CC BY
27
UDC: 547.1.13
FERROCENE AND CYMANTRENE NANOCOMPOSITE SOLUTIONS. PREPARATION AND USE OF THEM AS CATALYSTS OF EXHAUST GASES FOR DIESEL FUELS
G.Z.Suleymanov, Z.G.Gurbanov, R.M.Muradkhanov, A.R.Rzayeva
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
[email protected] Received 26.05.2016
The paper studies mainly the synthesis of new alkyl, oxyalkyl, carbinol (carbinolate) cluster and binuclear derivatives of ferrocene, carbinol and carbinolate derivatives of cymantrene. We presented the data on preparation of nanocomposite solutions used as neutralizers of exhaust gases for diesel fuels. Some aspects of producing non-waste technologies of ferrocene (cymantrene) and some of its derivatives were also studied.
Keywords: nanocomposite solutions, carbinol, carbinolate derivatives of ferrocene (cymantrene), antidetonation, neutralizers, exhaust gases, motor and diesel fuels.
Introduction
Recently a definite reorientation of research works caused both by development of technology and increase in demand for ecologically pure fuels and their combustion products has been occurred due to complication of ecologically problems caused mostly by motor vehicles [1].
In this connection the search and use of new ecologically safe and more effective or-ganometallic (aliphatic, cyclic, heterocyclic) compounds and their derivatives with various functional groups of most transition metals [2] are considered.
Such type high soluble organometallic compounds in relevant hydrocarbon fuel due to its high dispersity are effective neutralizers of unbur-ned residues thrown into atmosphere by engines.
The present work deals with the synthesis of new carbinol (carbinolate) derivatives of industrial organometallic compounds of ferrocene (C5H5)2Fe and cymantrene (OC)3MnC5H5 and studying the use of nanocomposite solutions as combustion catalysts and carbon deposition with low-octane number of diesel and motor fuels.
If we consider that at present hazardous substances of exhaust gases, particularly, un-burned residues of diesel and nonstandard motor fuels which contaminate the air are most pressing and urgent problems of ecology [3]. Great flow of motor vehicles led to that pollution level of atmosphere in major industrial cities is 5-10 times higher than sanitary norms.
Fuel resource shortages are also increased due to impetuous growth of transport fleet which account for about 50% of atmos-
pheric pollution with nitrogen oxide, carbon compound [4].
Under modern conditions expensive rhodium-platinum (palladium-ruthenic) catalysts are used as neutralizers for exhausted gases of both gasoline automobiles and piston engine vehicles [5, 6].
As many researchers state an effective work of such catalysts are provided only with complex microprocessor system with feedback fuel supply [7].
The quality of diesel and nonstandard motor fuels are of special interest. Their exhaust gases contain various unburned organic compounds and under solar light and rains and other factors they turn to complex and hazardous substances. That's why the aim of these investigations is directed to the search of cheaper and ecologically pure neutralizers for exhaust gases of diesel and motor fuels.
Experimental part
1. Synthesis of carbinol, carbonilate derivatives of ferrocene (cymantrene) I-IV, LMC5H4C(R1R2)OH (I-III); LMC5H4C(R1R2)OLi (II, IV); LM=C5H5Fe, (OC)3Mn; R1=R2=Ar, alk. Abovementioned derivatives of ferrocene and cymantrene were obtained by using the reaction (1) between lithic organometallic compounds of ferrocene C5H5FeC5H4Li (cyman-trene, (OC)3MnC5H4Li) obtained by method [8] and some aromatic and aliphatic ketons. For this purpose first 0.1 mol of ferrocene (cymantrene) is melallated with 25 ml of 1.2 N H-BuLi, then at subzero temperature (-100C) it is processed with 0.1mol of carbonyl compound.
After relevant processing of reaction solution I-IV compound is obtained.
