CN1940096A - Extraction of vanadium and molybdenum compound from refused materials containing vanadium and molybdenum etc. multiple elements - Google Patents
Extraction of vanadium and molybdenum compound from refused materials containing vanadium and molybdenum etc. multiple elements Download PDFInfo
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- CN1940096A CN1940096A CNA2005100473330A CN200510047333A CN1940096A CN 1940096 A CN1940096 A CN 1940096A CN A2005100473330 A CNA2005100473330 A CN A2005100473330A CN 200510047333 A CN200510047333 A CN 200510047333A CN 1940096 A CN1940096 A CN 1940096A
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Abstract
Extraction of vanadium and molybdenum from waste materials is carried out by physically or chemically pre-treating for raw materials by recovered oil, leaching out at a certain pH value, generating soluble sodium metavanadate and sodium molybdate, removing impurities, filtering, solid-liquid separating, precipitating ammonium metavanadate by amine salt, filtering, drying, decomposing, tabletting by smelting furnace to obtain sheeted vanadic anhydride, precipitating ammonium metavanadate filtrate, pouring it into vanadium extraction tank, extracting by organic phase, cleaning by saturated organic phase, reversed extracting, concentrating and crystallizing. It has better vanadium recovery rate and quality and more product yield.
Description
Technical field
The invention belongs to waste and old comprehensive utilization of resources field, particularly vanadium-molybdenum-containing spent catalyst, the slag that contains vanadium, red soil, red cake, putty, ashes etc. are carried out the comprehensive regulation, extracting wherein has valence component, as V
2O
5Deng method, be specially a kind of from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains.
Background technology
1, vanadium is because its physics and chemical property, be widely used in national defense construction and economic construction every field, in metallurgical industry,, improve the intensity of steel thermotolerance and steel, be usually used in producing stainless steel, tank steel and High Strength Construction Steel etc. because vanadium can make the refinement of brilliant material.In petrochemical industry, be mainly used in oil refining and produce the vitriolic catalyst, the catalyzer, aeronautical material, magneticsubstance, the superconducting material that also are used for rubber and other organic synthesis, because the physical property that the oxide compound of vanadium has also is widely used in the modern science and technology field, as optics (colour filter cake), high tension battery, power cell, industries such as temperature instrumentation.
The waste material wide material sources that contain vanadium, the recovery of vanadium in the ore dressing smelting process, is all attached great importance in the famous vanadium iron ore deposit that contains.As vanadium concentrate and v-bearing steel slag, the annual millions of tons of world wide production, some produce vanadium big countries, as the v-bearing steel slag of the annual consumption of states such as Russia, South Africa all more than 40～500,000 tons.China produces vanadium big country, and the annual v-bearing steel slag that produces still can not satisfy Flos Bombacis Malabarici and hold the needs of steel enterprise self to raw material more than 200,000 tons.Other produces vanadium enterprise will remove to buy raw material to the world market, as South Africa, Russia, New Zealand.
It is spent catalyst that another kind contains vanadium raw materials, it mainly is the waste of petroleum refining industry's Chemical Manufacture, wherein contain precious metal and rare metals such as vanadium, molybdenum, nickel, cobalt, osmium, iridium, palladium, rhodium, ruthenium, platinum, consider from the utilization again and the environmental protection of resource, reclaim valuable metal, it all is very necessary administering solid pollutant.The U.S., Japan, Korea S and some countries of Europe develop spent catalyst and use as secondary resources.
It is raw material production vanadium, molybdenum and coherent element nickel, cobalt etc. with the spent catalyst that the man enterprises of number are also arranged in the big-and-middle-sized product vanadium enterprise of China, as Huludao City's vanadium factory and jinzhou Ferroalloy Plant etc., all is main raw material with the spent catalyst.
Other contains the vanadium waste material, as putty is to be the power station of fuel with heavy oil, the combustion ash of heating boiler and large-scale oily kiln all has the content of vanadium that does not wait, though a this raw material year supply has 1,000,000 tons, but it is in batches very little, too assorted, do not have fixed type products form and composition to form, do not have the production technique of typing yet.
Other byproduct red soil and phosphate rock ore deposit, uranium navajoite of carrying behind the aluminium as aluminium manufacturer is carried the transuranium byproduct---and red cake is the raw material that contains vanadium.
The present invention is with above-mentioned raw material production V
2O
5, and develop alkaline process production technique with throughput.
2, the main source of used vanadium in various countries and compound thereof is the oxide compound that extracts vanadium from v-bearing steel slag in the world.Produce V more than ten thousand tons per year
2O
5The vanadium factory of Flos Bombacis Malabarici vanadium factory, Chengde Iron ﹠ Steel Corp., Ma Gang of extra large Wilder steel vanadium company, Muscovite Qiu Suofu Metallurgical Factory, Iron And Steel Company of Nizhni Tagil, China in South Africa all be to be the large-scale system vanadium enterprise of raw material with the v-bearing steel slag, all adopt acid system to extract vanadium.
