CN109734129A - A kind of method that zirconium silicate ball fluidizing chlorination method produces refined zirconium tetrachloride and by-produced tetrachlorosilane - Google Patents
A kind of method that zirconium silicate ball fluidizing chlorination method produces refined zirconium tetrachloride and by-produced tetrachlorosilane Download PDFInfo
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Abstract
A kind of method that zirconium silicate ball fluidizing chlorination method produces refined zirconium tetrachloride and by-produced tetrachlorosilane, weigh raw material zirconium silicate, reducing agent, lubricant and bonding agent, zirconium silicate mixture particle is made in investment strength marble forming machine, drying, and it feeds intake to 680 DEG C~1050 DEG C boiling chloridizing furnaces, it is passed through chlorine and carries out chlorination reaction, product zirconium chloride after chlorination reaction, silicon tetrachloride mixed gas, it is filtered by metal filtration separator, into in fused salt spray column, fused salt spray, then the zirconium chloride filtered through metal filtration separator, silicon tetrachloride mixed gas, it is cooling through zirconium chloride cooler again, cloth bag separator gas solid separation, silicon tetrachloride freezing elution is collected, respectively obtain refined zirconium tetrachloride, thick silicon tetrachloride.Advantage is: simple process, easy to operate, low in cost, and target zirconium chloride product purity is high, and by-produced tetrachlorosilane can be used for manufacturing organo-silicon compound, realizes industrial production waste zero-emission, energy conservation and environmental protection.
Description
Technical field
The present invention relates to a kind of production methods of refined zirconium tetrachloride, in particular to one kind is with zirconium silicate powder ball, using big
The method that type fluidizing chlorination method produces refined zirconium tetrachloride and by-produced tetrachlorosilane.
Background technique
Refined zirconium tetrachloride product purpose is extensive, is the intermediate huge market demand of zirconium product, can produce zirconium oxychloride, entirely
The production capacity of the zirconium oxychloride of ball 90% is in China, and production capacity is up to 240,000 tons or so.But due to having through zirconium chloride production capacity
Limit, at present domestic production zirconium oxychloride be substantially using zircon sand be raw material use " one acid and one bases method " production, process flow
Long, high production cost, wastewater discharge containing NaCl is big, and silicon slag nowhere digests conversion, and environmental pollution improvement's difficulty is big, and product matter
Amount cannot directly reach the quality standard of high zirconium oxychloride, and advanced Zirconium oxide enterprise needs to extract the zirconium oxychloride bought
It takes, except the impurity such as iron or recrystallization processing, to reduce impurity content, production cost is caused to increase.
Refined zirconium tetrachloride can also be directly used in production technical grade sponge zirconium, China's technical grade sponge zirconium annual output at this stage
At 1500 tons or so, price is per ton at 23.5 ten thousand yuan.Due to train high-speed rail conducting wire especially 350 kilometers or more and amorphous close
Golden dosage increases, and market demand increases year by year, and raw material zirconium chloride demand increases, and mainly uses electric smelting desiliconization at this stage
Zirconium fluidizing chlorination produces thick zirconium chloride, and electric smelting desilicated zirconia cost of material is higher, and 3.4 ten thousand yuan/ton of price or so.
Silicon tetrachloride is the primary raw material for manufacturing organo-silicon compound, such as organic siliconresin, high-temperature insulation paint, organic silicone oil
And silicon rubber.High purity silicon tetrachloride is the material for manufacturing polysilicon, high-purity silicon dioxide, inorganic silicon compound and optical fiber, together
Sample is also the good raw material of fumed silica.
104817110 A of CN discloses " a kind of zircon sand fluidizing chlorination method production high-purity zirconium oxychloride and four chlorination of coproduction
The method of silicon ", this method use zircon sand fluidizing chlorination furnace fluidised form chlorination reaction, and varigrained raw material is easy after chlorine purging
Layering, be easy to cause raw material zircon sand and reducing agent insufficient contact, so that reaction speed is influenced, entire technological reaction temperature
Height, reaction speed is slow, and reacts insufficient.