2. Synthesis of carbinol derivatives of ferrocene under phase-transfer catalysis. For this purpose first immiscible diphase system (water/petroleum ether) is created; the lower layer is inorganic, but upper layer is organic phase. Symmetrical and non-symmetrical ke-tons are introduced into organic phase, but catalyst (H2SO4) and carrier DЭАNaf are introduced into aqueous phase with ratio 2:1, correspondingly. After processing and neutralization of reaction mixture with NaHCO3 we obtained corresponding carbinolferrocenyl (I, III).
3. Preparation and use of nanocomposite solutions containing ferrocene (cymantrene) and their derivatives.
For preparation of relevant nanocompo-site solution we first 0.1 mol of composite forming agent [ferrocene (cymantrene) or its derivatives] is dissolved to 30 ml of solvating organic solvent, then 10 ml of antioxidant is added to it, then 70 ml of diluent is added. Formed homogeneous solution is mixed with a speed of 3600 rev/min for an hour. The solution attained light yellow color. In case of cyman-trene and its derivatives nanocomposite solution is stored in darkness or 3-5% of light-resistant stabilizer is added. Such solutions quickly become turbid and lose their catalytic activity.
Determination of exhaust gases was performed by using Bosch method on motor D-20. The method consists of transmission of certain
amount of exhaust motor gases through filtering material and measurement by weighting in mg amount of furnace black in 1 liter gas.
Results and discussion
Considering that 0.5-1 mas.% of various additives are added into fuels to improve the combustion of hydrocarbon fuels and to decrease amount of smoke in exhaust gases. Sul-pahtes, sulphites, metal carbonates of I and II groups of periodical system (Li, K, Na, Ba, Ca and Cu) are referred to such type additives. Barium-containing additive "CLD" (Belgium), additives "Lubrizol-565 (SVIA)" and "IKhP-706" of the Institute of Chemistry of Additives of NAS of Azerbaijan are widely used among an-tismoke and carbon deposition. Antismoke effect of ferrocene and its methyl (ethyl) alkyl derivatives were compared with effectiveness of abovementioned antismoke additives.
Results of experiments on sample of diesel fuel LDT in the work [9,10] were compared with abovementioned data (see Table 1).
As Table 1 shows, by adding LDT of 0.05% ferrocene to the composition amount of smoke is decreased up to 50%, but for achieving 10 times more antismoke additives "Lubrizol-565", "SLD" and additive IKhP-706 must be used.
Together with exhaust gases tens of thousands of barium sulfate, as well as 25% of toxic carbonate inorganic compounds are thrown into atmosphere.
No Fuel mixture Amount of ferrocene or its derivatives, mas.% Decrease of smokiness, %
1 LDT without ferrocene and other dditives 80
2 LDT + 0.05 mas.% ferrocene 55
3 LDT + 0.1 mas.% ferrocene 48
4 LDT + 0.2 mas.% ferrocene 50
5 LDT + 0.05 mas.% methylferrocene 38
6 LDT + 0.10 mas.% ethylferrocene 47
7 LDT + 0.30 mas.% ethylferrocene 52
8 LDT + 0.05 mas.% 1,1-dibutylferrocene 40
9 LDT + 0.10 mas.% 1,1-dibutylferrocene 45
10 LDT + 0.30 mas.% 1,1-dibutylferrocene 55
11 LDT + 0.5 mas.% "SLD" 50
12 LDT + 0.5 mas.% "Lubrizol-565" 50
13 LDT + 0.5 mas.% IKhP-706 47
Table 1. Smoke reducing effect of ferrocene and its derivatives
However in separate works it was noted that comparing with ferroceneferrocenylcarbinol and amine groups of derivatives have universal smoke reducing and octane increasing properties. They are more effective additives of both diesel and motor fuels. That's why recently several methods have been developed for synthesis of carbinol derivatives of ferrocene and cymantrene. However these methods are noted with the fact that used solvents and sorbents do not meet modern ecological standards [5, 6]. We proposed new more effective ecologically pure and technologically marketable methods of producing carbinolate (I, III) and carbinol (II,
