domestic yet there are no now the report objectively up to standard about vanadium-containing water NH_3-N treating, vanadium-containing water NH_3-N treating problem up to standard is the very thorny difficult problem that current domestic vanadium products factory wastewater treatment faces, current comparatively effective treatment process mainly contains " air stripping+oxidation removes ammonia " or " blowing ammonia nitrogen removal+evaporation concentration " or " blowing ammonia nitrogen removal+absorption " two stages for the treatment of technology and " electrolysis+catalyzed oxidation " technology, but the technical process of these methods is long, equipment is more complicated, investment is big, energy consumption height, there is secondary pollution, and still remain a large amount of thick slurry waste liquid after ammonia nitrogen removal and need to transport outward disposal.
Obviously, although above-mentioned technological method relates to the process of each pollutant in vanadium extracting waste water, but, technical process is long on the one hand, and investment is big, energy consumption height, cost height, on the other hand, still there is waste residue and concentrated solution needs problem to be processed and secondary pollution, and ignore the recycling of various composition in vanadium extracting waste water especially ammonia nitrogen, salt and moisture content resource, do not meet green, low carbon, recycling economy development theory.
Given this, the harmless treatment of vanadium extracting waste water urgently needs a kind of brand-new thinking and countermeasure, synchronously resolve the problems such as heavy metal contamination complicated in vanadium extracting waste water, the pollution of phenol cyanogen, ammonia and nitrogen pollution, high concentration chloride and sulfate pollution, the object that recycling is turned harm into good can be reached.
On the other hand, China is energy consumption big country, and the current mainly fossil energy consumed, the burning of annual Industrial Stoves billions of tons of fossil energies needs to implement environment-friendlydenitration denitration, for solving the environmental issue of denitration, need to consume a large amount of vanadium, chromium, titanium etc. is main denitration catalyzer and denitration reductive agent ammoniacal liquor, urea, wherein namely the catalyzer of tunnel gas catalytic denitration is the elements such as vanadium, chromium, titanium, and in kiln, namely the denitration reductive agent of (600～1200 DEG C) denitration is ammoniacal liquor and/or urea. It is well known that, the Industrial Stoves denitration effect in 600～1200 DEG C of temperature ranges that burns is hydrogen > hydrocarbon polymer (such as methane, ethane etc.) > ammonia, urea, but at present Industrial Stoves burn denitration raw material that the denitration in 600～1200 DEG C of temperature ranges adopts just can the ammoniacal liquor that transports of commercial scale production and being convenient to or urea.For the denitration in the stove of dry-process rotary kilns production line, clinker production line denitration every day reductive agent ammoniacal liquor (concentration 20～24%) of 2500t/d amount is generally 15～20 tons/day, and the design production capacity of the cement reality in the current whole nation is 3,500,000,000 tons/year. Obviously, adopt ammonia or urea to carry out environment-friendlydenitration denitration and strive fertilizer with agricultural on the one hand, on the other hand because production energy consumption height, the pollution of ammonia, urine add power consumption and environmental pollution greatly and indirectly. And vanadium extracting waste water contains the inorganic salt mineralising sintering agent needed for available denitrating catalyst metallic element, available ammonia nitrogen denitrfying agent and manufacture of cement such as a large amount of vanadium, chromium, titanium, how to break through traditional process pollutent thoughtcast, then the recycling vanadium extracting waste water turned harm into good, a kind of brand-new technological method of urgent needs.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, it is provided that the recycling vanadium extracting waste water that a kind of cost is lower produces the method for ammonia-hydrocarbon denitrfying agent.
The present invention is the technical barrier solving vanadium extracting waste water environmental protection treatment and recycling, there is provided a kind of can be easy, group part in the recycling vanadium extracting waste water of low cost, take vanadium extracting waste water as main material production ammonia-hydrocarbon denitrfying agent, namely directly with the water-soluble vanadium in vanadium extracting waste water, chromium, titanium plasma is as the denitrating catalyst of industrial furnace smoke, using the ammonia nitrogen in vanadium extracting waste water as available ammonia nitrogen denitrfying agent group part, using the moisture in vanadium extracting waste water as security solvent, in dry-process rotary kilns production application process, the mineralising sintering agent of cement clinker production it is converted into the metal ion in vanadium extracting waste water and sulphur chlorine fluorine phosphorus etc., and effectively admittedly melt whole heavy metal ion with silicon/aluminic acid root group, prevent secondary pollution.
