CN116283234A - Environment-friendly fireproof magnesia brick for cement kiln and preparation method thereof - Google Patents
Environment-friendly fireproof magnesia brick for cement kiln and preparation method thereof Download PDFInfo
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- CN116283234A CN116283234A CN202310322785.3A CN202310322785A CN116283234A CN 116283234 A CN116283234 A CN 116283234A CN 202310322785 A CN202310322785 A CN 202310322785A CN 116283234 A CN116283234 A CN 116283234A
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 266
- 239000011449 brick Substances 0.000 title claims abstract description 151
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000004568 cement Substances 0.000 title claims abstract description 33
- 235000012245 magnesium oxide Nutrition 0.000 claims abstract description 132
- 230000001070 adhesive effect Effects 0.000 claims abstract description 61
- 239000000853 adhesive Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 58
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011230 binding agent Substances 0.000 claims abstract description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 27
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 6
- 230000009970 fire resistant effect Effects 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 21
- 150000004706 metal oxides Chemical class 0.000 abstract description 21
- 238000010438 heat treatment Methods 0.000 abstract description 18
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005011 phenolic resin Substances 0.000 abstract description 4
- 229920001568 phenolic resin Polymers 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 16
- 238000001514 detection method Methods 0.000 description 10
- 239000001095 magnesium carbonate Substances 0.000 description 10
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 10
- 235000014380 magnesium carbonate Nutrition 0.000 description 10
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 10
- 239000011819 refractory material Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- OCYUQKSNQVZPED-UHFFFAOYSA-L aluminum;magnesium;dihydroxide Chemical compound [OH-].[OH-].[Mg+2].[Al+3] OCYUQKSNQVZPED-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
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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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
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- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
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- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
- C04B35/6306—Binders based on phosphoric acids or phosphates
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
The invention provides an environment-friendly fireproof magnesia brick for a cement kiln and a preparation method thereof, wherein the fireproof magnesia brick comprises the following raw materials in parts by mass: 60-65 parts of periclase, 1-5 parts of binder and 32-37 parts of fused magnesia; the raw materials of the adhesive are as follows: phosphoric acid: 40-60 parts of water: 30-40 parts of metal hydroxide powder: 8-12 parts of oxalic acid: 0-2 parts. Compared with the prior art, the invention uses phosphoric acid, metal oxide and oxalic acid as main raw materials to prepare the binder, avoids using the binder such as phenolic resin, paper pulp waste liquid, organic powder and the like, generates no gas in the preparation and heating process of the refractory brick, and generates no harmful gas to the environment. Moreover, the compressive strength of the green brick prepared by the adhesive is higher than that of a conventional green brick, which indicates that the adhesive has good adhesion.
Description
Technical Field
The invention belongs to the field of building materials. In particular to an environment-friendly refractory magnesia brick for a cement kiln and a preparation method thereof.
Background
The refractory material refers to an inorganic nonmetallic material with the refractoriness not lower than 1580 ℃, and the refractoriness refers to the temperature of a conical sample of the refractory material, which resists the action of high temperature without softening and melting down under the condition of no load. The refractory material is applied to various fields of national economy such as steel, nonferrous metal, glass, cement, ceramics, petrifaction, machinery, boilers, light industry, electric power, military industry and the like, is an essential basic material for ensuring the industrial production operation and the technical development, and plays an irreplaceable important role in the development of high-temperature industrial production.
Along with the increasing importance of the national environmental pollution and environmental protection, the environmental protection requirements of environmental protection departments on refractory material enterprises are also higher. In the production process of the refractory magnesia bricks, the adhesive is added to ensure that various raw materials of the refractory materials can be tightly adhered before firing, the stability and the deformation resistance of the refractory bricks before firing are ensured, and the stability and the integrity of the unburned bricks are important guarantees that the performance of the refractory materials in the later stage reach the standard.
The binder used in the existing refractory bricks is usually phenolic resin, pulp waste liquid, organic powder and the like. These binders act prior to green brick firing and these additives are an unstable impurity during firing of the brick and during high temperature use. In the process of using refractory materials by cement enterprises, binder impurities in the refractory bricks volatilize various harmful components such as organic matters, sulfides and the like, and the components not only influence cement performance, but also are very unfavorable to the environment. In particular, refractory bricks incorporating organic binders may undergo complex chemical reactions during the preparation process, which expel large amounts of detrimental VOCs to the environment.
