Beypazarı trona mineralinin çözelti madenciliği ile değerlendirilmesi
Evaluation of Beypazarı trona deposit by solution mining technique
- Tez No: 21698
- Danışmanlar: DOÇ. DR. HASANCAN OKUTAN
- Tez Türü: Doktora
- Konular: Kimya Mühendisliği, Chemical Engineering
- Anahtar Kelimeler: Ankara-Beypazarı, Soda, Trona, Çözelti madenciliği yöntemi, Ankara-Beypazarı, Soda, Trona, Solution mining method
- Yıl: 1992
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
ÖZET Soda üretimi için en önemli doğal kaynak trona mineralidir. Beypazarı trona yatakları, belirlenen özellikleri çerçevesinde rezerv durumu itibariyle, dünyanın ikinci büyük doğal sodyum karbonat depolanmasıdır. ABD Wyoming trona rezervinden sonra dünya soda pazarlarına yakın olması nedeniyle de büyük ticari potansiyele sahiptir. Ancak bu mineralden soda üretilmesi için henüz teknolojik bir yatırım yapılmamıştır. Rezervin değerlendirilmesi için uygun teknolojinin bir an önce seçilmesi gerekmektedir. Bu çalışmada, Beypazarı trona mineralinden soda üretimi için uygulanabilecek çözelti madenciliği yönteminin ön teknolojik araştırmaları yapılmıştır. Laboratuarda gerçekleştirilen denemelerde çözelti madenciliği için en önemli parametrelerden birisi olan tronanın çözünme hızı tespit edilmiş, ayrıca çözelti madenciliği yöntemine uygun proses geliştirilmesine çalışılmıştır. Laboratuarda elde, edilen sonuçlar çerçevesinde, çözelti madenciliği yöntemi için proses' tasarımı ve maliyet hesaplamalarının yapıldığı bir bilgisayar modeli geliştirilmiştir. Çözelti madenciliğine ait toplam yatırım, işletme giderleri, birim maliyet, karlılık ve geri ödeme gibi ekonomik değerler monohidrat ve sesqui karbonat yöntemlerine ait değerlerle mukayese edilmiştir.
Özet (Çeviri)
EVALUATION OF BEYPAZARI TRONA DEPOSIT BY SOLUTION MINING TECHNIQUE SUMMARY Soda ash is chemically known as sodium carbonate and is an important inorganic chemical. It has been produced for several centuries by processing certain vegetation and minerals. It has also been used in the world for nearly 300 years and it is not sup- rising that most of the end uses have reached maturity and tend to follow the population trend, which for the last several years has been levelling out. The major soda ash markets in the developed countries, are glass, chemicals, soaps and detergents, pulp and paper and water treatment industries. In recent years, the soda ash and sodium bicarbonate industry has also examined the potential of using, sodium minerals for fine gas desulfurization. All of these are the first basic consumer products produced by developing societies. About 3500 BC, soda ash was obtained from seaweed or from dried mineral incrustations around alkaline beds. Following the 18 th cen tury, the LeBlanc process used salt, sulfuric acid, coal and limesto ne, has became the major productions method. In the early 1860's, Solvay brothers successfully commercialized an ammonia-soda process to synthesize soda ash. This process produced a better quality product than the LeBlanc method. Large scale commercial production of natural soda ash began in U.S.A. in 1887 from surface crystalline material at alkaline lakes. In 1938, during exploration for oil and gas in Wyoming, a massive buried trona deposit, presumably the world's largest, was accidentally discovered. The synthetic method is straight forward, but does require quite precise control and is economical only on a large scale basis. The selling price of ash has not kept pace with the increased cost of most other chemicals, with the result that today the high capital cost relative to profit, explains why no new ammonia-soda plants have been built since 1935 and why the major ash producers are actively studying the ash from trona situation today. Soda ash from natural sources enjoys inherent production cost advantages over synthetic so da ash, especially with regard to raw materials and energy costs. Especially, the energy crisis which started in the early 1970's dra matically affected the world soda ash industry. On the other hand, the inability of most of the synthetic, soda ash plants to meet emmis- sion requirements imposed by antipollution legistation has been cited as one of the main reasons why that industry suffered. The costs to implement the pollution controls were too high to be recovered due to the growing competition from the natural soda ash industry. Alt hough, the proportion -of sodium carbonate produced from natural depo sits accounted for only 15 percent of the total production in 1950's, vithis figure is misleading. A very large number of locations in the U.S. contain natural sodium carbonate, but few of these deposits are commercial in sire, favorably located or have an adequate sodium carbonate concentration and purity. The natural form in which sodium carbonate occurs is either in brine solution or as a solid in a mine ral, the most prevalent