TW506860B - Reuse and product of calcium fluoride sludge - Google Patents

Abstract

This invention provides a reuse method of calcium fluoride (CaF2) sludge, which includes following steps: (1) drying the CaF2 sludge at a temperature below 150 DEG C before crashing and sieving into CaF2 powder; (2) blending the dry CaF2 powder, a binder and a mineralizing agent in a dry state and pelletizing the mixture into A earth; (3) blending feldspar, kaolin, quartz and clay by ball mill before spraying for pellet and ageing into basic earth material; and (4) blending the A earth, the binder, the basic earth material, a sintered kaolin, a pottery stone and a ceramic pigment in a dry state before pelletizing, sieving, ageing and press forming, cup body drying and high temperature sintering to achieve an optimal product while concurrently solve environment problem of the CaF2 sludge and to provide benefit of product with applicable value.

Description

506860 Case No. 90102099 Rev. V. Description of the invention (1) The present invention proposes a method for recycling calcium fluoride sludge and its products. More specifically, the present invention relates to a method for treating C generated from sewage treatment plants. a F2 sludge treatment / reprocessing becomes a useful product, especially the ceramic body method, which can simultaneously solve the environmental problems of CaF2 sludge and provide benefits of products with application value. The inventors of this case have considered the following facts: 1. The chemical composition analysis shows that the sewage treatment plant has obvious differences in the CaF2 ACaC03 content of the sludge composition CaF2 due to the reaction between different intermediates [CaC12 > aCa (OH) 2) and HF. The difference in data has a significant effect on subsequent high temperature chemical reactions. 2. It is known from the sintering reaction of separate sludge that when no mineral catalyst (mineralizing agent) is added, the temperature is still a stable compound in the range of 1,100 ° C, and the sintering situation is not ideal. When adding mineralizers (such as CaC03), the reaction temperature will be significantly reduced due to different chemical molar ratios. When the weight ratio CaF2 1: CaC03 1 is mixed, the reaction temperature will decrease by about 20 ° C. The results of differential analysis of TG / DTA were compared. 3. CaF2 has a significant endothermic reaction from 6 3 0 ° C to 81 9 ° C, showing that the mineral phase has changed in this temperature range, so the material difference of providing a low-temperature glass phase with high silica (S i 02) The high temperature compounds (such as F 2 S i 2 07) that will participate in the reaction will help to stabilize the activation of fluorine at high temperature T, and form a stable mineral crystal phase of energy level. 4. Add appropriate amount of high Ming (A 1 2 0 3) content substance in the proportion, can get sintered

900105901.ptc Page 4 506860 _Case No. 90102099_ Year, Month, and Day Amendment_ Five. Description of the invention (2) The stability of the volume contributes to the dimensional stability of the sintered product of the final product. 05. It is known from the experiment that CaF2 sludge is not suitable For wet grinding and mixing, due to the need to add a large amount of water (about 40%) in the process, the maximum drying temperature in the spray drying tower (S praydryer) can reach more than 650 ° C, and the moisture content is high. In the air, CaF2 may be partially converted into hydrolyzed compounds, which may cause secondary pollution. In addition, the high heat consumption requirements of the drying process are not in line with environmental protection and economic principles. 6. CaF2 sludge is dried at low temperature (150 ° C) and then pulverized to dryness to a particle diameter of less than 60 microns, which can effectively increase the specific surface area of CaF2 and promote the intact reaction at high temperature. 7. CaF2 sludge cannot react with alkaline substances at normal temperature. If it cannot be dissolved in water when solidified at ordinary temperature in normal way, this will cause secondary water pollution. The fluoride ion replaces the oxygen 1 ion of the glass phase Si 丨 02 to form a south-energy grade. The stable ore: crystallization of the substance can effectively prevent the fluoride ion from dissolving in the water to pollute the water source. 0 It is based on the inventor's many years of experience and intensive research. Propose a calcium fluoride sludge reuse method and its finished product 9 More specifically, the present invention proposes to treat / reprocess the C a F2 sludge produced by a sewage treatment plant into a useful product 5 in particular a ceramic body Method 5 can simultaneously solve the environmental protection problem of Ca F2 sludge and provide benefits of products with application value. The reuse method of calcium fluoride sludge of the present invention includes as shown in Figure 1. The main stages in the process: (1) Dry the Ca F2 sludge at a temperature below 150 ° C • Crush and sieve the powder to about 60 micrometers to form a dry Ca F2 powder;

