CN114368973A - Formula, production process and method of environment-friendly refractory material - Google Patents
Formula, production process and method of environment-friendly refractory material Download PDFInfo
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- CN114368973A CN114368973A CN202111594078.7A CN202111594078A CN114368973A CN 114368973 A CN114368973 A CN 114368973A CN 202111594078 A CN202111594078 A CN 202111594078A CN 114368973 A CN114368973 A CN 114368973A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 239000011819 refractory material Substances 0.000 title claims abstract description 54
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 81
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000003756 stirring Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000013535 sea water Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 38
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 38
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 38
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 38
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 26
- 239000010459 dolomite Substances 0.000 claims abstract description 23
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 23
- 239000008267 milk Substances 0.000 claims abstract description 23
- 210000004080 milk Anatomy 0.000 claims abstract description 23
- 235000013336 milk Nutrition 0.000 claims abstract description 23
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 22
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 22
- 239000004571 lime Substances 0.000 claims abstract description 22
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 86
- 238000010438 heat treatment Methods 0.000 claims description 44
- 238000001354 calcination Methods 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 7
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 42
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 34
- 239000002994 raw material Substances 0.000 abstract description 29
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 16
- 239000002912 waste gas Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 23
- 229910001430 chromium ion Inorganic materials 0.000 description 21
- -1 hydroxide ions Chemical class 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 150000001845 chromium compounds Chemical class 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 230000001988 toxicity Effects 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 7
- 238000007873 sieving Methods 0.000 description 6
- 229940117975 chromium trioxide Drugs 0.000 description 4
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 239000004744 fabric Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011821 neutral refractory Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
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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
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- 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
- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
- C04B2235/321—Dolomites, i.e. mixed calcium magnesium carbonates
-
- 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
- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a formula, a production process and a method of an environment-friendly refractory material, belonging to the technical field of refractory materials, the formula of the environment-friendly refractory material comprises the following components by mass: 30-40 parts of magnesium blank, 2-4 parts of lime milk, 30-40 parts of binding agent, 8-10 parts of water and 30-40 parts of chromium oxide, wherein the magnesium blank comprises 45-55 parts of magnesite, 45-55 parts of seawater magnesia and 5-15 parts of dolomite; also comprises sodium hydroxide and a mixture of manganese dioxide and oxalic acid; through after stirring raw materials intensive mixing, the material surface can cover one deck chromic oxide granule, the fire resistance of improvement material that can be very big, make its operational environment that can bear higher temperature, at the mixing stirring in-process, through adding sodium hydroxide, sodium hydroxide meets water and can hydrolysising into hydroxyl ion and sodium ion, accessible sodium ion absorbs the sulfide ion in the reaction raw materials, can effectually reduce the emission of sulfur dioxide waste gas in the production process, thereby reach environmental protection effect.
Description
Technical Field
The invention relates to the technical field of refractory materials, in particular to a formula, a production process and a method of an environment-friendly refractory material.
Background
The refractory material is an inorganic non-metallic material with refractoriness not lower than 1580 ℃. Refractoriness is the degree centigrade at which a sample of the refractory cone resists high temperatures without softening and melting down without loading. However, the definition of refractoriness alone does not fully describe the refractory material, and 1580 ℃ is not absolute. Materials that are now defined as materials whose physicochemical properties allow them to be used in high temperature environments are referred to as refractory materials. The refractory material is widely used in the industrial fields of metallurgy, chemical industry, petroleum, mechanical manufacturing, silicate, power and the like, and the use amount is the largest in the metallurgical industry and accounts for 50-60% of the total output;
the refractory materials in the prior art are mainly divided into acid refractory materials, neutral refractory materials and alkaline refractory materials, the alkaline refractory materials are commonly used in a plurality of chemical fields such as glass production, high-temperature furnace lining materials, kettle linings of petroleum and chemical industry, but when the alkaline refractory materials are produced in the prior art, a plurality of raw materials such as magnesium-containing ores and sulfurous acid pulp waste liquid are commonly used, the refractoriness is not high enough, the ultra-high temperature refractory cannot be achieved, a plurality of waste gases such as sulfur dioxide can be produced during production, the sulfur dioxide waste gas is a main waste gas polluting the environment, and the production process and the method of the environment-friendly refractory materials are particularly important for reducing the pollution of the waste gas to the environment.
