CN105776489B - A kind of method of recycling vanadium extracting waste water production catalytic combustion adjuvant for coal - Google Patents
A kind of method of recycling vanadium extracting waste water production catalytic combustion adjuvant for coal Download PDFInfo
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- CN105776489B CN105776489B CN201610226264.8A CN201610226264A CN105776489B CN 105776489 B CN105776489 B CN 105776489B CN 201610226264 A CN201610226264 A CN 201610226264A CN 105776489 B CN105776489 B CN 105776489B
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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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/029—Salts, such as carbonates, oxides, hydroxides, percompounds, e.g. peroxides, perborates, nitrates, nitrites, sulfates, and silicates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/0295—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/04—Catalyst added to fuel stream to improve a reaction
Abstract
A kind of method of recycling vanadium extracting waste water production catalytic combustion adjuvant for coal, includes the following steps：（1）Adjust 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 5.8~9.8, obtains solution A；（2）Produce catalytic combustion adjuvant for coal：By mass percentage for solution A 40~70%, rare earth series catalysts 29~50%, combustion adjuvant 1~10% ratio dispensing, under stiring will rare earth series catalysts, combustion adjuvant add in solution A in be made uniform liquid to get.The technology of the present invention method is simple and practical; it invests small; it is very low to handle operation energy consumption; the technical barrier seriously polluted of the vanadium-containing water of restriction vanadium product industrial sustainable development can thoroughly be solved; improve Business Economic Benefit; conducive to the with high investment of vanadium extracting waste water processing for a long time, high energy consumption, high cost and secondary pollution is solved the problems, such as, conducive to energy-saving and environmental protection.
Description
Technical field
The present invention relates to environmental protection and waste utilization fields, are helped more particularly, to a kind of production coal catalysis of recycling vanadium extracting waste water
Fire the method for agent.
Background technology
Vanadium product purpose is extensive, and the raw material of vanadium extraction includes the 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 the 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 given up
The maximum difference of water is sodium roasting using ammonium salt precipitation, general without the ammonia nitrogen concentration recycled in its disposable waste water
I.e. up to 5400mg/L or higher, and it is general in calcification baking technique do not use ammonium salt precipitation, therefore ammonia nitrogen concentration is very in its waste water
It is small.But no matter using which kind of raw material which kind of method vanadium extraction, can all be generated 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 produce 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 capacity 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,
Alkali-sodium oxide baking-water logging-acidity ammonia salt precipitation-washing ammonium poly-vanadate-thick vanadium-piece vanadium-powder vanadium-also primary
Produce V2O5Or V2O3Technique, during precipitation, vanadic acid root and ammonium ion largely combine and form ammonium poly-vanadate or ammonium metavanadate
Precipitation, chromate or dichromate ion be not because precipitating, with precipitating other titaniums, manganese etc. under halfway vanadic acid root and acid condition
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, in the waste water generated in precipitation, water-washing process containing ammonium chromate (（CH4)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 stablized relatively under same materials and process conditions.Often produce one ton of V2O5It 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 to implement comprehensive harmless treatment.But so far, it is useless to be concentrated mainly on extraction for the treatment technology 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）About in vanadium extracting waste water heavy metal vanadium, chromium, manganese etc. treatment technology, research and develop for a long time both at home and abroad
Application process is planted up to more than 20, these solve heavy metal vanadium in vanadium extracting waste waters, chromium, manganese etc. method be broadly divided into it is as follows
Four major class：
The first kind is Physical：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 technological process is long, investment is larger, operating cost is higher and brings two
Secondary pollution.
Second class is chemical method：Mainly there are 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 ripe, but technological process is long, and investment is big mostly, operating cost is high, and there are waste residues
The secondary pollutions such as processing.
Third class is physical-chemical process：Mainly there are ion-exchange, solvent extraction, membrane separation process（Hyperfiltration, electric osmose
Analysis, membrane extraction, ultrafiltration etc.）, electrolysis 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 technological process 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 into
This processing, but the selection and breeding of flora are extremely difficult for vanadium chrome waste water, and there are subsequent processings and secondary pollution.
