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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
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
  • C04B35/22—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in calcium oxide, e.g. wollastonite
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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
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  • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
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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
  • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3427—Silicates other than clay, e.g. water glass
  • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
  • C04B2235/3445—Magnesium silicates, e.g. forsterite
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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
  • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3427—Silicates other than clay, e.g. water glass
  • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
  • C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
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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
  • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3427—Silicates other than clay, e.g. water glass
  • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
  • C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
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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
  • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite

Definitions

• the invention relates to a pyroxene porcelain and a preparation method thereof, and belongs to the technical field of comprehensive utilization of ceramic preparation and solid waste resources.
• China is a big country that produces and consumes ceramic products. It not only has a long history, but also has a wide range of raw materials for making ceramics. However, with the declining natural resources, especially the lack of high-quality traditional ceramic raw materials, the production of ceramics by using traditional natural resources has been With restrictions, it is urgent to seek recyclable ceramic materials. At the same time, China's annual 800 million tons of industrial solid waste accumulated heap stock of over 6.7 billion tons, occupying land reached 654.12 million m 2, in addition to occupy a lot of land, the harmful ingredients contained serious pollution of land and groundwater Threatening the health of millions of people. Therefore, at home and abroad, the focus has been on the use of industrial and mining waste, by-products or low-quality mineral raw materials to manufacture ceramics.
• Traditional ceramics mainly composed of clay, supplemented with mineral components such as feldspar and quartz, which are manufactured by processes such as pulverization, compounding, granulation, forming, drying and sintering.
• the main crystalline phase is mullite. Quartz and glass are equal.
• Ordinary ceramics, also known as clay ceramics or three-component ceramics belong to the SiO 2 -Al 2 O 3 -K 2 O(Na 2 O) ternary system formula, which requires that the raw materials in the porcelain bricks should not contain excessive impurities, of which Fe 2 O 3 mass percentage is usually less than 0.8%, and CaO mass percentage is usually less than 3%. Therefore, traditional ceramics face the threat of high quality mineral resources shortage, depletion and price increase in the production process.
• Talc ceramics are ceramics prepared by using talc as the main raw material. They are mainly used in the field of electronics. They have excellent dielectric properties and low cost, high dielectric strength and good chemical stability, but talc.
• the main raw materials of ceramics are talc and some clay.
• the mass content of harmful impurities CaO and Fe 2 O 3 is less than 1%, and the main crystalline phase contains only MgO. It does not contain the hard pyroxene phase of CaO or Fe 2 O 3 , and therefore, the range of raw materials is narrower, and other low-quality raw materials cannot be utilized.
• Application No. CN101386528A proposes a method for producing ceramic bricks by using metallurgical steel slag, but it needs to increase the iron removal link, the process is complicated, and its magnesium content
• the raw material talc content is 1.0-12%, converted to MgO content of 0.03-3.6%.
• the diopside crystal phase is formed, it is not the main crystal phase, and the finished product size is 600mm*600mm*11mm, and the damage is broken.
• the strength is greater than 2300N, the flexural strength is greater than 20MPa, and the strength is lower; the application publication number is CN102924113A.
• the porous ceramic material is prepared by using copper tailings slag.
• the application number is CN102173740A
• the glazed brick is prepared by using silicon calcium residue.
• Many researches and inventions have been made, but the main crystal phases of the ceramic products are not high CaO, MgO or Fe 2 O 3 systems with pyroxene as the main crystal phase, and their mechanical properties are not high, and the added value is relatively low.
• ceramics having a pyroxene phase as a main crystalline phase not only have high mechanical properties, but also a theoretical composition (mass percentage) CaO of 25.9% of diopside. , MgO is 18.5%, SiO 2 is 55.6%; and the theoretical composition (mass percentage) of the hectorite is 22.6% for CaO, 29.0% for FeO, and 48.4% for SiO 2 .
• the composition of these pyroxene phases The ceramics have exceeded the limit of the content of calcium oxide, iron oxide and magnesium oxide in the raw material composition; at the same time, it is more advantageous that pyroxene is a general term for a class of minerals, in which Ca 2+ exists.
• this mineral phase can not only use a large amount of raw materials containing CaO, FeO, MgO components, but also solidify other Mn 2+ , Ni 2+, Cr 3+, Ti 3+ , such as different impurity ions, which makes the preparation containing the ceramic material into impurity ions green Products as possible.
• the object of the present invention is to provide a pyroxene porcelain and a preparation method thereof, which have a mineral structure with a pyroxene mineral as a main crystal phase, can stably dissolve solid metal ions, and have high mechanical properties.
• a pyroxene porcelain, a pyroxene porcelain (also known as a pyroxene ceramic) is a silica-calcium system ceramic of silica, calcium oxide, and magnesium oxide, aluminum oxide or iron oxide. Its main raw materials can come from solid waste containing calcium, iron or magnesium, and low-quality mineral raw materials, which can be produced in the same production process as traditional ceramics.
• the main components of the raw materials are silicon oxide and calcium oxide, and ceramic systems mainly composed of magnesium oxide, aluminum oxide or iron oxide, wherein the mass percentages of SiO 2 , CaO, MgO, Al 2 O 3 and Fe 2 O 3 are respectively : 30-56%, 12-30%, 3-25%, 2-18%, and 0.1-18%.
