CN105502423A - Method for producing high-grade zircon sand - Google Patents
Method for producing high-grade zircon sand Download PDFInfo
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- CN105502423A CN105502423A CN201610065831.6A CN201610065831A CN105502423A CN 105502423 A CN105502423 A CN 105502423A CN 201610065831 A CN201610065831 A CN 201610065831A CN 105502423 A CN105502423 A CN 105502423A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10715—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material
- C01B33/10721—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material with the preferential formation of tetrachloride
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/26—Chlorine; Compounds thereof
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention relates to a method for preparing zircon sand, in particular to a method for producing high-grade zircon sand. The method comprises the following steps: adding zircon sand and sulfuric acid at the mass ratio of (0.4-0.9): 1 into an immersion combustion reaction still; introducing smoke at 800-1000 DEG C after natural gas combustion to enable a chemical reaction to be carried out for 6-8 hours at 100-350 DEG C in the reaction still; removing impurities in the zircon sand; then carrying out stirring washing; filtering, washing and drying to obtain the high-grade zircon sand. High-purity zirconium oxychloride, gas-phase method silicon dioxide and high-grade zircon sand can be co-produced by using the production method disclosed by the invention, the method is a green, cyclic and economical industry chain, and the obtained product is good in quality, low in production cost and free of pollution.
Description
Technical field
The present invention relates to the method preparing zircon sand, specifically a kind of method of producing high-grade zircon sand.
Background technology
Zirconium oxychloride end-use is extensive, it is the basic material of zirconium chemical industry, the huge market demand, within 2014,240,000 tons are reached, but domestic zirconium oxychloride all " alkali fusion " is produced, production cost is high, and environmental pollution improvement's difficulty is very large, and quality product can not reach the quality standard of high-purity zirconium oxychloride.
Fumed silica is of many uses, and be high-grade industrialized nano material, main raw material is silicon tetrachloride, and the main source of silicon tetrachloride is the byproduct of polysilicon industry or the byproduct of organosilicon industry.
Polysilicon enterprise is in order to reduce production cost in recent years, have developed silicon tetrachloride cold hydrogenation technology, be trichlorosilane converting silicon tetrachloride, the byproduct monomethyl trichlorosilane of paying of organosilicon industry increases greatly in silane coupling agent industry usage quantity, and monomethyl trichlorosilane disproportionation technology is also in Application and Development simultaneously.
This makes silicon tetrachloride market value climb up and up, and market supply and demand is nervous, pulls fumed silica product price to climb up and up.
Zirconium silicate is the main raw material of pottery, and zircon sand radioactivity is harmful to HUMAN HEALTH, should reduce the radioactivity of zircon sand as far as possible, and then reduce the radioactivity of ceramic tile, so must control the radioactive indicator of silicon sand, diversified, superior zirconium silicate market, needs high-grade zircon sand.
Summary of the invention
The object of the invention is to provide a kind of method of producing high-grade zircon sand.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of method of producing high-grade zircon sand: by zircon sand and sulfuric acid, with the liquid-solid ratio of 0.4 ~ 0.9:1, be added in submerged combustion reactor, pass into 800 ~ 1000 DEG C of flue gases after combustion of natural gas, to make in reactor, at 100 ~ 350 DEG C, to carry out 6 ~ 8 hours chemical reactions, remove the impurity in zircon sand, then carry out agitator treating, namely filtration, washing, oven dry obtain high-grade zircon sand and co-product silicon tetrachloride.
After described reaction, vitriolated flue gas reclaims after washing, and recirculation uses; In described reactor, after reaction, zircon sand reclaims, as the mother liquor producing zirconium oxychloride through agitator treating, band filter filtration, filtrated stock and wash water.
Adopt zircon sand, reductive agent and stablizer, chlorine is passed in chlorination furnace under the gas speed of 0.07 ~ 0.12m/s, chlorination reaction is carried out with 1150 ~ 1200 DEG C, generate zirconium tetrachloride, silicon tetrachloride, then carry out gas solid separation, namely the zirconium tetrachloride solid hydrolysis that separation obtains, purifying, zirconyl chloride solution evaporation, crystallization, separation obtain high-purity zirconium oxychloride and co-product silicon tetrachloride;
The mass ratio of described zircon sand, reductive agent, stablizer and chlorine is 0.9 ~ 1.1:0.2 ~ 0.3:0.3 ~ 0.4:2.7 ~ 2.8.
Gas that described gas solid separation obtains, carry out the gas solid separation of gas, again be separated obtain zirconium tetrachloride Purify, zirconyl chloride solution evaporation, crystallization, after gained crystal water dissolution, namely evaporation, crystallization, filtration, washing, separation obtain high-purity zirconium oxychloride product, can obtain co-product silicon tetrachloride simultaneously.
The gas solid separation of described gas first adopts cyclonic separator to be separated in tail gas, and after making separation, gas temperature is at 150 ~ 180 DEG C, and then adopt whirlwind to add the gas-solid separator of cloth bag type structure, be separated, after making separation, temperature is at 80 ~ 100 DEG C.
Add catalyzer in described chlorination reaction, the mass ratio of catalyzer and zircon sand is 0.05 ~ 0.1:1;
Wherein, catalyzer is boron oxide or boratory oxide compound, as Na
2b
4o
7, Li
2b
4o
7, BLiO
2, BNaO
2deng.Preferred catalyst is the oxide compound of boratory oxide compound and metaborate, i.e. Li
2b
4o
7with BLiO
2according to the ratio mixing that mass ratio is 1:1.
Described stablizer is one or more in silicon carbide, Pure Silicon Metal, ferrosilicon, compound with the large silicon of chlorine reaction thermal discharge, titanium dioxide, titanyl compound;
Described reductive agent is after-smithing petroleum coke.
Described chlorination reaction after product cools in chlorination furnace, make gas cooling temperature at 450 ~ 500 DEG C, then gas is passed into quench tube and adopt direct spraying cooling, make gas cooling temperature at 430-450 DEG C, after cooling, gas is passed into strainer and proceed to quench tube again, spraying cooling mode is adopted to make gas temperature at 400 DEG C, after cooling, gas enters quencher again, adopt the direct spraying cooling of silicon tetrachloride, and adopt recirculated water indirectly to cool at quencher chuck, make gas temperature at 200 ~ 240 DEG C, after mixed gas cools in quencher, zirconium tetrachloride solid is separated with other gas in product.In order to reduce the foreign matter content such as silicon tetrachloride in zirconium tetrachloride further, in quencher, zirconium tetrachloride solid material enters two-stage continuous purifier, purifier chuck adopts heat-conducting oil heating (thermal oil establishes heat conduction petrol station), in control purifier, gas temperature is at 260 ± 10 DEG C, Si/Zr < 0.00006 in zirconium tetrachloride solid after purification, enters hydrolytic decomposition pot hydrolysis.
