CN102234114B - Method for preparing white carbon black - Google Patents
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- CN102234114B CN102234114B CN 201010165198 CN201010165198A CN102234114B CN 102234114 B CN102234114 B CN 102234114B CN 201010165198 CN201010165198 CN 201010165198 CN 201010165198 A CN201010165198 A CN 201010165198A CN 102234114 B CN102234114 B CN 102234114B
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- carbon black
- white carbon
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- silicon tetrachloride
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Abstract
The invention discloses a method for preparing white carbon black. The method is characterized by comprising the following steps of: mixing silicon tetrachloride and ice to react, separating hydrogen chloride gas; heating and hydrolyzing residual solid substances, and then drying and smashing to obtain the white carbon black. The method for preparing the white carbon black disclosed by the invention is simple, is easy to operate and requires no high temperature or high pressure environment, and energy and water are saved in a processing process. Processing equipment is of a general type. Ice is adopted as one reaction raw material, the raw materials are available, and the cost is extremely low. The final product can be applied to industrial use, silicon tetrachloride waste seriously polluting the environment in the polycrystalline silicon industry is treated, and a chemical raw material, namely white carbon black with wide industrial use is generated; and the obtained white carbon black has high purity and is white, the whiteness is high, the application range is wide, and the waste material is really changed into things of value.
Description
Technical field
The present invention relates to a kind of Preparative Method of White Carbon Black.
Background technology
WHITE CARBON BLACK is good rubber reinforcing filler, also is used as the stopping composition or the white pigment of lubricant, insulating material and plastics, paper, paint, textiles etc.
The method of producing WHITE CARBON BLACK is generally the gas-phase silica method; This method is a kind of meticulous, the special amorphous powder body material that utilizes chlorosilane to make through the oxyhydrogen flame pyrohydrolysis; Average primary particle diameter is about 7～40 nanometers, and the particle diameter of its aggregate is between 200～300 nanometers, specific surface area 50～380 meters squared per gram; Product purity is high, and the content of silicon-dioxide is greater than 99.8%.According to its production technique, its raw materials for production are generally silicon tetrachloride, METHYL TRICHLORO SILANE etc.The facility investment of such technology is than higher, and environmental pollution is bigger.
In addition, another method of the production WHITE CARBON BLACK that the home and abroad is the most frequently used is the precipitator method, and this method production cost is lower.One of precipitator method are to utilize water glass and sulfuric acid reaction to generate silicic acid, and silicic acid generates silicon-dioxide and water through heating hydrolysis, obtains pure silicon-dioxide after the drying, i.e. WHITE CARBON BLACK.This method need consume a large amount of sulfuric acid and soda ash (being used for the neutralization reaction residuum), need consume a large amount of water when washing in addition, and water loss is big, and energy consumption is high, and production cost is higher.Two of the precipitator method are to adopt the above-mentioned sulfuric acid of salt acid substitution, and this method need consume a large amount of hydrochloric acid and soda ash (being used for the neutralization reaction residuum) equally, and water loss is big, and energy consumption is high, and cost is higher.Simultaneously, the maximum shortcoming of the WHITE CARBON BLACK that the precipitator method are produced is that soda acid control is bad in the product, and product is prone to jaundice, influences quality.And to solve problem such as jaundice, and needing to consume great amount of water resources, the purity of raw material causes product gas purity not high simultaneously, influences quality product.
At present, the photovoltaic industry uses the main flow technology of polysilicon to be the improvement Siemens Method, and the maximum by product in this method production process is a silicon tetrachloride.One ton of polysilicon of every production generates 8 tons of silicon tetrachloride as by-product at least according to best technology controlling and process.Silicon tetrachloride is the poisonous and harmful liquid with severe corrosive.Estimate that the YO in 2010 of China's polysilicon will reach 1.7 ten thousand tons, will produce ten thousand tons of silicon tetrachloride by products of 1.7 * 8=13.6 when the time comes every year at least.Silicon tetrachloride has the intense stimulus effect to the eyes and the upper respiratory tract.High density can cause the corneal opacity, respiratory inflammation, even wet lung.Can cause tissue necrosis after the skin exposure.It is acute toxicity: LC508000ppm that toxicological information and environmental behaviour detect silicon tetrachloride, 4 hours (rat suction).Hazard property: be heated or meet the water decomposition heat release, emit deleterious corrosive fume, and when water exists, can corrode most metals.