Summary of the invention
Technical problems to be solved by the inivention are to provide a kind of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride and pair
The method for producing silicon tetrachloride, simple process is easy to operate, low in cost, and target zirconium chloride product purity is high, four chlorination of by-product
Silicon can be used for manufacturing organo-silicon compound, realize industrial production waste zero-emission, energy conservation and environmental protection.
The present invention is using technical solution:
A kind of method that zirconium silicate ball fluidizing chlorination method produces refined zirconium tetrachloride and by-produced tetrachlorosilane, specific steps are such as
Under:
(1) raw material zirconium silicate, reducing agent, lubricant and bonding agent are weighed, the reducing agent is carbon black fines or carburant fine powder；
The lubricant is high purity graphite powder；The binder is paper pulp, syrup, Rice & peanut milk, pectin or cellulose；Wherein, zirconium silicate with
Reducing agent, lubricant, binder mass ratio be respectively 1:0.1~1:0.12,1:0.08~1:0.12,1:0.05~1:0.1；
(2) solids zirconium silicate, reducing agent, lubricant are first thrown, then puts into binder to strength marble forming machine, diameter, which is made, is
The zirconium silicate mixture particle of 0.3mm~3mm；Spherolite is dried through micro-wave oven drying equipment after machine out, and drying temperature is no more than
380℃；Zirconium silicate mixture particle after drying is fed directly to boiling chloridizing furnace stokehold and measures the storehouse that feeds intake；
(3) reach 680 DEG C~1050 DEG C to boiling chloridizing furnace, feed intake, under the gas velocity of 0.15m/s~0.36m/s, be passed through
Chlorine is maintained at 680 DEG C~1050 DEG C progress chlorination reactions in boiling chloridizing furnace, when furnace pressure reaches 6500Pa
It skims；The mass ratio of the zirconium silicate and chlorine is 1:1.355~1:1.375；
(4) product zirconium chloride, silicon tetrachloride mixed gas after chlorination reaction settle cooling in the expanding reach of boiling chloridizing furnace,
Make the mixed gas temperature at 410 DEG C~430 DEG C；
(5) zirconium chloride of boiling chloridizing furnace acquisition, silicon tetrachloride mixed gas, are filtered by metal filtration separator, are entered
In fused salt spray column, use NaCl the and KCl mixture fused salt that mass ratio is 1:1 as spray liquid, spray is separated through metal filtration
The zirconium chloride of device filtering, silicon tetrachloride mixed gas, the control of fused salt spray column tower temperature is at 450 DEG C, the zirconium chloride, tetrachloro
The mass ratio of SiClx mixed gas and fused salt is 1:6；Then through the cooling of zirconium chloride cooler, cloth bag separator gas solid separation,
Silicon tetrachloride freezing elution is collected, and refined zirconium tetrachloride, thick silicon tetrachloride are respectively obtained.
Further, the bonding agent is paper pulp, syrup or Rice & peanut milk, and paper pulp, syrup, pectin can play the work of bonding
With also being carbonized after microwave drying, play the role of increasing charcoal, while moisture evaporation and substance Carbonization contract make ball
It is upper a lot of micro- holes occur, increase the specific surface area of reactant.
Further, the zirconium silicate is ceramic zirconium silicate, the pulvis obtained through air-flow crushing；The high purity graphite powder
Ash≤10ppm；The powder fineness of the reducing agent is -400 mesh > 90%, the powder fineness of lubricant be -300 mesh >
90%.
Further, when fused salt sprays, the gas velocity that zirconium chloride, silicon tetrachloride mixed gas enter fused salt spray column is
2m/s。
Further, when metal filtration separator filters, the temperature of metallic filter is controlled at 330 DEG C~370 DEG C, makes four
The dust that zirconium chloride, silicon tetrachloride mixed gas are carried secretly is separated with mixed gas.