The zirconium tetrachloride generated after described chlorination reaction, silicon tetrachloride mixed gas carry out first step cooling in the intercooling section of chlorination furnace, and one-level cooling section uses the indirect water-cooling of semi-canal type, control gas outlet temperature at 800 ~ 1000 DEG C;
The expanding reach that the cooled zirconium tetrachloride of one-level, silicon tetrachloride mixed gas enter chlorination furnace carries out second stage cooling, and chlorination furnace expanding reach adopts air jacket indirectly to cool, and controls gas temperature at 450 ~ 500 DEG C;
The cooled zirconium tetrachloride of secondary, silicon tetrachloride mixed gas is carried out in chlorination furnace, go out chlorination furnace outlet to enter first paragraph quench tube and carry out third stage cooling, adopt silicon tetrachloride liquid direct spraying cooling continuously in first paragraph quench tube, control gas cooling temperature at 430-450 DEG C;
After cooling, gas enters strainer, by strainer, then enters second segment quench tube and carries out the cooling of fourth stage level, and two sections of quench tube adopt the direct spraying coolings of silicon tetrachloride, controls gas temperature at 380-400 DEG C;
Cooled gas enters quencher again and carries out level V cooling, the direct spraying cooling of silicon tetrachloride is adopted in quencher, adopt recirculated water indirectly to cool at quencher chuck simultaneously, direct-cooled and cold combining cools, make gas temperature at 200 ~ 240 DEG C, after mixed gas cools in quencher, zirconium tetrachloride solid is separated with other gas in product, in order to reduce the foreign matter content such as silicon tetrachloride in zirconium tetrachloride further, in quencher, zirconium tetrachloride solid material enters two-stage continuous purifier, purifier chuck adopts heat-conducting oil heating (thermal oil establishes heat conduction petrol station), in control purifier, gas temperature is at 260 ± 10 DEG C, Si/Zr < 0.00006 in zirconium tetrachloride solid after purification, enter hydrolytic decomposition pot hydrolysis.
By above-mentioned gained zirconium tetrachloride solid at the temperature of 40 ~ 80 DEG C, be hydrolyzed under the stirring velocity of 100 ~ 120r/min, to hydrolyzed solution, zirconium concentration is at 90 ~ 110g/l, then filter the smart zirconyl chloride solution obtaining purifying, essence zirconyl chloride solution is added to two heating outer circulation type feed liquid circulation tank again, using the secondary steam of feed liquid circulation tank as thermal source, steam heating feed liquid is utilized to evaporate, to zirconyl chloride solution preheating, control vapor pressure 0.3MPa, vacuum tightness is at-0.04MPa--0.05MPa, be evaporated to zirconium dioxide concentration at 180 ~ 200g/l, proceed to crystallizer, crystallization treatment namely obtain direct crystallization rate up to more than 90% high purity oxygen zirconium chloride crystal, a mother liquor of described crystallization and filtration can be applied mechanically.
A mother liquor of described crystallization and filtration can be applied mechanically (to be undertaken evaporating by mother liquor, crystallization, filtration, washing, gained crystal dissolves again, carry out evaporating together with solid hydrolyzed solution, crystallization, filter, washing, be separated obtain high-purity zirconium oxychloride product).
By above-mentioned gained zirconium tetrachloride solid and water, evaporate acid and washings mixes, be then hydrolyzed; Wherein, zirconium tetrachloride solid and water, the weight ratio of evaporating acid and washings are 0.9-1.00:2.3-2.41:0.7-0.77:1-1.02; Described evaporation acid is 20% hydrochloric acid; Described washings is 18% hydrochloric acid.
Zircon sand after reaction in described reactor is filtered through agitator treating, band filter, filtrated stock and described zirconium oxychloride crystal is mother liquid obtained is mixed into mother liquid evaporation device, utilize steam heating mother liquid evaporation device, carry out mother liquid evaporation, control heating steam pressure 0.3 ~ 0.5MPa, vaporizer secondary pressure is at 0.2MPa-0.3MPa, be evaporated to zirconium dioxide concentration at 180 ~ 200g/l, namely obtain direct crystallization rate up to more than 90% zirconium oxychloride crystal.
By above-mentioned acquisition silicon tetrachloride, burn in oxyhydrogen flame, temperature of combustion is 1800 DEG C, and under 40 ~ 100m/s high flow rate, hydrolysis obtains into silicon-dioxide and dilute hydrochloric acid.
By above-mentioned acquisition dilute hydrochloric acid, utilize the hydrogen chloride gas in fumed silica tail gas, absorb through combined column and can obtain 31% hydrochloric acid, then electrolysis obtains chlorine and hydrogen respectively; Wherein, obtain after chlorine drying, compression for the preparation of high-purity zirconium oxychloride; Obtain hydrogen for the preparation of in silicon-dioxide process.
Fumed silica production technology scheme:
The smart silicon tetrachloride raw material magnetic drive pump that high-purity zirconium oxychloride operation is come enters vaporizer through flow control system, vaporize with hot water heating in vaporizer, vaporization temperature controls at 60 ~ 80 DEG C, the hydrogen that electrolysis of hydrochloric acid device comes and air are by well heater preheating, be preheated to 100 ~ 130 DEG C, three kinds of gases enter static mixer, fully mix, silicon tetrachloride: hydrogen: air ratio (mol ratio) is 1:2 ~ 3:8 ~ 10, enter in the outer the first layer sleeve pipe of burner centre pipe on hydrolysis stove top, the hydrogen that electrolysis of hydrochloric acid device comes also passes in the outer second layer sleeve pipe of burner centre pipe, dry air to pass into outside pipe core in third layer sleeve pipe, stable flame is formed after burning, fumed silica and hydrogenchloride water vapour is generated in hydrolysis stove, hydrolysis in-furnace temperature controls at 700 ~ 950 DEG C, after hot water boiler, enter the cyclonic separator of 3 to 5 grades of series connection, solid particulate under cyclonic separator is separated, 3 to 5 deacidification furnaces are sent into by passing into air, enter packing jar, the finished product wrapping machine entering packing jar is packaged into bag.
Cyclonic separator be separated after gas mixture enter exhaust treatment system by pipeline, enter pickling tower, after enter built-up type absorption tower, 20% hydrochloric acid that zirconium oxychloride operation is come, 5% hydrochloric acid, 17% hydrochloric acid that electrolysis of hydrochloric acid operation is come, also enter built-up type absorption tower, prepare 31% hydrochloric acid.
31% hydrochloric acid is used for electrolysis of hydrochloric acid, and in tail gas, chlorine secondary soda-wash tower absorbs, and prepares 10% clorox product, tail gas qualified discharge.
