CN106435221A - Method for preparing nuclear-grade sponge zirconium and nuclear-grade sponge hafnium - Google Patents
Method for preparing nuclear-grade sponge zirconium and nuclear-grade sponge hafnium Download PDFInfo
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- CN106435221A CN106435221A CN201610884806.0A CN201610884806A CN106435221A CN 106435221 A CN106435221 A CN 106435221A CN 201610884806 A CN201610884806 A CN 201610884806A CN 106435221 A CN106435221 A CN 106435221A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
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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
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/04—Halides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to nuclear-grade sponge zirconium, in particular to a method for preparing nuclear-grade sponge zirconium and nuclear-grade sponge hafnium. Chlorine generated by hydrochloric acid electrolysis is used for producing zirconium tetrachloride and zirconium oxychloride by a zircon sand boiling chlorination method; zirconium and hafnium are seperated to obtain zirconium oxide and hafnium oxide through a TBP-Hcl-HNO3 extraction method; and then, the chlorination and the purification are performed to obtain the nuclear-grade sponge zirconium and the nuclear-grade sponge hafnium. The method radically solves the environmental protecting environment difficultly treated in the zirconium oxychloride industry and the nuclear-grade sponge zirconium industry, and realizes complete industry chain circulation for combined production of the zirconium oxychloride industry, the gas-phase method silicon dioxide industry, the nuclear-grade sponge zirconium industry and the hydrochloric acid electrolysis industry.
Description
Technical field
The present invention relates to core level sponge zirconium, specifically a kind of method preparing core level sponge zirconium and core level hafnium sponge.
Background technology
Core level sponge zirconium is mainly used for the pile core involucrum of nuclear reactor, screen work etc., and core level sponge zirconium belongs to strategic material,
It is also the essential material of nuclear power, domestic annual requirement has reached more than 1000 tons, whole world annual requirement reaches more than 8000 tons, any
It is necessary to grasp so important strategic material technology, from this meaning, China sets up certainly for one country having nuclear power station
Oneself core level sponge zirconium industry is very necessary.
But the process for zirconium hafnium extract and separate, either MIBK-NH4SCN method, or N235-H2SO4Method,
TBP-HCl-HNO3Method, all there are " three wastes " can not be processed, and the serious problem of environmental pollution does not meet national requirements for environmental protection,
Cause zirconium hafnium extraction separation device cannot normally produce, so fundamentally constrain core level sponge zirconium industrial expansion.
Zirconium oxychloride product is the basic material of zirconium chemical industry, year market consumption reached 200,000 tons, but zirconium oxychloride is all " alkali
Molten method " produces, and production cost is high, and environmental pollution is serious, and product quality can not reach the quality standard of high-purity zirconium oxychloride, with
The reinforcement of national environmental protection policy, " alkali fusion " zirconium oxychloride will be died, and chloridising zirconium oxychloride is rising industry, must
Alkali fusion zirconium oxychloride will be substituted.
Fumed silica is high-grade industrialized nano material, is rising industry, primary raw material is silicon tetrachloride,
The source of silicon tetrachloride is the by-product silicon tetrachloride of polysilicon industry or the byproduct Trichloromethyl silane of organosilicon industry.
With the technological progress of polysilicon enterprise, have developed silicon tetrachloride cold hydrogenation technology, converting silicon tetrachloride be
Trichlorosilane, the byproduct Trichloromethyl silane disproportionation dimethyldichlorosilane technology of paying of organosilicon industry also has begun to greatly
Sizable application.
The silicon tetrachloride market price is raised, market supply and demand is nervous, fumed silica product price improves constantly.
The height standing in national economic development overall situation considers, exploitation is a kind of to utilize electrolysis of hydrochloric acid device, Joint Production core level
Sponge zirconium and core level hafnium sponge, high-purity zirconium oxychloride, the process unit of fumed silica and process, it appears very must
Will.
Content of the invention
Present invention aim at offer is a kind of prepares core level sponge zirconium and the side of core level hafnium sponge using electrolysis of hydrochloric acid device
Method.
For achieving the above object, the present invention using technical scheme is：
A kind of method preparing core level sponge zirconium and core level hafnium sponge, the chlorine being produced using electrolysis of hydrochloric acid, through zircon sand
Boiling chloration method for preparing ZrCl 4 and zirconium oxychloride, by TBP-HCl-HNO3Extraction, zirconium, hafnium are separated and obtain zirconium oxide
And hafnium oxide, then respectively through chlorination, purification, respectively obtain core level sponge zirconium and core level hafnium sponge.
The chlorine that described electrolysis of hydrochloric acid is produced is as chlorine used in zircon sand fluidizing chlorination method, zircon sand fluidizing chlorination
Obtain zirconium chloride, zirconium chloride further purifies i.e. acquisition refined zirconium tetrachloride, prepares zirconium oxychloride after hydrolysis；
Electrolysis of hydrochloric acid produces hydrogen and chlorine, and hydrogen is used as hydrolysis burning during obtaining silica using vapor phase method
Hydrogen feed；
Chlorine is as the chlorine used by chlorination in zircon sand fluidizing chlorination method；
Above-mentioned zircon sand fluidizing chlorination obtains zirconium chloride, silicon tetrachloride, and wherein gained zirconium chloride further purifies
I.e. obtain refined zirconium tetrachloride, refined zirconium tetrachloride hydrolysis can obtain zirconium oxychloride；Gained silicon tetrachloride is obtained as using vapor phase method
During silica, pyrohydrolysis is raw materials used, and then produces fumed silica.
Specifically, the zircon sand, silica flour and the petroleum coke that are more than 63% using zirconia content, are produced by electrolysis of hydrochloric acid
Chlorine, chlorine is passed through in chlorine reactor with the gas speed of 0.06～0.16m/s, and graphite conversion zone is carried out with 650～1100 DEG C
Chlorination reaction, controls expanding reach temperature at 380～500 DEG C, generates zirconium chloride, silicon tetrachloride.Described zircon sand, silica flour
With the mass ratio of petroleum coke and chlorine, controlled 0.8～1.2 according to material quality difference：0.1～0.4：0.4～0.5:2.8～
3.0.
Described TBP-HCl-HNO3Extraction is through dissolving, filtration by raw material, and filtrate makes total through salt adding acid, nitric acid regulation
Acidity reaches the feed liquid of 8N, adds TBP organic phase and feed liquid to mix in extraction tank, through extracting and demixing and then will after mixing
Zirconium, hafnium separate；Wherein, TBP organic phase is 60% tbp (TBP) and 40% kerosene by weight percentage.
The described organic phase containing zirconium solution through extracting and demixing upper strata, scrubbed rear organic phase passes through back extraction again, collects anti-
The aqueous phase of extraction, again through ammonia precipitation process, filtration, collects precipitation through calcining, calcined product is then further purified through chlorination and obtains final product
To core level hafnium oxide；Wherein, strippant is water；Calcining heat is 650～850 DEG C.
Described extracting and demixing lower floor contains the aqueous phase of hafnium solution, carries out enrichment extraction by the P204 organic phase washed through nitric acid
Take, organic phase again through ammonium hydrogen carbonate back extraction, again through ammonia precipitation process, filtration, collect precipitation through calcining, forge by the aqueous phase collecting back extraction
Burn product and be then further purified through chlorination again and obtain core level hafnium oxide；Wherein, P204 organic phase is by weight percentage
10% phosphate dialkyl ester (P204), 85% kerosene and 5% tbp (TBP)；Nitric acid acidity is 3～5N；Strippant
For 20%NH4HCO3Solution；Calcining heat is 650～850 DEG C.