IV) type derivatives of ferrocene and cyman-trene. Carbinol LMC5H4C(R1R2)OH (I, II), where LMC5H=C5H5Fe (I), (OC)3Mn (II) and carbinolate LMC5^C(R1R2)o (III, IV), derivatives of ferrocene and cymantrene were obtained by using reaction (1) between lithic or-ganometallic compounds of ferrocene C5H5FeC5H4Li and cymantrene (OC)3MnC5H4Li obtained by method [8] with aliphatic R2CO and aromatic Ph2CO keton compounds which depending on condition reaction was performed with relevant carbinolate (III, IV) or carbinol (I, II) derivatives:
LMC5 H 4 Li+R2 CO(Ph2 CO )
yO Li ^OLi
LMC5 H4 C-R + LMC5 H 4 C—Ph
54 5 4
R xPh
(1)
I, II
III, IV
where LMC5H4 Li - C5 H5 Fe ( III) , (OC)3 Mn(II, IV) , R=alk, Ph=C6 H5
The effect of carbinol (carbinolate) radical introduced into cyclopentadienyl ring essentially changes basic physical and chemical properties of compounds I-IV their solubility in different hydrocarbon solvents, antismoke and carbonization properties of diesel fuel L 0.5-40 prepared on GOST 500TU and bunker fuel of liquid black oil KT-40. Nanocomposite solutions containing 0.01-0.1 mol/l of organome-tallic compounds were added into diesel fuel at
0C, H2SO4
CH3
I
C5H5FeC5H5+CH3-C-CH2-C=CH2 CH3
V
Output of V - by reaction (2) is found to be 90-94%. Other derivatives of ferrocene, based on reaction (3) we have developed convenient method of producing polyalkyl substi-
6 H5 •
200C and mixed 1000 rev/min for an hour. With the aim of developing new more effective smoke reducing and octane - increasing nanocomposite solutions with minimum content of metals (Fe, Mn) in basic complexes we worked out single-stage obtaining method of monoalkyl substituted derivatives of ferrocene based on the reaction (2) between di-a-methylstyrene (DAMS) and ferrocene catalyzed H2SO4 at 00 temperature [6] :
CH3 Ph
I 3 I -C-CH2-C-CH3
Ph
Ph
(2)
tuted derivatives of ferrocene (VI) by direct al-kylation with its pyrolysis products (pyrocon-densate) containing 30-32 mas. % of saturated hydrocarbons:
C5H5FeC5H5+pyrocondensate C5^FeC5R5 .
VI, polyalkylferrocene
In the reaction (3) as a catalyst we used diisopropylether solution containing 3-5% of non-aqueous AlCl3. Total yield of polyalkyl substituted derivative of ferrocene by proposed method makes 76-80% [12]. It must be stated that before our investigations heterobinucle-
LM=C5H5Fe (VII), (OC)3Mn (VII, VIII).
Yield of derivatives VII by reaction (4) makes up 94%, VIII - 80%. All obtained mono-alkyl, polyalkyl and oxyalkyl derivatives are well soluble in most hydrocarbon solvents. They do not have clear melting temperature. Carbinol compounds under acidic conditions easily transforms into symmetric ethers [LMC5HJ2O [14].
Other practically valuable reaction direction is obtaining ether derivatives of binuclear ferrocenyl and cymantrenyl compounds with interaction of different alcohols of various nature and non-symmetric ethers [LMC5H4COR'].
By this way we determined compositions, structures and some physical and chemical characteristics of new synthesized carbinol (carbinolate) derivatives of ferrocene and cy-mantrene. We studied preparation of nanocom-posite solutions based on ferrocene and cyman-trene derivatives and use of them as neutralizers of exhaust gases for diesel fuels. Results of these studies are listed in Table 2.
Nanocomposite samples prepared by us were tested for antismoke and anti carbon deposit properties of carbinol and amine derivatives for diesel fuels.
