CN105540660B - Zircon sand fluidizing chlorination prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane - Google Patents
Zircon sand fluidizing chlorination prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane Download PDFInfo
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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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
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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
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Abstract
The present invention is the process units that a kind of zircon sand fluidizing chlorination prepares ultrapure zirconium oxychloride by-produced tetrachlorosilane.Belong to the preparation method of the halide of zirconium.High-purity zirconium oxychloride system is prepared including zircon sand fluidizing chlorination system, zirconium chloride condensation collection system, silicon tetrachloride distillation system and hydrolyzing silicon tetrachloride, it is characterised in that the also recycling system including tail gas；The recycling system of the tail gas includes tail gas storage device, chlorine separating and reclaiming device and CO and reclaims storage device；The chlorine in tail gas is separated and collected first, and the raw material as zircon sand fluidizing chlorination reaction is recycled；The raw material for the industrial installation that tail gas after separation chlorine is related to as the CO synthetic reactions participated in is utilized.Cl can be effectively utilized there is provided one kind2With CO resources, greenhouse gases CO is reduced2Discharge；The production cost of zircon sand fluidizing chlorination device product can be reduced, the zircon sand fluidizing chlorination for improving plant capacity prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane.
Description
Technical field
The present invention is the process units that a kind of zircon sand fluidizing chlorination prepares ultrapure zirconium oxychloride by-produced tetrachlorosilane.Belong to
The preparation method of the halide of zirconium.
Background technology
Zircon sand is zircon mineral by zircon (ZrSiO obtained by processing, ore dressing4) concentrate, its theory, which is constituted, is：
ZrO2Content is 67.21%, SiO2Content is 32.79%.Zircon sand is the primary raw material for producing metal zirconium and its chemicals.
For preparing silicon tetrachloride, zirconium oxychloride and zirconium dioxide etc..
Zirconium oxychloride (ZrOCl2·8H2O it is) important zirconium chemicalses, is to prepare metal zirconium, zirconium dioxide and many zirconates
And the basic material of other zirconium compounds.It can be used as coating drier, rubber additive, refractory material, ceramic paint, lubrication
Agent；Obtain wide in terms of ceramics, tanning, electronics, nuclear industry, jewelry, metallurgical industry, catalyst, medical treatment, purifying vehicle exhaust
General application.Moreover, zirconium oxychloride still prepares the important source material of reactor-grade metal zirconium hafnium.
Due to zirconium oxychloride (ZrOCl2·8H2O) widely used, domestic and international market demand constantly rises, zirconium oxychloride production
Product have wide market prospects.
The main source of current silicon tetrachloride is the accessory substance of organosilicon industry and polysilicon industry, due to polysilicon industry
Continued downturn, the industry utilization of capacity is low, causes the in short supply of silicon tetrachloride as by-product, and polysilicon industry is in recent years in order to reduce
Production cost, has developed out silicon tetrachloride cold hydrogenation technology, is trichlorosilane converting silicon tetrachloride, this is just considerably increased
The market demand of silicon tetrachloride so that the price of silicon tetrachloride constantly rises.
Zircon sand fluidizing chlorination technique is Direct Chlorination of Zircon Sand, refers to zircon sand with petroleum coke according to a certain ratio
After mixed grinding, in boiling chloridizing furnace at a temperature of 950~1100 DEG C, it is passed through chlorine and is reacted, generates zirconium chloride
(ZrCL4) and silicon tetrachloride (SiCl4) two kinds of primary products technical process.
Fluidizing chlorination, makes solid particle suspend under action of a fluid, therefore solid particle is provided with certain of fluid
A little apparent characteristics, the contact of storeroom is strengthened, therefore also referred to as fluidization technology.It is applied to zircon sand chloridization process
Referred to as zircon sand fluidizing chlorination.Main chemical reactions formula is as follows：
ZrSiO4+4Cl2+ 4C=ZrCl4+SiCl4+4CO
Pure ZrCl4It is solid-state at normal temperatures, its sublimation point is 331 DEG C, SiCl4Boiling point be 57 DEG C, in chlorination reaction
Under the conditions of, two kinds of products output in a gaseous form.ZrCl is collected first4Product, then, by ZrCl4Oxychlorination is made in hydrolysis
Zirconium.SiCl4Due to low boiling point, ZrCl is collected4Gas after product, is further continued for by condensation, refined, obtained SiCl4Product.
Zircon sand fluidizing chlorination device, the chlorination by chlorine to zircon sand, while obtained zirconium oxychloride product, system
By-product silicon tetrachloride was obtained, quality raw materials are provided for production vapor phase method zirconium dioxide.So that rare valuable zirconium
Sand mineral resources have obtained effective utilization.Thoroughly solve zircon sand decomposition to prepare in the industry of zirconium product, the row for the white residue that gives up
Put caused many drawbacks.
Therefore, the process of zircon sand fluidizing chlorination device, with the incomparable low cost of alkali fusion, low stain
Feature, while the SiO in product2、Na2O、TiO2, some impurity such as sulfate, reclaim ZrCl in cooling4When removed.Keep away
These impurity are exempted from into follow-up system.
Zircon sand raw material is directly converted into the raw material ZrCl of zirconium oxychloride by zircon sand fluidizing chlorination technique4And SiCl4By-product
Product, raw material availability is high, and production cost is low, and waste gas waste sludge discharge is less；With facility compact, operational efficiency is high, control
Stably, the advantages of automaticity is high.It is widely adopted.
