The main gradients of fly-ash are silica, alumina and iron oxide, which can serve as raw materials to produce the products including sodium silicate, white carbon black, alumina, cryolite, high purity ferric oxide, polymeric ferric sulfate and iron oxide red industrial paint and so on, and subsequently realize the comprehensive resource utilization of fly-ash.
1、Process principle：
Firstly, fly-ash was decomposed using a certain inorganic acid in the presence of catalyst, which makes aluminum and iron digesting and entering liquid phase, and at the same time, silica don’t react with the acid and is remained in the residue. After decomposition, the acid leaching solution containing aluminum ion and iron ion, along with the decomposition residue in which silica is the main ingredient, can be obtained by separation. Under certain technological conditions using specific processes, the aluminum and iron in the solution can be used to produce aluminum-based compounds (alumina, aluminum fluoride or cryolite), iron-based compounds (iron oxide red industrial paints, high purity iron oxide, polymeric ferric sulfate). The decomposition residue reacts with bases leads to the formation of sodium silicate, and the sodium silicate was treated using the acid method, and subsequently the high dispersed white carbon black with special used for tire, ultrafine white carbon black or instant sodium silicate can be obtained by controlling technological conditions. During the process, the waste gas was controlled, collected and recycled; the waste residue and waste water can be recycled by a total enclosed manner, which have no effect on the environment.
2、Chemical reactions：
Omission.
3、Technical process：
Omission.
4、The main econo-technical indicators：
5.1、Decomposition rate：
SiO2≥85%；Al2O3≥90%，Fe2O3≥90%。
5.2、Yield coefficient（based on the decomposition rate）：
SiO2≥95%；Al2O3≥95%，Fe2O3≥96%。
5、Economic benefits analysis：
Take Turkey fly-ash 2014051# provided by Koksol Iplik San.Ve.Tic.AS And Refmineral Group as an example, the chemical composition is as follows：SiO2：49.54%；Al2O3：18.47%；Fe2O3：12.32%；CaO：4.74%；MgO：1.51%。
Calculation based on the processing of 1000 kg of fly ash, the product direction is the cryolite, high dispersion white carbon black and iron oxide red industrial paint.
5.1、Total output：
Number Name Output（kg） Unit price（Yuan/kg） Amount（Yuan） Notes
1 Cryolite 696 5.3 3688.8 If producing aluminum fluoride, 265kg of aluminum fluoride can be obtained
2 Iron oxide red industrial paint 252 6.0 1512
3 High dispersed white carbon black 434 8.0 3472
4 Recycling of ordinary white carbon black 212 2.8 593.6 Recycling using ammonium fluoride process
5 Ammonium hydroxide 3822 0.2 764.4 Resulting from waste water treating and the fabrication of cryolite
6 Calcium sulphate dihydrate 2454 0.04 98.2 Produced by treating waste water
Sum 10129
Notes：The product price is calculated based on the market price in China. Both of the unit price and the amount are calculated based on RMB (Yuan).
5.2、Total cost：
Number Name Unit consumption
（kg） Unit price（Yuan/kg） Amount（Yuan） Notes
1 Fly-ash 1000 0.05 50
2 sulfuric acid 1573 0.35 550.6 98%
3 Sodium hydrate 637 2.5 1592.5 96% solid base
4 Ammonium hydroxide obtained from outside 343 0.65 223.0 18%
5 Recycled ammonium hydroxide 3822 0.2 764.4 18%
6 Iron sheet 139 0.6 83.4 60%
7 fluoride 1267 0.4 506.8 39%
8 Hydrogen peroxide 130.9 1.2 157.1 27%
9 Quick lime 888 0.6 532.8 85%
10 Auxiliaries 50
11 Catalyst 120
12 Coal 800 0.6 480
13 Electricity 250KWH 0.8 200
14 Water 6m3 2 12
15 Salary 100
16 Packing materials 55 2.5 137.5
17 Equipment maintenance cost
120
18 Tax 507
19 Sum 6187.1
Notes：The product price is calculated based on the market price in China. Both of the unit price and the amount are calculated based on RMB.
5.3、Annual net profit：
The net profit is 3941.9 Yuan per processing 1000 kg of fly-ash. Based on processing 60000 tons of fly-ash every year, the annual net profit and the tax amounts to 236514000 Yuan and 30420000 Yuan, respectively.
