“A revolution is possible in the energy sector”: what scared the “generals” the re-elected Rafinat Yarullin

They “forgot” to include Aleksey Pesoshin in the board of directors of Tatneftekhiminvest-holding, and at the meeting they put TAIF in the face of disrupting the plan

Despite the 1.5 billion profit, Tatneftekhiminvest-holding traditionally left shareholders without dividends, and the holding's board of directors was expectedly left without Ildar Khalikov. At the next meeting of the board of directors, the BUSINESS Online correspondent found out why petrochemists did not deliver 39% of the planned volume of plastics to Tatarstan processors and why the re-elected director of the holding, Rafinat Yarullin, is worried about Chinese combustible ice.

Rafinat Yarullin (in the center) / Photo: tatarstan.ru

RAFINAT YARULLIN AGAIN HEAD OF TATNEFTEKHIMINVEST-HOLDING

Today, a meeting of the annual general meeting of shareholders and a meeting of the board of directors of OAO Tatneftekhiminvest-holding with the participation of the President of the Republic of Tatarstan were held in the Cabinet of the Republic of Tatarstan Rustam Minnikhanov. As it became known, the holding completed 2016 without shocks, the free balance of profit amounted to 1.572 billion rubles. This is much more than in 2015, when the profit amounted to 1.165 billion rubles. But representatives of the holding asked the shareholders not to flatter themselves - the profit is mostly virtual. Its lion's share was obtained through revaluation in accordance with the market value of Tatneft shares on the balance sheet of the holding. So, by tradition, it was decided not to accrue dividends to shareholders for 2016. In general, the financial condition of the holding was assessed as stable, of course, there are no arrears in wages, taxes and payments.

Simultaneously with summarizing the results of 2016, a new composition of the Board of Directors of OAO Tatneftekhiminvest-Holding was elected, which included 24 people. Among them were the head of Tatarstan Minnikhanov and the permanent general director of OAO Tatneftekhiminvest-holding Rafinat Yarullin. The generals of the oil industry of the republic, headed by the general director of Tatneft, also remained in their place. Nail Maganov and General Director of TANECO Leonid Alekhin and bison of petrochemistry represented by the General Director of TAIF Alberta Shigabutdinova(although he was late, and as a result, the participants voted without him) and his deputy, concurrently the chairman of the board of directors of Nizhnekamskneftekhim PJSC Vladimir Busygin. The largest power engineers of the republic remained on the board of directors - the general director of JSC "Grid Company" Ilshat Fardiev and General Director of JSC "Tatenergo" Rauzil Khaziev, representatives of AK BARS Bank, three republican ministers and the head of the TIDA RT.

Taliya Minullina / Photo: tatarstan.ru

It is logical that the ex-prime minister of the Republic of Tatarstan left the council Ildar Khalikov, however, was not included in the council and the new head of government Alexey Pesoshin. According to rumors, they simply did not have time to add him to the new lists, and the 25th vacant seat on the board of directors of TNHI-X will still remain with him in the future. Minnikhanov again became chairman. Laughing, he asked: maybe the audience has other candidates? Forests of hands were not found, so the president's name was approved without discussion. Yarullin was also reappointed as the CEO of the company without further questions.

CONSTRUCTION OF LNG PLANT STARTS IN CHISTOPOL

Briefly, Yarullin told how 2016 ended for the enterprise in the petrochemical sector of the republic. In general, according to the results of 2015-2016, production volumes increased by 3.5%, which is 2.2 percentage points below the plan. The outlined plan for 2016 was fulfilled only by oil companies, who continue to increase oil production, despite Russia's agreements to limit production with OPEC countries. Tatneft also increased the production of ethane to 187 thousand tons per year for the needs of Kazanorgsintez, which allowed the latter to increase the production of polyethylene. In addition, the production of diesel fuel, mineral fertilizers, synthetic rubber, industrial sulfur, detergents and soaps, polymer plates and films has grown significantly in the republic.

Kazanorgsintez and Nizhnekamskneftekhim supplied 167,000 tons of plastic to republican companies in 2016, which is 39 percent below the plan. The price factor and branded assortment of plastics affected, import deliveries increased. As a result of the delay in the start-up of the alpha-olefins unit, the plan for the supply of polyethylene by Nizhnekamskneftekhim was only half completed, ”Yarullin said, As already“ BUSINESS Online ”, in The domestic market turned out to be simply overstocked with polyethylene, largely due to the growth in imports of low-pressure plastic from a new plant in Uzbekistan.

The head of the holding also noted that the implementation of some of the investment projects of Tatarstan companies is lagging behind (probably, he meant complex for deep processing of heavy residues TAIF-NK), in addition, few projects are being implemented in the field of plastics processing. “For further development, it is necessary to increase access to financial resources,” Yarullin traditionally summed up.

Among other things, Rafinat Samatovich announced the imminent start of construction by Gazprom for the production of liquefied natural gas in Chistopol. Recall that the construction agreement between Gazprom Gazomotornoye Toplivo LLC and Tatarstan was signed in December 2015. According to Yarullin, survey work is currently underway at the site. The plant's capacity will be 7 thousand tons per year, the total cost of the project is 9 billion rubles, the planned capacity is scheduled for 2019.