Therefore, the development of the refractory magnesia brick for the cement kiln, which is free from adding organic binders, is environment-friendly and production process-friendly, reduces the environmental pollution in the preparation process of refractory bricks, reduces the exhaust emission of cement enterprises and improves the kiln working condition, is needed.
Disclosure of Invention
The invention aims to provide an environment-friendly fireproof magnesia brick for a cement kiln and a preparation method thereof, wherein the adhesive is phosphoric acid and metal hydroxide powder, so that the fireproof magnesia brick does not have adverse effects on the environment and products in the use process.
The specific technical scheme of the invention is as follows:
an environment-friendly refractory magnesia brick for a cement kiln comprises the following raw materials in parts by mass:
60-65 parts of periclase, 1-5 parts of binder and 32-37 parts of fused magnesia;
the adhesive comprises the following raw materials in parts by mass:
phosphoric acid: 40-60 parts of water: 30-40 parts of metal hydroxide powder: 8-12 parts of oxalic acid: 0-2 parts.
The preparation method of the adhesive comprises the following steps: adding water into phosphoric acid, mixing uniformly, adding oxalic acid with formula amount, continuously stirring and mixing uniformly to obtain a solution, adding metal hydroxide powder into the solution under the stirring condition, stopping stirring after mixing uniformly, standing to cool the solution, and filtering to remove insoluble residues to obtain the liquid binder.
The metal hydroxide powder is added into the solution in a divided manner, and the total amount of the metal hydroxide powder is 2% -5% of the total amount of the metal hydroxide powder added each time; after the metal hydroxide powder added last time is dissolved into the liquid, continuing to add the next time; until the metal hydroxide powder is added, stirring is continued for 2-2.5h after the addition is finished; the metal hydroxide powder is added in portions to prevent the violent reaction of phosphoric acid and metal hydroxide from causing bumping.
The concentration of the phosphoric acid is more than or equal to 85wt%;
the metal hydroxide powder is a mixture of magnesium hydroxide and aluminum hydroxide;
the preparation method of the metal hydroxide powder comprises the following steps: and uniformly mixing the magnesium hydroxide and the aluminum hydroxide according to the mass ratio of 27-31:37-41.
The periclase has the following crushing particle size: d90:200-250 μm;
the fused magnesia: particle diameter D 90 ：40-50μm；
The invention provides a preparation method of an environment-friendly fireproof magnesia brick for a cement kiln, which comprises the following steps:
1) Mixing the periclase with the binder under stirring;
2) Adding the formula amount of fused magnesia, and continuously stirring and mixing;
3) Placing the mixture into a brick pressing mold, pressing bricks, demoulding, and firing at high temperature.
The stirring and mixing in the step 1) are carried out at the following stirring and mixing rate: 5-10r/min for 30-35 min;
stirring and mixing for 2-2.5h in the step 2);
in step 3), the brick pressing means: the highest pressure is set on the press: maintaining the pressure for 25-35s, and manufacturing green bricks;
and 3) after demoulding in the step 3), placing the green bricks in a high-temperature furnace, heating to a temperature of 10 ℃/min, keeping the temperature for 2-3h after the temperature reaches 200 ℃, continuously heating to 1600 ℃, and firing for 4-6h to obtain the refractory magnesia bricks.
The invention takes phosphoric acid, metal hydroxide and oxalic acid as main raw materials to prepare the binder, and the phosphoric acid, magnesium hydroxide and aluminum hydroxide generate magnesium phosphate, magnesium hydrogen phosphate and magnesium dihydrogen phosphate; the aluminum hydroxide has good solubility, and the magnesium hydroxide reacts with acid to release a large amount of heat, so that the reaction is further accelerated; the raw material reactant of the adhesive reacts and is dehydrated and condensed to form an inorganic macromolecule net structure, and the adhesive has a certain adhesive effect. The refractory material does not release harmful substances such as carbon oxides, sulfides and the like to the environment in the preparation process, and the carbon oxides released by the conventional refractory material can carry out complex reactions to generate harmful substances such as VOCs and the like; the invention is an environment-friendly adhesive, and the physical properties of the refractory brick prepared from the used materials are good.