But, also exist in the prior art following not enough：
1. in the tail gas that zircon sand fluidizing chlorination device is discharged, contain the more Cl of quantity2, CO, be with very usury use
The precious resources of value.Not yet efficiently separated and utilized.Cause the wasting of resources.
2. the gaseous products that in the prior art, zircon sand fluidizing chlorination technique is produced, through separating and collecting ZrCl first4With
Afterwards, it is further continued for collecting and refining SiCl4, finally, tail gas is after simple alkali liquor absorption, and CO is after igniter is lighted, combustion
Burn discharge.Or feeding boiler is used as fuel.It is not only waste of resource, and there is the safety such as CO burnings, blast, poisoning
Hidden danger.
The CO that 3.CO enthalpy of combustions are produced2, CO2It is main greenhouse gases, the greenhouse effects of air can be aggravated, cause the whole world
Warm, and thus trigger natural calamity, the serious survival and development that threaten the mankind.
4. in the prior art, Cl2As the primary raw material of chlorination reaction, due to no recycle and reuse, cause raw material
Consumption increase, the raising of production cost.
5. in the prior art, Cl2As the primary raw material of chlorination reaction, due to no recycle and reuse, zircon sand with
Cl2Mol ratio, can be only sustained at 1：6 or so, limit the reaction speed of zircon sand chlorination reaction.It has impact on the life of device
The raising of production capacity power.
One kind can effectively utilize Cl2With CO resources, greenhouse gases CO is reduced2Discharge；Avoid firing caused by CO is discharged
The security incidents such as burning, blast, poisoning occur；Zircon sand fluidizing chlorination can be reduced and prepare ultrapure zirconium oxychloride by-produced tetrachlorosilane
The production cost of device product, the zircon sand fluidizing chlorination for improving plant capacity prepares the ultrapure chlorination of zirconium oxychloride by-product four
The process units of silicon, is that people are expected.
The content of the invention
It is an object of the invention to avoid above-mentioned weak point of the prior art, and providing one kind can effectively utilize
Cl2With CO resources, greenhouse gases CO is reduced2Discharge；Avoid the security incident hair such as burning, blast, poisoning caused by CO is discharged
It is raw；The production cost that zircon sand fluidizing chlorination prepares ultrapure zirconium oxychloride by-produced tetrachlorosilane device product can be reduced, is improved
The zircon sand fluidizing chlorination of plant capacity prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane.
The purpose of the present invention can be reached by following measure：
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, including zirconium English
Sand fluidizing chlorination system, zirconium chloride condensation collection system, silicon tetrachloride distillation system and hydrolyzing silicon tetrachloride prepare high pure oxygen
Zirconium chloride system, it is characterised in that the also recycling system including tail gas；The recycling system of the tail gas includes tail gas
Storage device, chlorine separating and reclaiming device and CO reclaim storage device；The chlorine in tail gas is separated and collected first, as zircon sand
The raw material of chlorination reaction, is recycled；The industry that tail gas after separation chlorine is related to as the CO synthetic reactions participated in is raw
The raw material for producing device is utilized.
Chlorine is the complete recycling of chlorine in the raw material of zircon sand fluidizing chlorination, tail gas, undoubtedly for reduction
ZrCl4、SiCl4And the cost-benefit of zirconium oxychloride product.And because raw material chlorine can be recycled completely, in raw material
ZrSiO4, C and Cl2Mol ratio in, can be by properly increasing Cl2Mol ratio come improve chlorination reaction reaction speed
Degree so that direction movement of the chlorination reaction balance towards generation chlorizate.So as to improve the conversion ratio of reaction.Improve equipment
Production capacity.
ZrSO4+4Cl2+ 4C=ZrCl4+SiCl4+4CO
From above zircon sand fluidizing chlorination reaction equation, it can be seen that：Every mole of ZrSO4Chlorination, 1 mole of generation
ZrCl4, while producing 4 moles of CO.The quantity of CO in tail gas is larger, is related to process units as the CO synthetic reactions participated in
Raw material utilize.Undoubtedly there is good economic benefit and environmental protection benefit.
The purpose of the present invention can also be reached by following measure：
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, and its feature exists
It is in the described CO synthetic reactions participated in：
1. the reaction that CO is converted into hydrogen of synthetic ammonia installations CO conversion sections
CO+H2O→H2+CO2
2. the reaction of .CO synthesizing methanol by hydrogenating
2H2+CO→CH3OH
3. the carbonylation of unsaturated compounds, for example：
CH2=CH2+CO+H2→CH3CH2CHO
4. the carboxylation reaction of methanol
CH3OH+CO→CH3COOH
(v) the alternating copolymerization that .CO is participated in.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, described CO
The industrial installation that the synthetic reaction of participation is related to is：Synthetic ammonia installation, synthesizing methanol device, methanol carboxylation synthesis of acetic acid dress
Put, the methylate device for preparing corresponding aldehyde, ethene and CO of alkene hydrogen prepares the device of polyketone.It is preferred technical scheme.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, the tail gas
Storage device is dry gas-holder.It is preferred technical scheme.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, the chlorine
Separating and reclaiming device is chlorine condensation liquefaction device, including chlorine liquefier, refrigeration unit and other auxiliary devices, and chlorine is in chlorine
Liquid is condensed into gas liquefaction device, refrigeration unit provides low-temperature receiver for chlorine liquefier.