Emphasizing the importance of the project, he recalled that competition in the global gas market is intensifying. In May, China announced the start of the development of a gas hydrate deposit - the so-called combustible ice, which looks like snow or loose ice. “Gas hydrates contain 10 times more gas than shale deposits. A revolution in the energy sector is possible in a few decades,” the head of the holding predicted. He noted that Russian scientists are already working in this direction - recently the first Russian ice gas carrier was sent on its first voyage, which will serve to transport liquefied gas produced in the Far North. Yarullin made it clear that it is important not to miss the topic, so that it does not turn out like with shale gas production, which our country actually “missed”.

The plans for 2017 of the companies supervised by Yarullin included the launch of the very lagging complex for deep processing of heavy residues at TAIF-NK OJSC, the start of the production of Euro-5 gasolines at TANECO, and the increase in the production of isoprene rubber at Nizhnekamskneftekhim ”, reconstruction of the preparatory production at Nizhnekamskshina, the launch of the production of flexible packaging “Danaflex” in the SEZ “Alabuga”.

"EDELWEISS" FOR POLYMER WASTE AND WITH STICKS FOR FIRE

Further, the businessmen invited to the council offered their projects to the management of the holding. Representative of the German Krauss Maffei Berstorff Konstantin Tyutko spoke about new technologies for the processing of polymer waste. It is no secret that the number of products made from polymers is growing, but most of them are buried. The company's idea is to process polymer waste into high-quality compounds ( thermoset, thermoplastic polymer resin — approx. ed.). This technology, which was called "Edelweiss", is interesting in that it involves only one stage of processing raw materials, while traditionally it requires two. At the same time, the cost of the final product is lower, and the quality does not deteriorate. Minnikhanov offered to get acquainted with the technology to companies that are engaged in the processing of polymer waste in the Republic of Tatarstan.

Business Development Director of Moscow Termoelectrica LLC Alexey Lesiv spoke about a new technology for early warning of electrical equipment malfunctions. The idea is to notify staff of an impending plant fire before it starts - after all, up to 28% of fires occur due to electrical equipment failure. Technically, the ThermoSensor system looks like this: special stickers with thermal sensors are attached to the electrical wires, they give a signal if the wiring is heated above normal. Lesiv emphasized that his stickers are much cheaper than imported analogues.

Minnikhanov was noticeably interested in the novelty - he recommended it for use at energy enterprises, grid and generation companies, as well as thinking about the use of such stickers in public buildings and large facilities.

- The question is this: in the old schools we still have aluminum wiring, it is always hot. Will your sensors work? the minister of construction asked the businessman Irek Faizullin.

“If the wiring heats up to 120 degrees, it will already be a fire, you have to change the wiring,” Minnikhanov answered him with surprise. - What's the point of putting on the old wiring? The idea itself is very interesting.

The resident of Innopolis, CJSC PB SKB Kontur from Yekaterinburg, offered Tatarstan residents a new solution for optimizing the activities of enterprises in the petrochemical complex and for budgetary organizations of Tatarstan. Minnikhanov realized that the system could also automate the procurement system, leaving intermediaries out. He instructed the Minister of Informatization and Communications of the Republic of Tatarstan Roman Shaikhutdinov explore the idea and, if possible, bring it to life.

The new composition of the Board of Directors of OAO Tatneftekhiminvest-holding: President of Tatarstan Rustam Minnikhanov, General Director of OJSC TANECO Leonid Alekhin, General Director of PJSC Nizhnekamskneftekhim Azat Bikmurzin, Chairman of the Board of Directors of PJSC Nizhnekamskneftekhim, Deputy General Director of PJSC TAIF Vladimir Busygin, Chairman of the Board of PJSC AK BARS BANK Zufar Garayev , Minister of Industry and Trade of the Republic of Tatarstan Albert Karimov, Minister of Economy of the Republic of Tatarstan Artem Zdunov, Minister of Architecture, Construction and Housing and Public Utilities Irek Fayzullin, General Director of OJSC Kazanorgsintez Farid Minigulov, General Director of OJSC Tatneft Nail Maganov, General Director of OJSC SEZ Innopolis Igor Nosov, Head of the Development Agency of the Republic of Tatarstan Taliya Minullina, Consultant to the President of the Republic of Tatarstan on the development of oil and oil and gas producing fields, Professor of the Department of Geology, Oil and Gas, IGiNGT KFU Renat Muslimov, Assistant to the President of the Republic of Tatarstan Rinat Sabirov, General Director of OAO HC Tatnefteprodukt Rustam Sabirov, General Director director of TAIF OJSC Albert Shigabutdinov, assistant to the presi Dent of the Republic of Tatarstan on Oil Industry, Member of the Board of Directors of PJSC Tatneft Shafagat Takhautdinov, Chairman of the Board of Directors of JSC Kazan Fat Plant Dmitry Samarenkin, Chairman of the Board of Directors of PJSC AK BARS BANK, General Director of JSC Svyazinvestneftekhim Valery Sorokin, Director of JSC "Tatenergosbyt" Rifnur Suleymanov, General Director of JSC "Grid Company" Ilshat Fardiev, General Director of JSC "Tatenergo" Rauzil Khaziev, General Director of SEZ "Alabuga" Timur Shagivaleev, General Director of JSC "Tatneftekhiminvest-holding" Rafinat Yarullin.

