PROCESSING TECHNOLOGY OF UNIQUE RUSSIAN CARBON-BEARING ROCKS-SHUNGITE

SERGO ORDZHONIKIDZE RUSSIAN STATE UNIVERSITY FOR GEOLOGICAL PROSPECTING FEDERAL SCIENTIFIC CENTRE VIEV
SHEMYAKIN-OVCHINNIKOV INSTITUTE OF BIOORGANIC CHEMISTRY, RUSSIAN ACADEMY OF SCIENCES


PROCESSING TECHNOLOGY OF UNIQUE RUSSIAN CARBON-BEARING ROCKS - SHUNGITE

VLADIMIR A. RAFIENKO VLADISLAV V. BELIMENKO


Translated (from Russian) by Daria V. Dementieva


ACADEMUS
    Publishing

Academus Publishing
2019

ACADEMUS
Publishing



Academus Publishing, Inc.

1999 S, Bascom Avenue, Suite 700 Campbell CA 95008 Website: www.academuspublishing.com E-mail: info@academuspublishing.com
© Publisher, Academus Publishing, Inc., 2019
The right of Vladimir A. Rafienko, PhD in Mining and Engineering, Federal State Budgetary Institution of Higher Professional Education “Sergo Ordzhonikidze Russian State University for Geological Prospecting”;
Vladislav V. Belimenko, PhD in Biology,
Federal State Budget Scientific Institution “Federal Scientific Centre VIEV” is identified as author of this work.
Translator: Darya V. Dementyeva, PhD in Bioorganic Chemistry, Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences
For e-mail correspondence:
Dementyeva D.V. — dasha160370@icloud.com, npp-f@yandex.ru;
ORCID: https://orcid.org/0000-0001-9123-9866, Researcher ID: Y-7312-2018
Rafienko V.A. — vrafienko@mail.ru
ORCID: https://orcid.org/0000-0002-4349-5539, Researcher ID: Y-8759-2018
Belimenko V.V. — vlad_belimenko@mail.ru
ORCID: https://orcid.org/0000-0001-8871-7863, Researcher ID: A-7954-2017
Reviewers:
Ilias, Nicolae
Professor, PhD Engineering
Member of the Academy for Technical Sciences of Romania
Volfson, Iosif
PhD in Mineralogy and Geochemistry Academic Secretary of Russian Geological Society
ISBN 10: 1 4946 0012 9
ISBN 13: 978 1 4946 0012 9
DOI 10.31519/1192
Major problems of processing technology of shungite rocks are illustrated in the book; ultimately new integrated technological classification of all shungite rock types, which has allowed to expand their application sphere by far, is given. On the basis of proposed classification, the technological evaluation methodology has been carried out and its theoretical substantiation is given. It is shown that sulfides and carbonates, contained in the shungite rock, should be exposed to chemical leaching process. For the first time, physico-chemical parameters of leaching process technology of sulfides have been established; deformation mechanism of sulfides during their drying has been figured out. It is proved that by the charring way, paroptesis and autoclave processing the series of valuable products can be obtained from the shungite rocks: liquid glass, sodium carbide, calcium chloride, metallic calcium, lime, cement. The book can cause significant scientific and practical interest for wide range of specialists, working in the sphere of natural resource enrichment that allows to recommend it for scientists and technical school teachers. It can also work as a valuable guidebook for engineers-technologists, projectors and employees of spheres allied with enrichment, and, thanks to availability and systematics narration of scientific research and technological bases of shungite raw processing -for technical students of mining specializations.

                INTRODUCTION




      The following book is devoted to the theoretical and practical technology evaluation of physico-chemical properties of shungite rocks — the new raw material as the substitute to such row of traditional materials as: chark, silica white, technical carbon and other components. Currently, shungite rocks have been widely used in ferrous and non-ferrous metallurgy, construction industry as well as in rubber technical goods production. The shungite rocks have been found for applications as mineral fertilizers, pigment for earth colors and other spheres.
      Shungite rocks of Zazhogino deposit in Karelia is the unique natural multimineral formation, consisting of two components — carbonaceous matter, mineralogically close to graphite, and micro-crystal earth silicon. These rocks possess high strength, density, chemical stability and conductivity. The shungite rocks are very active in redox processes, especially at high temperatures. This gives an opportunity of their wide application in the iron metallurgy and the metallurgy of non-ferrous metals. They are also used while fusion of phosphorus-containing rocks to produce yellow phosphorus.
      The shungite rocks — is a valuable mineral that can be widely used in different industry branches. In near years, it is planned to start construction of the houses with shielding properties that will reduce a harmful impact of electromagnetic waves of technogenic origin on human organism. This is extremely important in the house construction nearby airports, flag and transmission cell phone towers. These questions settlement can be reached thanks to regular shungite rocks addition into the construction materials.
      The shungite rocks were formed from neptunic ones 2 billions years ago. Today, there is no consolidated view on their occurrence mechanism. A mechanism of physico-chemical interaction of shungite rocks with other mineral formations also has not been studied. The majority of specialists consider shungite rocks to be formed from sediment beds of lakes, seas and ancient sapropels. Nowadays, Zazhogino deposit — the largest and rather explored deposit of shungite rocks. It is in Karelia in the area of Onega Bay of the White Sea.
      From ancient times, the peasants used shungite rocks as a remedy, a black ink, a local fuel and a decorative stone. Their specific and rather multi-side practical application has given scientists an opportunity to find a series of their new more promising properties. Thus, it has been observed that shungite rocks can be used as a filler in rubber technical goods, including automobile tires. The tires with shungite rock addition are more temperature-, cold- and wear-resistant. As well as they have become promising in the construction of warm floors with shielding properties in the residential buildings.