Currently, chemical precipitation method is industrially taken mostly for the processing of the heavy metal in vanadium extracting waste water（Iron barium salt process, iron
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）Treatment technology 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 and chemistry for such ammonia nitrogen waste water
Method.
Physical 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 technological process length of the above method,
Investment is big, running cost is high, and can cause certain secondary pollution.
Secondly Biochemical method, in recent years, culture utilization is aerobic or the Study on processing method of anaerobic bacteria is in the ascendant,
Especially Anammox（Bacterium）The cultivation and exploitation technique of technique has become one important development of vanadium-containing water treatment technology and has become
Gesture, but different kind organism method is objectively still in laboratory stage.
It is now industrial mostly to use air stripping method, and chemical precipitation method（Such as it is precipitated as NH4MgPO4·6H2O crystalline solid）
Effect is limited, there is not yet for industrial production.
3）About the high concentration chloride of vanadium extracting waste water and the treatment technology of sulfate pollution
Under laboratory condition, barium salt process can be used in the removing for sulfate radical（Barium chloride, barium hydroxide etc.）Effectively precipitation
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, the removing for chlorine root, resin such as D201 anion exchange resin, which can be used, to be had
Effect removal part chlorion, 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, according to《Vanadium emission of industrial pollutants standard》（GB26452—2011）Related sewage discharge control refer to
In mark, vanadium, chromium and PH after the reduction of the higher cost by complex process, neutralisation treatment in waste water are easy to up to standard, but NH4-N
（Ammonia nitrogen）、COD（COD）、SS（Suspended matter）It is difficult control, the intractability of especially ammonia nitrogen is very big, domestic to go back now
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 have
" 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 technological process of these methods is long, equipment is more complicated, investment is big, high energy consumption, 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, invests big, high energy consumption, is of 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, there is an urgent need to have a kind of completely new idea and method-synchronize and resolve for the harmless treatment of vanadium extracting waste water
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 recycling is turned harm into good.
On the other hand, the production of our times industrial catalyst to vanadium, chromium, titanium, manganese, nickel, iron, copper, molybdenum, tungsten, strontium, caesium,
The consumption of the products such as indium, gallium, lithium, potassium, sodium, silicon, rare earth increases day by day, especially about energy-saving, energy-saving and emission-reduction emerging works
Industry kiln coal used additives（Such as catalytic combustion adjuvant for coal）Application, for the big country using fire coal as main energy sources, with greater need for one kind
Inexpensive catalytic combustion adjuvant for coal promotes energy-saving and emission reduction.And contain a large amount of vanadium, chromium, titanium, manganese, iron in vanadium extracting waste water
Etc. the inorganic salts mineralising sintering aid needed for available catalysis burning-rate accelerator metallic element, available ammonia nitrogen and manufacture of cement, how to dash forward
Broken traditional processing pollutant thoughtcast, then the recycling vanadium extracting waste water turned harm into good, there is an urgent need to a kind of completely new
Technical method.
Invention content
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 vanadium extracting waste water production catalytic combustion adjuvant for coal.
Technical barrier of the present invention to solve vanadium extracting waste water environmental protection treatment and recycling, provide it is a kind of can be easy,
Component in the recycling vanadium extracting waste water of low cost is burnt as main material production industrial furnace coal fines using vanadium extracting waste water and used
Catalysis burning-rate accelerator fires that is, directly using water-soluble vanadium, chromium, titanium, manganese, potassium, sodium plasma and the ammonia nitrogen in vanadium extracting waste water as coal dust
Available combustion-supporting or catalytic combustion-supporting component is burnt, the safety solvent using the moisture in vanadium extracting waste water as catalytic combustion adjuvant for coal,
Clinker is converted into during dry-process rotary kilns production application with the metal ion in vanadium extracting waste water and sulphur chlorine fluorine phosphorus etc.
The mineralising sintering aid of production, and whole heavy metal ion are effectively melted with aluminosilicate root ball admittedly, prevent secondary pollution.