JSC "Tatneftekhiminvest-holding" was established in September 1994 as an industrial and financial company uniting the largest enterprises of the petrochemical complex of Tatarstan. The largest shareholders are Svyazinvestneftekhim JSC, Tatneft PJSC, Nizhnekamskneftekhim PJSC, Kazanorgsintez PJSC, Nizhnekamskshina PJSC.

The owners of the patent RU 2596624:

The invention relates to a group of new extractants for extracting nitric acid from aqueous solutions, including wastewater, which can be used for liquid extraction of nitric acid and separation of hydrochloric and nitric acids. The proposed extractants may include one or more dialkyl sulfones of the formula, where each independently represents a linear or branched alkyl containing 1-8 carbon atoms, while the total number of carbon atoms in the compound of formula (I) is 6-12. The extractant may be a mixture of dialkyl sulfones obtained as a result of the oxidation of three products of the interaction of two aliphatic C 4 -C 5 alcohols with hydrogen sulfide. The extractant may additionally include other extractants, such as TBP or MiBC, or diluents such as kerosenes, C 6 -C 10 aliphatic alcohols, halogenated C 6 -C 10 ketones, linear or cyclic siloxanes. 14 w.p. f-ly, 14 ill., 9 tab., 24 pr.

The present invention relates to chemical engineering, specifically to liquid extraction extractants capable of extracting nitric acid from aqueous solutions, comprising one or more dialkyl sulfones of formula (I)

where R 1 and R 2 represent linear or branched alkyl containing 1-8 carbon atoms.

The invention can be used most effectively in the chemical, metallurgical and mining industries, as well as for the treatment of waste and waste water.

Extraction of nitric and other acids from aqueous solutions is an important industrial process. The need for extraction of nitric acid arises during the purification of waste water from nitrate ions [US patent US 4169880 (1979)], separation of acid mixtures [US patents US 4668495 (1987), US 4364914 (1982), US 4378342 (1983), US 4285924 (1981)], extraction, separation and purification of non-ferrous metals [US patents US 4647438 (1987), US 5338520 (1994), application US 20130259777 A], isolation of uranium, thorium and other actinides and lanthanides [application RU 2009119466 A].

Tributyl phosphate (TBP) is the most widespread among the extractants currently used for the extraction of nitric acid [(US patents US 4668495 (1987) and US 4364916 (1982), Chang-HoonShin, et al, Journal of Hazardous Materials 163 (2009) , 729-734), as well as water-insoluble aliphatic ketones, such as methyl isobutyl ketone (MiBK) (Ion Exchange and Solvent Extraction: A Series of Advances, Vol. 19, Ed. BA Moyer, CRC Press, Boca Raton, 2010, 673 p.).

In addition to TBP, other phosphorus compounds are also used as extractants, such as di(2-ethylhexyl)phosphoric acid (D2EHPA), mono(2-ethylhexyl)2-ethylhexylphosphonic acid (ENENPA), bis(2-ethylhexyl)phosphinic acid , phosphine oxide of different radicals (FOR), mixtures based on the above esters and their homologues (for example, mixtures under the CYANEX trademark).

It is known that for the extraction of nitric acid using solutions of aliphatic trialkylamines in appropriate solvents, for example, trioctylamine in kerosene [US patents US 4285924 (1981) and US 4169880 (1977)].

The analogues of the claimed extractants are substances of the same purpose, such as TBP, MiBC, FOR, ENENRA, etc. These analogues were used for comparison in experiments to study the extracting ability and other properties of the claimed extractants. The closest analogues of the claimed extractants are TBP and MiBC. Despite the high extracting ability and wide application, these analogues are not without drawbacks. The disadvantages of methylisobutylketone are its toxicity (LC 50 =8.2 mg/l) and insufficient chemical stability in strongly acidic environments. The disadvantages of TBP as an extractant are its high density and viscosity (therefore, it is necessary to add a diluent to reduce the viscosity), as well as easy hydrolyzability with the formation of mono- and dibutyl phosphates. TBP, which is widely used for extraction, was chosen as a prototype.

Despite the variety of known and used extractants, the selection of an extraction system for a particular technology is a difficult task, since it is necessary to take into account many factors that affect the productivity and selectivity of the process. Among such factors, the most important are extraction ability, selectivity, viscosity, stability of the extractant, solubility, compliance with environmental requirements, cost of the extractant, ease of stripping, etc.

It is impossible to choose an extractant that would simultaneously meet all the requirements, there is a need for new extractants that could be used in specific industrial processes. The search for such extractants, which expand the arsenal of extraction agents and make it possible to improve the technologies of a number of industries, seems to be very relevant.

The objective of the invention is the development of new extractants for the extraction of nitric acid from aqueous solutions, which would not be inferior to known extractants in terms of their extraction ability and would allow the extraction of nitric acid from mixtures with other acids.

The problem is solved by a new extractant for extracting nitric acid and nitrates from aqueous solutions, including one or more dialkyl sulfones of formula (I)

where R 1 and R 2 each independently represents a linear or branched alkyl containing 1-8 carbon atoms, while the total number of carbon atoms in the compound of formula (I) is from 6 to 12.

The inventive extractant may be a pure dialkyl sulfone, such as dibutyl sulfone, or a mixture of dialkyl sulfones of formula (I), which in some cases is eutectic.