Concise and to the point technology: with the pulverulence of slag crushing to certain particle size, with magnetic separation or sieve method deironing, slag iron content 5～10% after the qualified choosing.Be equipped with an amount of additive, additive commonly used is Na
2CO
3(anhydrous) is aided with its weight proportion of NaCl is 1: 0.2～0.4.The material that mixes with additive carries out abundant batch mixing, and sprays into 4～5% moisture content, and material and additive are evenly bondd mutually, at 800 ℃～850 ℃, finishes the oxidation sodium of the vanadium in the material with rotary kiln or multiple hearth furnace in 4～6 hours.Grog is milled down to～80 orders, control liquid-solid ratio 3～5: 1, pH is between 8～9 in control, in leaching 30 minutes more than 85 ℃, adds proper C a
2+Or Mg
2+Ion is removed metal cations Fe, Ni, Co, Cu, Bi, Sn, the Ti etc. that can enter solution, also can remove PO simultaneously
4 3-, AsO
4 3-Deng negatively charged ion.Filter washery slag, contain vanadium mother liquid adding between sulfuric acid accent pH=4～5, add ammonium salt, regulate between pH=2～2.5 with sulfuric acid, reheat, stirring 2～2.5 hours then are settled out the xanchromatic ammonium poly-vanadate.Ammonium poly-vanadate is moisture 20～60%, and domestic each vanadium factory and each vanadium factory of Russia adopt reverberatory furnace that drying, decomposition ammonium vanadate and melting film-making one stove are carried out, and furnace temperature is 1000～1200 ℃.To producing the sheet vanadium ideal rate of recovery less than 95%, the yield of generally producing vanadium only is 90% from ammonium vanadate.And advanced countries such as America and Europe adopt three-step approach to make sheet V
2O
5, the deamination in rotary kiln again that dewaters in moisture eliminator earlier advances in the electric furnace to melt the V of fusing again
2O
5Cast certain thickness Vanadium Pentoxide in FLAKES through water-cooled system.Producers such as Germany and Austria adopt this method.
It is the dry ammonium poly-vanadate of rotative heater that adopts external electric that the gulf spy of sea, South Africa Wilder draws, and takes off the ammonium device with external electric again and decomposes ammonium poly-vanadate, uses silicon carbon rod electrosmelting V at last
2O
5, with the V of casting sheet machine with fusing
2O
5Cast certain thickness sheet.This advanced three-step approach makes ammonium poly-vanadate reach 99% to making the piece of Vanadium rate of recovery.
Vanadium extraction from spent catalyst, cause the concern of the scientific and technological circle of Japan, Germany, Russia, the U.S. already, and successively did extensive studies work the eighties in last century, some achievement in research has been built up the factory from spent catalyst extraction vanadium, molybdenum, nickel, cobalt of industrially scalable.
Japan Sun Company Inc., the bay chemical company of U.S. free port take the lead in last century late nineteen seventies use Na respectively to early eighties
2CO
3With NaCl be additive, be that stoving oven is finished oxidation, the sodium process to vanadium in the spent catalyst and molybdenum with rotary kiln and multiple hearth furnace.This process will be finished 750～800 ℃ of furnace temperature with 2.5～3 hours.Grog after the roasting in carrying out water logging more than 80 ℃, and is used Ca through levigate
2+And Mg
2+Ion, in the 8.5 condition removal of impurities of pH value, sedimentary impurity cation Ti, Fe, Al, Si etc., negatively charged ion PO
4 3-, AsO
4 3-, SiO
4 2-In the condition of pH=9, temperature is less than 20 ℃ Deng, the solution after the removal of impurities, is settled out ammonium meta-vanadate with the ammonium of 1.5 times of the required theoretical amount of precipitation.Molybdenum in the supernatant water after the precipitation adds acid, and acidifying precipitates into molybdic acid in 80 ℃, and the filtration drying roasting becomes MoO
3
Putty is that the background technology of the compound of vanadium extraction is seldom found, being seen technology report is water law, it is light because the putty body is thin, be not suitable for oxidation, the sodium process (putty major part in this atmosphere is blown into flue) of multiple hearth furnace, the big air flow quantity of rotary kiln, the water law production method is putty to be milled down to～100 orders, NaOH with 8Mol/L, solid-liquid is 1: 2.5, solution boiled 4 hours, so boil three times, 67% vanadium is leached in the putty, and three times the leaching result is respectively 43%, 16%, 8%.Soaking the hydrochloric acid that also has 37% usefulness 8Mol/L in the slag leaches.
Because the vanadium that NaOH leaches can directly sink ammonium vanadate, with vanadium and the nickel in the extraction process extraction acid solution, through back extraction recovery vanadium, makes the rate of recovery of vanadium reclaim 90% in water law.
Please (publication number CN1631797A) a kind of method of utilizing vanadium-containing wasting catalyst and Petroleum Ash to extract Vanadium Pentoxide in FLAKES be proposed in the Chinese invention patent, the background technology of this application partly provides the composition statistics of spent catalyst, and its production method is: determine the V in spent catalyst or the Petroleum Ash earlier
2O
5Content, add excessive N a then in molar ratio
2CO
3, through mixing, be crushed to 20～60 orders; The material of pulverizing entered continuously through feed bin carry out high-temperature roasting in the rotary kiln, about 4～6 hours of roasting time; Material after the roasting stirs down and is dissolved in the hot water again, adds CaCl simultaneously
2Remove foreign matter of phosphor, filter through filter and make solid-liquid separation, reclaim vanadic acid sodium and sodium molybdate solution; In pH=8～9.5 o'clock, in containing vanadic acid sodium and sodium molybdate solution, add excessive ammonium chloride under the normal temperature, generate the ammonium meta-vanadate precipitation, Sodium orthomolybdate is then stayed the vanadium molybdenum is separated; Ammonium meta-vanadate after the separation makes fused V through pyrolytic decomposition
2O
5, be finished product through film-making.Its weak point is: this patent has almost been copied word by word the technical process and the working condition of Texas, USA free port bay chemical company, what differed from only is to replace multiple hearth furnace with rotary kiln, just the same with Japanese Sun Company Inc., Japan environmental protection requires to administer the SO of discharging
2, this patent is administered imagination all not to be had.Japan and the United States two tame enterprises all are built in 70～eighties of last century, and its technical equipment is much better than its " invention " used backward equipment, and the present invention only outstanding request extracts V with alkaline process from raw materials such as v-bearing steel slag, putty, red soil, ashes
2O
5
Summary of the invention
The purpose of this invention is to provide a kind ofly,, produce vanadium, molybdenum compound to be applicable to the plurality of raw materials that contains elements such as vanadium by the alkaline process production technique of reform from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains.
