CN107353020A - A kind of composite refractory brick and preparation method thereof - Google Patents

A kind of composite refractory brick and preparation method thereof Download PDF

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Publication number
CN107353020A
CN107353020A CN201710526931.9A CN201710526931A CN107353020A CN 107353020 A CN107353020 A CN 107353020A CN 201710526931 A CN201710526931 A CN 201710526931A CN 107353020 A CN107353020 A CN 107353020A
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refractory brick
parts
composite refractory
antistatic additive
composite
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佘建锋
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Changxing Hongkuang Furnace Burden Co Ltd
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Changxing Hongkuang Furnace Burden Co Ltd
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
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Abstract

The invention provides a kind of composite refractory brick and preparation method thereof, the composite refractory brick is made up of the raw material of following parts by weight：0.15~0.2 part of 65~75 parts of mullite, natural 30~50 parts of zircon sand, 10~15 parts of titanium dioxide, 4~8 parts of forsterite, 12~17 parts of combined binder and antistatic additive.Wherein, the antistatic additive is PEO, polyether ester amides, the one or more in carboxyl betaine graft inter polymer.The thermal shock resistance of the composite refractory brick of the present invention is high, and content of free aldehyde is low, green；It is high with stable antistatic effect, security performance；Preparation technology is simple, and parameter is easily controllable, expands application field, increases the performance of enterprises.