Level of smokiness and anti carbon deposit was determined by method [3] which consists of transmission of certain amount of ex-
aroxyalkyl derivatives of ferrocene or cyman-trene have not been described in literature. To produce these compounds we first studied the reaction (4) between magnesium derivatives of ferrocene and acetyl (formyl) ferrocene or formylcymantrene [13]:
(4)
haust gas through filtering material and we found unburned hydrocarbon residue (carbon black) by measuring it. As a result of systematic testing works we found out that during operation of diesel motors more effective was neu-tralizer of exhaust gases if ferrocenyl carbinol derivatives, were used but for bunker fuels manganese-containing both carbinol and car-bonilate metal complexes are more suitable. Consumption of manganese derivatives is lower than ferrocene derivatives for both diesel and bunker fuels. In Table 2 we presented some exploitation parameters of diesel L 0.2-40 and KT-40 bunker fuel after introducing nanocom-posite solutions (NCS), which contain ferrocene and its carbinol and amine derivatives.
As Table 2 shows introduction of 0.0020.006 mol% mass of ferrocene (cymantrene) or their amine derivatives into L 0.2-40 diesel fuels smokiness decreases in the range of 14-17 mas.% but carbon deposition decreases 7-14 mas.% that is 10 times less than alkyl ferro-cenes "SLD", "Lubrizol- 565" and IKhP-706, which opens a new possibility of using these compounds in practice. We developed obtaining method [15] of cyclopentadienyl manganese triple carbinol and additive composition was prepared for motor fuels on the basis of it [16].
Table 2. Effect of composite solutions on operational properties of the fuels
Compound Consumption of NCS Consumption of fuel Smokiness, % Carbon deposit of samples, %
limits mol/l
I. diesel fuel - L 0.2-40 0.854 88-90 28-32
1. (C5H5)2Fe Lower limit 0.002 0,7314 29 14
Upper limit 0.006 0.685 17 10
2. C5H5FeC5H4C(CH3)2OH Lower limit 0.002 0.626 20 11
Upper limit 0.006 0.696 12 8
3. C5H5FeC5H4 -CH2-NH2 Lower limit 0.002 0.608 38 10
Upper limit 0.006 0.644 24 10
4. C5H5FeC5H4-N(CH3)2 Lower limit 0.002 0.618 42 10
Upper limit 0.006 0.602 33 7
II. Bunker fuel KT-40
1. (C5H5)2Fe Lower limit 0.002 74 12
Upper limit 0.006 36 10
2. (OC)3MnC5H5 Lower limit 0.002 25 8
Upper limit 0.006 14 6
This additive composition allows increasing octane number of motor fuels with lower octane numbers 3-4 unit higher. Obtaining method of di-a-methylstyrene alkylation product of ferrocene - ferrocenyl 4-methyl-2,4-di-phenylpentylene was developed and this decreases Fe mass in molecule to 13% and increases its application possibilities [17]. By using cluster MnX2 and CoX2 (X=Cl, Br, J)
heterobinuclear compounds of ferrocene distilled mercaptane was used for dimercap-tanization of motor and diesel fuels [18, 19]. In Figure technological chart of obtaining ferrocene with non-waste technology was presented.
As mentioned above, ferrocene (C5H5)2Fe is a chemical product and is used as a raw material for obtaining it and its different derivatives.
Full description of technological block scheme for obtaining ferrocene
Ferrocene and some of its derivatives are used in chemistry, petrochemistry, defense, fuel energetic complexes as burning catalysts, medical preparations in anemia diseases, as well radio protectors for effective absorption of y-rays, obtaining of additive composite materials and reducers for diesel fuels.
In the work we have developed more advanced method by using a new reaction to obtain ferrocene.
The method is counted on activation of monocyclopentadien with pyridine or any double (triple) amine by giving it yield shape, and then obtaining ¿/s-ira-cyclopentadienyl iron (ferrocene) by interaction of it with FeCl2(Py)2 solvate salt under average polar solvent condition. As a result of this reaction yield of ferrocene depends on several factors [purity degree of an activator, presence of water in FeCl2(Py)2 solvate salt and so on] and it was obtained with 75-90% yield. We have developed non-waste method which provides to obtain it with high purity. Ferrocene shows high soluble ability in hydrocarbon type solvents.