The present invention solve its technical problem the technical solution adopted is that, a kind of recycling vanadium extracting waste water production coal is with urging
Change the method for combustion adjuvant, using vanadium extracting waste water as main material production industrial furnace coal fines burning catalysis burning-rate accelerator, mainly include
Following steps：
（1）Adjust vanadium extracting waste water property：Vanadium extracting waste water is placed in tank or pond, adds aqueous property regulator adjustment pH value extremely
5.8~9.8, obtain solution A；
The aqueous property regulator is containing-NH2、-NH-、、NH4 +、NH3Compound, preferably monoethanolamine, diethyl
In hydramine, triethanolamine, isopropanolamine, (2-hydroxyethyl)methylamine), dimethyl monoethanolamine, ammonia, ammonium hydrogencarbonate, ammonium carbonate etc.
It is at least one.The dosage of the aqueous property regulator is with the pH value of aqueous solution to 5.8~9.8（It is preferred that PH 6.8~8.8）For
It is accurate.
（2）Produce catalytic combustion adjuvant for coal：With step（1）The solution A of gained is catalyzed for the auxiliary Rare Earth that is equipped with of primary raw material
Agent, combustion adjuvant are by mass percentage solution A 40~70%, the ratio of rare earth series catalysts 29~50%, combustion adjuvant 1~10%
Rare earth series catalysts, combustion adjuvant are added in solution A uniform liquid is made to get coal catalytic combustion-supporting under stiring by dispensing
Agent.
Step（2）In, water soluble compound of the rare earth series catalysts for rare earth element, preferably group of the lanthanides light rare earth lanthanum,
The water soluble compound of at least one of cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium element, preferably gently
In the water-soluble naphthenate of rare earth element, salicylate, citrate, tartrate, villaumite, perchlorate, nitrate etc.
At least one.
Step（2）In, the combustion adjuvant is water soluble lithium compounds, preferably lithium nitrate, lithium chlorate, aphthenic acids lithium, bigcatkin willow
At least one of sour lithium, lithium tartrate, lithium citrate, lithium perchlorate etc.；The dosage of combustion adjuvant regards water-soluble in vanadium extracting waste water
Chromium, vanadium, manganese, titanium, sodium, potassium equal size height adjust dosage to ensure combustion-supporting effect, when in vanadium extracting waste water water-soluble vanadium,
When chromium, manganese, titanium, potassium, sodium equal size are relatively low, combustion adjuvant matches dosage and concrete condition raising dosage is regarded in the range of 1~10wt%,
Such as 6 ~ 10wt% of combustion adjuvant dosage.
Further, step（1）In, 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 of generation（Such as through chemical precipitation method or ion-exchange
Processing）The high ammonia nitrogen vanadium extracting waste water of high chlorine afterwards.
Further, step（1）In, during ammonia nitrogen vanadium extracting waste water high using high chlorine after pretreatment, step（2）In quality
Percentage proportioning is solution A 42 ~ 50%, rare earth series catalysts 42 ~ 50%, combustion adjuvant 6 ~ 10%.
Further, the dosage of the catalytic combustion adjuvant for coal is preferably the 0.1~0.5% of coal dust gross mass.
The technical principle of the present invention：
1）For in the feature of vanadium extracting waste water, especially 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, be considered as three big material components, the first big material component objectively can be used as the group of catalytic combustion-supporting
Part include elements and the combustibles such as water-soluble vanadium, chromium, manganese, titanium, iron, potassium, sodium, ammonia nitrogen and micro nickel, cobalt, copper；Second largest original
Material component is in fact helped for that can improve cement slurry burn-ability, reduction sinter leaching heat consumption, the mineralising of raising sinter leaching quality
It burns agent and includes suitable vanadium Cr-Mn-Ti potassium sodium thion chloride fluoride element；The third-largest material component is water.Recycling vanadium extracting waste water
In the three big material components that form of all material, directly in vanadium extracting waste water water-soluble vanadium, chromium, titanium, manganese, potassium, sodium etc. from
Son and ammonia nitrogen are helped as coal dust firing is available combustion-supporting or catalytic combustion-supporting composition, using the moisture in vanadium extracting waste water as coal with being catalyzed
Fire the effective safety solvent of agent；I.e. using vanadium extracting waste water as primary raw material, the catalysis of supplement insufficient coal, combustion-supporting component, use
In production industrial furnace coal fines burning catalysis burning-rate accelerator.