Technical scheme of the present invention is:
From the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains, concrete steps are as follows:
(1) determines to contain V in vanadium, the molybdenum waste material earlier
2O
5Content, will contain vanadium, molybdenum waste material through after the pre-treatment, make wherein insoluble vanadium, molybdenum compound sodium become sodium metavanadate, the Sodium orthomolybdate of solubility;
(2) after leaching, filtering, the filtrate of solid-liquid separation places setting tank, feeds ammonia, adds ammonium salt, and wherein the ammonia add-on is 20～25% of an ammonium salt adding weight, and the ammonium salt add-on is precipitation NH
4VO
31.2～1.5 times of required theoretical molar amount make sodium metavanadate generate the ammonium meta-vanadate precipitation, and Sodium orthomolybdate is stayed and reached the vanadium molybdenum in the solution and separate; Add ammonia salt and can be beneficial to the ammonium meta-vanadate precipitation, feed ammonia, produce excessive N H in the solution
4 +, make that precipitation is more complete, the pH value is more stable;
(3) with the moisture of the dry ammonium meta-vanadate filter cake of expansion drying stove, 150 ℃～200 ℃ of drying temperatures, dried powder moisture 1～2%, thermal source use the waste heat of 700～800 ℃ in flash stove to heat;
(4) decompose dried ammonium meta-vanadate with thermal decomposition furnace, with the airtight thermal decomposition furnace of sending into of exsiccant powder, the chemical reaction that under 350～500 ℃, the powder of ammonium meta-vanadate is decomposed, the solid materials that decomposes the back generation enters the melting of flash stove, and gas imports the ammonia that reclaims in the ammonia absorber in the gas;
(5) enter V in the flash stove
2O
5Powder is smelted into liquid V under 700 ℃ of-800 ℃ of conditions of flash stove
2O
5, flow into pelleter and make sheet V
2O
5
The present invention precipitates the filtered liquid of ammonium meta-vanadate in the molybdenum extraction tank, cleans to reextraction through organic extractant phase, saturated organic phase, and saturated strip liquor generates ammonium paramolybdate through condensing crystal.
In the above-mentioned steps (2), to the pre-treatment of spent catalyst, slag: measure V in the raw material
2O
5Content is Na in molar ratio
2CO
3: V
2O
5Add Na at=1.2～1.3: 1
2CO
3, add NaCl simultaneously, Na
2CO
3With the ratio of weight and number of NaCl input amount be 1: 0.15-0.25, allocate Na into
2CO
3, behind the NaCl, through multiple hearth furnace or rotary kiln roasting, maturing temperature is 800 ℃-850 ℃, the time is 4～6 hours, makes material oxidation, sodium, and insoluble vanadium, molybdenum compound sodium are become sodium metavanadate, the Sodium orthomolybdate of solubility, extracts Vanadium Pentoxide in FLAKES for leaching.
In the above-mentioned steps (2), to the red soil pre-treatment: under normal pressure, use 3mol/L Na
2CO
3Leach after the solution sodium, leach liquor is NaVO
3Solution.
In the above-mentioned steps (2), to red cake pre-treatment: be 10% Na in the ebullient weight percent concentration
2CO
3Leach after the sodium in the solution, leach liquor is NaVO
3Solution.
In the above-mentioned steps (2), to putty and ashes pre-treatment: measure V in the raw material
2O
5Content adds V
2O
5It is excessive 10% to react the theoretical molar amount of required NaOH, is 1.7～2.0MPa at pressure, and temperature is under 190 ± 5 ℃ of conditions, and the blowing air sodium leached after 2.5～3.0 hours, and leach liquor is NaVO
3Solution.
In the above-mentioned steps (2), leaching is to utilize sodium metavanadate and the water-soluble character of Sodium orthomolybdate, with pretreated vanadium, the molybdenum waste material of containing of 80～90 ℃ hot water dissolving, sodium metavanadate and Sodium orthomolybdate is fully dissolved, simultaneously by adding MgCl
2, NH
4The Cl dephosphorization, wherein, MgCl
2Add-on is 1.2～1.5 times of the phosphorous mole number of leach liquor, NH
4The Cl add-on is 1～1.1 times of the phosphorous mole number of leach liquor, can adjust the pH value in 8.5 ± 0.5 scopes simultaneously.
The present invention precipitates NH
4VO
3Ammonium salt be NH
4Cl.