Disclosure of Invention
The invention aims to provide a formula, a production process and a method of an environment-friendly refractory material, aiming at solving the problems that the refractory material in the prior art cannot be used in a working environment with ultrahigh-temperature fire resistance and sulfur dioxide waste gas which affects the environment can be discharged in the production process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the formula of the environment-friendly refractory material comprises the following components in parts by mass: 30-40 parts of magnesium blank, 2-4 parts of lime milk, 30-40 parts of bonding agent, 8-10 parts of water and 30-40 parts of chromium oxide.
Preferably, the magnesian blank comprises 45-55 parts of magnesite, 45-55 parts of seawater magnesite and 5-15 parts of dolomite.
Preferably, the material formulation further comprises sodium hydroxide and a mixture of manganese dioxide and oxalic acid.
Preferably, the binding agent is spent sulfite pulp liquor.
A production method of an environment-friendly refractory material comprises the following steps:
step one, adding 45-55 parts of magnesite into a high-temperature fire furnace for firing for 30-50min, taking out and then putting into a crusher for crushing;
step two, taking the seawater precipitate, putting the seawater precipitate into a barrel, firing the seawater precipitate at a high temperature for 1 to 2 hours, and extracting 45 to 55 parts of fired seawater magnesite;
step three, putting 30-40 parts of prepared chromium oxide, 2-4 parts of lime milk and 5-15 parts of dolomite into a crusher for crushing;
screening by a screen;
putting 45-55 parts of sieved magnesite, 45-55 parts of seawater magnesia, 30-40 parts of chromium oxide, 2-4 parts of lime milk, 5-15 parts of dolomite and 8-10 parts of water into a stirring barrel, and fully mixing and stirring for 30-50 min;
sixthly, heating the stirring barrel at high temperature;
seventhly, adding 30-40 parts of the sulfite pulp waste liquid into a stirring barrel, and fully mixing and stirring for 2-4 hours;
step eight, adding the mixture of sodium hydroxide, manganese dioxide and oxalic acid into a stirring barrel, and fully mixing and stirring for 1-3 hours;
step nine, taking out the colloidal substance in the stirring barrel, pouring the colloidal substance into a storage container, and cooling for 8-10 h;
step ten, a production process and a method for obtaining the environment-friendly refractory material by molding.
Preferably, the screen in the fourth step is a 600-800 mesh screen.
Preferably, the heating temperature in the sixth step is 1000-.
Preferably, the preparation method of the chromic oxide is a method of calcining chromic anhydride,
the chemical formula is as follows: na (Na)2Cr2O7+2H2SO4→2CrO3+2NaHSO4+H2And O, the specific steps are as follows:
step 1, adding sodium dichromate into a reaction barrel, injecting concentrated sulfuric acid, heating and stirring;
step 2, pouring the mixture in the reaction barrel into a standing barrel, and standing for 6-8 h;
step 3, taking out the sodium bisulfate on the upper layer in the standing barrel, and heating the standing barrel;
step 4, adding water for washing, and taking chromic anhydride out of the standing barrel;
step 5, putting chromic anhydride into a high-temperature heating furnace for heating and calcining;
and step 6, washing with clear water, and filtering to obtain the chromium sesquioxide.
Preferably, the mass ratio of the sodium hydroxide to the mixture of manganese dioxide and oxalic acid is 3: 1.
preferably, the preparation method of the chromium oxide can also adopt an ammonium chloride reduction method or a calcined chromium hydroxide method.
Compared with the prior art, the invention provides a formula, a production process and a method of an environment-friendly refractory material, and the environment-friendly refractory material has the following beneficial effects:
1. the formula, the production process and the method of the environment-friendly refractory material are characterized in that magnesite, seawater magnesia, dolomite, lime milk, sulfurous acid pulp waste liquid and water are mixed, heated and stirred, in the processing process, the chromium sesquioxide is added, the temperature is raised, after the mixture is fully mixed and stirred, the surface of the material is covered with a layer of chromium sesquioxide particles, the chromium sesquioxide is the oxide with the best corrosion resistance in high-temperature oxides, and the hardness and the fire resistance of the chromium sesquioxide are good, the added chromium oxide can greatly improve the fire resistance of the refractory material, so that the refractory material can bear a higher-temperature working environment, in the mixing and stirring process, sodium hydroxide is added and can be hydrolyzed into hydroxide ions and sodium ions when meeting water, the sulfur ions in the reaction raw material can be absorbed by sodium ions, and the reaction equation is 2NaOH + SO.2→Na2SO3+H2O, can effectively reduce the emission of sulfur dioxide waste gas in the production process, thereby achieving the effect of environmental protection.