Therefore, the reasonable processing of polysilicon industry silicon tetrachloride as by-product not only is related to environment, HUMAN HEALTH, also is related to the development of polysilicon industry.The silicon tetrachloride pollution problem that polysilicon production process produced has become the bottleneck problem of restriction polysilicon industry development.
Regrettably, the effective ways of industry a large amount of silicon tetrachloride as by-product of also not having at present to produce in a kind of energy-saving and environmental protection, the simple process polysilicon production process.
Summary of the invention
The objective of the invention is in order to solve the problems of the prior art, providing a kind of is the method for raw material production WHITE CARBON BLACK with the silicon tetrachloride as by-product in the polysilicon production process.
For realizing above purpose, the present invention realizes through following technical scheme:
Preparative Method of White Carbon Black is characterized in that, makes silicon tetrachloride and ice hybrid reaction, separating hydrogen chloride gas; Remaining solid material heating hydrolysis, and then dry, pulverizing obtain WHITE CARBON BLACK.
The reaction equation of silicon tetrachloride and water is:
SiCl
4+4H
2O＝H
4SiO
4+4HCl
Or SiCl
4+ 3H
2O=H
2SiO
3+ 4HCl
Silicon tetrachloride and water reaction are thermopositive reaction, and abnormal reaction is fierce.The heat that is produced in the reaction process in reaction process, emit heat, and the boiling point of silicon tetrachloride is 57.6 ℃, if can't in time be eliminated; The reaction environment temperature will make silicon tetrachloride be evaporated to gaseous state after raising, and the gasiform silicon tetrachloride mixes with hydrogen chloride gas that reacts generation and water vapor etc., generates acid mist; Both be difficult to separate, and can in transport pipe, have reduced and crystallization by Yin Wendu again, blocked pipeline; Make the processing of silicon tetrachloride be difficult to continue, can't obtain any single separated product.Among the present invention; Adopt ice as reaction raw materials; Ice can absorb heat in reaction process, make the heat that produces in the reaction process in time to be absorbed, and too fastly too highly causes above-mentioned multiple material to mix and can't isolating phenomenon thereby can avoid temperature of charge to raise.Because adopt ice in time to absorb heat, the temperature of reaction mixture can be avoided being elevated to more than the boiling point of silicon tetrachloride, so the inventive method can make silicon tetrachloride under controllable state, continue hydrolysis and effectively separate.And hydrogenchloride is insoluble to solid ice.In reaction process, silicon tetrachloride consumes most ice and water.So hydrogenchloride seldom can be water-soluble, therefore and the hydrochloric acid that generates seldom, hydrogenchloride is also very little to the interference of reaction.
The H that reaction generates
4SiO
4Decomposition reaction takes place, H in heating
4SiO
4=H
2SiO
3+ H
2O
H
2SiO
3Heating is further decomposed, H
2SiO
3=SiO
2+ H
2O
Preferably, remaining solid material at first water cleans out hydrochloric acid wherein, and then heating hydrolysis, and dry, pulverizing obtains WHITE CARBON BLACK.
Preferably, after the flushing of remaining solid material water, in use demineralizing acid material and its reaction, behind the adjusting pH value, water flushing back reheat hydrolysis, dry, pulverizing obtains WHITE CARBON BLACK.
Preferably, described adjusting pH value is adjusted to 5～8 with the pH value.
Remove hydrochloric acid, can increase the purity of the WHITE CARBON BLACK of generation, avoid cl ions to influence quality product.