The inventive extractant may be a mixture of dialkyl sulfones obtained as a result of the oxidation of three products of the interaction of two aliphatic C 4 -C 5 alcohols with hydrogen sulfide.

The claimed extractant, including dialkyl sulfone or mixtures of dialkyl sulfones, may additionally contain one or more phosphorus-containing compounds, such as trialkyl phosphates, dialkyl phosphates, alkyl phosphonates, phosphinic acids, phosphine oxides, or one or more C 6 -C 10 ketones.

The proposed extractant may include one or more diluents selected from the group: kerosenes, aliphatic C 6 -C 10 alcohols, halogenated C 6 -C 10 ketones, linear or cyclic siloxanes.

The extractant may be mixtures of the following compositions (wt. parts):

The inventive extractant allows you to extract nitric acid from aqueous solutions containing other acids, such as hydrochloric, sulfuric or methanesulfonic, it can be used to extract nitric acid from wastewater.

The choice of dialkyl sulfones and their mixtures for use as extractants was dictated by their properties, which satisfy a number of requirements for extractants. Dialkylsulfones are characterized by high chemical and thermal stability (General organic chemistry, vol. 5. Compounds of phosphorus and sulfur. // Edited by NK Kochetkov, M., Chemistry, 1983 p. 318). Dialkyl sulfones have high selectivity, low water solubility, sufficiently high flash point, and compatibility with diluents. In addition, unlike phosphates, phosphonates, and aliphatic ketones, dialkyl sulfones are stable in strongly acidic environments. Some properties of dialkyl sulfones and their mixtures are presented in table 1.

Dialkyl sulfones of formula (I) are obtained by oxidation of the corresponding sulfides, which for the most part are readily available compounds (Suter C. Chemistry of organic sulfur compounds. Translated from English. M., Izdatinlit, 1951; A. Schoberl, A. Wagnerin Houben-Weyl. Methoden der Organishe; EP 2441751 A1; Kuchin AV, et al, Russian Journal of Organic Chemistry, 36(12), 1819-1820, 2000; Moshref J., Maedeh et al, Polyhedron, 72, 19-26, 2014; Postigo, Lorena et al, Catalysis Science & Technology, 4(1), 38-42, 2014; Doherty, S. et al, Green Chemistry, 17(3), 1559-1571, 2015).

The shorter the length of the alkyl substituents, the lower the viscosity of the dialkyl sulfones, therefore, the faster the mass transfer during extraction. But dialkyl sulfones of formula (I), where R 1 and R 2 are linear or branched alkyl having from 1 to 4 carbon atoms, and where the sum of carbon atoms in the groups R 1 and R 2 is not more than 7, such as, for example, isobutyl isopropyl sulfone, not suitable for use as extractants, because they are highly soluble in water. The use of additives that limit the solubility in water in this case is impractical due to their lability in strongly acidic media, or due to a decrease in the extraction characteristics of sulfones.

Dialkyl sulfones in which both R 1 and R 2 substituents are normal are generally solids at room temperature. Compounds of formula (I), where the sum of the carbon atoms in the groups R 1 and R 2 is not less than 10, such as, for example, ethyl (2-ethylhexyl) sulfone, are solids or highly viscous liquids and extract nitric acid significantly worse.

Melting points for the dialkyl sulfones of formula (I) are shown in Table 2.

In some cases mixtures of dialkyl sulfones are eutectic. The use of eutectic compositions allows extraction separation at low temperatures. The need to reduce the temperature during extraction arises, for example, when separating nitric and hydrochloric acids, which is advisable to be carried out at a temperature below 5°C, which makes it possible to prevent the decomposition of nitric acid and the formation of toxic NOCl and NO 2 Cl.

The most preferred properties for use as extractants are compounds of formula (I) such as dibutylsulfone, diisobutylsulfone, butylisobutylsulfone, diisoamylsulfone, isoamylisobutylsulfone and isoamylisopropylsulfone.

But obtaining pure unsymmetrical dialkyl sulfones is much more difficult than obtaining symmetrical ones. An alternative to asymmetric sulfones can be low-melting three-component mixtures obtained according to the scheme:

Such mixtures are prepared in the manner shown above using C 4 -C 5 alcohols taken in equimolar amounts.

The possibility of using dialkyl sulfones as extractants has been confirmed experimentally. The extraction of nitric acid from aqueous solutions with various dialkyl sulfones and their mixtures has been studied. The extraction of nitric acid from aqueous solutions containing other acids has been studied. For comparison, experiments were carried out with known extractants under similar conditions. The extraction of acids by mixtures of dialkylsulfones with known extractants and mixtures of dialkylsulfones with diluents was studied.

The invention is illustrated in the figures below.

In FIG. 1 shows isotherms of nitric acid extraction from aqueous solutions with various dialkyl sulfones or their mixtures.

In FIG. Figure 2 shows extraction isotherms of nitric acid from aqueous solutions using diisobutyl sulfone as an extractant, and for comparison, extraction isotherms of HNO 3 with tributyl phosphate (TBP) and methyl isobutyl ketone (MiBK) are shown.

In FIG. Figure 3 shows an isotherm of the extraction of nitric and hydrochloric acid from aqueous solutions using diisobutyl sulfone as an extractant, illustrating the effectiveness of this extractant for the separation of these acids.