In the above-mentioned steps (4), adopt ammonium and recovery decomposing N H in the hot pressing gas water lift
3Detailed process is as follows: the waste water of ammonium salt-containing 2～2.5g/l imports gas stripping column, ammonium salt under superheated vapo(u)r heating and stirring in the water resolves into ammonia, the superheated vapo(u)r temperature is 260～280 ℃, discharge and import the ammonia that the ammonia absorber recovery is decomposed with crossing hot gas, the pressure that this method 0.1MPa because of the overheated band of gas is called hot pressing gas formulation.Ammonia is through decomposition gas in the water, and the ammonia content in the discharge water is 2mg/1～4mg/l, the emission standard of ammonia nitrogen in the attached water, standard No.: DB21-60-89 (new extension primary standard) NH
3The emission standard of-N is 5.0mg/l.
It is vanadium-molybdenum-containing spent catalyst that the present invention contains vanadium, molybdenum waste material, contain slag, red soil, red cake, putty or the ashes of vanadium.
Principle of the present invention is as follows:
1, from v-bearing steel slag, extracts in the production process of Vanadium Pentoxide in FLAKES, all adopt the method for acid system precipitation ammonium poly-vanadate both at home and abroad, though the process flow sheet that has is marked with alkaline process, there is not the concrete Production Flow Chart of alkali method process, alkaline process and acid system difference are to contain in the aftertreatment of vanadium solution in leaching.Acid system is that solution is regulated between pH=4～5 with sulfuric acid, adds ammonium salt, regulates between pH=2～2.5 reheat, stirring 2～2.5 hours, NaVO in the solution again with sulfuric acid
3Separate out with the yellow red precipitation of ammonium poly-vanadate.This precipitation condition of acid system is unsuitable for the production of spent catalyst, because most spent catalyst all contains the molybdenum of certain percentage composition.The Na that molybdenum is produced in the sodium process
2MoO
4Water-soluble, under acid precipitation condition, sedimentary while of ammonium poly-vanadate, Na
2MoO
4Also with H
2MoO
4Form precipitation, two kinds of sedimentary mixtures are difficult to separate, and have increased the industrial production difficulty, consider the variation of raw materials for production, the flow process of setting up alkaline process is very necessary.Alkaline process production is to use (NH4) in the pH value under 8.2～9.0 conditions
2SO
4Or NH
4Cl precipitates NH
4VO
3, be called for short alkaline process; In leaching process, roughly can reach the requirement of pH=8.5 ± 0.5 at the grog of the add-on gained of roasting process control alkali.Not only can save a large amount of sulfuric acid that the acid system adjust pH consumes with alkaline process, because the precipitated product difference, that alkaline process generates is NH
4VO
3, be single molecule in precipitation, discord impurity generates the polymolecular multipolymer, product purity is easy to guarantee, and the throw out of acid system is an ammonium poly-vanadate, meets acid group negatively charged ion such as PO in this many minutes polymerization processes
4 3-, AsO
4 3-, SiO
4 2-, SO
4 2-Deng, there is this negatively charged ion living heteropoly acid ammonium that will participate in being polymerized, become very troublesome impurity, so the V that alkaline process is produced
2O
5Purity generally exceeds the V that acid system is produced
2O
5Purity 1～2%, the main drawback of alkaline process production are that the consumption of ammonia is big, from molecular composition, and ammonium meta-vanadate (NH as can be seen
4VO
3) be that a vanadium consumes an ammonia, and the molecular composition of ammonium poly-vanadate is (NH
4)
6V
10O
28As long as each vanadium is 0.6 ammonium combination, the ammonium meta-vanadate of producing with alkaline process manys the ammonium of consumption 40% than acid system, in order to solve the consumption of ammonium in the production, set up the retrieving arrangement of ammonia in the technology, to reclaim the ammonia in gas and the water, promptly realized recycling of ammonia, reduced production cost significantly and administered in gas, the water ammonium again the pollution of environment.
2, from contain the vanadium waste material, in the production process of the oxide compound of extraction vanadium, all to through and using the ammonium salt precipitation.No matter product is NH
4VO
3Or (NH
4)
6V
10O
28Ammonium poly-vanadate, all contain nearly 40～50% moisture in its filter cake.For the product of moisture vanadium compounds is made flaky Vanadium Pentoxide in FLAKES.Russian and Chinese ownership system vanadium producer all adopt reverberatory furnace handle dry, decompose ammonium and melting V
2O
5The method of Yu Yilu reaches 95% from vanadate to making sheet vanadium ideal vanadium recovery in this way.The general yield of producing vanadium only is 90～92%, if the excessive ammonium meta-vanadate dry powder that causes of wind-force flies away with air-flow in melting process, temperature is higher than 900 ℃ makes V again
2O
5Volatilization, the ammonia of decomposition at high temperature is broken down into H again
2And N
2, hydrogen reducing pentavalent vanadium is dystectic low price barium oxide, it is the low-melting V of high price that the low price barium oxide is reoxidised into
2O
5, this production decision constantly drops into virgin material, and the ammonium input is constantly arranged, and constantly carry out redox, so the single stage method melting cycle is long, the energy consumption height, and thermo-efficiency is less than 15%.Therefore in reform technology, use the advanced person's of states such as South Africa, West Germany three-step approach experience, adopt the powder technology of Chinese new development.