Use of reaction (5) equation allows us to create considerably profitable technology for developing new method of obtaining ferrocene. Reaction (5) can be considered to be double stage reaction.
In the I stage, activation of it occurs by converting to yield intermediate complex with cyclic or aliphatic amines of organic ligand -monocyclopentadiene [C5H5-Py].
In the II stage conversion of FeCl2(Py)2 solvate salt to ferrocene by interacting with [C5H5 Py] yield intermediate complex takes place:
C5H5 + Py ^ [C5H5Py] I stage, (5)
2[C5H5Py]+FeCl2-(Py)2^(C5H5)2Fe+4Py+HCl
II stage.
Pyridine hydrochloride obtained by reaction equation can be returned back to the process by treating it with NaHCO3 and neutralizing up to Py and NaCl.
Study of the reaction (I) showed that the use of calcinated FeCl2 instead of FeCl2(Py)2 solvate salt for reaction significantly effects on purposeful product yield. During this reaction
FeCl2 is very sensitive to water and during synthesis compound with iron-carbon (Fe-C) chemical bond is hydrolyzed by water molecules. In the work by using reaction (5) we determined and studied the main factors which influence on the yield of product - ferrocene. Many methods for obtaining ferrocene and its compounds have a preparative significance for fire safety or availability of initial reagents. Thus, among of the main and necessary conditions of technological significance for synthesis of ferrocene are prevention of atmospheric injection of harmful impurities, recycling of auxiliary chemical reagents and compounds, possibility of using them in other chemical processes after relevant formations [20]. This is possible only by using exchange reactions, as a result of which neutral safe chemical compounds are formed. Interaction of non-aqueous iron dihalo-genide with cyclopentadienate of alkali metals (Li, Na, K) can be related to such reactions and this leads to formation of ferrocene and relevant neutral halogenides of these metals [21].
The other synthesis method of ferrocene is based on the reaction between FeO and C5H6 at 5000C. Obtained ferrocene and water do not cause ecological problem. However, when using other industrial synthesis methods of ferrocene due to polycondensation and other conversions of cyclopentadiene together with basic product, a number of by-products appear which require additional resources for their utilization [22, 23].
In one-step synthesis of ferrocene one of the important experimental tasks is selection of such reaction conditions in which hydrogen chloride released in interaction of FeCl2 and cyclopentadiene will be neutralized, and the re-acti on wi ll proceed towards formation of ferrocene. With this aim for investigation we selected the reaction between non-aqueous iron di-chloride and cyclopentadiene activated with pyridine at absolute isopropanol.
It must be stated that cyclopentadiene by itself as a weak CH-acid (pKa 15.5) in reaction with FeCl2 does not allow to produce ferrocene. According to [24] for realization of this reaction cyclopentadiene should have pKa 22.
For obtaining of ferrocene by reaction (5) we studied activation of cyclopentadiene with several amines. In literature there are data on interaction of cyclopentadiene with amines like (CH3)3N, C6H5CH2NH2, C6H5NH2, which leads to formation of intermediate active bipolar im-ide complex [22]. According to [23] chemical stability of formed cyclopentadienyl anions depends on electron-acceptance of substituents in nitrogen atom and decreases in the row: C6H5NH2 > C6H5CH2NH2 > (CHb)bN. By using this poperty of substituted amines we studied activation of cyclopentadiene with amines of industrial production. With this aim we used
diethylamine, triethylamine, methylamine, di-methylaniline and pyridine.
Studying spectra of NMR 1H mixture of pyridinecyclopentadiene showed only presence of two signals relating to protons of pyridine-cyclopentadienyl complex. One of them is in strong field and has chemical shift 0.75 m.d., but signal of protons of cyclopentadienyl anion is in weak field (5 16.57 m.d.).