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       Being a good adsorbent, the shungite rocks have been already applied for sewage purification today. It is known about the practice of their use in the sewage managing facilities in Moscow. With the help of these rocks, flow waters from Moscow Ring Automobile Highway are being purified from oil and other organic compounds.
       Taking into account the perspective of shungite goods application with various classes of coarseness — from finely-dispersed (5—70 microns) to coarse-grained (40—100 microns) — in Moscow and Moscow region, Moscow Government has adopted the decision on the construction of experimental-industrial enterprise for the production of shungite goods at Liano-zovo district (OJSC “MKK-Holding”, Moscow) and allocated the money for that purpose.
       Simultaneously, large complex of research on further investigation of physico-chemical properties of shungite goods is being held and the sphere of their application in different industry branches and household are being specified.
       Current manuscript is not claiming exhaustive generalization and research of all the problem of shungite goods application. It presents one of the first attempts to clarify all complex redox features, occurring while shungite products usage, especially in rubber technical goods, construction industry as well as in pyrometallurgical fusions in ferrous and non-ferrous metallurgy, and to find on the obtained results basis the new economically substantiated spheres of its application.
       Sufficiently full settlement of the problem is possible only in longtime industrial usage as far as shungite products, selected at different deposit points, vary a little in their chemical composition and physico-chemical properties. But an impact of separate varieties has not been yet fully substantiated by practice, as well as there has not been yet specified the chemical composition of shungite rocks, the content of carbonaceous matter, earth silicon and other constituents in the rocks compositions that can be effectively used in different industrial branches. For practical usage in different branches, one should, first of all, be aware of the content of carbonaceous matter and earth silicon in shungite rock.
       The current monograph analyses the earlier research on shungite rocks from the point of their possible usage in various industrial branches.
       It is shown that major jobs in this direction were fulfilled mostly on rocks with average carbonaceous mater content of 25—40 %, while there is a big quantity of various rocks in the deposit with carbonaceous matter content from 5 to 20 %; together, there are rocks, where carbonaceous matter concentration constitutes 40—98 %. A little attention was paid to these rock groups 4

    at technological evaluation earlier. That is why we have put a purpose — to work out the principally new technological classification of all shungite rock varieties with account of their chemical and mineral composition.
       The obtained classifying complex technological scheme of shungite rocks is arranged by us with account of genetic features of all their existing varieties at the deposit and is demonstrated in triangle diagram.
       On the basis of the elaborated complex classification and also the balancing theoretical diagram and the ratio of all existing shungite rocks, we have worked out methodology of technological evaluation of high-grade as well as low-grade shungite rocks. It is established that among low-grade shungite (shungitous) rocks one can specify the following kinds: silicate, aluminosilicate, silicate sodium, aluminosilicate carbon-bearing, carbon-bearing.
       It has been proved that every kind of shungitous rocks can have only its own, based on its physico-chemical properties, conditions of application. Such assessment of these rocks has become possible due to the made classification. For each considered rock kind an own specific application is distinguished. Such complex approach widens a little bit the application area of such rocks and gives a chance to come up with new ways of their further perfection by further additional beneficiation.
       Due to set classification, according to developed technological evaluation of shungite rocks one can quickly state their kind and potential application sphere.
       Herein, the properties and specificities of physico-chemical behavior of all rocks kinds have been considered while their usage in various branches of industry.
       It was figured out with the help of differential-scanning calorimetry that physico-chemical properties of different kinds of shungite rocks essentially vary. Thus, massive and brecciated rocks have different physico-chemical properties despite the same chemical composition. Along this, in such rocks kinds, the sizes of crystals of cherty minerals in the major matrix of carbonaceous matter range by far. So, in the massive rocks they constitute 1—2 microns, in the brecciated — 5—10 microns. It is shown that crystal lattice structure in the massive and brecciated rocks is also different. It says that, in the process of industrial usage of various massive and brecciated rocks, their activity mechanism will differ. These questions should be, certainly. taken into account while their usage in different industrial branches.
       The mechanism of acid-forming characteristics in shungite rocks has been elucidated and the ways of their elimination in the industry processing flow are put forward.

