CN109734128A - Zircon sand chlorination prepares the process of zirconium chloride by-produced tetrachlorosilane - Google Patents
Zircon sand chlorination prepares the process of zirconium chloride by-produced tetrachlorosilane Download PDFInfo
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Abstract
The invention discloses the processes that a kind of zircon sand chlorination prepares zirconium chloride by-produced tetrachlorosilane, which comprises the following steps: (1) crushes: zircon sand is carried out dry grinding crushing；(2) it dries: smashed zircon sand is dried；(3) chlorination: drying zircon sand is added in boiling chloridizing furnace and CCl is added in furnace bottom4Carry out chlorination；(4) it prepares: after reaction, in the ZrCl of fluidizing fluid-bed interior generation4And SiCl4Gas carries out gas solid separation through dust-precipitator at the top of chlorination furnace, collects the dust to get off and returns in furnace that the reaction was continued, the gas after separation is through fused salt spray washing.The present invention has the advantage that utilizing zircon sand and CCl4Reaction process by the CCl of chloromethanes industrial by-product4It is converted into ZrCl4And SiCl4, it is green reaction technique, will has and significantly economical and environmentally friendly be worth；For the chemical reaction of solid+gas, reaction temperature is low, and reaction speed is fast, and production capacity is high.Exhaust carbon dioxide gas liquefaction after reaction, as by-product sale.
Description
Technical field
The present invention relates to zirconium chloride preparation technical fields, in particular to a kind of zircon sand chlorination to prepare zirconium chloride by-product
The process of silicon tetrachloride.
Background technique
Zircon sand is crushed 200-325 mesh, petroleum coke is crushed to 100-200 mesh, and zircon sand and petroleum coke are pressed 100:20-
28 ratio is sufficiently mixed, dries, and is at the uniform velocity added in boiling chloridizing furnace later, and chlorination furnace internal heat generation body uses graphite tube,
Chlorination furnace external power supply uses intermediate frequency or line-frequency induction coil, heats to graphite in boiling chloridizing furnace, for supplementing chlorination
Heat needed for reaction, reaction temperature are controlled at 1100-1200 DEG C, and bottom is passed through chlorine, the silicon tetrachloride of generation and four chlorinations
Zirconium gas is collected lower unreacted reactant, is condensed into zirconium chloride condenser, through the first, second and third line condenser through dust arrester installation
After condensation, lower than 120 DEG C incondensable gases enter thick silicon tetrachloride collection system, after the spray elution of low temperature silicon tetrachloride, give up
Gas is handled through lye absorption tower and is emptied.Also silicon powder can be added in the patent having or carborundum powder emphasizes additional heat, reduce power consumption.
The prior art has the following disadvantages:
1. zircon sand is not easy to match with petroleum coke partial size, easily it is layered, is formed " dead furnace ", deslagging is frequent.
2. material particular diameter is small, continue to become smaller in reaction process, elegant chlorination furnace out enters dust-precipitator, makes metal recovery
Rate reduces.
3. reaction temperature is high, under conditions of having excessive chlorine, service life of equipment is reduced.
4. this reaction is solid+solid+gas chemical reaction, reaction speed is slow, causes unit area production capacity low.
5. product quality is low, zirconium chloride and silicon tetrachloride are after the condensation of the first, second and third line condenser, product matter
It measures inconsistent, and is all thick zirconium chloride, collects the silicon tetrachloride grade got off and also there was only 80% or so, it cannot be commercially available.
6. having added concurrent heating agent, the yield of silicon tetrachloride can be made to increase, but benefit does not increase, because price zirconium chloride is
10 times or more of silicon tetrachloride.
Summary of the invention
In order to solve the above technical problems, technical solution provided by the invention is that a kind of zircon sand chlorination prepares zirconium chloride pair
Produce the process of silicon tetrachloride, which comprises the following steps:
(1) it crushes: zircon sand is subjected to dry grinding crushing；
(2) it dries: smashed zircon sand is dried；
(3) chlorination: drying zircon sand is added in boiling chloridizing furnace and CCl is added in furnace bottom4Carry out chlorination；
(4) it prepares: after reaction, in the ZrCl of fluidizing fluid-bed interior generation4And SiCl4Gas, through dust-precipitator at the top of chlorination furnace
Gas solid separation is carried out, the dust to get off is collected and returns in furnace that the reaction was continued, the gas after separation is through fused salt spray washing, then into four
Solid ZrCl is obtained after the condensation of zirconium chloride condenser4Incondensable gas is through gas-solid separating device, then chilled SiCl4Liquid spray,
SiCl4It is able to absorb, remaining gas produces after the neutralization of solid caustic soda tower through carbon dioxide adsorption, desorption, compression, condensation
Liquid CO 2；
(5) it exhaust emissions: is discharged after the scrubbed tower washing of tail gas.