of which is trona, the final desiccation product of the sodium carbonate content of lakes and springs. Trona is a gray-white or yellowish-white combination of sodium carbonate -bicarbonate from which soda ash in produced by calcination. This industrial mineral is a double salt which forms depending largely on the physico-chemical conditions. Many ways exist to produce soda ash from trona (ore and/or brine). Various sodium compounds can be crystallized in intermediate steps by manipu lation of brine compositions, temperature and pressure These are, 1. Ses qui carbonate 2. Anhydrous carbonate 3. Monohydrate 4. Bicarbonate. Calcination any of these Compounds yields soda ash having various <“ physical properties crystal size, shape and resulting bulk density. The first produces crystals of excellent flow characteristics and a semidense ash; the second, a ”super dense ash“; the third, dense ash directly; and the fourth, bicarbonate and conventional Tight ash. A combination of factors-. has led to the rapid development of trona as a source of soda ash. These factors include huge reserves, good mining conditions, location in an industrialized country with large markets. The trend toward natural soda ash production has stimulated industry to interest in a new mining technology as solu tion mining. Solution mining of salt is a well established techno logy which began in the 1860's in U.S.A. by explorers drilling for oil. The single well solution mining process spread quickly through out the salt domes. After the 1950' s, multiple well systems using fracturing and other connection method have predominated. Research on soda ash solution mining is scheduled to begin in 1981 at two sites in U.S.A. The field of solution mining may be considered under the head ings of (a) mining economics and ore evaluation, (b) elements of the leaching phase, (c) preparation of ores, (d) practical aspects of in situ leaching, (e) reagent generation and regeneration, and (f) reco very of target commodity from pregnant solution. Proposed use of in situ leaching for the ore deposit Is not without risk. The ma jor risks of the in situ leaching method include inability to control fluid flow, inadequate solution-mineral contact within the ore depo sit, barrier design and construction limitations which may preclude containment of leaching solutions. VXlBeypazarı Trona deposit was discovered by Mineral Research and Exploration Institute (MTA) in 1979 during coal explorations. Taking into account of the whole features of the deposit, it is possible to state that the Beypazarı Trona deposits are ttie second biggest natural sodium carbonate formation in the world. The studies showed ttıa t trona is present at a depth of 150-400 m. Total reserves of trona mineral is. about 300 millions tons. The average grade is 84% trona. The deposits are accumulated in two disconnected levels, and have se veral veins in the upper and lower levels. The deposits consist en tirely of tronas and the grade of them changes in short distances completely. The minerals of the enclosing sedimentary rocks of the trona levels generally consist of dolomite, analcime, potassium felds par, quartz and clay minerals. This mineral resource may allow the natural production of che micals such as soda ash, sodium hydroxide and other sodium derivati ves for about a hundred years. If the possibilities of underground and solution mining methods have been considered and this project proceeds, it could result in substantial changes in the Europan soda ash market. On the other hand, it is known that, US producers want to become active partners and to obtain a competitive foodhold in foreign sodium mineral deposits by providing needed capital and tech nology, there by eliminating the higher transportation costs incorpo rated in the delivered prices of US soda ash. However, Turkey should develop her own technology and not to accept key-delivery project^ The main objective of this study is to investigate the applica- bilty of solution mining technique to Beypazarı trona deposit. For this purpose, laboratory bench-scale experiments were conducted. To / show advantages of the solution mining over conventional mining tech- \ niques, a model calculating process design and cost analysis of solu tion mining technique for Beypazarı Trona deposit were developed. The laboratory experiments were carried out conducted by using the several trona ore samples obtained from MTA and ETÎBANK. In or der to characterise the trona samples various chemical analysis, X- ray diffraction and SEM analysis were performed. One of the most important factors is rate of dissolution to evaluate the potential for trona solution mining and to provide en gineering data for future economic evaluations, The dissolution rate affects flow rates and ultimately, the productivity of each well. A higher flow rate, given a high rate of