Ooo "icht". "A revolution is possible in the energy sector": what scared the "generals" by the re-elected Rafinat Yarullin
Supervisor:
General Director: Alexey Lesiv
- 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, house 44, room XIV ET 8 KOM 11.
The registrar assigned the company INN 7733754795 PSRN 5107746050209. Registration number in the Pension Fund: 087309024538. Registration number in the FSS: 771704297677191.
The main 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.
Requisites
| OGRN | 5107746050209 |
| INN | 7733754795 |
| Checkpoint | 771501001 |
| Organizational and legal form (OPF) | Limited liability companies |
| Full name of the legal entity | LIMITED LIABILITY COMPANY "INNOVATIVE CHEMICAL TECHNOLOGIES" |
| Abbreviated name of a legal entity | LLC "IKhT" |
| Region | Moscow city |
| Legal address | |
| Registrar | |
| Name | Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746 |
| The address | 125373, Moscow, Pokhodny proezd, household 3, building 2 |
| Registration date | 23.12.2010 |
| Date of PSRN assignment | 23.12.2010 |
| Accounting in the Federal Tax Service | |
| Date of registration | 22.01.2018 |
| Tax authority | Inspectorate of the Federal Tax Service No. 15 for Moscow, No. 7715 |
| Information on registration with the FIU | |
| Registration number | 087309024538 |
| Registration date | 24.01.2018 |
| Name of the territorial body | State institution - Main Directorate of the Pension Fund of the Russian Federation No. 6 in Moscow and the Moscow region, municipal district Otradnoye, Moscow, No. 087309 |
| Registration information in the FSS | |
| Registration number | 771704297677191 |
| Registration date | 01.09.2018 |
| Name of the executive body | Branch No. 19 of the State Institution - Moscow Regional Branch of the Social Insurance Fund of the Russian Federation, No. 7719 |
OKVED codes
| Additional activities (9): | |
|---|---|
| 20.1 | Production of basic chemicals, fertilizers and nitrogen compounds, plastics and synthetic rubber in primary forms |
| 20.13 | Manufacture of other basic inorganic chemicals |
| 20.14 | Manufacture of other basic organic chemicals |
| 20.16 | Manufacture of plastics and synthetic resins in primary forms |
| 20.3 | Manufacture of paints, varnishes and similar coating materials, printing inks and mastics |
| 20.41 | Manufacture of soap and detergents, cleaning and polishing products |
| 20.59 | Manufacture of other chemical products, not elsewhere classified |
| 20.60 | Chemical fiber production |
| 72.20 | Research and development in social sciences and humanities |
other information
History of changes in the Unified State Register of Legal Entities
- Date: 23.12.2010
GRN: 2107749322976
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: - Date: 23.12.2010
GRN: 5107746050209
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: Creation of a legal entity
Documentation:
- Р11001 Statement on the creation of a legal entity
- Document confirming the payment of the state fee
- Legal entity charter
- Decision to establish a legal entity
- COP. Of the statute
- COP. SVID., GARANT. LETTER, REQUEST, QUIT. 209 - Date: 27.12.2010
GRN: 2107749472169
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: - Date: 27.12.2010
GRN: 2107749490363
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: - Date: 22.01.2018
GRN: 2187746895532
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: State registration of amendments made to the constituent documents of a legal entity related to amendments to the information about the legal entity contained in the Unified State Register of Legal Entities, on the basis of an application
Documentation:
- Р13001 APPLICATION ON CHANGES MADE TO THE INSTITUTIONAL DOCUMENTS
- DOCUMENT ON PAYMENT OF STATE DUTIES
- CHANGES TO THE CHARTER OF LE
- DECISION TO CHANGE THE CONSTITUTIONAL DOCUMENTS