Electrolysis of hydrochloric acid technical scheme:
1. electrolysis of hydrochloric acid
Electrolysis of hydrochloric acid groove passes into hydrochloric acid soln, and chlorine discharges at anode; Hydrogen discharges at negative electrode, and electrolysis of hydrochloric acid production technique has that quality product is high, energy consumption is low, pollution-free, operational load elasticity large, take up an area the advantages such as little, start-stop appearance of vehicle is easy, becomes and processes waste hydrochloric acid industrial expansion direction from now on.
2. chlorine gas treatment process
By electrolyzer moist chlorine out, temperature is high and carry a large amount of water vapors and a small amount of acid mist secretly, has stronger corrodibility, must carry out washing, cooling and drying treatment.
Chlorine treatment system is divided into the parts such as washing, cooling, drying, conveying.
Select two-stage drying: one section is paddle dryer tower, two sections adopt bubble-cap drying tower.
Chlorine enters one-level successively, and secondary drying tower sulfuric acid carries out drying from tower top spray, strict controls spray sulfuric acid concentration at different levels, and one section is more than 75%, and secondary is more than 93%, make dried go out tower chlorine water content be less than 50wtppm.Chlorine gas transfer selects chlorine centrifugal compressor, send zirconium oxychloride operation.
3. hydrogen treat technique
The wet hydrogen come from electrowinning process is cooled to about 40 DEG C through the direct spray washing of flush of hydrogen gas tower washing water, compresses laggard hydrogen cooler and cools, then be sent to fumed silica operation through water smoke trap, hydrogen dispense station by hydrogen gas compressor.
Described vitriolated flue gas carries out sulfuric acid spray washing at one-level sulfuric acid absorption tower, and the gas after washing carries out the sulfuric acid absorption of secondary, then absorbs through one-level water, finally adopts Alkali absorption tower, and the final Determining Micro Acid absorbed in flue gas, guarantees expellant gas qualified discharge; The sulfuric acid absorbed is applied mechanically; Described operational condition is: control washing tower service temperature at 200 ~ 250 DEG C, one-level sulfuric acid absorption tower service temperature controls at 120 ~ 180 DEG C, and secondary sulfuric acid absorption tower service temperature controls at 80 ~ 100 DEG C, and water wash column service temperature is≤40 DEG C.
Zircon sand is obtained after stirring washing after described reaction, enter band filter to filter, filtrated stock enters stirring tank and carries out stirring washing, recycle, to increase zirconium ion concentration in mother liquor, cycle index is 8 ~ 10 times, and recycle rear mother liquor and enter secondary mother liquid tank in chlorination process zirconium oxychloride evaporative process, described washing conditions is: the mass ratio of washing water and zircon sand is 1.5 ~ 2:1;
A washing water part for band filter is used for zircon sand agitator treating, lefts in part and enters the hydrolytic decomposition pot of chlorination process zirconium oxychloride hydrolyzing process as hydrolysis water.
Filtration, washing process are 5 roads washings, and the special band filter technique of 3 road back washings ensure that high-grade zirconium zircon sand quality product.
The present invention have advantage be:
The present invention utilizes electrolysis of hydrochloric acid device fluidizing chlorination legal system for high-grade zircon sand, obtains chlorine, hydrogen and combination producing high-purity zirconium oxychloride simultaneously, vapor phase process obtains high-purity silicon dioxide.
Solve the predicament of fumed silica enterprise without raw material, also digested the by-produced tetrachlorosilane that fluidizing chlorination method produces high-purity zirconium oxychloride, solved the problem that zirconium silicate product radioactivity is high, killing three birds with one stone.
Specifically, electrolysis of hydrochloric acid device, can be chlorine and hydrogen by electrolysis of hydrochloric acid, chlorine can be used for zirconium oxychloride device, hydrogen supply fumed silica device, namely solves by-product hydrochloric acid problem, substantially solves again zirconium oxychloride chlorine feed problem, fumed silica hydrogen feed problem, killing three birds with one stone.It is supplied raw materials for high-purity zirconium oxychloride, and the circulating mother liquor of the submerged combustion reactor of high-grade zircon sand together enters high-purity zirconium oxychloride device, can obtain zirconium oxychloride product, thus achieves industrial chain circulation.
In preparation process, the by-produced tetrachlorosilane of high-purity zirconium oxychloride and the hydrogen of electrolysis of hydrochloric acid production all produce fumed silica as raw material supplying fumed silica device simultaneously, and a large amount of hydrochloric acid of fumed silica device by-product electrolysis of hydrochloric acid device as raw material supplying again, the chlorine that electrolysis of hydrochloric acid device is produced is for giving zirconium oxychloride device, the zircon sand mother liquor that the zircon sand of submerged combustion reactor obtains after stirring washing together enters the secondary mother liquid tank of chlorination process zirconium oxychloride evaporation section, evaporate, crystallization, be separated, washing, reclaim the metal ions such as the rare earth in mother liquor and enter three mother liquors, three times mother liquor is sold to the Rare Earth Company with fund, scandium in circulating mother liquor is extremely valuable metallic element, be worth high, so namely, reclaimed the zirconium in zircon sand and sulfuric acid reaction process, solve again the uranium of zircon sand and sulfuric acid leaching, thorium, the very unmanageable environmental issue of the metal ions such as rare earth, achieve zirconium oxychloride industry, fumed silica industry, the combination producing of zirconium silicate industry and electrolysis of hydrochloric acid four major trades, these four devices have accomplished complete industrial chain circulation, can be rated as world's chemical industry recycling economy, the example of cleaner production.
And then adopt production method products obtained therefrom quality of the present invention good, production cost is low, pollution-free.
Further, the effect adopting method of the present invention to produce high-grade zircon sand product is specially:
1. produce high-grade zircon sand quality product
South Africa C
4product quality indicator contrast before and after zircon sand process
2. tooling cost is low
| Title | Consume unit | Consumption indicators | Unit price (yuan/ton) | Total price (yuan/ton) |
| Zircon sand rate of loss | t/t | 0.02 | 7300 | 146 |
| Sweet natural gas | Nm3/t | 105 | 3.6 | 420 |
| 98% sulfuric acid | t/t | 0.1 | 200 | 20 |
| Water | t/t | 20 | 2 | 40 |
| Power current | kwh/t | 30 | 0.5 | 15 |
| Add up to | 641 |
3. adopt alkali fusion and chlorination process of the present invention two kinds of production methods to produce the contrast of high-purity zirconium oxychloride product quality indicator
4. the production cost index contrast of alkali fusion and chlorination process two kinds of production methods
5. the present invention obtains the production cost of silica product
| Title | Consume unit | Consumption indicators | Unit price (yuan/ton) | Total price (yuan/ton) |
| Silicon tetrachloride | t/t | 2.9 | 900 | 2610 |
| Hydrogen | Nm3/t | 1200 | 1.5 | 1800 |
| Steam | t/t | 1 | 200 | 200 |
| Water | t/t | 20 | 4 | 80 |
| Power current | kwh/t | 3000 | 0.5 | 1500 |
| Add up to | 6190 |
6. the present invention obtains chlorine, hydrogen product quality
Purity of chlorine gas feeding: > 99.5
Hydrogen purity: > 99
7. the present invention obtains chlorine, hydrogen gas production cost (in chlorine)
| Title | Consume unit | Consumption indicators | Unit price (yuan/ton) | Total price (yuan/ton) |
| HCL (100%) | t/t | 1.07 | 10 | 10.7 |
| Deionized water | t/t | 0.2 | 10 | 2 |
| Steam | t/t | 1.0 | 200 | 200 |
| Water | t/t | 20 | 4 | 80 |
| Power current | kwh/t | 1700 | 0.5 | 850 |
| Hydrogen | Nm3/t | -315 | 1.5 | -472.5 |
| Add up to | 670.2 |
Accompanying drawing explanation
Fig. 1 is process flow sheet provided by the invention.