It is that a kind of recycling vanadium extracting waste water produces the method for ammonia-hydrocarbon denitrfying agent, take vanadium extracting waste water as main material production ammonia-hydrocarbon denitrfying agent, mainly comprises the steps: that the present invention solves the technical scheme of its technical problem employing
(1) vanadium extracting waste water character is adjusted: be placed in by vanadium extracting waste water in tank or pond, the fluidity that adds water matter adjusting agent adjustment preferred PH6～9 of PH value to 5.5～11(), obtain solution A;
Described water fluidity matter adjusting agent is for containing-NH2、-NH-、NH4 +Or/and NH3Compound, it is preferable that at least one in Monoethanolamine MEA BASF, diethanolamine, trolamine, α-amino isopropyl alcohol, (2-hydroxyethyl)methylamine), dimethyl Monoethanolamine MEA BASF, ammonia, volatile salt etc. The consumption of described water fluidity matter adjusting agent is with preferred PH6～9 of PH value to 5.5～11(of vanadium extracting waste water) it is as the criterion.
(2) ammonia-hydrocarbon denitrfying agent is produced: using the solution A of step (1) gained as main raw material and NOXReductive agent, denitration promotor are prepared burden together, are solution A 40～90%, NO by mass percentageXReductive agent 9.9～50%, denitration promotor 0.1～10% ratio batching, (preferred mass per-cent be solution A 50～85%, reductive agent 14～45%, promotor 1～5% ratio batching), under agitation by NOXReductive agent, denitration promotor add makes uniform liquid in solution A, i.e. obtained ammonia-hydrocarbon denitrfying agent.
Described NOXReductive agent refer to can to realize in 600～1200 DEG C of temperature ranges denitration reaction containing amino (-NH2、-NH-、、NH4 +And/or NH3) and/or the compound containing aldehyde radical and/or phenolic hydroxy group and/or hydroxyl and/or the compound containing C=C double bond at least one, it is preferable that at least one in the acid of polyalcohol amine, methyldiethanolamine, Monoethanolamine MEA BASF, diethanolamine, trolamine, diisopropanolamine (DIPA), dimethylamine, aniline, hydroxyethylethylene diamine, quadrol, tyrasamine, ammonia, urea, volatile salt, ammonium hydrogencarbonate, acetic acid ammonia, acetaldehyde, propionic aldehyde, glucose, phenol, propyl alcohol, Virahol, C6～12 alkene etc.
Described denitration promotor refers to produce ionic hydrogen, the material of hydrogen and/or has the material of denitration catalyst effect, it is preferable that at least one in commercially available hydrazine hydrate, hydrazonium sulfate, hydrazine hydrochloride, hydrazine nitrate, carbohydrazide, acethydrazide, diformylhydrazine, two (2-methoxy ethoxy) sodium aluminate, ammonium meta-vanadate, the ammonium chromate etc. of two hydrogen.
Further, above-mentioned vanadium extracting waste water, water fluidity matter adjusting agent, NOXReductive agent, denitration promotor each raw material composition select the resistance short of money and synergetic property that need to consider each other.
Further, in step (1), described vanadium extracting waste water is the vanadium-containing water produced in all kinds of vanadium extraction production process, or the high density vanadium-containing water that vanadium-containing water recycle produces, or the high chlorine height ammonia nitrogen vanadium extracting waste water after pre-treatment (as processed through chemical precipitation method or ion exchange method).