- CONTRACT, SVID. LETTER, DECISION
- POWER OF ATTORNEY G. S. KUZNETSOV - Date: 22.01.2018
GRN: 2187746898986
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: Submission of information about the registration of a legal entity with a tax authority - Date: 22.01.2018
GRN: 2187746898997
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: Submission of information about the registration of a legal entity with a tax authority - Date: 24.01.2018
GRN: 2187746974600
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: Submission of information on the registration of a legal entity as an insured in the territorial body of the Pension Fund of the Russian Federation - Date: 25.01.2018
GRN: 6187746035086
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: Submission of information on the registration of a legal entity as an insured in the territorial body of the Pension Fund of the Russian Federation - Date: 04.10.2018
GRN: 6187749382826
Tax authority: Interdistrict Inspectorate of the Federal Tax Service No. 46 in Moscow, No. 7746
Reason for the change: Submission of information on the registration of a legal entity as an insurant with the executive body of the Social Insurance Fund of the Russian Federation
Legal address on the city map
Other organizations in the directory
- , Yekaterinburg - Liquidated
INN: 6672249938, OGRN: 1076672039510
620100, Sverdlovsk region, city of Yekaterinburg, Bolshakova street, 21, apt. 169
General Director: Ginter Evald Vladimirovich - , Moscow region - Liquidated
INN: 5040094660, OGRN: 1095040005972
140153, Moscow region, Ramensky district, Bykovo village, Teatralnaya street, 10, A 323
General Director: Nikitin Konstantin Nikolaevich - , Novosibirsk - Operating
INN: 5402169687, OGRN: 1025401027101
630132, Novosibirsk region, city of Novosibirsk, Narymskaya street, building 23, office 3
Director: Popov Ruslan Alexandrovich - , St. Petersburg - Liquidated
INN: 7839375300, OGRN: 1089847049412
191119, city of Saint Petersburg, Obvodny Canal embankment, 93A
General Director: Alexander N. Zadorozhny - , Volgograd - Liquidated
INN: 814170107, OGRN: 1060814083648
400005, Volgograd region, the city of Volgograd, avenue im. V.I.lenina, 86
General Director: Georgy Zurabievich, Craftsman - , Suddenly - Liquidated
INN: 3324011382, OGRN: 1033303002479
601351, Vladimir region, the city of Sudogda, Gagarin street, 5
Director: Shuraleva Nadezhda Borisovna - , Saratov - Liquidated
INN: 6452109910, OGRN: 1146450003765
410005, Saratov region, city of Saratov, 1st Sadovaya street, 104
Director: Alexey Buyanov - , Moscow - Active
INN: 7707732178, OGRN: 1107746693064
127051, Moscow, Kolobovskiy lane 2, 9/2, building 1
General Director: Martyshov Viktor Petrovich - , St. Petersburg - Active
INN: 7825427526, OGRN: 1037843102857
192029, St. Petersburg, Obukhovskoy Oborony Avenue, 86, letter K, pom. 5-H
General Director: Shikhalev Boris Vladimirovich - , Kirov - Active
INN: 4345371525, OGRN: 1134345026100
610020, Kirov region, city of Kirov, Karl Liebknekht street, 55
Director: Menshikov Konstantin Alexandrovich
- - Active
INN: 7733754795, OGRN: 5107746050209
127566, Moscow, Altufevskoe shosse, 44, pom XIV ET 8 KOM 11
General Director: Alexey Lesiv
They "forgot" to include Alexei Pesoshin in the board of directors of Tatneftekhiminvest-holding, and at the meeting they made it appear that TAIF was thwarting the plan
Despite the $ 1.5 billion in profit, Tatneftekhiminvest-holding traditionally left shareholders without dividends, and the holding's board of directors, as expected, was left without Ildar Khalikov. At a regular meeting of the board of directors, the correspondent of "BUSINESS Online" learned why the petrochemists did not supply Tatarstan refiners with 39% of the planned volume of plastics and why the re-elected director of the holding, Rafinat Yarullin, is worried about the Chinese combustible ice.