2. Under the high-temperature environment in the production process, chromium sesquioxide is oxidized into hexavalent chromium ions, a mixture of manganese dioxide and oxalic acid is added in the reaction process, the manganese dioxide is used as a catalyst, oxalic acid is hydrolyzed into oxalate ions, and the hexavalent chromium ions are reduced into trivalent chromium ions, so that the hexavalent chromium compounds generated in the production process are effectively reduced, and the toxicity of the chromium compounds is effectively reduced.
3. Through crossing the screen cloth to the material after the breakage in production, can effectually select impurity, and the mesh number through the screen cloth is 700 meshes, can effectually be meticulous material with the material screening, the effectual reaction area of contact that has improved, and then the effectual reaction efficiency and effect that has improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1:
a production process and a method of an environment-friendly refractory material are disclosed, wherein raw materials for preparing the refractory material are prepared according to the composition of equal parts by mass, and the components comprise: 32 parts of magnesium blank, 3 parts of lime milk, 8 parts of water and 33 parts of chromium oxide;
the magnesium blank comprises magnesite ore, seawater sediment and 4 parts of dolomite;
after the preparation of the material is finished, 47 parts of magnesite are taken and added into a high-temperature fire furnace for burning for 30min, and the magnesite is taken out and then put into a crusher for crushing;
taking the seawater precipitate, putting into a barrel, firing at high temperature for 1.5h, and extracting 47 parts of fired seawater magnesia;
the chromic oxide is prepared by a chromic anhydride calcining method, which comprises the following specific steps: adding sodium dichromate into a reaction barrel, injecting concentrated sulfuric acid, heating and stirring; pouring the mixture in the reaction barrel into a standing barrel, and standing for 7 hours; taking out the sodium bisulfate on the upper layer in the standing barrel, and heating the standing barrel; adding water for washing, and taking chromic anhydride out of the standing barrel; putting chromic anhydride into a high-temperature heating furnace for heating and calcining; washing with clear water, filtering to obtain 33 parts of chromium sesquioxide, adding the prepared chromium sesquioxide into a reaction barrel, heating and fully stirring to obtain the high-temperature resistant material. The magnesite, seawater magnesite, dolomite, lime milk, sulfurous acid paper pulp waste liquid and water are mixed, heated and stirred, in the processing process, chromium sesquioxide is added, after the temperature is increased, and after full mixing and stirring, the surface of the material can be covered with a layer of chromium sesquioxide particles, the chromium sesquioxide is the oxide with the best corrosion resistance in high-temperature oxides, the hardness and the fire resistance of the chromium sesquioxide are good, and the added chromium sesquioxide can greatly improve the fire resistance of the refractory material and enable the refractory material to bear the working environment with higher temperature.