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 metal ions such as sodium and sulphur chlorine fluorine phosphorus etc. improve the hydraulicity vivacity of coal ash lime-ash, are given birth in particular for dry-process rotary kilns
Production feature is given birth to using the metal ions such as the limited amount vanadium Cr-Mn-Ti potassium sodium in vanadium extracting waste water and sulphur chlorine fluorine phosphorus equal to cement produced with the dry method
The mineralising sintering aid of clinker production is converted into production application, without causing chloride ion in cement exceeded.
3）It is industrialness grinding for coal dust used in Industrial Stoves（It has a certain amount of compared with rough coal grain）, and be big flow
Coal dust firing（Be difficult to obtain in pulverized coal flow sufficient oxygen always have certain reducing atmosphere, kiln space it is limited always have it is a small amount of
The not timely after-flame of coal grain and fall into coal ash lime-ash or kiln and reduction generated in material）The characteristics of, by high price toxic vanadium, chromium etc. also
Originally it was the nontoxic metal ion of lower valency, and with dynamics and thermodynamic condition caused by pulverized coal flame high temperature, promotes ash
Silicic acid root ball or aluminic acid root ball or aluminosilicate root ball lattice in slag or clinker melt admittedly or the admittedly molten whole heavy metals of package from
Son such as forms the complicated ion exchange type mineral that aluminosilicate chromium sodium calcium or aluminosilicate vanadium sodium calcium are stablized, and thoroughly eliminates vanadium extraction and gives up
The possible heavy metal pollution of water.
4）Utilize the ammonia nitrogen and possible organic in the hot conditions oxidation after-flame vanadium extracting waste water of industrial furnace coal fines burning
Object, as utilized in 1650~2000 DEG C of coal dust firing thermal-flames in dry-process rotary kilns production line rotary kiln and dore furnace 900
℃（Edge）~1200 DEG C（Center）Coal dust firing high temperature and strong basicity（Containing a large amount of high activity CaO）Ambiance aoxidizes after-flame
Ammonia nitrogen and other possible organic matters in vanadium extracting waste water, and eliminate the Production conditions of bioxin.
5）With aqueous property regulator leniently solve the problems, such as vanadium extracting waste water deep-etching and with rare earth series catalysts, combustion-supporting
Agent can simply compound fused and synergistic effect function problem.
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 barrier seriously polluted of the vanadium-containing water of product industrial sustainable development improves Business Economic Benefit.
2）Conducive to solving the problems, such as the with high investment of the processing of vanadium extracting waste water for a long time, high energy consumption, high cost and secondary pollution, profit
In energy-saving and environmental protection.
3）The all material component of energy recycling innoxious use vanadium extracting waste water, can save resource, 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 energy-saving, energy-saving and emission-reduction new material and technology,
Conducive to the energy saving and emission reduction of promotion.
5）The present invention is green, low-carbon, recycling economy development technology, conducive to implementing industrial transformation and making new growth
Point.
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
In the present embodiment, vanadium extracting waste water selects certain, and with the vanadium wastewater of vanadium slag sodium roasting, aqueous property regulator is selected
Commercially available monoethanolamine, rare earth series catalysts select the water-soluble V-type rare earth catalyst of Central South University's base exploitation（Commercially available production
Product）（For not separated light rare earth elements mixture, main ingredient is group of the lanthanides light rare earth lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium,
Holmium, the water-soluble salicylate of erbium multielement, nitrate and villaumite compound）, the commercially available lithium perchlorate of combustion adjuvant selection.