It is specially and the feed liquid of above-mentioned configuration is added feed liquid in extraction section, feed liquid is mixed with TBP organic phase, blended
It is layered after extraction, organic phase, on upper strata, mainly contains zirconium, enters next stage extracting and washing workshop section.Aqueous phase, in lower floor, mainly contains hafnium,
Adverse current is walked, and discharges from extraction section, enters extracting and enriching section.
Organic phase enters washing section washing, is layered, organic phase, on upper strata, enters next strip stages after adding washing lotion.Water
In lower floor, adverse current enters on last stage.
Organic phase enters strip stages, and addition strip liquor is pure water, and stripping section is equally layered, and organic phase, on upper strata, enters
Next processing stage.Aqueous phase in lower floor, the extraction conditions due to water destruct, zirconium material is dissolved in aqueous phase, releases in this section.Release
The ammoniacal liquor adding 20% containing aqueous zirconium precipitated, then filter, the liquid that filters out enters utilization of wastewater resource system
System.The solid filtering out enters pushed bat kiln and is calcined, and after calcining, solid is oxidized semifinished product zirconium.The waste gas that calcination process produces
Utilization of wastewater resource system is entered through water after absorbing.
Organic phase enters alkali cleaning (sodium carbonate and sodium acid carbonate mixed liquor) and water washing stage wash, and releases alkali lye.Again
Wash with water, and release washings, alkali lye and washings enter utilization of wastewater resource system, and organic phase circulates through saturated acid section
Use.
Liquid phase adverse current in extraction process is walked, and enters hafnium extracting and enriching workshop section, and in extraction conditions lower leaf, upper strata is to have
Machine phase, mainly contains hafnium, enters enrichment back extraction operation.Lower floor is liquid phase, and predominantly waste hydrochloric acid, nitric acid is collected and entered waste water resource
Change and utilize system.
Organic phase enters enrichment strip stages, and addition back washing agent is 20% ammonium bicarbonate soln.Because extraction conditions destroys,
Hafnium enters in lower floor's liquid phase.Upper organic phase enters extraction acid and can step cycle use.Lower floor's liquid phase ammonification water adjustment pH value again.
Precipitation supernatant is extracted out and is entered utilization of wastewater resource system.The precipitation generating enters pushed bat kiln calcining, and organic phase enters enrichment
Souring stage, adds acidifying acid, layering, organic phase, on upper strata, collects reuse from discharging.Lower floor's liquid phase is mainly saturated acid, adjusts
Whole rear reuse.
In above-mentioned extraction process, the extraction waste acid water of generation, alkali waste water, useless ammonia nitrogen water pass through anode membrane, cavity block diffusion dialysis,
Homogeneous EDBM, bipolar membrane electrodialysis technology, acid, alkali can recycle or sell outward it is achieved that extraction process " three wastes " zero
Discharge, extraction waste acid water, alkali waste water, useless ammonia nitrogen water achieve recycling.
Described homogeneous membrane electrodialytic technique, bipolar membrane electrodialysis technology, NF membrane and resins exchange column technology of receiving, diffusion barrier
Osmotic technique, innoxious, the recycling treatment system technical scheme of composition：
1., prepare the abraum salt that separating zirconium and hafnium adopted P204 organic extractant phase technique during core level zirconium oxide produce
Acid, nitric acid mixing acid treatment
Prepare the waste hydrochloric acid of separating zirconium and the generation of hafnium adopted P204 organic extractant phase technique during core level zirconium oxide zirconium,
Nitric acid mixed acid, enters cavity block diffuser, and mixed acid (accounting for more than a 90%) part for recovery is used for feed liquid and washing acid dispensing,
It is partly into hydrochloric acid, nitric acid mixed acid evaporimeter, according to the difference of hydrochloric acid, nitric acid boiling point, hydrochloric acid is separated with nitric acid, hydrochloric acid
It is used for dispensing with a nitric acid part, unnecessary hydrochloric acid send fumed silica device.
Mixed acid containing metal ion (accounting for more than 10%) enters neutralization pond, is produced using homogeneous bipolar electrodialysis equipment
Ammonium hydroxide neutralization, process through sludge drying, the solid beyond the region of objective existence containing zirconium, the solids of scandium sells.
Extraction process zirconium hydroxide solution, hafnium hydroxide solution and zirconium hydroxide, hafnium hydroxide calcining produce ammonium chloride,
Ammonium nitrate solution enters neutralization pond.
Neutralization pond clear liquid enters more medium filter, nanofiltration device, active carbon adsorption device, resin-column of receiving, and filters out miscellaneous
Matter, enters homogeneous bipolar electrodialysis equipment and improves salinity, enters bipolar membrane electrodialysis equipment, and one surveys generation ammonium hydroxide,
A portion is used for neutralization pond and neutralizes, the neutralization sedimentation with zirconium, hafnium strip liquor for the another part, and opposite side produces hydrochloric acid, nitre
Sour mixed acid is used for dispensing, redundance, enters hydrochloric acid, nitric acid evaporimeter, and evaporation, condensation obtain nitric acid, hydrochloric acid, be used for joining
Material, system so recycles (referring to Fig. 2).
2. three mother liquid disposals during, zirconium oxychloride produces
Three mother liquors during zirconium oxychloride produces enter cavity block diffuser, and the hydrochloric acid (accounting for more than 90%) of recovery is supplied gas
Phase method silica device.
Hydrochloric acid containing metal ion (accounting for more than 10%) enters neutralization pond, and core level sponge zirconium device extracts TBP organic phase
The spent lye of alkali process, the waste water of water process are also into neutralization pond, the NaOH being produced using homogeneous bipolar electrodialysis equipment
Neutralization, neutralization, using pond in three-level, respectively obtains the solids of iron content, the solids containing zirconium, the solids containing scandium, does through mud
Change is processed, and the solids containing zirconium returns zirconium oxychloride device, reuses, the solids of iron content, the solid beyond the region of objective existence containing scandium is sold.
Neutralization pond clear liquid enters more medium filter, nanofiltration device, active carbon adsorption device, resin-column of receiving, and filters out miscellaneous
Matter, enters homogeneous bipolar electrodialysis equipment and improves salinity, enters bipolar membrane electrodialysis equipment, and one surveys generation NaOH,
For in neutralization pond and acid, opposite side produce watery hydrochloric acid, send fumed silica device, system so recycle (referring to
Fig. 3).
Advantage for present invention：
1. electrolysis of hydrochloric acid process, can be chlorine and hydrogen by electrolysis of hydrochloric acid, chlorine can supply zirconium oxychloride and be given birth to
Produce zirconium oxychloride and silicon tetrachloride.
The hydrogen of the by-produced tetrachlorosilane of high-purity zirconium oxychloride and electrolysis of hydrochloric acid production all supplies vapor phase method two as raw material
Silica device produces fumed silica.
A large amount of hydrochloric acid of fumed silica device by-product supply to give electrolysis of hydrochloric acid as raw material again, and electrolysis of hydrochloric acid produces
Chlorine for giving zirconium oxychloride production process, and then realize recycling.
2nd, homogeneous membrane electrodialytic technique, bipolar membrane electrodialysis technology, NF membrane and resins exchange column technology of receiving, diffusion barrier oozes
Innoxious, the recycling treatment system technology of analysis technology composition, can adopt P204 organic phase during preparing core level zirconium oxide
The waste hydrochloric acid that extraction process produces, nitric acid mixed acid are recycled, and prepare for feed liquid, and washing lotion is prepared.
Ammonium nitrate, the ammonium chloride solution Bipolar membrane water splitting by the system, can obtain ammonium hydroxide in the side of film molten
Liquid, opposite side can obtain hydrochloric acid, nitric acid mixed acid, and Ammonia is used for zirconium liquid, the zirconium of hafnium liquid, hafnium sedimentation, and hydrochloric acid,
Nitric acid mixed acid passes through the neutralization of the produced spent acid of diffusion dialysis film.Hydrochloric acid, nitric acid mixed acid are used for feed liquid and prepare, and washing lotion is prepared.