Preferably, the smashed granularity of the zircon sand is -80-200 mesh.
Preferably, when the reaction zone temperature of the boiling chloridizing furnace reaches 750-999 DEG C, zircon sand, fluidizing chlorination is added
The reaction temperature of furnace conversion zone is 750-999 DEG C.
Preferably, the zircon sand drying temperature is 120-150 DEG C.
Preferably, the charging rate that the zircon sand is added in chlorination furnace is 125-450kg/h.
Preferably, the charging rate that the carbon tetrachloride is added in chlorination furnace is 108-388kg/h.
Preferably, the fluidizing fluid-bed pressure is 0.0015-0.008MPa.
Preferably, the chlorination furnace conversion zone internal diameter is 300-1300mm.
Preferably, the fused salt is NaCl, KCl, MgCl2, ratio 1:1:0.2-0.5.
The invention has the following advantages over the prior art: 1. due to having fatal destruction, CCl to ozone layer4
It is strictly limited trade waste.It is provided according to Montreal protocol, China must completely eliminate conduct from 2010
The CCl of final products4.However, CCl can be inevitably generated in the production process of the chloromethanes such as methylene chloride, chloroform4
Byproduct.Utilize zircon sand raw material and CCl4Reaction process by the CCl of chloromethanes industrial by-product4It is converted into ZrCl4And SiCl4
Product is green reaction technique, will have and significantly economical and environmentally friendly be worth.2. zircon sand crushes, size controlling to 80-200
Mesh, bigger than original process processing partial size, the dust of formation is few, and raw material availability is high.3. this reaction is that solid+gas chemistry is anti-
It answers, reaction temperature is low, and reaction speed is fast, and production capacity is high.4. lamination is not present in chlorination furnace, infrequently deslagging, production is continuous
Smooth, the slag of discharge is also thick zircon sand, is used again after can crushing.5.CCl4Boiling point is higher than chlorine, CCl4Cook chlorinating agent more than chlorine
Safety, environment are good.(76.8 DEG C of carbon tetrachloride boiling point, -34.6 DEG C of liquid chlorine boiling point) 6. unit area production capacity of the present invention is high, and metal returns
High income.7. zirconium chloride produced by the invention is refined zirconium tetrachloride, the production of sponge zirconium and zirconium compounds can be directly used for.8.
Silicon tetrachloride grade height produced by the invention, can be directly commercially available in 92-97%.9. the exhaust gas dioxy generated in present invention production
Carbon will liquefy, and commercially available.10. equipment is because reaction temperature is low, corrosion rate slows down, and extends its service life.
Detailed description of the invention
Fig. 1 is the process structural representation that a kind of zircon sand chlorination of the present invention prepares zirconium chloride by-produced tetrachlorosilane
Figure.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings.
Trade waste is utilized it is an object of the invention to be directed to the defect of existing zircon sand chlorination technique in conjunction with attached drawing
CCl4Substitution chlorine cooks chlorinating agent and substitution petroleum coke makees reducing agent, makes itself and 21, and providing one kind has metering, can be continuous
Charging discharging, raw material particle size is loose, chlorinating agent and the matched fluidization of material, ideal zircon sand low temperature chlorination method, can be big
It is big to reduce energy consumption, the rate of recovery and product quality are improved, service life of equipment is extended.Reaction principle: ZrSiO4+2CCl4=ZrCl4+
SiCl4+2CO2
The present invention has following key technical feature: 1. use CCl4Chlorination zircon sand prepares refined zirconium tetrachloride by-product simultaneously
Silicon tetrachloride.2. zircon sand crushes, size controlling to 80-200 mesh.3. reaction temperature is controlled at 750-999 DEG C.4. dust arrester installation
It is located at the top of chlorination furnace, the dust of collection flows back into chlorination furnace that the reaction was continued through connecting pipe.5. reacting four chlorinations generated
Silicon and zirconium chloride gas are through fused salt device spray washing.6. fused salt is NaCl, KCl, MgCl2, ratio are as follows: 1:1:0.2-0.5.
7. it is 330~400 DEG C that fused salt, which sprays temperature,.8. the co 2 liquefaction that reaction generates is collected.
