Equipment for obtaining soluble humate materials from mineral coal

Abstract

The invention describes an installation, which serves for obtaining humate materials from mineral coal base material, and is provided with raw material depository (1), and a suitable mixer (5) for mixing of the raw material and the reagent, and where a dryer (3) for drying the raw material is attached to the raw material depository, and through a transporter (4) a mixer (5) is attached in order to mix the mineral coal base material with the solid state alkali reagent, furthermore there is a solid alkali feeder equipment (5a) and through a transporter (6) an ozonizing chamber (9) is attached to mixer (5), where the chamber (9) has an ozone inlet hole (78) attached to the ozone generator (8), and there is a mechano-chemical activator (10) attached to the outlet hole (79) of the chamber (9).

Claims

1. Equipment for recovering humate substances from mineral coal raw material, provided with a depository (1) for the raw material and a closed mixer (5), suitable for mixing the raw material and a solid state alkali reagent wherein attached to the raw material depository (1) is a conveyor (2) to a dryer (3), sealed from the environment and suitable for producing dried mineral coal raw material, and the dryer (3) attached, through a transporter (4), sealed from the environment, to the mixer (5), suitable for mixing of the dried mineral coal raw material with the solid state alkali reagent, and where a closed solid state alkali reagent feeder (5a) is attached to the mixer (5), and through another transporter (6) and a feeder (7), sealed from the environment, additionally a closed ozonizing chamber (9) is attached to the feeder (7), where the ozonizing chamber has an ozone inlet hole (78) attached to an ozone generator (8), and an outlet hole (79) of the ozonizing chamber is attached to a mechano-chemical reactor (10), sealed from the environment.

2. Equipment as of claim 1 wherein the mechano-chemical reactor (10) is a centrifugal vibration ball mill.

3. Equipment as of claim 2 wherein the ball mill is filled up with wear resistant steel balls of diameter 15-25 mm to 25-40% of reactor volume.

4. Equipment as of claim 3 wherein the ball mill can accelerate balls to a minimum of 30 m/s.sup.2.

5. Equipment as of claim 1 wherein the mechano-chemical reactor (10) is a planetary-vibration ball mill capable of at least 30 m/s.sup.2 acceleration of the balls.

6. Equipment as of claim 1 wherein the mechano-chemical reactor (10) is an impeller mill.

7. Equipment as of claim 1 wherein the mechano-chemical reactor (10) is a pneumatic jet stream mill having a pneumatic flow rate of 10 to 120 m/s.

8. Equipment as of claim 1 wherein the ozone generator (8) can produce an air-ozone mixture having temperature of 0-60 C., and an ozone partial pressure of 0-0.1 MPa.

9. Equipment as of claim 1 wherein the mechano-chemical reactor (10) is provided with a dust filter unit (11).

Description

(1) Further on the invention is described in details with reference to the attached drawing.

(2) FIG. 1 illustrates the equipment as of the invention. As raw material, mineral coal, preferably peat or leonardit type brown coal is used. Leonardit contains humic-compounds in 65 wt %, other substances (mostly inorganic oxides): ash30 wt %, carbon15 wt %. Other components in wt %: nitrogen0.18, phosphorus (in P.sub.2O.sub.5 equivalent)0.05, potassium (in K.sub.2O equivalent)0.06, magnesium0.37, iron0.67, manganese0.01.

(3) Leonardit is disintegrated to a particle size below 3 mm and conducted from 1 raw material depository by 2 conveyor to 3 dryer, sealed from the environment, where it is conditioned to a moisture content of 8-16 wt %, while the moisture content is measured continuously by an adequate instrument. Also in the further parts of the equipment, the moisture content of the material will be held on the value of 8-16 wt % established in 3 dryer. In this description, the terms: sealed from the environment, closed equipment, etc. shall have the meaning that, air from the environment cannot penetrate in unhindered and/or in an uncontrolled manner into the equipment or into the attaching tubes, that means the entire technological line of the various connected equipment can be considered a closed system.