900105901.ptc Page 5 506860 Case No. 90102099 V. Description of the invention (3) Correction (2) Dry mixing and granulation of Ca F2 dry powder 5 binder and mineralizer into A soil, (3) feldspar, Shang Lingite quartz and clay ball mill wet mixing J spray granulation, aging to become the basic soil; and (4) A clay, binder basic soil calcined kaolin, pottery grain% and ceramic color dry mixing , Granulation and sieving 5 aging j compression molding j green body drying and high temperature sintering to obtain the best product 0 in the first stage of the calcium fluoride sludge reuse method of the present invention, the 5 series will be Ca F2 sludge at 150 Below ° C, preferably 1 00-1 50 ° C, dried in a rotary kiln at 5 ° C, then closed and pulverized, and sieved &lt; 20ι me sh particles into Ca F2 dry powder. In the calcium fluoride sludge of the present invention, In the first stage of the utilization method5, the binder used is silicon-containing aluminum Metal test compounds, such as Si (, Al2 0 3, and the mineralizer used is Ca &lt; CO, etc. 0 * * * section. Medium 'CaF〇 Sludge J Mineralizer and binder after dry mixing Granulated into particles with a particle size of <20 microns. In the third stage of the calcium fluoride sludge recycling method of the present invention, feldspar clay, quartz and clay are ball-milled and wet-mixed, and spray-granulated to form Particles with a particle size of 90% &lt; 50 micron particles 5 are aged and become the basic soil material. In the fourth stage of the calcium fluoride sludge reuse method of the present invention, the A soil binder, Basic material calcined kaolinite and ceramic pigments are dry-mixed. 5 Granulation j sieving to obtain particles with a particle size of <20 microns' Miao; post-ageing j high-pressure forming with a -400 ton hydraulic press, , Drying the green body at 1 50 ° C, and then at 1, 0 0 0-1, 2 8 0 Ί C under high interference from the final sintered product ί 0

900105901.ptc Page 6 506860 Case No. 90102099 Amendment V. Description of the Invention (4) The products made according to the method of the present invention are mainly ceramic products, including those used for the following: 1. Ceramic outdoor flooring or wall surface Building materials. 2. Porous permeable ceramic building materials. The invention is illustrated by the following examples, but the invention is not limited thereto. Example i Basic chemical analysis of CaF0 sludge] The chemical composition of C a F 2 sludge from a sludge treatment plant was analyzed as loach FAB8-E. FAB-6A. FAB-8AB ^ FAB-8F, 13.21 %. 1.65% ^ 5.42%. 1.81%. Αΐ2〇3 ^ 3.78 ^ 3.06 ^ 4.36- 4.2 ^ Na2〇1.62. 0.47 ^ 0.08 0.41 ^ κ2ο. 0.05 ^ 0.10. 0.14 0.04 M name 〇 1.27 ^ 2.14 0.57. 2.52 ^ CaFy 74.92. 86_17v 51.95, 52.07 ^ Ti02, 0.02- 0.04. 0.02, 0.04. F02〇3 ^ 0.12 ^ 0.38. 0.13, 0.40 ^ CaC03 'face_order; j —4? 25.60 ^ 26.21, loss of combustion p 5.00. 6 · 0〇ρ 11 · 0〇ρ 12.30 ^ Porphyrin 100.00 ^ 100.00, 100.00, 100.00, [CaF9 sludge pre-treatment] CaF9 sludge is dried in a rotary kiln at a temperature below 150 ° C, and then closed and crushed. ' And sieved to about 60 microns of powder to become CaF9 dry powder. [Preparation of ceramic product composition]

The C a F9 dry powder prepared above was drilled with S ί 09, A 19 0q and C a C 0q, j and mineralizers were dry-mixed, and then granulated into particles A with a particle size &lt; 20 microns.