6、The product quality：
High dispersed white carbon black：Execution the standard that recognized by passenger car tyres industry；
Ordinary white carbon black：Execution the standard of HG/T 3061-2009；
Cryolite：Execution the standard of GB/T 4291-2007；
Iron oxide red industrial paint：Execution the standard of GB/T 1863-2008；
7、The main equipment and investment estimation：
The total equipment investment is about 85000000 Yuan, which is calculated based on the considering of processing 60000t of fly-ash every year.
8、The basic construction and investment estimation：
Based on the considering of processing 60000t of fly-ash every year:
The table of the basic construction and investment estimation
Number Name Floor space（m2） Unit price（Yuan/m2） Amount（ten thousand Yuan）
1 Decomposition workshop 2400 500 120
2 White carbon black workshop 3000 500 150
3 Cryolite workshop 2400 500 120
4 The workshop for waste comprehensive utilization 2400 500 120
5 Iron oxide red workshop 1200 500 60
6 Other accessory workshop 1200 500 60
7 Thermal workshop 600 500 30
8 Switching room 200 800 16
9 Storage room 2400 500 120
10 Guard 175 800 14
11 Other accessory factory 600 500 30
12 Sum 16575 8400000 Yuan
9、The products introduction of comprehensive utilization of fly-ash：
9.1、Cryolite：
9.1.1、Physical and chemical properties：
Cryolite，Na3AlF6, molecular weight：209.94. At room temperature, pure natural cryolite crystal is colorless and displays monoclinic crystalline form (d type) with prism’s shape, exhibiting approximate cube appearance. It usually displays pale, light yellow or reddish, along with black color, when it is mixed with impurities. Commonly, it is a dense integral block with vitreous luster, the gloss shows transparent and wex-like appearance with white stripe. This material is slightly soluble in water and the solution is acidic.
Commonly, the appearance of synthetic cryolite is white or gray and pale red. The material is crystal powder or sand particles with no smell, and is easy to absorb water when it is exposed to moisture.
The colorless cryolite is easily decomposed by the moist air. Under white hot temperature, the water vapor can make the molten cryolite transform into alumina, and the gaseous HCl can make the cryolite transform into NaCl and AlF3. The synthetic cryolite is easily decomposed by sulfuric acid, but the cryolite after melting and solidification once again are difficult to be decomposed by hot concentrated sulfuric acid. Cryolite can be also dissolved by hydrochloric acid and acetic acid.
9.1.2、Application：
It is mainly used as the cosolvent for electrolytic aluminium, which can reduce the electrolytic temperature to less than 1000℃. During the process, it will consume 4~10kg of cryolite when 1t of electrolytic aluminium is used. Besides, it can be also used as the enamel opal agent, the sunscreen and cosolvent for glass or enamel production, pesticides, the aluminum alloy casting cosolvent, ferroalloy, the wear-resisting filler for the production of rimmed steel along with the resin and rubber filler, etc.
9.1.3、The current product prices in the domestic market and the preliminary forecast of sales price：
The market sale price is between 5300~6000 Yuan/t.
9.2、White carbon black
9.2.1、Physical and Chemical properties
White carbon black，is also called hydrated silica, active silica and precipitated silica, the chemical formula is SiO2·nH2O。
White carbon black is amorphous powder or flocculent powder with high dispersion, which exhibits qualitative light, very high electric insulation, porosity and water absorption. Its original particle size is less than 3 um with high specific surface area, very good reinforcing and viscous effect, good dispersion and suspension along with vibration liquefaction characteristics, which is widely used in more than a dozen areas such as plastics, rubber, paper, paint, dye, ink and so on. Especially in the rubber industry, white carbon black receives widely application owing to the superior reinforcing and transparency.
9.2.2、Variety and application
In the area of tyre, white carbon black was mainly used as the beam layer for meridian tyre in the past years to enhance adhesive properties of the steel wire and rubber. There also has some tire enterprises who use white carbon black as radial truck tire tread to improve the tread stung and resistance to collapse resistance, its dosage is less and generally is 10 ~ 15. In the recent 15 years, since Europe and North America is becoming more and more strict to the requirement of environmental protection and energy saving, the white carbon black used in tire surface significantly reduce the tire rolling resistance and can keep good ice slippery and wet resistance, its wear resistance is only slightly reduced. In 1992, Michelin company firstly made "green tyre" with full use of white carbon black, the tire rolling resistance is reduced by about 30% compared with ordinary ones, the effects of fuel efficiency and reducing automobile exhaust is remarkable. But because of the bad dispersion of traditional white carbon black, although the tread compound with white carbon black, displays lower rolling resistance than that with carbon black, but its wear-resisting performance is worse than that with carbon black.
