CN105366934A - Pretreatment method used for preparing continuous volcanic fiber raw materials - Google Patents
Pretreatment method used for preparing continuous volcanic fiber raw materials Download PDFInfo
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- CN105366934A CN105366934A CN201510898005.5A CN201510898005A CN105366934A CN 105366934 A CN105366934 A CN 105366934A CN 201510898005 A CN201510898005 A CN 201510898005A CN 105366934 A CN105366934 A CN 105366934A
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Abstract
The invention discloses a pretreatment method used for preparing continuous volcanic fiber raw materials. According to the pretreatment method, volcanic is smashed into powder with a particle size ranging from 30 to 500 meshes; an oxidizing agent is added, or the air or oxygen is added; oxidation reaction is carried out at high temperature so as to obtain a volcanic molten material, wherein the mass amount of FeO in the volcanic molten material accounts for 33.3% or lower of the total amount of iron oxides. Diathermancy of the volcanic molten material is increased greatly; thermal expansion coefficient is low; and it is beneficial for stable production of continuous volcanic fiber, and for increasing of fiber tensile strength.
Description
Technical field
The present invention relates to and use volcanics to prepare continuous fibre field, be specifically related to a kind of pretreatment process for the preparation of continuous volcanic rock fibre raw material.
Background technology
The rock that the effect such as magma condensation, diagenesis that volcanics is volcano to be sprayed when being vulcanism is formed.According to SiO
2content divides from high to low, and volcanics comprises: acid volcanic rock, Intermediate volcanic rocks, alkalic volcanic rock and hyperalkaline volcanics.Volcanics reason volcanic explosion and being formed, its reserves are huge and be a kind of raw material of sustainable use.At present, volcanics has been widely used in the fields such as building stone, pipeline, roadbed aggregate and water treatment, and being wherein used to prepare continuous fibre is domestic and international emerging industry, as produced continuous basalt fiber and andesite fiber.CN100509670C discloses the method and apparatus that a kind of basalt fibre is produced, and this patent mentions the component requirements of raw material and this process broken, but does not mention raw material pre-oxidation treatment.CN1210094A discloses a kind of raw material fitting method and the tank furnace design of preparing alkaline-resisting basalt fibre.The pre-treatment of this patent to raw material is by introducing zircon and fluorite etc. to improve the alkali resistance of basalt fibre.CN103429543A discloses a kind of formula preparing continuous basalt fiber raw material, is specially the basalt or diabase that comprise 30%-70%, the quartz components of 8%-40%, 5%-30% slag.This patent essence is a kind of method being adjusted to requirement formula by physical mixed.CN103502160A discloses a kind of method preparing continuous basalt fiber raw material; be specially and use at least one tackiness agent basalt, quartz sand or slag particle mixed and be prepared into the molding that upper dimension bound is 1mm for 30mm and lower limit; this patent also adjusts to for a kind of the method requiring formula by physical mixed, be manufactured with the one-tenth molding of dimensional requirement especially in order to adapt to prepare the feed way of the general use particulate material of continuous basalt fiber.
But current global matrix material continuous fibre still accounts for the absolute market share with glass fibre; Carbon fiber and aramid fiber occupy high-end aerospace, weaponry, the vehicles and sports goods market; Continuous volcanic rock fibre industry is still at an early stage of development.Continuous volcanic rock fibre industry technology problem is mainly: produce the platinum rhodium bushing hole count of continuous volcanic rock fibre both at home and abroad still based on 400 holes, and the bushing hole count of glass fibre tank furnace producer reaches 4000 holes substantially, even more than 6000 holes; Continuous volcanic rock fibre is produced still based on crucible or small-sized kiln, fails to realize large tank furnace fusing wire-drawing technology, and glass fibre has achieved large tank furnace fusing wire-drawing technology; The full cylinder rate of continuous volcanic rock fibre production wire drawing is low, fiber not timing fracture of wire, produces continuous volcanic rock fibre cost and remains high.And the essential reason of the problems referred to above is a balanced reaction affected by oxidation/reduction atmosphere when temperature and fusing in volcanics fusing and drawing process:
The type of above-mentioned two kinds of ferriferous oxides and ratio directly affect the performance such as network structure and diathermancy of volcanics melt.The ligancy of FeO is 6, and Fe
2o
3ligancy be 6 or 4, therefore in the network of volcanics melt, FeO and Fe
2o
3be considered to network outer body and network intermediate respectively.The Fe of network intermediate
2o
3can Network former be changed into, and improve the viscosity of melt, reduce thermal expansivity, be conducive to the production stability of continuous volcanic rock fibre and improve the tensile strength of fiber.Meanwhile, the diathermancy of volcanics melt is low, owing to being rich in FeO and Fe in volcanics composition
2o
3, the ferriferous oxide of high-content makes melt be dark brown, and diathermancy is about common shallow glass diathermic 1/5th.The FeO of same amount is about Fe in the receptivity of visible range
2o
310 times, i.e. same amount two kinds of volcanics, FeO volcanics melt diathermancy is only about Fe
2o
31/10 of volcanics.FeO in sum in volcanics melt is unfavorable for that producing it produces continuous fibre, and fe even can cause platinum rhodium bushing poisoning, and namely core of the present invention is that its part or all of FeO in volcanics is oxidized to Fe
2o
3.