dissolution, increases produc tivity and reduces the number of wells required for a given production rate. To investigate the order of dissolution rate of Beypazarı Tro na, dissolution experiments were conducted by using water and the solution containing dissolved ground trona. Three trona core samples were tested at various solution concentrations to determine the shape of the dissolution rate versus concentration curve. The solution concentrations ranged from 0.1 M Na to 2.3 M Na, which is near satura tion. The temperature was kept at 25°C during all experiments. The experiments showed that the dissolution rate of the Beypazarı Trona ore is 2.3x1 0~4 g/cm2.sec. in distilled water. This result agrees viii Î I'with the result which was determined for Wyoming trona. A mathematical formula, based on salt dissolution mechanism and boundary layer theory was derived to evaluate theoretical dissolution rate of trona mineral. This theoretical equation requires an other important parameter, diffusion coefficient to be determined. There fore, determination of diffusion coefficient of Beypazarı trona in water and the solution ”has been the second stage of the experimental study. Several tests were conducted to investigate the relationship between diffusion coefficient of Beypazarı trona and the sol ui ton concentration. From the result of diffusion coefficient experiments, following equation was obtained. 0=8.6xl0“6 + 1.19xl0”6 C Theoretical and experimental dissolution rate curves are in good ag reement. As expected, the rate of dissolution decreases as solution concentration increases. The second objective of the laboratory experiments was to deve- lope a process which can be used as a solution mining technique. For this purpose two processes were studied, to produce soda ash from Bey pazarı trona mineral. These processes are sesquicarbonate and alka line extraction process. The tests were carried out to obtain the optimum process conditions. It is a well known fact that, the pro cess conditions affect crystal shape, purity, size, uniformity, breakage resistance and the most important the bulk density. Gene rally these conditions can be evaluated in four steps for these two processes: Dissolution, filtration, crystallization and calcination. During sesquicarbonate experiments, both cooling and evapora tive crystallization techniques were used to produce sesquicarbonate crystals from the dissolved trona. The optimum trona dissolution tem perature is 60°C. The best sesquicarbonate crystal was obtained from the hot solution by cooling crystallization. The experimental results showed that sesquicarbonate process can not be used as a solution mining technique, it is a refinement process for grounded trona mineral. The most important parameters in alkaline extraction process are the dissolution temperature, concentration of sodium hydroxide in solution system and evaporative crystallization temperature. The results of alkaline extraction experiments revealed that appropriate temperatures for the dissolution and evaporative crystallization are 30OC and 100°C respectively. During laboratory tests the concentra tion of agueos sodium hydroxide is reduced to the level of '6%, and high purity soda ash was obtained at 150-200°C calcination temperature from monohydrate crystals. The experiments performed, showed that alkaline extraction process in more efficient than sesquicarbonate process. ixInvestigation of the economic, feasibility of the solution mining of trona requires the calculation of unit cost of soda produced by the method. To achieve this scope a computer aided design and cost estimation model were developed for the alkaline extraction process, and the results were compored with sesquicarbon^te and monohydrate process costs. The model consists of following subnodels: a. Material balance b. Wellfield analysis c. Surface plant analysis d. Cost analysis Developed computer program calculates the size of the equipments, fix ed capital, working capital, manufacturing expenses, product cost, net annual profit and rate of return for the different production of soda ash capacities. As the main result of this study, alkaline ex traction process was more advantageous when compared the mono- hydrate and sesquicarbonate process. The advantages of alkaline pro cess can be summarized with lower investiment, production and unit costs and as a consequence. of these, a higher profit. All these laboratory and economic studies indicated that the alkali process, which can be applied as a solution mining method, has many advantages over the conventional mining' techniques. Therefore, it is concluded that, recovery of Beypazarı trona deposit by solution mining technique can produce soda ash with lower cost. This provides great advantages for Turkey to compete" in foreign soda ash markets.
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