White carbon black has developed three generations of products at present: the first generation is known as the "standard" or traditional varieties of white carbon black. The second generation is called "the high dispersion white carbon black" (High Dispersible silica, HDS) and "Easily dispersed white carbon black" (Easy Dispersible silica, EDS). High dispersed white carbon black is a kind of white carbon black product with high dispersion and without dust, which is suitable for green tire. Easily dispersed white carbon black is developed in the mid 90 s with performance between HDS and traditional white carbon black product, its price was lower than those of HDS, is a kind of product with high cost performance ratio instead of HDS product; The third generation is called "high dispersed white carbon black with unique structure ", it has more better dispersion and reinforcement, which is in the research and development process or extended application process in the current stage. There also have some people call the third generation products as the "high dispersed white carbon black", and collectively call the second generation products as "easily dispersed white carbon black" or "half dispersion white carbon black ".
Owing to the rapid development of modern highway, the requirements for engineering tire is very high, many developed countries take the lead in the successful tires with high dispersed white carbon black to improve the tearing temperature resistance of the tire, stretching temperature, stretching stress, pull cutting growth, resistance to bend thermal performance, reducing the heat, increasing the service life, at the same time can improve the tires on the ice holding ability, make the vehicle fuel economy, is the critical filling reinforcing agent for creating "green tyre" and "ecological tire". Compared with ordinary silica, high dispersed white carbon black can be go smoothly when it is mixed with rubber, displaying low roll temperature, reduced energy consumption, low Mooney viscosity, extended scorch time and high safety performance. Additionally, due to the good compatibility with rubber, there will not be "cluster" phenomenon, and can produce combined rubber with high proportion. The proportion of combined rubber determines the physical property. This is the reason for the high reinforcing of the high dispersed white carbon black.
9.2.3、The supply and demand situation in the domestic market
In 2014, the total white carbon black production enterprises are 67 in the domestic, the total production capacity is 2010000t/year, the actual output is 995000t/year, the main product is ordinary white carbon black obtained by precipitation, the import is 73658t，the export is 377585t. The main consume area and scale: shoe industry with 38%; tire industry with 20%; other rubber products with 12%; Pesticide and feed with 11%; Coating with 5%; Toothpaste with 2%; the other with 12%. Ordinary precipitated silica is overcapacity; the supply of the product exceeds demand. However, with the development of car industry, the dosage of the high-grade car tyre for high dispersed white carbon black increased year by year, it is expected in 2017 will reach 700000 tons/year, the prospect is considerable. In addition, the added value of fumed silica and ultra thin white carbon black is high, exhibiting a certain market space.
9.2.4、The current product prices in the domestic market and the preliminary forecast of sales price
At present, the factory cost of precipitated white carbon black used in shoes manufacture and ordinary rubber industry is between 2800~3500 Yuan/t，high dispersed white carbon black specially used in tyre is between 8000~9800 Yaun/t，ultrafine white carbon black is about 12000 Yuan/t。
9.3、Iron oxide red industrial paint：
9.3.1、Physical and chemical properties
Iron oxide red, with chemical formula of Fe2O3, is also called rust red, which is red iron oxide powder, displaying light resistance, resistance to high temperature and atmospheric effects, resistance to foul gas and all base classes. It can be dissolved gradually only in concentrated acid under the heating condition.
Appearance：
Orange and purple powder with trigonal system, having two kinds: natural one and synthetic one. The natural one is called west red with relative density of 55.25, fineness of 0.4 ~ 20 μm, and melting point of 1565 (decomposition). Calcination the sample leads to the release of oxygen. The sample can be reduced into iron by carbon oxide and hydrogen. This sample also has the following properties: insoluble in water but soluble in hydrochloric acid, sulfuric acid, and slightly soluble in nitric acid and yeast. Additionally, the sample displays excellent light resistance, high temperature resistant, acid and alkali resistance, anti-rust property and has good dispersion along with strong tinting strength and hiding power, without oil permeability and water permeability, non-toxic. In the air, the maximum allowable concentration is 5 mg/m3.