Compared with the prior art, the invention avoids using binders such as phenolic resin, paper pulp waste liquid, organic powder and the like, generates no gas in the preparation and heating processes of the refractory bricks, generates no harmful gas to the environment, reduces the environmental pollution in the preparation processes of the refractory bricks, and reduces the exhaust emission of cement enterprises. Moreover, the compressive strength of the green brick prepared by the adhesive is higher than that of a conventional green brick, which indicates that the adhesive has good adhesion.
Drawings
FIG. 1 is a thermal weight curve of an adhesive of the present invention versus a conventional adhesive;
FIG. 2 is an infrared spectrum of the released gas observed from ambient to 500℃for the binder of the present invention and the existing binder;
FIG. 3 is an infrared spectrum of the gas release observed between 500-1400℃for the binder of the present invention and the prior art binders;
FIG. 4 is a graph showing the change in mass of a refractory brick made using the binder of the present invention and a commercially available binder after being heated;
FIG. 5 is an infrared plot of the adhesive of example 2 during three temperature ranges from ambient temperature to 1400 ℃;
fig. 6 is an infrared detection graph of the adhesive of example 3 during three temperature ranges from ambient temperature to 1400 ℃.
Detailed Description
The invention provides an environment-friendly fireproof magnesia brick for a cement kiln, which comprises the following raw materials in parts by mass:
60-65 parts of periclase, 1-5 parts of binder and 32-37 parts of fused magnesia;
the periclase is crushed into the following components in particle size: d (D) 90 ：200-250μm；
The fused magnesia: particle diameter D 90 ：40-50μm；
The binder is as follows: is synthesized by phosphoric acid and metal hydroxide powder: the weight percent is as follows: phosphoric acid (concentration not less than 85%): 40-60 parts of water: 30-40 parts of metal hydroxide powder: 8-12 parts of oxalic acid: 0-2 parts.
The preparation method of the metal oxide powder comprises the following steps: the magnesium hydroxide and aluminum hydroxide were mixed in an automatic mixer in a mass ratio of 27-31:37-41 for 30min, based on 1kg of the metal oxide powder.
The preparation process of the adhesive comprises the following steps: phosphoric acid was first mixed with water and stirred for 5 minutes, then oxalic acid was added and stirring was continued for 5 minutes. And then slowly adding metal hydroxide powder into the solution while stirring, adding a small amount of the metal hydroxide powder every time, adding 2% -5% of the total amount of the metal hydroxide powder every time, continuously and slowly sprinkling the metal hydroxide powder after the powder added last time is fused into the liquid, continuously stirring for 2 hours after all the powder is sprinkled into the liquid until the properties of the solution are uniform, stopping stirring, standing to cool the solution, and filtering to discard insoluble residues to obtain the liquid binder.
The preparation method of the environment-friendly refractory magnesia brick for the cement kiln comprises the following steps: adding periclase and a binder into a sample mixing pot according to the formula proportion, and setting proper rotating speed: 5-10r/min, mixing for 30min, adding the mixed powder into fused magnesia, and mixing for 2h. Placing the mixed mixture into a brick pressing mold, and setting the highest pressure on a press machine: maintaining the pressure for 30s, manufacturing the green bricks, demoulding, placing the green bricks in a high-temperature furnace, programming the temperature to be 10 ℃/min, keeping the temperature for 2h after the temperature reaches 200 ℃, continuously heating to 1600 ℃, and firing for 4h to obtain the refractory magnesia bricks.