Using the chlorine in the method separation tail gas of chlorine gas liquefaction, separative efficiency >=98.5%, obtained purity of chlorine gas feeding is high,
It disclosure satisfy that zircon sand chloridization process requirement.It is a preferred technical scheme.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, described chlorine
Gas condensation liquefaction uses low-pressure ammonia-calcium chloride brine indirect refrigeration liquefying plant.It is a preferred technical scheme.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, described chlorine
Gas condensation liquefaction uses low pressure freon R-22 directly freezed liquefying plants.It is most preferred technical scheme.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, and the CO is returned
It is dish gas holder or dry gas-holder to store up cryopreservation device.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, the zirconium English
Sand fluidizing chlorination prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, and its application method comprises the following steps：
1. zircon sands chlorination
Quartz sand is crushed to 300-350 targeted fine powders first, pressed with 150~180 mesh petroleum cokes and catalyst boron oxide
According to 100：20~23：0.4~0.5 ratio is well mixed, and is added in boiling chloridizing furnace and is carried out chlorination reaction, zircon sand and chlorine
The mol ratio of gas is 1：8~10, reaction temperature is 950~1100 DEG C, and it is 1.0~1.5m to control logical chlorine speed3/ h,
2. separates and collects zirconium chloride
Gaseous product from step 1., is cooled down through multi-stage condensing device, and cooling temperature of charge is to 210~230 DEG C, into rotation
General mood solid separator, carries out gas solid separation, and control outlet temperature isolates zirconium chloride solid at 100~110 DEG C；Point
The zirconium chloride solid input continous way purifies and separates device separated out, progress secondary purification separation, heated separator temperature to 270~
280 DEG C so that lower boiling a small amount of silicon tetrachloride and other impurity gasification, gas solid separation is re-started, high-purity four isolated
Reaction is hydrolyzed into hydrolysis kettle in zirconium chloride solid；And tail gas then enters silicon tetrachloride distillation system and reclaimed；
3. silicon tetrachlorides is refined
Gas after 2. separating and collecting zirconium chloride through step, into silicon tetrachloride distillation system, distillation system is literary mound
In formula pipeline spray column, tower is connected with condenser, and condenser is connected to cryogenic freezing salt solution, and the temperature of chilled brine is at -40 DEG C
Hereinafter, while chilled brine is opened, silicon tetrachloride liquid spray system in tower is opened, gas outlet temperature 30~35 is controlled
DEG C, obtained silicon tetrachloride liquid enters back into rectifying column and carries out rectifying, controls the temperature of rectifying column reboiler at 70 DEG C, cooling
45 DEG C of coolant-temperature gage, content of silicon tetrachloride >=99.6% that rectifying goes out；
4. hydrolysis, crystallization
Solid zirconium chloride from step 2. enters hydrolysis kettle by screw feeder, hydrolyzes in acid condition
Reaction, solid zirconium chloride, water, the weight ratio of hydrochloric acid are 1：2.5~2.6:0.4~0.5, the hydrogen chloride gas of hydrolysis generation
Body is reclaimed with graphite condenser condenser system, is applied mechanically as next group hydrolysis acid, control zirconium oxychloride hydrolysis concentration 180~
At 190 g/l, filtering and impurity removing, filtrate squeeze into crystallization kettle carry out crystallization reaction, crystallization time 10~12 hours, crystallization is finished, material
Liquid enters hydro-extracting cage drying, and with after a small amount of pure water wash, continues to dry, obtain ultrapure zirconium oxychloride crystal product.Water dumping
After mother liquor and leacheate are collected, the bottom water jacket hydrolyzed as next group is used；
5. the recycling of tail gas
Enter the recycling system of tail gas from the step tail gas that 3. silicon tetrachloride refining system is discharged；Time of tail gas
Receive to utilize and comprise the following steps：
A. exhaust collection is stored
From zircon sand fluidizing chlorination device through collecting ZrCl4And SiCl4After product, the discharge of silicon tetrachloride distillation system
Tail gas, is all collected and enters dry gas-holder storage, and back-up is recycled from rear；
B. chlorine separation and recovery is utilized
The tail gas in dry gas-holder is stored in, chlorine recycling system is sent into by compressor, chlorine is initially entered cold
Condenser, 0.1~0.2MPa of control pressure, under the conditions of≤- 35 DEG C, the chlorine in tail gas is condensed into liquid；Send into chlorine storage
Groove, the raw material as chlorination reaction is recycled；
C.CO is recycled
Tail gas CO content >=95% after separation chlorine through step b, CO gas holders of making a gift to someone, the synthetic reaction that standby CO is participated in
Process units is used as raw material CO.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, the step
5. in the recycling of tail gas c, the tail gas after separating chlorine through step b is further purified through sodium hydroxide solution scrubbing tower
Afterwards, tail gas CO content >=99%, CO gas holders of making a gift to someone, the process units for the synthetic reaction that standby CO is participated in is used as raw material CO.It is suitable
For for the harsh technique productions device of raw material CO quality requirements.
The zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, compared to existing
Technology can produce following good effect：
1. it can effectively utilize Cl there is provided one kind2With CO resources, greenhouse gases CO is reduced2Discharge；Avoid because CO is discharged
The security incidents such as caused burning, blast, poisoning occur；The production cost of zircon sand fluidizing chlorination device product can be reduced,
The zircon sand fluidizing chlorination for improving plant capacity prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane.