Further, when zirconium chloride cooler is cooling, the outlet temperature of zirconium chloride cooler is controlled at 180 DEG C, four
Zirconium chloride is cooled to solid, collects, and gas continues to be fed into cloth bag separator, will be entrained in the zirconium chloride powder of silicon tetrachloride gas
Body separation.
Further, at 160 DEG C, the outlet temperature of cloth bag separator controls 100 for the inlet temperature control of cloth bag separator
℃。
Further, it when silicon tetrachloride freezing elution, is sprayed using -10 DEG C of silicon tetrachloride liquids, makes silicon tetrachloride gas
Liquefaction.
Further, the zirconium silicate and reducing agent, lubricant, binder mass ratio be respectively 1:0.1~1:0.12,
1:0.093~1:0.12,1:0.07~1:0.1.
Further, the internal diameter of the boiling chloridizing furnace is 850mm~1500mm.
Beneficial effects of the present invention:
The present invention wants raw material, addition chemical reaction reducing agent (carbon black or carburant) based on zirconium silicate powder, and lubrication is added
Agent (graphite powder and reducing agent) is mixed with binder (paper pulp, syrup, Rice & peanut milk, pectin, cellulose) forces ball processed, through microwave
After drying, using large-scale boiling chloridizing furnace chlorination, zirconium chloride is obtained, the mixed gas such as silicon tetrachloride utilize advanced metal
Separation, fused salt spraying technique, rapidly condensation, gas solid separation obtain the refined zirconium tetrachloride solid and thick silicon tetrachloride liquid of purity is high
Body, advantage are as follows:
1. using good product quality obtained by the present invention
The comparison of fluidizing chlorination method, such as table 1:
Thick content of silicon tetrachloride 90~92%.78% grade of silicon tetrachloride thicker than zircon sand chlorination is much higher.
2. production cost is low, obtains refined zirconium tetrachloride and no longer need to be flushed with hydrogen reduction or fused salt purification.
3. the ball processed such as zirconium silicate fine powder and carbon black, graphite powder, paper pulp increases material reaction area, reaction speed is accelerated
Degree, there is no oxides and reducing agent partial size to mismatch for the fixed particle of reactant, and the problem of be layered, and select reducing agent carbon black
Or the structure of carburant is better than petroleum calcined coke used in electric smelting desilicated zirconia and zirconium English sand fluidizing chlorination, reaction speed is fast.
4. it is lubricant that graphite powder, which is added, reduces the frictional force of reaction mass and heater graphite, extend heater
Service life, while having the function of reducing agent again.
5. scientific and reasonable with carbon total amount, fluidizing chlorination is without frequently slagging tap, and reaction speed is fast, and reaction temperature is low.
6. under furnace diameter because gas velocity of the present invention is larger thus feed intake it is voluminous can be high.
Production refined zirconium tetrachloride by-produced tetrachlorosilane method of the invention, can not only produce refined zirconium tetrachloride product, also
Available by-product silicon tetrachloride, the big added value of product profit is high, and no solid waste discharge belongs to clearer production technology, can solve
The problem of entire entire " one acid and one bases " method high production cost of zirconium oxychloride industry, profit is low, environmental pollution refractory power, improves zirconium
Product specification.
