CN102941014B - Method and device for eliminating chlorine generated in vapor phase method oxide production process - Google Patents
Method and device for eliminating chlorine generated in vapor phase method oxide production process Download PDFInfo
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- CN102941014B CN102941014B CN201210423377.9A CN201210423377A CN102941014B CN 102941014 B CN102941014 B CN 102941014B CN 201210423377 A CN201210423377 A CN 201210423377A CN 102941014 B CN102941014 B CN 102941014B
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Abstract
The invention discloses a method for eliminating chlorine generated in vapor phase method oxide production process and a device thereof. According to the invention, by connecting a hydrogenation dechlorination unit on a gas conveying pipeline through which chlorine-containing tail gas discharged by a separator and a deacidification furnace leads to a tail gas treatment system to emlinate the chlorine in the tail gas; the temperature of the tail gas discharged by the separator and the deacidification furnace is lower than 400 DEG C, at the moment hydrogen is introduced into to react with chlorine to generate hydrogen chloride; in such an environment, hydrogen chloride is no longer able to react with oxygen to generate chlorine, thus good dechlorination effect can be achieved.
Description
Technical field
The invention belongs to vapor phase method oxide production field, particularly a kind of method and device of eliminating chlorine in vapor phase method oxide production process.
Background technology
Vapor phase method oxide as fumed silica, aluminium oxide, titanium oxide etc. be with presoma chloride, in oxyhydrogen flame, to carry out pyrohydrolysis polycondensation reaction and the superfine powder that obtains.Its reaction mechanism is as follows:
Wherein M is Si, Al, Ti etc.
Adopt gas-phase process to produce oxide, substantially all comprise reaction (hydrogen and oxygen reaction, presoma hydrolysis condensation reaction), particle is assembled the operations such as (primary partical Collision coagulation becomes aggregation, agglomerate, is convenient to separation and collection), gas solid separation (oxide particle and gas separated), depickling (removing the hydrogen chloride that is adsorbed on particle surface), particle collection, vent gas treatment.About vapor phase method, produce the patent many (as CN200610035301.3, CN98114270.2, CN200610033695.9, CN200610033694.4 etc.) of the technique of oxide.
In vapor phase method oxide production process, for guaranteeing to react completely and obtain needed high-temperature field, hydrogen and oxygen (air) are all generally higher than theoretical amount of calculation, therefore, in vapor phase method oxide production technology, have following feature:
1) reaction temperature is high, 1000 ~ 2000 ℃ of the reaction zone temperatures being formed by hydrogen and oxygen combustion, and in the operations such as gathering and depickling, temperature is also higher than 400 ℃;
2) produce byproduct hydrogen chloride (HCl);
3) in system, contain aerobic.
In above-mentioned environment, under the existence of high temperature and oxygen, easily there is redox reaction in HCl, generates chlorine G&W, reacts suc as formula (3):
The generation of chlorine, brings very large trouble for producing.Usual way is to adopt alkali lye (as NaOH, calcium hydroxide etc.) to carry out washing absorption to it, thereby generates hypochlorite (as calcium hypochlorite or clorox).Yet hypochlorite is unstable, under acid condition, easily discharge again chlorine, therefore do not reach the object of eliminating chlorine.
In CN 200610035301.3, mentioned hydrogenation plant has been set on collector, in collector, added a certain amount of hydrogen, allowed hydrogen and chlorine reaction generate hydrogen chloride, thereby reached the object of eliminating chlorine.Yet by description and formula (3) above, known, hydrogen chloride at high temperature again easily and oxygen reaction, regenerates chlorine, and dechlorination effect is undesirable.So find the method for the chlorine in a kind of effective elimination vapor phase method oxide production process to be necessary very much.
In traditional technique, have at collector and hydrogenation plant is set as CN200610035301.3, CN102120580A etc., yet from practical application, the temperature in reactor is 1000-2000 ℃, enters after collector, even in collector rear end, temperature is also higher than 400 ℃.By analysis above, can be known, pass into after hydrogen, although chlorine can generate hydrogen chloride with hydrogen reaction, yet at high temperature, hydrogen chloride will react with oxygen again, regenerate chlorine.In addition, even chlorine has been eliminated at collector, yet enter after deacidification furnace, still need through the high-temperature field higher than 400 ℃, have again partial oxidation hydrogen and oxygen reaction to generate chlorine, therefore this technique is for dechlorination DeGrain.