Rafinat Yarullin (center) / Photo: tatarstan.ru
Rafinat Yarullin HEADED TATNEFTEKHIMINVEST-HOLDING AGAIN
Today the Cabinet of Ministers of the Republic of Tatarstan hosted 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 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 was 1.165 billion rubles. But the representatives of the holding asked the shareholders not to flatter themselves - the profits are mostly virtual. Its lion's share was obtained through revaluation in accordance with the market value of the shares of Tatneft on the balance sheet of the holding. So, according to 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 summing up 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, remained in their place. Nail Maganov and CEO of TANECO Leonid Alekhin and bison of petrochemistry represented by the general director of TAIF Alberta Shigabutdinova(though he was late, and as a result, the participants voted without him) and his deputy, concurrently chairman of the board of directors of PJSC "Nizhnekamskneftekhim" 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" Rausil Khaziev, representatives of AK BARS Bank, three republican ministers and the head of the AIR 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, he was simply not included in the new lists, and the 25th vacant seat on the board of directors of TNHI-X will remain with him in the future. Minnikhanov became the chairman again. Laughing, he asked: maybe the audience has other candidates? No forest of hands was found, so the name of the president was approved without discussion. Yarullin was also reappointed as CEO of the company.
CONSTRUCTION OF LNG PLANT STARTED IN CHISTOPOL
Briefly, Yarullin told how the year 2016 ended for an enterprise in the oil and gas chemical sector of the republic. In general, at the end of 2015 - 2016, production volumes increased by 3.5%, which is 2.2 percentage points below the plan. The planned plan for 2016 was fulfilled only by oilmen, who continue to increase oil production, even despite Russia's agreements on limiting production with the OPEC countries. TATNEFT also increased ethane production for Kazanorgsintez's needs to 187 thousand tons per year, which allowed the latter to increase its polyethylene output. In addition, the republic has significantly increased the production of diesel fuel, mineral fertilizers, synthetic rubbers, technical sulfur, detergents and soap, polymer plates and films.
Kazanorgsintez and Nizhnekamskneftekhim supplied 167 thousand tons of plastic to republican companies in 2016, which is 39 percent below the plan. The price factor and the brand assortment of plastics affected, and imports increased. As a result of the delay in the start-up of the alpha-olefin unit, the polyethylene supply plan by Nizhnekamskneftekhim has been only half completed, ”Yarullin said. The domestic market was 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. As a reminder, the construction agreement between Gazprom Gazomotornoye Toplivo and Tatarstan was signed back in December 2015. According to Yarullin, exploration work is underway at the moment. The capacity of the enterprise will be 7 thousand tons per year, the total cost of the project is 9 billion rubles, reaching the planned capacity is scheduled for 2019.
Stressing the importance of the project, he recalled that competition in the world gas market is intensifying. In May, China announced the beginning of the development of a gas hydrate field - 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 - the other day the first Russian ice tanker-gas carrier was sent on the 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 work out as with shale gas production, which our country actually "missed".
The plans for 2017 of the companies supervised by Yarullin called 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 gasoline at TANECO, the increase in the production of isoprene rubber at Nizhnekamskneftekhim ”, Reconstruction of preparatory production at“ Nizhnekamskshina ”, launch of the production of flexible packaging“ Danaflex ”in the SEZ“ Alabuga ”.
"EDELWEISS" - ON POLYMER WASTE, AND STICKERS - ON FIRE
Then the businessmen invited to the council proposed 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 polymer products is growing, but most of them are buried. The idea of the company is to recycle waste polymer into high quality compounds ( thermoactive, thermoplastic polymer resin — approx. ed.). This technology, which received the name "Edelweiss", is interesting in that it involves only one stage of processing raw materials, while traditionally it requires two. In this case, the cost of the final product turns out to be lower, and the quality does not deteriorate. Minnikhanov suggested that companies that process polymer waste in the Republic of Tatarstan get acquainted with the technology.