Description

A kind of composite refractory brick and preparation method thereof
Technical field
The present invention relates to technical field of refractory materials, more particularly to it is a kind of it is green, there is the compound resistance to of antistatic behaviour Firebrick and preparation method thereof.
Background technology
It is all have used on stove masonry project, fusing point higher than more than 1588 DEG C material product general designation " refractory product " Also it is refractory brick, refractory brick is divided into as its chemistry and mineral matter：Clayey, High-Alumina, siliceous, semi silica, magnesia, magnalium Matter, magnesium are siliceous, magnesium chromium matter, dolomite matter, corundum, Zirconium corundum, mullite, zirconium mullite matter, quartziferous, aluminum oxide With silicon carbide etc..Traditional refractory brick composition is single, and impermeabilisation damage performance is bad, and deterioration is fast, short life, phenolic aldehyde tree used There is fat bonding agent harmful substance, the pitches used such as free phenol, free aldehyde can give out the toxic smog of yellow at high temperature, apply Work inclement condition, the serious health for damaging worker.In addition, refractory brick does not have certain antistatic property at present, it is long-term use of During easily adsorption of dust, flocking etc., but the laboratory environment such as increasing scientific research, medical science is to dust-proof, antistatic requirement Take much count of, such as computer floor, microelectronics clean room, clean plant, petrochemical industry workshop, hospital operating room needs are prevented The place of dirt, antistatic, it is necessary to which one kind both has heat resistance, has dust-proof, anti-static function composite refractory again.
" refractory brick " is disclosed in Chinese patent literature, its notification number is CN104949514A, and the invention is strengthened resistance to energetically The heat-insulating capability of firebrick, the deformation of rotary kiln metal shell is reduced, so as to reduce the requirement to refractory brick rigidity.But give patent Bonding agent species used is not referred to, is not related to the research in antistatic field yet.
The content of the invention
The problem of present invention is in order to overcome single existing refractory brick composition, pollution environment, easy bonding dust, there is provided one The composite refractory brick high, green, that there is antistatic behaviour of kind thermal shock resistance.
Present invention also offers a kind of preparation method for the composite refractory brick that technique is simple, and parameter is easily controlled.
To achieve these goals, the present invention uses following technical scheme：
A kind of composite refractory brick, the composite refractory brick are made up of the raw material of following parts by weight：65~75 parts of mullite, natural zirconium 30~50 parts of sand, 10~15 parts of titanium dioxide, 4~8 parts of forsterite, 12~17 parts of combined binder and antistatic additive 0.15 ~0.2 part.
The present invention is using mullite and major ingredient of the natural zircon sand as composite refractory brick, the lightweight of existing aluminum oxide, again There is the toughening effect of zirconium oxide, thermal shock resistance obtains composite strengthening.Titanium dioxide is added in raw material, the effect of catalysis can be played It fruit, can be acted synergistically with aluminum oxide, play the effect of toughness reinforcing, in addition, titanium dioxide has preferable ultraviolet masking to make With being used in composite refractory brick as sun-screening agent and antioxidant, the service life of composite refractory brick can be extended.
Preferably, the antistatic additive is PEO, polyether ester amides, in carboxyl betaine graft inter polymer It is one or more of.
PEO selected by the present invention, polyether ester amides and carboxyl betaine graft inter polymer are that macromolecule is permanent Type antistatic additive, belongs to hydrophilic polymer, and its action principle is as follows：After itself and composite refractory brick major ingredient matrix are blended, a side Face is intermolecular to be easy to proton to move because the locomitivity of its strand is stronger, conducts and discharge generation by ionic conduction Electrostatic charge；On the other hand, antistatic effect is embodied by its special dispersing morphology.Research shows：Macromolecule is permanent Type antistatic additive is mainly distributed in article topsheet in fine stratiform or tendon shape, forms electric conductivity top layer, and in core It is in almost spherical distribution, is formed so-called " core shell structure ", and electrostatic charge is leaked as path.Because macromolecule permanent type resists Electrostatic agent is to reduce material volume resistivity to reach antistatic effect, not exclusively rely on water absorbent surface, so by environment Humidity influences almost not having, and macromolecule permanent antistatic agent will be added in the composite refractory brick of the present invention, enabled to compound Refractory brick has stable antistatic effect, security performance height.
Preferably, the combined binder is made up of the raw material of following parts by weight：6~8 parts of phenolic resin, absolute ethyl alcohol 5~6 parts, 0.2~1 part of borate, 0.3~0.5 part of graphene, 0.5~1.5 part of formaldehyde sealer.
Preferably, the formaldehyde sealer be 1- (3- aminopropyls) imidazoles, asparagine and valine one kind or It is several.
The formaldehyde sealer that the present invention selects contains primary amine group, formula R-NH2, can with phenolic resin system Free aldehyde is reacted, and on the one hand can block the diffusion of free aldehyde, and sealing process is played to aldehyde radical；On the other hand reaction generation Stable polymeric crosslinker can further enhance the heat resistance and caking property of phenolic resin.Its reaction principle is：Acid bar Under part, parent can occur under the conditions of 45~60 DEG C for the carbonyl of free aldehyde in the primary amine group and phenolic resin in formaldehyde sealer Core addition reaction generates RNHCH2OH, the structural stability is very poor, can generate RNH=CH with rapid dehydration2, and send out from each other Raw condensation reaction, forms polymeric crosslinker.