The know-why of the present invention:
1) for the feature of vanadium extracting waste water, the physicochemical property feature of the high density vanadium-containing water that the vanadium-containing water especially produced in the acid ammonia salt precipitation art production process of sodium roasting water logging or cycling utilization of wastewater produce, according to each material composition feature in vanadium extracting waste water, from being functionally considered as three big material components, first big functional raw material group part is objectively can be used as element and the denitrification reducing agent ammonia nitriding compounds such as denitrating catalyst group part vanadium of catalytic denitration, chromium, titanium; Second largest functional raw material group part in fact for improving cement slurry burn-ability, reduce sinter leaching hear rate, improve the mineralising sintering agent of sinter leaching quality, comprises appropriate vanadium Cr-Mn-Ti potassium sodium thion chloride fluoride element; 3rd big material component is water, and current common denitrification reducing agent ammonia used, urea all adopt the aqueous solution, and wherein ammonia generally adjusts into concentration 20～24% aqueous solution, and urea is generally dissolved in water into the aqueous solution of concentration about 40%. The three big material components that all material in recycling vanadium extracting waste water of the present invention is formed, directly using elements such as the water-soluble vanadium in vanadium extracting waste water, chromium, titaniums as denitrating catalyst and ammonia nitrogen as denitrification reducing agent; Using the moisture in vanadium extracting waste water as security solvent. Namely using vanadium extracting waste water as main raw material, vanadium extracting waste water character, supplementary not enough NO is adjustedXReductive agent group part, it is aided with NOXDenitration promotor, for producing industrial kiln denitrfying agent ammonia-hydrocarbon denitrfying agent.
2) big for industrial furnace coal fines consumption, the ash quantity of slag is big, utilizes metal ion and the sulphur chlorine fluorine phosphorus etc. such as the limited amount vanadium Cr-Mn-Ti potassium sodium in vanadium extracting waste water to improve the hydraulicity reactivity coefficient of coal ash lime-ash. Especially for dry-process rotary kilns productive prospecting, utilizing the metal ions such as the limited amount vanadium Cr-Mn-Ti potassium sodium in vanadium extracting waste water and sulphur chlorine fluorine phosphorus to equal the mineralising sintering agent being converted into cement clinker production in cement produced with the dry method production application, caning be controlled in chloride ion in cement content can not exceed standard.
3) it is industrialness powder mill (having a certain amount of relatively rough coal grain) for Industrial Stoves coal dust used, and be that large discharge coal dust firing (is difficult in coal dust stream obtain sufficient oxygen, always there is certain reducing atmosphere, kiln limited space always have a small amount of coal grain in time after-flame and fall into material in coal ash lime-ash or kiln and produce reduction) feature, by vanadium poisonous for high price, chromium etc. are reduced to the metal ion that state is nontoxic at a low price, and the kinetics caused with pulverized coal flame high temperature and thermodynamic condition, the group of the silicate in lime-ash or cement clinker or aluminic acid root group or sial acid group group lattice is impelled admittedly to melt or admittedly melt the whole heavy metal ion of parcel as formed the ion exchange type mineral of the stable complexity such as silicoaluminate chromium sodium calcium or silicoaluminate vanadium sodium calcium, thoroughly eliminate the possible heavy metal contamination of vanadium extracting waste water.
4) with water fluidity matter adjusting agent gentle solve vanadium extracting waste water deep-etching problem and with NOx reductive agent, out of stock promotor each raw material composition can simple composite fused and synergy function problem.
The useful effect of the present invention:
1) the technology of the present invention method is simply practical, invests little, and process operation energy consumption is very low, it is possible to thoroughly solve the technical barrier of the severe contamination of the vanadium-containing water of restriction vanadium product industrial sustainable development, it is to increase business economic benefit.
2) it is beneficial to high investment, high energy consumption, the high cost that solve vanadium extracting waste water process for a long time and secondary pollution problem, it is beneficial to energy-saving and cost-reducing and environment protection.
3) all material group part of energy resource utilization innoxious use vanadium extracting waste water, it is possible to save resource, be beneficial to and build environmentally friendly conservation-minded society.
4) for the coal-fired industrial furnace that has a large capacity and a wide range provides a kind of new environmental protection to reduce discharging novel material and technology, it is beneficial to and promotes energy-conservation and reduce discharging.
5) the present invention is green, low carbon, recycling economy development technology, is beneficial to and implements industrial transformation and make new growth point.
Embodiment
The method of the recycling vanadium extracting waste water ammonia-hydrocarbon denitrfying agent of the present invention is set forth further below in conjunction with specific embodiment.