Hydrochloric acid, nitric acid mixed acid carry out separating using evaporation technique, and nitric acid is used for preparing 6N nitric acid and 4N nitric acid, a part
Hydrochloric acid and nitric acid are used for feed liquid and prepare, and washing lotion is prepared, and send the production of silica more than hydrochloric acid.
The ammonium hydroxide producing can be used for zirconium liquid, the ammonium of hafnium liquid sinks.
Homogeneous membrane electrodialytic technique, bipolar membrane electrodialysis technology, NF membrane and resins exchange column technology of receiving, spread film dialysis
Three mother liquors of zirconium oxychloride device are also recycled by innoxious, the recycling treatment system technology of technology composition.
Simultaneously also by the spent lye of core level sponge zirconium device organic phase alkali process, the waste water of organic phase water process is recycled,
The caustic soda that Bipolar Membrane produces is used for the neutralization of diffusion dialysis spent acid, and the hydrochloric acid that bipolar membrane electrodialysis technology produces send vapor phase method dioxy
SiClx device
So fundamentally solve zirconium oxychloride industry and the very intractable environmental issue of core level sponge zirconium industry, realize
Zirconium oxychloride industry, fumed silica industry, the Joint Production of core level sponge zirconium industry and electrolysis of hydrochloric acid four major trades,
This four devices have accomplished complete industrial chain circulation.
Brief description
Fig. 1 is the process chart producing core level sponge zirconium and core level hafnium sponge provided in an embodiment of the present invention.
Fig. 2 is nuclear grade zirconium waste acid water provided in an embodiment of the present invention, useless ammoniacal liquor recycling block diagram.
Fig. 3 is provided in an embodiment of the present invention
Specific embodiment
Embodiment 1
The process unit of core level sponge zirconium and core level hafnium sponge and process (referring to Fig. 1)
1st, each section of feed liquid of extraction is prepared
Feed liquid is prepared：By the zirconium oxychloride metering in raw material through dissolving, zirconium chloride is through hydrolysis, the two kinds of solution that will obtain
Control ZrO2 concentration 80～95g/l in feed liquid, filter through purpose ceramic-film filter, using nitric acid and hydrochloric acid, be configured to 8N acidity
Qualified feed liquid；
Washing lotion is prepared：Using reclaiming hydrochloric acid, nitric acid compound, hydrochloric acid, nitric acid be configured to the mixing pickle of 5N acidity；
TBP organic phase is prepared：By weight percentage 60% tbp (TBP) and 40% kerosene, TBP is organic for preparation
Phase；
Saturated acid is prepared：Nitric acid is configured to the TBP saturated acid of 6N acidity；
Alkali liquid compounding：Sodium carbonate and sodium acid carbonate, sodium carbonate basicity 1.6N, sodium acid carbonate basicity 0.3N；
P204 organic phase is prepared：By weight percentage 10% phosphate dialkyl ester (P204), 85% kerosene and 5% phosphoric acid
Tri butyl ester (TBP)；
P204 organic phase back extraction Alkali liquid compounding：Ammonium hydrogen carbonate；
Prepare precipitation alkali lye using ammoniacal liquor；
2nd, separation of zirconium and hafnium and prepare core level sponge zirconium and core level hafnium sponge：
The feed liquid of above-mentioned configuration is made feed liquid and TBP organic be harmonious uniform (TBP organic phase and material liquid volume ratio in extraction section
Example is 15:7), it is layered after blended extraction, organic phase, on upper strata, mainly contains zirconium, enters next stage extracting and washing workshop section.Aqueous phase
In lower floor, mainly contain hafnium, adverse current is walked, and discharges from extraction section, enters extracting and enriching section.
Organic phase enters washing section washing, and (organic phase and cleaning solution volume ratio are 15:3) it is layered after, adding washing lotion, have
Machine, on upper strata, enters next strip stages.Aqueous phase enters on last stage in lower floor, adverse current.
Organic phase enters strip stages, and addition strip liquor is that (organic phase and strip liquor volume ratio are 15 to pure water:15), instead
Extraction section is equally layered, and organic phase, on upper strata, enters next processing stage.Aqueous phase in lower floor, the extraction conditions due to water destruct, zirconium
Material is dissolved in aqueous phase, releases in this section.The ammoniacal liquor adding 20% containing aqueous zirconium released is precipitated (controls pH value 9
～11), then filter, the liquid filtering out enters utilization of wastewater resource system.The solid filtering out enters pushed bat kiln to be carried out
Calcining (650～850 DEG C of calcining heat), after calcining, solid is oxidized semifinished product zirconium.The waste gas that calcination process produces absorbs through water
Enter utilization of wastewater resource system afterwards.
Organic phase enters alkali cleaning (sodium carbonate and sodium acid carbonate mixed liquor, Na2CO3With NaHCO3Weight is than for 4:3, organic phase
It is volume 15 with alkali cleaning liquid proportional:5) and water washing stage wash (organic phase and water volume ratio are 15:, and release alkali lye 8).
It is washed with water and washs, and release washings, alkali lye and washings enter utilization of wastewater resource system.
Liquid phase (aqueous phase) adverse current in extraction process is walked, and enters hafnium extracting and enriching workshop section, by wash through nitric acid
P204 organic phase carries out extracting and enriching (the P204 organic phase of nitric acid washing and liquid phase (aqueous phase) volume ratio 12:10), in extraction
Condition lower leaf, upper strata is organic phase, mainly contains hafnium, and organic phase enters back extraction operation, adopts and make 20%NH4HCO3Solution is as anti-
(organic phase and strip liquor volume ratio are 18 to extraction liquid:10).Lower floor's liquid phase ammonification water adjustment pH value again.Precipitation supernatant extract out into
Enter utilization of wastewater resource system.The precipitation generating enters pushed bat kiln calcining, 650～850 DEG C of calcining heat.
Because extraction conditions destroys, upper organic phase enters acidifying acid phase, and acidifying acid adopts [HNO3] concentration be 3～5N
Recycle.
Enter utilization of wastewater resource system from entering the acid out of enrichment operation.
3. above-mentioned prepare core level sponge zirconium and core level hafnium sponge each purification process is core level sponge zirconium
First, purifying technique flow process：
1st, low temperature degasification：Thick zirconium chloride is loaded in purification tank and evacuates, heat up, tank deck, center, tank bottom respectively keep certain
Temperature and regular hour, carry out low temperature degasification, remove lower boiling metal chloride.
2nd, distillation condensation：After low temperature degasification, heat up and so that zirconium chloride is volatilized and in the condensation of top tank skin, control cold simultaneously
Solidifying temperature and purification furnace programming rate, volatilization terminates final temperature and is 600 DEG C -650 DEG C.
3rd, venting is reclaimed：In purification process, removal of impurities of regularly exitting from tank, also inevitably arrange in discharge gas
Go out a small amount of zirconium chloride gas must be recycled.Reclaim through one-level recover condensation zirconium chloride, then through Water spray
Empty after gas is up to standard.
Purifying technology parameter
1st, shove charge
2nd, evacuate：Exhaust is evacuated when 0～270 DEG C
3rd, distillation condensation：Volatilization temperature：400～500 DEG C, condensation
4th, central temperature：450℃
5th, end temp：600℃
2nd, reducing process flow process
General principle
Zirconium chloride is loaded in volatilization bucket, more a certain amount of magnesium metal is loaded in reduction mould, and together load also
Former tank is airtight, heats up and allows zirconium chloride intensification volatilize after first making magnesium fusing again, zirconium chloride gas is reacted with molten magnesium, its temperature
Degree is at 800 DEG C about.Reaction equation is as follows：
ZrCl4+ 2Mg====Zr+2MgCl2
Reduction obtains the mixture of zirconium, magnesium chloride and superfluous magnesium.