Use can and generate water-soluble salt and the material and the hydrochloric acid reaction of water or gas with hydrochloric acid reaction, and water-soluble salt of generation is removed after the water flushing, removes behind the gaseous volatilization of generation.Preferably, said demineralizing acid material is selected from one or more in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate, salt of wormwood and the saleratus.
Preferably, adopt dry, the pulverizing of rotary flashing drying method.The kiln temperature is 200 ℃～550 ℃.
Preferably, in the rotary flashing drying method, the temperature of kiln inlet air is 250 ℃～600 ℃.More preferably 400 ℃～550 ℃
Preferably, the kiln outlet air temperature is 60～90 ℃.
When rotary flashing drying method drying, pulverizing, the warm air tangent line gets into the moisture eliminator bottom, the strong rotation wind field of formation under whisking appliance drives; Reacted remaining solid thing gets in the moisture eliminator, and under the strong effect of high speed rotating stirring rake, material is impacted, obtain disperseing under the effect of friction and shearing force; Lumpy material is pulverized rapidly, fully contacts with warm air, is heated, the dry material after dry, the dehydration rises with hot gas flow; Collect product by cyclonic separator; Fly-ash separator recovery dust does not parch or oversize material is got rid of to wall by centrifugal action, falls the bottom drying and crushing again.
Preferably, silicon tetrachloride mixes the back at-10 ℃～100 ℃ scope internal reactions with ice.
More preferably be that silicon tetrachloride mixes the back at-10 ℃～55 ℃ scope internal reactions with ice.Through control reaction process temperature, can more effectively reduce silicon tetrachloride and evaporation of water, avoid interference reaction continue carry out.
Preferably, the volume ratio of said silicon tetrachloride and ice is 1: 0.05～2.0.
Preferably, in reaction process, the gas phase temperature that all the time reaction product is produced remains on-10 ℃～55 ℃, stirs, treat its complete reaction after, remove hydrogen chloride gas and hydrochloric acid.Temperature of reaction is controlled at-10 ℃～55 ℃, can further reduces the interference of silicon tetrachloride and evaporation of water reaction.
In reaction process, separating hydrogen chloride gas.Influence the processing of silicon tetrachloride for reducing the water-soluble generation hydrochloric acid of hydrogen chloride gas that produces in the reaction process, can in reaction process, be about to hydrogen chloride gas and remove, reduce the interference of hydrogen chloride gas reaction.For a small amount of hydrogenchloride that in reaction process, can't remove fully, can, reaction adopt cleaning and neutralization method to remove after accomplishing.The higher hydrogen chloride gas of resultants in reaction process purity through volume compression as high-end industrial chemicals; The hydrochloric acid of remaining water-soluble generation is used for industrial use, as chemical feedstocks; Produce inorganic salt such as calcium chloride, bariumchloride.
Even the water-soluble generation hydrochloric acid of small portion HCl is arranged, also removes easily.
Preferably, in silicon tetrachloride and ice reaction process, stir solid matter is smashed, make its further sufficient reacting, isolate more hydrogen chloride gas.
Because silicon tetrachloride and reaction product possibly lumpd in reaction process.For increasing separating effect and improving utilization ratio of raw materials.Beat the block that pure last stage reaction back generates through stirring in reaction kettle, the part hydrogen chloride gas that is wrapped up in the separation block with separate the last stage once more and react incomplete part material.This step be because: in initial reaction process, water and silicon tetrachloride can evaporate a part unavoidably to be mixed with hydrogenchloride, and is wrapped in the packaged thing that reacts generation.Processings of lowering the temperature once more after initial reaction is accomplished, after the cooling, silicon tetrachloride is a liquid state with water vapor liquefaction, under agitation, most hydrogen chloride gas can be separated.Stirring can also make silicon tetrachloride fully contact with ice, helps unreacted raw material and continues reaction.Improve the reaction raw materials utilization ratio.Can improve the comprehensive reutilization rate of silicon tetrachloride.