9.3.2、Application
In the building materials industry, it is mainly used in the colored cement, color cement tile, color cement tile, glazed tile and floor tile, color mortar, color asphalt concrete, terrazzo, Mosaic tiles, artificial marble and metope paint, etc.;
It can be used for a variety of coatings to protect material and color, including waterborne external walls coatings, powder coatings, etc.; it also can be used in various kinds of primers and paint such as epoxy resin, alkyd, amino and so on; it can also be used for toy paint, decoration paint, furniture paint, electrophoresis paint and enamel. Iron red primer has the antirust function, can replace expensive red lead paint and save non-ferrous metals
It can be used for coloring plastics such as thermosetting plastics and thermoplastic plastics, coloring rubber products. For instance, used in automobile inner tube, inner tube, bicycle inner tube, etc.
It can be used for high fine grinding material, used in precision hardware instruments and optical glass polishing. The high purity one is the main basic material of powder metallurgy, used for smelting various magnetic alloy and other advanced alloy steel, which is fabricated by high temperature calcination using ferrous sulfate, iron oxide yellow or waste iron mixture or directly from the liquid medium.
9.3.3、The supply and demand situation in the domestic
China is one of the large production countries of iron oxide pigment in the world, the production accounts for about 1/3 of the global. Which is 341600 tons in 2000 and 600000 tons in 2010. Among the 600000 tons of production, iron oxide red is 600000 tons. Its main consumption is paint and building materials industry, and the other is used in plastics, cosmetics, tobacco, food, pharmaceutical, electronics and other industries.
At present，there has nearly hundred iron oxide pigment production enterprises in China, mostly distributed in Jiangsu province, Zhejiang province, Shanghai city and central south region. Among them, some enterprises have a certain scale and strong comprehensive strength: Shanghai yipin international paint co., LTD., Jiangsu Yixing city yu xing paint factory, Shanghai new sino-american pigment co., LTD., bayer Shanghai pigments co., LTD., Shanghai iron oxide pigment factory, Shandong east jia group co., LTD., Shandong zhucheng schroder chemical co., LTD., Hunan three-ring pigments co., LTD., Shanxi yangquan Evergrande ferric oxide iron works co., LTD., Jiangsu qidong oxidation, sea of this company in Shenzhen, Guangdong, Guangxi Liuzhou leap chemical plant, Tianjin dagang huaming chemical plant, Jiangsu Changshu iron red iron oxide factory in Changshu, Jiangsu Wuxi black pearl ferric oxide co., LTD., Zhejiang gorge state huasheng fine chemical plant, etc. In addition to these larger capacity manufacturer (the capacity is more than 10000 T/a), there also have other smaller domestic production enterprises, the distribution is wide and not concentrated. The central plains, central south, and the coastal all have the distribution.
9.3.4、The current product prices in the domestic market and the preliminary forecast of sales price
At present, China's iron oxide red executes the standard of GB/T 1863-2008, the main types are: 101 type, 110 type, 130 type, 180 type, 190 type, etc. The products meet the national ex-factory price standard, which are between 5000 ~ 8500 Yuan/t (except to circulate on the market of inferior red iron oxide) according to difference of the quality. The iron oxide red prepared by the current project is high purity iron oxide red with high quality and the factory price is taken a middle price at 6500 Yuan / t.
10、Technical status：
After seven times test, four industrialized production test (5000 t/a level), the process was gone through the test of practice, and was further perfected and developed in practice. Now, it has been developed into a industrial technology with practical application value. The core technology has been applicated with intellectual property rights.
11、The technical cooperation way and scope：
11.1、The technical service manner
Technology transfer. For reliable investors we can consider to become a shareholder with technology use right.
Other technical services: according to different investors and resource conditions, we can perform the targeted pilot test and industrialized production verification to test our technology and the applicability of fly-ash resources obtained from different regions and different chemical composition, and subsequently avoid technical risk.
11.2、The technical service scope
Responsible for process optimization, process design, suitable design for standard equipment, non-standard equipment production and equipment design, equipment layout design, pipe network instrument installation and design; and providing the equipment installation guide, equipment commissioning, production debugging, engineer training, analyzing labor training, the main operating worker training; Responsible for the compilation of the project proposal, feasibility study report, process procedures, raw material and product analysis method, and the intermediate control analysis method. Ensuring the decomposition rate, yield, quality, environmental protection meet the standard. According to the requirements of the project owner, we can undertake turn-key project.
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