To compare the effectiveness of the claimed extractant with TBP, in Fig. Figure 4 shows the isotherm of the extraction of nitric and hydrochloric acids from aqueous solutions with tributyl phosphate.

In FIG. Figure 5 shows isotherms of extraction of nitric and hydrochloric acids from aqueous solutions using diisobutylsulfone, TBP, and MiBA as extractants, which make it possible to compare the efficiency of these extractants for the separation of nitric and hydrochloric acids.

In FIG. Figure 6 shows extraction isotherms of nitric, hydrochloric, sulfuric, and methanesulfonic acids from aqueous solutions using diisobutylsulfone as an extractant. 6 illustrates the selectivity of diisobutyl sulfone for various acids and the ability to separate acids with widely differing distribution coefficients by extraction. For example, nitric acid can be separated from hydrochloric, sulfuric, and methanesulfonic acids.

In FIG. Figure 7 shows isotherms of nitric acid extraction from aqueous solutions using pure diisobutylsulfone, a mixture of diisobutylsulfone with TBP, and a mixture of diisobutylsulfone with MiBA as an extractant.

In FIG. Figure 8 shows isotherms of nitric acid extraction from aqueous solutions using pure diisobutyl sulfone and mixtures of diisobutyl sulfone with various diluents, such as 2-ethylhexanol, kerosenes, etc., as extractants.

In FIG. 9-13 shows graphs of the dependence of the distribution coefficients of nitric and hydrochloric acids on the composition of the extractant, including dialkyl sulfone in a mixture with a known extractant, where point 0 on the abscissa axis corresponds to pure dialkyl sulfone, point 100 corresponds to pure known extractant: MiBK (Fig. 9), TBP ( Fig. 10), FOR (Fig. 11), ENENRA (Fig. 12) and D2EGFK (Fig. 13).

14 refers to example 24, it schematically shows a five-stage countercurrent extraction cascade in which a mixture of nitric acid and hydrochloric acid is separated, and diisobutyl sulfone is used as the extractant.

The advantages of dialkyl sulfones over organophosphorus compounds are their low cost, low viscosity, low melting point, and high extractability. In addition, unlike phosphates and phosphonates, sulfones are stable in strongly acidic environments. For example, the formation of decomposition products of sulfones by NMR was not recorded when keeping it for a month in 35% HCl, 96% H 2 SO 4 , 90% HNO 3 and 6M NaOH.

The chemical stability, low toxicity, and high flash point of dialkyl sulfones also set them apart from the 6-carbon aliphatic ketones (MiBK) widely used for nitric acid extraction.

Dialkylsulfones can be used as diluents for known extractants such as TBP, D2EHPA, VOR, etc. By varying the ratio of the known extractant: dialkylsulfone, you can choose the optimal values ​​of the distribution coefficient, providing the highest efficiency of extraction/re-extraction (Fig. 9-13). In addition, the addition of dialkyl sulfones leads to an increase in the selectivity of nitric acid extraction and a reduction in the cost of the obtained extractants. The use of diluents in a mixture with dialkylsulfones also makes it possible to reduce the cost of the extractant and make it less viscous (Example 3, Fig. 8).

The extraction efficiency with a Shell Chemicals ShelSolD60 (D60) diisobutylsulfone/kerosene mixture or with a diisobutylsulfone/2-ethylhexanol mixture is close to that of pure diisobutylsulfone. So, at an initial concentration of nitric acid 3M, the separation factors when using pure diisobutylsulfone as an extractant and its 33% mixture with D60 are 0.261 and 0.213, respectively, at a concentration of 5M, 0.363 and 0.326, respectively. When diisobutylsulfone was used in a mixture with kerosene D60 during the extraction process, a three-phase separation of the system into an aqueous phase, a sulfone containing nitric acid (heavy organic phase), and kerosene D60 containing pure sulfone (light organic phase) was observed. In the process of stripping, free diisobutylsulfone passes into the kerosene phase, the volume of the heavy organic phase decreases, while the acid concentration in this phase remains unchanged. Thus, the formation of a three-phase system in this case facilitates the back-extraction process.

It has been experimentally shown that the distribution coefficients of hydrochloric, sulfuric and methanesulfonic acids are significantly lower than the distribution coefficient of nitric acid (Example 3, Fig. 6). Thus, using diisobutylsulfone as an extractant, it is possible to selectively extract nitric acid from mixtures with HCl, H 2 SO 4 or MsOH.

A significant disadvantage of TBP and MiBC is the formation of stable emulsions after mixing with hydrochloric acid solutions. The divergence time of MiBK emulsions with 3M, 4M and 5M hydrochloric acid and TBP emulsions with 1M hydrochloric acid was approximately one day.

In the case of diisobutylsulfone, the emulsion divergence time over the entire range of concentrations studied was 3–5 minutes.

Thus, an important advantage of dialkyl sulfones as extractants for the selective extraction of nitric acid is that dialkyl sulfones do not form stable emulsions with hydrochloric acid, in contrast to TBP and MiBA.

The results show that the extraction ability of dialkyl sulfones with respect to nitric acid is close to that of MiBC.