Preparative Method of White Carbon Black among the present invention, simple, operation need not high temperature, hyperbaric environment easily, energy-conservation, the water saving of treating processes.Treatment facility is a universal equipment.And adopt ice as one of reaction raw materials, and raw material sources are extensive, provide easily, and cost is extremely low.Final product can be used for industrial use; Both solved the serious silicon tetrachloride waste treatment of polysilicon industry environmental pollution, and generated chemical feedstocks WHITE CARBON BLACK again, and the WHITE CARBON BLACK purity that obtains is high with extensive industrial use; Color is a white; Whiteness is high, applied range, and real the realization turned waste into wealth.
Embodiment
Below in conjunction with embodiment the present invention is carried out detailed description:
Embodiment 1
Preparative Method of White Carbon Black, making volume ratio is that 1: 0.2 silicon tetrachloride mixes with ice, stirs the mixture, and stops stirring after the reaction beginning.Collect the hydrogen chloride gas that produces in the reaction process.In the reaction process, control silicon tetrachloride and ice are at-10 ℃～55 ℃ scope internal reactions.Making silicon tetrachloride and ice is in order to prevent that silicon tetrachloride volatilization post crystallization from stopping up the reaction vessel pipeline at-10 ℃～55 ℃ scope internal reactions, and its actual temp value can be confirmed according to actual production.After reaction is accomplished, the temperature of reaction product is reduced to 0 ℃, stirs.Question response stops fully.
Choose silicon tetrachloride and the suitable volume ratio of ice, the heat that reaction is produced is iced fast to be absorbed, and the water that ice heat absorption back thawing produces can be used as one of reaction raw materials and participates in reaction.Can also use heat sink in addition, the temperature of reaction mixture is remained in the suitable scope.
After reaction stops, making water wash remaining solid matter five times, and then use the hydrochloric acid in the sodium hydroxide neutralization reaction product, its pH value is adjusted into 6, re-use the water flushing, sodium-chlor is water-soluble by eccysis.Dry, the pulverizing of surplus materials use Rotatingandflashstreamingdrier, the temperature of kiln inlet air is 300 ℃, and the kiln temperature is 250 ℃, and the material after collection drying, the pulverizing obtains WHITE CARBON BLACK.
Embodiment 2
The treatment process of silicon tetrachloride, making volume ratio is that 1: 0.8 silicon tetrachloride mixes with ice, stirs the mixture, and stops stirring after the reaction beginning.The hydrogen chloride gas that produces in the reaction process is collected immediately.In the reaction process, control silicon tetrachloride and ice are at-10 ℃～55 ℃ scope internal reactions.In the reaction process, solid phase and the gas phase temperature with reactant remains in-10～55 ℃ of scopes all the time.After reaction is accomplished, the temperature of reaction product is reduced to 10 ℃, stirs.Question response stops fully.
Choose silicon tetrachloride and the suitable volume ratio of ice, the heat that reaction is produced is iced fast to be absorbed, and the water that ice heat absorption back thawing produces can be used as one of reaction raw materials and participates in reaction.Can also use heat sink in addition, the temperature of reaction mixture is remained in the suitable scope.
After reaction stops, making water wash remaining solid matter, and then use yellow soda ash to remove the hydrochloric acid in the reaction product, solid matter pH value is adjusted into 7, re-use the water flushing after reaction is accomplished, sodium-chlor is water-soluble by eccysis with other salt.Dry, the pulverizing of surplus materials use Rotatingandflashstreamingdrier, the temperature of kiln inlet air is 350 ℃, and the kiln temperature is 300 ℃, and the kiln outlet air temperature is 90 ℃, and the material after collection drying, the pulverizing obtains WHITE CARBON BLACK.
