Размещено на http: //www. allbest. ru/

1M. Auezov South-Kazakhstan State university, Shymkent city, Kazakhstan, 160019

ЮКГУ им.М.Ауезова, город Шымкент, Казахстан, 160019

Research the process of receiving polymeric sulfur and selection of optimum conditions

Исследование процесса получения полимерной серы и подбор оптимальных условий

M.R. Sattarova, U.B.Tozhimamatov, S.А. Sakibaeva, N.O. Zhakipbekova

М.Р. Саттарова, У.Б. Тожимаматов, С.А. Сакибаева, Н.О.Джакипбекова

miss.madinur@mail.ru 8-702-728-16-75

ubay-93@mail.ru 8-705-171-88-55

Abstract

Nowadays the way of use and improvement of qualities of products of oil processing remains topical issue. In this work properties and qualities of the modified sulfur are considered.

The purpose of this work is receiving water-soluble colloid sulfur with sidementatsionny stability to 95-98%, good water solubility, high biological activity, and also use of SO2 off-gas for receiving sulfuric acid.

Received the results of researches the process of a modification of by-product of oil production sulfur of PKOP LLP (Petrokazakhstanoilprodakts, Shymkent city) and its further use as the vulcanizing component in a rubber stock.

Key words: sulfur, oil products, rubber tire, rubber compound, curing, curing agent, cure system.

Introduction

Sulfur is a yellow powder. There are several modifications differing from each other in a structure of molecules and some properties.

Sulfur meets in the free (native) state and the bound look. Sulfur is applied to production of sulfuric acid, rubber curing as a fungicide in agriculture and as sulfur the colloid -- a medicinal preparation.

It is also being in structure of sulfur - bituminous compositions is applied to receiving a sulfurasphalt, and as the deputy of a portland cement -- to receiving a sulfur - concrete.

In the Republic of Kazakhstan at production and petroleum refining a wastage of lump sulfur which goes to a dump are formed.

For receiving polymeric sulfur, initial raw materials-free sulfur, it was received on Claus's installations at the Petrokazakhstanoilprodakts LLP plant which in 2015 processed 4,493 million tons of raw materials, at the same time depth of processing made - 75%, and the output of light oil products - 56,7%.

In 2015 the company received the positive decisions of state examination on the feasibility study and the design and estimate documentation "The project of modernization and reconstruction Shymkent petro organic synthesis of oil refinery" which realization is enabled within GPFIIR RK for 2015-2019. Within 1 stage in 2015 projects of reconstruction of installation of hydrotreating of solar oil and construction of a new object are complete - installation of production are gray. Within the 2nd stage until the end of 2017 construction new and reconstruction of the existing technological installations and objects of OZH for restitution of capacity of plant to 6 million tons per year and increase in depth of processing is planned.

Ultimate goal of implementation of the Project of modernization is transition to production of oil products of the Euro-4 and Euro-5 standards, increase in depth of processing and production of refined oils.

Claus's installations called also by installations of receiving the free sulfur are necessary elements of oil processing production now. Extraction of sulfur from refined oils is caused by ecological requirements: as on decrease in toxicity of engine fuels, and, in not smaller degree, on decrease in emissions of oxides of sulfur in a surrounding medium. Therefore any modern project of reconstruction of the oil processing enterprise does not do without construction or deep modernization of installations of Claus.

1. The key diagram of receiving are sulfur by Claus's method

Figure 1 1, 4, 7 - gas combustion furnaces; 2 - the thermal reactor with steam oscillation knot; 3, 6, 9 - coolers (condensers); 5, 8 - reactors of the second and third stage; 10 - sulfur catcher; 11 - furnace of a dozhig; 12 - gas tertiary treatment block (process "CATTLE"); 13 - receiving capacity of sulfur; I-sour gas; II - air; III - fuel gas; IV-water; V - steam; VI - sulfur; VII and VIII - the departing and purified flue gas