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       For the first time, the elimination mechanism of sulphides from shungite rocks has been developed. The essence of this mechanism is that original rock with 2—4 % sulfide content acidifies initially by air oxygen in the apparatus of Pauchuk type, and then is exposed to leachate such as sulfuric acid medium at pH 3.5—3.8. It is shown that sulfides can be deleted from shungite rock in alkaline medium at pH values of more than 8.
       It has been established that at pH from 4 to 9, the leaching of sulfides does not proceed, and vise versa, in fluid weak sulfurous and alkaline mediums, the sulfide buildup proceeds, while cellular pyrite is formed at 4—6 pH and pyrite — at 6—8 pH. This should be taken in consideration while pursuing the process of leaching; the developed mechanism is based on that matter. On the basis of obtained data, the technological scheme of leaching of sulfides from all shungite rock kinds has been developed
       According to this principle, analogously, we have developed the technology of boart leaching in slightly acidic medium at pH from 4 to 6 with the help of hydrochloric acid. The resulting in the process of exposition, the calcium chloride solution is needed to be separated from solid body. Following such scheme, one can completely eliminate all of the boarts from shungite rocks.
       Shungite rocks acquire novel properties after sulfide and boart leaching. This allows to widen the area of their application. Also, the technology of elimination of boarts from carbonate shungite rocks has been carried out.
       Novel mechanism of shungite rocks drying-out has been developed that has allowed to substantiate the temperature and technological parameters of this process. Drying-out temperature should be no more than 300 °C.
       Novel technology of closed water cycle with additional elimination of sulfurous gases and with acid waters neutralization has been theoretically stated.
       With the purpose of pollution reduction, in addition to major project, the technology of air purification from sour gases, such as SO₂ and SO₃, and finely-dispersed solid shungite particles with coarseness from 0.1 to 5 microns has been offered. This technology provides with 100 % capture of harmful gases and finely-dispersed particles. To embody the given technology it has been proposed to organize the closed water cycle with gases neutralization with the help of calx and by removal of sediment with filtration.

     Chapter 1




                CHARACTERISTICS OF SHUNGITE ROCKS
                AND GROUNDS FOR TECHNOLOGICAL WAYS
                OF THEIR PROCESSING




            1.1. Common Characteristics
            of Zazhogino Deposit Shungite Rocks


     Big group of diverse by their physico-chemical composition carbon-bearing pre-Cambrian rocks has got a title shungite rocks. This group is unique in its mineral and chemical composition. The content of carbonaceous matter in these rocks ranges from 0.5 to 98 %, hence they can be divided into rich and low-grade ones. Low-grade shungite rocks with carbonaceous matter content from 0.5 to 5 % were called as shungite-containing, and with 5 to 20 % content — as low-shungitous [Kalinin, 1975; Kalinin, 1984]. The rocks with carbonaceous matter from 20 to 55 % is accepted to call shungite, their ratio in Zazhogino deposit is about 65 %; the ratio of shungite rocks with C of 55—98 % reaches approximately 10-20 % [Borisov, 1956].
     There are separate sections with carbonaceous matter content from 80 to 98 % in the deposit. The extent of these rocks is not large, they are spread as a kind of small clusters along all deposit. While conducting mining-geological works it is rather important to recede and store these rocks separately as their applications spheres are rather specific. Rich in carbonaceous matter rocks are more homogeneous. Besides the carbonaceous matter these rocks contain mainly fine dispersed earth silicon and just a little amount of other admixtures such as loam, aluminosilicate, carbonates and iron-bearing minerals.
     Shungite rocks with low content of carbonaceous matter from 1.0 to 15 % have inconstant material composition, hence it is important to classify them with account of possible application area. Nevertheless, such classification by the processing technology of different kinds of shungite raw materials is absent. Big diversity of shungite rocks by the content of carbonaceous matter and other chemical components demands their classification with the purpose to group them by branches of possible implementation.
     For the first time shungite rocks were classified by Borisov P.A. [Borisov, 1956]. This classification was simple and on the first stage of investigation, it turned out to be rather comfortable for practical application (Table 1.1), it was used by the majority of scientists.