Business Development Director of the Moscow Termoelectrica LLC Alexey Lesiv told about the new technology of early warning of electrical equipment malfunctions. The idea is to notify the staff of an impending fire in the enterprise even before it starts - after all, up to 28% of fires happen due to electrical equipment malfunction. Technically, the "ThermoSensor" system looks like this: special stickers with temperature sensors are attached to the electric wires, they give a signal if the wiring is heated above normal. Lesiv stressed that his stickers are much cheaper than imported counterparts.
Minnikhanov was noticeably interested in the novelty - he recommended it for use at energy enterprises, Grid and Generation companies, and also to think about the use of such stickers in public buildings and at large facilities.
- The question is this: in old schools we still have aluminum wiring, it is always hot. Will your sensors work? - the Minister of Construction asked the businessman Irek Fayzullin.
- 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 is the point of putting on the old wiring? And the idea itself is very interesting.
The resident of Innopolis, ZAO PB SKB Kontur from Yekaterinburg, offered the Tatarstan residents a new solution to optimize the activities of enterprises of the petrochemical complex and for budgetary organizations of Tatarstan. Minnikhanov realized that the system could also automate the procurement system, leaving intermediaries behind. He instructed the Minister of Informatization and Communications of the Republic of Tatarstan Roman Shaikhutdinov study the idea and, if possible, bring it to life.
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 , 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 Communal Services 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 AID RT Taliya Minullina, Consultant to the President of the Republic of Tatarstan on the development of oil and oil and gas fields, Professor of the Department of Geology, Oil and Gas of IGiNGT Kazan Federal University Renat Muslimov, Assistant to the President of the Republic of Tatarstan Rinat Sabirov, General Director of JSC "HC" Tatneftepabirovt "Rustam General Director Director of PSC "TAIF" Albert Shigabutdinov, Assistant to the President Denta RT on the 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 Suleimanov, 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.
OJSC Tatneftekhiminvest-holding was established in September 1994 as an industrial and financial company uniting the largest enterprises of the oil and gas chemical complex of Tatarstan. The largest shareholders are Svyazinvestneftekhim JSC, Tatneft PJSC, Nizhnekamskneftekhim PJSC, Kazanorgsintez PJSC, Nizhnekamskshina PJSC.
Holders of the patent RU 2596624:
The invention relates to a group of new extractants for the extraction of 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 can 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, for example TBP or MiBC, or diluents such as kerosene, C 6 -C 10 aliphatic alcohols, halogen substituted C 6 -C 10 ketones, linear or cyclic siloxanes. 14 p.p. f-crystals, 14 dwg., 9 tbl., 24 ex.
The present invention relates to chemical technology, specifically to liquid extraction extractants capable of recovering nitric acid from aqueous solutions, comprising one or more dialkyl sulfones of formula (I)
where R 1 and R 2 are linear or branched alkyls containing 1-8 carbon atoms.
The invention can be most effectively used in the chemical, metallurgical and mining industries, as well as for the treatment of waste and waste water.
The extraction of nitric and other acids from aqueous solutions is an important industrial process. The need for the 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)], the extraction, separation and purification of non-ferrous metals [US patents US 4647438 (1987), US 5338520 (1994), application US 20130259777 A], the separation of uranium, thorium and other actinides and lanthanides [application RU 2009119466 A].
The most widespread among the extractants currently used for the extraction of nitric acid are tributyl phosphate (TBP) [(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 (EHENPA), bis (2-ethylhexyl) phosphinic acid , various radical phosphine oxide (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, solutions of aliphatic trialkylamines in appropriate solvents are used, for example, trioctylamine in kerosene [US patents US 4285924 (1981) and US 4169880 (1977)].
The analogs of the claimed extractants are substances of the same purpose, such as TBP, MiBK, FOR, ENENRA, etc. These analogs were used for comparison in experiments to study the extraction ability and other properties of the claimed extractants. The closest analogues of the claimed extractants are TBF and MiBK. Despite the high extraction capacity and widespread use, these analogs are not without drawbacks. The disadvantages of methyl isobutyl ketone 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 hydrolysability with the formation of mono- and dibutyl phosphates. The widely used TBP for extraction was chosen as a prototype.