Technological process
Reduction reaction is the magnesium metal reduction that zirconium chloride gas is melted, and generates the mixture of sponge zirconium and magnesium chloride.
Shove charge：Zirconium chloride is loaded in volatilization bucket, magnesium loads reduction mould sealed shell of tank according to a certain percentage.
Leak detection：With the leak detection of mechanical pump depletion, leakage rate is made within 10 minutes to be qualified within claimed range, applying argon gas keep
Malleation.
Cryopumping：Reductive jar is hung in stove, heating is raised to uniform temperature, removes impurity gas with water ring pump depletion simultaneously
Body.
Reduction：After reduction furnace bottom heat temperature raising makes magnesium metal fusing in reduction mould, ZrCl4Volatilization section heat temperature raising,
Allow ZrCl4Distillation volatilization, is reacted with the magnesium of melting, and reaction is carried out under an argon atmosphere, and must keep malleation.Reaction
Speed is certain to be required steadily, the sponge zirconium product that could have obtained.Reaction speed, reaction speed can be controlled using the partial pressure of argon gas
Degree is most important to the quality improving sponge zirconium and raising yield.After reaction terminates, discharge MgCl2, applying argon gas, keep malleation,
Have a power failure cooling.This process also will constantly rush argon gas.When reductive jar is cooled to uniform temperature, hangs in water-cooling jacket cooling, treat cold
But fill the crucible of sponge zirconium and magnesium chloride to when 50 DEG C it is possible to opening jar and taking out.
Reducing process technical parameter
1st, shove charge evacuates leak detection：With mechanical pump depletion leak detection qualified after, applying argon gas.
2nd, tinning：Load zirconium chloride by a certain percentage and Mg enters stove feeding temperature-raising：Heat up in top, use water ring pumping simultaneously
Empty degasification.
3rd, heat up：400 DEG C of top；650 DEG C of bottom.
4th, reaction temperature：760～800 DEG C of bottom
5th, partial pressure：Argon filling, venting, quadruplication
6th, terminate：800 DEG C of temperature of lower, 600 DEG C of upper temp, constant temperature, pressure drop, venting is observed judgement and is terminated.
3rd, vacuum distillation technological process
General principle
Reduction is obtained sponge zirconium and magnesium chloride and the mixture of excessive magnesium loads in retort, evacuate heating and borrow high temperature high
Magnesium chloride in sponge zirconium and magnesium are removed by vacuum with liquids and gases state, obtain the sponge zirconium product conforming to quality requirements.
Technological process
Distilled reducing products obtained therefrom by means of high temperature, high vacuum, removed magnesium chloride therein and superfluous magnesium.
1 preparation：Cleaning, drying, tinning, the various pipelines of connection etc.
2 evacuate in advance：a：Vacuum pipe evacuates leak detection
b：Alembic evacuates leak detection
3 shove charges：Reduction is filled black powder argon gas in sponge zirconium crucible clean out, flaw-piece sponge zirconium is rooted out, load
Alembic.
4 evacuations：Open each vavuum pump by the order of vacuum system, after being evacuated to certain vacuum degree, can be by heating furnace power transmission
Heat up, 900 DEG C of constant temperature are risen to certain programming rate.Open anti-vacuum pump depletion at the same time.Each cooling water pipe during power transmission
Connect, when the vacuum in tank reaches capacity vacuum, can have a power failure after the insulation regular hour and terminate.
5 coolings：After being cooled to uniform temperature in tank, capable of hoisting open heating furnace, when being cooled to applying argon gas temperature in tank, close
All vacuum valves, into tank, applying argon gas keep malleation.
6 passivation：
a：Start to be passivated after tank is cooled to uniform temperature.
b：Drive oil-sealed rotary pump to evacuate, be filled with dry air to after certain vacuum degree, keep one
Fix time.
c：After opening oil-sealed rotary pump evacuation again, it is filled with dry air, is repeated three times, passivation terminates.
Vacuum distillation technical data
1st, preparation：Connect including cleaning, tinning, each vacuum system pipeline and water pipe etc.
2nd, give evacuation：
1. vacuum pipe evacuates leak detection, drives oil-sealed rotary pump and evacuates, and shuts pipeline valve leak detection qualified.
2. tank body evacuates leak detection：Tank body is evacuated, opens vacuum system evacuation leak detection qualified.
3rd, shove charge：The Zr+MgCl that reduction is obtained2Black powder on+Mg crucible blows clean, and on flaw-piece, sponge zirconium shovel falls, dress
Enter alembic.
4th, evacuate：First start tool pump depletion, open again lobe pump, open heater for diffusion pump, open diffusion pump valve evacuate, distillation
Stove feeding temperature-raising, opens anti-vacuum pump depletion at the same time, and connects cooling water.
5th, heating and heat preservation：Heat up 900 DEG C of constant temperature, when in alembic, vacuum is constant, at this moment can determine whether the chlorine in sponge zirconium
Change magnesium and superfluous magnesium is removed, distillation finishes, and power transmission can terminate.
6th, cool down：When being cooled to uniform temperature in tank, hang out heating furnace, shut whole valves.The applying argon gas into tank.
7th, passivation operation：Start to be passivated after being cooled to 30 DEG C in tank.
Start tool pump depletion is filled with dry air, repeatedly for three times.
4th, crushing packing technological process
Technological process
The sponge zirconium that distillation is obtained takes out from reduction mould, cuts into after certain lumpiness through hydraulic press, then with tilting
Formula forcing press is cut into 3～25mm, screening, picking, batch mixing, barrelling, evacuation argon filling sealing.
Technical parameter
1st, take out sponge zirconium from the reduction mould after distillation
2nd, about 100 × 100 lumpiness are cut into 1000t hydraulic press
3rd, it is cut into 25mm granularity with tilting forcing press
4th, sieve：Sponge zirconium granularity necessary 100 is passed through 25 and is sieved, containing 3 ＜ 5
5th, batch mixing：Many batches of qualified material merge and mix
6th, pack：Plastic bag sponge zirconium 100, evacuation, argon filling, sealing is used in each bucket.
Part II：Core level hafnium sponge
First, purifying technique flow process：
1st, low temperature degasification：Thick hafnium tetrachloride is loaded in purification tank and evacuates, heat up, tank deck, center, tank bottom respectively keep certain
Temperature and regular hour, carry out low temperature degasification, remove lower boiling metal chloride.
2nd, distillation condensation：After low temperature degasification, heat up and so that hafnium tetrachloride is volatilized and in the condensation of top tank skin, control cold simultaneously
Solidifying temperature and purification furnace programming rate, volatilization terminates final temperature and is 600 DEG C -650 DEG C.
3rd, venting is reclaimed：In purification process, removal of impurities of regularly exitting from tank, also inevitably arrange in discharge gas
Go out a small amount of hafnium tetrachloride gas must be recycled.Reclaim through one-level recover condensation hafnium tetrachloride, then through Water spray
Empty after gas is up to standard.
Purifying technology parameter
1st, shove charge
2nd, evacuate：Exhaust is evacuated when 0～270 DEG C
3rd, distillation condensation：Volatilization temperature：400～500 DEG C, condensation
4th, central temperature：450℃
5th, end temp：600℃
2nd, reducing process flow process
General principle
Hafnium tetrachloride is loaded in volatilization bucket, more a certain amount of magnesium metal is loaded in reduction mould, and together load also
Former tank is airtight, heats up and allows hafnium tetrachloride intensification volatilize after first making magnesium fusing again, hafnium tetrachloride gas is reacted with molten magnesium, its temperature
Degree is at 800 DEG C about.Reaction equation is as follows：
HrCl4+ 2Mg====Hr+2MgCl2
Reduction obtains the mixture of zirconium, magnesium chloride and superfluous magnesium.