2. the complete recycling of chlorine in tail gas, reduce the raw material of zirconium oxychloride product and SiCl4 byproducts into
This 25~40%.
3. the CO in tail gas is reclaimed completely, the raw material for being related to process units as the CO synthetic reactions participated in is utilized.Save
Valuable fossil resource.
4. using the chlorine in the method separation tail gas of chlorine gas liquefaction, separative efficiency >=98.5%, obtained purity of chlorine gas feeding
Height, disclosure satisfy that zircon sand chloridization process requirement.
5. chlorine is separated from tail gas using the method first using chlorine gas liquefaction, and the chlorine in tail gas point
From thorough.Obtained CO can synthetic ammonia installation, synthesizing methanol device, methanol carboxylation synthesis of acetic acid device, alkene hydrogen methylate
The device, ethene and CO for preparing corresponding aldehyde prepare technological requirement of the device for raw material CO of polyketone.
6. the CO that the burning for avoiding CO in the prior art is discharged again2For the pollution of atmospheric environment.
7. reducing the cost of zircon sand fluidizing chlorination device product, the economic benefit of manufacturing enterprise is improved.
8. provide quality raw materials for synthetic ammonia installation, synthesizing methanol device or synthesis of acetic acid device.Reduce simultaneously
The production cost of product, improves the economic benefit of manufacturing enterprise.
9. zircon sand and Cl2Mol ratio, bring up to 8~10, improve the reaction speed of zircon sand chlorination reaction.Zirconium
The production capacity that sand fluidizing chlorination prepares ultrapure zirconium oxychloride by-produced tetrachlorosilane device improves 25~40%.
Embodiment
The present invention will now be further detailed embodiment：
Embodiment 1
A kind of zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, including
Following steps：
1. zircon sands chlorination
Quartz sand is crushed to 300-350 targeted fine powders first, pressed with 150~180 mesh petroleum cokes and catalyst boron oxide
According to 100：20~23：0.4~0.5 ratio is well mixed, and is added in boiling chloridizing furnace and is carried out chlorination reaction, zircon sand and chlorine
The mol ratio of gas is 1：8, reaction temperature is 950~1100 DEG C, and it is 1.0~1.5m to control logical chlorine speed3/h；
2. separates and collects zirconium chloride
Gaseous product from step 1., is cooled down through multi-stage condensing device, and cooling temperature of charge is to 210~230 DEG C, into rotation
General mood solid separator, carries out gas solid separation, and control outlet temperature isolates zirconium chloride solid at 100~110 DEG C；Point
The zirconium chloride solid input continous way purifies and separates device separated out, progress secondary purification separation, heated separator temperature to 270~
280 DEG C so that lower boiling a small amount of silicon tetrachloride and other impurity gasification, gas solid separation is re-started, high-purity four isolated
Reaction is hydrolyzed into hydrolysis kettle in zirconium chloride solid；And tail gas then enters silicon tetrachloride distillation system and reclaimed；
3. silicon tetrachlorides is refined
Gas after 2. separating and collecting zirconium chloride through step, into silicon tetrachloride distillation system, distillation system is literary mound
In formula pipeline spray column, tower is connected with condenser, and condenser is connected to cryogenic freezing salt solution, and the temperature of chilled brine is at -40 DEG C
Hereinafter, while chilled brine is opened, silicon tetrachloride liquid spray system in tower is opened, gas outlet temperature 30~35 is controlled
DEG C, obtained silicon tetrachloride liquid enters back into rectifying column and carries out rectifying, controls the temperature of rectifying column reboiler at 70 DEG C, cooling
45 DEG C of coolant-temperature gage, content of silicon tetrachloride >=99.6% that rectifying goes out；
4. hydrolysis, crystallization
Solid zirconium chloride from step 2. enters hydrolysis kettle by screw feeder, hydrolyzes in acid condition
Reaction, solid zirconium chloride, water, the weight ratio of hydrochloric acid are 1：2.5~2.6:0.4~0.5, the hydrogen chloride gas of hydrolysis generation
Body is reclaimed with graphite condenser condenser system, is applied mechanically as next group hydrolysis acid, control zirconium oxychloride hydrolysis concentration 180~
At 190 g/l, filtering and impurity removing, filtrate squeeze into crystallization kettle carry out crystallization reaction, crystallization time 10~12 hours, crystallization is finished, material
Liquid enters hydro-extracting cage drying, and with after a small amount of pure water wash, continues to dry, obtain ultrapure zirconium oxychloride crystal product.Water dumping
After mother liquor and leacheate are collected, the bottom water jacket hydrolyzed as next group is used；
5. the recycling of tail gas
Enter the recycling system of tail gas from the step tail gas that 3. silicon tetrachloride refining system is discharged；Time of tail gas
Receive to utilize and comprise the following steps：
A. exhaust collection is stored
From zircon sand fluidizing chlorination device through collecting ZrCl4And SiCl4After product, the discharge of silicon tetrachloride distillation system
Tail gas, is all collected and enters dry gas-holder storage, and back-up is recycled from rear；
B. chlorine separation and recovery is utilized
The tail gas in dry gas-holder is stored in, chlorine recycling system is sent into by compressor, chlorine is initially entered cold
Condenser, 0.1~0.2MPa of control pressure, under the conditions of≤- 35 DEG C, the chlorine in tail gas is condensed into liquid；Send into chlorine storage
Groove, the raw material as chlorination reaction is recycled；Chlorine condensation liquefaction is using low-pressure ammonia-calcium chloride brine indirect refrigeration liquefaction
Technique.