Example 2:
a production process and a method of an environment-friendly refractory material are disclosed, wherein raw materials for preparing the refractory material are prepared according to the composition of equal parts by mass, and the components comprise: 39 parts of magnesium blank, 3 parts of lime milk, 9 parts of water and 37 parts of chromium oxide;
the magnesium blank comprises magnesite ore, seawater sediment and 4 parts of dolomite;
after the preparation of the material is finished, adding 44 parts of magnesite into a high-temperature fire furnace for firing for 40min, taking out and then putting into a crusher for crushing;
taking the seawater precipitate, putting the seawater precipitate into a barrel, firing the seawater precipitate at a high temperature for 1.5 hours, and extracting 44 parts of fired seawater magnesia;
the chromic oxide is prepared by a chromic anhydride calcining method, which comprises the following specific steps: adding sodium dichromate into a reaction barrel, injecting concentrated sulfuric acid, heating and stirring; pouring the mixture in the reaction barrel into a standing barrel, and standing for 7 hours; taking out the sodium bisulfate on the upper layer in the standing barrel, and heating the standing barrel; adding water for washing, and taking chromic anhydride out of the standing barrel; putting chromic anhydride into a high-temperature heating furnace for heating and calcining; washing with clear water, filtering to obtain 37 parts of chromium sesquioxide, putting the prepared raw materials into a 700-mesh screen for sieving, heating the sieved raw materials in a reaction barrel, and fully stirring to obtain the high-temperature resistant material. The method comprises the following steps of mixing, heating and stirring magnesite, seawater magnesia, dolomite, lime milk, sulfurous acid pulp waste liquid and water, adding chromium oxide in a processing process, raising the temperature, fully mixing and stirring, covering a layer of chromium oxide particles on the surface of a material, wherein the chromium oxide is an oxide with the best corrosion resistance in high-temperature oxides, the hardness and the fire resistance of the chromium oxide are good, the added chromium oxide can greatly improve the fire resistance of a refractory material, so that the refractory material can bear a working environment with higher temperature, passing the crushed material through a screen in production, effectively screening impurities, and effectively screening the material into fine materials, effectively improving the reaction contact area, and further effectively improving the reaction efficiency and the reaction effect.
Example 3:
a production process and a method of an environment-friendly refractory material are disclosed, wherein raw materials for preparing the refractory material are prepared according to the composition of equal parts by mass, and the components comprise: 35 parts of magnesium blank, 3 parts of lime milk, 9 parts of water and 35 parts of chromium oxide;
the magnesium blank comprises magnesite ore, seawater sediment and 4 parts of dolomite;
after the preparation of the material is finished, 50 parts of magnesite are added into a high-temperature fire furnace to be fired for 40min, and the magnesite is taken out and then put into a crusher to be crushed;
taking the seawater precipitate, putting into a barrel, firing at high temperature for 1.5h, and extracting 50 parts of fired seawater magnesia;
the chromic oxide is prepared by a chromic anhydride calcining method, which comprises the following specific steps: adding sodium dichromate into a reaction barrel, injecting concentrated sulfuric acid, heating and stirring; pouring the mixture in the reaction barrel into a standing barrel, and standing for 6-8 h; taking out the sodium bisulfate on the upper layer in the standing barrel, and heating the standing barrel; adding water for washing, and taking chromic anhydride out of the standing barrel; putting chromic anhydride into a high-temperature heating furnace for heating and calcining; washing with clear water, filtering to obtain 35 parts of chromium sesquioxide, putting the prepared raw materials into a 700-mesh screen for sieving, adding a mixture of sodium hydroxide, manganese dioxide and oxalic acid into a reaction barrel of the sieved raw materials after stirring for 30min, and heating and fully stirring to obtain the high temperature resistant material. Magnesite, seawater magnesia, dolomite, lime milk, sulfurous acid pulp waste liquid and water are mixed, heated and stirred, in the processing process, chromium sesquioxide is added, after the temperature is increased and fully mixed and stirred, the surface of a material can be covered with a layer of chromium sesquioxide particles, the chromium sesquioxide is the oxide with the best corrosion resistance in high-temperature oxides, the hardness and the fire resistance of the chromium sesquioxide are good, the fire resistance of a refractory material can be greatly improved through the added chromium sesquioxide, the refractory material can bear the working environment with higher temperature, the crushed material passes through a screen in production, impurities can be effectively screened, and the mesh number of the screen is 700The method can effectively screen materials into fine materials, effectively improve the reaction contact area and further effectively improve the reaction efficiency and effect; in the mixing and stirring process, sodium hydroxide is added, the sodium hydroxide can be hydrolyzed into hydroxide ions and sodium ions when meeting water, the sulfur ions in the reaction raw materials can be absorbed by the sodium ions, and the reaction equation is 2NaOH + SO2→Na2SO3+H2O, the emission of sulfur dioxide waste gas in the production process can be effectively reduced, so that the environment-friendly effect is achieved; under the high-temperature environment in the production process, chromium sesquioxide is oxidized into hexavalent chromium ions, a mixture of manganese dioxide and oxalic acid is added in the reaction process, the manganese dioxide is used as a catalyst, oxalic acid is hydrolyzed into oxalate ions, and the hexavalent chromium ions are reduced into trivalent chromium ions, so that the hexavalent chromium compounds generated in the production process are effectively reduced, and the toxicity of the chromium compounds is effectively reduced.