With the moisture of the dry ammonium meta-vanadate filter cake of expansion drying stove, 150～200 ℃ of drying temperatures, dried powder moisture 1～2%, thermal source heats the energy consumption of having saved transpiring moisture with 700 ℃ waste heat of flash stove.Decompose dry back ammonium meta-vanadate with thermal decomposition furnace, with the airtight thermal decomposition furnace of sending into of exsiccant powder, the chemical reaction that under 350～500 ℃ the powder of ammonium meta-vanadate is decomposed decomposes the solid materials that the back produces and enters the melting of flash stove, and gas imports the ammonia that reclaims in the ammonia absorber in the gas.Enter the V in the flash stove
2O
5Powder is smelted into liquid V fast under 700～800 ℃ of conditions of flash stove
2O
5, flow into pelleter and make sheet V
2O
5These three kinds of equipment from aqueous ammonium meta-vanadate to making flaky V
2O
5Process in, fully realized serialization and automatization, material all carries out in airtight, has guaranteed that not only the quality of product has also reduced workman's operation.
3, reaction principle: contain vanadium, molybdenum waste material after crushed, add Na
2CO
3, NaCl is through peroxidation, sodium roasting, and insoluble vanadium, molybdenum compound are oxidized to metal oxide, and generates the sodium metavanadate and the Sodium orthomolybdate of solubility with the sodium reaction, makes vanadium, molybdenum compound enter in the aqueous solution through water logging, adds an amount of NH behind the solution purification
4Cl generates ammonium meta-vanadate, and the ammonium meta-vanadate decomposition makes V under proper temperature
2O
5Filtered liquid extraction in the molybdenum extraction tank of precipitation ammonium meta-vanadate, reextraction, condensing crystal obtain ammonium paramolybdate.Concrete reaction formula is as follows:
Roasting:
Leach: solid NaVO
3And Na
2MoO
4Water-soluble
Dephosphorization:
Precipitation: NaVO
3+ NH
4Cl → NH
4VO
3↓+NaCl
Decompose:
The invention has the beneficial effects as follows:
1, the present invention builds a cover alkaline process and extract V from v-bearing steel slag
2O
5Technical process, and be applicable to that spent catalyst, putty, red soil etc. contain the production needs of vanadium raw materials.
From v-bearing steel slag, extract V
2O
5Production technique, all adopt the acid system precipitation both at home and abroad.The concise and to the point technology of acid system precipitation is oxidation, sodium 2.5 hours.Vanadium in the material changes into sodium metavanadate, uses CaCl in leaching process
2Dephosphorization removal of impurities, the cleaner liquid after the removal of impurities are with sulfuric acid adjust pH to 2.5, in the presence of an amount of sulfuric acid, with (NH
4)
2SO
4The precipitation vanadic acid sodium generates ammonium poly-vanadate, so because be that acid system is in precipitation in acidic solution.
The present invention adopts alkaline process to produce v-bearing steel slag to extract V during reality is produced
2O
5, under alkaline condition, use NH
4Cl precipitation ammonium meta-vanadate abbreviates alkaline process as, and alkaline process is to carry out under pH value 8.5 ± 0.5 conditions, controls sodium and Na in rotary kiln well
2CO
3Input amount, the pH value of solution value of burning till the grog leaching can reach this pH value scope, therefore save adjust pH and the used sulfuric acid of precipitation, solution purification and leaching are finished synchronously, and the ammonium meta-vanadate of generation generates the high 1-2% of purity of co-precipitation than acid system because of no heteropoly acid ammonium.
2, the present invention with new technology, reform old technology, improve the rate of recovery of vanadium, improve the thermo-efficiency of fuel oil, reduce production costs.
V-bearing steel slag all contains 40～50% moisture content in the filter cake of precipitation ammonium poly-vanadate or ammonium meta-vanadate, handle this filter cake no matter with reverberatory furnace or electric furnace or the dry melting V of additive method
2O
5All finish, will dehydrate, decompose ammonium salt exactly to melting film-making shape V with a stove
2O
5, all be with calcining under the furnace temperature condition, discharge as early as possible in order to make water vapour, fuel oil fully burns, and calcining blasts air and can not exempt from, and furnace temperature remains on 1000 ℃-1200 ℃.With the moisture content of such high temperature devaporation 40～50%, it is extremely low to remove to decompose its thermo-efficiency of 50～60% ammonium salts, is lower than 15%.A large amount of gas flow makes the V of part exsiccant ammonium salt or distillation
2O
5Discharge from flue with air-flow, cause the V of 8-10%
2O
5Loss, the gaseous ammonia major part of decomposing ammonium salt is broken down into N
2And H
2, the hydrogen that is generated has reduction 5 valency vanadium to become the chemical reaction of dystectic 3 valency vanadium and 4 valency vanadium.Make and constantly carry out reaction that this redox reoxidizes in the process of calcining vanadium and empty power consumption source.