Technological process
Reduction reaction is the magnesium metal reduction that hafnium tetrachloride gas is melted, and generates the mixture of hafnium sponge and magnesium chloride.
Shove charge：Hafnium tetrachloride is loaded in volatilization bucket, magnesium loads reduction mould sealed shell of tank according to a certain percentage.
Leak detection：With the leak detection of mechanical pump depletion, leakage rate is made within 10 minutes to be qualified within claimed range, applying argon gas keep
Malleation.
Cryopumping：Reductive jar is hung in stove, heating is raised to uniform temperature, removes impurity gas with water ring pump depletion simultaneously
Body.
Reduction：After reduction furnace bottom heat temperature raising makes magnesium metal fusing in reduction mould, HrCl4Volatilization section heat temperature raising,
Allow HrCl4Distillation volatilization, is reacted with the magnesium of melting, and reaction is carried out under an argon atmosphere, and must keep malleation.Reaction
The certain sponge requiring steadily, could obtain of speed closes product.Reaction speed, reaction speed can be controlled using the partial pressure of argon gas
Degree is most important to the quality improving hafnium sponge and raising yield.After reaction terminates, discharge MgCl2, applying argon gas, keep malleation,
Have a power failure cooling.This process also will constantly rush argon gas.When reductive jar is cooled to uniform temperature, hangs in water-cooling jacket cooling, treat cold
But fill the crucible of hafnium sponge and magnesium chloride to when 50 DEG C it is possible to opening jar and taking out.
Reducing process technical parameter
1st, shove charge evacuates leak detection：With mechanical pump depletion leak detection qualified after, applying argon gas.
2nd, tinning：Load hafnium tetrachloride by a certain percentage and Mg enters stove feeding temperature-raising：Heat up in top, use water ring pumping simultaneously
Empty degasification.
3rd, heat up：400 DEG C of top；650 DEG C of bottom.
4th, reaction temperature：760～800 DEG C of bottom
5th, partial pressure：Argon filling, venting, quadruplication
6th, terminate：800 DEG C of temperature of lower, 600 DEG C of upper temp, constant temperature, pressure drop, venting is observed judgement and is terminated.
3rd, vacuum distillation technological process
General principle
Reduction is obtained hafnium sponge and magnesium chloride and the mixture of excessive magnesium loads in retort, evacuate heating and borrow high temperature high
Magnesium chloride in hafnium sponge and magnesium are removed by vacuum with liquids and gases state, obtain the hafnium sponge product conforming to quality requirements.
Technological process
Distilled reducing products obtained therefrom by means of high temperature, high vacuum, removed magnesium chloride therein and superfluous magnesium.
1 preparation：Cleaning, drying, tinning, the various pipelines of connection etc.
2 evacuate in advance：a：Vacuum pipe evacuates leak detection
b：Alembic evacuates leak detection
3 shove charges：Reduction is filled black powder argon gas in hafnium sponge crucible clean out, flaw-piece hafnium sponge is rooted out, load
Alembic.
4 evacuations：Open each vavuum pump by the order of vacuum system, after being evacuated to certain vacuum degree, can be by heating furnace power transmission
Heat up, 900 DEG C of constant temperature are risen to certain programming rate.Open anti-vacuum pump depletion at the same time.Each cooling water pipe during power transmission
Connect, when the vacuum in tank reaches capacity vacuum, can have a power failure after the insulation regular hour and terminate.
5 coolings：After being cooled to uniform temperature in tank, capable of hoisting open heating furnace, when being cooled to applying argon gas temperature in tank, close
All vacuum valves, into tank, applying argon gas keep malleation.
6 passivation：
a：Start to be passivated after tank is cooled to uniform temperature.
b：Drive oil-sealed rotary pump to evacuate, be filled with dry air to after certain vacuum degree, keep one
Fix time.
c：After opening oil-sealed rotary pump evacuation again, it is filled with dry air, is repeated three times, passivation terminates.
Vacuum distillation technical data
1st, preparation：Connect including cleaning, tinning, each vacuum system pipeline and water pipe etc.
2nd, give evacuation：
1. vacuum pipe evacuates leak detection, drives oil-sealed rotary pump and evacuates, and shuts pipeline valve leak detection qualified.
2. tank body evacuates leak detection：Tank body is evacuated, opens vacuum system evacuation leak detection qualified.
3rd, shove charge：The Hr+MgCl that reduction is obtained2Black powder on+Mg crucible blows clean, and on flaw-piece, sponge zirconium shovel falls, dress
Enter alembic.
4th, evacuate：First start tool pump depletion, open again lobe pump, open heater for diffusion pump, open diffusion pump valve evacuate, distillation
Stove feeding temperature-raising, opens anti-vacuum pump depletion at the same time, and connects cooling water.
5th, heating and heat preservation：Heat up 900 DEG C of constant temperature, when in alembic, vacuum is constant, at this moment can determine whether the chlorine in hafnium sponge
Change magnesium and superfluous magnesium is removed, distillation finishes, and power transmission can terminate.
6th, cool down：When being cooled to uniform temperature in tank, hang out heating furnace, shut whole valves.The applying argon gas into tank.
7th, passivation operation：Start to be passivated after being cooled to 30 DEG C in tank.
Start tool pump depletion is filled with dry air, repeatedly for three times.
4th, crushing packing technological process
Technological process
The hafnium sponge that distillation is obtained takes out from reduction mould, cuts into after certain lumpiness through hydraulic press, then with tilting
Formula forcing press is cut into 3～25mm, screening, picking, batch mixing, barrelling, evacuation argon filling sealing.
Technical parameter
1st, take out hafnium sponge from the reduction mould after distillation
2nd, about 100 × 100 lumpiness are cut into 1000t hydraulic press
3rd, it is cut into 25mm granularity with tilting forcing press
4th, sieve：Hafnium sponge granularity necessary 100 is passed through 25 and is sieved, containing 3 ＜ 5
5th, batch mixing：Many batches of qualified material merge and mix
6th, pack：Plastic bag hafnium sponge 100, evacuation, argon filling, sealing is used in each bucket.
5th, in extraction process, the extraction waste acid water of generation, alkali waste water, useless ammonia nitrogen water pass through diffusion dialysis, homogeneous membrane electric osmose
Analysis, bipolar membrane electrodialysis technology, acid, alkali can recycle or sell outward it is achieved that extraction process " three wastes " zero-emission, extracts useless
Sour water, alkali waste water, useless ammonia nitrogen water achieve recycling.
Embodiment 2
The acquisition of above-described embodiment raw material：The method producing high-purity zirconium oxychloride
1st, chlorination reaction
Zircon sand, silica flour, petroleum coke and chlorine, ratio is 0.8～1.2：0.1～0.4：0.4～0.5:2.8～3.0,
It is passed through chlorine in chlorination furnace under the gas speed of 0.06～0.16m/s, carry out chlorination reaction with 650～1100 DEG C, this reaction
Belong to autothermal reaction, control expanding reach temperature at 380～500 DEG C, generate zirconium chloride, silicon tetrachloride.
Chlorination reaction equation：
ZrSiO4+4C+4Cl2=ZrCl4+SiCl4+4CO (1)
ZrSiO4+2C+4Cl2=ZrCl4+SiCl4+2CO2(2)
Si+2Cl2=SiCl4(3)
2nd, reacted Mixed Gas Condensation, separation
Reacted mixed gas enter level Four condenser, using circulating water, control offgas outlet temperature 150～
160 DEG C, in four condensers, control different condensation temperatures, the zirconium chloride of different purity can be obtained, in the first condensation
The higher zirconium chloride of quantity more than 90% purity can be obtained in device, second, third, the 4th condenser purity reduce successively,
Quantity reduces successively.