Embodiment 1
Vanadium extracting waste water selects certain with the vanadium wastewater of vanadium slag sodium roasting, and water fluidity matter adjusting agent selects commercially available Monoethanolamine MEA BASF, NOXTrolamine selected by reductive agent, and denitration promotor selects hydrazine hydrate. Direct according to the following steps is that main raw material produces ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent) taking vanadium extracting waste water:
(1) adjusting vanadium extracting waste water character: be placed in stirred pot by vanadium extracting waste water, the fluidity that adds water matter adjusting agent Monoethanolamine MEA BASF adjustment PH value to 6.1, obtains solution A;
(2) ammonia-hydrocarbon denitrfying agent is produced: using the solution A of gained as main raw material and NOXReductive agent trolamine, denitration promotor hydrazine hydrate are prepared burden together, it is the ratio batching of solution A 81%, reductive agent trolamine 17%, promotor hydrazine hydrate 2% by mass percentage, under agitation reductive agent trolamine, promotor hydrazine hydrate are added and solution A is made uniform solution, be i.e. obtained ammonia-hydrocarbon denitrfying agent.
Embodiment 2
Vanadium extracting waste water selects certain with the vanadium wastewater of Rock coal containing alum sodium roasting, and water fluidity matter adjusting agent selects commercially available (2-hydroxyethyl)methylamine), NOXReductive agent selects commercially available carbonic acid ammonia and Virahol, and denitration promotor selects carbohydrazide. Direct according to the following steps is that main raw material produces ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent) taking vanadium extracting waste water:
(1) adjusting vanadium extracting waste water character: be placed in stirred pot by vanadium extracting waste water, the fluidity that adds water matter adjusting agent (2-hydroxyethyl)methylamine) adjustment PH value to 6.3, obtains solution A;
(2) ammonia-hydrocarbon denitrfying agent is produced: using the solution A of gained as main raw material and NOXReductive agent carbonic acid ammonia is prepared burden together with Virahol, denitration promotor carbohydrazide, be solution A 75%, reductive agent 21%(wherein carbonic acid ammonia 15%+ Virahol 6% by mass percentage), the ratio of denitration promotor carbohydrazide 4% batching, under agitation reductive agent carbonic acid ammonia and Virahol, promotor carbohydrazide are added and solution A is made uniform solution, be i.e. obtained ammonia-hydrocarbon denitrfying agent.
Embodiment 3
Vanadium extracting waste water selects certain factory that Rock coal containing alum carries out the vanadium wastewater of saltless roasting with fluidizing furnace, and water fluidity matter adjusting agent selects commercially available volatile salt, NOXReductive agent selects commercially available ammoniacal liquor (mass concentration 27%) and glucose (waste liquid), and denitration promotor selects hydrazine hydrate.Direct according to the following steps is that main raw material produces ammonia-hydrocarbon denitrfying agent taking vanadium extracting waste water:
(1) adjusting vanadium extracting waste water character: be placed in stirred pot by vanadium extracting waste water, the fluidity that adds water matter adjusting agent volatile salt adjustment PH value to 7.8, obtains solution A;
(2) ammonia-hydrocarbon denitrfying agent is produced: the solution A of gained prepared burden together with glucose, denitration promotor hydrazine hydrate with reductive agent ammoniacal liquor as main raw material, be solution A 60%, NO by mass percentageXReductive agent 39%(is ammoniacal liquor 35%+ glucose 4% wherein), the ratio of promotor hydrazine hydrate 1% batching, under agitation reductive agent ammoniacal liquor and glucose, promotor hydrazine hydrate are added and solution A are made uniform solution, be i.e. obtained ammonia-hydrocarbon denitrfying agent.
Embodiment 4
Vanadium extracting waste water select certain namely to process with chemical precipitation method with the pretreated vanadium wastewater of Rock coal containing alum sodium roasting technique (in iron reduction, sodium carbonate and filtration treatment) after the high chlorine dense salt waste water of height ammonia nitrogen, water fluidity matter adjusting agent selects commercially available (2-hydroxyethyl)methylamine), NOXReductive agent selects commercially available ammoniacal liquor (mass concentration 27%) and polyalcohol amine, and denitration promotor selects hydrazine hydrate. Direct according to the following steps is that main raw material produces ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent) taking vanadium extracting waste water:
1) adjusting vanadium extracting waste water character: be placed in stirred pot by vanadium extracting waste water (the dense salt waste water of high-content ammonia nitrogen), the fluidity that adds water matter adjusting agent (2-hydroxyethyl)methylamine) adjustment PH value to 8, obtains solution A;
(2) ammonia-hydrocarbon denitrfying agent is produced: using the solution A of gained as main raw material and NOXReductive agent ammoniacal liquor, polyalcohol amine are prepared burden together with denitration promotor hydrazine hydrate, be solution A 57%, reductive agent 41%(wherein ammoniacal liquor 31%+ polyalcohol amine 10% by mass percentage), the ratio of promotor hydrazine hydrate 2% batching, under agitation reductive agent ammoniacal liquor, polyalcohol amine and promotor hydrazine hydrate are added and solution A is made uniform solution, be i.e. obtained denitrfying agent.