The present invention changes three steps refining vanadium into from stove refining vanadium, divides for three steps finished dry moisture content, decomposition ammonium salt, fusion film-making.The equipment of realizing for three steps is respectively the dry expansion drying stove of using, and 150 ℃ of-200 ℃ of thermals source of furnace temperature heat with the flash roaster waste heat.Dry ammonium salt decomposes with decomposing furnace and decomposes 350 ℃-500 ℃ of furnace temperature, and the ammonia of decomposition is recycled into (NH
4)
2SO
4, utilize again in the production.Melting system vanadium keeps 700 ℃-800 ℃ to guarantee V with the flash roaster furnace temperature
2O
5Refining in blocks, institute's heat extraction gas returns to the expansion drying stove and carries out UTILIZATION OF VESIDUAL HEAT IN, rate of recovery drying oven＞99.5% of practical vanadium as a result; Decomposing furnace＞99.5%; Flash roaster＞99.5%; V
2O
5Total yield＞98.5%; Than reverberatory furnace one stove refining V
2O
5Rate of recovery 90%-94% improve 6.5%-8.5%.Thermo-efficiency brings up to 50%, manufacture order ton V from 15%
2O
5Oil consumption drops to 0.5 ton of fuel-economizing 1.l ton from 1.6 tons.
3, the present invention reclaims the ammonia in gas and the liquid, realizes recycling of ammonia, reduces consumption of auxiliary materials, reduces production costs, and improves environment, has administered two kinds of pollutions.
No matter all the ammonia major part of decomposing is burnt till hydrogen and nitrogen with roasting method with containing vanadium material production Vanadium Pentoxide in FLAKES acid system and alkaline process.Part NH
3From the flue high altitude discharge.
2.2% ammonia in the process using heat air formulation recovery waste water of the present invention.Ammonia quantity is 15mg/L in the water of recovery back, and directly reclaims the gas NH that decomposing furnace decomposes
3, contain ammonia 0.12g/m in the gas after the recovery
3Design output day is reclaimed 100%NH
316 tons, 7.5 tons/d of present unsaturated operation throughput, the annual 4200T/ NH that reclaims
3The ammonium salt of making recycles, can reduce and produce,, can save and prop up 2,500 ten thousand yuan if reach designed productive capacity with 1,200 ten thousand yuan of auxiliary material expenses, the recovery technology of the ammonia in ammonia nitrogen in the gas and the water is introduced the production technique of vanadium, and gas, the water of promptly having administered environmental protection pollute has created considerable value again.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
As shown in Figure 1, narrate the technical process and the processing parameter of spent catalyst, v-bearing steel slag, red soil and red cake, putty and ashes below respectively:
1, spent catalyst: with the spent catalyst is raw material, the heavy oil of contained 15～20% weight in continuous centrifuge recovery raw material, and the spent catalyst after the de-oiling is oil-containing 3～5% only.This raw material powder to～40 orders, is added Na
2CO
3Be 120～130% of the required theoretical molar amount of vanadium sodium, weight ratio is NaCl: Na
2CO
3=0.15～0.25: 1, mixing to rotary kiln in 800～850 ℃ of roastings 4～6 hours, be milled to～60 orders to wet-milling, to batch extractor in leaching 30 minutes more than 85 ℃, use MgCl
2, NH
4The Cl dephosphorization, MgCl
2Add-on is 1.2～1.5 times of the phosphorous mole number of leach liquor, NH
4The Cl add-on is 1～1.1 times of the phosphorous mole number of leach liquor, and removes P, Si, Al etc., filtering separation, and wash heat discards only.Filtrate is cooled to less than 20 ℃, adds NH in setting tank
4Cl, add-on is precipitation NH
4VO
3150% of required theoretical molar amount, and adding accounts for NH
4Cl adds the NH of weight 25%
3,, filter after precipitation is finished to guarantee the complete of precipitation, solid contains 40～50% moisture, enters the expansion drying stove, in 150～200 ℃ of dryings, thermal source heats with the waste heat of 700～800 ℃ in flash stove, and dried powder contains moisture 1～2%, and vanadium recovery is greater than 99.5%.Dried NH
4VO
3Enter the ammonium decomposing furnace, make NH in 350～500 ℃
4VO
3Be decomposed into NH
3, powdery V
2O
5And moisture, the rate of recovery of its vanadium is greater than 99.5%.Powdery V
2O
5Go into the flash stove and make flaky V in 700～800 ℃ of meltings
2O
5, the rate of recovery of vanadium is greater than 99.5%.
2, v-bearing steel slag: because of containing a large amount of metallic irons, remove the visible metallic iron earlier in the v-bearing steel slag, the v-bearing steel slag after the deironing is allocated Na into after comminution is again with iron removal by magnetic separation for this reason
2CO
3And NaCl, both add-ons are identical with the method for calculation of the add-on of spent catalyst, and its roasting sodium condition is the same, until making sheet V
2O
5, all with top described.
3, red soil: red soil is byproduct behind aluminium manufacturer's extraction aluminium, is mainly commercially pure many vanadic salts precipitations, under normal pressure, uses 3mol/L Na
2CO
3Solution, temperature are 85 ℃, leach 1.5 hours, can finish the NaVO of red soil
3Conversion, clear liquid can be gone into setting tank and be given the processing precipitation.
4, red cake: red cake is the intermediates that vanadium already produces vanadium, and this product mostly is acid precipitation product, is 10% Na in the ebullient weight percent concentration
2CO
3Again after the sodium, filter ammonium salt in the solution, precipitation becomes NH
4VO
3, filtering, filter cake is made sheet V through three steps
2O
5
5, putty and ashes: putty and ashes are two-stage byproducts of oil-fired furnace, and this raw material is thin and light, in the rotary kiln or multiple hearth furnace of big wind speed, promptly blows away from flue without the oxidation sodium, with this raw material of conventional production method intractable.The method that the present invention directly soaks with high pressure base without kiln, one step vanadium extraction from putty and ashes, the oxidation sodium of vanadium in the realization raw material.The NaOH of 2mol/L solution add the solid-liquid weight ratio be 1: 2.5 raw material in autoclave, be 1.7MPa at pressure, temperature is under 190 ℃ the condition, to be incubated 2.5 hours, leach liquor is NaVO
3Solution, vanadium leaching yield are 94.5%, are 89% from the total recovery that leaches into the output vanadium.