3rd, zirconium chloride purification
Zirconium chloride enters spin-drier, and the purity of zirconium chloride purification and efficiency greatly improve, the essence after purification
Zirconium chloride, can directly be used for extracting dispensing as the raw material of zirconium, hafnium extract and separate.It is also possible to straight after zirconium chloride is purified
Connect dispensing hydrolysis, without evaporation, direct crystallization, obtain high-purity zirconium oxychloride product it is also possible to evaporation, crystallization are through evaporation, crystallization
Obtain high-purity zirconium oxychloride product.
4th, silicon tetrachloride washing, rectifying
Silicon tetrachloride in tail gas, carbon monoxide, carbon dioxide enter one-level through silicon tetrachloride hydraulic ejector
Silicon tetrachloride scrubbing tower controls temperature at 20 DEG C, enters two grades of silicon tetrachloride scrubbing towers and controls temperature at -15 DEG C, tail gas enters tail
Gas condenser controls temperature at -35 DEG C, and the silicon tetrachloride condensing out enters one-level rectifying column, and tower reactor controls temperature at 60 DEG C,
Tower top controls temperature at 40 DEG C, and the silicon tetrachloride of one-level rectifying column enters two-stage rectification tower, and tower reactor controls temperature at 70 DEG C, tower top
Control temperature at 40 DEG C, tower top obtains smart silicon tetrachloride purity 99.8%.
The tail gas going out silicon tetrachloride condenser, after level Four pickling tower, obtains 20% hydrochloric acid and sends into fumed silica
Device, the tail gas after pickling enters three-level caustic wash tower, obtains 10% sodium, the titanium blower fan of tail gas containing carbon monoxide, send boiler to fire
Pour.
5th, hydrolyze
Above-mentioned go out purifier zirconium chloride solid can deliver to core level sponge zirconium device it is also possible to pass through nitrogen binder, enter
Enter hydrolytic decomposition pot, add pure water, evaporative condenser acid, cleaning solution to be hydrolyzed, control material addition is zirconium chloride solid：Pure
Water：Evaporation acid：Cleaning solution is 1：2.5：0.8：1.1 (weight ratios), control hydrolysis temperature at 40-90 DEG C, treat hydrolyzate zirconium concentration
In 90 ± 10g/l, with being pumped into chamber-type press filter, filter out the solids carried secretly, obtain the smart zirconium oxychloride purifying
Solution, the recyclable recycling of cleaning solution during hydrolysis.Wherein, evaporating sour is 19% hydrochloric acid for 19% hydrochloric acid, cleaning solution.
Hydrolysis equation
ZrCl4+H2O=ZrOCl2+2HCl
6th, evaporation, crystallization
Above-mentioned acquisition essence zirconyl chloride solution is added to double heating outer circulation graphite evaporators, heats material using steam
Liquid, is evaporated, and by the use of the indirect steam of evaporimeter as thermal source, smart zirconyl chloride solution is preheated, and control steam pressure is
0.3-0.6MPa, in 0.02MPa 0.05MPa, to feed liquid, zirconium dioxide concentration, in 180 ± 10g/l, obtains evaporation to vacuum
Feed liquid after qualified enters crystallizing tank, crystallization treatment 24h at 25 DEG C, crystallizes the oxychlorination solution completing, by belt type filter
Machine is filtered, and after filtration, crystal with 18% salt acid elution, that is, obtains zirconium oxychloride crystal, and gained filtrate is as once female
Liquid.
Zirconium oxychloride crystal puts into making beating tank, is stirred the salt acid elution with 18%, enters slurry outstanding after washing
Formula centrifuge, carries out being centrifuged the zirconium oxychloride crystal that depickling respectively obtains percent crystallization in massecuite up to more than 90%, is obtained high-purity after packaging
Zirconium oxychloride product.
The indirect steam of the containing hydrogen chloride obtaining during evaporation condenses out, and enters the cooling of graphite exhaust gas cooler, recovery
Condensation watery hydrochloric acid concentration only has 3～5% and 17～20%, and as by-product hydrochloric acid, for hydrolyzing, redundance delivers to vapor phase method two
The chlorine hydride absorption system in silica workshop.
Mother liquor and the cleaning solution of washing crystal, respectively from flowing into mother liquor holding tank, washing in liquid storage tank, treated follow-up
Continue and apply mechanically.
One time mother liquor can get secondary mother liquid after evaporation, crystallization.Secondary mother liquid available three mothers after evaporation, crystallization
Liquid.
7th, three mother liquid disposals
Three mother liquors send homogeneous membrane electrodialytic technique, bipolar membrane electrodialysis technology, NF membrane and resins exchange column technology of receiving,
Innoxious, the recycling treatment system of diffusion barrier osmotic technique composition, reclaims the rare precious metal ion such as hydrochloric acid and scandium.
Embodiment 3
Vapor phase method prepares silica：
1st, aerosil synthesis and process
The smart silicon tetrachloride that high-purity zirconium oxychloride operation is come enters the vaporization of silicon tetrachloride vaporization device, uses hot water in vaporizer
Heating vaporization, vapourizing temperature controls at 70～80 DEG C, and the hydrogen that electrolysis of hydrochloric acid device comes and air are preheated by heater, preheating
To 120～130 DEG C, three kinds of gases enter reacting gas homogenizer, homogenizing, silicon tetrachloride：Hydrogen：Air ratio (mol ratio)
It is 1：2～4:9～11, enter the multilayer combustion device on silica high-temperature reactor top, after burning, form stable flame,
Fumed silica and hydrogen chloride vapor, temperature in silica high-temperature reactor is generated in silica high-temperature reactor
Control at 800～1000 DEG C, do not have after warm gas cooler through reaction, enter the cyclone separator of 3 grades of series connection, cyclone separator
Solid particle under separating, sends into 1 grade of extracting tower and two grades of extracting towers by being passed through air, is entering three-level extracting tower and dehydrating tower
Afterwards, enter packing jar, the finished product packing machine entering packing jar is packaged into bag.
2nd, vent gas treatment
Gaseous mixture pipeline after three-stage cyclone separator separates enters exhaust treatment system, enters pickling tower, entrance group afterwards
Box-like absorption tower, 19% hydrochloric acid that zirconium oxychloride operation is come, 3% hydrochloric acid；17% hydrochloric acid that electrolysis of hydrochloric acid operation is come；Waste acid water,
Alkali waste water, useless ammonia nitrogen water, innoxious, the recycling treatment system of three mother liquors of zirconium oxychloride device, 8% hydrochloric acid of generation,
Also into combined type absorption tower, prepare 31% hydrochloric acid.
31% hydrochloric acid is used for electrolysis of hydrochloric acid, and in tail gas, chlorine is absorbed with two grades of caustic wash towers, prepares 10～13% sodium hypochlorite
Product, tail gas qualified discharge electrolysis of hydrochloric acid：
Embodiment 4：
1st, electrolysis of hydrochloric acid
Obtain 31% hydrochloric acid that combined tower absorbs during vapor phase method obtains silica, after subcooler, enter
Enter barrier film chamber-type press filter press filtration, suspension content fall 600wtppm in hydrochloric acid.Then pass through inorganic ceramic filter again
Make suspension content drop to 1～3wtppm level below to mix with the diluted acid after electrolysis, to ensure to add the salt in electrolytic cell
Acid concentration and purity.
In electrolytic cell, hydrochloric acid is decomposed into chlorine and hydrogen at the electrode surface, and the chlorine of generation and hydrogen respectively enter
In respective processing unit.
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 is absorbed with two grades of caustic wash towers, and in control tower, temperature is 35～40
DEG C, prepare 10% sodium hypochlorite product, tail gas qualified discharge.