Embodiment
Embodiment 1
Zircon sand submerged combustion produces the method for high-grade zircon sand
1, first by finite concentration, a certain amount of fresh sulfuric acid liquid, recovered acid liquid and a certain amount of water, add in complex acid tank, the sulfuric acid of mixing acquisition 70% concentration, then by 70% sulfuric acid, be pumped in submerged combustion reactor, then zircon sand is added, liquid-solid ratio is 0.5:1, then pass into and heat through combustion of natural gas, obtain gained flue gas after 800 ~ 1000 DEG C of high-temp combustions, high-temperature flue gas is through conducting heat with sulfuric acid in reactor, and then to the zircon sand in still, sulfuric acid heats, and the temperature of sulfuric acid is adjusted by the air input of adjustment high-temp combustion gas.According to processing requirement, first sulfuric acid is heated to 240 DEG C ~ 260 DEG C, is incubated 2 hours, reheats 260 DEG C ~ 320 DEG C, be incubated 2 hours.Therebetween, various impurity in sulfuric acid and zircon sand carry out chemical reaction, generate various metal sulfate and water, in zircon sand, the impurity such as uranium, thorium reduces, after reaching processing requirement, continue to be warming up to 350 DEG C, reacting by heating 2 ~ 4 hours, by sulfate liquid evaporate to dryness in zircon sand, stop heating, the solid in reaction product is moved in steel basin and carry out stirring washing, the zircon sand slurry going out steel basin enters band filter to carry out filtering, washing, the zircon sand going out band filter enters in drying kiln dries, and is high-grade zircon sand, packing and selling after drying.
The chemical reaction equation of sulfuric acid leaching zircon sand:
2UO
2+O
2+2H
2SO
4＝2UO
2SO
4+2H
2O
The main chemical reactions of sulfuric acid leaching thorium:
ThO
2+2H
2SO
4＝Th(SO
4)
2+2H
2O
The reaction of sulfuric acid and zirconium silicate is very faint:
ZrSiO
4+2H
2SO
4＝Zr(SO
4)
2+2H
2O+SiO
2
The chemical reaction of sulfuric acid and ferric oxide:
3H
2SO
4+Fe
2O
3＝Fe
2(SO
4)
3+3H
2O
The chemical reaction of sulfuric acid and aluminium sesquioxide:
3H
2SO
4+Al
2O
3＝Al
2(SO
4)
3+3H
2O
The chemical reaction of sulfuric acid and titanium dioxide:
2H
2SO
4+TiO
2＝Ti(SO
4)
2+2H
2O
The chemical reaction of sulfuric acid and scandium oxide:
3H
2SO
4+Sc
2O
3＝Sc
2(SO
4)
3+3H
2O
2. after the high-temperature flue gas entering into submerged burner and the intermediate water steam produced at submerged combustion reactor and acid vapour enter sulfur acid flue gas washing tower, one-level sulfuric acid absorption tower, secondary sulfuric acid absorption tower (and then realizing the sulfuric acid absorption of two-stage), water wash column, soda-wash tower alkali cleaning successively, qualified discharge.The flue gas of discharge can be pumped in reactor at this to be applied mechanically; In secondary tower, dilute sulphuric acid enters the dense sulphur tower of one-level, vitriol oil external adding water, the by a certain percentage vitriol oil in the vitriol oil of outsourcing and first stage tower: sulfuric acid in first stage tower: water=1:7.5:2.55, get in complex acid tank, carry out complex acid, pump into after qualified in submerged combustion reactor and carry out next still reactor.
Wherein, one-level sulfuric acid absorption tower tower reactor liquid out (sulfuric acid concentration is 90%), carry out complex acid, one-level sulfuric acid absorption tower temperature controls at 120 ~ 180 DEG C, and secondary sulfuric acid absorption tower temperature controls at 80 ~ 100 DEG C, water wash column service temperature≤40 DEG C.
3, above-mentioned go out the zircon sand slurry of steel basin enter band filter and filter, filtrated stock enters stirring tank and carries out stirring washing, recycles, cycle index is 8 ~ 10 times, reach the mother liquor after cycle index, enter chlorination process zirconium oxychloride device, as the mother liquor producing zirconium oxychloride.
A washing water part for band filter is used for zircon sand agitator treating, lefts in part and enters the hydrolytic decomposition pot of chlorination process zirconium oxychloride hydrolyzing process as hydrolysis water.
Gained zircon sand quality product is as follows:
Embodiment 2
Produce the method for high-purity zirconium oxychloride
1. chlorination reaction
By raw material zircon sand, after-smithing petroleum coke and silicon carbide, it is zircon sand according to mass ratio: calcined coke: the ratio of silicon carbide=1:0.22:0.34 adds mixing machine by mixing of materials, be added to stokehold feed bin after mixing, added continuously in chlorination furnace by worm conveyor.
Chlorination furnace furnace bottom passes into the chlorine that electrolysis of hydrochloric acid produces, intake weight is zircon sand: chlorine=1:2.78, chlorine is made to enter conversion zone and raw material reaction by sparger, control temperature of reaction at 1170 DEG C, within controlling furnace pressure 3000Pa, simultaneously according to furnace pressure determination chlorination furnace slag-removing time, control chlorine flow velocity at 0.009m/s, reaction can be carried out rapidly, can be maintained the thermal equilibrium of chlorination furnace reaction mass by chemical reaction stablizer, chlorination reaction is stablized and carries out.
Reaction equation is as follows:
ZrSiO
4+4C+4Cl
2＝ZrCl
4+SiCl
4+4CO(1)
ZrSiO
4+2C+4Cl
2＝ZrCl
4+SiCl
4+2CO
2(2)
SiC+2Cl
2＝SiCl
4+C(3)
Above-mentioned each prepared using Raymond mill is levigate, and concrete granularity requirements is:
After-smithing petroleum coke: 400 order screen underflow≤35%100 order screen overflow≤8%
Zircon sand: 400 order screen underflow≤35%, 200 order screen overflow≤5%
Silicon carbide: 400 order screen underflow≤35%, 120 order screen overflow≤5%.