Example 4:
a production process and a method of an environment-friendly refractory material are disclosed, wherein raw materials for preparing the refractory material are prepared according to the composition of equal parts by mass, and the components comprise: 30 parts of magnesium blank, 3 parts of lime milk, 9 parts of water and 30 parts of chromium oxide;
the magnesium blank comprises magnesite ore, seawater sediment and 4 parts of dolomite;
after the preparation of the material is finished, adding 40 parts of magnesite into a high-temperature furnace for firing for 40min, taking out and then putting into a crusher for crushing;
taking the seawater precipitate, putting into a barrel, firing at high temperature for 1.5h, and extracting 40 parts of fired seawater magnesia;
the chromic oxide is prepared by a chromic anhydride calcining method, which comprises the following specific steps: adding sodium dichromate into a reaction barrel, injecting concentrated sulfuric acid, heating and stirring; pouring the mixture in the reaction barrel into a standing barrel, and standing for 6-8 h; taking out the sodium bisulfate on the upper layer in the standing barrel, and heating the standing barrel; adding water for washing, and taking chromic anhydride out of the standing barrel; putting chromic anhydride into a high-temperature heating furnace for heating and calcining; washing with clear water, filtering to obtain 30 parts of chromium sesquioxide, and placing the prepared raw materials into a 700-mesh screenAnd (3) sieving, namely adding a mixture of sodium hydroxide, manganese dioxide and oxalic acid into a reaction barrel of the sieved raw materials after stirring for 30min, and heating and fully stirring to obtain the high-temperature-resistant material. The method comprises the following steps of mixing, heating and stirring magnesite, seawater magnesia, dolomite, lime milk, sulfurous acid pulp waste liquid and water, adding chromium sesquioxide in the processing process, raising the temperature, fully mixing and stirring, covering a layer of chromium sesquioxide particles on the surface of a material, wherein the chromium sesquioxide is an oxide with the best corrosion resistance in high-temperature oxides, and has better hardness and fire resistance; in the mixing and stirring process, sodium hydroxide is added, the sodium hydroxide can be hydrolyzed into hydroxide ions and sodium ions when meeting water, the sulfur ions in the reaction raw materials can be absorbed by the sodium ions, and the reaction equation is 2NaOH + SO2→Na2SO3+H2O, the emission of sulfur dioxide waste gas in the production process can be effectively reduced, so that the environment-friendly effect is achieved; under the high-temperature environment in the production process, chromium sesquioxide is oxidized into hexavalent chromium ions, a mixture of manganese dioxide and oxalic acid is added in the reaction process, the manganese dioxide is used as a catalyst, oxalic acid is hydrolyzed into oxalate ions, and the hexavalent chromium ions are reduced into trivalent chromium ions, so that the hexavalent chromium compounds generated in the production process are effectively reduced, and the toxicity of the chromium compounds is effectively reduced.