Preferred embodiments of the invention are as follows:
example 1
An environment-friendly refractory magnesia brick for a cement kiln comprises the following raw materials in parts by mass:
60 parts of periclase, 3 parts of binder and 37 parts of fused magnesia;
particle size of periclase: d90:200 μm; electric smelting magnesite: particle diameter D 90 ：50μm；
The binder is as follows: the weight percent is as follows: phosphoric acid (85% concentration): 60 parts of water 30 parts, 10 parts of metal hydroxide powder and 0 part of oxalic acid; the preparation method of the metal hydroxide powder comprises the following steps: mixing magnesium hydroxide and aluminum hydroxide in the ratio of 29:39 in an automatic sample mixer for 30min to obtain the final product; the preparation process of the adhesive comprises the following steps: the formula amount of phosphoric acid is firstly mixed with water, and the mixture is stirred for 5 minutes. And then slowly adding metal oxide powder into the solution while stirring, adding a small amount of the metal oxide powder every time, adding 3% of the total amount of the metal oxide powder every time, continuously and slowly sprinkling the solution after the powder added last time is fused into the liquid, continuously stirring for 2 hours after all the powder is sprinkled into the liquid until the solution is uniform, stopping stirring, standing to cool the solution, filtering, and discarding a small amount of insoluble solids to obtain the liquid binder.
The preparation method of the environment-friendly refractory magnesia brick for the cement kiln comprises the following steps: adding periclase and a binder into a sample mixing pot according to the formula proportion, and setting proper rotating speed: 5r/min, mixing for 30min, adding the mixed powder into fused magnesia, and continuing mixing for 2h. The mixed mixture was placed in a 230X 165X 65mm mold and the highest pressure was set on the press: maintaining pressure, making the green bricks, demoulding, placing the green bricks in a high-temperature furnace, programming to heat up to 10 ℃/min, keeping the temperature for 2 hours after the temperature reaches 200 ℃, continuously heating up to 1600 ℃, and firing for 4 hours to obtain the refractory magnesia bricks.
And (3) performing test characterization:
1. the heating maximum temperature is set to 1400 ℃, and the substances generated in the heating process of the self-made adhesive and the conventional organic adhesive (the conventional phenolic resin, starch dextrin and paper pulp waste liquid) used by the refractory material company are detected and compared through the combination of thermogravimetric and infrared. FIG. 1 shows the thermogravimetric curves of two adhesives, and as can be seen from FIG. 1, the mass loss of the adhesive after heating is 93.69% and the mass loss of the adhesive is 36.3%. As can be seen from fig. 1, the adhesive of the present invention emits less substances to the environment after being heated at high temperature, whereas the existing adhesive emits almost all substances to the environment after being heated.
2. In fig. 2, the upper graph shows the absorption peak of the substance released by the conventional adhesive after infrared detection before 500 ℃, and the lower graph in fig. 2 shows the absorption peak of the substance released by the adhesive after infrared detection before 500 ℃, and as can be seen by comparing the infrared absorption graphs of the two adhesives after heating, the absorption peak of carbon dioxide appears after the conventional adhesive is heated, and the corresponding absorption peak is not detected in the process of heating the adhesive to 500 ℃, which indicates that the adhesive does not release substances such as carbon dioxide to the environment.
3. In FIG. 3, the upper graph shows the absorption peak of the adhesive at 500-1400 ℃ when the adhesive is infrared-detected, and the lower graph in FIG. 3 shows the absorption peak of the adhesive of the invention at the same temperature Duan Ben, wherein the absorption peak of sulfide appears in the conventional adhesive as compared with the infrared absorption graph after the two adhesives are heated, and 2350cm -1 The peak appearing around is carbon dioxide absorption peak, 1350cm -1 The left and right peaks are sulfide absorption peaks; in the process of heating the adhesive to 1400 ℃, no corresponding absorption peak is detected, which indicates that the adhesive does not release sulfide and other substances to the environment.
The above results show that the binder of the present invention does not contain carbide and sulfide, compared to conventional binders, which release harmful components such as carbide and sulfide to the environment.
4. The gas infrared when the refractory magnesia bricks prepared by two different binders are heated is detected by combining thermal weight infrared, the heating maximum temperature is set to 1200 ℃, and the detection result is shown in figure 4. The mass residual quantity of the refractory brick prepared by the adhesive is 99.5 percent after being heated, and the mass residual quantity of the refractory brick prepared by the existing adhesive is 96.5 percent after being heated.