2. prepare pure zirconium tetrachloride solid
Chlorination furnace is divided into three sections, conversion zone, intercooling transition section, the expansion cooling section of gathering dust.Carry out chemical reaction at conversion zone, the zirconium tetrachloride of generation, silicon tetrachloride mixed gas, the intercooling section through chlorination furnace carries out first step cooling, and one-level cooling section uses semi-canal type indirect water-cooling, controls gas outlet temperature at 900 ± 10 DEG C.
The expanding reach that the cooled zirconium tetrachloride of one-level, silicon tetrachloride mixed gas enter chlorination furnace carries out second stage cooling, and chlorination furnace expanding reach adopts air jacket indirectly to cool, and controls gas temperature at 480 ± 10 DEG C.
The cooled zirconium tetrachloride of secondary, silicon tetrachloride mixed gas is carried out in chlorination furnace, go out chlorination furnace outlet to enter first paragraph quench tube and carry out third stage cooling, adopt the direct spraying cooling of silicon tetrachloride in first paragraph quench tube, control gas cooling temperature at 440 ± 10 DEG C.
After cooling, gas enters strainer, by strainer, then enters second segment quench tube and carries out the cooling of fourth stage level, and two sections of quench tube adopt the direct spraying coolings of silicon tetrachloride, controls gas temperature at 390 ± 10 DEG C.
Cooled gas enters quencher again and carries out level V cooling, the direct spraying cooling of silicon tetrachloride is adopted in quencher, adopt recirculated water indirectly to cool at quencher chuck simultaneously, a direct-cooled and cold process for cooling combined, control gas temperature at 230 ± 10 DEG C, after mixed gas cools in quencher, achieve being separated of zirconium tetrachloride solid and the gases such as silicon tetrachloride gas, aluminum chloride, titanium tetrachloride.
In order to reduce the foreign matter content such as silicon tetrachloride in zirconium tetrachloride further, in quencher, zirconium tetrachloride solid material enters two-stage continuous purifier, purifier chuck adopts heat-conducting oil heating (thermal oil establishes heat conduction petrol station), in control purifier, gas temperature is at 260 ± 10 DEG C, Si/Zr < 0.00006 in zirconium tetrachloride solid after purification, enters hydrolytic decomposition pot hydrolysis.
Enter the gas solid separation of gas containing silicon tetrachloride tail gas in quencher, first tail gas is carried out one-level gas-solid separator, control gas temperature at 170 ± 10 DEG C, enter secondary gas-solid separator again, control temperature is at 90 ± 10 DEG C, and one-level gas solid separation adopts cyclonic separator form, secondary gas-solid separator adopts whirlwind to add cloth bag type structure, realize gas solid separation, enter silicon tetrachloride distillation system containing silicon tetrachloride tail gas, the solid that gas solid separation obtains is stand-by.
3. prepare smart zirconyl chloride solution
Above-mentioned go out the zirconium tetrachloride solid of purifier pass through worm conveyor, enter hydrolytic decomposition pot, add pure water, evaporation acid, washings is hydrolyzed, controlling material add-on is zirconium tetrachloride solid: pure water: evaporation acid: washings is 0.95:2.40:0.75:1.01 (weight ratio), controlled hydrolysis temperature is at 40-50 DEG C, hydrolytic decomposition pot stirrer rotating speed is 100r/min, when hydrolyzed solution zirconium concentration is at 100 ± 10g/l, with being pumped into chamber-type press filter, filter out the solids carried secretly, obtain the smart zirconyl chloride solution of purifying, the recyclable recycling of washings during hydrolysis.Wherein, evaporate that acid is 20% hydrochloric acid, washings is 18% hydrochloric acid.
Hydrolysis reaction equation
ZrCl
4+H
2O＝ZrOCl
2+2HCl
4. smart zirconyl chloride solution evaporation, crystallization, prepare high-purity zirconium oxychloride
By above-mentioned gained zirconium tetrachloride solid at the temperature of 40 ~ 80 DEG C, be hydrolyzed under the stirring velocity of 100 ~ 120r/min, to hydrolyzed solution, zirconium concentration is at 90 ~ 110g/l, then filter the smart zirconyl chloride solution obtaining purifying, essence zirconyl chloride solution is added to two heating outer circulation type feed liquid circulation tank again, using the secondary steam of feed liquid circulation tank as thermal source, steam heating feed liquid is utilized to evaporate, to zirconyl chloride solution preheating, control vapor pressure 0.3MPa, vacuum tightness is at-0.04MPa--0.05MPa, water of condensation is obtained after the condensation of vaporizer secondary steam, be and contain the dilute hydrochloric acid that acid is 3 ~ 5%.
Be evaporated to zirconium dioxide concentration at 180 ~ 200g/l, proceed to crystallizer, crystallization treatment, band filter is utilized to filter, obtain mother liquor, crystal washs, obtain washings, zirconium oxychloride crystal puts into making beating tank, carry out stirring the salt acid elution with 18%, after washing, slurry is entered top-suspended basket centrifuge, be 970 (rpm) to be separated rotating speed, discharging speed 90 (rpm), , separating factor is 658, disengaging time 40 minutes, carry out centrifugal depickling obtain respectively percent crystallization in massecuite up to more than 90% zirconium oxychloride crystal, obtained high-purity zirconium oxychloride product after packaging, (seeing table).
High-purity zirconium oxychloride quality product
| Project | Zr(Hf)O2 | SiO 2 | Fe 2O 3 | TiO 2 | Na 2O | SO 4 |
| Index (%) | ≥36.0 | ≤0.0002 | ≤0.0005 | ≤0.0002 | ≤0.0001 | 0.0001 |
Washings is used for zirconium tetrachloride hydrolysis, mother liquor enters mother liquid evaporation device, utilize steam heating mother liquid evaporation device, carry out mother liquid evaporation, control heating steam pressure 0.3 ~ 0.5MPa, vaporizer secondary pressure, at 0.2MPa-0.3MPa, is evaporated to zirconium dioxide concentration at 180 ~ 200g/l, namely obtain direct crystallization rate up to the zirconium oxychloride crystal of more than 90%, after this dissolution of crystals, enter hydrolytic decomposition pot.
Mother liquid evaporation device adopts the principle of azeotropic vaporization, obtains water of condensation after the condensation of vaporizer secondary steam, is and contains the dilute hydrochloric acid that acid is 20%.
The dilute hydrochloric acid of 3 ~ 5% and the dilute hydrochloric acid of 20% send into fumed silica operation, and utilize the hydrogenchloride in fumed silica tail gas, tail gas enters saturated acid washing tower, is entering in built-up type hydrochloric acid absorption tower, is preparing 31% hydrochloric acid.