Using vanadium extracting waste water as primary raw material, industrial furnace coal fines burning catalysis burning-rate accelerator is produced as follows：
（1）Adjust vanadium extracting waste water property：Vanadium extracting waste water is placed in agitator tank, adds aqueous property regulator monoethanolamine tune
Whole pH value obtains solution A to 6.8；
（2）Produce catalytic combustion adjuvant for coal：It is by mass percentage solution A 62%, V-type rare earth catalyst 37%, combustion adjuvant
The ratio dispensing of lithium perchlorate 1% under stiring sequentially adds V-type rare earth catalyst, combustion adjuvant lithium perchlorate in solution A,
Uniform liquid is made to get catalytic combustion adjuvant for coal.
Embodiment 2
Vanadium extracting waste water selects certain, and with the vanadium wastewater of Rock coal containing alum sodium roasting, aqueous property regulator selects commercially available N-
Methyl monoethanolamine, rare earth series catalysts select the water-soluble V-type rare earth catalyst of Central South University's base exploitation（For without dividing
From light rare earth elements mixture, main ingredient for group of the lanthanides light rare earth lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, holmium, erbium multielement
Water-soluble salicylate, nitrate and villaumite compound）, the commercially available lithium nitrate of combustion adjuvant selection.
Using vanadium extracting waste water as primary raw material, industrial furnace coal fines burning catalysis burning-rate accelerator is produced as follows：
（1）Adjust vanadium extracting waste water property：Vanadium extracting waste water is placed in agitator tank, adds aqueous property regulator N- methyl list second
Hydramine adjusts pH value to 7, obtains solution A；
（2）Produce catalytic combustion adjuvant for coal：It is by mass percentage solution A 68%, V-type rare earth catalyst 29%, combustion adjuvant
The ratio dispensing of lithium nitrate 3% under stiring sequentially adds V-type rare earth catalyst, combustion adjuvant lithium nitrate in solution A, is made
Even liquid is to get catalytic combustion adjuvant for coal.
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 liquefied ammonia is selected in agent, and rare earth series catalysts select the water-soluble VI types rare earth catalyst of Central South University's base exploitation（For
Not separated light rare earth elements mixture, main ingredient are group of the lanthanides light rare earth lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, holmium, erbium
The compound of the water-soluble citrate of multielement, nitrate and villaumite）, the commercially available lithium nitrate of combustion adjuvant selection.
Using vanadium extracting waste water as primary raw material, industrial furnace coal fines burning catalysis burning-rate accelerator is produced as follows：
（1）Adjust vanadium extracting waste water property：Vanadium extracting waste water is placed in agitator tank, aqueous property regulator liquefied ammonia is added to adjust PH
Value obtains solution A to 8.8；
（2）Produce catalytic combustion adjuvant for coal：It is by mass percentage solution A 51%, VI types rare earth catalyst 47%, combustion-supporting
The ratio dispensing of agent lithium nitrate 2% under stiring sequentially adds VI types rare earth catalyst, combustion adjuvant lithium nitrate in solution A, system
Into uniform liquid to get catalytic combustion adjuvant for coal.
Embodiment 4
Vanadium extracting waste water selects 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), rare earth series catalysts select the water-soluble V-type rare earth catalyst of Central South University's base exploitation
Agent（For not separated light rare earth elements mixture, main ingredient be group of the lanthanides light rare earth lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium,
Holmium, the water-soluble salicylate of erbium multielement, nitrate and villaumite compound）, the commercially available lithium perchlorate of combustion adjuvant selection.
With vanadium extracting waste water（The high dense salt vanadium extracting waste water of the high ammonia nitrogen of chlorinity）For primary raw material, industry kiln is produced as follows
Stove coal dust firing catalysis burning-rate accelerator：
（1）Adjust vanadium extracting waste water property：By vanadium extracting waste water（The dense salt waste water of high-content ammonia nitrogen）It is placed in agitator tank, adds aqueous
Property regulator (2-hydroxyethyl)methylamine) adjusts pH value to 9, obtains solution A；
（2）Produce catalytic combustion adjuvant for coal：It is by mass percentage solution A 45%, V-type rare earth catalyst 45%, combustion adjuvant
V-type rare earth catalyst, the high chlorine lithium nitrate of combustion adjuvant are sequentially added solution A by the ratio dispensing of lithium perchlorate 10% under stiring
In, uniform liquid is made to get catalytic combustion adjuvant for coal.