6, ammonium decomposing furnace: ammonia to the recovery tower that the ammonium decomposing furnace decomposes reclaims gaseous ammonia, and gas is gone into 110 ℃ of the temperature of recovery tower, and during discharge 30 ℃, processing power 8000M per hour
3, the gas that contains ammonia 2% (volumn concentration) produces saturated NH by inhaling the hydrochloric acid 30% of ammonia
4Cl returns into setting tank, the precipitation ammonium vanadate.
7, the lean solution of precipitation after-filtration contains the molybdenum of 4g/L in the vanadium settling tank, directly squeeze into the counter-current extraction groove, by volume the per-cent meter is a mixed extractant with trialkylamine 15%, 2-Ethyl Hexanol 5%, kerosene 80%, secondary extraction percentage extraction is 99.7%, is 10% (NH with weight percent concentration
4)
2CO
3Back extraction, back extraction ratio are 99.7%, and the strip liquor that will contain the ammonium paramolybdate of 84g/L concentrates, and promptly separates out the ammonium paramolybdate white crystals.
8, the lean solution behind the collection molybdenum, ammonia in hot pressing gas water lift, its ammonia are also reclaimed by the absorption tower, are used for precipitation.Adopt ammonium and recovery decomposition ammonia in the hot pressing gas water lift, detailed process is as follows: the waste water of ammonium salt-containing 2～2.5g/l imports gas stripping column, ammonium salt under superheated vapo(u)r heating and stirring in the water resolves into ammonia, the superheated vapo(u)r temperature is 260～280 ℃, discharge and import the ammonia that the ammonia absorber recovery is decomposed with crossing hot gas, the pressure that this method 0.1MPa because of the overheated band of gas is called hot pressing gas formulation.Ammonia is through decomposition gas in the water, and the ammonia content in the discharge water is 2mg/l～4mg/l, the emission standard of ammonia nitrogen in the attached water, standard No.: DB21-60-89 (new extension primary standard) NH
3The emission standard of-N is 5.0mg/l.
Embodiment 1
Table 1 from moisture ammonium meta-vanadate filter cake to sheet V
2O
5Material balance and oil consumption
| Ammonium meta-vanadate filter cake (T) | Moisture %wt | Theoretical amount (T) | Butt ammonium vanadate (T) | The rate of recovery %wt of dry back vanadium | Should produce V after the decomposition 2O 5 (T) | Decompose the real V of producing in back 2O 5Powder (T) | The rate of recovery %wt that decomposes the back vanadium | Flash furnace raw material vanadium amount (T) | The real sheet V that produces 2O 5 (T) | The yield %wt of vanadium after refining | Total yield %wt | Oil consumption in the production (T) | Ton sheet vanadium oil consumption (T) |
| 30.00 | 44.00 | 16.80 | 16.77 | 99.8 | 12.98 | 12.941 | 99.7 | 12.941 | 12.9 | 99.68 | 99.18 | 9.16 | 0.71 |
| 38.00 | 42.00 | 22.04 | 21.964 | 99.64 | 17.00 | 16.138 | 99.8 | 16.138 | 16.074 | 99.6 | 99.04 | 11.7 | 0.728 |
| 44.00 | 48.00 | 22.88 | 22.70 | 99.2 | 17.57 | 17.52 | 99.7 | 17.52 | 17.47 | 99.7 | 98.6 | 12.9 | 0.74 |
The listed material balance actual measurement of last table is 200 ℃ of expansion drying temperature, finishes under 500 ℃ of cracked ammonium furnace temperature and 700 ℃ of conditions of flash furnace temperature.
The foregoing description is three groups of material balance measurement results, and with the method for this three step system vanadium, not only product recovery rate makes the finished product vanadium increase by 6～7 percentage points up to 99%, and the unit oil consumption is also saved one ton of oil fuel than reverberatory furnace refining sheet vanadium.
Produce the Vanadium Pentoxide in FLAKES home and abroad and do not pay attention to the recovery of cracked ammonium and water ammonium formulating technology with containing the vanadium waste material, the way that is adopted is with the most of further decomposing H of the ammonia that decomposes under the high temperature
2And N
2The small portion high altitude discharge.The present invention first the production technique of vanadium adopt the recovery way be consider that decomposing furnace will discharge 6～7 tons of ammonias by throughput every day and also contain in the water after the precipitation concentration be the ammonium salt of 2g/L from discharge of wastewater, produce now and drop into auxiliary material NH every day
425～30 tons of Cl, 1600 yuan of ton values.40000 yuan of introductions of reclaiming the ammonia technology not only reduce cost, and ammonia is recycled, and have administered the gas ammonia and the water ammonium environmental pollution of environmental protection.Ammonium and recovery decomposing N H in the hot pressing gas water lift
3Applying to the production technique of vanadium, also is the innovation of production technique.
Adopt vanadium of the present invention and molybdenum recovery height, vanadium reaches 90%, and molybdenum reaches 95%.Present online designed productive capacity year 5000 tons of Vanadium Pentoxide in FLAKESs, produce 1800 tons of ammonium paramolybdates per year, its throughput can continue to enlarge.Quality product meets national top grade standard up to more than 99%.
