CN1087332A - Produce graphite coat of silicon carbide and carbon-silicon compound with rice hulls - Google Patents

Produce graphite coat of silicon carbide and carbon-silicon compound with rice hulls Download PDF

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CN1087332A
CN1087332A CN 92111736 CN92111736A CN1087332A CN 1087332 A CN1087332 A CN 1087332A CN 92111736 CN92111736 CN 92111736 CN 92111736 A CN92111736 A CN 92111736A CN 1087332 A CN1087332 A CN 1087332A
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sic
graphite
rice husk
whisker
carbon
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CN 92111736
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CN1042830C (en
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徐振民
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5057—Carbides
    • C04B41/5059—Silicon carbide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Produce graphite coat of silicon carbide and carbon-silicon compound with rice hulls, be that the rice husk coking is handled, ball milling, add catalyzer by certain weight ratio, after mixing, put into the graphite tube that needs the graphite of SiC coating blank is housed, and place pyrocarbon pipe furnace heat preservation zone to carry out high temperature sintering, make graphite SiC coating, β SiC powder and β SiC whisker.The employed rice husk aboundresources of this law, and cheap, the technical process simple possible, quality reaches national standard, does not need postprocessing working procedures, has economic worth and comprehensive utilization value widely.

Description

Produce graphite coat of silicon carbide and carbon-silicon compound with rice hulls
The invention belongs to the chemical metallurgy field.
Chinese patent 92107329 utilizes the method for rice husk, rice straw system SiC, mainly is to utilize depleted rice husk rice straw, and coarse-grain SiC, bubbling air burn off excess carbon are made in repressed destructive distillation and secluding air reaction.Shenyang metal institute has delivered relevant article with rice husk system SiC whisker on " progress in materials science " second phase in 1989.After the rice husk coking, according to SiO 2/ C=1: 2, add boric acid or ferrous sulfate, make SiC whisker and residual carbon mixture, behind the blowing air burn off carbon, obtain β SiC whisker, but the residual carbon burning is unclean.
The purpose of this invention is to provide and a kind ofly produce graphite SiC coating, produce the technology of β SiC whisker, β SiC fine powder simultaneously with rice husk.
It is raw material that the present invention adopts rice husk, and the rice husk coking is handled, and destructive distillation is just handled, or the burnt rice husk that utilizes rice husk power generating factory to burn.For rice husk coking treatment temp is 600 ℃～650 ℃, and 1～1.5 hour time, temperature must not surpass 700 ℃, in case after the rice husk coking, make SiO wherein 2Grain coarsening influences whisker growth.The burnt rice husk that obtains after the coking processing is put into roller ball mill ball milling, and making burnt rice husk be crushed to granularity is 0.115mm.Add catalyzer such as NaCl, it mainly acts on is when high temperature and the reaction of the Si in the burnt rice husk generates SiCl 4For improving the whisker growth rate, also can add FeSO 4, Fe(OH) 3, H 3BO 3And Na 2S etc.Add a kind of catalyzer, its amount is 5～10% of burnt rice husk total amount, as adds multiplely, and total amount then is no more than 15% of burnt rice husk total amount.According to chemical equation SiO 2+ 3C=SiC+2CO will keep SiO in the compound during batch mixing 2The weight ratio of/C is 60: 32～60: 35.Its proportioning can be with containing different SiO 2/ C obtains after the collocation mutually than two kinds of material of gained, does not need to join in addition metallurgical carbon black.To adorn boat behind the above-mentioned material mixing of being furnished with catalyzer, the graphite blank that needs the SiC coating is imbedded in the graphite boat, made burnt rice husk compound cover the graphite blank fully, and suitably compress, so that and want the graphite blank of coating to keep excellent contact, and the temperature of each several part is kept evenly.If need to obtain more β SiC whisker, then graphite tube (or graphite boat) need leave a part of space behind the coking powdered rice hulls of packing into.With the graphite cover plate graphite boat is sealed then, the material boat is put into High Temperature Furnaces Heating Apparatus carry out pyroreaction.If only require scoria China ink SiC coating and β SiC fine powder, then can adopt the high-temperature horizontal stove that pushes away boat continuously, temperature is easy to control, is fired by hydrogen shield, and temperature is controlled at about 1650 ℃.If will obtain graphite SiC coating, β SiC fine powder and β SiC whisker simultaneously, preferably adopt shaft furnace or high temperature graphitization kiln.The temperature of bottom reaction material remains on 1600～1700 ℃, and space, top temperature remains on 1400～1450 ℃ better, soaking time 4～6 hours.If fire different thickness SiC coating, can repeatedly graphite SiC coated products be repeated to burn repeatedly with aforesaid method, the SiC coating surpasses and does not also come off more than the 2mm, in conjunction with very firm, and does not influence the original size of graphite product.Can control the needed thickness of SiC coating according to customer requirements.