• the main raw materials may be various types of solid waste containing calcium, iron or magnesium in the metallurgical, chemical, energy, mining, municipal and materials industries.
• it may be converter slag, electric furnace slag, refining slag, blast furnace slag, stainless steel.
• the ceramic raw material may contain a metal element such as Mn, Ni, Cr, or Ti.
• the main raw materials can be not only traditional ceramic mineral raw materials or solid waste, but also low-quality mineral raw materials, such as low-grade or associated ore, low-quality feldspar minerals, quartz minerals, clay minerals, and One or more of low-quality calcium-containing, magnesium ceramic raw materials, and the like.
• the preparation method of the pyroxene porcelain adopts the solid waste material containing calcium, iron or magnesium, and the low-quality mineral raw material, and adopts the same production process as the traditional ceramic, and the raw material is wet-ground without the iron removal process.
• the highest firing temperature is the actual temperature of the kiln measured by the temperature measuring ring, and the temperature range is 1120 to 1250 °C.
• the product produced by the invention forms a glass phase and a mineral structure mainly composed of a pyroxene mineral, wherein the main crystal phase comprises diopside, hypodiaop, iron diopside, calcite, common Pyroxene, neolithic, Neonite, jadeite, spodumene, stubborn pyroxene, bronze pyroxene, perilla pyroxene, ore pyroxene, chrome diopside, aluminum diopside, aluminum-rich titanium diopside, manganese calcium One or more of stone.
• the main crystal phase comprises diopside, hypodiaop, iron diopside, calcite, common Pyroxene, neolithic, Neonite, jadeite, spodumene, stubborn pyroxene, bronze pyroxene, perilla pyroxene, ore pyroxene, chrome diopside, aluminum diopside, aluminum-rich titanium diopside, manganes
• Pyroxene can be used to replace traditional three-component (quartz-feldspar-clay) ceramics in building ceramics, high-strength ceramics, and corrosion-resistant ceramics, and has better mechanical properties, in which the flexural strength (fracture modulus) More than 50 MPa, under better conditions, it can exceed 100 MPa.
• the prepared pyroxene ceramic can stably dissolve solid waste containing harmful metal element components such as Mn, Ni, Cr, Ti;
• the prepared pyroxene ceramic can utilize a raw material containing a large amount of Fe 2 O 3 component, the iron process can be omitted after the raw material is wet-ground;
• the prepared pyroxene ceramics can not only fully adopt the existing ceramic production process, but also has a quartz phase because the main crystal phase is a pyroxene phase, and the cooling process after firing can adopt a rapid cooling method. Can shorten the preparation time;
• the pyroxene ceramics prepared have excellent properties, and the modulus of rupture is more than 50 MPa, and can even exceed 100 MPa significantly (to 3-4 times the 35 MPa required by the national standard for wall tiles).
• the preparation process of the invention is easy to implement, the iron removal process is omitted, the firing time can be shortened, the energy consumption is saved, and the industrialization promotion and application thereof is beneficial, which has great economic, social value and application prospect.
• the steel slag, talc, clay and pyrophyllite were mixed into a mixture.
• the mass fractions of SiO 2 , CaO, MgO, Al 2 O 3 and Fe 2 O 3 in the mixture were 49.14%, 17.53%, 17.07% and 4.67%, respectively.
• the low-quality iron tailings (Fe 2 O 3 content is 23.63%), steel slag, clay and quartz are mixed into a mixture, and the mass fractions of the main components SiO 2 , CaO, MgO, Al 2 O 3 and Fe 2 O 3 are respectively 45.94%, 21.87%, 3.93%, 5.41% and 17.52%, and added 0.1% sodium hydroxymethylcellulose in the mixture, 0.3% sodium tripolyphosphate was sent to the ball mill and wetted with water, the ball mill slurry passed directly Sieving and drying the powder, pressing and forming, the formed blank is fired into the kiln equipment, the highest sintering temperature is 1120 ° C, the rapid cooling process is used in the firing cooling process, the firing time is 60 minutes, and the main crystalline phase of the product after firing It is a diopside and a calcium pyrite phase with a flexural strength of 71.5 MPa.
• the low-quality iron tailings (Fe 2 O 3 content is 23.63%), steel slag, clay and quartz are mixed into a mixture.
• the main components and composition of the iron removal process are: SiO 2 49.99%, CaO 19.7%, MgO. 4.08%, Al 2 O 3 5.98%, Fe 2 O 3 15.53%, and added 0.1% sodium hydroxymethyl cellulose in the mixture, 0.3% sodium tripolyphosphate was sent to the ball mill and wet-grinded with water, and the ball mill slurry passed.
• the sieve and iron removal process are further spray-dried to form a powder, and the formed body is fired into a kiln apparatus.
• the highest sintering temperature is 1120 ° C, and the firing cooling process uses a rapid cooling process, and the firing time is 60 minutes. After firing, the main crystalline phase of the product is diopside and calcite, and the flexural strength is 75.0 MPa.