(4) The low humidity content makes possible to enhance the efficiency of further reactions on the one hand, and to prevent sticking of the raw material to the wall of different parts in the equipment on the other hand. The well dried material is transported from 3 dryer by means of hermetically attached, 4 conveyor, sealed from the environment, into the 5 mixer (e.g. Zucchetti, Italy), where it is mixed with the reagent, preferably with solid alkali. As an alkali, metal-hydroxides with a particle size of below 3 mm, and with a main component content of minimum 90% are used, mainly NaOH, KOH, or metal-carbonatesmainly potassium or sodium carbonate; these are transported from 5a alkali-feeder, hermetically sealed from the atmosphere, into 5 mixer. Application of solid state alkali prevents escaping of liquid contaminating materials, e.g. caustic lye solutions, and eventually solved hazardous materials therein, into the environment. The 5a alkali-feeder and 5 mixer are also attached to each other by hermetically sealed conducts, in order to prevent both the raw material and the strongly hygroscopic solid alkali from absorbing humidity from the ambience after drying. In addition, solid alkali may form carbonates with the CO.sub.2 content of the atmosphere, which are inadequate for application as reagent.

(5) The mixture is transported from 5 mixer by 6 conveyor, closed and sealed from the environment, into 7 feeder, which sends the solid mixture with controlled flux into 9 ozone-chamber. The 9 ozone-chamber has a 78 inlet hole attached to 8 ozone generator, while its 79 outlet hole is attached to the 10 mechano-chemical activator. Ozone can be produced by 8 ozone-generator, for example type Ionic Zone Ozone Generators (Ionic Zone LLC, Las Vegas, USA). 7 feeder, 9 ozone-chamber and 10 mechano-chemical reactor form a sealed unit as well.

(6) 8 ozone-generator produces an ozone containing gas-mixture with the air, with a temperature of 0-60 C., and a partial pressure of 0-0.1 MPa, having defined relative humidity, and will send the mixture into 9 ozonising chamber, and after that into 10 mechano-chemical activator.

(7) We observed that, the lower is the moisture content of the air introduced to the 8 ozone-generator, the higher will be the quantity of ozone produced. Therefore, dried air with lowest possible humidity is conducted from the atmosphere into 8 ozone-generatornot only in order to decrease the humidity, but also in order to increase the yield of ozone-generation.

(8) Preferably, the ozone content of the gas mixture is between 0.1-2.0%.

(9) When the mineral coal-alkali solid mixture meats the air-ozone mixture in the 9 ozonizing chamber, and then in 10 mechano-chemical activator, under strong mechanical action intensive oxidation of humic acid and neutralization of oxidized humic acid by alkali take place and formation of humates start. The installation as of the invention is provided with 11 dust filtering unit, which is attached to the 11 dust filtering unit through 11a sealed tube, in order to prevent leakage of powder-form product particles into the environment, and entering of moisture into the 10 activator respectively.

(10) The composition of the ozone-air gas mixture is determined by the amount of alkali needed to neutralize humic acid and to catalyze the alkaline depolymerization of the humic compound, and ranges from 5 to 25 wt %. The amount of ozone is determined based on the number of oxygen-containing groups needed to increase the solubility of humate, and ranges from 0.1- to 3% by weight, based on the weight of mineral coal, e.g. leonardit used in the process. Alkali content below 5% is not sufficient for increasing the solubility of coal; on the other hand alkali content over 25% will enhance the solubility of coal, but will significantly raise the cost of the process and increase the pH of the coal product solutions to 9-10, which does not permit its conventional application. Ozone introduced in an amount below 0.1% does not increase the solubility of the product, while ozone used in an amount over 3% oxidizes humic acids and leads to the formation of oxidation-resistant, low molecular weight carboxylic- and dicarboxylic acids, decreasing thereby the yield of humic acids.