The above results show that the binders currently used by refractory companies contain a large amount of organic and sulphide compounds, which are not detected after firing of the refractory magnesia bricks, indicating that these materials have been discharged into the atmosphere during the preparation of the refractory magnesia bricks. In contrast, the adhesive of the invention does not generate gas in the heating process and does not generate harmful gas to the environment.
5. After the refractory magnesia brick is pressed and formed, certain strength is required to be maintained, so that the refractory magnesia brick is prevented from being lost in the transfer process. The compressive strength of the green bricks formed by the materials is detected by a pressure tester, so that the vulnerability of the environment-friendly refractory magnesia brick prepared by the invention to the existing refractory magnesia brick is compared. The two refractory magnesia bricks have the same preparation process, the difference is that the raw materials are different, and the green compressive strength and the physical property detection result of the fired refractory magnesia brick are shown in the following table 1, wherein the green compressive strength and the physical property detection result of the conventional refractory magnesia brick are obtained by the environment-friendly refractory magnesia brick prepared in the embodiment 1 of the invention.
TABLE 1 results of physical property tests of the inventive and conventional refractory magnesite bricks
As can be seen from the detection results, the green brick compressive strength of the adhesive is higher than that of the conventional green brick, which shows that the adhesive provided by the invention has good adhesion, and the self-made refractory magnesia brick of the invention shows physical properties which are not inferior to those of the conventional magnesia brick, and the conventional physical properties of the refractory magnesia brick of the invention are not inferior to those of the conventional refractory magnesia brick except that the refractory magnesia brick of the invention shows environmental friendliness.
Example 2
An environment-friendly refractory magnesia brick for a cement kiln comprises the following raw materials in parts by mass:
65 parts of periclase, 5 parts of binder and 32 parts of fused magnesia;
particle size of periclase: d90:220 μm; electric smelting magnesite: particle diameter D 90 ：40μm；
The binder is as follows: the weight percent is as follows: 40 parts of phosphoric acid (with the concentration of 85 wt%) 40 parts of water, 8 parts of metal oxide powder and 2 parts of oxalic acid; the preparation method of the metal oxide powder comprises the following steps: mixing magnesium hydroxide and aluminum hydroxide in a ratio of 27:41 in an automatic sample mixer for 30min to obtain the magnesium hydroxide-aluminum hydroxide composite material; the preparation process of the adhesive comprises the following steps: the formula amount of phosphoric acid is firstly mixed with water, mixed and stirred for 5 minutes, then oxalic acid is added, and stirring is continued for 5 minutes. And then slowly adding metal oxide powder into the solution while stirring, adding a small amount of the metal oxide powder every time, adding 2% of the total amount of the metal oxide powder every time, slowly sprinkling the solution after the powder added last time is fused into the liquid, continuously stirring for 2 hours after all the powder is sprinkled into the liquid until the solution is uniform, stopping stirring, standing to cool the solution, filtering, and discarding a small amount of insoluble solids to obtain the liquid binder.
The preparation method of the environment-friendly refractory magnesia brick for the cement kiln comprises the following steps: adding periclase and a binder into a sample mixing pot according to the formula proportion, and setting proper rotating speed: 5r/min, mixing for 30min, adding the mixed powder into fused magnesia, and continuing mixing for 2h. The mixed mixture was placed in a 230X 165X 65mm mold and the highest pressure was set on the press: maintaining pressure, making the green bricks, demoulding, placing the green bricks in a high-temperature furnace, programming to heat up to 10 ℃/min, keeping the temperature for 2 hours after the temperature reaches 200 ℃, continuously heating up to 1600 ℃, and firing for 4 hours to obtain the refractory magnesia bricks.
Test characterization:
1. the adhesive prepared in example 2 has no obvious absorption peak in the infrared spectrogram from room temperature to 1400 ℃, and fig. 5 is an infrared spectrogram detected in different temperature sections, and as can be seen from fig. 5, the adhesive of the invention has no obvious infrared absorption peak, which shows that the adhesive does not release harmful gas to the environment when being heated.
2. After the refractory magnesia brick is pressed and formed, certain strength is required to be maintained, so that the refractory magnesia brick is prevented from being lost in the transfer process. The compressive strength of the green bricks after the molding of the materials was measured by a pressure tester to compare the vulnerability of the environment-friendly type refractory magnesia bricks prepared in example 2 with the existing refractory magnesia bricks. The two refractory magnesia bricks were prepared in the same process except that the raw materials were selected differently, and the compressive strength of the green brick and the physical properties of the fired refractory magnesia brick are shown in Table 2 below.