• the silicon calcium slag, clay, feldspar, pyrophyllite, quartz and talc are compounded into a mixture.
• the main components and compositions are: SiO 2 48.99%, CaO 13.87%, MgO 7.67%, Al 2 O 3 11.95%, Fe 2 O 3 8.68%, and added 0.1% sodium hydroxymethyl cellulose in the mixture, 0.9% sodium tripolyphosphate was sent to the ball mill and wet-grinded with water, and the ball mill slurry was sieved and dried to be powdered, pressed and formed, and formed.
• the green body was fired into the kiln equipment, and the highest sintering temperature was 1155 ° C.
• the ceramic material with the main crystal phase as diopside, ordinary pyroxene, calcite and anorthite was prepared, and the flexural strength was 102.08 MPa.
• Red mud low-quality clay (including CaO 17.77%, containing Fe 2 O 3 6.82%), feldspar, low-grade quartz ore (containing SiO 2 97.6%, Fe 2 O 3 0.96%), talc formulated into a mixture
• the main components and composition of the mixture were: SiO 2 52.30%, CaO 13.63%, MgO 7.89%, Al 2 O 3 11.24%, Fe 2 O 3 7.48%, and added 0.1% hydroxymethyl cellulose.
• Sodium, 0.3% sodium tripolyphosphate, 1% debonding agent is sent to the ball mill and wet-grinded with water. The ball mill slurry is sieved, dried and powdered, and pressed and molded.
• the formed body is fired into the furnace equipment, and the highest sintering is performed.
• a ceramic material with a main crystal phase of diopside, ordinary pyroxene, calcite and anorthite was prepared, and its flexural strength was 127.39 MPa.
• the blast furnace slag, quartz, clay, talc and burnt talc are compounded into a mixture.
• the main components and composition of the mixture are: SiO 2 44.30%, CaO 25.38%, MgO 7.28%, Al 2 O 3 14.26%, Fe 2 O 3 1.32%, adding 0.1% sodium hydroxymethylcellulose, 0.3% sodium tripolyphosphate and feeding into a ball mill with water wet grinding, ball mill slurry sieving and spray drying to make powder, press forming, after molding
• the billet is fired into the kiln equipment, and the highest sintering temperature is 1145 ° C.
• the ceramic material with the main crystal phase is diopside, ordinary diopside, pyrophorite and yellow feldspar is prepared, and the flexural strength is 68.30 MPa.
• the electric furnace slag, Laiyang soil, Laiwu feldspar, quartz and talc are compounded into a mixture.
• the main components and composition are: SiO 2 37.06%, CaO 33.88%, MgO 10.55%, Al 2 O 3 9.59%, Fe 2 O. 3 0.60%, adding 0.1% sodium hydroxymethylcellulose, 0.3% sodium tripolyphosphate, and feeding it to a ball mill and adding water to wet grinding. After removing the iron and sieving the ball mill slurry, the slurry is dried.
• the powder is further pressed and formed, and the formed blank is fired into a kiln apparatus, and the highest sintering temperature is 1155 ° C, and a ceramic material whose main crystal phase is ordinary pyroxene, diopside, and pyrophorus is prepared.
• the strength is 89.22 MPa.
• the steelmaking refining slag, Laiyang soil, Laiwu feldspar, pyrophyllite, quartz, talc are compounded into a mixture, and 0.1% of sodium hydroxymethylcellulose, 0.3% sodium tripolyphosphate, and the ball mill are added to the mixture.
• Wet grinding, ball milling slurry by iron removal, sieving, drying, its main components and composition are: SiO 2 40.13%, CaO 29.58%, MgO 11.72%, Al 2 O 3 10.47%, Fe 2 O 3 0.70%,
• the dried slurry is powdered and pressed, and the formed body is fired in a kiln apparatus.
• the highest sintering temperature is 1180 ° C, and the main crystal phase is prepared as ordinary pyroxene, diopside, and pyrophoric.
• the ceramic material has a flexural strength of 98.39 MPa.
• the stainless steel slag (including Cr 2 O 3 containing 5.70%), quartz, feldspar, clay and talc is compounded into a mixture, and its main components and composition are: SiO 2 48.37%, CaO 14.09%, MgO 7.52%, Al 2 O 3 17.73%, Fe 2 O 3 1.74%, Cr 2 O 3 1.71%, MnO 0.39%, adding 1:1 water for compounding, ball milling into a ball mill, slurry sieving and drying to make powder, press forming, The formed blank is fired into the kiln equipment, and the highest sintering temperature is 1135 ° C.
• the ceramic material with the main crystal phase is diopside, chrome diopside and common pyroxene is prepared, and the chromium, lead and cadmium heavy metal ions are prepared.
• the dissolution rate is 25.17, 0.01, 0.01 mg/kg, which is far lower than the national standard requirements of 100, 20, 5 mg/kg, and the modulus of rupture and wear volume are 57.3 MPa and 126 mm, respectively, which is better than the national standard (GB/T4100-2006). ) 35MPa and 175mm.

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• 2014
  • 2014-03-04 CN CN201410077167.8A patent/CN103864407A/zh active Pending
• 2015
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