Summary of the invention
The object of the invention is to overcome existing deficiency, a kind of method and device of eliminating chlorine in vapor phase method oxide production process is provided.
The technical solution used in the present invention is:
A kind of method of eliminating chlorine in vapor phase method oxide production process, comprise the following steps: after the chloride exhaust temperature producing in vapor phase method oxide production process is lower than 400 ℃, pass into hydrogen catalysis itself and chlorine reaction and generate hydrogen chloride, then through exhaust treatment system, process discharge.
Preferably, before exhaust emissions, eliminate hydrogen excessive in tail gas.
A kind of device of eliminating chlorine in vapor phase method oxide production process, comprise reactor (1), collector (2), separator (3), deacidification furnace (4) and exhaust treatment system (6), reactant mixture is from reactor enters aggregator aggregates, enter separator, isolated solids enter deacidification furnace depickling, the chloride tail gas that separator and deacidification furnace are discharged enters exhaust treatment system and processes discharge, it is characterized in that: on the gas transmission pipeline between separator and/or deacidification furnace and exhaust treatment system, be connected with hydrogenation chlorine remover (5), hydrogenation chlorine remover is connected in series with exhaust temperature in gas transmission pipeline and higher than 400 ℃, does not locate.
Above-mentioned hydrogenation chlorine remover is the pipeline configuration connecting with flange, offers at least one inside puff prot on this pipeline, and puff prot outside is connected to sources of hydrogen.
Preferably, the pipeline of hydrogenation chlorine remover is provided with the ultraviolet position of transmissive, and this position is outside equipped with ultraviolet source.Or, in the pipeline of hydrogenation chlorine remover, be provided with catalysis H
2and Cl
2the catalyst of reaction.
Preferably, at exhaust treatment system to being provided with between exhaust port for eliminating the dehydrogenation device of tail gas excess hydrogen.
The invention has the beneficial effects as follows:
The chloride tail gas that the present invention discharges with deacidification furnace at separator leads on the gas transmission pipeline of exhaust treatment system and is connected hydrogenation chlorine remover, because from the exhaust temperature of separator and deacidification furnace discharge lower than 400 ℃, now pass into hydrogen, generate hydrogen chloride with chlorine reaction, under this environment, hydrogen chloride will no longer generate chlorine with oxygen reaction, thereby can obtain good dechlorination effect.
Accompanying drawing explanation
Fig. 1 is method and the device schematic diagram of eliminating chlorine in vapor phase method oxide production process;
Fig. 2 is hydrogenation chlorine remover schematic diagram.
The specific embodiment
A kind of method of eliminating chlorine in vapor phase method oxide production process, comprise the following steps: after the chloride exhaust temperature producing in vapor phase method oxide production process is lower than 400 ℃, pass into hydrogen catalysis itself and chlorine reaction and generate hydrogen chloride, then through exhaust treatment system, process discharge.
Preferably, before exhaust emissions, eliminate hydrogen excessive in tail gas.
A kind of device of eliminating chlorine in vapor phase method oxide production process, comprise reactor (1), collector (2), separator (3), deacidification furnace (4) and exhaust treatment system (6), reactant mixture is from reactor enters aggregator aggregates, enter separator, isolated solids enter deacidification furnace depickling, the chloride tail gas that separator and deacidification furnace are discharged enters exhaust treatment system and processes discharge, it is characterized in that: on the gas transmission pipeline between separator and/or deacidification furnace and exhaust treatment system, be connected with hydrogenation chlorine remover (5), hydrogenation chlorine remover is connected in series with exhaust temperature in gas transmission pipeline and higher than 400 ℃, does not locate.
Above-mentioned hydrogenation chlorine remover is the pipeline configuration connecting with flange, offers at least one inside puff prot on this pipeline, and puff prot outside is connected to sources of hydrogen.
Preferably, the pipeline of hydrogenation chlorine remover is provided with the ultraviolet position of transmissive, and this position is outside equipped with ultraviolet source.Or, in the pipeline of hydrogenation chlorine remover, be provided with catalysis H
2and Cl
2the catalyst of reaction.