5. the preparation of silicon tetrachloride
The above-mentioned gas solid separation entering gas in quencher containing silicon tetrachloride tail gas, first carries out one-level gas-solid separator by tail gas, then carries out secondary gas-solid separator again and carry out gas solid separation, enter silicon tetrachloride distillation system containing silicon tetrachloride tail gas,
Namely enter Venturi-type spray column, the additional water cooler of spray column, with the circulating water of 30 DEG C, and with the direct spraying cooling mixed gas of silicon tetrachloride liquid, control gas outlet temperature at 45 ~ 50 DEG C.Wherein, Venturi-type spray column is set to 4 layers on the basis of conventional spray column, establishes 32 nozzles for every layer.
After spray process, mixed gas enters plate washer spray column again, the additional water cooler of spray column, with the chilled brines of-35 DEG C cooling, and with the direct spraying cooling of silicon tetrachloride liquid, control gas outlet temperature at 30 ~ 40 DEG C, tail gas enters exhaust gas cooler, indirectly cools with the chilled brine of-35 DEG C, controls offgas outlet temperature at-25 DEG C, tail gas truncates gas disposal operation, can obtain 10% clorox, 31% hydrochloric acid and Co mixed gas, can be used for boiler combustion.Wherein, 14 layers of plate washer established by plate washer spray column on the basis of conventional spray column.
By entering rectifying above by silicon tetrachloride liquid after two-step washing condensation, cooling, rectifying tower reactor reboiler temperature is 70 DEG C, and overhead condensation actuator temperature is 50 DEG C, namely obtains purity 99.5% silicon tetrachloride product (seeing table).
Silicon tetrachloride quality index
| Project | SiCL 4 |
| Index (%) | ≥99.5 |
The impurity liquid contained at the bottom of eluting column tower send titanium tetrachloride tower purification & isolation, prepares titanium tetrachloride product, and solid impurity enters hydrolyzing process washing, separation by shaking table, after oven dry, recycles.
Embodiment 3
By zircon sand after reaction in reactor in embodiment 1 through agitator treating, band filter filters, filtrated stock mixes with the washings of a mother liquor and washing crystal in embodiment 2 and is directed into mother liquid evaporation device, utilize steam heating mother liquid evaporation device, carry out mother liquid evaporation, control heating steam pressure 0.3 ~ 0.5MPa, vaporizer secondary pressure is at 0.2MPa-0.3MPa, be evaporated to zirconium dioxide concentration at 180 ~ 200g/l, then carry out crystallization according to the mode recorded in above-described embodiment 2, filter, washing, gained crystal dissolves again, evaporate together with solid hydrolyzed solution, crystallization, filter, washing, separation obtains high-purity zirconium oxychloride product) namely obtain direct crystallization rate up to more than 90% zirconium oxychloride crystal.
Embodiment 4
Vapor phase process prepares silicon-dioxide:
Burner is made up of 4 layers of sleeve pipe, and be positioned at hydrolysis stove top, pass in different sleeve pipe the one in hydrogen, silicon tetrachloride, air, two kinds or three kinds.
Wherein, pass into hydrogen in pipe core and adopt ejection at a high speed; Pass into the air of fully premixed conjunction, hydrogen and silicon tetrachloride vapor in the first layer sleeve pipe outside pipe core and adopt ejection at a high speed, burning forms circular flame; Second layer sleeve pipe outside pipe core, hydrogen ejection burning; Third layer sleeve pipe air ejection outside pipe core.In this flame structure, make flame more stable, silicon dioxide granule is more even.
3 to 5 grades of deacidification furnaces are by the deacidification furnace series connection gained of 3 to 5 fluidized-bed structures, wherein, in deacidification furnace, hydrogen and excessive air are formed after burning is with the warm air of water vapor to be directly blown into bottom extracting tower, or employing electrically heated, saturation steam adds, and makes powder fluidization, can obtain finished product.
By hydrogen, air and silicon tetrachloride in burner the first layer sleeve pipe, burn with other layer of gas and vapor permeation, hydrolysis obtains silicon-dioxide.
The hydrogen obtained by the electrolysis of electrolysis of hydrochloric acid device is passed in the pipe core of burner;
The silicon tetrachloride magnetic drive pump that above-described embodiment 2 prepares coproduction in high-purity zirconium oxychloride process enters vaporizer through flow control system, with the hot water heating vaporization of 60 ~ 80 DEG C in vaporizer, stand-by; The hydrogen obtained by the electrolysis of electrolysis of hydrochloric acid device and air well heater preheating at 100 ~ 130 DEG C respectively, stand-by;
Above-mentioned preheating is obtained silicon tetrachloride, hydrogen and air, and three kinds of gases enter static mixer, fully mix, wherein, and silicon tetrachloride: hydrogen: air ratio (mol ratio) is 1:2:8.
Above-mentioned mixed silicon tetrachloride, hydrogen and air enter in the outer the first layer sleeve pipe of burner centre pipe on hydrolysis stove top, the hydrogen that electrolysis of hydrochloric acid device comes also passes in the outer second layer sleeve pipe of burner centre pipe, dry air to pass into outside pipe core in third layer sleeve pipe, stable flame is formed after burning, fumed silica and hydrogenchloride water vapour is generated in hydrolysis stove, in hydrolysis stove, cooling temperature controls at 800 DEG C, after hot water boiler hydrolysis, enter the cyclonic separator of 3 to 5 grades of series connection, solid particulate under cyclonic separator is separated, 3 to 5 grades of deacidification furnaces of connecting are sent into by passing into air, enter packing jar, the finished product wrapping machine entering packing jar is packaged into bag.Namely fumed silica product is obtained.
Gas mixture after cyclonic separator is separated, containing hydrogen chloride gas, exhaust treatment system is entered by pipeline, enter saturated acid washing tower, in control tower, temperature is at 40 DEG C, enters combined column and absorb after washing, in control tower, temperature is at 40 DEG C, above-described embodiment is obtained the dilute hydrochloric acid of obtain in zirconium oxychloride process 20% and the dilute hydrochloric acid of 5% simultaneously, also enter built-up type absorption tower respectively, obtain 31% hydrochloric acid.
In tail gas, chlorine secondary soda-wash tower absorbs, and prepares 10% clorox product, tail gas qualified discharge.
Pass into the different concns dilute hydrochloric acid of above-mentioned acquisition in described combined column, then add water and carry out absorbing, passing into hydrogen chloride gas again, carry out processing the absorption tower namely obtaining 31% hydrochloric acid.
Electrolysis of hydrochloric acid:
Obtain silicon-dioxide process from vapor phase process 31% hydrochloric acid obtaining and absorb through combined column, after supercooler, enter the press filtration of barrier film chamber-type press filter, in hydrochloric acid, suspension content drops to about 500wtppm.The level then making suspension content drop to 1 ~ below 5wtppm by inorganic ceramic strainer again mixes with the diluted acid after electrolysis, to ensure the concentration of hydrochloric acid added in electrolyzer.