Specific embodiment
Embodiment 1
Implement by process flow chart, it is specific to prepare are as follows:
1) raw material preparation
Zirconium silicate powder, carbon black, high purity graphite powder (ash≤10ppm) and paper pulp are claimed according to mass ratio 1:0.1:0.096:0.07
Raw material is taken, is then added in strength marble forming machine, zirconium silicate powder, carbon black and graphite powder is first thrown when feeding intake, then put into binder, is made
Ball, is made the zirconium silicate mixture particle that average grain diameter is 0.85mm, and balling ratio is greater than 98.5%, is then placed in microwave drying
Machine is dried at 360 ± 20 DEG C；
Above-mentioned each material composition requires to make: zirconium oxide and hafnium oxide resultant (ZrHf) O in zirconium silicate powder2>=63.5%；
Above-mentioned each raw material degree requires: zirconium silicate powder D50≤ 2.0 μm of m, D98≤10.0μmm；- 400 mesh > 90% of carbon black；Graphite
- 300 mesh > 90% of powder；
2) chlorination reaction
Stokehold feed bin is added in the zirconium silicate mixture particle of drying, being continuously added to internal diameter by screw conveyor is 850mm
Boiling chloridizing furnace in, fluidizing chlorination furnace bottom is passed through chlorine, so that chlorine is reacted with zirconium silicate mixture particle, generate tetrachloro
Change zirconium, silicon tetrachloride mixed gas, control reaction temperature is 950 DEG C, and the speed that is passed through of chlorine is 0.236m/s, controls siege pressure
Power within the scope of 3000Pa~6500Pa, skim when reaching 6500Pa by furnace pressure, wherein zirconium silicate mixture particle with
The mass ratio of chlorine is 1:1.375；Product zirconium chloride, silicon tetrachloride mixed gas are in boiling chloridizing furnace after the chlorination reaction
Expanding reach settle cooling, make mixed gas cooling temperature at 410 DEG C；
3) zirconium chloride and the thick silicon tetrachloride purification of by-product, separation
Then zirconium chloride, silicon tetrachloride mixed gas enter metallic filter, burn through the metal in sedimentation and metallic filter
The dust that zirconium chloride, silicon tetrachloride mixed gas are carried secretly and mixed gas are carried out gas solid separation, metal mistake by the filtering of netting
The temperature of filter is controlled at 330 DEG C；
Gas by metallic filter separation is entering fused salt spray column, is sprayed with NaCl the and KCl fused salt of mass ratio 1:1,
At 450 DEG C, zirconium chloride, silicon tetrachloride mixed gas are washed by fused salt for tower temperature control, are made containing Fe, Ti, Al impurity and fused salt
Double salt is formed to remove；
By the zirconium chloride and silicon tetrachloride gas of fused salt spray washing, into zirconium chloride cooler, zirconium chloride is cooling
It is solid that the outlet temperature of device, which controls the zirconium chloride to cool down at 180 DEG C, collects solid, as refined zirconium tetrachloride, gas
Continue to be fed into cloth bag separator；
By the cooling gas of zirconium chloride cooler, for the silicon tetrachloride gas for carrying a small amount of zirconium chloride solid powder secretly,
Into cloth bag separator, the outlet temperature of cloth bag separator controls 100 DEG C, and the inlet temperature of cloth bag separator is controlled at 160 DEG C,
Make silicon tetrachloride gas and zirconium chloride solid powder through cloth bag gas solid separation, collects solid, as refined zirconium tetrachloride；
- 10 DEG C of use of the silicon tetrachloride gas silicon tetrachloride liquid spray-absorptions below through cloth bag separator gas solid separation, obtain
Silicon tetrachloride liquid (SiCl4), through detecting silicon tetrachloride purity > 90%.