(11) According to the invention, the 10 mechano-chemical activator, used for the mechanical and chemical transformation of the powder-form material treated with alkali and reacted with ozone, is expediently a centrifugal-vibration ball-mill, where the acceleration of the balls must reach the optimal value of 30 m/s.sup.2. If the acceleration of the balls is lower than the above value, significantly will decrease the velocity of the reaction and the performance of the activator. This effect can also be reached by centrifugal-elliptic mills, preferably with planetary-vibration ball-mills, for example in those produced by Novic, Novosibirsk, Russia. Preferably 25-40% of the volume of the ball-mill is filled up with balls made of wear-resistant steel or medical metal, having a diameter of 15-25 mm. The performance of the ball-mill, expressed with the acceleration of the balls, is minimum 30 m/s.sup.2.

(12) For the treatment of the product in ozone-containing medium, equipment with less intensity, like gravitational ball mills, or disintegrator-type grinding machines, jet and vortex mills are also applicable instead of centrifugal ball mills, which can be used in the following operating modes: in paddle-wheel (roller) mill with the rate of impeller blades rotating at a speed from 10 to 120 m/s, for a time period of 0.2-2.0 minutes, in pneumatic and jet stream mill with a flow rate of 10 to 120 m/s, for a time period of 0.2-2.0 minutes.

(13) The lower threshold value of effect-intensity (ball acceleration of 30 m/s.sup.2) can be determined by the threshold value of the intensity of mechanical effect required for the progress of the mechanical and chemical process (Avvakumov J. G.: Mechanical Methods of Activation of Chemical Processes. Novosibirsk, Nauka, Siberian branch. 1986, page 303).

(14) The upper threshold value of effect intensity is 60 m/s.sup.2, which can be determined by the beginning of the degradation process of humic compounds, as well as by their transformation to amorphous carbon structure.

(15) At the end of the mechanical and chemical treatment, we receive powder form product, advancing from 10 activator in the direction of arrow N, into the tank for finished product. That means, the equipment as of invention forms a closed technological line between 3 dryer and the finished product tank, where only 8 ozone-generator employs ambient air in determined quantity and humidity content.

(16) The product can directly be used in farm breeding as fertility- and growth stimulating feed-supplement for the cattle-, pig- and poultry population. Furthermore, the composition can be used in the plant cultivation too, as growth stimulating agent, through seed-dressing, or by adding it to the irrigation water in order to promote sprouting, the growth of the parts over the soil surface, increase of root development, and, in generally, in order to enhance the fertility of plants. Positive advantages of the powder-form composition compared to the liquid preparations: the ease of transport and storage. In case of necessity, the powder-form product can be extracted; in this case we can get preparations with soluble materials in higher concentrations and high quality products with better performance.

(17) The operation of the installation as of the invention is illustrated by the following example:

(18) Brown coal type leonardit raw material (place of occurrence: Dudar, Hungary) having a moisture content of 15 wt % was previously disintegrated to a granulation below 1 mm in the crasher, then dried in the dryer 3. Then coal was mixed in mixer 5 with pure or technical purity sodium hydroxide (KOH or NaOH) coming from 5a feeder, then treated in centrifugal vibration ball mill, (type CEM 20, manufacturer: Novic, Novosibirsk, Russia) as 10 activator, with an acceleration of the balls of 30 m/s.sup.2, for a time period of 1 minute, simultaneously exposed to the effect of ozone-air mixture entering from 8 generator. The resulted material was fine powder-form, soluble preparation with rich humate content.

(19) Thus, the advantages of the equipment as of the invention comparing to the other equipment representing up-to-date technology, include the implementation in industrial scale of the dry process in a closed technological system, suitable for increasing the concentration of humate compounds, enhancing the solubility of the preparation, reducing the consumption of chemicals and the cost of production, and where the processing of humic-containing raw material is performed in the presence of a gas-form substanceozonewhich disintegrates the structure of humic compounds, in a mixture of brown coal and alkali, where the ozone ensures the process of oxidative polymerization, forming of humates, and the enhanced presence of oxygen-containing groups in these humates respectively, meanwhile environmentally dangerous/harmful materials do not get out from the equipment.