Embodiment 5
Vanadium extracting waste water selects certain (containing vanadium) bone coal power station to the vanadium wastewater of Rock coal containing alum saltless roasting, and water fluidity matter adjusting agent selects commercially available ammoniacal liquor, NOXReductive agent selects commercial urea and Virahol, and denitration promotor selects ammonium meta-vanadate and ammonium chromate. Direct according to the following steps is that main raw material produces ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent) taking vanadium extracting waste water:
(1) adjusting vanadium extracting waste water character: be placed in stirred pot by vanadium extracting waste water, the fluidity that adds water matter adjusting agent ammoniacal liquor adjustment PH value to 7.1, obtains solution A;
(2) ammonia-hydrocarbon denitrfying agent is produced: using the solution A of gained as main raw material and NOXReductive agent, denitration promotor are prepared burden together, are solution A 60%, NO by mass percentageXReductive agent 39%(is urea 25%+ Virahol 14% wherein), promotor 1%(wherein ammonium meta-vanadate 0.5%+ ammonium chromate 0.5%) ratio batching, under agitation reductive agent urea and Virahol and promotor ammonium meta-vanadate and ammonium chromate are added and solution A is made uniform solution, i.e. the obtained hydrocarbon denitrfying agent of ammonia one.
Embodiment 6
Each 5 tons of the ammonia-hydrocarbon denitrfying agent (abbreviation denitrfying agent) of 5 kinds of component differences is amounted to above-described embodiment 1～embodiment 5, to certain Φ 4x64m dry-process rotary kiln production line, carrying out pilot scale simultaneous test with ammoniacal liquor denitration, the normal production denitration of this factory adopts the ammoniacal liquor of mass concentration 21% to make denitrfying agent, NOX(< 200mg/Nm up to standard3) discharge time ammonia volume be on average 0.76t/h.
Pilot plant test shows:
1) the 5 kinds of ammonia-hydrocarbon denitrfying agent of embodiment 1 to embodiment 5 all has good denitration effect, and when consumption 0.51～0.67t/h NOXOn-line checkingi < 200mg/Nm3, environment-friendlydenitration denitration index all can be up to standard, and denitration effect is better than traditional ammoniacal liquor denitrfying agent.
2) grog of gained carries out heavy metal leaching toxicity test, all non-detection vanadium, chromium by standard GB/T 5086.2-1997 " solid waste leaches toxicity leaching method ", illustrates that the sial acid group hot setting of heavy metal element is very thoroughly very stable.
3) grog of gained carries out chloride test, and with blank grog (namely not adding the grog of catalytic combustion adjuvant for coal) contrast, in grog, chloride ion content is without obvious increase (chloride ion content change is in the limit of error of detection).
The test-results of five groups of pilot scales can confirm: the method that the recycling vanadium extracting waste water of the present invention produces ammonia-hydrocarbon denitrfying agent is feasible. The technology of the present invention method is simply practical, invests little, and process operation energy consumption is very low, it is possible to thoroughly solve the technical barrier of the severe contamination of the vanadium-containing water of restriction vanadium product industrial sustainable development, it is to increase business economic benefit. It is beneficial to high investment, high energy consumption, the high cost and secondary pollution problem that solve vanadium extracting waste water process for a long time, it is beneficial to environment protection.