Preferably, at exhaust treatment system to being provided with between exhaust port for eliminating the dehydrogenation device of tail gas excess hydrogen.
Gas solid separation can be by methods such as conventional cyclonic separation, sedimentation separations, and the present invention adopts cyclonic separation.
For impelling chlorine reaction in the hydrogen that adds and tail gas, can on the pipeline of hydrogenation chlorine remover, offer the ultraviolet position of transmissive, outside this position, ultraviolet source is set, by ultraviolet irradiation, promote H
2and Cl
2reaction; Certainly, also catalysis H can be set in the pipeline of hydrogenation chlorine remover
2and Cl
2the catalyst of reaction, its reaction of catalysis.In this specific embodiment, adopt the method for ultraviolet irradiation.
Hydrogenation chlorine remover, except being connected on the position of Fig. 1 sign, certainly, also can be arranged at A or the B place of Fig. 1.If be arranged at A place, the tail gas of simultaneously discharging at deacidification furnace is provided with catalyst in the pipeline of exhaust treatment system, and the excess hydrogen that hydrogenation chlorine remover passes into is still enough to guarantee that the chlorine that deacidification furnace is discharged is eliminated below; If hydrogenation chlorine remover is arranged at B place, method and principle are the same.
For the potential safety hazard that prevents from having brought when dechlorination has passed into excessive hydrogen at exhaust emissions in hydrotreater, before exhaust emissions, need to eliminate excessive hydrogen in tail gas, so, the present invention, is equipped with catalyst or adsorbent or is adopted combustion method to eliminate the hydrogen in tail gas to being provided with dehydrogenation device between exhaust port at exhaust treatment system in dehydrogenation device.In this specific embodiment, adopt and be heated to the cupric oxide of 150 ~ 300 ℃ and the hydrogen reaction in tail gas.
In the deacidification of deacidification furnace, for better removing the sour gas that is adsorbed on particle surface, except deacidification furnace is heated, also can pass into depickling assist medium as steam, inert gas, alkaline gas etc.Preferably pass into the alkaline gas such as the inert gases such as nitrogen or ammonia, thereby avoid producing extra chlorine in case locking system is brought excessive oxygen into.
Below in conjunction with accompanying drawing and following examples, the present invention is specifically described, but is not limited to this.
With reference to Fig. 1, method and the device of eliminating chlorine in vapor phase method oxide production process are: after former material precursor chloride and hydrogen, oxygen mix are even, enter reactor 1, carry out high-temperature hydrolysis; The gases such as the oxide particle that reaction generates and HCl enter collector 2; Gas-solid mixture after assembling enters separator 3; After separator separation, solids flow downward and enter deacidification furnace 4, and gas is discharged from separator top; After deacidification furnace depickling, be adsorbed on the hydrogen chloride of solid particle surfaces and chlorine by desorption, from deacidification furnace top, to discharge, the particle after depickling is delivered to feed bin 7, carries out the packing of product; Tail gas in separator and deacidification furnace discharge arranges a hydrogenation chlorine remover 5 on the gas transmission pipeline of exhaust treatment system 6, the exhaust temperature of herein discharging is not higher than 400 ℃, under ultraviolet lighting, the chlorine that separator and deacidification furnace are discharged in tail gas reacts at this with the hydrogen adding, and generates hydrogen chloride; Then tail gas enters exhaust treatment system and processes; After processing, enter dehydrogenation device 8, eliminate after hydrogen excessive in tail gas emission.
With reference to Fig. 2, hydrogenation chlorine remover is the pipeline configuration connecting with flange 9, offers at least one inside puff prot 10 on this pipeline, the outside sources of hydrogen that connects of puff prot, and hydrogen sprays into pipe interior by this spout; The pipeline of hydrogenation chlorine remover is provided with the ultraviolet position 11 of transmissive, and this position is outside equipped with ultraviolet source 12, and ultraviolet light sees through this position and irradiates pipe interior, and under ultraviolet lighting, chlorine reacts at this with hydrogen, generates hydrogen chloride.
Claims (7)
1. a method of eliminating chlorine in vapor phase method oxide production process, it is characterized in that: after the chloride exhaust temperature producing in vapor phase method oxide production process is lower than 400 ℃, pass into hydrogen catalysis itself and chlorine reaction and generate hydrogen chloride, then through exhaust treatment system, process discharge.