A kind of zircon sand chlorination of the present invention prepares the process of zirconium chloride by-produced tetrachlorosilane, which is characterized in that packet
Include following steps:
(1) it crushes: zircon sand is subjected to dry grinding crushing；
(2) it dries: smashed zircon sand is dried；
(3) chlorination: drying zircon sand is added in boiling chloridizing furnace and CCl is added in furnace bottom4Carry out chlorination；
(4) it prepares: after reaction, in the ZrCl of fluidizing fluid-bed interior generation4And SiCl4Gas, through dust-precipitator at the top of chlorination furnace
Gas solid separation is carried out, the dust to get off is collected and returns in furnace that the reaction was continued, the gas after separation is through fused salt spray washing, then into four
Solid ZrCl is obtained after the condensation of zirconium chloride condenser4Incondensable gas is through gas-solid separating device, then chilled SiCl4Liquid spray,
SiCl4It is able to absorb, remaining gas produces after the neutralization of solid caustic soda tower through carbon dioxide adsorption, desorption, compression, condensation
Liquid CO 2；
(5) it exhaust emissions: is discharged after the scrubbed tower washing of tail gas.
The smashed granularity of zircon sand is -80-200 mesh.
When the reaction zone temperature of the boiling chloridizing furnace reaches 750-999 DEG C, zircon sand, boiling chloridizing furnace conversion zone is added
Reaction temperature be 750-999 DEG C.
The zircon sand drying temperature is 120-150 DEG C.
The charging rate that the zircon sand is added in chlorination furnace is 125-450kg/h.
The charging rate that the carbon tetrachloride is added in chlorination furnace is 108-388kg/h.
The fluidizing fluid-bed pressure is 0.0015-0.008MPa.
The chlorination furnace conversion zone internal diameter is 300-1300mm.
The fused salt is NaCl, KCl, MgCl2, ratio 1:1:0.2-0.5.
ZrCl4It is the basic material for producing sponge zirconium and zirconium oxychloride, zirconium compounds, the life of the zirconium oxychloride in the whole world 90%
Production capacity power is in China, and production capacity is up to 240,000 tons or so, but production is substantially the production of " one acid and one bases " method, and process flow is long,
High production cost, wastewater discharge containing NaCl is big, and silicon slag nowhere digests conversion, and environmental pollution improvement's difficulty is big.ZrCl4Hydrolyze method
Produce zirconium oxychloride has process compact compared with " one acid and one bases " method, and " three wastes " are few, and easy to handle, environmental protection investments are few, and profitable is excellent
Point.Advanced zirconium oxychloride enterprise is all actively carrying out technological innovation, improves quality, energy-saving, reduces cost.Improve production
Operating environment.
Zirconium chloride can be also used for production technical grade sponge zirconium, China at this stage technical grade sponge zirconium annual output 2000
Ton or so, price is per ton at 23.5~24.5 ten thousand yuan.Due to train high-speed rail conducting wire especially 350 kilometers or more and amorphous close
Golden dosage increases, and market reserve strength is larger, and electricity consumption at this stage melts desilicated zirconia fluidizing chlorination and produces thick zirconium chloride, and electric smelting desilicated zirconia is sold
It 3.4 ten thousand yuan/ton of valence or so, no longer needs to purify with the zirconium chloride that existing method produces.Technical grade sponge zirconium can be directly produced, it is made
Direct cost reduces by 25% or so.
Produce technical grade sponge zirconium Cost comparisons
While producing zirconium chloride product, by-product silicon tetrachloride can also be obtained, the big added value of product profit is high, nothing
Solid waste discharge, belongs to clearer production technology, and silicon tetrachloride is also chiefly used in manufacturing organo-silicon compound, such as organic siliconresin, high temperature
Insulated paint, organic silicone oil and silicon rubber high purity silicon tetrachloride are manufacture polysilicon, high-purity silicon dioxide and inorganic silicon compound, light
Fine material, 3200 yuan of the silicon tetrachloride market price per ton, is the good raw material of fumed silica.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., is all included in the scope of protection of the present invention.
Claims (9)
1. the process that zircon sand chlorination prepares zirconium chloride by-produced tetrachlorosilane, which comprises the following steps:
(1) it crushes: zircon sand is subjected to dry grinding crushing；
(2) it dries: smashed zircon sand is dried；
(3) chlorination: drying zircon sand is added in boiling chloridizing furnace and CCl is added in furnace bottom4Carry out chlorination；
(4) it prepares: after reaction, in the ZrCl of fluidizing fluid-bed interior generation4And SiCl4Gas is carried out through dust-precipitator at the top of chlorination furnace
Gas solid separation collects the dust to get off and returns in furnace that the reaction was continued, and the gas after separation is through fused salt spray washing, then into four chlorinations
Solid ZrCl is obtained after the condensation of zirconium condenser4Incondensable gas is through gas-solid separating device, then chilled SiCl4Liquid spray,
SiCl4It is able to absorb, remaining gas produces after the neutralization of solid caustic soda tower through carbon dioxide adsorption, desorption, compression, condensation
Liquid CO 2；
(5) it exhaust emissions: is discharged after the scrubbed tower washing of tail gas.
2. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
Be characterized in that: the smashed granularity of zircon sand is -80-200 mesh.
3. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
It is characterized in that: when the reaction zone temperature of the boiling chloridizing furnace reaches 750-999 DEG C, zircon sand, boiling chloridizing furnace reaction is added
The reaction temperature of section is 750-999 DEG C.
4. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
Be characterized in that: the zircon sand drying temperature is 120-150 DEG C.
5. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
Be characterized in that: the charging rate that the zircon sand is added in chlorination furnace is 125-450kg/h.
6. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
Be characterized in that: the charging rate that the carbon tetrachloride is added in chlorination furnace is 108-388kg/h.
7. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
Be characterized in that: the fluidizing fluid-bed pressure is 0.0015-0.008MPa.
8. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
Be characterized in that: the chlorination furnace conversion zone internal diameter is 300-1300mm.
9. a kind of zircon sand chlorination according to claim 1 prepares the process of zirconium chloride by-produced tetrachlorosilane,
Be characterized in that: the fused salt is NaCl, KCl, MgCl2, ratio 1:1:0.2-0.5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357110A (en) * | 2019-07-31 | 2019-10-22 | 锦州中特电炉有限公司 | A method of silicon tetrachloride is produced with polysilicon slice 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 |
| CN115108559A (en) * | 2022-07-14 | 2022-09-27 | 才敏 | Process for producing silicon tetrachloride by comprehensively utilizing superfine silicon powder waste |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035446A1 (en) * | 2003-10-14 | 2005-04-21 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing aqueous solution of chlorination product of zirconium |
| CN102491394A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | Method for producing aluminum chloride by using fly ash |
| CN104058454A (en) * | 2014-07-08 | 2014-09-24 | 王卓 | Process method for producing zirconium tetrachloride through fluidizing chlorination method |
| CN104817110A (en) * | 2015-03-04 | 2015-08-05 | 郭志斌 | Method for producing high-purity zirconium oxychloride and co-producing silicon tetrachloride through zircon sand boiling chlorination method |
| CN105174307A (en) * | 2015-08-25 | 2015-12-23 | 王卓 | Method for cooling zirconium tetrachloride produced through fluidizing chlorination method |
| CN105502491A (en) * | 2015-12-31 | 2016-04-20 | 淄博广通化工有限责任公司 | Method for preparing ultrapure zirconium oxychloride and byproduct silicon tetrachloride through zircon sand boiling chlorination |
-
2019
- 2019-03-05 CN CN201910165719.3A patent/CN109734128A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035446A1 (en) * | 2003-10-14 | 2005-04-21 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing aqueous solution of chlorination product of zirconium |
| CN102491394A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | Method for producing aluminum chloride by using fly ash |
| CN104058454A (en) * | 2014-07-08 | 2014-09-24 | 王卓 | Process method for producing zirconium tetrachloride through fluidizing chlorination method |
| CN104817110A (en) * | 2015-03-04 | 2015-08-05 | 郭志斌 | Method for producing high-purity zirconium oxychloride and co-producing silicon tetrachloride through zircon sand boiling chlorination method |
| CN105174307A (en) * | 2015-08-25 | 2015-12-23 | 王卓 | Method for cooling zirconium tetrachloride produced through fluidizing chlorination method |
| CN105502491A (en) * | 2015-12-31 | 2016-04-20 | 淄博广通化工有限责任公司 | Method for preparing ultrapure zirconium oxychloride and byproduct silicon tetrachloride through zircon sand boiling chlorination |
Non-Patent Citations (1)
| Title |
|---|
| P. K. JENA等: "Mineral Processing and Extractive Metallurgy Review:An International Journal", 《MIN. PROC. EXT. MET. REVIEW》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357110A (en) * | 2019-07-31 | 2019-10-22 | 锦州中特电炉有限公司 | A method of silicon tetrachloride is produced with polysilicon slice silicon powder |
| 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 |
| 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 |
| CN115108559A (en) * | 2022-07-14 | 2022-09-27 | 才敏 | Process for producing silicon tetrachloride by comprehensively utilizing superfine silicon powder waste |
| CN115108559B (en) * | 2022-07-14 | 2023-11-14 | 才敏 | Process for producing silicon tetrachloride by comprehensively utilizing superfine silicon powder waste |
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