So, at an initial concentration of nitric acid of 5M, the distribution coefficients for diisobutylsulfone and MiBK were 0.363 and 0.381, and at a concentration of 2M - 0.199 and 0.197, respectively.

The present invention proposes a new extractant for the extraction of nitric acid, which has a sufficiently high extraction ability, comparable to the extraction ability of currently used extractants, high selectivity towards nitric acid, exceeding the selectivity of TBP.

The inventive extractant is stable in strongly acidic environments, allows extraction at low temperatures, makes it possible to selectively extract nitric acid from mixtures with other acids.

The technical result is the expansion of the creation of new extractants for liquid extraction and an increase in the selectivity of the extraction of nitric acid from aqueous solutions containing other acids, such as hydrochloric, sulfuric and methanesulfonic.

The invention is illustrated by the following examples and figures.

For the experiment, an initial solution of nitric acid of a given concentration was prepared. Extraction was carried out with equal volumes of acid and extractant mixed by shaking with a shaker in a 20 ml vial for 3 minutes at room temperature (20-25°C), then the emulsion was allowed to separate. For n-Bu(i-Bu)SO 2 the experiment was carried out at a temperature of 10°C. The acid concentration in the aqueous and organic phases was determined by titration. Based on the measurement results, the distribution coefficients (D) for nitric acid were calculated.

D (HNO 3) \u003d C (HNO 3) o / C (HNO 3) in,

where C(HNO 3) o is the concentration of nitric acid in the organic phase, C(HNO 3) in is the concentration of nitric acid in the aqueous phase.

In FIG. 1 shows isotherms of nitric acid extraction from aqueous solutions with various sulfones. The distribution coefficients (D) calculated on the basis of the experiment for nitric acid are presented in Table 3.

In FIG. 2 shows the results obtained using diisobutylsulfone as an extractant for the extraction of HNO 3 , and for comparison shows the results obtained for TBP and MiBC under similar conditions.

It is shown that the extraction ability of dialkylsulfones with respect to nitric acid is close to that of MiBA, but somewhat lower than the extraction ability of TBP.

So, at an initial concentration of nitric acid of 5M, the distribution coefficients for diisobutylsulfone and MiBK were 0.363 and 0.381, and at a concentration of 2M - 0.199 and 0.197, respectively.

To assess the selectivity of extractants with respect to nitric acid, isotherms of extraction of nitric and hydrochloric acids from aqueous solutions were constructed (Fig. 3-5). The extraction was carried out in the same way as in Example 1, using the initial solutions of nitric and hydrochloric acids of given concentrations. According to the results of the experiments, the distribution coefficients (D) for nitric and hydrochloric acids and the separation factor (SF) were calculated (Tables 3 and 4).

So, at an acid concentration of 2M, the distribution coefficient of nitric acid during extraction with diisobutylsulfone is 66 times greater than the distribution coefficient of hydrochloric acid, for MiBA it is 26 times greater, while for TBP it is only 8.6 times greater, at a concentration of nitric acid of 3M, the ratio of the distribution coefficients of acids are, respectively, 22, 66 and 4.8. It is shown that, unlike the claimed extractants, TBP and MiBC form stable emulsions after mixing with hydrochloric acid solutions. The time of emulsion divergence with increasing acid concentration increased for MiBA and decreased for TBP. The divergence time of MiBK emulsions with 3M, 4M and 5M hydrochloric acid and TBP emulsions with 1M hydrochloric acid was approximately one day. In the case of diisobutylsulfone, the emulsion divergence time in the entire range of the studied concentrations is 3-5 minutes.

An experiment similar to that described in Example 2 was carried out for a larger set of acids. In FIG. 6 shows isotherms of extraction of nitric, hydrochloric, sulfuric and methanesulfonic acids from aqueous solutions with diisobutylsulfone.

The distribution coefficients of hydrochloric, sulfuric and methanesulfonic acids are significantly lower than the distribution coefficient of nitric acid. Thus, at a concentration of 2M acid, the distribution coefficients for nitric, hydrochloric, sulfuric, and methanesulfonic acids were 0.199, 0.003, 0.006 (at conc. 20%, which corresponds to 2.3M) and 0.005, respectively, for a concentration of 5M - 0.363, 0.01, 0.051 (at 40% conc., corresponding to 5.3M) and 0.047, respectively (Table 5).

Thus, using diisobutylsulfone as an extractant, it is possible to selectively extract nitric acid from mixtures with HCl, H 2 SO 4 or MsOH.

In FIG. Figures 7 and 8 show isotherms of nitric acid extraction with pure diisobutylsulfone, as well as mixtures of diisobutylsulfone with TBP, MiBC, and various diluents: 2-ethylcyclohexanol, chloroform, and ShelSol D60 (D60) and ShelSol A100 (A100) kerosenes produced by Shell Chemicals. The extraction conditions are similar to those indicated in Example 1. The proportion of diisobutylsulfone in the organic phase was 33% by volume.

The experimental results show that the extraction efficiency with a mixture of diisobutylsulfone and D60 or with a mixture of diisobutylsulfone and 2-ethylhexanol is close to the efficiency of extraction with pure diisobutylsulfone. At an initial concentration of nitric acid of 3M, the separation factors when using pure diisobutylsulfone as an extractant and its 33% mixture with 2-ethylhexanol D60, respectively, are 0.261, 0.272 and 0.213, respectively, at a concentration of 5M - 0.363, 0.331 and 0.326, respectively (Table 6).