It was established that at equimolar ratio of reagents with FeCl2 in isopropanol at 200C after 2 hours of mixing with reaction products for dimethylaniline is ferrocene (22-26%)
A+
^NH-
>
H
+I
N» ••
CH3
CH3
The higher activating property of pyridine comparing to other aromatic amines is related to its structural feature, thus in aromatic ring nitrogen atom shows high basicity and forms firmer intermediate complex with cyclopentadiene than other amines.
From the other point, abovementioned experimental data confirm assumption that in exothermal reaction conditions (5) more stable imide complex easily dissociates to initial compounds and cyclopentadiene is converted to di-
mer, trimer and polymer forms, and complicates separation of ferrocene from reaction mixture. That's why pyridine is more effective activator of cyclopentadiene.
Obtained intermediate imide complex with pyridine was used for synthesis of ferrocene by interaction of solvated isopropanol with non-aqueous iron dichloride in absolute isopropanol at 30-400C. After processing reaction mixture yield of pure ferrocene was more than 70%:
FeCl2(7-C3H7OH)2 + 2[C5H5NHC5H5]
7-C3H7OH
» (C5H5)2Fe + 2[C5H5N HCl].
(6)
Release of ferrocene from reaction mixture was conducted by extraction method. As a reagent we used light fraction of gasoline №oil.= 40-700C).
For monomethylaniline the yield of ferrocene reaches 37-43%, reaction mixture con-taines 10-15% cyclopentadiene dimer. When using pyridine intermediate complex the yield of ferrocene exceeds 70%.
Thus, according to obtained data on complexation ability of cyclopentadiene with studied amines we established decrease of activity depending on nature of organic radical.
It was found out that after extraction of product, the residue contains pyridine hydro-
chloride C5H5NHCl, small amount of ferrocene, isopropyl alcohol, 1.2% pyridine and other non-identified compounds [25].
Neutralization of pyridine hydrochloride, its purification and recycling as an activatior of cyclopentadiene in reaction (1) are of great interest. With this aim we selected a neutralizer which allows us to conduct this reaction more selectively. As a neutralizer the most traditional and economically useful reagent - NaOH can be used. However, using NaOH as a neutralizer for destruction of C5H5NHCl turned to be impossible, since in the reaction (1) interaction both with C5H5N HCl and mixtures of i-C3H7OH, (C5H5)2Fe and others which compli-
cates further purification of C5H5N. That's why for neutralization we used i-C3H7ONa (2). This helped to return neutralizer in the form of i-C3H7OH to the reaction, secondly, excluded the
possibility of decomposition of the rest ferrocene and other compounds. As a result of reaction (6) only NaCl exists as a by-product:
C5H5NHCI + 2/-C3H7ONa А
2C5H5N + 2i-C3H7OH + 2NaCl].
(7)
Thus, we studied the reaction between non-aqueous iron dichloride in the form of solvated salt FeCl2^( i-C3H7OH)2 and cyclopen-tadiene, activated with pyridine in absolute iso-propanol and showed possibility of producing ferrocene with high yield. It was established that ferrocene is easily separated from pyridine hydrochloride and after neutralization of the latter with sodium isopropylate, pyridine can be recycled as an activator of cyclopentadiene and allows to obtain ferrocene with ecologically pure and non-waste method.
Temperature factor. According to results of study when carrying out the reaction (5) in the range of -5- +500C it was found that -5-+100C temperature interval influences positively on the reaction, but +20- +500C temperature interval influences negatively on the reaction and yield of the product was more than 15-20%.
Nature of activator factor. Selection of an activator and optimum condition for reaction (5) is very important. Being as weak C-H carbonic acid C5H5 molecule conforms to pKa=10-11 acidic unit and enters to exchange reaction with FeCl2 and by separating HCl turns reaction equilibrium to the right. To obtain (C5H5)2Fe the pyridine activator which increases acidic unit of C5H6 up to pKa=22-23 unit is considered to be more expedient. Relative to aliphatic amines cyclic amines C5H5 cyclic amines are more effective activators.
Water factor. During obtaining ferrocene with reaction (1) presence of water in the system does not allow us to produce the product by hydrolizing Fe-C (carbon-iron) chemical bond.