Despite the variety of known and used extractants, the selection of an extraction system for a specific technology is a difficult task, since it is necessary to take into account many factors on which the productivity and selectivity of the process depends. Among these factors, the most important are the extraction capacity, selectivity, viscosity, stability of the extractant, solubility, compliance with environmental requirements, cost of the extractant, ease of re-extraction, etc.
It is impossible to find an extractant that would simultaneously satisfy all the requirements; there is a need for new extractants that could be used in specific industrial processes. The search for such extractants, expanding the arsenal of means for extraction and allowing 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 the known extractants in their extraction ability and would allow to extract nitric acid from mixtures with other acids.
The problem is solved by a new extractant for the extraction of nitric acid and nitrates from aqueous solutions, including one or more dialkyl sulfones of formula (I)
where R 1 and R 2 each independently represent a linear or branched alkyl containing 1-8 carbon atoms, the total number of carbon atoms in the compound of formula (I) is from 6 to 12.
The inventive extractant can 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 can be a mixture of dialkyl sulfones obtained by oxidation of three products of the interaction of two aliphatic C 4 -C 5 alcohols with hydrogen sulfide.
The inventive extractant comprising 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: kerosene, aliphatic C 6 -C 10 alcohols, halogen substituted C 6 -C 10 ketones, linear or cyclic siloxanes.
The extractant can be a mixture of the following compositions (parts by weight):
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. Dialkyl sulfones are characterized by high chemical and thermal stability (General organic chemistry, vol. 5. Compounds of phosphorus and sulfur. // Ed. By NK Kochetkov, M., Chemistry, 1983 p. 318). Dialkyl sulfones have high selectivity, low water solubility, a fairly high flash point, and compatibility with diluents. In addition, unlike phosphates, phosphonates, and aliphatic ketones, dialkyl sulfones are stable in highly acidic environments. Some properties of dialkyl sulfones and mixtures thereof 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 Ch. 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 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 alkyls having from 1 to 4 carbon atoms, and where the sum of the carbon atoms in the groups R 1 and R 2 is not more than 7, such as, for example, isobutylisopropyl 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 because of their lability in strongly acidic media, or because of a decrease in the extraction characteristics of sulfones.
Dialkyl sulfones in which both R 1 and R 2 are normal are generally solids at room temperature. Compounds of formula (I), where the sum of 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 much worse.
Melting points for 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 lower the temperature during extraction arises, for example, when separating nitric and hydrochloric acids, which is expediently carried out at temperatures below 5 ° C, which prevents the decomposition of nitric acid and the formation of toxic NOCl and NO 2 Cl.
Particularly preferred properties for use as extractants are those of the compounds of formula (I) such as dibutyl sulfone, diisobutyl sulfone, butyl isobutyl sulfone, diisoamyl sulfone, isoamyl isobutyl sulfone and isoamyl isopropyl sulfone.
But the preparation of pure unsymmetrical dialkyl sulfones is much more difficult than the preparation of symmetric ones. An alternative to unsymmetrical sulfones can be low-melting three-component mixtures obtained according to the following scheme:
Such mixtures are obtained by the method 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 with mixtures of dialkyl sulfones with known extractants and mixtures of dialkyl sulfone with diluents has been studied.
The invention is illustrated in the following figures.
FIG. 1 shows isotherms of extraction of nitric acid from aqueous solutions with various dialkyl sulfones or their mixtures.
FIG. 2 shows the isotherms of extraction of nitric acid from aqueous solutions using diisobutyl sulfone as an extractant, and for comparison isotherms of the extraction of HNO 3 with tributyl phosphate (TBP) and methyl isobutyl ketone (MiBK).
FIG. 3 shows the 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 separating these acids.