Summary of the invention
[technical problem that will solve]
The object of the invention is to solve above-mentioned prior art problem, a kind of pretreatment process for the preparation of continuous volcanic rock fibre raw material is provided.The method is by being oxidized to Fe by its part or all of FeO in volcanics
2o
3, with the viscosity of stable volcanics melt, the diathermancy increasing volcanics melt, reduction thermal expansivity, be conducive to the production stability of continuous volcanic rock fibre.
[technical scheme]
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
For the preparation of a pretreatment process for the raw material of continuous volcanic rock fibre, it comprises the following steps:
After volcanic rock powder being broken into 30 ~ 500 object powders, be placed in high temperature service and after passing into air or oxygen high temperature oxidation process 1 ~ 800min, make FeO in its composition account for massfraction≤33.3% of total ferriferous oxide, then add in the oxidation crucible preparing continuous basalt fiber of atmosphere, smelting furnace or tank furnace;
Or after volcanic rock powder being broken into 30 ~ 500 object powders, adding oxygenant and mix, described oxygenant add-on is 1 ~ 24% of volcanics quality, then add in the crucible preparing continuous basalt fiber of oxidation atmosphere, smelting furnace or tank furnace.
According to the present invention's further technical scheme, described volcanics to be silicon-dioxide quality content be 46 ~ 65% Intermediate volcanic rocks or alkalic volcanic rock.
According to the present invention's further technical scheme, described volcanics is selected from diorite, andesite, basaltic andesite, basalt, gabbro or diabase.
According to the present invention's further technical scheme, the mode of described pulverizing for first utilizing jaw crusher broken as one-level, then selects cone crusher as two-stage crushing, finally selects grinding machine to be worked into 50 ~ 500 object powders.
According to a preferred embodiment of the invention, described volcanic rock powder is broken into 200 object powders.
According to the present invention's further technical scheme, described high temperature service is selected from rotary kiln, rotary kiln, fluidized-bed, tube furnace, convolution stove, calcining furnace, circulation flow dynamic furnace or suspended calcining kiln.
According to another preferred embodiment of the present invention, described in pass into air or oxygen time be 10 ~ 800min.
According to another preferred embodiment of the present invention, described high temperature oxidation process temperature is 550 ~ 900 DEG C.
According to the present invention's further technical scheme, described oxygenant is selected from nitrate and hydrate, vitriol and hydrate thereof, the oxide compound of arsenic, cerium oxide, cerous hydroxide, dichromate, chromic salt, manganese oxide or manganous hydroxide.
According to the present invention's further technical scheme, described nitrate is selected from nitrocalcite, saltpetre, SODIUMNITRATE, nitrate of baryta or ammonium nitrate; Described vitriol is selected from sodium sulfate, calcium sulfate or potassium sulfate; The oxide compound of described arsenic is selected from white arsenic or arsenic powder; Described dichromate is selected from potassium bichromate or sodium dichromate 99; Described chromic salt is selected from potassiumchromate or Sodium chromate.
According to the present invention's further technical scheme, described in mix use mixing equipment be selected from and copy act formula mixer, rotary drum mixer, Ai Liheshi mixer, oar blade type mixer or convection current and force mixer.
The present invention will be explained below.
The present invention is by being partly or entirely oxidized to Fe by FeO
2o
3, be more conducive to prepare continuous volcanic rock fibre to make acquiring volcanics raw material.In the present invention, described high temperature oxidation refers to that Optimal Temperature is 800 DEG C by temperature to the second-order transition temperature of volcanics to a certain temperature of fusing point.And the high temperature service that the present invention uses is with heating function, volcanics powder can be heated to said temperature, high temperature service is also with the part allowing high temperature volcanic rock powder body flow or to rotate simultaneously, to make powder contact and Quick Oxidation with air or oxygen fully, to improve oxidation rate and efficiency.The air and the oxygen that pass into 1 ~ 800min contain abundant oxygen in order to ensure in high temperature service, is beneficial to the high temperature oxidation of volcanics.Described FeO accounts for total ferriferous oxide massfraction≤33.3%, i.e. massfraction/the Fe of FeO in volcanics powder
2o
3massfraction≤1/2.Oxygenant described in the present invention is found to decompose the raw material discharging oxygen together with volcanics.Only have when oxygenant add-on is 1 ~ 24% of volcanics quality, in the volcanics melt obtained after its pre-treatment, FeO just can account for total ferriferous oxide massfraction≤33.3%.