C.CO is recycled
Tail gas CO content >=95% after separation chlorine through step b, CO gas holders of making a gift to someone, standby synthetic ammonia installation, synthesis first
The methylate device for preparing corresponding aldehyde, ethene and CO of alcohol device, methanol carboxylation synthesis of acetic acid device, alkene hydrogen prepares polyketone
The raw material of device is utilized.
Chlorine recovery utilization rate >=98.5%, CO recycles >=99.0%.
Embodiment 2
A kind of zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, including
Following steps：
1. zircon sands chlorination
Quartz sand is crushed to 300-350 targeted fine powders first, pressed with 150~180 mesh petroleum cokes and catalyst boron oxide
According to 100：20~23：0.4~0.5 ratio is well mixed, and is added in boiling chloridizing furnace and is carried out chlorination reaction, zircon sand and chlorine
The mol ratio of gas is 1：9, reaction temperature is 950~1100 DEG C, and it is 1.0~1.5m to control logical chlorine speed3/h；
2. separates and collects zirconium chloride
Gaseous product from step 1., is cooled down through multi-stage condensing device, and cooling temperature of charge is to 210~230 DEG C, into rotation
General mood solid separator, carries out gas solid separation, and control outlet temperature isolates zirconium chloride solid at 100~110 DEG C；Point
The zirconium chloride solid input continous way purifies and separates device separated out, progress secondary purification separation, heated separator temperature to 270~
280 DEG C so that lower boiling a small amount of silicon tetrachloride and other impurity gasification, gas solid separation is re-started, high-purity four isolated
Reaction is hydrolyzed into hydrolysis kettle in zirconium chloride solid；And tail gas then enters silicon tetrachloride distillation system and reclaimed；
3. silicon tetrachlorides is refined
Gas after 2. separating and collecting zirconium chloride through step, into silicon tetrachloride distillation system, distillation system is literary mound
In formula pipeline spray column, tower is connected with condenser, and condenser is connected to cryogenic freezing salt solution, and the temperature of chilled brine is at -40 DEG C
Hereinafter, while chilled brine is opened, silicon tetrachloride liquid spray system in tower is opened, gas outlet temperature 30~35 is controlled
DEG C, obtained silicon tetrachloride liquid enters back into rectifying column and carries out rectifying, controls the temperature of rectifying column reboiler at 70 DEG C, cooling
45 DEG C of coolant-temperature gage, content of silicon tetrachloride >=99.6% that rectifying goes out；
4. hydrolysis, crystallization
Solid zirconium chloride from step 2. enters hydrolysis kettle by screw feeder, hydrolyzes in acid condition
Reaction, solid zirconium chloride, water, the weight ratio of hydrochloric acid are 1：2.5~2.6:0.4~0.5, the hydrogen chloride gas of hydrolysis generation
Body is reclaimed with graphite condenser condenser system, is applied mechanically as next group hydrolysis acid, control zirconium oxychloride hydrolysis concentration 180~
At 190 g/l, filtering and impurity removing, filtrate squeeze into crystallization kettle carry out crystallization reaction, crystallization time 10~12 hours, crystallization is finished, material
Liquid enters hydro-extracting cage drying, and with after a small amount of pure water wash, continues to dry, obtain ultrapure zirconium oxychloride crystal product.Water dumping
After mother liquor and leacheate are collected, the bottom water jacket hydrolyzed as next group is used；
5. the recycling of tail gas
Enter the recycling system of tail gas from the step tail gas that 3. silicon tetrachloride refining system is discharged；Time of tail gas
Receive to utilize and comprise the following steps：
A. exhaust collection is stored
From zircon sand fluidizing chlorination device through collecting ZrCl4And SiCl4After product, the discharge of silicon tetrachloride distillation system
Tail gas, is all collected and enters dry gas-holder storage, and back-up is recycled from rear；
B. chlorine separation and recovery is utilized
The tail gas in dry gas-holder is stored in, chlorine recycling system is sent into by compressor, chlorine is initially entered cold
Condenser, 0.1~0.2MPa of control pressure, under the conditions of≤- 35 DEG C, the chlorine in tail gas is condensed into liquid；Send into chlorine storage
Groove, the raw material as chlorination reaction is recycled；Chlorine condensation liquefaction is using low pressure freon R-22 directly freezeds liquefaction work
Skill.
C.CO is recycled
Tail gas CO content >=98% after separation chlorine through step b, CO gas holders of making a gift to someone, standby synthetic ammonia installation, synthesis first
The methylate device for preparing corresponding aldehyde, ethene and CO of alcohol device, methanol carboxylation synthesis of acetic acid device, alkene hydrogen prepares polyketone
The raw material of device is utilized.
Chlorine recovery utilization rate >=99%, CO recycles >=99.5%.