Example 5:
a production process and a method of an environment-friendly refractory material are disclosed, wherein raw materials for preparing the refractory material are prepared according to the composition of equal parts by mass, and the components comprise: 30 parts of magnesium blank, 3 parts of lime milk, 9 parts of water and 30 parts of chromium oxide;
the magnesium blank comprises magnesite ore, seawater sediment and 4 parts of dolomite;
after the preparation of the material is finished, adding 40 parts of magnesite into a high-temperature furnace for firing for 40min, taking out and then putting into a crusher for crushing;
taking the seawater precipitate, putting into a barrel, firing at high temperature for 1.5h, and extracting 40 parts of fired seawater magnesia;
the chromic oxide is prepared by a chromic anhydride calcining method, which comprises the following specific steps: adding sodium dichromate into a reaction barrel, injecting concentrated sulfuric acid, heating and stirring; pouring the mixture in the reaction barrel into a standing barrel, and standing for 6-8 h; taking out the sodium bisulfate on the upper layer in the standing barrel, and heating the standing barrel; adding water for washing, and taking chromic anhydride out of the standing barrel; putting chromic anhydride into a high-temperature heating furnace for heating and calcining; washing with clear water, filtering to obtain 30 parts of chromium sesquioxide, putting the prepared raw materials into a 700-mesh screen for sieving, adding a mixture of sodium hydroxide, manganese dioxide and oxalic acid into a reaction barrel of the sieved raw materials after stirring for 30min, and heating and fully stirring to obtain the high temperature resistant material. The method comprises the following steps of mixing, heating and stirring magnesite, seawater magnesia, dolomite, lime milk, sulfurous acid pulp waste liquid and water, adding chromium sesquioxide in the processing process, raising the temperature, fully mixing and stirring, covering a layer of chromium sesquioxide particles on the surface of a material, wherein the chromium sesquioxide is an oxide with the best corrosion resistance in high-temperature oxides, and has better hardness and fire resistance; in the mixing and stirring process, sodium hydroxide is added, the sodium hydroxide can be hydrolyzed into hydroxide ions and sodium ions when meeting water, the sulfur ions in the reaction raw materials can be absorbed by the sodium ions, and the reaction equation is 2NaOH + SO2→Na2SO3+H2O, sulfur dioxide waste gas in the production process can be effectively reducedThe environment-friendly effect is achieved; under the high-temperature environment in the production process, chromium sesquioxide is oxidized into hexavalent chromium ions, a mixture of manganese dioxide and oxalic acid is added in the reaction process, the manganese dioxide is used as a catalyst, oxalic acid is hydrolyzed into oxalate ions, and the hexavalent chromium ions are reduced into trivalent chromium ions, so that the hexavalent chromium compounds generated in the production process are effectively reduced, and the toxicity of the chromium compounds is effectively reduced.
The ceramic refractory and wear resistance using files were tested in conjunction with the above examples and the performance parameters were as follows:
TABLE 1
Example 6:
a production process and a method of an environment-friendly refractory material are disclosed, wherein raw materials for preparing the refractory material are prepared according to the composition of equal parts by mass, and the components comprise: 30 parts of magnesium blank, 3 parts of lime milk, 9 parts of water and 30 parts of chromium oxide;
the magnesium blank comprises magnesite ore, seawater sediment and 4 parts of dolomite;
after the preparation of the material is finished, adding 40 parts of magnesite into a high-temperature furnace for firing for 40min, taking out and then putting into a crusher for crushing;
taking the seawater precipitate, putting into a barrel, firing at high temperature for 1.5h, and extracting 40 parts of fired seawater magnesia;
preparing chromic oxide by adopting an ammonium chloride reduction method to obtain 30 parts of chromic oxide, putting the prepared raw materials into a 700-mesh screen for sieving, adding the sieved raw materials into a reaction barrel, stirring for 30min, adding a mixture of sodium hydroxide, manganese dioxide and oxalic acid into the reaction barrel, heating and fully stirring to obtain the high-temperature resistant material. Mixing magnesite, seawater magnesite, dolomite and limeThe method comprises the following steps of mixing, heating and stirring milk, sulfurous acid paper pulp waste liquid and water, adding chromium trioxide in the processing process, after the temperature is increased and fully mixing and stirring are carried out, covering a layer of chromium trioxide particles on the surface of a material, wherein the chromium trioxide is an oxide with the best corrosion resistance in high-temperature oxides, and the chromium trioxide is good in hardness and fire resistance; in the mixing and stirring process, sodium hydroxide is added, the sodium hydroxide can be hydrolyzed into hydroxide ions and sodium ions when meeting water, the sulfur ions in the reaction raw materials can be absorbed by the sodium ions, and the reaction equation is 2NaOH + SO2→Na2SO3+H2O, the emission of sulfur dioxide waste gas in the production process can be effectively reduced, so that the environment-friendly effect is achieved; under the high-temperature environment in the production process, chromium sesquioxide is oxidized into hexavalent chromium ions, a mixture of manganese dioxide and oxalic acid is added in the reaction process, the manganese dioxide is used as a catalyst, oxalic acid is hydrolyzed into oxalate ions, and the hexavalent chromium ions are reduced into trivalent chromium ions, so that the hexavalent chromium compounds generated in the production process are effectively reduced, and the toxicity of the chromium compounds is effectively reduced.