900105901.ptc Page 7 506860 _Case No. 90102099_Year, month, day, amendment V. Description of the invention (5) The chemical agent is dry-mixed, and granulated into particles with a particle size of <20 micrometers A after the absence of feldspar kaolin quartz Wet-mix with clay ball milling, spray granulation into particles with a particle size of 90 ° / 〇 &lt; 50 micron particles; and then ageing to become the basic soil. Basic binder of soil binder% Dry-mixed terrarium granules and ceramic pigments are granulated and sieved to obtain particles with a particle size of &lt; 20 micron J. Aging after lacking 9 Use a 400-ton hydraulic press to form The green body is dried at 150 ° C, and then sintered at a high temperature of 1,000-1,280 ° C to obtain the final product. Analysis of ceramic products The chemical composition of the ceramic products produced above is analyzed as follows As shown • AJL2Q3 15.61% Si02 59.39% K20 2.9.9% N a9〇2. 2 8 ° / 〇CaO 1.57% MgO 0.22% CaF2 12.17% 'Lost combustion 5.77% The ceramic products made above can be used in the following Theoretical molecular formula table: 1 (RO, R90, CaF9): 0.56 AUO,: 3.67 S i 09 The sidewalk paving ceramic products manufactured according to the above have the following characteristics according to CNS-1 3 4 3 1 inspection:

900105901.ptc Page 8 506860 Case No. 90102099 Amendment V. Description of the Invention (6) Water absorption of 0.5%; Flexural strength up to 33.1 kgf / cm; and Acid and alkali resistance test * No response The characteristics and benefits of inventing the reuse method of calcium fluoride sludge are: 1 1 · CaF9 sludge is squeezed into a cake-shaped cake in the original factory area · and packed in anti-seal bags to prevent leakage and pollution during storage and transportation 0 2. Ca f2 sludge of sewage treatment plant is different according to the output of each plant, and δ is counted as 10 0%. The proportion of total reuse is used for raw materials 2 § t 匕 ′ 5 So there will be no remaining CaF2 in the future The sludge must be reprocessed. 03. CaF2 sludge and other raw materials can be converted into non-water-soluble and stable crystalline phases such as ceramics and feldspar through high-temperature solid-state liquid-phase sintering after being formulated in accordance with the design ratio. 5 Very stable Weather resistance and chemical resistance, etc., is a safe and effective final treatment method for Ca F2 sludge. C a F9 sludge is mixed CaF9 than its average content of 60% J: raw material breaks, the ceramic body of the requirements. 5. The ceramic body formed by adding CaF2 sludge has a flexural strength of 3 3.1 kg f / cm, a water absorption rate <1%, good acid and alkali resistance, and T C L P (T o x i c i t y

(Characteristic Leaching Procedure) The results of the toxicant dissolution test related to the content of Cr, Cu, Pb, Zn, Cd, Hg, As, etc. are also far below the environmental protection regulations (EPA) limit (1 ppm). The treated C a F 2 sludge is a safe and once and for all approach.

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Claims (1)

506860 _Case No. 9Q102099_Year Month Date__ VI. Application Patent Scope 1. A method for recycling calcium fluoride (CaF2) sludge, which includes the following stages (1) CaF9 sludge to be taken from a sludge treatment plant Place at 150t: dry, crush and sieve into CaF2 dry powder at the following temperature; (2) dry mix and granulate CaF2 dry powder, binder and mineralizer into A soil, (3) feldspar, kaolin, quartz and clay It is ball-milled and mixed by mixing, spraying materials, and aging to become basic soil; and (4) dry-mixing A soil, binder, basic soil, calcined kaolin, pottery grain, and ceramic color. , Granulation, sieving, aging, high pressure forming, bad body drying, high temperature sintering into the best product. 2. The calcium fluoride sludge reuse method as described in item 1 of the scope of patent application, wherein the sludge is treated and reused at 100% ° 3. A product containing CaF9 sludge, which is used as described in the patent application scope Produced by the method of item 1. 4. If the product in the scope of application for item 3 of the patent is ceramic outdoor flooring or wall building material, or porous water-permeable ceramic building material. 900105901.ptc Page 11