The maximal exit of sulfur on a first stage makes 60 - 70% of its overall yield. The second stage consists furnaces 4 for combustion of the rest of sour gas and transformation of the oxide of sulfur which is contained in gas after a first stage. Reactions at this step proceed at a temperature of 240 - 250 °C in the catalytic reactor 5 filled with the express catalyst (the activated adamant). Recently catalysts on the basis of dioxide of a titanium of the CRS-31, CRS-32 brand began to be used widely. On escaping of the reactor 5 temperature reaches about 330 °C, and gas then is cooled in a cooler to 170 °C with selection from it the condensed sulfur. Gas from a cooler 6 comes on a third stage, in the beginning to the furnace 7 where its temperature increases to 2200C (due to combustion of fuel gas III), then gas passes the catalytic reactor 8 in which temperature of gas increases on 20 - 300C (to 250 °C). After that gas is again cooled in a cooler 9 from which the condensed sulfur is taken away through a serozatvor, and the leaving gas through a separator 10 goes on burned up in the furnace 11.

In this furnace at 500 - 550 °C oddments of an unreacted hydrogen sulfide then tail gas VII is thrown out through a flue are burned up.

For the purpose of decrease in pollution of the atmosphere on many installations of Claus use the block of purification of tail gas on the CATTLE block 12 - the absorptive absorption by SO2 solution of sulphanole and diisopropanolamine.

Process temperature - 1100-1300 °C.

Pressure-0,012-0,017 of MPa

Catalysts: As catalysts usually use the fissile Al2O3 form with additives Na2O, Fe2O3, TiO2.

2. Material and methods

The purpose of this work is receiving water-soluble colloid sulfur with sidementation stability to 95-98%, good water solubility, high biological activity, and also use of SO2 off-gas for receiving sulfuric acid.

It is known that the more the content of the free sulfur in the colloidal solution, the more its biological activity (akaratsidnost). For the purpose of increase in the free sulfur in the colloidal solution we made preliminary experiments. According to preliminary experiences it was established that the more in solution of shallow particles of sulfur, the more its biological effectiveness. Optimum conditions of process from the experimental factors were established: temperature 1101200C, concentration of the surface-active substance (SAS) of 4-5%, process time - 3 hours, concentration of additives of the stabilizer (4-5%).

Sulfur from “PKOP” has passed analysis in our university laboratory.

Figure 2 Chemical composition of sulphur of "PetroKazakhstanOilProducts"

The results showed that the sulfur content is 99.53%, indicating a high purity product.

Figure3 Result of a structure analysis of PKOP LLP sulfur

For modification of sulfur were investigated various modifiers. In literature there are data on application as the modifier various surfactant, extracts from a withdrawal of the oil and fat industry of gossipolov pitch, inorganic compounds.

In this work were used modifiers of a series of polyelectrolytes: "To", Poligel, Uniflok, "COPAN".

Modifiers of a series K are the polyelectrolytes received on the basis of alkali treatment of a wastage on the basis of alkali treatment of a wastage of fiber Nitron with additives of fatty acids and a nitrolignine.

Modifiers of the Poligel series are the polyelectrolytes received on the basis of the ethylene carboxylic acid by alkali treatment.

Modifiers of the Uniflok series are the modifiers received on the basis of the poly(acrylic acid) by alkali treatment with additives of a wastage of MZhK.

Modifiers of the "MEA (PAA), DEA, TEA" series

A series of the used polyelectrolytes for sulfur modification is shown in table 1.

Table 1 Modifiers are sulfur

Figure 4 The key harmless flow diagram of receiving medicine "The colloid sulfur" 1 - a ball grinder, 2 - a bolter, 3 - the conveyor, 4 - a measurer, 5 - the electric motor, 6 - a reducer of transfers, 7 - the reactor, 8 - capacity for the modifier, 9 - flowmeters, 10 - a quartz tube with the heater, 11 - capacity for surfactant, 12 - a bubbler from 30% H2O2 solution, 13 - capacities for collecting H2SO4, 14 - the centrifuge, 15 - a half-internal sushilnik, 16 - a zatarochny uzel, 17 - a screw mixer, 18 - elektrotena