Embodiment 5
Vanadium extracting waste water selects certain（Containing vanadium）Bone coal power plant is to the vanadium wastewater of Rock coal containing alum saltless roasting, aqueous property tune
Whole dose is selected commercially available ammonium hydroxide, and rare earth series catalysts select the water-soluble VI types rare earth catalyst of Central South University's base exploitation
（For not separated light rare earth elements mixture, main ingredient be group of the lanthanides light rare earth lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, holmium,
The compound of the water-soluble citrate of erbium multielement, nitrate and villaumite）, the commercially available lithium perchlorate of combustion adjuvant selection.
Using vanadium extracting waste water as primary raw material, industrial furnace coal fines burning catalysis burning-rate accelerator is produced as follows：
（1）Adjust 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 7.2；
（2）Produce catalytic combustion adjuvant for coal：It is by mass percentage solution A 55%, VI types rare earth catalyst 43%, combustion-supporting
VI types rare earth catalyst, combustion adjuvant lithium perchlorate are sequentially added solution A by the ratio dispensing of agent lithium perchlorate 2% under stiring
In, uniform liquid is made to get catalytic combustion adjuvant for coal.
Embodiment 6
Amount to each 3 tons of the catalytic combustion adjuvant for coal of 5 kinds of component differences with 1~embodiment of above-described embodiment 5, until certain Φ
(factory is using local sulphur coal for 4x64m dry-process rotary kilns production line（Sulfur content 4.5~7.5%）, into factory's raw coal and enter kiln coal dust
Quality fluctuation is big) carry out five groups of energy-saving and energy-saving and emission-reduction contrast tests（If blank assay, that is, it is not added with urging for the present embodiment
Change combustion adjuvant, because coal quality fluctuation is big, delay length, energy-saving effect comparison is without practical significance between different catalytic combustion adjuvant for coal）.
Pilot scale contrast test is shown：
1）Embodiment 1 to embodiment 55 kinds of catalytic combustion adjuvant for coal dosage be coal dust gross mass 0.1~0.5% when,
There is good catalytic combustion-supporting coal-saving consumption reduction effect, and increase with catalytic combustion adjuvant for coal dosage, energy conservation and consumption reduction effects increase, with
Computer statistics data and daily coal dust Industrial Analysis data meter, coal saving rate are differed 6.3~17.2%.
2）Embodiment 1 to embodiment 55 kinds of catalytic combustion adjuvant for coal dosage be coal dust total amount more than 0.15% when,
Line detects SO2Content can be reduced to 200mg/Nm3Below（During blank test, on-line checking SO2Content is up to 1200mg/Nm3With
On）, there is good desulfurization emission reduction effect.
3）Every group takes catalytic combustion adjuvant for coal dosage when being total coal amount 0.5%, and the clinker of gained presses national standard
GB5086.2-1997<Solid waste Leaching leaching method》Carry out Leaching Heavy Metals experiment, do not detect vanadium,
Chromium illustrates that the sial acid group hot setting of heavy metal element is very thoroughly very stable.
4）Every group takes catalytic combustion adjuvant for coal dosage when being total coal amount 0.5%, and the clinker of gained carries out chloride test, with
Blank clinker（Do not add the clinker of catalytic combustion adjuvant for coal）It compares, chloride ion content is without obvious increase in clinker（Chlorion contains
Amount variation is in the error range of detection）.
The result of the test of five groups of pilot scales can be confirmed：The recycling vanadium extracting waste water production coal catalytic combustion-supporting of the present 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 barrier seriously polluted of the vanadium-containing water of vanadium product industrial sustainable development 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, conducive to energy-saving and environment
Protection.
