CN101774813A - Method for preparing small-sized silicon carbide or silicon nitride nano particles from waste plastics - Google Patents
Method for preparing small-sized silicon carbide or silicon nitride nano particles from waste plastics Download PDFInfo
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Abstract
The invention relates to a method for preparing small-sized silicon carbide or silicon nitride nano particles from waste plastics. The method comprises the following steps: carbonizing cleaned waste plastics in the argon gas atmosphere to obtain the carbonized product; soaking silicon oxide in a ferric nitrate solution, heating to 50-80 DEG C until the solvent is evaporated to dryness, grinding and mixing with the carbonized product to obtain the mixture, making the mixture be subject to the carbothermic reduction reaction in the argon gas or nitrogen gas atmosphere, then natural cooling to the room temperature to obtain the primary reaction product; calcining at 600-800 DEG C in the air to remove the unreacted carbon; soaking the reaction product in the mixed acid of hydrochloric acid and hydrofluoric acid to remove the ferric nitrate and the silicon oxide, water washing, filtering and drying to finally obtain the silicon carbide or silicon nitride nano material. The invention has the advantages of simple device, safe operation, simple process flow, low manufacturing cost, short production cycle and high product purity.
Description
Technical field
The invention belongs to a kind of non-oxidized substance nano material and preparation method thereof, relate in particular to a kind of preparation method who utilizes waste plastic for synthetic small-sized silicon carbide of raw material or silicon nitride nano particles.
Background technology
Waste plastic, i.e. high molecular polymer goods such as the derelict solid waste in use back such as plastics bag, Plastic Bottle such as polystyrene, polypropylene, polyvinyl chloride.Because these plastic refuses are difficult to degraded, not only contaminated soil and water source bring threat for human health and animal survival, but also can cause visual pollution, influence the style and features of city and physical environment.How utilizing these wastes, turn waste into wealth, is a very significant research topic.
Silicon carbide (SiC) is wide with its forbidden band, saturated electron drift velocity is big, critical avalanche breakdown electric field height and the high characteristics of thermal conductance, is worth having important use aspect high-power, high temperature resistant and the radioprotective device.Compare with conventional SiC material, nano SiC has stronger quantum size effect, and its optics and field emission performance are more superior.Silicon nitride (Si
3N
4) be a kind of advanced person's engineering ceramics and semiconductor material, have good performance, as wide band gap, high strength, high rigidity and favorable mechanical performance.Silicon carbide, silicon nitride are because their good performances are widely used in every field such as metallurgy, machinofacture, aerospace.
A lot of preparation SiC, Si have been arranged at present
3N
4The method of nano particle, Chinese patent (application number: CN 10121857) have been reported the method for burning synthesis of nano silicon carbide powder.In this method, silica flour, carbon dust, silicon nitride or silicon carbide additive and tetrafluoroethylene are mixed with the plumbago crucible of packing into behind the reaction mass according to a certain percentage, and the crucible that material is housed is put into airtight reaction under high pressure synthesizer; Charge into nitrogen after reaction unit vacuumizes to suitable pressure, cause combustion synthesis reaction by adopting local electric heat ignition or local high-frequency induction heating mode; Question response finishes, and product collection is handled, and can obtain homogeneous nano silicon carbide powder.Chinese patent (application number: CN 10020098) has been reported a kind of method for preparing cubic silicon carbide ultrafine powder with waste plastic at low temperature, come synthesizing silicon carbide with plastic waste as carbon source and silica flour, sodium Metal 99.5, metal magnesium powder are reductive agent, the sulphur powder is an auxiliary, reaction 10-30 hour under 300-500 ℃, 0.5-10MPa condition in autoclave; Through obtaining product after washing, the purification.Chinese patent (application number: CN 10015133) has been reported a kind of method of utilizing iodine aid preparation silicon nitride nano-material.After silica flour, iodine and sodiumazide are pressed the certain mol proportion mixing, place under the autoclave 190-300 ℃ temperature condition and reacted 5-20 hour; Reaction product after PH neutrality is washed, is washed in acidleach, centrifugation and desciccate, and then remove unreacted elemental silicon with the mixed liquid washing of hydrofluoric acid and nitric acid, vacuum-drying promptly obtains α and β two-phase blended silicon nitride nano-material.Chinese patent (application number: CN 10045575) has been reported a kind of single step reaction low temperature preparation method of beta-silicon nitride powder material.This method is to do the silicon source with silicon tetrachloride, makes nitrogenous source with sodium azide, and adding a spot of tetracol phenixin is solvent, mixture is packed into behind the reactor, reactor is heated to 150-200 ℃ in process furnace, reaches and stop heating behind the design temperature, make reactor in process furnace, naturally cool to room temperature.Reaction product is removed Residual reactants through raw spirit cleaning, suction filtration, removes byproduct of reaction sodium-chlor with washed with de-ionized water again, and last products therefrom was dried 3 hours under 60 ℃ of temperature, obtains the canescence alpha-silicon nitride powders.