TABLE 2 physical Property test results of the inventive and conventional refractory magnesite bricks
As can be seen from the detection results, the compressive strength of the green brick using the adhesive is higher than that of the conventional green brick, which shows that the adhesive provided by the invention has good adhesion, and the self-made refractory magnesia brick of the invention shows no physical properties inferior to those of the conventional magnesia brick, so that the refractory magnesia brick of the invention has no physical properties inferior to those of the conventional refractory magnesia brick except that the refractory magnesia brick of the invention shows environmental friendliness.
Example 3
An environment-friendly refractory magnesia brick for a cement kiln comprises the following raw materials in parts by mass:
62 parts of periclase, 1 part of binder and 34 parts of fused magnesia;
particle size of periclase: d90:200 μm; electric smelting magnesite: particle diameter D 90 ：46μm；
The binder is as follows: the weight percent is as follows: 45 parts of phosphoric acid (with the concentration of 85 wt%) and 35 parts of water, 12 parts of metal oxide powder and 1 part of oxalic acid; the preparation method of the metal oxide powder comprises the following steps: mixing magnesium hydroxide and aluminum hydroxide in an automatic sample mixer for 30min according to the proportion of 28:38 to obtain the magnesium hydroxide-aluminum hydroxide composite material; the preparation process of the adhesive comprises the following steps: the formula amount of phosphoric acid is firstly mixed with water, mixed and stirred for 5 minutes, then oxalic acid is added, and stirring is continued for 5 minutes. And then slowly adding metal oxide powder into the solution while stirring, adding 2.5% of the total amount each time, slowly sprinkling the solution after the powder added last time is fused into the liquid, continuously stirring for 2 hours after all sprinkling, stopping stirring until the solution is uniform, standing to cool the solution, filtering, and discarding a small amount of insoluble solids to obtain the liquid binder.
The preparation method of the environment-friendly refractory magnesia brick for the cement kiln comprises the following steps: adding periclase and a binder into a sample mixing pot according to the formula proportion, and setting proper rotating speed: 5r/min, mixing for 30min, adding the mixed powder into fused magnesia, and continuing mixing for 2h. The mixed mixture was placed in a 230X 165X 65mm mold and the highest pressure was set on the press: maintaining pressure, making the green bricks, demoulding, placing the green bricks in a high-temperature furnace, programming to heat up to 10 ℃/min, keeping the temperature for 2 hours after the temperature reaches 200 ℃, continuously heating up to 1600 ℃, and firing for 4 hours to obtain the refractory magnesia bricks.
Test characterization:
1. the adhesive of example 3 of the present invention did not find obvious absorption peaks in the infrared spectrum from room temperature to 1400 ℃, fig. 6 is an infrared spectrum of detection at different temperature ranges, and it can be observed from fig. 6 that the adhesive of the present invention has no obvious infrared absorption peaks, indicating that the adhesive does not release harmful gas to the environment when the adhesive is heated.
2. After the refractory magnesia brick is pressed and formed, certain strength is required to be maintained, so that the refractory magnesia brick is prevented from being lost in the transfer process. The compressive strength of the green bricks formed by the materials is detected by a pressure tester, so that the vulnerability of the environment-friendly refractory magnesia bricks and the existing refractory magnesia bricks is compared. The two refractory magnesia bricks were prepared in the same process except that the raw materials were selected differently, and the compressive strength of the green brick and the physical properties of the fired refractory magnesia brick are shown in Table 3 below.
TABLE 3 physical property test results of the inventive and conventional refractory magnesite bricks
As can be seen from the detection results, the compressive strength of the green brick using the adhesive is higher than that of the conventional green brick, which shows that the adhesive provided by the invention has good adhesion, and the self-made refractory magnesia brick of the invention shows no physical properties inferior to those of the conventional magnesia brick, so that the refractory magnesia brick of the invention has no physical properties inferior to those of the conventional refractory magnesia brick except that the refractory magnesia brick of the invention shows environmental friendliness.