Embodiment 3
The treatment process of silicon tetrachloride, making volume ratio is that 1: 0.3 silicon tetrachloride mixes with ice, stirs the mixture, and stops stirring after the reaction beginning.The hydrogen chloride gas that produces in the reaction process is collected immediately.In the reaction process, control silicon tetrachloride and ice are at-10 ℃～55 ℃ scope internal reactions.After reaction is accomplished, the temperature of reaction product is reduced to 6 ℃.Stir, question response stops fully.
After reaction stops, making water wash remaining solid matter, and then use sodium hydroxide to remove the hydrochloric acid in the reaction product, solid matter pH value is adjusted into 7, re-use the water flushing after reaction is accomplished, water-soluble sodium-chlor and alkali are water-soluble by eccysis.Dry, the pulverizing of surplus materials use Rotatingandflashstreamingdrier, the temperature of kiln inlet air is 450 ℃, and the kiln temperature is 400 ℃, and the kiln outlet air temperature is 80 ℃, and the material after collection drying, the pulverizing obtains WHITE CARBON BLACK.
Embodiment 4
The treatment process of silicon tetrachloride, making volume ratio is that 1: 0.5 silicon tetrachloride mixes with ice, stirs the mixture, and stops stirring after the reaction beginning.The hydrogen chloride gas that produces in the reaction process is collected immediately.In the reaction process, control silicon tetrachloride and ice are at-10 ℃～55 ℃ scope internal reactions.After reaction is accomplished, the temperature of reaction product is reduced to 9 ℃.Stir, question response stops fully.
After reaction stops, making water wash remaining solid matter, and then use sodium hydroxide to remove the hydrochloric acid in the reaction product, solid matter pH value is adjusted into 7, re-use the water flushing, water-soluble sodium-chlor and alkali are water-soluble by eccysis.Dry, the pulverizing of surplus materials use Rotatingandflashstreamingdrier, the temperature of kiln inlet air is 500 ℃, and the kiln temperature is 460 ℃, and the kiln outlet air temperature is 85 ℃, and the material after collection drying, the pulverizing obtains WHITE CARBON BLACK.
Embodiment 5
The treatment process of silicon tetrachloride, making volume ratio is that 1: 0.4 silicon tetrachloride mixes with ice, stirs the mixture, and stops stirring after the reaction beginning.The hydrogen chloride gas that produces in the reaction process is collected immediately.In the reaction process, control silicon tetrachloride and ice are at-10 ℃～55 ℃ scope internal reactions.After reaction is accomplished, the temperature of reaction product is reduced to 2 ℃.Stir, question response stops fully.
After reaction stops, making water wash remaining solid matter, and then use sodium hydroxide to remove the hydrochloric acid in the reaction product, solid matter pH value is adjusted into 7, re-use the water flushing, water-soluble sodium-chlor and alkali are water-soluble by eccysis.Dry, the pulverizing of surplus materials use Rotatingandflashstreamingdrier, the temperature of kiln inlet air is 600 ℃, and the kiln temperature is 540 ℃, and the kiln outlet air temperature is 75 ℃, and the material after collection drying, the pulverizing obtains WHITE CARBON BLACK.
Embodiment 6
The treatment process of silicon tetrachloride, making volume ratio is that 1: 0.65 silicon tetrachloride mixes with ice, stirs the mixture, and stops stirring after the reaction beginning.The hydrogen chloride gas that produces in the reaction process is collected immediately.In the reaction process, control silicon tetrachloride and ice are at-10 ℃～55 ℃ scope internal reactions.After reaction is accomplished, the temperature of reaction product is reduced to 7 ℃.Stir, question response stops fully.
After reaction stops, making water wash remaining solid matter, and then use sodium hydroxide to remove the hydrochloric acid in the reaction product, solid matter pH value is adjusted into 7, re-use the water flushing, water-soluble sodium-chlor and alkali are water-soluble by eccysis.Dry, the pulverizing of surplus materials use Rotatingandflashstreamingdrier, the temperature of kiln inlet air is 500 ℃, and the kiln temperature is 430 ℃, and the kiln outlet air temperature is 60 ℃, and the material after collection drying, the pulverizing obtains WHITE CARBON BLACK.