Present existing silicon carbide and silicon nitride patent technology of preparing are generally strict to conversion unit, require the vacuum high-pressure reactor as Chinese patent (application number: CN 10121857) etc., and use the cost of material height, be difficult to obtain (as being nitrogenous source with sodium azide among application number: the CN 10045575).
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of equipment is simple, be easy to scale operation nanometer silicon carbide or silicon nitride particle.
The present invention utilizes waste plastic to be the carbon source presoma, and silicon-dioxide is the silicon source, and iron nitrate is a catalyst precursor, and reaction makes the nanometer silicon carbide particle of size between 10～70nm under the normal pressure argon gas atmosphere; Reaction then obtains silicon nitride nano particles under nitrogen atmosphere.This technology utilizes waste plastic for raw material production goes out the nanometer silicon carbide and the silicon nitride material of high added value, not only has remarkable economic efficiency, and has obvious social.
The present invention finishes according to the following steps:
(1), pre-treatment: the waste plastic after cleaning is carried out carbonization under 600～1000 ℃ of argon gas atmosphere, carbonization time obtained carbonized product at 0.5～5 hour;
(2), silicon-dioxide is immersed in the iron nitrate solution, under agitation condition, be heated to 50～80 ℃, be dispersed on the silica sphere up to solvent evaporate to dryness iron nitrate, then with the carbonized product ground and mixed, obtain mixture, mix the mass ratio 1: 0.1～5: 0.005～0.3 of back carbon, silicon-dioxide and iron nitrate;
(3), carbothermic reduction: with mixture under argon gas or nitrogen atmosphere 1100～1400 ℃ carried out carbothermic reduction reaction 3～20 hours, naturally cool to room temperature after the reaction, obtain the primary reaction product;
(4), thermal treatment:, remove unreacted carbon with 600～800 ℃ of roastings 1～5 hour in air of primary reaction product;
(5), pickling: reaction product is immersed in 12-48h removes iron nitrate and silicon-dioxide in the nitration mixture of the hydrochloric acid of volume ratio 1: 1-5 and hydrofluoric acid,, finally obtains silicon carbide or silicon nitride nano-material again through washing, filtration, drying.
Silicon carbide or silicon nitride that the present invention obtains are nano particle, and its size is between 10～70 nanometers.
Compare with existing patented method, characteristics of the present invention are to adopt a kind of simple carbothermic reduction technology to prepare small-sized silicon carbide, silicon nitride nano particles.In this technology, waste plastic is as carbon source, and silicon-dioxide has realized that for for the silicon source waste plastic utilizes again.Produce that required equipment is simple, operational safety, technical process is simple, production cost is low, with short production cycle, product purity is high.
Embodiment
Embodiment 1
1, with the 600 ℃ of carbonizations 5 hours under argon gas atmosphere of a certain amount of clean mineral water bottle, obtains a certain amount of carbonized product.
2,0.1 gram iron nitrate is dissolved in 20 ml distilled waters, adds 2 gram silicon-dioxide simultaneously, 50 ℃ flood down.8 grams are gone up step gained carbonized product silicon-dioxide uniform mixing therewith.
3, mixture is naturally cooled to room temperature in 1100 ℃ of isothermal reactions under the argon gas atmosphere after 20 hours.
4, gained reaction product roasting 5 hours in 600 ℃ of air is 1: 1 HCl and HF nitration mixture pickling 48h again with volume ratio, after washing, filtration, drying make the silicon-carbide particle of size between 10-30nm.
Embodiment 2
1, with the 700 ℃ of following carbonizations 4 hours under argon gas atmosphere of a certain amount of clean cutlery box, obtains a certain amount of carbonized product.