Claims (8)
1. the method for recycling vanadium extracting waste water production ammonia-hydrocarbon denitrfying agent, it is characterised in that, comprise the steps:
(1) vanadium extracting waste water character is adjusted: being placed in by vanadium extracting waste water in tank or pond, the fluidity that adds water matter adjusting agent adjusted to ph to 5.5～11, obtain solution A;
Described water fluidity matter adjusting agent is for containing-NH2、-NH-、NH4 +Or/and NH3Compound;
(2) ammonia-hydrocarbon denitrfying agent is produced: using the solution A of step (1) gained as main raw material and NOXReductive agent, denitration promotor are prepared burden together, are solution A 40～90%, NO by mass percentageXThe ratio batching of reductive agent 9.9～50%, denitration promotor 0.1～10%, under agitation by NOXReductive agent, denitration promotor add makes uniform liquid in solution A, i.e. obtained ammonia-hydrocarbon denitrfying agent;
Described NOXReductive agent refer to can to realize in 600～1200 DEG C of temperature ranges denitration reaction containing amino and/or containing the compound of aldehyde radical and/or phenolic hydroxy group and/or hydroxyl and/or containing at least one in the compound of C=C double bond;
Described denitration promotor refers to produce ionic hydrogen, the material of hydrogen and/or has the material of denitration catalyst effect.
2. recycling vanadium extracting waste water according to claim 1 produces the method for ammonia-hydrocarbon denitrfying agent, it is characterised in that, in step (1), the fluidity that adds water matter adjusting agent adjustment vanadium extracting waste water pH value to 6～9.
3. recycling vanadium extracting waste water according to claim 1 and 2 produces the method for ammonia-hydrocarbon denitrfying agent, it is characterized in that, in step (1), described water fluidity matter adjusting agent is at least one in Monoethanolamine MEA BASF, diethanolamine, trolamine, α-amino isopropyl alcohol, (2-hydroxyethyl)methylamine), dimethyl Monoethanolamine MEA BASF, ammonia, volatile salt.
4. recycling vanadium extracting waste water according to claim 1 and 2 produces the method for ammonia-hydrocarbon denitrfying agent, it is characterised in that, in step (2), each quality of material per-cent is solution A 50～85%, reductive agent 14～45%, promotor 1～5%.
5. recycling vanadium extracting waste water according to claim 1 and 2 produces the method for ammonia-hydrocarbon denitrfying agent, it is characterised in that, in step (2), described amino is-NH2、-NH-、、NH4 +And/or NH3。
6. recycling vanadium extracting waste water according to claim 1 and 2 produces the method for ammonia-hydrocarbon denitrfying agent, it is characterised in that, in step (2), described NOXReductive agent is at least one in polyalcohol amine, methyldiethanolamine, Monoethanolamine MEA BASF, diethanolamine, trolamine, diisopropanolamine (DIPA), dimethylamine, aniline, hydroxyethylethylene diamine, quadrol, tyrasamine acid, ammonia, urea, volatile salt, ammonium hydrogencarbonate, acetic acid ammonia, acetaldehyde, propionic aldehyde, glucose, phenol, propyl alcohol, Virahol, C6～12 alkene.
7. recycling vanadium extracting waste water according to claim 1 and 2 produces the method for ammonia-hydrocarbon denitrfying agent, it is characterized in that, in step (2), described denitration promotor is at least one in hydrazine hydrate, hydrazonium sulfate, hydrazine hydrochloride, hydrazine nitrate, carbohydrazide, acethydrazide, diformylhydrazine, two hydrogen two (2-methoxy ethoxy) sodium aluminate, ammonium meta-vanadate, ammonium chromate.
8. recycling vanadium extracting waste water according to claim 1 and 2 produces the method for ammonia-hydrocarbon denitrfying agent, it is characterized in that, in step (1), described vanadium extracting waste water, for the vanadium-containing water produced in all kinds of vanadium extraction production process, or the high density vanadium-containing water that vanadium-containing water recycle produces, or high chlorine height ammonia nitrogen vanadium extracting waste water after pretreatment.
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| CN112246080A (en) * | 2020-09-14 | 2021-01-22 | 佛山市粤罡环保设备有限公司 | Organic amine denitration agent and preparation method thereof |
| CN112811660A (en) * | 2021-01-05 | 2021-05-18 | 长沙有色冶金设计研究院有限公司 | Treatment process for waste gas and alum precipitation wastewater generated in integration of stone coal navajoite and navajoite |
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