Embodiment 2
Implement by process flow chart, it is specific to prepare are as follows:
1) raw material preparation
By zirconium silicate powder, carbon black, high purity graphite powder (ash≤10ppm) and syrup are according to mass ratio 1:0.11:0.093:0.07
Raw material is weighed, is then added in strength marble forming machine, zirconium silicate powder, carbon black and graphite powder is first thrown when feeding intake, then put into binder, is made
Ball, is made the zirconium silicate mixture particle that average grain diameter is 0.75mm, and balling ratio is greater than 98.5%, is then placed in microwave drying
Machine is dried at 360 ± 20 DEG C；
Above-mentioned each material composition requires to make: zirconium oxide and hafnium oxide resultant (ZrHf) O in zirconium silicate powder2>=63.5%；
Above-mentioned each raw material degree requires: zirconium silicate powder D50≤ 2.0 μm of m, D98≤10.0μmm；- 400 mesh > 90% of carbon black；Graphite
- 300 mesh > 90% of powder；
2) chlorination reaction
Stokehold feed bin is added in the zirconium silicate mixture particle of drying, boiling chloridizing furnace is continuously added to by screw conveyor
Interior, fluidizing chlorination furnace bottom is passed through chlorine, and chlorine is made to react with zirconium silicate mixture particle, generates zirconium chloride, four chlorinations
Silicon mixed gas, control reaction temperature are 900 DEG C, and the speed that is passed through of chlorine is 0.258m/s, control siege pressure in 3000Pa
Within the scope of~6500Pa, furnace pressure is skimmed when reaching 6500Pa, wherein being passed through quality of chlorine gas are as follows: zirconium silicate mixture
The mass ratio 1:1.355 of particle and chlorine,
Product zirconium chloride, silicon tetrachloride mixed gas settle cooling in the expanding reach of boiling chloridizing furnace after the chlorination reaction,
Make mixed gas cooling temperature at 410 DEG C；
3) zirconium chloride and the thick silicon tetrachloride purification of by-product, separation
Then zirconium chloride, silicon tetrachloride mixed gas enter metallic filter, burn through the metal in sedimentation and metallic filter
The dust that zirconium chloride, silicon tetrachloride mixed gas are carried secretly and mixed gas are carried out gas solid separation, metal mistake by the filtering of netting
The temperature of filter is controlled at 350 DEG C；
Gas by metallic filter separation is entering fused salt spray column, is sprayed with NaCl the and KCl fused salt of mass ratio 1:1,
At 450 DEG C, zirconium chloride, silicon tetrachloride mixed gas are washed by fused salt for tower temperature control, are made containing Fe, Ti, Al impurity and fused salt
Double salt is formed to remove；
By the zirconium chloride and silicon tetrachloride gas of fused salt spray washing, into zirconium chloride cooler, zirconium chloride is cooling
It is solid that the outlet temperature of device, which controls the zirconium chloride to cool down at 180 DEG C, collects solid, as refined zirconium tetrachloride, gas
Continue to be fed into cloth bag separator；
By the cooling gas of zirconium chloride cooler, for the silicon tetrachloride gas for carrying a small amount of zirconium chloride solid powder secretly,
Into cloth bag separator, the outlet temperature of cloth bag separator controls 100 DEG C, and the inlet temperature of cloth bag separator is controlled at 160 DEG C,
Make silicon tetrachloride gas and zirconium chloride solid powder through cloth bag gas solid separation, collects solid, as refined zirconium tetrachloride；
- 10 DEG C of use of the silicon tetrachloride gas silicon tetrachloride liquid spray-absorptions below through cloth bag separator gas solid separation, obtain
Silicon tetrachloride liquid (SiCl4), through detecting silicon tetrachloride purity > 90%.
Embodiment 3
Implement by process flow chart, it is specific to prepare are as follows:
1) raw material preparation
By zirconium silicate powder, carbon black, high purity graphite powder (ash≤10ppm) and paper pulp are according to mass ratio 1:0.12:0.093:0.07
Raw material is weighed, is then added in strength marble forming machine, zirconium silicate powder, carbon black and graphite powder is first thrown when feeding intake, then put into binder, is made
The zirconium silicate mixture particle that average grain diameter is 1.2mm is made in ball, and balling ratio is greater than 98.5%, is then placed in microwave dryer,
It is dried at 360 ± 20 DEG C；
Above-mentioned each material composition requires to make: zirconium oxide and hafnium oxide resultant (ZrHf) O in zirconium silicate powder2>=63.5%；