Example 4 (as a comparison)
An environment-friendly refractory magnesia brick for a cement kiln comprises the following raw materials in parts by mass:
65 parts of periclase and the like,adhesive 0.5 part32 parts of fused magnesite;
particle size of periclase: d90:220 μm; electric smelting magnesite: particle diameter D 90 ：40μm；
The binder is as follows: the weight percent is as follows: 40 parts of phosphoric acid (with the concentration of 85 wt%) 40 parts of water, 8 parts of metal oxide powder and 2 parts of oxalic acid; the preparation method of the metal oxide powder comprises the following steps: mixing magnesium hydroxide and aluminum hydroxide in a ratio of 27:41 in an automatic sample mixer for 30min to obtain the magnesium hydroxide-aluminum hydroxide composite material; the preparation process of the adhesive comprises the following steps: the formula amount of phosphoric acid is firstly mixed with water, mixed and stirred for 5 minutes, then oxalic acid is added, and stirring is continued for 5 minutes. And then slowly adding metal oxide powder into the solution while stirring, adding 2.5% of the total amount each time, slowly sprinkling the solution after the powder added last time is fused into the liquid, continuously stirring for 2 hours after all sprinkling, stopping stirring until the solution is uniform, standing to cool the solution, filtering, and discarding a small amount of insoluble solids to obtain the liquid binder.
The preparation method of the environment-friendly refractory magnesia brick for the cement kiln comprises the following steps: adding periclase and a binder into a sample mixing pot according to the formula proportion, and setting proper rotating speed: 5r/min, mixing for 30min, adding the mixed powder into fused magnesia, and continuing mixing for 2h. The mixed mixture was placed in a 230X 165X 65mm mold and the highest pressure was set on the press: maintaining pressure, making the green bricks, demoulding, placing the green bricks in a high-temperature furnace, programming to heat up to 10 ℃/min, keeping the temperature for 2 hours after the temperature reaches 200 ℃, continuously heating up to 1600 ℃, and firing for 4 hours to obtain the refractory magnesia bricks.
Test characterization:
after the refractory magnesia brick is pressed and formed, certain strength is required to be maintained, so that the refractory magnesia brick is prevented from being lost in the transfer process. The compressive strength of the green bricks formed by the materials is detected by a pressure tester, so that the vulnerability of the environment-friendly refractory magnesia bricks and the existing refractory magnesia bricks is compared. The two refractory magnesia bricks have the same preparation process, and the difference is that the raw materials are selected differently, the compressive strength of the green brick of the refractory magnesia brick of the embodiment 4 of the invention is 5.6MPa, and the green brick has small compressive strength, so that the green brick is easy to damage in the transferring process, mainly due to the small using amount of the binder.
Example 5 (as a comparison)
An environment-friendly refractory magnesia brick for a cement kiln comprises the following raw materials in parts by mass:
62 parts of periclase, 6 parts of binder and 34 parts of fused magnesia;
particle size of periclase: d90:200 μm; electric smelting magnesite: particle diameter D 90 ：46μm；
The binder is as follows: the weight percent is as follows: 45 parts of phosphoric acid (with the concentration of 85 wt%) and 35 parts of water, 12 parts of metal oxide powder and 1 part of oxalic acid; the preparation method of the metal oxide powder comprises the following steps: mixing magnesium hydroxide and aluminum hydroxide in an automatic sample mixer for 30min according to the proportion of 28:38 to obtain the magnesium hydroxide-aluminum hydroxide composite material; the preparation process of the adhesive comprises the following steps: the formula amount of phosphoric acid is firstly mixed with water, mixed and stirred for 5 minutes, then oxalic acid is added, and stirring is continued for 5 minutes. And then slowly adding metal oxide powder into the solution while stirring, adding 3.5% of the total amount of the metal oxide powder each time, slowly sprinkling the solution after the powder added last time is fused into the liquid, continuously stirring for 2 hours after all the powder is sprinkled into the liquid until the solution is uniform, stopping stirring, standing to cool the solution, filtering, and discarding a small amount of insoluble solids to obtain the liquid binder.