Example 7:
a production process and a method of an environment-friendly refractory material are disclosed, wherein raw materials for preparing the refractory material are prepared according to the composition of equal parts by mass, and the components comprise: 30 parts of magnesium blank, 3 parts of lime milk, 9 parts of water and 30 parts of chromium oxide;
the magnesium blank comprises magnesite ore, seawater sediment and 4 parts of dolomite;
after the preparation of the material is finished, adding 40 parts of magnesite into a high-temperature furnace for firing for 40min, taking out and then putting into a crusher for crushing;
taking the seawater precipitate, putting into a barrel, firing at high temperature for 1.5h, and extracting 40 parts of fired seawater magnesia;
preparing chromic oxide by adopting a method of calcining chromium hydroxide to obtain 30 parts of chromic oxide, putting the prepared raw materials into a 700-mesh screen for sieving, putting the sieved raw materials into a reaction barrel, stirring for 30min, adding a mixture of sodium hydroxide, manganese dioxide and oxalic acid into the reaction barrel, heating and fully stirring to obtain the high-temperature resistant material. The method comprises the following steps of mixing, heating and stirring magnesite, seawater magnesia, dolomite, lime milk, sulfurous acid pulp waste liquid and water, adding chromium sesquioxide in the processing process, raising the temperature, fully mixing and stirring, covering a layer of chromium sesquioxide particles on the surface of a material, wherein the chromium sesquioxide is an oxide with the best corrosion resistance in high-temperature oxides, and has better hardness and fire resistance; in the mixing and stirring process, sodium hydroxide is added, the sodium hydroxide can be hydrolyzed into hydroxide ions and sodium ions when meeting water, the sulfur ions in the reaction raw materials can be absorbed by the sodium ions, and the reaction equation is 2NaOH + SO2→Na2SO3+H2O, the emission of sulfur dioxide waste gas in the production process can be effectively reduced, so that the environment-friendly effect is achieved; under the high-temperature environment in the production process, chromium sesquioxide is oxidized into hexavalent chromium ions, a mixture of manganese dioxide and oxalic acid is added in the reaction process, the manganese dioxide is used as a catalyst, oxalic acid is hydrolyzed into oxalate ions, and the hexavalent chromium ions are reduced into trivalent chromium ions, so that the hexavalent chromium compounds generated in the production process are effectively reduced, and the toxicity of the chromium compounds is effectively reduced.
As can be seen from Table 1, examples 6 and 7, magnesite clinker and dolomite were prepared by optimizing and comparing raw materialsThe stone, lime milk, sulfurous acid paper pulp waste liquid, water mix and heat the stirring, in the course of working, through adding chromium sesquioxide, after raising the temperature, after the intensive mixing stirring, the material surface can cover one deck chromium sesquioxide granule, chromium sesquioxide is the best oxide of corrosion resistance among the high temperature oxide, and chromium sesquioxide hardness, fire resistance are all comparatively good, through the chromium sesquioxide that adds, can be very big improvement refractory material's fire resistance, make it can bear the operational environment of higher temperature, in the mixing stirring process, through adding sodium hydroxide, sodium hydroxide can hydrolyze into hydroxyl ion and sodium ion in meeting water, accessible sodium ion absorbs the sulfur ion in the reaction raw materials, the reaction equation is 2NaOH + SO2→Na2SO3+H2O, the emission of sulfur dioxide waste gas in the production process can be effectively reduced, so that the environment-friendly effect is achieved;
under the high-temperature environment in the production process, chromium sesquioxide is oxidized into hexavalent chromium ions, a mixture of manganese dioxide and oxalic acid is added in the reaction process, the manganese dioxide is used as a catalyst, oxalic acid is hydrolyzed into oxalate ions, and the hexavalent chromium ions are reduced into trivalent chromium ions, so that the hexavalent chromium compound generated in the production process is effectively reduced, and the toxicity of the chromium compound is effectively reduced;
impurities can be effectively screened out by passing the crushed materials through a screen in production, and the mesh number of the screen is 700 meshes, so that the materials can be effectively screened out into fine materials, the reaction contact area is effectively increased, and the reaction efficiency and effect are further effectively improved;
the chromic oxide is prepared by adopting a chromic anhydride calcining method, so that the generation of hexavalent chromium compounds can be effectively reduced, the generation of hexavalent chromium compounds is further effectively reduced, and the harm of the production process and the method of the environment-friendly refractory material to human bodies is effectively reduced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. The formula of the environment-friendly refractory material is characterized in that the refractory material comprises the following components in parts by mass: 30-40 parts of magnesium blank, 2-4 parts of lime milk, 30-40 parts of bonding agent, 8-10 parts of water and 30-40 parts of chromium oxide.