Electrolytic process is：
In electrolyzer anode chamber, hydrochloric acid decomposes generation chlorine after electrolysis.Reaction equation is as follows：
Cl- e → 1/2Cl2↑
Electrolysis watery hydrochloric acid out flows into watery hydrochloric acid groove, returns to the anode chamber of electrolytic cell after some and mixed in hydrochloric acid,
And another part is with being pumped to hydrochloric acid absorption tower circulating tank.
In electric tank cathode room, water is decomposed generation hydrogen, and reaction equation is as follows：
H++e→1/2H2↑
The watery hydrochloric acid that electrolytic cell generates flows to watery hydrochloric acid groove.The negative electrode of electrolytic cell is returned after a part and mixed in hydrochloric acid
Room, and another part then send hydrochloric acid absorption tower circulating tank.
Electrolyzer anode chamber and the Cl of cathode chamber generation2And H2Delivered to chlorine hydrogen treatment process respectively to process.
A, anode circulation
It is total by the anolyte charging of hydrochloric acid head tank feeding electrolytic cell that what absorption by Hydrochloric Acid, filter progress were sent filters hydrochloric acid
Pipe.Filter hydrochloric acid to be electrolysed in the anode compartment, produce chlorine, HCL concentration reduces, and going out electrolytic cell concentration of hydrochloric acid is simultaneously
17%.
Reaction equation is as follows：Cl-- e → 1/2Cl2↑
Because hydrochloric acid is electrolysed, reduction is changed into weak hydrochloric acid by its HCl concentration, and the chlorine of weak hydrochloric acid and electrolysis generation is through going out
Discharge header pipe delivered to by material flexible pipe and here completes gas-liquid separation.It is total that the chlorine that every electric groove discharge header pipe is isolated collects in chlorine
Pipe, enters the moisture to be separated off further in chlorine for the watery hydrochloric acid groove top, is then sent to chlorine and processes.
The watery hydrochloric acid that every electrolytic cell discharge header pipe is isolated collects in watery hydrochloric acid house steward, enters watery hydrochloric acid groove, one
Watery hydrochloric acid is divided to be recycled to hydrochloric acid feed pipe, remaining watery hydrochloric acid delivers to hydrochloric acid absorption tower, chlorine under the Liquid level of watery hydrochloric acid groove
After gas is cooled and separated, it is recycled to moist chlorine house steward.
B, cathode circulation
In cathode chamber, water is as follows through being electrolysed the generation hydrogen that is decomposed, reaction equation：
H++e→1/2H2↑
The hydrogen of watery hydrochloric acid and electrolysis generation delivers to discharge header pipe through discharge tube and here completes gas-liquid separation.
The hydrogen that every electric groove discharge header pipe is isolated collects in hydrogen manifold, enters watery hydrochloric acid groove top with further
It is separated off the moisture in hydrogen, be then sent to hydrogen and process.
The dilute hydrochloric acid liquid that every electric groove discharge header pipe is isolated collects in acid solution house steward, enters acid solution groove, by acid pump
The part acid solution sent sends into acid solution head tank, is then flowed out by acid solution head tank and enters catholyte charging with the hydrochloric acid after filtration
House steward, then cathode chamber is entered by feed hose, add the Flow-rate adjustment DC current flow serials control of hydrochloric acid, and by negative electrode
Liquid cooler controls the temperature to keep groove acid solution for the acid liquor temperature entering acid solution head tank；Its remaining part being pumped out by acid solution
Divide and deliver to absorption by Hydrochloric Acid under the Liquid level of acid solution groove.
2nd, chlorine is processed from the next about moist chlorine of electrowinning process through Chlorine Scrubber chlorine water wash cooling, subsequently into titanium tube
Cooler, is cooled to 18 DEG C about with chilled water.Then chlorine is through the condensing drip in the lower chlorine of water smoke trap trapping
Afterwards, sequentially enter one-level paddle dryer tower sulfuric acid to be dried from tower top spray, strictly control spray sulfuric acid concentrations at different levels, one
Section be more than 75%, dried chlorine is further dried with the 98wt% concentrated sulfuric acid through bubble column again, make dried go out tower chlorine
Gas water content is less than 50ppm.After chlorine drips through acid mist eliminator removing acid mist after drying, enter chlorine gas compressor, finally enter
Chlorine distribution platform is sent to zirconium oxychloride device by pipeline.
Sulfate system is unloaded on the spot by tank car for 98wt% sulfuric acid and is sent into concentrated sulfuric acid storage tank, is pumped into the concentrated sulfuric acid through the concentrated sulfuric acid
Head tank, enters bubble-cap drying tower with after freezing water cooling.A part recycles, and another part overflow enters paddle dryer tower
The sulfuric acid circulatory system, when acid concentration drops to 75wt%, is sent to Waste Sulfuric Acid tank field through dilute sulfuric acid circulating pump.
3rd, hydrogen treat
The wet hydrogen coming from electrowinning process is cooled to 40 DEG C about through the direct spray washing of flush of hydrogen gas tower washings, by
Hydrogen gas compressor compression laggard hydrogen cooler cooling, then it is sent to fumed silica through water smoke trap, hydrogen distribution platform
Operation.
Embodiment 5：
Homogeneous membrane electrodialytic technique, bipolar membrane electrodialysis technology, NF membrane and resins exchange column technology of receiving, spread film dialysis
Innoxious, the recycling treatment system technical scheme of technology composition
1st, the waste hydrochloric acid of nuclear grade zirconium device P204 organic extractant phase technique generation, nitric acid mixing acid treatment
The waste hydrochloric acid of nuclear grade zirconium device P204 organic extractant phase technique generation, nitric acid mixed acid, enter cavity block diffuser, return
The mixed acid (accounting for more than 90%) received, a recovery acid part is used for feed liquid and washing acid dispensing, is partly into hydrochloric acid, nitric acid mixes
Close sour evaporimeter, according to the difference of hydrochloric acid, nitric acid boiling point, hydrochloric acid separated with nitric acid, hydrochloric acid and a nitric acid part are used for dispensing,
Unnecessary hydrochloric acid send fumed silica device.
From the cavity block diffuser unrecovered mixed acid containing metal ion (accounting for more than 10%) out, enter neutralization
Pond, the ammonium hydroxide neutralization being produced using homogeneous bipolar electrodialysis equipment, process through sludge drying, obtain the solid containing zirconium, scandium
Thing, sells to outward Rare Earth Company.
Extraction process zirconium hydroxide solution, hafnium hydroxide solution and zirconium hydroxide, hafnium hydroxide calcining produce ammonium chloride,
Ammonium nitrate solution enters neutralization pond.
Neutralization pond clear liquid enters more medium filter, nanofiltration device, active carbon adsorption device, resin-column of receiving, and filters out miscellaneous
Matter, enters homogeneous bipolar electrodialysis equipment and improves salinity, enters bipolar membrane electrodialysis equipment, and one surveys generation ammonium hydroxide,
A portion is used for neutralization pond spent acid and neutralizes, the neutralization sedimentation with zirconium, hafnium strip liquor for the another part.
Opposite side produces hydrochloric acid, nitric acid mixed acid is used for TBP organic phase washing lotion dispensing, redundance hydrochloric acid, nitric acid mixing
Acid, enters hydrochloric acid, nitric acid evaporimeter, respectively obtains nitric acid, hydrochloric acid through evaporation, condensation, prepares for zirconium feed liquid, saturated acid is joined
System, acidifying acid are prepared.
2nd, three mother liquors that zirconium oxychloride device produces enter cavity block diffuser, and the hydrochloric acid (accounting for more than 90%) of recovery is supplied gas
Phase method silica device.