The preparation method of the environment-friendly refractory magnesia brick for the cement kiln comprises the following steps: adding periclase and a binder into a sample mixing pot according to the formula proportion, and setting proper rotating speed: 5r/min, mixing for 30min, adding the mixed powder into fused magnesia, and continuing mixing for 2h. The mixed mixture was placed in a 230X 165X 65mm mold and the highest pressure was set on the press: maintaining pressure, making the green bricks, demoulding, placing the green bricks in a high-temperature furnace, programming to heat up to 10 ℃/min, keeping the temperature for 2 hours after the temperature reaches 200 ℃, continuously heating up to 1600 ℃, and firing for 4 hours to obtain the refractory magnesia bricks.
Test characterization:
1. after the refractory magnesia brick is pressed and formed, certain strength is required to be maintained, so that the refractory magnesia brick is prevented from being lost in the transfer process. The compressive strength of the green bricks formed by the materials is detected by a pressure tester, so that the vulnerability of the environment-friendly refractory magnesia bricks and the existing refractory magnesia bricks is compared. The two refractory magnesia bricks were prepared in the same process except that the raw materials were selected differently, and the compressive strength of the green brick and the physical properties of the fired refractory magnesia brick are shown in Table 4 below.
TABLE 4 physical property test results of the inventive and conventional refractory magnesite bricks
From the above results, it was found that the use of example 5 exhibited a lower bulk density and compressive strength, and that the binder amount, i.e., the solid content of the refractory brick, was reduced, resulting in a reduction in bulk density and compressive strength.
Claims (10)
1. The environment-friendly refractory magnesia brick for the cement kiln is characterized by comprising the following raw materials in parts by mass:
60-65 parts of periclase, 1-5 parts of binder and 32-37 parts of fused magnesia;
the adhesive comprises the following raw materials in parts by mass:
phosphoric acid: 40-60 parts of water: 30-40 parts of metal hydroxide powder: 8-12 parts of oxalic acid: 0-2 parts.
2. The environment-friendly refractory magnesia brick for cement kiln according to claim 1, wherein the preparation method of the binder is as follows: stirring and mixing the formula amount of phosphoric acid with water, adding the formula amount of oxalic acid, continuously stirring and mixing uniformly, adding metal hydroxide powder into the solution under the stirring condition, stopping stirring after mixing uniformly, standing to cool the solution, and filtering to remove insoluble residues to obtain the liquid binder.
3. The environmentally friendly refractory magnesia brick for cement kiln according to claim 2, wherein the metal hydroxide powder is added to the solution in divided portions, each of which is 2% -5% of the total amount.
4. The environmentally friendly refractory magnesia brick for cement kiln according to claim 1 or 2, wherein the metal hydroxide powder is a mixture of magnesium hydroxide and aluminum hydroxide.
5. The environmentally friendly refractory magnesia brick for cement kiln according to claim 1 or 4, wherein the metal hydroxide powder is a mixture of magnesium hydroxide and aluminum hydroxide in a mass ratio of 27-31:37-41.
6. The environmentally friendly refractory magnesia brick for cement kiln according to claim 1, wherein the periclase has a crushed grain size: d90:200-250 μm.
7. The environmentally friendly refractory magnesia brick for cement kiln according to claim 1, wherein the fused magnesia: particle diameter D 90 ：40-50μm。
8. A method for preparing the environment-friendly refractory magnesia brick for a cement kiln according to any one of claims 1 to 7, which is characterized by comprising the following steps:
1) Mixing the periclase with the binder under stirring;
2) Adding the formula amount of fused magnesia, and continuously stirring and mixing;
3) Placing the mixture into a brick pressing mold, pressing bricks, demoulding, and firing at high temperature.
9. The method of claim 8, wherein the stirring and mixing in step 1) is performed at a stirring and mixing rate of: 5-10r/min for 30-35min.
10. The preparation method according to claim 8, wherein after demoulding in the step 3), the green brick is placed in a high temperature furnace, the temperature is programmed to be 10 ℃/min, the temperature is kept for 2-3 hours after reaching 200 ℃, the temperature is continuously increased to 1600 ℃, and the fire-resistant magnesia brick is prepared.
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