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Table 1.1. Shungite rocks classification [Borisov, 1956]

Component, %        Shungite kind      
                    I  II III IV   V  
Carbonaceous matter 98 60 35  20 5-10 
SiO2                2  40 65  80 90-95

       Following the classification, the shungite rocks were divided into five groups due to the content of carbonaceous matter and ingrained finely-dispersed earth silicon.
       This classification shows that with the reduction of carbonaceous matter in the considered rock the content of earth silicon grows. In the frames of the deposit, mainly moderately-shungitous and shungitous rocks of three kinds (II, III, IV) are developed, their total extent constitutes approximately 70—80 %. All works to investigate shungite rocks were usually being conducted on following kinds: second. third and forth groups, while the attention was not being paid to rocks of first and fifth groups, and the area of their application has not been yet determined.
       The major drawback of this classification was the absence of other chemical components within it, especially in shungite rocks with low-content carbonaceous matter. There is large quantity of bends, feldspars, carbonates, silicates, aluminosilicates, sulfides, which role in the industrial production is very big. These admixtures lend the rocks a series of new features that essentially influence the technological processes.
       On the first stage of scientific investigations this classification had appeared to be major to develop all works on shungite rocks physico-chemical properties evaluation. At present, it has been collected the sufficiently large factual material on chemical composition and physical properties of all known low-grade as well as rich shungite rocks that are not included into this classification. That is why the necessity has been occurred to carry out principally novel classification, allowing to substantiate the structural and chemical properties of all possible shungite rocks. The novel technological classification of rich and low-grade shungite rocks with account of their chemical composition and technological properties will be considered in the Chapter 2.
       Shungite rocks represent elementary carbon with globular and su-pramolecular structure that exits in metastable state, close to the form of technical carbon and white carbon. The shungite rocks differ from graphite ones by absence of crystal structure. They also differ from pitches and coals with low tenor of volatile matter components: oxygen, hydrogen, stink damp, Their approximate content in a whole in the deposit

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   constitutes 1—2 %. The characteristic specificities of shungite rocks, their subtle concretion with other rock-making minerals, their qualitative- quantitative ratio define physico-chemical properties of shungite products, used in the industries.
      The interest to shungite products as a new source of non-traditional raw is educed in following industrial branches: metallurgical, chemical, rubber, construction, vanish-and-paint and others. The experiments to apply shungite rocks in different industries were being carried out mainly on samples with carbonaceous matter content of about 25—40 % [Maslakov etc., 2005].
      As it follows from various sources [Filippov, Romashkin, 1996], the application area of shungite products is very manifold and is not completely established; so far as industrial exploration of Zazhogino deposit it can be vastly widened.
      The usage of shungite rocks that are low-grade by carbonaceous matter will be being defined after the mastering of industrial production under construction, taking into account of accumulated experience and statistical data, which will be being itemized during industrial introduction.
      Zazhogino shungite rocks have been known for a long time, for more than 200 years. Initially, they were used by locals as paint [Kalinin, Gorlov 1968]. As it was mentioned above, the attempts to apply them as a power fuel with carbonaceous matter average content of 25—40 % did not meet the necessary efficiency because of high ash-content (about 70 %) of the rocks and bad capability to burn. Initially, all industrial experiments with shungite rocks were being pursued with the purpose to use them as a power fuel. These testings were fulfilled yet in 30’s of last century, but were not brought to industrial introduction [Kryzhanovsky, 1931; Yagodkina, 1984].
      There were attempts to apply the shungite rocks while the decoration of different industrial and residential buildings. The floors of Isaciy and Kazan cathedrals of Saint-Petersburg, some of the buildings in Petrozavodsk are decorated with shungite slabs. While the floor garnish of the Cathedral of the Redeemer in Moscow the shungite stone was used also.
      Zahogino deposit is located on the West part of Onega Lake. The deposit stretches towards North-West direction on 20 km with the width of 4 km. The total square of deposit is 120 km² (Fig. 1.1).
      The shungite rocks of the deposit are rich with carbonaceous matter and non-homogeneous in their structure and properties. Chemical composition of the rocks dramatically differ at different points of the deposit and also at different depths of their attitude.

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Nigozero deposit

Zazhogino deposit, Zazhogino section

                                                       Zazhogino deposit, Maxovo delf













Fig. 1.1. Location scheme of Zazhogino deposit

      The deposit was explored in the details in 1989, and has been being exploited from 1974. Initially, the getter volume was 50 000 tons/year. Factually, the same volume was preserved till 2006, i.e. through almost 20 years.
      The supply with electric power of all of the deposit is being carried out from high-tension electric transmission line of city Medvezhyegorsk (Karelia). The distance from main railway of city Medvezhyegorsk till the deposit is 70 km.
      From all the available shungite deposits in Karelia (Table 1.2) Za-zhogino is the most explored and prepared one for the industrial introduction. Its stated resources constitute 149,3 million tons, in particular, by categories: В — 6,5; С₁ — 25,0; С₂ — 117,8. The supposed yet nonstated resources is another 173 million tons. Besides, there are several promising sections in Medvezhyegorsk, Eastern Medvezhyegorsk, and Western. The supposed resource of these sections by geologists datum is about 1 billion tons. The mineral assets of these groups have been investigated yet scarcely, and their values are not stated.

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