Embodiment 3
A kind of zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, including
Following steps：
1. zircon sands chlorination
Quartz sand is crushed to 300-350 targeted fine powders first, pressed with 150~180 mesh petroleum cokes and catalyst boron oxide
According to 100：20~23：0.4~0.5 ratio is well mixed, and is added in boiling chloridizing furnace and is carried out chlorination reaction, zircon sand and chlorine
The mol ratio of gas is 1：10, reaction temperature is 950~1100 DEG C, and it is 1.0~1.5m to control logical chlorine speed3/h；
2. separates and collects zirconium chloride
Gaseous product from step 1., is cooled down through multi-stage condensing device, and cooling temperature of charge is to 210~230 DEG C, into rotation
General mood solid separator, carries out gas solid separation, and control outlet temperature isolates zirconium chloride solid at 100~110 DEG C；Point
The zirconium chloride solid input continous way purifies and separates device separated out, progress secondary purification separation, heated separator temperature to 270~
280 DEG C so that lower boiling a small amount of silicon tetrachloride and other impurity gasification, gas solid separation is re-started, high-purity four isolated
Reaction is hydrolyzed into hydrolysis kettle in zirconium chloride solid；And tail gas then enters silicon tetrachloride distillation system and reclaimed；
3. silicon tetrachlorides is refined
Gas after 2. separating and collecting zirconium chloride through step, into silicon tetrachloride distillation system, distillation system is literary mound
In formula pipeline spray column, tower is connected with condenser, and condenser is connected to cryogenic freezing salt solution, and the temperature of chilled brine is at -40 DEG C
Hereinafter, while chilled brine is opened, silicon tetrachloride liquid spray system in tower is opened, gas outlet temperature 30~35 is controlled
DEG C, obtained silicon tetrachloride liquid enters back into rectifying column and carries out rectifying, controls the temperature of rectifying column reboiler at 70 DEG C, cooling
45 DEG C of coolant-temperature gage, content of silicon tetrachloride >=99.6% that rectifying goes out；
4. hydrolysis, crystallization
Solid zirconium chloride from step 2. enters hydrolysis kettle by screw feeder, hydrolyzes in acid condition
Reaction, solid zirconium chloride, water, the weight ratio of hydrochloric acid are 1：2.5~2.6:0.4~0.5, the hydrogen chloride gas of hydrolysis generation
Body is reclaimed with graphite condenser condenser system, is applied mechanically as next group hydrolysis acid, control zirconium oxychloride hydrolysis concentration 180~
At 190 g/l, filtering and impurity removing, filtrate squeeze into crystallization kettle carry out crystallization reaction, crystallization time 10~12 hours, crystallization is finished, material
Liquid enters hydro-extracting cage drying, and with after a small amount of pure water wash, continues to dry, obtain ultrapure zirconium oxychloride crystal product.Water dumping
After mother liquor and leacheate are collected, the bottom water jacket hydrolyzed as next group is used；
5. the recycling of tail gas
Enter the recycling system of tail gas from the step tail gas that 3. silicon tetrachloride refining system is discharged；Time of tail gas
Receive to utilize and comprise the following steps：
A. exhaust collection is stored
From zircon sand fluidizing chlorination device through collecting ZrCl4And SiCl4After product, the discharge of silicon tetrachloride distillation system
Tail gas, is all collected and enters dry gas-holder storage, and back-up is recycled from rear；
B. chlorine separation and recovery is utilized
The tail gas in dry gas-holder is stored in, chlorine recycling system is sent into by compressor, chlorine is initially entered cold
Condenser, 0.1~0.2MPa of control pressure, under the conditions of≤- 35 DEG C, the chlorine in tail gas is condensed into liquid；Send into chlorine storage
Groove, the raw material as chlorination reaction is recycled；Chlorine condensation liquefaction is using low-pressure ammonia-calcium chloride brine indirect refrigeration liquefaction
Technique.
C.CO is recycled
Tail gas CO content >=97% after separation chlorine through step b, CO gas holders of making a gift to someone, standby synthetic ammonia installation, synthesis first
The methylate device for preparing corresponding aldehyde, ethene and CO of alcohol device, methanol carboxylation synthesis of acetic acid device, alkene hydrogen prepares polyketone
The raw material of device is utilized.
Chlorine recovery utilization rate >=98.8%, CO recycles >=99.0%.
Embodiment 4
A kind of zircon sand fluidizing chlorination of the present invention prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, including
Following steps：
1. zircon sands chlorination
Quartz sand is crushed to 300-350 targeted fine powders first, pressed with 150~180 mesh petroleum cokes and catalyst boron oxide
According to 100：20~23：0.4~0.5 ratio is well mixed, and is added in boiling chloridizing furnace and is carried out chlorination reaction, zircon sand and chlorine
The mol ratio of gas is 1：10, reaction temperature is 950~1100 DEG C, and it is 1.0~1.5m to control logical chlorine speed3/h；
2. separates and collects zirconium chloride
Gaseous product from step 1., is cooled down through multi-stage condensing device, and cooling temperature of charge is to 210~230 DEG C, into rotation
General mood solid separator, carries out gas solid separation, and control outlet temperature isolates zirconium chloride solid at 100~110 DEG C；Point
The zirconium chloride solid input continous way purifies and separates device separated out, progress secondary purification separation, heated separator temperature to 270~
280 DEG C so that lower boiling a small amount of silicon tetrachloride and other impurity gasification, gas solid separation is re-started, high-purity four isolated
Reaction is hydrolyzed into hydrolysis kettle in zirconium chloride solid；And tail gas then enters silicon tetrachloride distillation system and reclaimed；