The extraction efficiency with a mixture of diisobutylsulfone and D60 or with a mixture of diisobutylsulfone and 2-ethylhexanol is close to that of pure diisobutylsulfone. So, at an initial concentration of nitric acid 3M, the separation factors when using pure diisobutylsulfone as an extractant and its 33% mixture with D60 are 0.261 and 0.213, respectively, at a concentration of 5M, 0.363 and 0.326, respectively. When using diisobutylsulfone in a mixture with kerosene D60, a three-phase separation of the system into an aqueous phase, a sulfone containing nitric acid (heavy organic phase), and ShelSolD60 containing pure sulfone (light organic phase) was observed during the extraction process. In the process of stripping, free diisobutylsulfone passes into the kerosene phase, the volume of the heavy organic phase decreases, while the acid concentration in this phase remains unchanged. Thus, the formation of a three-phase system in this case facilitates the back-extraction process.

Examples 5-22.

To evaluate the selectivity of extractants, including sulfones and mixtures of sulfones with known extractants with respect to nitric acid, the following experiments were carried out. An aqueous 3M solution of nitric acid or hydrochloric acid was added to the investigated extractants, which could include 3 components (A, B and C), (the ratio of the aqueous and organic phases was 1:1 by volume) and stirred for 3 min at room temperature (20 -25°C). The acid concentration in the aqueous and organic phases was determined by titration. From the results, the distribution coefficients for nitric D(HNO 3 ) and hydrochloric D(HCl) acids and the separation factor (SF)(SF=D(HNO 3 )/D(HCl) were calculated (Table 7).

Example 23.

A mixture of i-BuSO 2 n-Am (61 wt.%) and (iBu) 2 SO 2 (39 wt.%) was prepared by simply mixing the components. The extraction was carried out according to the method described in example 1 at a temperature of 5°C. The composition of the eutectic mixture was determined as described below.

Thermoanalytical measurements were carried out on a DSK-500 device at a heating rate of 57 min in the temperature range of -70-30°C.

The samples were weighed on an analytical balance ViBRA AF 225DRCE with an accuracy of 1·10 -2 mg. The following temperature program was used during the survey:

Cooling down to -70°C at 5°C/min;

Isotherm -70°C for 3 minutes;

Heating up to 25-35°C at a rate of 5°C/min.

Crystallization proceeds non-equilibrium (the temperature maximum clearly depends on the cooling rate, strong overcooling is observed (more than 20°C), therefore, only parts of the curves corresponding to the heating of the samples were used. The melting points of the initial sulfones and the mixtures formed by them are given in Table 8.

The results of experiments on the extraction of acids with the resulting eutectic mixture at 5°C are shown in Table 9.

Example 24.

Separation of a mixture of nitric and hydrochloric acids was carried out using a five-stage countercurrent extraction cascade (Fig. 14). Each extraction unit in the diagram is a mixer-settler cell. The volume of each cell is 0.5 liters. Diisobutylsulfone was used as the extractant, the extractant feed rate from the system was 1 l/h.

The initial solution was a mixture of nitric and hydrochloric acids, the concentration of each of which was 3M. The ratio of the aqueous and organic phases in the cells was 1:3; it was controlled by changing the phase feed rate. Stirring and separation was carried out at room temperature. The system went to stationary mode for 8 hours.

The organic phase obtained at the outlet of the cascade was sent to a washing unit to remove HCl. Two-stage washing with water was carried out at room temperature at a ratio of organic and aqueous phases of 1:1. Under these conditions, HCl is almost completely removed from the extract (the content of HCl in the aqueous phase after stripping is given below). The aqueous phase obtained from washing and containing a mixture of acids was added to the initial mixture of acids supplied to the input of the extraction cascade.

The organic phase after washing enters the stripping cascade, consisting of 5 cells. Mixing of the extract with water was carried out at a temperature of 40-60°C at a ratio of organic and aqueous phases of 1:1.

The aqueous phase after stripping was 8.5% nitric acid containing less than 0.1% hydrochloric acid. The recovery factor of HNO 3 was 88.5%. The aqueous phase at the outlet of the extractor contained a mixture of HCl and HNO 3 in a ratio of 9:1.

Graphs of the dependence of the distribution coefficients of nitric and hydrochloric acids on the composition of the extractant are shown in Fig. 11-15. Point 0 on the abscissa axis corresponds to pure sulfone, point 100 corresponds to pure phosphorus-containing extractant or MiBC.

In general, the addition of dialkyl sulfones to known extractants leads to a change in the extraction characteristics and a decrease in the time of separation of the resulting emulsions. Compared to dialkylsulfones, MiBK provides a better separation factor for nitric and hydrochloric acids, but is unstable in concentrated nitric acid, moreover, it forms emulsions that are difficult to dissolve. The addition of sulfones to TBP and FOR leads to a significant increase in selectivity, as well as a significant reduction in the cost of the resulting mixture.

1. An extractant for extracting nitric acid and nitrates from aqueous solutions, comprising one or more dialkyl sulfones of formula (I)
,
where R 1 and R 2 each independently represents a linear or branched alkyl containing 1-8 carbon atoms, while the total number of carbon atoms in the compound of formula (I) is 6-12.