2. a kind of method of eliminating chlorine in vapor phase method oxide production process according to claim 1, is characterized in that: before exhaust emissions, eliminate hydrogen excessive in tail gas.
3. a device of eliminating chlorine in vapor phase method oxide production process, comprise reactor (1), collector (2), separator (3), deacidification furnace (4) and exhaust treatment system (6), reactant mixture is from reactor enters aggregator aggregates, enter separator, isolated solids enter deacidification furnace depickling, the chloride tail gas that separator and deacidification furnace are discharged enters exhaust treatment system and processes discharge, it is characterized in that: on the gas transmission pipeline between separator and/or deacidification furnace and exhaust treatment system, be connected with hydrogenation chlorine remover (5), hydrogenation chlorine remover is connected in series with exhaust temperature in gas transmission pipeline and higher than 400 ℃, does not locate.
4. device according to claim 3, is characterized in that: described hydrogenation chlorine remover, for the pipeline configuration with flange connection, offers at least one inside puff prot on this pipeline, puff prot outside is connected to sources of hydrogen.
5. device according to claim 4, is characterized in that: the pipeline of described hydrogenation chlorine remover is provided with the ultraviolet position of transmissive, and this position is outside equipped with ultraviolet source.
6. device according to claim 4, is characterized in that: in the pipeline of described hydrogenation chlorine remover, be provided with catalysis H
2and Cl
2the catalyst of reaction.
7. device according to claim 3, is characterized in that: at exhaust treatment system to being provided with between exhaust port for eliminating the dehydrogenation device of tail gas excess hydrogen.
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|---|---|---|---|
| CN201210423377.9A CN102941014B (en) | 2012-10-30 | 2012-10-30 | Method and device for eliminating chlorine generated in vapor phase method oxide production process |
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| CN201210423377.9A CN102941014B (en) | 2012-10-30 | 2012-10-30 | Method and device for eliminating chlorine generated in vapor phase method oxide production process |
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| CN107963634A (en) * | 2017-12-12 | 2018-04-27 | 宜昌汇富硅材料有限公司 | Collector for fume colloidal silica production |
| CN110371990A (en) * | 2019-07-02 | 2019-10-25 | 新疆晶硕新材料有限公司 | A kind of hydrolysis furnace producing fumed silica and system |
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| US7265254B2 (en) * | 2001-07-30 | 2007-09-04 | Taiheiyo Cement Corporation | Waste processing method, waste processing system, integrated waste processing method, and integrated waste processing system |
| CN100369811C (en) * | 2006-04-29 | 2008-02-20 | 广州吉必时科技实业有限公司 | Comprehensive utilization method of by-product for poycrystalline silicon production process |
| CN102120580B (en) * | 2011-03-10 | 2013-01-02 | 上海竟茨环保科技有限公司 | Pipeline hydrogenation device used for producing gaseous phase method silicon dioxide |
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Effective date of registration: 20191031 Address after: Nanxiang three road, Science City high tech Industrial Development Zone, Guangzhou city of Guangdong Province, No. 15 510663 Patentee after: Guangzhou GBS High-Tech & Industry Co., Ltd. Address before: Three road 510663 Guangdong city of Guangzhou province Luogang District Science City Nanxiang No. 15 Co-patentee before: Lianyungang Jibi Shenggui Materials Co.,Ltd. Patentee before: Guangzhou GBS High-Tech & Industry Co., Ltd. |
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Effective date of registration: 20200402 Address after: 443007 66-2, Lanting Avenue, Lanting District, Yichang City, Hubei Province Patentee after: YICHANG HUIFU SILICON MATERIAL Co.,Ltd. Address before: Nanxiang three road, Science City high tech Industrial Development Zone, Guangzhou city of Guangdong Province, No. 15 510663 Patentee before: GUANGZHOU GBS HIGH-TECH & INDUSTRY Co.,Ltd. |
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Address after: 66-2 No. 443007 Hubei city of Yichang province located in Xiaoting District Road Patentee after: Hubei HuiFu nano materials Co., Ltd Address before: 443007 66-2, Lanting Avenue, Lanting District, Yichang City, Hubei Province Patentee before: YICHANG HUIFU SILICON MATERIAL Co.,Ltd. |