Study and Obtaining of the Humine Acids Based Soluble Polymers for Clay Suspensions Stabilization

O. Koblanova, M. Temirbekova, D. Absalova, G. Abramova

Drilling works scale and drilling depth constantly increasing leads to the necessity of formation of the thermal salt resistant drilling solutions, possessing the stable coagulation –tixothrope structure. Usually the natural mineral raw clay, with the definite crystal site is used; its clay particle structure provides for the system aggregate – stable structure formation (for example, palygorskit).

Other clays usage is also possible when the effective structural forming clays are not available, but the washing system should contain the low- and high molecular surface – tyxothrope structure.

Imported clay powders and foreign expensive chemical reagents (KMTs, GIPAN, K-4, SAIPAN, K-9, PAA and others) are used in Kazakhstan till nowadays.

However, our Republic possesses great clay source deposits.

A new Darbasa deposit has been discovered along with the known deposits, such as Monrak, Keless, but it is used only as the raw material for the ceramzite. Their practical utilization in the other branches of national economy is limited, for there are no data concerning the physical-chemical, structural-mechanical, and taxithrope characteristcs of the clay water dispersions; besides there is no manufacturing of the water soluble polymers in our Republic, though the great deposits of raw material resources are available as the great amount wastes of the hydrolize production and drilling coals of the Lenger deposit. The latter are of great advantage for their low manufacturing cost, transportation, ecological value and the existence of the humine compounds, easy extractable and capable of producing water - soluble surfactant additives – stabilizers.

Research objective is the study of the structure formation processes and aggregate stability of the Darbasy clay deposit montmorilonite hydro sludisto suspensions, along with the available new akrilic humate poly electrolites (which manufacture is based on the humine acids and acrylic monomers), and polymer wastes of the nitron fibre.

The followings tasks have been determined in accordance with the objective stated:

- study of the Darbasy clay dispersions water solutions tyxothope coagulation structure formation and aggregate stability processes, depending on the solid phase content;

- development of the methods and optimal conditions of producing water soluble co-polymers based on the humine acids from the dark coal and acrylic monomers (methylmetacrilamide metacrylic acid), and the nitron fibre wastes, determination of the co-polymer functional composition and their nature;

- study of the influence of the water soluble acrylic – humate polyam-folites on the active aggregate stability of the water dispersions of the montmorilonite hydro sludisto clays and development of their optimal compostions in the conditions of the agents’ high mineralization and long storage period;

- recommendations compiling on their usage in the deep drilling operation.

We have initiated the complex research of the Darbasi deposit natural and enriched clays physical – chemical, structural - mechanical, reological and filtration characteristics.

Structure formation and salt resistance in the water dispersions of these clays process has been discussed; we have determined if it is possible to use them for the salt resistant clayous suspensions preparation, because it is exploitated for the deep wells drilling in oil, gas and mineral resources prospecting.

We have obtained new water soluble poly electrolites, studied their functional composition and physical – chemical characteristics in the water sutions; we used the humine acid with the metacrylic acid, metacilamide and the nitron fibre manufacture wet wastes conception method

It has been stated that clayous suspensions salt resistance is increased and keeps their stabilizing capacity for a long period (not less than 15 days) due to the introduction into the macro molecule of theamid groups humine acids in the poly electrolite SUMMA, synthesized on the base of the humine acids and the nitron fibre manufacture wastes, and increasing of the carboxylate groups number in the CYMAK poly – electrolite, based on the metacrylic acid humine acids. It has been stated that water soluble acryl humate poly electolite structure formation capacity is determined by the nature of their functional groups.

We have proved the possibility of using Darbasi deposit natural and enriched hydrosludisto – montmoril clays clay powders instead of the imported ones for the production of the calyous suspensions, possessing the coagulation –tixothrope structure ans are uasble in the well drilling in the high mineralization conditions.

We have also stated he practical advantage of using instead of the imported reagents along with the coal alkali reagent the new acrylic humate poly electrolites based on the dark coals of the Lenger deposit in the South-Kazakh oblast.

Water Soluble poly Ampholites Based on the Humine Acids

O. Koblanova, M. Temirbekova, D. Absalova, G. Abramova

For the purpose of manufacturing the water souble poly-ampholites we have taken the samples of the Lenger deposit dark coal, and as the modifying additives – metacrylic acid (MAA), methy metacryl amid (MMA), and nitron fibre manufacture wastes (NFW). The research results on the development of the ways of the conditions optimization of the water soluble poly electrolites based on the Lenger deposit dark coal humine acids (HA) have been obtained.

The way of manufacturing the coal alkali reagent (CAR) by hydrolizing of the Lenger deposit cheap dark coal, mainly containing the humine acids. The CAR manufacturing optomal conditions have been determined: the proportion of the coal to the natrium hydroxide equals 1:0,3, hydrolize temperature – 338-343K, hydrolize period - 3,5- 4 hrs. It has been shown that the componential composition is presented mainly by the natrium humates, and the functional composition - by the hydroxile and carboxilate groups.

It was revealed that that the CAR dispersions are of the poly electrolite nature and of the surfactants characterisitics. 40% natrium hydroxide water solution was used as the soap agent in these reactions. The reaction was as follows: the humine acids were added into the aqua conditions and it was initiated by the potassium persulphate. Metacrylic acid, methylmetacrylamid and lye was added into the mixture step-by-step along with the intensive stirring in the water condition.

We have determined the optimal conditions of obtaining of the water soluble acrylic humate stabilizers: proportion of the reacting components in the co-polymers is, mass% : Gk: monomer: initiator: NaOH =1:2:0,2:0,45. During the reaction period the 10% viscous temper mass is formed, it is of high solubility characteristics, it has a sharp smell of the amiak. The manufactured polymers were conventionally titled ‘SUMAK’ – reagent of HA and MAA, ‘SUMMA’ – reagent of HA and MAA, and ‘SUOVN’- reagent of HA and NFW.

Based on the test results the folowing conditions were considered to be optimal for the manufacturing of the water soluble co polymers from the nitron fibre production wastes and humine acid in the presence of the natrium hydroxide: NFW:HA: NaOH=1:0,3:0,5, soap period – 3 hrs, and the soap temperature is 368-371 K. We have chosen the modern physical-chemical methods of investigation in order to determine the composition and characteristics of the initial and synthesized polymer specimen, they are: thermal gravimetry, IR spectroscopy, viscosimetry, potentiometry, conductometry; analytical research methods have also been used.

According to the element analysis data at the HA modification by the monomer in the co polymer molecule the carbon content is insignificantly changed from 40, 61 to 42, 91 %. General nitrat in the specimen obtained are fluctuating from 2, 51 to 5, 41%, i.e. 2 -3 times more, than in HA.

The Infra red spectrum analysis has shown that the co polymers under study contain carboxilate, amid, phenol, hydroxile and cyclic amid groups.