Claims (10)
1, from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains, it is characterized in that concrete steps are as follows:
(1) determines to contain V in vanadium, the molybdenum waste material earlier
2O
5Content, will contain vanadium, molybdenum waste material through after the pre-treatment, make wherein insoluble vanadium, molybdenum compound sodium become sodium metavanadate, the Sodium orthomolybdate of solubility;
(2) after leaching, filtering, the filtrate of solid-liquid separation places setting tank, feeds ammonia, adds ammonium salt, and wherein the ammonia add-on is 20～25% of an ammonium salt adding weight, and the ammonium salt add-on is precipitation NH
4VO
31.2～1.5 times of required theoretical molar amount make sodium metavanadate generate the ammonium meta-vanadate precipitation, and Sodium orthomolybdate is stayed and reached the vanadium molybdenum in the solution and separate;
(3) moisture of the dry ammonium meta-vanadate filter cake of usefulness expansion drying stove, 150 ℃～200 ℃ of drying temperatures, dried powder moisture 1～2%;
(4) decompose dried ammonium meta-vanadate with thermal decomposition furnace, with the airtight thermal decomposition furnace of sending into of exsiccant powder, the chemical reaction that under 350～500 ℃, the powder of ammonium meta-vanadate is decomposed, the solid materials that decomposes the back generation enters the melting of flash stove, and gas imports the ammonia that reclaims in the ammonia absorber in the gas;
(5) enter V in the flash stove
2O
5Powder is smelted into liquid V under 700 ℃ of-800 ℃ of conditions of flash stove
2O
5, flow into pelleter and make sheet V
2O
5
2, described according to claim 1 from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains, it is characterized in that: the filtered liquid of precipitation ammonium meta-vanadate is in the molybdenum extraction tank, clean to reextraction through organic extractant phase, saturated organic phase, saturated strip liquor generates ammonium paramolybdate through condensing crystal.
3, it is characterized in that in the described step (2) from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains according to claim 1 is described, to the pre-treatment of spent catalyst, slag: measure V in the raw material
2O
5Content is Na in molar ratio
2CO
3: V
2O
5Add Na at=1.2～1.3: 1
2CO
3, add NaCl simultaneously, Na
2CO
3With the ratio of weight and number of NaCl input amount be 1: 0.15-0.25, allocate Na into
2CO
3, behind the NaCl, through multiple hearth furnace or rotary kiln roasting, maturing temperature is 800 ℃-850 ℃, the time is 4～6 hours, makes material oxidation, sodium, and insoluble vanadium, molybdenum compound sodium are become sodium metavanadate, the Sodium orthomolybdate of solubility, extracts Vanadium Pentoxide in FLAKES for leaching.
4, it is characterized in that in the described step (2) from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains according to claim 1 is described, to the red soil pre-treatment: under normal pressure, use 3mol/L Na
2CO
3Leach after the solution sodium, leach liquor is NaVO
3Solution.
5, it is characterized in that in the described step (2) from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains according to claim 1 is described, to red cake pre-treatment: be 10% Na in the ebullient weight percent concentration
2CO
3Leach after the sodium in the solution, leach liquor is NaVO
3Solution.
6, it is characterized in that in the described step (2) from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains according to claim 1 is described, to putty and ashes pre-treatment: measure V in the raw material
2O
5Content adds V
2O
5It is excessive 10% to react the theoretical molar amount of required NaOH, is 1.7～2.0MPa at pressure, and temperature is under 190 ± 5 ℃ of conditions, and the blowing air sodium leached after 2.5～3.0 hours, and leach liquor is NaVO
3Solution.
7, described according to claim 1 from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains, it is characterized in that: in the described step (2), leaching is to utilize sodium metavanadate and the water-soluble character of Sodium orthomolybdate, with pretreated vanadium, the molybdenum waste material of containing of 80～90 ℃ hot water dissolving, sodium metavanadate and Sodium orthomolybdate are fully dissolved, add MgCl simultaneously
2, NH
4The Cl dephosphorization, wherein, MgCl
2Add-on is 1.2～1.5 times of the phosphorous mole number of leach liquor, NH
4The Cl add-on is 1～1.1 times of the phosphorous mole number of leach liquor.
8, described according to claim 1 from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains, it is characterized in that: precipitation NH
4VO
3Ammonium salt be NH
4Cl.
9, described according to claim 1 from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains, it is characterized in that: in the described step (4), adopt ammonium and recovery decomposing N H in the hot pressing gas water lift
3Detailed process is as follows: the waste water of ammonium salt-containing 2～2.5g/l imports gas stripping column, ammonium salt under superheated vapo(u)r heating and stirring in the water resolves into ammonia, the superheated vapo(u)r temperature is 260～280 ℃, discharge and import the ammonia that the ammonia absorber recovery is decomposed with crossing hot gas, the pressure that this method 0.1MPa because of the overheated band of gas is called hot pressing gas formulation.
10, described from the multiple method of extracting vanadium, molybdenum compound vanadium, the molybdenum waste material that contains according to claim 1, it is characterized in that: described to contain vanadium, molybdenum waste material be vanadium-molybdenum-containing spent catalyst, contain slag, red soil, red cake, putty or the ashes of vanadium.
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