2,0.2 gram iron nitrate is dissolved in 30 ml distilled waters, adds 3 gram silicon-dioxide simultaneously, 60 ℃ flood down.0.9 gram is gone up step gained carbonized product silicon-dioxide uniform mixing therewith.
3, mixture is naturally cooled to room temperature in 1200 ℃ of isothermal reactions under the argon gas atmosphere after 10 hours.
4, gained reaction product roasting 4 hours in 700 ℃ of air is 1: 2 HCl and HF nitration mixture pickling 36h again with volume ratio, after washing, filtration, drying make the silicon-carbide particle of size between 10-50nm.
Embodiment 3
1, with the 800 ℃ of following carbonizations 3 hours under argon gas atmosphere of a certain amount of clean mineral water bottle, obtains a certain amount of carbonized product
2,0.2 gram iron nitrate is dissolved in 30 ml distilled waters, adds 3 gram silicon-dioxide simultaneously, 70 ℃ flood down.4 grams are gone up step gained carbonized product silicon-dioxide uniform mixing therewith.
3, mixture is naturally cooled to room temperature in 1300 ℃ of isothermal reactions under the argon gas atmosphere after 8 hours.
4, gained reaction product roasting 3 hours in 800 ℃ of air is 1: 3 HCl and HF nitration mixture pickling 24h again with volume ratio, after washing, filtration, drying make the silicon-carbide particle of size between 10-50nm.
Embodiment 4
1, with the 900 ℃ of following carbonizations 2 hours under argon gas atmosphere of a certain amount of clean cutlery box, obtains a certain amount of carbonized product.
2,0.1 gram iron nitrate is dissolved in 30 ml distilled waters, adds 6 gram silicon-dioxide simultaneously, 80 ℃ flood down.2 grams are gone up step gained carbonized product silicon-dioxide uniform mixing therewith.
3, mixture is placed on the following 1400 ℃ of isothermal reactions of nitrogen atmosphere after 5 hours, naturally cools to room temperature.
4, gained reaction product roasting 3 hours in 700 ℃ of air is 1: 4 HCl and HF nitration mixture pickling 12h again with volume ratio, after washing, filtration, drying make the silicon nitride particle of size between 10-70nm.
Embodiment 5
1, with the 1000 ℃ of following carbonizations 1 hour under argon gas atmosphere of a certain amount of clean plastics bag, obtains a certain amount of carbonized product.
2,0.05 gram iron nitrate is dissolved in 60 ml distilled waters, adds 5 gram silicon-dioxide simultaneously, 60 ℃ flood down.5 grams are gone up step gained carbonized product silicon-dioxide uniform mixing therewith.
3, the following 1300 ℃ of isothermal reactions of mixture nitrogen atmosphere after 6 hours, are naturally cooled to room temperature.
4, gained reaction product roasting 2 hours in 800 ℃ of air is 1: 1 HCl and HF nitration mixture pickling 24h again with volume ratio, after washing, filtration, drying make the silicon nitride particle of size between 10-70nm.
Embodiment 6
1, with the 800 ℃ of following carbonizations 2 hours under argon gas atmosphere of a certain amount of clean cutlery box, obtains a certain amount of carbonized product.
2,0.1 gram iron nitrate is dissolved in 20 ml distilled waters, adds 3 gram silicon-dioxide simultaneously, 80 ℃ flood down.6 grams are gone up step gained carbonized product silicon-dioxide uniform mixing therewith.
3, mixture is naturally cooled to room temperature in 1300 ℃ of isothermal reactions under the nitrogen atmosphere after 7 hours.
4, gained reaction product roasting 5 hours in 700 ℃ of air is 1: 2 HCl and HF nitration mixture pickling 20h again with volume ratio, after washing, filtration, drying make the silicon nitride particle of size between 10-70nm.