To compare the effectiveness of the claimed extractant with TBP in Fig. 4 shows the isotherm of the extraction of nitric and hydrochloric acids from aqueous solutions with tributyl phosphate.
FIG. 5 shows isotherms of extraction of nitric and hydrochloric acid from aqueous solutions using diisobutylsulfone, TBP, and MIBK as extractants, which make it possible to compare the efficiency of these extractants for separating nitric and hydrochloric acids.
FIG. 6 shows isotherms of extraction of nitric, hydrochloric, sulfuric and methanesulfonic acids from aqueous solutions using diisobutyl sulfone as an extractant. 6 illustrates the selectivity of diisobutylsulfone for different acids and the ability to separate acids with highly different partition coefficients by extraction. For example, nitric acid can be separated from hydrochloric, sulfuric, and methanesulfonic acids.
FIG. 7 shows isotherms of extraction of nitric acid from aqueous solutions using pure diisobutyl sulfone, a mixture of diisobutyl sulfone with TBP, and a mixture of diisobutyl sulfone with MiBS as an extractant.
FIG. 8 shows isotherms of extraction of nitric acid from aqueous solutions using pure diisobutyl sulfone and mixtures of diisobutyl sulfone with various diluents such as 2-ethylhexanol, kerosene, etc. as extractants.
FIG. 9-13 are 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 corresponds to pure dialkyl sulfone, point 100 to pure known extractant: MiBC (Fig. 9), TBP ( Fig. 10), FOR (Fig. 11), ENENRA (Fig. 12) and D2EHPA (Fig. 13).
Fig. 14 refers to example 24, it schematically shows a five-stage countercurrent extraction cascade, in which a mixture of nitric and hydrochloric acid is separated, and diisobutyl sulfone is used as an extractant.
The advantages of dialkyl sulfones over organophosphorus compounds are their low cost, low viscosity, low melting point, and high extraction ability. In addition, unlike phosphates and phosphonates, sulfones are stable in highly acidic environments. For example, the formation of decomposition products of sulfones by NMR was not recorded when it was kept 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 distinguish them favorably from aliphatic ketones containing 6 carbon atoms (MiBC), widely used for the extraction of nitric acid.
Dialkyl sulfones can be used as diluents for known extractants such as TBP, D2EHPA, FOR, etc. By varying the ratio of the known extractant: dialkylsulfone, it is possible to select the optimal values of the distribution coefficient that provide the highest extraction / re-extraction efficiency (Figs. 9-13). In addition, the addition of dialkyl sulfones leads to an increase in the selectivity of the extraction of nitric acid and a reduction in the cost of the extractants obtained. The use of diluents in a mixture with dialkyl sulfones also makes it possible to reduce the cost of the extractant and make it less viscous (Example 3, Fig. 8).
The efficiency of extraction with a mixture of diisobutylsulfone and kerosene manufactured by Shell Chemicals ShelSolD60 (D60) or a mixture of diisobutylsulfone and 2-ethylhexanol is close to the efficiency of extraction with pure diisobutylsulfone. So, at the initial concentration of nitric acid 3M, the separation coefficients when using pure diisobutylsulfone as an extractant and its 33% mixture with D60 are 0.261 and 0.213, respectively, at a 5M concentration of 0.363 and 0.326, respectively. When using diisobutyl sulfone in a mixture with kerosene D60, during the extraction process, a three-phase separation of the system into an aqueous phase, sulfone containing nitric acid (heavy organic phase), and kerosene D60 containing pure sulfone (light organic phase) was observed. In the process of re-extraction, free diisobutyl sulfone 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 re-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 diisobutyl sulfone 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 MiBK is the formation of stable emulsions after mixing with hydrochloric acid solutions. The time of divergence of the MiBK emulsions with 3M, 4M and 5M hydrochloric acid and the TBP emulsions with 1M hydrochloric acid was about a day.
In the case of diisobutyl sulfone, the emulsion divergence time over the entire range of investigated concentrations 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 MiBC.
