RU2387694C2 - Method of preparing carboxyl-containing resin from pitch coal - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: pitch coal crushed to particle size of 500 mcm is added to water-soluble salts of high-molecular compounds and then high-molecular organic acids consisting of a water-insoluble component in form of hydrogel and soluble component in form of a paste, the components are combined and then reacted with glacial acetic acid in the presence of lead (II) acetate to obtain a carboxyl-containing resin at the output through extraction, where the said resin contains oxygen-containing organic compounds with lower molecular weight.

EFFECT: obtaining oxygen-containing soluble organic compounds from pitch coal without using hydrogen at high pressure.

1 ex, 1 tbl, 2 dwg

Description

The invention relates to the field of production of liquid coal products and can be used to obtain oxygen-containing soluble organic compounds from brown coal.

Among the known methods for producing liquid products from coal, the author's certificate is known (USSR Author's Certificate No. 881109. Publ. 15.11.81. Bull. No. 42), in which the total liquid products of hard or brown coals are obtained by hydrogenation of coal, and then separated by filtration of hydrogenate into extract and solid components, followed by distillation of the extract into fractions. The high boiling fraction of the extract with a boiling point above 320 ° C is subjected to further heat treatment with separation into liquid and solid components, followed by feeding the liquid components of the fraction with a boiling point of 200-320 ° C as a solvent again to the stage of coal hydrogenation.

The closest in technical essence to the proposed method is a method for producing liquid products from coal (USSR Patent No. 795499. Publ. 07.01.81. Bull. No. 1), selected as a prototype.

The disadvantages of the prototype. The use of complex and expensive catalysts, a significant amount of residual solid component, high pressure of hydrogen at the stages of dissolution, hydrogenation and decomposition of hydrogenation products.

The aim of the invention is to obtain oxygen-containing soluble organic compounds from brown coal without the use of high hydrogen pressures.

This goal is achieved by the fact that brown coal is first transferred in a flow mill activator (Mills and mechanical activators. Promotional brochure of the Institute of Solid State Chemistry and Mechanochemistry of the SB RAS) into water-soluble salts of high molecular weight compounds, which are then converted into free high molecular weight acids and cleaved using known techniques to oxygen-containing soluble organic compounds with lower molecular weight. Among the known techniques used for the cleavage of cyclic compounds, Hill RK, Carlson RM // J. Org. Chem. 1965. - V.30. - P.2414) showed the cleavage of cyclooctatetraene to 1,4-diacetoxybutadiene with divalent mercury acetates. In another known work (Wolf FJ, Weijlard J. // Org. Syn., Coll. Vol. 1963. - V.4. - P.124), di-n-butyl-D-tartrate was digested with n-butyl glyoxalate using lead tetraacetate.

The proposed system is illustrated by the technological scheme (figure 1) and a description of the process. Lignite is ground in a mechanical ball mill 1 with steel balls to a particle size of 0-500 microns. From the ball mill, brown coal is loaded into the screw feeder of raw material 2. A 5% sodium hydroxide solution is poured into the raw material meter 3, which is then poured into the intermediate collector 4. The activator mill 5 is turned on and the sodium hydroxide solution is pumped through the pipe 6 through the mill through the mill -activator 5. When the mill-activator 5 is operating, a screw doser of raw material 2 is turned on and finely ground coal is introduced into the sodium hydroxide solution. In the mill activator 5, they are mixed and at the same time additional grinding of coal. After all the coal from the dispenser enters the activator mill 5, the suspension is pumped through the activator mill 5 for a certain amount of time until the maximum conversion of brown coal to the water-soluble salts of high molecular weight compounds occurs. As the process ends, the activator mill 5 is stopped and the finished solution of water-soluble salts of macromolecular compounds from the collector 4 is pumped by pump 7 through the control filter 9 into the receiving collector 12. The suspension that has not passed through the control filter is poured into the collector 8 and sent to a precipitation filter as it accumulates. centrifuge 10, where the water-soluble salts of high molecular weight compounds are separated from the residual brown coal, which, as it accumulates in the collector 11, is sent for re-grinding in the intermediate th collection 4. From the collection 12, water-soluble salts of high molecular weight compounds are pumped by pump 13 into a container 15, where, using a 10% solution of hydrochloric acid supplied from measuring unit 14, water-soluble salts of high molecular weight compounds are transferred at pH 2 to free acids, some of which are dissolved in water (fulvic acids), and the other part is not soluble in water (humic acids). In collection 16, sedimentation and separation of free acids into two layers takes place, which are finally separated in a precipitation-filtering centrifuge 17. A water-insoluble component in the form of acidic hydrogels of high molecular weight humic acids is sent to a collection 18, and a soluble aqueous component of high molecular weight fulvic acids is sent to a measuring device 19, from where it is passed to the distillation cube 20 to distill off the excess hydrochloric acid. The distillation cube 20 is equipped with a heater and a water cooler 22. As a certain volume of hydrochloric acid is distilled into the receiver 23, the wet technical substance of high molecular weight acids in the form of an acid paste is discharged into the collection 21. The isolated acid hydrogels of high molecular acids from the collection 18 are loaded into the bath 28. They are also loaded there acidic paste of high molecular weight acids from the collection 21. The required amount of acetic acid lead is also loaded into the bath 28. All components are mixed well, after which the reaction mixture is transferred to the reactor 31, where the required volume of glacial acetic acid is added from the measuring unit 30 and mixed again. The reactor 31 is closed and gradually heated at a speed of 10 deg / min to a temperature of 400 ° C. At this temperature, the reaction mixture is kept for 1 hour, after which the reactor is cooled with tap water. From the cooled reactor 31, an excess of unreacted acetic acid is filtered through a Druk filter 32 into a collector of acetic acid extract 34. A specific volume of pyridine is poured from a measuring device 29 into a reactor 31, mixed and forced through a Druk filter 32 into a pyridine extract collector 35. Extraction with pyridine is carried out until complete extraction of organic products. The solid component (catalysis) from the Druk filter 32 is transferred to the collector 33 for further use in the catalytic process. The resulting pyridine extract from collector 35 is sent to distill off the pyridine using a distillation cube 27 and a water cooler 25. The distilled pyridine is collected in collector 24, and the finished product is discharged into collector 26. Acetic acid from collector 34 and pyridine from collector 24 are again used in the technological process . The cleavage reaction of high molecular acids proceeds in an excess of glacial acetic acid quantitatively without residual solid product. All oxygen-containing compounds that make up the carboxyl-containing resin are completely dissolved in pyridine.