In electrolyzer, hydrochloric acid is decomposed into chlorine and hydrogen at the electrode surface, and the chlorine of generation and hydrogen enter in respective processing unit respectively.
17% hydrochloric acid that electrolysis of hydrochloric acid operation is come, prepares 31% hydrochloric acid.
31% hydrochloric acid is used for electrolysis of hydrochloric acid, and in tail gas, chlorine secondary soda-wash tower absorbs, and in control tower, temperature is at 35 ~ 40 DEG C, prepares 10% clorox product, tail gas qualified discharge.
Electrolytic process is:
In electrolyzer anode chamber, hydrochloric acid decomposes generation chlorine after electrolysis.Reaction formula is as follows:
Cl－﹣e→1/2Cl
2↑
Electrolysis dilute hydrochloric acid out flows into dilute hydrochloric acid groove, a part of with mixed in hydrochloric acid after return to the anolyte compartment of electrolyzer, and another part is with being pumped to hydrochloric acid absorption tower circulation tank.
In electric tank cathode room, water is decomposed generation hydrogen, and reaction formula is as follows:
H++e→1/2H
2↑
The dilute hydrochloric acid that electrolyzer generates flows to dilute hydrochloric acid groove.Return the cathode compartment of electrolyzer after a part and mixed in hydrochloric acid, another part then send hydrochloric acid absorption tower circulation tank.
The Cl that electrolyzer anode chamber and cathode compartment produce
2and H
2delivered to the process of chlorine hydrogen treatment process respectively.
A, anode circulation
The filtration hydrochloric acid that absorption by Hydrochloric Acid, filter progress are sent here sends into the anolyte charging house steward of electrolyzer by hydrochloric acid header tank.Filter hydrochloric acid and carry out electrolysis in the anode compartment, produce chlorine, HCL concentration reduces simultaneously, and going out electrolyzer concentration of hydrochloric acid is 17%.
Reaction formula is as follows: Cl--e → 1/2Cl
2↑
Because hydrochloric acid is by electrolysis, reduction is become weak hydrochloric acid by its HCl concentration, and the chlorine that weak hydrochloric acid and electrolysis produce is delivered to discharge header pipe through discharge tube and completes gas-liquid separation at this.The isolated chlorine of every platform electricity groove discharge header pipe collects in chlorine house steward, enters dilute hydrochloric acid groove top to be separated the moisture in removing chlorine further, then delivers to chlorine process.Chlorine house steward is provided with pressure regulator valve to control chlorine gas pressure.
The isolated dilute hydrochloric acid of every platform electrolyzer discharge header pipe collects in dilute hydrochloric acid house steward, enter dilute hydrochloric acid groove, a part of dilute hydrochloric acid is circulated to hydrochloric acid feed-pipe, and all the other dilute hydrochloric acid deliver to hydrochloric acid absorption tower under the Liquid level of dilute hydrochloric acid groove, chlorine, after cooling, being separated, is recycled to moist chlorine house steward.
B, cathode circulation
At cathode compartment, water to be decomposed generation hydrogen through electrolysis, and reaction formula is as follows:
H++e→1/2H
2↑
The hydrogen that dilute hydrochloric acid and electrolysis produce is delivered to discharge header pipe through discharge tube and completes gas-liquid separation at this.
The isolated hydrogen of every platform electricity groove discharge header pipe collects in hydrogen manifold, enters dilute hydrochloric acid groove top to be separated the moisture in removing hydrogen further, then delivers to hydrogen process.Be 400mmH to keep the pressure reduction of hydrogen and chlorine
2o, the pressure of hydrogen manifold regulates and carries out serials control with chlorine gas pressure.
The isolated dilute hydrochloric acid liquid of every platform electricity groove discharge header pipe collects in acid solution house steward, enter acid solution groove, the part acid solution sent by acid pump sends into acid solution header tank, then catholyte charging house steward is entered by the outflow of acid solution header tank and the hydrochloric acid after filtering, cathode compartment is entered again by feed hose, add the Flow-rate adjustment DC current flow serials control of hydrochloric acid, and the acid liquor temperature being controlled to enter acid solution header tank by catholyte water cooler keeps the temperature of groove acid solution; The rest part sent by acid pump delivers to absorption by Hydrochloric Acid under the Liquid level of acid solution groove.
Chlorine treatment process
About moist chlorine from electrowinning process, through Chlorine Scrubber chlorine water wash cooling, then enters titanium pipe water cooler, is cooled to about 18 DEG C with refrigerated water.Then chlorine is after the condensing drip in the lower chlorine of water smoke trap trapping, enter one-level paddle dryer tower sulfuric acid successively and carry out drying from tower top spray, strict control spray sulfuric acid concentration at different levels, one section is more than 75%, dried chlorine is dry further through the bubble-plate column 98wt% vitriol oil again, make dried go out tower chlorine water content be less than 50wtppm.After dry, chlorine is after acid mist eliminator removing acid mist drips, and enters chlorine gas compressor, finally enters chlorine dispense station and be sent to zirconium oxychloride device by pipeline.
To be 98wt% sulfuric acid by tank car unload sulfate system on the spot sends into vitriol oil storage tank, is pumped into vitriol oil header tank, enters bubble-cap drying tower with after refrigerated water cooling through the vitriol oil.A part recycles, and another part overflow enters the paddle dryer tower sulfuric acid recycle system, when acid concentration drops to 75wt%, is sent to Waste Sulfuric Acid tank field through dilute sulphuric acid recycle pump.
Hydrogen treat operation
The wet hydrogen come from electrowinning process is cooled to about 40 DEG C through the direct spray washing of flush of hydrogen gas tower washing water, compresses laggard hydrogen cooler and cools, then be sent to fumed silica operation through water smoke trap, hydrogen dispense station by hydrogen gas compressor.
Claims (10)
1. produce the method for high-grade zircon sand for one kind, it is characterized in that: by zircon sand and sulfuric acid, be added in submerged combustion reactor with the mass ratio of 0.4 ~ 0.9:1, pass into 800 ~ 1000 DEG C of flue gases after combustion of natural gas, to make in reactor, at 100 ~ 350 DEG C, to carry out 6 ~ 8 hours chemical reactions, remove the impurity in zircon sand, then carry out agitator treating, namely filtration, washing, oven dry obtain high-grade zircon sand.
2. by the method for the high-grade zircon sand of production according to claim 1, it is characterized in that: after described reaction, vitriolated flue gas reclaims after washing, recirculation uses; In described reactor, after reaction, zircon sand reclaims, as the mother liquor producing zirconium oxychloride through agitator treating, band filter filtration, filtrated stock and wash water.