2. The extractant according to claim 1, characterized in that it includes a mixture of dialkyl sulfones obtained as a result of the oxidation of three products of the interaction of two aliphatic C 4 -C 5 alcohols with hydrogen sulfide.

3. An extractant according to claim 1 or 2, characterized in that the mixture of dialkyl sulfones of formula (I) is eutectic.

4. The extractant according to claim 1 or 2, additionally comprising one or more phosphorus-containing compounds selected from the group: trialkyl phosphates, dialkyl phosphates, alkyl phosphonates, phosphinic acids, phosphine oxides.

5. The extractant according to claim 1 or 2, additionally including one or more C 6 -C 10 ketones.

6. The extractant according to claim 1 or 2, additionally including one or more diluents selected from the group: kerosenes, chloroform, aliphatic C 6 -C 10 alcohols, halogenated C 6 -C 10 ketones, linear or cyclic siloxanes.

7. The extractant according to claim 1, characterized in that it is dibutyl sulfone.

8. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (wt. parts):

9. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (wt. parts):

10. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (wt. parts):

11. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (wt. parts):

12. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (wt. parts):

13. An extractant according to claim 1 or 2, characterized in that it is capable of extracting nitric acid from aqueous solutions containing other acids, such as hydrochloric, sulfuric or methanesulfonic.

14. An extractant according to claim 1 or 2, characterized in that it can be used to separate mixtures of nitric and hydrochloric acids by extraction from aqueous solutions.

15. An extractant according to claim 1 or 2, characterized in that it can be used to extract nitric acid from wastewater.

Similar patents:

The invention relates to derivatives of sulfur-containing dicarboxylic acids of the formula (1) in which at: X=NH2, m=1, n=2, 3, 4, 5, 6, 7, 8, 10; X=NH2, m=2, n=1, 2, 3, 4, 5, 6, 7, 8, 10; X=NHNH2, m=1, n=1, 2, 3, 5, 6, 7, 8, 10; X=NHNH2, m=2, n=1, 2, 3, 4, 5, 6, 7, 8, 10. The invention also relates to derivatives of sulfur-containing dicarboxylic acids of the formula (2) in which at: m=1, n= 2, 3, 4, 5, 6, 7, 8, 10; m=2, n=3, 4, 5, 6, 7, 8, 10; used to obtain compounds of formula (1).

Supervisor:
General Director: Lesiv Alexey Valerievich
- is a leader in 2 organizations.
- is a founder in 6 organizations (active - 5, inactive - 1).

The company with the full name "LIMITED LIABILITY COMPANY "INNOVATIVE CHEMICAL TECHNOLOGIES"" was registered on December 23, 2010 in the Moscow region at the legal address: 127566, Moscow, Altufevskoe shosse, 44, room XIV ET 8 KOM 11.

The registrar "" assigned the company TIN 7733754795 PSRN 5107746050209. Registration number in the Pension Fund: 087309024538. Registration number in the FSS: 771704297677191.

Primary activity according to OKVED: 72.19. Additional activities according to OKVED: 20.1; 20.13; 20.14; 20.16; 20.3; 20.41; 20.59; 20.60; 72.20.

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History of changes in the Unified State Register of Legal Entities

1. Date of: 23.12.2010
   UAH: 2107749322976
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change:
2. Date of: 23.12.2010
   UAH: 5107746050209
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change: Creation of a legal entity
   The documents:
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   - KOP. CHARTER
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3. Date of: 27.12.2010
   UAH: 2107749472169
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change:
4. Date of: 27.12.2010
   UAH: 2107749490363
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change:
5. Date of: 22.01.2018
   UAH: 2187746895532
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change: State registration of changes made to the constituent documents of a legal entity related to changes in the information about the legal entity contained in the Unified State Register of Legal Entities, based on an application
   The documents:
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   - DOCUMENT ON PAYMENT OF THE STATE DUTY
   - CHANGES TO THE CHARTER OF LE
   - DECISION TO AMEND THE FOUNDING DOCUMENTS
   - AGREEMENT, CERTIFICATE. LETTER, DECISION
   - POWER OF ATTORNEY G.S. KUZNETSOV
6. Date of: 22.01.2018
   UAH: 2187746898986
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change: Submission of information on the registration of a legal entity with a tax authority
7. Date of: 22.01.2018
   UAH: 2187746898997
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change: Submission of information on the registration of a legal entity with a tax authority
8. Date of: 24.01.2018
   UAH: 2187746974600
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change: Submission of information on the registration of a legal entity as an insurant in the territorial body of the Pension Fund of the Russian Federation
9. Date of: 25.01.2018
   UAH: 6187746035086
   Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
   Reason for the change: Submission of information on the registration of a legal entity as an insurant in the territorial body of the Pension Fund of the Russian Federation
10. Date of: 04.10.2018
    UAH: 6187749382826
    Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 for Moscow, No. 7746
    Reason for the change: Submission of information on the registration of a legal entity as an insurant in the executive body of the Social Insurance Fund of the Russian Federation

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1. — Current
   TIN: 7733754795, OGRN: 5107746050209
   127566, Moscow, Altufevskoe shosse, 44, room XIV ET 8 ROOM 11
   General Director: Lesiv Alexey Valerievich