RU75656U1 - HUMIC AND FULVO ACID PREPARATION SYSTEM - Google Patents

Abstract

Designed to produce humic and fulvic acids in the form of hydrogels and technical pastes, respectively, suitable for subsequent use in the synthesis of various organic products. The description of the Utility Model Patent contains 1 independent claim, 1 ill.

Description

The proposed utility model relates to the non-fuel use of brown coals and can be used in the synthesis of various organic products based on humic and fulvic acids.

The study of the properties of humic and fulvic acids has been carried out for a long time, it is important, it helps to predict the yields and properties of the target products in the processing of solid fossil fuels (brown coal, peat, sapromixites) rich in humic and fulvic acids [1].

There are various systems used in technological processes [2, 3].

The closest in technical essence to the proposed utility model is the production of humic acids for the battery industry [4].

The disadvantages of the prototype: low yield of target products, the loss of fulvic acids, which together with the filtrate go into production waste, as well as a significant content of residual brown coal, unsuitable for further use due to high ash content.

The purpose of the proposed utility model is to significantly increase the yield of target products with low-waste technology.

This goal is achieved by the fact that brown coal is exposed to high energies in a flow mill-activator [5].

The proposed system is illustrated by the technological scheme and description of the process. Before loading into a flow mill-activator, brown coal is ground in a mechanical mill with steel balls to a particle size of 0-500 microns. To transfer brown coal to water-soluble compounds, a TsEM-7 vibrocentrifugal mill is used (developed by the Institute of Solid State Chemistry and Mechanochemistry of СО

RAS). The mill [5] is made with a horizontal arrangement of 2 pipe grinding drums and is intended for the preparation of highly dispersed suspensions.

The process is as follows. Brown coal with a grain size of 0-500 μm is loaded into a screw feeder of raw materials (1). A 5% sodium hydroxide solution is pre-pumped into the raw material meter (2), which is then poured into an intermediate collector (3). The activator mill (4) is turned on and the sodium hydroxide solution is pumped through the pipeline circuit with a pump (5). When the mill is operating, the screw feed meter is turned on (1), and finely ground coal is introduced into the sodium hydroxide solution. In the mill (4) they are mixed and the coal is crushed simultaneously. After all the coal from the dispenser enters the mill, the suspension is pumped through the activator mill (4) for a certain time until the maximum formation of water-soluble sodium salts of humic acids occurs. As the process ends, the mill (4) is stopped and the finished solution of water-soluble sodium salts of humic acids from the collection (3) is pumped through the control filter (8) into the collection container (11) with a pump (6). The suspension that has not passed through the control filter is poured into the collection tank (7) and, as it accumulates, it is sent to a precipitation-filtering centrifuge (9), where sodium humates are separated from the residual brown coal, which, as it accumulates in the collection tank (10), is sent for re-grinding into the intermediate collection (3). From the collection (11), sodium humates are pumped by pump (12) into the container for preparing humic acids (14). A 10% solution of hydrochloric acid from a mernik (13) is poured into the container for preparing humic acids (14) until the flakes of humic acids are completely separated at pH 2. After adding hydrochloric acid and mixing the solution, sedimentation is carried out in the collection (15). As a result of settling in the collection (15), the solution is divided into two phases. Brown flakes of humic acids settle to the bottom, and on top is slightly colored

fulvic acid solution. Both components are separated in a precipitation-filtering centrifuge (16). Humic acid hydrogels are sent to a collection (17), where they are stored in a wet state for further use in organic syntheses, and a fulvic acid solution is sent to a collection (18), from where it is transferred to a cube (19) for distillation of hydrochloric acid. The distillation cube (19) is equipped with a heater and a water cooler (21). As a certain volume of hydrochloric acid is distilled off to a receiver (22), the wet technical substance of fulvic acids is discharged into a collector (20), where it is stored in a wet state for further use in organic syntheses. Hydrochloric acid from the receiver (22) is again used to precipitate humic acids. The proposed system is highly efficient and virtually waste-free due to the use of the centrifugal mill TsEM-7.

As a result of mechanical activation treatment, the yield of water-soluble sodium salts of humic acids increases to 90%. This effect is explained by the shock-shear effect, accompanied by the destruction and disordering of the structure of brown coal. The resulting new structural surface groups are active and interact with surrounding molecules, which ultimately increases the yield and facilitates the isolation of the final products. Since the size of coal particles decreases from 500 μm to 5 μm during mechanical activation treatment, micropores previously unavailable for contact are also opened, from which additional native humic substances are extracted that can react with sodium hydroxide, thereby increasing the yield of water-soluble sodium salts of humic acids.

An example of brown coal processing.

For processing, we used a commercial sample of coal grade 2B of the Kaychaksky open pit mine (Barandatskoye deposit, Kuzbass).

Characteristics of the original brown coal:

The moisture content,% by weight ........... 5,0 Ash content,% by weight .................. 9.8 Higher calorific value, kcal / kg ....... 4700 The yield of volatiles,% by weight ...... 45.8

The content of elements,% by weight:

carbon ............................ 72.9 hydrogen ............................ 5.3

1000 g of dry brown coal with a grain size of 0-500 microns is treated in a vibrocentrifugal mill with a 5% sodium hydroxide solution taken in an amount of 3 liters. Next, carry out all the operations specified in the description of the process. The result is 100.0 g of solid residual coal and 3 liters of water-soluble sodium salts of humic acids. The degree of conversion of coal is 90%. Residual coal is accumulated and then crushed again in a vibrocentrifugal mill. In almost several cycles, all residual coal also passes into the water-soluble sodium salts of humic acids, from which humic and fulvic acids are then isolated. When distilling hydrochloric acid vapors from a fulvic acid solution in a technical paste of bottoms, water-soluble fulvic acids and ballast metal chlorides remain, which, if necessary, are separated from fulvic acids by special cleaning methods.

Information sources:

1. A.V. Kravtsov, D.A. Bazhenov, L.I. Tarnovskaya, S.G. Maslov Assessment of the thermodynamic probability of thermolysis of humic and fulvic acids. // Chemistry of solid fuels. - 1998. - No. 1. - S. 38-47.

2. USSR Author's Certificate No. 1041807 A. Publ. 09/15/83. Bull. Number 34.

3. Copyright certificate of the USSR No. 1295150 A2. Publ. 03/07/87. Bull. No. 9.

4. T.A. Kukharenko, S.A. Shapiro Humic acids for the battery industry. // Chemistry of solid fuels. - 1967. - No. 1. - C.112-118.

5. Mills and mechanical activators. // Advertising brochure of the Institute of Solid State Chemistry and Mechanochemistry SB RAS, (Novosibirsk, Kutateladze St., 18).

Claims (1)

A humic and fulvic acid preparation system, characterized in that, in order to increase the yield of the target products, low-waste closed technology is used, in which a TsEM-7 vibrocentrifugal mill is used as a chemical reactor, equipped with a centrifugal pump mounted on the mill feed line for repeatedly pumping coal suspension through the mill, and the final target products are released in the form of hydrogels of humic acids and technical paste of fulvic acids, allowing to separate the residual drill second coal and regenerated hydrochloric acid with the aim of returning them to the production cycle recycle.