Rice husk raw material resources used in the present invention are abundant, and cheap, if the coking rice husk that utilizes rice husk power generating factory to burn more can make full use of resource, turn waste into wealth.Technical process simple possible of the present invention is grasped SiO 2With the proportioning of C, add appropriate amount of catalysts, just can obtain graphite product SiC coating simultaneously through high temperature sintering, β SiC fine powder and β SiC whisker.The quality of β SiC powder reaches α-SiC standard GB-2480-83, does not need postprocessing working procedures.Have economic benefit and comprehensive utilization value widely.
Description of drawings:
Accompanying drawing 1 is for firing the shaft furnace synoptic diagram of graphite SiC coating, β SiC powder and β SiC whisker, wherein: 1 is coking rice husk batching (before not burning till SiC); 2 is furnace shell; 3 is lagging material; 4 is heating unit; 5 is fire-resistant boiler tube; 6 are coke insulation filler; 7 is β SiC whisker; 8 is β SiC powder; 9 for needing the graphite blank of coating; 10 is graphite tube (boat); 11 is heat insulating mattress.
Accompanying drawing 2 is for firing the vertical kiln loading of kiln synoptic diagram of graphite SiC coating, β SiC powder and β SiC whisker, and wherein: 12 is the fixed electorde furnace wall; 13 is the electrically conductive graphite electrode bar; 14 is the coke grain; 15 is coke, quartz sand insulation filler; 16 are graphite burning boat; 17 are coking rice husk batching; 18 for needing the graphite blank of coating, and 19 is lead.
Accompanying drawing 3 is the vertical view of accompanying drawing 2, and wherein 20 is the kiln abutment wall; 21 is coke, quartz sand insulation material.
Also can utilize the heat-insulation layer placing graphite boat of graphitization kiln to fire. Become number row to place graphite electrode base top heat preservation zone the graphite boat that the graphite blank is housed and is mixed with the coking powdered rice hulls of catalyst, thereafter repave and cover insulation material (being mixed by coke granule and quartz sand) and carry out sintering, this method is utilized the waste heat of graphitization kiln, does not need extra many power supplies.
Embodiment 1, and the coking rice husk is milled to 0.115 millimeter, adds NaCl 10wt% and H then 3BO 35wt% controls C/SiO as mixed catalyst 2Be 33/60, mix.The graphite rod that will be of a size of Φ 85 * 560mm is put into the burning boat that is of a size of Φ 115 * 8.5 * 600mm, and loading with the coking rice husk compound that is mixed with catalyzer plug around sample on every side expires, and puts into the pyrocarbon pipe furnace and carries out pyroreaction.1600～1700 ℃ high-temperature zone insulation is 6 hours in the pyrocarbon pipe furnace, go out boat after, generate the SiC coating of 0.5 millimeter thickness on the graphite rod, its clout is a β SiC fine powder.Pack into about coking rice husk compound 600 grams, outside the removing coating, also can obtain about β SiC powder 250 grams, β SiC powder purity is 94.4%, and uncombined carbon is 0.45%, and mean particle size is 10 μ m, dry grinds 16 hours, and granularity reaches 1.5～2 μ m.
Embodiment 2, and the coking rice husk is handled with example 1 same, C/SiO 2Be 34/60, add NaCl 5wt%, Na 2S 5wt% and FeSO 45wt% mixes, and the graphite sample that will be of a size of Φ 25 * 10mm and Φ 10 * 15mm is packed into and is of a size of in the graphite boat of Φ 70 * 6 * 320mm, and pine is equipped with the coking rice husk of catalyzer on every side, and dress boat to 3/4 length is stayed 1/4 space.The boat that material is housed is placed the pyrocarbon pipe horizontal chamber oven of Φ 80 * 1080mm, and space one end of boat places 1600 ℃ of high-temperature zones earlier, advances by per speed that pushed away 1/2 boat in 2 hours, send boat to watercooling jacket to go out boat after half an hour continuously.Must make reaction material be placed on the high-temperature zone, low about 150 ℃ of the temperature of gap becomes the whisker effect better.After going out boat, the gap covers with white β SiC whisker, and the whisker back is a β SiC fine powder, and β SiC powder purity is 94.7wt%, uncombined carbon＜0.3%.Wherein graphite sample all is coated with the β SiC coating about last layer 0.3mm.Adopt vertical high temperature stove better effects if to generating β SiC whisker.As to utilize Fig. 2 and Fig. 3 greying kiln be to promote the equipment that suitability for industrialized production is suitable for, and temperature is high slightly, is 1700～1800 ℃.