Above-mentioned each raw material degree requires: zirconium silicate powder D50≤ 2.0 μm of m, D98≤10.0μmm；- 400 mesh > 90% of carbon black；Graphite
- 300 mesh > 90% of powder；
2) chlorination reaction
Stokehold feed bin is added in the zirconium silicate mixture particle of drying, boiling chloridizing furnace is continuously added to by screw conveyor
Interior, fluidizing chlorination furnace bottom is passed through chlorine, and chlorine is made to react with zirconium silicate mixture particle, generates zirconium chloride, four chlorinations
Silicon mixed gas, control reaction temperature are 1000 DEG C, and the speed that is passed through of chlorine is 0.296/s, control siege pressure in 3000Pa
Within the scope of~6500Pa, furnace pressure is skimmed when reaching 6500Pa, wherein being passed through quality of chlorine gas are as follows: zirconium silicate mixture
The mass ratio 1:1.355 of particle and chlorine；Product zirconium chloride, silicon tetrachloride mixed gas are in boiling chlorine after the chlorination reaction
The expanding reach for changing furnace settles cooling, makes mixed gas cooling temperature at 430 DEG C；
3) zirconium chloride and the thick silicon tetrachloride purification of by-product, separation
Then zirconium chloride, silicon tetrachloride mixed gas enter metallic filter, burn through the metal in sedimentation and metallic filter
The dust that zirconium chloride, silicon tetrachloride mixed gas are carried secretly and mixed gas are carried out gas solid separation, metal mistake by the filtering of netting
The temperature of filter is controlled at 370 DEG C, and separating solid obtained can make pellet again into Molten salt chlorination furnace progress chlorination reaction；
Gas by metallic filter separation is entering fused salt spray column, is sprayed with NaCl the and KCl fused salt of mass ratio 1:1,
At 450 DEG C, zirconium chloride, silicon tetrachloride mixed gas are washed by fused salt for tower temperature control, are made containing Fe, Ti, Al impurity and fused salt
Double salt is formed to remove；
By the zirconium chloride and silicon tetrachloride gas of fused salt spray washing, into zirconium chloride cooler, zirconium chloride is cooling
It is solid that the outlet temperature of device, which controls the zirconium chloride to cool down at 180 DEG C, collects solid, as refined zirconium tetrachloride, gas
Continue to be fed into cloth bag separator；
By the cooling gas of zirconium chloride cooler, for the silicon tetrachloride gas for carrying a small amount of zirconium chloride solid powder secretly,
Into cloth bag separator, the outlet temperature of cloth bag separator controls 100 DEG C, and the inlet temperature of cloth bag separator is controlled at 160 DEG C,
Make silicon tetrachloride gas and zirconium chloride solid powder through cloth bag gas solid separation, collects solid, as refined zirconium tetrachloride；
- 10 DEG C of use of the silicon tetrachloride gas silicon tetrachloride liquid spray-absorptions below through cloth bag separator gas solid separation, obtain
Silicon tetrachloride liquid (SiCl4), through detecting silicon tetrachloride purity > 90%.
Embodiment 4
1) raw material preparation:
By zirconium silicate powder, carbon black, high purity graphite powder (ash≤10ppm) and paper pulp claim according to mass ratio 1:0.1:0.08:0.075
Take raw material；The zirconium silicate mixture particle that average grain diameter is 0.3mm is made；
2) chlorination reaction
Boiling chloridizing furnace reaction temperature is 680 DEG C, and the speed that is passed through of chlorine is 0.15m/s, zirconium silicate mixture particle and chlorine
Mass ratio 1:1.355；Product zirconium chloride after the chlorination reaction, silicon tetrachloride mixed gas boiling chloridizing furnace expansion
Section sedimentation cooling, makes mixed gas cooling temperature at 410 DEG C；
Other are same as Example 1.
Embodiment 5
1) raw material preparation
By zirconium silicate powder, carbon black, high purity graphite powder (ash≤10ppm) and paper pulp are weighed according to mass ratio 1:0.12:0.1:0.1
Raw material；The zirconium silicate mixture particle that average grain diameter is 3mm is made；
2) chlorination reaction
Boiling chloridizing furnace reaction temperature is 1050 DEG C, and the speed that is passed through of chlorine is 0.36m/s, zirconium silicate mixture particle and chlorine
Mass ratio 1:1.355；Product zirconium chloride after the chlorination reaction, silicon tetrachloride mixed gas boiling chloridizing furnace expansion
Section sedimentation cooling, makes mixed gas cooling temperature at 430 DEG C；
Other are same as Example 1.