The results show that the extraction ability of dialkyl sulfones with respect to nitric acid is close to that for MIBK.
Thus, at an initial concentration of nitric acid of 5M, the distribution coefficients were 0.363 and 0.381 for diisobutyl sulfone and MiBK, and 0.199 and 0.197, respectively, at a concentration of 2M.
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 with respect to nitric acid, exceeding the selectivity of TBP.
The inventive extractant is stable in strongly acidic environments, allows extraction at low temperatures, and 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 extracting 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 stirring equal volumes of acid and extractant by shaking with a shaker in a 20 ml vessel 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. The distribution coefficients (D) for nitric acid were calculated from the measurement results.
D (HNO 3) = C (HNO 3) o / C (HNO 3) c,
where C (HNO 3) o is the concentration of nitric acid in the organic phase, C (HNO 3) в is the concentration of nitric acid in the aqueous phase.
FIG. 1 shows isotherms of extraction of nitric acid from aqueous solutions with various sulfones. Experimentally calculated distribution coefficients (D) for nitric acid are shown in Table 3.
FIG. 2 shows the results obtained using diisobutyl sulfone as an extractant for the extraction of HNO 3, and for comparison, the results obtained for TBP and MIBK under similar conditions are shown.
It has been shown that the extraction ability of dialkyl sulfones with respect to nitric acid is close to that for MIBK, but slightly lower than that of TBP.
Thus, at an initial concentration of 5M nitric acid, the distribution coefficients were 0.363 and 0.381 for diisobutyl sulfone and MiBK, and 0.199 and 0.197 at a concentration of 2M, 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 (Figs. 3-5). The extraction was carried out in the same way as in Example 1, using stock solutions of nitric and hydrochloric acids of specified 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 MiBK it is 26 times higher, while for TBP it is only 8.6 times higher, at a nitric acid concentration of 3M the ratio of the distribution coefficients of acids are, respectively, 22, 66 and 4.8. It is shown that, in contrast to the claimed extractants, TBP and MiBK form stable emulsions after mixing with hydrochloric acid solutions. The dissolution time of the emulsion with an increase in the acid concentration for MiBK increased, and for TBP it decreased. The time of divergence of the MiBK emulsions with 3M, 4M and 5M hydrochloric acid and the TBP emulsions with 1M hydrochloric acid was about a day. In the case of diisobutyl sulfone, the emulsion divergence time over the entire range of investigated concentrations is 3-5 minutes.
An experiment similar to that described in Example 2 was carried out for a larger set of acids. FIG. 6 shows isotherms of extraction of nitric, hydrochloric, sulfuric, and methanesulfonic acids from aqueous solutions with diisobutyl sulfone.
The distribution coefficients of hydrochloric, sulfuric and methanesulfonic acids are significantly lower than the distribution coefficient of nitric acid. So, at an acid concentration of 2M, the distribution coefficients for nitric, hydrochloric, sulfuric and methanesulfonic acids were 0.199, 0.003, 0.006 (at a concentration of 20%, which corresponds to 2.3M) and 0.005, respectively, for a concentration of 5M - 0.363, 0.01, 0.051 (at conc. 40%, which corresponds to 5.3M) and 0.047, respectively (Table 5).
Thus, using diisobutyl sulfone as an extractant, nitric acid can be selectively extracted from mixtures with HCl, H 2 SO 4 or MsOH.