[beneficial effect]
The present invention compared with prior art, has following beneficial effect:
The volcanics melt diathermancy obtained after pre-treatment of the present invention significantly promotes, thermal expansivity is low, and it is conducive to the production stability of continuous volcanic rock fibre and improves the tensile strength of fiber.
And utilize the present invention's pretreated volcanic rock powder body to prepare continuous volcanic rock fibre, it produces average fracture of wire interval >=2h, full cylinder rate >=85% of wire drawing; Its 13 micrometer fibers monofilament tensile strength >=4000MPa prepared, 13 microns of roving impregnation yarn tensile strength >=2800MPa, tensile modulus >=90GPa.
Embodiment
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
First flour is carried out to the volcanics in following embodiment, namely first utilizes jaw crusher broken as one-level, then select cone crusher as two-stage crushing, finally select grinding machine to be worked into the powder of certain order number.
Embodiment 1:
By 100 order basalt fibre powder, calcine 2h in 800 DEG C of tube-type atmosphere furnaces after, naturally cooling is for subsequent use; Basalt fibre powder after high temperature oxidation process is sorrel, and its most of FeO is converted into Fe
2o
3, the FeO/Fe of the basalt fibre powder after test chemical result display high temperature oxidation process
2o
3be 1/3, meet the demands.
Embodiment 2
By 500 object andesite powder, add continuously in 900 DEG C of atmosphere formula rotary kilns, pass into industrial oxygen in atmosphere formula rotary kiln, and from import to Outlet time, be about 0.5h by regulating body of heater rotating speed to control raw material, oxide treatment powder is collected in exit.
Embodiment 3
Ai Liheshi mixer is used to mix with 15 part of 100 order anhydrous plaster powder in 100 part of 200 order basalt fibre powder.The silicate reaction of mixed admixtion in high-temperature fusion process, oxygenant put the O of FeO in oxygen and basalt fibre powder and oxygenant release
2high temperature oxidation reaction, impel basalt fibre powder formation high-temperature fusant after, its FeO can be converted into Fe as far as possible
2o
3, the fiber water wire drawing sample F eO/Fe that test is produced
2o
3be similar to and reach 2/5.
Embodiment 4
KWQ convection current is used to force mixer to mix with 8 parts of cerium oxide 100 part of 400 order trachyte fiber powder.Mixed admixtion, in atmosphere furnace, through high temperature oxidation reaction, obtains oxygen, makes its FeO can be converted into Fe as far as possible from furnace atmosphere and oxygenant
2o
3, FeO/Fe
2o
3be similar to and reach 1/3.
The volcanics melt utilizing above-described embodiment 1 ~ 4 to obtain carries out the preparation of continuous volcanic rock fibre, and in preparation process, it produces average fracture of wire interval >=2h, full cylinder rate >=85% of wire drawing; And prepare 13 micrometer fibers monofilament tensile strength >=4000MPa, the 13 microns of roving impregnation yarn tensile strength >=2800MPa utilizing this fiber to prepare, tensile modulus >=90GPa.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only the present invention's preferably embodiment, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.
Claims (9)
1., for the preparation of a pretreatment process for continuous volcanic rock fibre raw material, it is characterized in that it comprises the following steps:
After volcanic rock powder being broken into 30 ~ 500 object powders, be placed in high temperature service and after passing into air or oxygen high temperature oxidation process 1 ~ 800min, make FeO in its composition account for massfraction≤33.3% of total ferriferous oxide, then add in the oxidation crucible preparing continuous basalt fiber of atmosphere, smelting furnace or tank furnace;
Or after volcanic rock powder being broken into 30 ~ 500 object powders, adding oxygenant and mix, described oxygenant add-on is 1 ~ 24% of volcanics quality, then add in the crucible preparing continuous basalt fiber of oxidation atmosphere, smelting furnace or tank furnace.
2. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 1, is characterized in that described volcanics to be silicon-dioxide quality content is Intermediate volcanic rocks or the alkalic volcanic rock of 46 ~ 65%.
3. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 2, is characterized in that described volcanics is selected from diorite, andesite, basaltic andesite, basalt, gabbro or diabase.
4. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 1, it is characterized in that the mode of described pulverizing is for first utilizing jaw crusher broken as one-level, select cone crusher as two-stage crushing again, finally select grinding machine to be worked into 50 ~ 500 object powders.
5. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 1, is characterized in that described high temperature service is selected from rotary kiln, rotary kiln, fluidized-bed, tube furnace, convolution stove, calcining furnace, circulation flow dynamic furnace or suspended calcining kiln.
6. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 1, the time passing into air or oxygen described in it is characterized in that is 10 ~ 800min.
7. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 1, is characterized in that described high temperature oxidation process temperature is 550 DEG C ~ 900 DEG C.
8. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 1, is characterized in that described oxygenant is selected from nitrate and hydrate, vitriol and hydrate, the oxide compound of arsenic, cerium oxide, cerous hydroxide, dichromate, chromic salt, manganese oxide or manganous hydroxide.
9. the pretreatment process for the preparation of continuous volcanic rock fibre raw material according to claim 8, is characterized in that described nitrate is selected from nitrocalcite, saltpetre, SODIUMNITRATE, nitrate of baryta or ammonium nitrate; Described vitriol is selected from sodium sulfate, calcium sulfate or potassium sulfate; The oxide compound of described arsenic is selected from white arsenic or arsenic powder; Described dichromate is selected from potassium bichromate or sodium dichromate 99; Described chromic salt is selected from potassiumchromate or Sodium chromate.
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| CN201510898005.5A CN105366934A (en) | 2015-12-08 | 2015-12-08 | Pretreatment method used for preparing continuous volcanic fiber raw materials |
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| CN201510898005.5A CN105366934A (en) | 2015-12-08 | 2015-12-08 | Pretreatment method used for preparing continuous volcanic fiber raw materials |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280274A (en) * | 2016-08-10 | 2017-01-04 | 袁春华 | A kind of preparation method of high thermally conductive LED fin |
| CN106396421A (en) * | 2016-09-05 | 2017-02-15 | 东南大学 | Production method for continuous basalt fiber |
| CN109437576A (en) * | 2018-12-12 | 2019-03-08 | 李瑞德 | A kind of rock wool and preparation method thereof, the preparation multi-functional total oxygen natural gas smelting furnace of rock wool |
| CN112520998A (en) * | 2020-12-29 | 2021-03-19 | 江苏绿材谷新材料科技发展有限公司 | Preparation method of high-temperature-resistant basalt fiber |
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| FR2419258A1 (en) * | 1978-03-09 | 1979-10-05 | Univ Washington | PROCESS FOR FORMING BASALT FIBERS HAVING BETTER TENSILE STRENGTH |
| CN1230526A (en) * | 1998-04-01 | 1999-10-06 | 鸡西市梨树区人民政府 | Continuous basalt fiber and its production technology |
| CN1814561A (en) * | 2005-02-01 | 2006-08-09 | 玄武岩纤维复合材料科技发展有限公司 | Ore melting and moltenmass modulating method and equipment for continuous basalt fiber production |
| CN101723587A (en) * | 2009-11-16 | 2010-06-09 | 戴洪明 | Manufacture method of igneous rock crystal glass material |
| CN103951268A (en) * | 2014-04-08 | 2014-07-30 | 东南大学 | High temperature-resistant basalt fiber composition |
-
2015
- 2015-12-08 CN CN201510898005.5A patent/CN105366934A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2419258A1 (en) * | 1978-03-09 | 1979-10-05 | Univ Washington | PROCESS FOR FORMING BASALT FIBERS HAVING BETTER TENSILE STRENGTH |
| CN1230526A (en) * | 1998-04-01 | 1999-10-06 | 鸡西市梨树区人民政府 | Continuous basalt fiber and its production technology |
| CN1814561A (en) * | 2005-02-01 | 2006-08-09 | 玄武岩纤维复合材料科技发展有限公司 | Ore melting and moltenmass modulating method and equipment for continuous basalt fiber production |
| CN101723587A (en) * | 2009-11-16 | 2010-06-09 | 戴洪明 | Manufacture method of igneous rock crystal glass material |
| CN103951268A (en) * | 2014-04-08 | 2014-07-30 | 东南大学 | High temperature-resistant basalt fiber composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280274A (en) * | 2016-08-10 | 2017-01-04 | 袁春华 | A kind of preparation method of high thermally conductive LED fin |
| CN106396421A (en) * | 2016-09-05 | 2017-02-15 | 东南大学 | Production method for continuous basalt fiber |
| CN106396421B (en) * | 2016-09-05 | 2019-05-21 | 东南大学 | A kind of production method of continuous basalt fiber |
| CN109437576A (en) * | 2018-12-12 | 2019-03-08 | 李瑞德 | A kind of rock wool and preparation method thereof, the preparation multi-functional total oxygen natural gas smelting furnace of rock wool |
| CN112520998A (en) * | 2020-12-29 | 2021-03-19 | 江苏绿材谷新材料科技发展有限公司 | Preparation method of high-temperature-resistant basalt fiber |
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Application publication date: 20160302 |