Figure 2 shows a chromatogram of a pyridine extract containing synthesized oxygen-containing compounds.

Chromatographic analysis was performed on an Agilent 6890N / 5973 Inert chromatograph with an HP-5MS capillary column (5% diphenyl - 95% dimethylglyoxane). Column dimensions 30 m × 0.25 mm. The carrier gas is helium.

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:

Moisture Content, W ^a ,% by mass 5,0 Ash content, A ^d ,% by weight 9.8 Higher calorific value, Q _s ^daf , kcal / kg 4700 The yield of volatiles, V ^daf ,% by weight 45.8 Carbon, C ^daf 72.9 Hydrogen, H ^daf 5.3

Dry brown coal with a grain size of 0-500 μm in an amount of 1000 g is treated in a vibrocentrifugal mill with a 5% solution of sodium hydroxide taken in an amount of 3 l. 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 l of water-soluble sodium salts of high molecular weight acids. The degree of conversion of coal is 90%.

Residual coal is accumulated and then crushed again in a vibrocentrifugal mill. After isolation of free high molecular weight acids in the form of hydrogels and paste, a reaction mixture containing 10 g of hydrogels, 5 g of paste, 5 g of acetic acid divalent lead and 30 ml of glacial acetic acid is loaded into the reactor 38. After the synthesis, 17 g of a mixture of oxygen-containing soluble organic compounds with 100% splitting of high molecular weight acids are obtained.

The table shows the data of mass spectrometric analysis of some components of the brown coal carboxyl-containing resin.

Table Characterization of some components of a carboxyl-containing resin. No. p / p Retention time, min Peak area,% The degree of reliability of mass spectrometric identification,% Connection Name one 7.4153 0.195 71 2-Ethoxyethyl Acetate 2 8,190 95 γ-Butyrolactone 3 8.227 3,749 75 2-Hydroxytetrahydrofuran four 13,406 0.262 71 α-n-Propyl-γ-butyrolactone 5 14,462 0.257 72 Pantoic acid lactone 6 16,064 2,809 71 Glutaric acid 7 16,609 12,276 83 Tetrahydro-2-furanylmethyl butyrate 8 17,216 1,678 79 Butyric anhydride 9 18,150 80 Tetrahydrofurfuryl acetate 10 18,300 0.688 79 1,4-butanediol diacetate eleven 20,219 0.955 73 4-methyl-2-phenyl-dioxalan 12 20,786 0.549 74 Monoethyl succinate

Claims (1)

A method of preparing a carboxyl-containing resin from brown coal, characterized in that the brown coal crushed to a particle size of less than 500 microns is converted into water-soluble salts of high molecular weight compounds, and then into high molecular weight organic acids consisting of a water-insoluble component in the form of hydrogels and a soluble component in the form of paste , combine the components and act on them with glacial acetic acid in the presence of acetic acid divalent lead to obtain carboxy by extraction at the outlet lsoderzhaschey resin containing a carbon-oxygen bond with a lower molecular weight.

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