Preferably, the borate be butyl borate, sodium tetraborate, eight Boratexes and one kind in ten Boratexes and It is several.
Butyl borate, sodium tetraborate, eight Boratexes and ten Boratexes are easily dissolved in phenol resin solution, Neng Gouyu Phenolic resin is well mixed.When temperature be higher than 120 DEG C, the solidification of eight Boratexes and ten Boratex subparticipation phenolic resin, energy Enough greatly improve the heat resistance of phenolic resin.
A kind of preparation method of composite refractory brick, comprises the following steps：
(1) according to said ratio weighing, by mullite, natural zircon sand, titanium dioxide and forsterite are at 200~400 DEG C Blending is crushed to obtain the major ingredient that particle diameter is 100~150 mesh after 2~3h of insulation；
(2) combined binder and antistatic additive are slowly added into major ingredient, 20~30min of batch mixing under the conditions of 60~80 DEG C, Obtain pre-composition；
(3) pre-composition for obtaining step (2) carries out high-pressure molding, is burnt in 1100 DEG C~1300 DEG C of hyperthermia tunnel Kiln Into, be incubated 8~12h, obtain composite refractory brick after cooling.
The present invention has the advantages that：
(1) thermal shock resistance is high, and content of free aldehyde is low, green；
(2) there is stable antistatic effect, security performance height；
(3) preparation technology is simple, and parameter is easily controllable, expands application field, increases the performance of enterprises.
Embodiment
Below by specific embodiment, technical scheme is described in further detail.
In the present invention, if not refering in particular to, all devices and raw material are commercially available or the industry is conventional, following Method in embodiment, it is this area conventional method unless otherwise instructed.
Embodiment 1
It is stand-by that 12g combined binders are made according to following proportioning：Phenolic resin 6g, absolute ethyl alcohol 5g, butyl borate 0.2g, stone Black alkene 0.3g, 1- (3- aminopropyls) imidazoles 0.5g；
(1) according to following proportioning weighing, by mullite 65g, natural zircon sand 30g, titanium dioxide 10g and forsterite 4g in Blending is crushed to obtain the major ingredient that particle diameter is 100 mesh after 3h is incubated at 200 DEG C；
(2) 12g combined binders and 0.15g PEOs are slowly added into major ingredient, the batch mixing under the conditions of 60 DEG C 30min, obtain pre-composition；
(3) pre-composition for obtaining step (2) carries out high-pressure molding, is burnt in 1100 DEG C~1300 DEG C of hyperthermia tunnel Kiln Into, be incubated 8h, obtain composite refractory brick after cooling.
Embodiment 2
It is stand-by that 17g combined binders are made according to following proportioning：Phenolic resin 8g, absolute ethyl alcohol 6g, eight Boratex 0.5g, ten boron Sour sodium 0.5g, graphene 0.5g, asparagine 0.5g, valine 1g；
(1) according to following proportioning weighing, by mullite 75g, natural zircon sand 50g, titanium dioxide 15g and forsterite 8g in Blending is crushed to obtain the major ingredient that particle diameter is 150 mesh after 2h is incubated at 400 DEG C；
(2) 17g combined binders, polyether ester amides 0.1g and 0.1g carboxyl betaine graft inter polymer are respectively added slowly to In major ingredient, batch mixing 20min, obtains pre-composition under the conditions of 80 DEG C；
(3) pre-composition for obtaining step (2) carries out high-pressure molding, is burnt in 1100 DEG C~1300 DEG C of hyperthermia tunnel Kiln Into, be incubated 12h, obtain composite refractory brick after cooling.
Embodiment 3
It is stand-by that 14.5g combined binders are made according to following proportioning：Phenolic resin 7g, absolute ethyl alcohol 5.5g, sodium tetraborate 0.3g, Ten Boratex 0.3g, graphene 0.4g, 1- (3- aminopropyls) imidazoles 0.7g, asparagine 0.3g；
(1) according to following proportioning weighing, by mullite 70g, natural zircon sand 40g, titanium dioxide 12g and forsterite 6g in Blending is crushed to obtain the major ingredient that particle diameter is 130 mesh after 2.5h is incubated at 300 DEG C；
(2) 14.5g combined binders and 0.18g carboxyl betaine graft inter polymers are respectively added slowly in major ingredient, in 70 Batch mixing 25min under the conditions of DEG C, obtains pre-composition；
(3) pre-composition for obtaining step (2) carries out high-pressure molding, is burnt in 1100 DEG C~1300 DEG C of hyperthermia tunnel Kiln Into, be incubated 10h, obtain composite refractory brick after cooling.
Comparative example
Comparative example uses commercial alumina refractory brick.
Embodiment 1-3 and the refractory brick of comparative example physical and chemical index are detected, as a result as shown in table 1.
The physical and chemical index result of table 1.
Physical and chemical index Embodiment 1 Embodiment 2 Embodiment 3 Comparative example
Free aldehyde, wt% 0.3 0.2 0.5 5
Heat resistance, DEG C 2345 2350 2380 2005
The Electrostatic Absorption of cotton chip Nothing Nothing Nothing Have
Thermal shock resistance (1000 DEG C, secondary) 28 26 30 18
As can be seen from Table 1, traditional refractory brick is modified by adding the combined binder of the sealer containing formaldehyde, obtained Composite refractory brick it is higher relative to the thermal shock resistance of commercial alumina refractory brick, and greatly reduce the content of free aldehyde, It is more green.By adding antistatic additive in formula system, obtained refractory fibre has stable anti-static ability, Security performance is high.
The thermal shock resistance of the composite refractory brick of the present invention is high, and content of free aldehyde is low, green；With the anti-quiet of stabilization Electric energy power, security performance are high；Preparation technology is simple, and parameter is easily controllable, expands application field, increases the performance of enterprises.