3. silicon tetrachlorides is refined
Gas after 2. separating and collecting zirconium chloride through step, into silicon tetrachloride distillation system, distillation system is literary mound
In formula pipeline spray column, tower is connected with condenser, and condenser is connected to cryogenic freezing salt solution, and the temperature of chilled brine is at -40 DEG C
Hereinafter, while chilled brine is opened, silicon tetrachloride liquid spray system in tower is opened, gas outlet temperature 30~35 is controlled
DEG C, obtained silicon tetrachloride liquid enters back into rectifying column and carries out rectifying, controls the temperature of rectifying column reboiler at 70 DEG C, cooling
45 DEG C of coolant-temperature gage, content of silicon tetrachloride >=99.6% that rectifying goes out；
4. hydrolysis, crystallization
Solid zirconium chloride from step 2. enters hydrolysis kettle by screw feeder, hydrolyzes in acid condition
Reaction, solid zirconium chloride, water, the weight ratio of hydrochloric acid are 1：2.5~2.6:0.4~0.5, the hydrogen chloride gas of hydrolysis generation
Body is reclaimed with graphite condenser condenser system, is applied mechanically as next group hydrolysis acid, control zirconium oxychloride hydrolysis concentration 180~
At 190 g/l, filtering and impurity removing, filtrate squeeze into crystallization kettle carry out crystallization reaction, crystallization time 10~12 hours, crystallization is finished, material
Liquid enters hydro-extracting cage drying, and with after a small amount of pure water wash, continues to dry, obtain ultrapure zirconium oxychloride crystal product.Water dumping
After mother liquor and leacheate are collected, the bottom water jacket hydrolyzed as next group is used；
5. the recycling of tail gas
Enter the recycling system of tail gas from the step tail gas that 3. silicon tetrachloride refining system is discharged；Time of tail gas
Receive to utilize and comprise the following steps：
A. exhaust collection is stored
From zircon sand fluidizing chlorination device through collecting ZrCl4And SiCl4After product, the discharge of silicon tetrachloride distillation system
Tail gas, is all collected and enters dry gas-holder storage, and back-up is recycled from rear；
B. chlorine separation and recovery is utilized
The tail gas in dry gas-holder is stored in, chlorine recycling system is sent into by compressor, chlorine is initially entered cold
Condenser, 0.1~0.2MPa of control pressure, under the conditions of≤- 35 DEG C, the chlorine in tail gas is condensed into liquid；Send into chlorine storage
Groove, the raw material as chlorination reaction is recycled；Chlorine condensation liquefaction uses low pressure freon R-22 directly freezed liquefaction process
C.CO is recycled
Tail gas after separation chlorine through step b, after sodium hydroxide solution scrubbing tower further purification, tail gas CO contents
>=99%, CO gas holders of making a gift to someone, the process units for the synthetic reaction that standby CO is participated in is used as raw material CO.
Chlorine recovery utilization rate >=99%, CO recycles >=99.5%.
Claims (6)
1. a kind of zircon sand fluidizing chlorination prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, including zircon sand boiling
Chlorination system, zirconium chloride condensation collection system, silicon tetrachloride distillation system and zirconium chloride hydrolysis prepare high-purity zirconium oxychloride
System, it is characterised in that the also recycling system including tail gas；The recycling system of the tail gas includes tail gas and stores dress
Put, chlorine separating and reclaiming device and CO reclaim storage device；The chlorine in tail gas is separated and collected first, as zircon sand boiling chlorine
Change the raw material of reaction, recycle；The industrial installation that tail gas after separation chlorine is related to as the CO synthetic reactions participated in
Raw material utilize；
The synthetic reaction that described CO is participated in is any one clock in following reaction：
1. the reaction that CO is converted into hydrogen of synthetic ammonia installations CO conversion sections
CO+H2O→H2+CO2
2. the reaction of .CO synthesizing methanol by hydrogenating
2H2+CO→CH3OH
3. the carbonylation of unsaturated compounds,
CH2=CH2+CO+H2→CH3CH2CHO
4. the carboxylation reaction of methanol
CH3OH+CO→CH3COOH
5. the alternating copolymerization that .CO is participated in；
The industrial installation that the synthetic reaction that described CO is participated in is related to is：Synthetic ammonia installation, synthesizing methanol device, methanol carboxylic
It is combined to acetic acid device, alkene hydrogen and methylates prepare device either ethene and the CO of corresponding aldehyde and prepare the device of polyketone；
The zircon sand fluidizing chlorination prepares the application method of the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, including such as
Lower step：
1. zircon sands chlorination
Zircon sand is crushed to 300-350 targeted fine powders first, with 150~180 mesh petroleum cokes and catalyst boron oxide according to
100：20~23：0.4~0.5 ratio is well mixed, and is added in boiling chloridizing furnace and is carried out chlorination reaction, zircon sand and chlorine
Mol ratio be 1：8~10, reaction temperature is 950~1100 DEG C, and it is 1.0~1.5m to control logical chlorine speed3/ h,
2. separates and collects zirconium chloride
Gaseous product from step 1., is cooled down through multi-stage condensing device, and cooling temperature of charge is to 210~230 DEG C, into whirlwind gas
Solid separator, carries out gas solid separation, and control outlet temperature isolates zirconium chloride solid at 100~110 DEG C；Isolating
Zirconium chloride solid input continous way purifies and separates device, carry out secondary purification separation, heated separator temperature to 270~280
DEG C so that lower boiling a small amount of silicon tetrachloride and other impurity gasification, gas solid separation is re-started, high-purity four chlorination isolated