The performance index of the WHITE CARBON BLACK for preparing among the above embodiment are following:
| Embodiment | Primary particle diameter (um) | Specific surface area (m 2/g) | PH value (5% suspension-s) | SiO 2Content (%) | Whiteness |
| 1 | Less than 10 | 165.3 | ?6-7 | 93 | 94 |
| 2 | Less than 8 | 176.8 | ?6-7.5 | 94.53 | 95 |
| 3 | Less than 5 | 176.8 | ?6-7.5 | 94.53 | 96 |
| 5 | Less than 2 | 225.4 | ?6-8 | 96 | 96 |
| 6 | Less than 2 | 218.7 | ?6-8 | 95 | 95 |
Embodiment among the present invention only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other substituting of being equal in fact that those skilled in that art can expect are all in protection domain of the present invention.
Claims (9)
1. Preparative Method of White Carbon Black is characterized in that, makes silicon tetrachloride and ice hybrid reaction, separating hydrogen chloride gas; Remaining solid material heating hydrolysis, and then dry, pulverizing obtain WHITE CARBON BLACK; Silicon tetrachloride mixes the back at-10 ℃～55 ℃ scope internal reactions with ice; The volume ratio of said silicon tetrachloride and ice is 1:0.05～2.0.
2. Preparative Method of White Carbon Black according to claim 1 is characterized in that, remaining solid material at first water cleans out hydrochloric acid wherein, and then heating hydrolysis, and dry, pulverizing obtains WHITE CARBON BLACK.
3. Preparative Method of White Carbon Black according to claim 2 is characterized in that, remaining solid material water re-uses demineralizing acid material and its reaction after washing, after the adjusting pH value, and water flushing back reheat hydrolysis, dry, pulverizing obtains WHITE CARBON BLACK.
4. Preparative Method of White Carbon Black according to claim 3 is characterized in that, described adjusting pH value is adjusted to 5～8 with the pH value.
5. Preparative Method of White Carbon Black according to claim 3 is characterized in that, said demineralizing acid material is selected from one or more in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate, salt of wormwood and the saleratus.
6. according to the described Preparative Method of White Carbon Black of the arbitrary claim of claim 1～5, it is characterized in that, adopt dry, the pulverizing of rotary flashing drying method.
7. Preparative Method of White Carbon Black according to claim 6 is characterized in that, in the rotary flashing drying method, the temperature of kiln inlet air is 250 ℃～600 ℃.
8. Preparative Method of White Carbon Black according to claim 7 is characterized in that, the kiln outlet air temperature is 60 ℃～90 ℃.
9. Preparative Method of White Carbon Black according to claim 1 is characterized in that, in reaction process, the gas phase temperature that all the time reaction product is produced remains on 0 ℃～55 ℃, stirs, treat its complete reaction after, remove hydrogen chloride gas and hydrochloric acid.
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| CN 201010165198 CN102234114B (en) | 2010-04-29 | 2010-04-29 | Method for preparing white carbon black |
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| CN102234114B true CN102234114B (en) | 2012-12-19 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1376488A1 (en) * | 1986-07-14 | 1994-11-30 | Институт Химии Силикатов Им.И.В.Гребенщикова | Process for manufacture of powderous synthetic silicon dioxide |
| CN101659416A (en) * | 2009-10-12 | 2010-03-03 | 魏丽芳 | Method for preparing white carbon black co-product calcium chloride |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1376488A1 (en) * | 1986-07-14 | 1994-11-30 | Институт Химии Силикатов Им.И.В.Гребенщикова | Process for manufacture of powderous synthetic silicon dioxide |
| CN101659416A (en) * | 2009-10-12 | 2010-03-03 | 魏丽芳 | Method for preparing white carbon black co-product calcium chloride |
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