Claims (4)

1, produce graphite coat of silicon carbide and carbon-silicon compound with rice hulls, be with rice husk through the destructive distillation coking, control Si/C ratio is produced SiC powder or β SiC whisker, adds 5～15% catalyzer after the invention is characterized in the rice husk destructive distillation, keeps SiO 2The weight ratio of/C is 60: 32～60: 35, and fill out in the graphite tube that the graphite blank is being housed through the uniform compound of ball milling, and place 1600～1800 ℃ High Temperature Furnaces Heating Apparatus to fire the graphite tube, make graphite SiC coating, β SiC fine powder and β SiC whisker thus simultaneously.
2, method according to claim 1 is characterized in that rice husk destructive distillation coking temperature is 600～650 ℃, and the time is 1～1.5 hour.
3, method according to claim 1, the adding total amount that it is characterized in that catalyzer is 5%～15% of a burnt rice husk amount.
4, method according to claim 1, the temperature that it is characterized in that pyroreaction is 1600～1800 ℃, and the temperature of long whisker part remains on 1400～1450 ℃, and soaking time is 4～6 hours.
CN92111736A 1992-11-27 1992-11-27 Preparing graphite silicon carbide coating and carbon silicon compound by using rice husk Expired - Fee Related CN1042830C (en)

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CN1087332A true CN1087332A (en) 1994-06-01
CN1042830C CN1042830C (en) 1999-04-07

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100348547C (en) * 2005-12-26 2007-11-14 西北工业大学 Process for preparing silicon carbide coating on surface of carbon/carbon composite material
CN100369863C (en) * 2006-03-30 2008-02-20 中国科学院山西煤炭化学研究所 Method for preparing ball shaped, porous ceramic material contg. silicon carbide with biological structure
CN101864619A (en) * 2010-06-18 2010-10-20 吉林大学 Method for preparing nanometer-diameter carborundum brief fiber and whisker by utilizing rice hulls
CN106282927A (en) * 2016-08-05 2017-01-04 宁波高新区斯汀环保科技有限公司 A kind of preparation method of molybdenum carbon modified SiClx/copper composite electron encapsulating material
CN106800420A (en) * 2016-12-30 2017-06-06 河南工业大学 A kind of silicon carbide whisker in-situ composite corindon high-temperature ceramic materials and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1294297C (en) * 2005-05-24 2007-01-10 西北工业大学 Process for preparing silicon carbide crystal whisker

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248844A (en) * 1980-01-28 1981-02-03 Great Lakes Carbon Corporation Production of SiC from rice hulls and silica
US4283375A (en) * 1980-01-28 1981-08-11 Great Lakes Carbon Corporation Production of SiC whiskers
JPS599516B2 (en) * 1981-06-18 1984-03-02 東海カ−ボン株式会社 Method for manufacturing silicon carbide whiskers
JPS61295272A (en) * 1985-06-20 1986-12-26 工業技術院長 Manufacture of silicon carbide formed body with high pore rate
CN1064062A (en) * 1992-03-20 1992-09-02 徐以达 With rice husk, rice straw is the method for raw material preparing silicon carbide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100348547C (en) * 2005-12-26 2007-11-14 西北工业大学 Process for preparing silicon carbide coating on surface of carbon/carbon composite material
CN100369863C (en) * 2006-03-30 2008-02-20 中国科学院山西煤炭化学研究所 Method for preparing ball shaped, porous ceramic material contg. silicon carbide with biological structure
CN101864619A (en) * 2010-06-18 2010-10-20 吉林大学 Method for preparing nanometer-diameter carborundum brief fiber and whisker by utilizing rice hulls
CN106282927A (en) * 2016-08-05 2017-01-04 宁波高新区斯汀环保科技有限公司 A kind of preparation method of molybdenum carbon modified SiClx/copper composite electron encapsulating material
CN106800420A (en) * 2016-12-30 2017-06-06 河南工业大学 A kind of silicon carbide whisker in-situ composite corindon high-temperature ceramic materials and preparation method thereof
CN106800420B (en) * 2016-12-30 2021-07-16 河南工业大学 Silicon carbide whisker in-situ composite corundum high-temperature ceramic material and preparation method thereof

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