Claims (7)
1. a kind of method of recycling vanadium extracting waste water production catalytic combustion adjuvant for coal, which is characterized in that using vanadium extracting waste water as
Main material production industrial furnace coal fines burning catalysis burning-rate accelerator, mainly includes the following steps：
（1）Adjust 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 5.8
~9.8, obtain solution A；
The aqueous property regulator is containing-NH2、-NH-、、NH4 +Or/and NH3Compound；
（2）Produce catalytic combustion adjuvant for coal：With step（1）The solution A of gained, which is that primary raw material is auxiliary, to be equipped with rare earth series catalysts, helps
Agent is fired, is by mass percentage solution A 40~70%, the ratio dispensing of rare earth series catalysts 29~50%, combustion adjuvant 1~10%,
Rare earth series catalysts, combustion adjuvant are added in solution A under stirring, uniform liquid is made to get catalytic combustion adjuvant for coal；
Step（2）In, the combustion adjuvant is water soluble lithium compounds；
Step（2）In, the rare earth series catalysts for group of the lanthanides light rare earth lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium,
The water soluble compound of at least one of erbium, thulium, ytterbium, lutetium element；
The rare earth series catalysts are the water-soluble naphthenate of light rare earth elements, salicylate, citrate, tartrate,
At least one of villaumite, perchlorate, nitrate.
2. the method for recycling vanadium extracting waste water production catalytic combustion adjuvant for coal according to claim 1, feature exist
In the dosage of, the aqueous property regulator be subject to vanadium extracting waste water pH value to 6.8~8.8.
3. the method for recycling vanadium extracting waste water production catalytic combustion adjuvant for coal according to claim 1 or 2, feature
It is, step（2）In, the combustion adjuvant for lithium nitrate, lithium chlorate, aphthenic acids lithium, lithium salicylate, lithium tartrate, lithium citrate,
At least one of lithium perchlorate.
4. the method for recycling vanadium extracting waste water production catalytic combustion adjuvant for coal according to claim 1 or 2, feature
It is, step（1）In, the vanadium extracting waste water, for the vanadium-containing water or vanadium-containing water generated in all kinds of vanadium extraction production processes
Recycle the high concentration vanadium-containing water of generation or the high ammonia nitrogen vanadium extracting waste water of high chlorine after pretreatment.
5. the method for recycling vanadium extracting waste water production catalytic combustion adjuvant for coal according to claim 1 or 2, feature
It is, step（1）In, during ammonia nitrogen vanadium extracting waste water high using high chlorine after pretreatment, step（2）In mass percent proportioning
For solution A 42 ~ 50%, rare earth series catalysts 42 ~ 50%, combustion adjuvant 6 ~ 10%.
6. the method for recycling vanadium extracting waste water production catalytic combustion adjuvant for coal according to claim 1 or 2, feature
It is, the dosage of the catalytic combustion adjuvant for coal is the 0.1~0.5% of coal dust gross mass.
7. the method for recycling vanadium extracting waste water production catalytic combustion adjuvant for coal according to claim 1 or 2, feature
Be, the aqueous property regulator for monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, (2-hydroxyethyl)methylamine),
At least one of dimethyl monoethanolamine, ammonia, ammonium hydrogencarbonate, ammonium carbonate.
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|---|---|---|---|---|
| US6117302A (en) * | 1998-08-18 | 2000-09-12 | Aluminum Company Of America | Fuel cell aluminum production |
| CN102061212A (en) * | 2009-11-16 | 2011-05-18 | 中冶建筑研究总院有限公司 | Fire coal efficient catalysis combustion-supporting agent and preparation method and use method thereof |
| CN102199458A (en) * | 2011-04-20 | 2011-09-28 | 江苏科创石化有限公司 | Multifunctional ashless combustion accelerant of heavy oil |
| CN102476887A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method of vanadium recovery wastewater |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117302A (en) * | 1998-08-18 | 2000-09-12 | Aluminum Company Of America | Fuel cell aluminum production |
| CN102061212A (en) * | 2009-11-16 | 2011-05-18 | 中冶建筑研究总院有限公司 | Fire coal efficient catalysis combustion-supporting agent and preparation method and use method thereof |
| CN102476887A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method of vanadium recovery wastewater |
| CN102199458A (en) * | 2011-04-20 | 2011-09-28 | 江苏科创石化有限公司 | Multifunctional ashless combustion accelerant of heavy oil |
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