Comparative example 1
This method uses reducing agent for petroleum coke, and the mass ratio of zirconium silicate and petroleum coke is 1:0.24, and reaction temperature is 1150 DEG C,
Gas velocity is 0.2165m/s, other are the same as embodiment 1.
The example output table of comparisons is as shown in table 2:
Table 2
| Title | Zirconium silicate powder, carbon black, graphite powder, paper pulp is according to mass ratio | Raw material chlorine ratio | Reaction temperature DEG C | Zirconium chloride yield kg/h |
| Embodiment 1 | 1:0.1:0.096:0.07 | 1:1.375 | 950 | 268 |
| Embodiment 2 | 1:0.11:0.093:0.07 | 1:1.355 | 900 | 310 |
| Embodiment 3 | 1:0.12:0.093:0.07 | 1:1.355 | 1000 | 326 |
| Embodiment 4 | 1:0.1:0.12:0.75 | 1:1.355 | 680 | 219 |
| Embodiment 5 | 1:0.12:0.1:0.1 | 1:1.355 | 1050 | 378 |
| Comparative example 1 | 1:0.24 | 1:1.24 | 1150 | 245 |
4 zirconium chloride product index of 1- of embodiment of the present invention embodiment is as shown in table 3
Table 3
It no longer needs to purify with the zirconium chloride that existing method produces.Technical grade sponge zirconium can be directly produced, the reduction of its direct cost is made
25% or so.
850 comparison of production of diameter is as shown in table 4:
Table 4
| Method | Temperature DEG C | Raw material Kg/h | Gas velocity m/S | Zirconium chloride Kg/h |
| Zircon sand fluidizing chlorination | 1150 | 248 | 0.236 | 239 |
| Embodiment 1 | 950 | 340 | 0.236 | 268 |
| Embodiment 2 | 900 | 313 | 0.258 | 310 |
| Embodiment 3 | 1000 | 331 | 0.296 | 326 |
| Embodiment 4 | 680 | 223.6 | 0.15 | 219 |
| Embodiment 5 | 1050 | 387 | 0.36 | 378 |
| Comparative example 1 | 1150 | 254.5 | 0.2165 | 245 |
Zircon sand fluidizing chlorination is the prior art in upper table, wherein reducing agent is petroleum coke.
The above is only specific embodiments of the present invention, are not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride and by-produced tetrachlorosilane, it is characterized in that:
Specific step is as follows:
(1) raw material zirconium silicate, reducing agent, lubricant and bonding agent are weighed, the reducing agent is carbon black fines or carburant fine powder；
The lubricant is high purity graphite powder；The binder is paper pulp, syrup, Rice & peanut milk, pectin or cellulose；Wherein, zirconium silicate with
Reducing agent, lubricant, binder mass ratio be respectively 1:0.1~1:0.12,1:0.08~1:0.12,1:0.05~1:0.1；
(2) solids zirconium silicate, reducing agent, lubricant are first thrown, then puts into binder to strength marble forming machine, diameter, which is made, is
The zirconium silicate mixture particle of 0.3mm~3mm；Spherolite is dried through micro-wave oven drying equipment after machine out, and drying temperature is no more than 380
℃；Zirconium silicate mixture particle after drying is fed directly to boiling chloridizing furnace stokehold and measures the storehouse that feeds intake；
(3) reach 680 DEG C~1050 DEG C to boiling chloridizing furnace, feed intake, under the gas velocity of 0.15m/s~0.36m/s, be passed through
Chlorine is maintained at 680 DEG C~1050 DEG C progress chlorination reactions in boiling chloridizing furnace, when furnace pressure reaches 6500Pa
It skims；The mass ratio of the zirconium silicate and chlorine is 1:1.355~1:1.375；
(4) product zirconium chloride, silicon tetrachloride mixed gas after chlorination reaction settle cooling in the expanding reach of boiling chloridizing furnace,
Make the mixed gas temperature at 410 DEG C~430 DEG C；
(5) zirconium chloride of boiling chloridizing furnace acquisition, silicon tetrachloride mixed gas, are filtered by metal filtration separator, are entered
In fused salt spray column, use NaCl the and KCl mixture fused salt that mass ratio is 1:1 as spray liquid, spray is separated through metal filtration
The zirconium chloride of device filtering, silicon tetrachloride mixed gas, the control of fused salt spray column tower temperature is at 450 DEG C, the zirconium chloride, tetrachloro
The mass ratio of SiClx mixed gas and fused salt is 1:6；Then through the cooling of zirconium chloride cooler, cloth bag separator gas solid separation,
Silicon tetrachloride freezing elution is collected, and refined zirconium tetrachloride, thick silicon tetrachloride are respectively obtained.
2. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method, it is characterized in that: the bonding agent is paper pulp, syrup or Rice & peanut milk.
3. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method, it is characterized in that: the zirconium silicate is ceramic zirconium silicate, the pulvis obtained through air-flow crushing；The ash of the high purity graphite powder
Part≤10ppm；The powder fineness of the reducing agent is -400 mesh > 90%, and the powder fineness of lubricant is -300 mesh > 90%.
4. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method, it is characterized in that: the gas velocity that zirconium chloride, silicon tetrachloride mixed gas enter fused salt spray column is 2m/s when fused salt sprays.
5. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method makes four chlorinations it is characterized in that: the temperature of metallic filter is controlled at 330 DEG C~370 DEG C when metal filtration separator filters
The dust that zirconium, silicon tetrachloride mixed gas are carried secretly is separated with mixed gas.
6. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method, it is characterized in that: when zirconium chloride cooler is cooling, the outlet temperature control of zirconium chloride cooler is at 180 DEG C, zirconium chloride
It is cooled to solid, is collected, gas continues to be fed into cloth bag separator, will be entrained in the zirconium chloride powder point of silicon tetrachloride gas
From.
7. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method, it is characterized in that: the inlet temperature control of cloth bag separator is at 160 DEG C, the outlet temperature of cloth bag separator controls 100 DEG C.
8. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method, it is characterized in that: being sprayed using -10 DEG C of silicon tetrachloride liquids when silicon tetrachloride freezing elution, making silicon tetrachloride gas liquefaction.
9. the side of zirconium silicate ball fluidizing chlorination method production refined zirconium tetrachloride according to claim 1 and by-produced tetrachlorosilane
Method, it is characterized in that: the mass ratio of the zirconium silicate and reducing agent, lubricant, binder is respectively 1:0.1~1:0.12,1:
0.093~1:0.12,1:0.07~1:0.1.
10. zirconium silicate ball fluidizing chlorination method according to claim 1 production refined zirconium tetrachloride and by-produced tetrachlorosilane
Method, it is characterized in that: the internal diameter of the boiling chloridizing furnace is 850mm~1500mm.
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| CN110846935A (en) * | 2019-11-29 | 2020-02-28 | 湖北淡雅香生物科技股份有限公司 | Preparation method of tipping base paper for flexographic printing |
| CN111268683A (en) * | 2019-12-30 | 2020-06-12 | 武汉新硅科技潜江有限公司 | Reaction ignition device and ignition method for preparing silicon tetrachloride through chlorination of silicon powder |
| 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 |
| CN115744975A (en) * | 2022-10-31 | 2023-03-07 | 新疆晶硕新材料有限公司 | Zirconium tetrachloride apparatus for producing |
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| CN110240196A (en) * | 2019-07-31 | 2019-09-17 | 辽宁华祥新材料有限公司 | The method and zirconium chloride of zirconium chloride are prepared using zircon sand fluidizing chlorination method |
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| 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 |
| CN115744975A (en) * | 2022-10-31 | 2023-03-07 | 新疆晶硕新材料有限公司 | Zirconium tetrachloride apparatus for producing |
| CN115744975B (en) * | 2022-10-31 | 2024-05-07 | 新疆晶硕新材料有限公司 | Zirconium tetrachloride apparatus for producing |
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