Hydrochloric acid containing metal ion (accounting for more than 10%) enters neutralization pond, and core level sponge zirconium device extracts TBP organic phase
The spent lye of alkali process, the waste water of water process are also into neutralization pond, the NaOH being produced using homogeneous bipolar electrodialysis equipment
Neutralization, neutralization, using pond in three-level, respectively obtains the solids of iron content, the solids containing zirconium, the solids containing scandium, does through mud
Change is processed, and the solids containing zirconium returns zirconium oxychloride device, reuses, the solids of iron content, the solid beyond the region of objective existence containing scandium is sold.
Neutralization pond clear liquid enters more medium filter, nanofiltration device, active carbon adsorption device, resin-column of receiving, and filters out miscellaneous
Matter, enters homogeneous bipolar electrodialysis equipment and improves salinity, enters bipolar membrane electrodialysis equipment, and one surveys generation NaOH,
For in neutralization pond and sour, opposite side generation watery hydrochloric acid, send fumed silica device, system so recycles.
Claims (6)
1. a kind of method preparing core level sponge zirconium and core level hafnium sponge it is characterised in that：The chlorine being produced using electrolysis of hydrochloric acid,
Produce zirconium chloride and zirconium oxychloride through zircon sand fluidizing chlorination method, by TBP-HCl-HNO3Extraction, zirconium, hafnium are separated and obtain
Obtain zirconium oxide and hafnium oxide, then respectively through chlorination, purification, respectively obtain core level sponge zirconium and core level hafnium sponge.
2. the method preparing core level sponge zirconium and core level hafnium sponge as described in claim 1 it is characterised in that：Described by salt
The produced chlorine of acid electrolysis obtains zirconium chloride as chlorine used in zircon sand fluidizing chlorination method, zircon sand fluidizing chlorination,
Zirconium chloride further purifies and obtains refined zirconium tetrachloride and zirconium oxychloride；
Electrolysis of hydrochloric acid produces hydrogen and chlorine, and hydrogen is as the hydrogen obtaining hydrolysis burning during silica using vapor phase method
Gas raw material；
Chlorine is as the chlorine used by chlorination in zircon sand fluidizing chlorination method；
Above-mentioned zircon sand fluidizing chlorination obtains zirconium chloride and silicon tetrachloride, and wherein zirconium chloride further purifies hydrolysis and can obtain
Obtain zirconium oxychloride, gained silicon tetrachloride is raw materials used as pyrohydrolysis during obtaining silica using vapor phase method, and then
Produce fumed silica.
3. the method preparing core level sponge zirconium and core level hafnium sponge as described in claim 1 it is characterised in that：Described TBP-
HCl-HNO3Extraction is through dissolving, filtration by raw material, and filtrate adjusts, through salt adding acid, nitric acid, the material making total acidity reach 8N
Liquid, adds TBP organic phase and feed liquid to mix in extraction tank, separates through extracting and demixing and then by zirconium, hafnium after mixing；Its
In, TBP organic phase is 60% tbp and 40% kerosene by weight percentage.
4. the method preparing core level sponge zirconium and core level hafnium sponge as described in claim 1 or 3 it is characterised in that：Described warp
Extracting and demixing upper strata contains the organic phase of zirconium solution, and scrubbed rear organic phase passes through back extraction again, collects the aqueous phase warp again of back extraction
Ammonia precipitation process, filtration, collect precipitation through calcining, calcined product is then further purified through chlorination and obtains core level hafnium oxide；
Wherein, strippant is water；Calcining heat is 650～850 DEG C.
5. the method preparing core level sponge zirconium and core level hafnium sponge as described in claim 1 or 3 it is characterised in that：Described extraction
Take layering lower floor to contain the aqueous phase of hafnium solution, extracting and enriching is carried out by the P204 organic phase washed through nitric acid, organic phase is again through carbon
Sour hydrogen ammonium back extraction, the aqueous phase collecting back extraction, again through ammonia precipitation process, filtration, collects precipitation through calcining, calcined product is again through chlorination
Then it is further purified and obtain core level hafnium oxide；Wherein, P204 organic phase is 10% phosphoric acid dialkyl group by weight percentage
Ester (P204), 85% kerosene and 5% tbp；Nitric acid acidity is 3～5N；Strippant is 20%NH4HCO3Solution；Forge
Burn temperature and be 650～850 DEG C.
6. the method preparing core level sponge zirconium and core level hafnium sponge as described in claim 3 it is characterised in that：Described extraction,
The waste water,waste gas and industrial residue producing in back extraction and washing process, all using homogeneous EDBM, bipolar membrane electrodialysis, nanofiltration
Film and resin-column of receiving, diffusion one or more of film dialysis mode processed so that after being processed produced water with
Gas can reclaim and repeat to recycle.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN108998683A (en) * | 2017-06-06 | 2018-12-14 | 叶安祺 | The method for separating zirconium oxide and hafnium oxide mixture |
| CN109536718A (en) * | 2018-12-07 | 2019-03-29 | 江苏科技大学 | A method of zr element in recycling abraum salt containing zirconium monochloride |
| CN109553130A (en) * | 2018-12-07 | 2019-04-02 | 江苏科技大学 | A method of zr element in recycling zirconium metallurgy solid waste |
| CN111606788A (en) * | 2020-05-27 | 2020-09-01 | 杭州富阳永星化工有限公司 | Post-treatment system and post-treatment method for preparing glyoxal through catalytic oxidation of ethylene glycol |
| CN113184904A (en) * | 2021-06-15 | 2021-07-30 | 辽宁华锆新材料有限公司 | Method and equipment for purifying zirconium tetrachloride |
| CN113753950A (en) * | 2021-10-14 | 2021-12-07 | 云南国钛金属股份有限公司 | Preparation method of nuclear grade zirconia |
| CN115679124A (en) * | 2022-11-07 | 2023-02-03 | 南通晶朋新材料科技有限公司 | Process for separating hafnium and zirconium |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416842A (en) * | 2017-05-22 | 2017-12-01 | 赤峰盛森硅业科技发展有限公司 | A kind of method for comprehensively utilizing byproduct of reaction and preparing silica and zirconium oxychloride |
| CN108998683A (en) * | 2017-06-06 | 2018-12-14 | 叶安祺 | The method for separating zirconium oxide and hafnium oxide mixture |
| CN109536718A (en) * | 2018-12-07 | 2019-03-29 | 江苏科技大学 | A method of zr element in recycling abraum salt containing zirconium monochloride |
| CN109553130A (en) * | 2018-12-07 | 2019-04-02 | 江苏科技大学 | A method of zr element in recycling zirconium metallurgy solid waste |
| CN111606788A (en) * | 2020-05-27 | 2020-09-01 | 杭州富阳永星化工有限公司 | Post-treatment system and post-treatment method for preparing glyoxal through catalytic oxidation of ethylene glycol |
| CN111606788B (en) * | 2020-05-27 | 2023-03-17 | 杭州富阳永星化工有限公司 | Post-treatment system and post-treatment method for preparing glyoxal through catalytic oxidation of ethylene glycol |
| CN113184904A (en) * | 2021-06-15 | 2021-07-30 | 辽宁华锆新材料有限公司 | Method and equipment for purifying zirconium tetrachloride |
| CN113184904B (en) * | 2021-06-15 | 2023-02-14 | 辽宁华锆新材料有限公司 | Method and equipment for purifying zirconium tetrachloride |
| CN113753950A (en) * | 2021-10-14 | 2021-12-07 | 云南国钛金属股份有限公司 | Preparation method of nuclear grade zirconia |
| CN113753950B (en) * | 2021-10-14 | 2023-09-26 | 云南国钛金属股份有限公司 | Preparation method of nuclear-grade zirconia |
| CN115679124A (en) * | 2022-11-07 | 2023-02-03 | 南通晶朋新材料科技有限公司 | Process for separating hafnium and zirconium |
| CN115679124B (en) * | 2022-11-07 | 2023-08-18 | 南通晶朋新材料科技有限公司 | Process for separating hafnium and zirconium |
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