Claims (2)
1. a plastic waste prepares the method for small-sized silicon carbide or silicon nitride nano particles, it is characterized in that comprising the steps:
(1), pre-treatment: the waste plastic after cleaning is carried out carbonization under 600～1000 ℃ of argon gas atmosphere, carbonization time obtained carbonized product at 0.5～5 hour;
(2), silicon-dioxide is immersed in the iron nitrate solution, under agitation condition, be heated to 50～80 ℃, be dispersed on the silica sphere up to solvent evaporate to dryness iron nitrate, then with the carbonized product ground and mixed, obtain mixture, mix the mass ratio 1: 0.1～5: 0.005～0.3 of back carbon, silicon-dioxide and iron nitrate;
(3), carbothermic reduction: with mixture under argon gas or nitrogen atmosphere 1100～1400 ℃ carried out carbothermic reduction reaction 3～20 hours, naturally cool to room temperature after the reaction, obtain the primary reaction product;
(4), thermal treatment:, remove unreacted carbon with 600～800 ℃ of roastings 1～5 hour in air of primary reaction product;
(5), pickling: reaction product is immersed in 12-48h removes iron nitrate and silicon-dioxide in the nitration mixture of the hydrochloric acid of volume ratio 1: 1-5 and hydrofluoric acid,, finally obtains silicon carbide or silicon nitride nano-material again through washing, filtration, drying.
2. a kind of plastic waste as claimed in claim 1 prepares the method for small-sized silicon carbide or silicon nitride nano particles, it is characterized in that the silicon carbide or the silicon nitride that obtain are nano particle, and its size is between 10～70 nanometers.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432011A (en) * | 2011-10-08 | 2012-05-02 | 江苏佳宇资源利用股份有限公司 | Method for synchronously removing iron and silicon impurities in silicon carbide micro-powder |
| CN103079994A (en) * | 2010-08-02 | 2013-05-01 | Crl能量有限公司 | Systems, methods and compositions for the production of silicon nitride nanostructures |
| CN105037660A (en) * | 2015-05-29 | 2015-11-11 | 安徽大学 | One-dimensional nano-particle polymeric chain and preparation method thereof |
| CN108439408A (en) * | 2018-02-12 | 2018-08-24 | 中山大学 | A method of preparing silicon carbide powder material using circuit base plate is discarded |
| CN111484017A (en) * | 2020-06-22 | 2020-08-04 | 黑龙江冠瓷科技有限公司 | Method for preparing SiC nanoparticles based on silica microspheres @ C |
| CN113830767A (en) * | 2020-06-24 | 2021-12-24 | 浙江大学 | Method for preparing activated carbon by using waste lunch boxes |
| CN114132928A (en) * | 2021-12-24 | 2022-03-04 | 江苏理工学院 | Method for preparing silicon carbide nano material by using waste silicon dioxide |
| CN114835124A (en) * | 2022-05-24 | 2022-08-02 | 内蒙古海特华材科技有限公司 | Preparation method of nano silicon carbide particles based on ferric nitrate shape regulator |
-
2010
- 2010-01-20 CN CN2010101002133A patent/CN101774813B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103079994A (en) * | 2010-08-02 | 2013-05-01 | Crl能量有限公司 | Systems, methods and compositions for the production of silicon nitride nanostructures |
| CN102432011A (en) * | 2011-10-08 | 2012-05-02 | 江苏佳宇资源利用股份有限公司 | Method for synchronously removing iron and silicon impurities in silicon carbide micro-powder |
| CN105037660A (en) * | 2015-05-29 | 2015-11-11 | 安徽大学 | One-dimensional nano-particle polymeric chain and preparation method thereof |
| CN105037660B (en) * | 2015-05-29 | 2018-02-16 | 安徽大学 | Nanometer particle polymeric chain and preparation method thereof |
| CN108439408A (en) * | 2018-02-12 | 2018-08-24 | 中山大学 | A method of preparing silicon carbide powder material using circuit base plate is discarded |
| CN111484017A (en) * | 2020-06-22 | 2020-08-04 | 黑龙江冠瓷科技有限公司 | Method for preparing SiC nanoparticles based on silica microspheres @ C |
| CN113830767A (en) * | 2020-06-24 | 2021-12-24 | 浙江大学 | Method for preparing activated carbon by using waste lunch boxes |
| CN114132928A (en) * | 2021-12-24 | 2022-03-04 | 江苏理工学院 | Method for preparing silicon carbide nano material by using waste silicon dioxide |
| CN114835124A (en) * | 2022-05-24 | 2022-08-02 | 内蒙古海特华材科技有限公司 | Preparation method of nano silicon carbide particles based on ferric nitrate shape regulator |
| CN114835124B (en) * | 2022-05-24 | 2023-11-28 | 内蒙古海特华材科技有限公司 | Preparation method of nano silicon carbide particles based on ferric nitrate shape regulator |
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| CN101774813B (en) | 2012-02-15 |
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