2. The formulation of the environment-friendly refractory according to claim 1, wherein the magnesia blank comprises 45-55 parts of magnesite, 45-55 parts of seawater magnesite, and 5-15 parts of dolomite.
3. The formulation of environment-friendly refractory according to claim 2, further comprising sodium hydroxide and a mixture of manganese dioxide and oxalic acid.
4. The formulation of the environment-friendly refractory according to claim 2, wherein the binder is a waste sulfite pulp liquor.
5. The production method of the environment-friendly refractory material is characterized by comprising the following steps:
step one, adding 45-55 parts of magnesite into a high-temperature fire furnace for firing for 30-50min, taking out and then putting into a crusher for crushing;
step two, taking the seawater precipitate, putting the seawater precipitate into a barrel, firing the seawater precipitate at a high temperature for 1 to 2 hours, and extracting 45 to 55 parts of fired seawater magnesite;
step three, putting 30-40 parts of prepared chromium oxide, 2-4 parts of lime milk and 5-15 parts of dolomite into a crusher for crushing;
screening by a screen;
putting 45-55 parts of sieved magnesite, 45-55 parts of seawater magnesia, 30-40 parts of chromium oxide, 2-4 parts of lime milk, 5-15 parts of dolomite and 8-10 parts of water into a stirring barrel, and fully mixing and stirring for 30-50 min;
sixthly, heating the stirring barrel at high temperature;
seventhly, adding 30-40 parts of the sulfite pulp waste liquid into a stirring barrel, and fully mixing and stirring for 2-4 hours;
step eight, adding the mixture of sodium hydroxide, manganese dioxide and oxalic acid into a stirring barrel, and fully mixing and stirring for 1-3 hours;
step nine, taking out the colloidal substance in the stirring barrel, pouring the colloidal substance into a storage container, and cooling for 8-10 h;
step ten, a production process and a method for obtaining the environment-friendly refractory material by molding.
6. The method as claimed in claim 5, wherein the screen in the fourth step is 600-800 mesh screen.
7. The method as claimed in claim 5, wherein the heating temperature in the sixth step is 1000-1200 ℃.
8. The method for producing the environment-friendly refractory according to claim 5, wherein the chromic oxide is prepared by a method of calcining chromic anhydride,
the chemical formula is as follows: na (Na)2Cr2O7+2H2SO4→2CrO3+2NaHSO4+H2And O, the specific steps are as follows:
step 1, adding sodium dichromate into a reaction barrel, injecting concentrated sulfuric acid, heating and stirring;
step 2, pouring the mixture in the reaction barrel into a standing barrel, and standing for 6-8 h;
step 3, taking out the sodium bisulfate on the upper layer in the standing barrel, and heating the standing barrel;
step 4, adding water for washing, and taking chromic anhydride out of the standing barrel;
step 5, putting chromic anhydride into a high-temperature heating furnace for heating and calcining;
and step 6, washing with clear water, and filtering to obtain the chromium sesquioxide.
9. The method for producing the environment-friendly refractory material as claimed in claim 5, wherein the mass ratio of the sodium hydroxide to the mixture of manganese dioxide and oxalic acid is 3: 1;
the preparation method of the chromic oxide can also adopt an ammonium chloride reduction method or a calcined chromium hydroxide method.
10. A process for producing an environment-friendly refractory, characterized by comprising the step of producing the environment-friendly refractory according to claim 8.
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| CN102020478A (en) * | 2010-12-10 | 2011-04-20 | 河南瑞泰耐火材料科技有限公司 | Magnesium-chromium prefabticated member |
| CN104876318A (en) * | 2015-05-29 | 2015-09-02 | 华中师范大学 | Water treatment method for reducing and removing hexavalent chromium with manganese dioxide/oxalic acid substances |
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