Lump sulfur which is a withdrawal of oil and gas production or oil processing of JSC PetroKazakhstan moves in a ball grinder of the MK-2000 brand (poz.1). Sulfur is ground on particles up to 0,25 mm in size, then passed through a bolter (poz.2) and on the conveyor (poses. 3) gets enough sleep in a measurer (poses. 4). From a measurer the particular amount of sulfur moves in the reactor (poses. 7), where there is a sulfur fusion. Through a particular time term temperature is lifted to 110-1200C and add the TE series modifier (poses. 8,9). After carrying out process of modification within 3 clocks at continuous hashing by a screw mixer (poses. 17), through a reducer of transfers (poses. 6) and by means of the electric motor (poses. 5), in the reactor temperature is reduced to 80850C and bring 4-5% of the surface-active substance (SAS) (poses. 11). The received suspension is mixed within 10-15 minutes and given to the FVSh-1320 brand centrifuge (poses. 14). After office of solid and fluid phases, KS paste moves on half-internal drying (poses. 15), then in the packing device (poses. 16). Heating in the reactor is carried out by elektrotenam (poses. 18), hashing - a screw mixer (poses. 17). Pakovanny to 10 kg plastic bags transfer medicine KS to a finished goods warehouse.

For processing of off-gases and for ecological purity of the offered technology we used the following technology. Off-gases (the main maintenance of SO2 - 99%) through the quartz tube heated to 1000C moves in a bubbler like Tyshchenko's bottle (poses. 12), which is filled with 30% H2O2 solution where there is a reaction:

SO2 + О2 * SO3.

The formed SO3 gas is supplied through a borbaterny tube in capacity (poses. 12), H2SO4 filled 0,5% with an aqueous solution. In process of receipt of SO3 concentration of H2SO4 increases in solution and KS received finally in three processes of receiving concentration of H2SO4 reaches 62,5% to value.

Apparently from the above-offered technology from a withdrawal of oil and gas production and oil processing there is an opportunity to receive the useful products: an agricultural fungicide of KS and sulfuric acid which in the industry has broad application. And this technology waste-free and pollution-free.

RESULT AND DISCUSSION

Dependence of viscosity of the modified sulfur on concentration of modifiers is given in the figure 3.

Figure 5 Curve 1 - the МЭА modifier, the Curve 2 - the Poligel modifier, the Curve 3 - the Uniflok modifier, the Curve 4 - the K-9 modifier

Apparently from the drawing that concentration of the modifier pass 3 graphs through a maximum depending on their concentration. The greatest maximum is observed when using the TK-04 or MEA modifier at concentration of 5,5%. Therefore further works were carried out with the TK-04 modifier in the range of concentration from 3,5 to 6% mass when receiving medicine the colloid sulfur.

Approbation of this technology was carried out on the semi-plant as shown in the figure 2.

On the basis of results of the semi-production researches we offer the following waste-free technology of receiving medicine KS.

Further the question of influence of the modified polymeric sulfur received by us on physicomechanical properties of rubbers will be considered.

References

1. The process for producing a colloidal sulfur Dzhakipbekova NO. Number innovative patent: 23444

2. The rubber compound Sakibaeva SA Patent number: 10783

3. A.S. no. 1703016, A1. SU. Bjul. no. 1 / Bezothodnaja tehnologija, kolloidnaja sera, sernaja kislota, othody neftegazodobychi i neftepererabotki / S.G. Kamarjan, L.E. Kushheeva, U.K. Ahmedov. Opubl. 07.01.92.

4. A.S. no. 1412223, A1. SU. Bjul. no. 9 /Sposob poluchenija smachivajushhego poroshka sery/ Abrosimov V.A., V.N. Ljapunov, I.D. Krivosheev. Opubl. 09.03.76.

5. Abdulova Je.N., Imangaliev T.A., Dzhakipbekova N.O. Bezothodnaja tehnologija poluchenija preparata «Kolloidnaja sera» dlja zashhity selhozkultur. Trudy mezhdunarodnoj nauchno-prakticheskoj konferencii «Perspektivnye napravlenija alternativnoj jenergetiki i jenergosberegajushhih tehnologij. Shymkent: The SKSU of M.Auezova, 2010. 177 р.

6. Abdulova Je.N. Imangaliev T.A., Vysockaja N.A.. Jekologicheskoe vlijanie othodov dobychi uglevodorodnogo syrja na pochvennyj pokrov. Respublikanskij nauchnyj zhurnal «Nauka i obrazovanie Juzhnogo Kazahstana», no. 5 (78), 2009. 110 р.

7. Gorelik S.S., Skakov Ju.A., Rastorguev L.N. Rentgenografi cheskij i jelektronno-opticheskij analiz. M.: MISiS, 2002.

Размещено на Allbest.ru