Claims (6)

1. a kind of composite refractory brick, it is characterised in that the composite refractory brick is made up of the raw material of following parts by weight：Mullite 65 ~75 parts, natural 30~50 parts of zircon sand, 10~15 parts of titanium dioxide, 4~8 parts of forsterite, 12~17 parts of combined binder With 0.15~0.2 part of antistatic additive.
A kind of 2. composite refractory brick according to claim 1, it is characterised in that the antistatic additive is PEO, Polyether ester amides, the one or more in carboxyl betaine graft inter polymer.
3. a kind of composite refractory brick according to claim 1, it is characterised in that the combined binder is by following parts by weight Raw material be made：6~8 parts of phenolic resin, 5~6 parts of absolute ethyl alcohol, 0.2~1 part of borate, 0.3~0.5 part of graphene, formaldehyde 0.5~1.5 part of sealer.
4. a kind of composite refractory brick according to claim 1, it is characterised in that the formaldehyde sealer is 1- (3- amino Propyl group) imidazoles, asparagine and valine one or more.
5. a kind of composite refractory brick according to claim 1, it is characterised in that the borate is butyl borate, four Boratex, eight Boratexes and one kind in ten Boratexes and several.
6. the preparation method of a kind of composite refractory brick as described in claim 1-5 is any, it is characterised in that including following step Suddenly：
(1) according to said ratio weighing, by mullite, natural zircon sand, titanium dioxide and forsterite are at 200~400 DEG C Blending is crushed to obtain the major ingredient that particle diameter is 100~150 mesh after 2~3h of insulation；
(2) combined binder and antistatic additive are slowly added into major ingredient, 20~30min of batch mixing under the conditions of 60~80 DEG C, Obtain pre-composition；
(3) pre-composition for obtaining step (2) carries out high-pressure molding, is burnt in 1100 DEG C~1300 DEG C of hyperthermia tunnel Kiln Into, be incubated 8~12h, obtain composite refractory brick after cooling.
CN201710526931.9A 2017-06-30 2017-06-30 A kind of composite refractory brick and preparation method thereof Pending CN107353020A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101693821A (en) * 2009-10-16 2010-04-14 江苏苏嘉集团新材料有限公司 Boron modified phenolic resin binder for refractory materials
CN102211164A (en) * 2011-05-13 2011-10-12 无锡德乾能源设备有限公司 Application of refractory brick in casting field
CN102912637A (en) * 2012-11-16 2013-02-06 中复神鹰碳纤维有限责任公司 Carbon fiber sizing agent
CN103242047A (en) * 2012-02-08 2013-08-14 訾然 Method for producing zirconium corundum firebrick for glass kiln
CN103282395A (en) * 2010-10-01 2013-09-04 迪纳化学公司 Low free formaldehyde phenolic resins for abrasive products
CN104449500A (en) * 2014-12-15 2015-03-25 济南圣泉集团股份有限公司 Modified phenolic resin adhesive, preparation method thereof and tire rubber

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101693821A (en) * 2009-10-16 2010-04-14 江苏苏嘉集团新材料有限公司 Boron modified phenolic resin binder for refractory materials
CN103282395A (en) * 2010-10-01 2013-09-04 迪纳化学公司 Low free formaldehyde phenolic resins for abrasive products
CN102211164A (en) * 2011-05-13 2011-10-12 无锡德乾能源设备有限公司 Application of refractory brick in casting field
CN103242047A (en) * 2012-02-08 2013-08-14 訾然 Method for producing zirconium corundum firebrick for glass kiln
CN102912637A (en) * 2012-11-16 2013-02-06 中复神鹰碳纤维有限责任公司 Carbon fiber sizing agent
CN104449500A (en) * 2014-12-15 2015-03-25 济南圣泉集团股份有限公司 Modified phenolic resin adhesive, preparation method thereof and tire rubber

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