FIG. Figures 7 and 8 show isotherms of nitric acid extraction with pure diisobutyl sulfone, as well as mixtures of diisobutyl sulfone with TBP, MiBK, and various diluents: 2-ethylcyclohexanol, chloroform, and ShelSol D60 (D60) and ShelSol А100 (А100s) kerosene 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 efficiency of extraction with a mixture of diisobutylsulfone and D60 or a mixture of diisobutylsulfone and 2-ethylhexanol is close to the efficiency of extraction with pure diisobutylsulfone. At the initial concentration of nitric acid 3M, the separation coefficients when using pure diisobutyl sulfone as an extractant and its 33% mixture with 2-ethylhexanol and 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 efficiency of extraction with a mixture of diisobutylsulfone and D60 or a mixture of diisobutylsulfone and 2-ethylhexanol is close to the efficiency of extraction with pure diisobutylsulfone. So, at the initial concentration of nitric acid 3M, the separation coefficients when using pure diisobutyl sulfone as an extractant and its 33% mixture with D60 are 0.261 and 0.213, respectively, at a 5M concentration of 0.363 and 0.326, respectively. When using diisobutyl sulfone in a mixture with kerosene D60, during the extraction process, a three-phase separation of the system into an aqueous phase, sulfone containing nitric acid (heavy organic phase), and ShelSol D60, containing pure sulfone (light organic phase) was observed. In the process of re-extraction, free diisobutyl sulfone 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 re-extraction process.
Examples 5-22.
To assess the selectivity of extractants, including sulfones and mixtures of sulfones with known extractants in relation to nitric acid, the following experiments were carried out. An aqueous 3M solution of nitric acid or hydrochloric acid was added to the test extractants, which could include 3 components (A, B, and C) (the ratio of the aqueous to organic phase 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. Based on 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 simple mixing of 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 a ViBRA AF 225DRCE analytical balance with an accuracy of 1 × 10 -2 mg. During the shooting, the following temperature program was used:
Cooling down to -70 ° C at a rate of 5 ° C / min;
Isotherm -70 ° C for 3 minutes;
Heating up to 25-35 ° C at a rate of 5 ° C / min.
Crystallization proceeds in a non-equilibrium manner (the temperature maximum clearly depends on the cooling rate, strong supercooling is observed (more than 20 ° C), therefore, only the portions 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. Diisobutyl sulfone was used as an extractant; the rate of extractant feed 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 regulated by changing the phase feed rate. Stirring and separation were 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 flushing unit to remove HCl. Two-stage washing with water was carried out at room temperature at a ratio of organic to aqueous phases of 1: 1. Under these conditions, HCl is almost completely removed from the extract (the HCl content in the aqueous phase after stripping is given below). The aqueous phase obtained from the washing and containing the mixture of acids was added to the initial mixture of acids supplied to the inlet of the extraction cascade.
After washing, the organic phase enters the stripping cascade, consisting of 5 cells. Stirring 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 an 8.5% nitric acid solution 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.
The 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 corresponds to pure sulfone, point 100 to pure phosphorus-containing extractant or MiBK.
In general, the addition of dialkyl sulfones to known extractants leads to a change in the extraction characteristics and a decrease in the dissolution time of the resulting emulsions. Compared to dialkyl sulfones, 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 the extraction of nitric acid and nitrates from aqueous solutions, comprising one or more dialkyl sulfones of the formula (I) 
,
where R 1 and R 2 each independently represent a linear or branched alkyl containing 1-8 carbon atoms, the total number of carbon atoms in the compound of formula (I) is 6-12.
2. An extractant according to claim 1, characterized in that it comprises 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, further comprising one or more phosphorus-containing compounds selected from the group: trialkyl phosphates, dialkyl phosphates, alkyl phosphonates, phosphinic acids, phosphine oxides.
5. An extractant according to claim 1 or 2, additionally comprising one or more C 6 -C 10 ketones.
6. An extractant according to claim 1 or 2, additionally comprising one or more diluents selected from the group: kerosene, chloroform, aliphatic C 6 -C 10 alcohols, halogen-substituted 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 (parts by weight):
9. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (parts by weight):
10. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (parts by weight):
11. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (parts by weight):
12. The extractant according to claim 1 or 2, characterized in that it is a mixture of the following composition (parts by weight):
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 recover nitric acid from wastewater.
Similar patents:
The invention relates to derivatives of sulfur-containing dicarboxylic acids of the formula (1) in which when: 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 when: 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).