Reaction is hydrolyzed into hydrolysis kettle in zirconium solid；And tail gas then enters silicon tetrachloride distillation system and reclaimed；
3. silicon tetrachlorides is refined
Gas after 2. separating and collecting zirconium chloride through step, into silicon tetrachloride distillation system, distillation system is venturi type
Pipeline spray column, tower is connected with condenser, and condenser is connected to cryogenic freezing salt solution, the temperature of chilled brine below -40 DEG C,
While chilled brine is opened, silicon tetrachloride liquid spray system in tower is opened, 30~35 DEG C of gas outlet temperature is controlled, obtains
The silicon tetrachloride liquid arrived, enters back into rectifying column and carries out rectifying, controls the temperature of rectifying column reboiler in 70 DEG C, cooling water temperature
45 DEG C, content of silicon tetrachloride >=99.6% that rectifying goes out；
4. hydrolysis, crystallization
Solid zirconium chloride from step 2. enters hydrolysis kettle by screw feeder, hydrolysis occurs in acid condition anti-
Should, solid zirconium chloride, water, the weight ratio of hydrochloric acid are 1：2.5~2.6:0.4~0.5, the hydrogen chloride gas of hydrolysis generation
Reclaimed, applied mechanically as next group hydrolysis acid, control zirconium oxychloride hydrolyzes concentration 180~190 with graphite condenser condenser system
G/l when, filtering and impurity removing, filtrate squeeze into crystallization kettle carry out crystallization reaction, crystallization time 10~12 hours, crystallization is finished, feed liquid
Enter hydro-extracting cage drying, and with after a small amount of pure water wash, continue to dry, obtain ultrapure zirconium oxychloride crystal product, water dumping is female
After liquid and leacheate are collected, the bottom water jacket hydrolyzed as next group is used；
5. the recycling of tail gas
Enter the recycling system of tail gas from the step tail gas that 3. silicon tetrachloride refining system is discharged；The recovery profit of tail gas
With comprising the following steps：
A. exhaust collection is stored
From zircon sand fluidizing chlorination device through collecting ZrCl4And SiCl4After product, the tail gas of silicon tetrachloride distillation system discharge,
All collect and enter dry gas-holder storage, back-up is recycled from rear；
B. chlorine separation and recovery is utilized
The tail gas in dry gas-holder is stored in, chlorine recycling system is sent into by compressor, chlorine condenser is initially entered,
0.1~0.2MPa of control pressure, under the conditions of≤- 35 DEG C, the chlorine in tail gas is condensed into liquid；Chlorine storage tank is sent into, is used as
The raw material of chlorination reaction, is recycled；
C.CO is recycled
Tail gas CO content >=95% after separation chlorine through step b, sends into CO gas holders, the production for the synthetic reaction that standby CO is participated in
Device is used as raw material CO.
2. the zircon sand fluidizing chlorination according to claim 1 prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, its
Be characterised by that the chlorine separating and reclaiming device is chlorine condensation liquefaction device, including chlorine liquefier, refrigeration unit and other
Auxiliary device, chlorine is condensed into liquid in chlorine liquefier, and refrigeration unit provides low-temperature receiver for chlorine liquefier.
3. the zircon sand fluidizing chlorination according to claim 2 prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, its
It is characterised by that described chlorine condensation liquefaction device uses low-pressure ammonia-calcium chloride brine indirect refrigeration liquefying plant.
4. the zircon sand fluidizing chlorination according to claim 2 prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, its
It is characterised by that described chlorine condensation liquefaction device uses low pressure freon R-22 directly freezed liquefying plants.
5. the zircon sand fluidizing chlorination according to claim 1 prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, its
It is dish gas holder or dry gas-holder to be characterised by that the CO reclaims storage device.
6. the zircon sand fluidizing chlorination according to claim 1 prepares the process units of ultrapure zirconium oxychloride by-produced tetrachlorosilane, its
The step is characterised by 5. in recycling c of tail gas, the tail gas after separating chlorine through step b, through sodium hydroxide solution
Scrubbing tower is further after purification, and tail gas CO content >=99% sends into CO gas holders, and the process units for the synthetic reaction that standby CO is participated in is made
Used for raw material CO.
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| CN107337236B (en) * | 2017-06-29 | 2023-08-25 | 赤峰盛森硅业科技发展有限公司 | Zirconium tetrachloride quenching device and method |
| CN109019682B (en) * | 2018-08-20 | 2020-01-17 | 新特能源股份有限公司 | Zirconium oxychloride and preparation method thereof |
| CN109593098B (en) * | 2018-12-11 | 2020-01-10 | 新特能源股份有限公司 | Combined preparation process and combined preparation equipment for zirconium oxide and methyl chlorosilane |
| CN109678194B (en) * | 2019-01-09 | 2024-02-23 | 中国原子能科学研究院 | Cerium dioxide chlorination device |
| CN111762788A (en) * | 2019-04-01 | 2020-10-13 | 新特能源股份有限公司 | Combined preparation system and method of trichlorosilane and zirconium tetrachloride |
| CN112142055A (en) * | 2019-06-28 | 2020-12-29 | 新特能源股份有限公司 | Slag slurry recycling method in cold hydrogenation process and recycling system used in same |
| CN110357110B (en) * | 2019-07-31 | 2022-06-10 | 锦州中特电炉有限公司 | Method for producing silicon tetrachloride by using polycrystalline silicon sliced silicon powder |
| 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 |
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| CN104817110B (en) * | 2015-03-04 | 2016-08-24 | 郭志斌 | A kind of zircon sand fluidizing chlorination method produces high-purity zirconium oxychloride and the method for coproduction Silicon chloride. |
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