3. by the method for the high-grade zircon sand of production according to claim 1, it is characterized in that: adopt zircon sand, reductive agent and stablizer, chlorine is passed in chlorination furnace under the gas speed of 0.07 ~ 0.12m/s, chlorination reaction is carried out with 1150 ~ 1200 DEG C, generate zirconium tetrachloride, silicon tetrachloride, then carry out gas solid separation, namely the zirconium tetrachloride solid hydrolysis that separation obtains, purifying, zirconyl chloride solution evaporation, crystallization, separation obtain high-purity zirconium oxychloride and co-product silicon tetrachloride;
The mass ratio of described zircon sand, reductive agent, stablizer and chlorine is 0.9 ~ 1.1:0.2 ~ 0.3:0.3 ~ 0.4:2.7 ~ 2.8.
4. by the method for the high-grade zircon sand of production according to claim 3, it is characterized in that: gas that described gas solid separation obtains, carry out the gas solid separation of gas, again be separated obtain zirconium tetrachloride Purify, zirconyl chloride solution evaporation, crystallization, after gained crystal water dissolution, namely evaporation, crystallization, filtration, washing, separation obtain high-purity zirconium oxychloride product, can obtain co-product silicon tetrachloride simultaneously.
5. by the method for the high-grade zircon sand of production according to claim 3, it is characterized in that: described chlorination reaction after product cools in chlorination furnace, make gas cooling temperature at 450 ~ 500 DEG C, then gas is passed into quench tube and adopt direct spraying cooling, make gas cooling temperature at 430-450 DEG C, after cooling, gas is passed into strainer and proceed to quench tube again, spraying cooling mode is adopted to make gas temperature at 400 DEG C, after cooling, gas enters quencher again, adopt the direct spraying cooling of silicon tetrachloride, and adopt recirculated water indirectly to cool at quencher chuck, make gas temperature at 200 ~ 240 DEG C, after mixed gas cools in quencher, zirconium tetrachloride solid is separated with other gas in product.
6. by the method for the high-grade zircon sand of production according to claim 5, it is characterized in that: the zirconium tetrachloride generated after described chlorination reaction, silicon tetrachloride mixed gas carry out first step cooling in the intercooling section of chlorination furnace, one-level cooling section uses the indirect water-cooling of semi-canal type, controls gas outlet temperature at 800 ~ 1000 DEG C;
The expanding reach that the cooled zirconium tetrachloride of one-level, silicon tetrachloride mixed gas enter chlorination furnace carries out second stage cooling, and chlorination furnace expanding reach adopts air jacket indirectly to cool, and controls gas temperature at 450 ~ 500 DEG C;
The cooled zirconium tetrachloride of secondary, silicon tetrachloride mixed gas is carried out in chlorination furnace, go out chlorination furnace outlet to enter first paragraph quench tube and carry out third stage cooling, adopt silicon tetrachloride liquid direct spraying cooling continuously in first paragraph quench tube, control gas cooling temperature at 430-450 DEG C;
After cooling, gas enters strainer, by strainer, then enters second segment quench tube and carries out the cooling of fourth stage level, and two sections of quench tube adopt the direct spraying coolings of silicon tetrachloride, controls gas temperature at 380-400 DEG C;
Cooled gas enters quencher again and carries out level V cooling, the direct spraying cooling of silicon tetrachloride is adopted in quencher, adopt recirculated water indirectly to cool at quencher chuck simultaneously, direct-cooled and cold combining cools, make gas temperature at 200 ~ 240 DEG C, after mixed gas cools in quencher, zirconium tetrachloride solid is separated with other gas in product.
7. by the method for the high-grade zircon sand of production according to claim 5, it is characterized in that: by above-mentioned gained zirconium tetrachloride solid at the temperature of 40 ~ 80 DEG C, be hydrolyzed under the stirring velocity of 100 ~ 120r/min, to hydrolyzed solution, zirconium concentration is at 90 ~ 110g/l, then filter the smart zirconyl chloride solution obtaining purifying, essence zirconyl chloride solution is added to two heating outer circulation type feed liquid circulation tank again, using the secondary steam of feed liquid circulation tank as thermal source, steam heating feed liquid is utilized to evaporate, to zirconyl chloride solution preheating, control vapor pressure 0.3MPa, vacuum tightness is at-0.02MPa--0.05MPa, be evaporated to zirconium dioxide concentration at 180 ~ 200g/l, proceed to crystallizer, crystallization treatment namely obtain direct crystallization rate up to more than 90% high purity oxygen zirconium chloride crystal, a mother liquor of described crystallization and filtration can be applied mechanically.
8. by the method for the high-grade zircon sand of the production described in claim 2 or 5, it is characterized in that: zircon sand after reaction in described reactor to be filtered through agitator treating, band filter, filtrated stock and described zirconium oxychloride crystal is mother liquid obtained is mixed into mother liquid evaporation device, utilize steam heating mother liquid evaporation device, carry out mother liquid evaporation, control heating steam pressure 0.3 ~ 0.5MPa, vaporizer secondary pressure is at 0.2MPa-0.3MPa, be evaporated to zirconium dioxide concentration at 180 ~ 200g/l, namely obtain direct crystallization rate up to more than 90% zirconium oxychloride crystal.
9. by the method for the high-grade zircon sand of production according to claim 3, it is characterized in that: by above-mentioned acquisition silicon tetrachloride, burn in oxyhydrogen flame, temperature of combustion is 1800 DEG C, and under 40 ~ 100m/s high flow rate, hydrolysis obtains into silicon-dioxide and dilute hydrochloric acid.
10. by the method for the high-grade zircon sand of production according to claim 9, it is characterized in that: by above-mentioned acquisition dilute hydrochloric acid, absorb the concentrated hydrochloric acid of process acquisition 31% through combined absorbing tower, then electrolysis obtains chlorine and hydrogen respectively; Wherein, obtain after chlorine drying, compression for the preparation of high-purity zirconium oxychloride; Obtain hydrogen for the preparation of in silicon-dioxide process.
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| CN109205669A (en) * | 2018-11-19 | 2019-01-15 | 新特能源股份有限公司 | The combined preparation process of zirconium chloride and ocratation |
| WO2020124238A1 (en) * | 2018-12-19 | 2020-06-25 | Rio Tinto Iron And Titanium Canada Inc. | Process for purifying a zircon sand |
| CN112028626A (en) * | 2020-08-03 | 2020-12-04 | 山东金三河新材料科技有限公司 | Preparation method of zirconia bioactive ceramic |
| CN112723366A (en) * | 2020-12-30 | 2021-04-30 | 泉州市利芝新材料科技有限公司 | Process for removing iron and titanium from zircon sand |
| CN113860319A (en) * | 2021-09-23 | 2021-12-31 | 广东粤桥新材料科技有限公司 | Zircon sand production method |
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