On the other hand, to obtain ferrocene from reaction mixture with high purity and non-waste method we obtained biscyclopentadienyl iron with 80-87% yield and 98.2% purity by using liquid phase extraction method. According to results of elemental analysis C10H10Fe conforms to Brutto formula.
Treatment of ammonium salt A obtained
by reaction (6) with natrium isopropilat (i-C3H7ONa) leads to the formation of i-C3H7OH, C5H5N and NaCl, with it is possible to recyrcu-late in the process of synthesis of ferrocene, creation the wastless technology of its obtaining.
The method which operates with ecologically more profitable technological curcuit is proposed by reaction (5).
As a result of interaction of bispyridine iron chloride with monocyclopentadiene activated with cyclic and aliphatic amines we have developed the method which can obtain ferrocene with high yield. To obtain it from reaction mixture with high purity and non-waste method we used the liquid phase extraction method.
References
1. Захарова Э.Л. Автотранспорт и окружающая среда. М.: Автотранспорт, 2001. 212 с.
2. Гуреев А.А. Квалификационные методы испытаний нефтяных топлив. М.: Химия, 2004. 380 с.
3. Присадки для улучшения экологических свойств моторных и дизельных топлив / Под ред. А.А.Гуреева М.: Химия, 2001. 427 с.
4. Ковтун Г.А., Талисман Е.А., Горбунов Г.В. Экологические проблемы дизельных топлив // Нефтепереработка и нефтехимия. 1991. № 68. С. 16-20.
5. Данилов А.М. Присадки к топливам // Химия и технология топлив и масел. 1992. № 5. С. 34-40.
6. Колобова Н.Э., Валуева З.П., Анисимов К.Н., Сулейманов Г.З. О некоторых свойствах ли-тийциклопентадиенилтрикарбoнила марганца и литийциклопентадиенилтрикарбонила рения в тетрагидрофуране // Изв. АН СССР. Сер. Хим. 1978. № 4. С. 730-732.
7. Несмеянов А.Н., Марданов М.А., Кулиев К.Г. Противодымные присадки к дизельному топливу //Химия и технология топлив и масел. 1975. № 3. С. 40-42.
8. Сулейманов Г.З., Мудунов А.Г., Мамедов Е.Ш., Литвишков Ю.Н., Алиев А.М. Алкили-рование ферроцена продуктами пиролиза нафтабензинов в присутствии алтивированных некоторыми эфирами каталитических систем Al-CCl4 // Химия и хим. технол. 2005. Т. 48. № 12. С. 85-88.
9. Рустамов М.И., Аскеров Г.Р., Мамедов Е.Ш., Сулейманов Г.З. Особенности и антидетонационная эффектинвость композиций, приготов-
ленных на основе моно- и диалкильных производных ферроцена и цимантрена //Химия и хим. технол. 2005. Т. 48. №.12. С.73-76.
10. Ра! Az.R. № 0288. Способ получения антидетонационной присадки / Рустамов М.И., Су-лейманов Г.З., Бабаев А.И., Абдуллаев Р.И., Мамедов Д.Н., Мамедов Е.Ш. 2005.
11. Сулейманов Г.З., Мамедов Е.Ш., Рустамов А.И., Бабаев А.И., Курбанов З.Г. Экологически чистые антидетонационные топливные композиции, приготовленные на основе окси-алкильных производных ферроцена, и их растворимость в различных марках бензинов и их компонентах //Химия и хим. технол. 2007. Т. 50. № 5. С. 82-87.
12. Lenchevsky V.V., Pinayev A.S., Ratenale for no z zle splasli plate choninge trays in chemical and petrochemical production reactor //J. Oil Refinig and Petro Chemistry. 2005. № 6. P. 1217-1223.
13. Süleymanov G.Z., Litviçkov Yu.N., Qadirova E.M. Ferrosenin fazalararasi kataliz çaraitinda yeni karbinol toramalarinin sintezi va xassalarinin tad-qiqi. Azarb. kimya jurnali. 2006. № 1. S. 37-42.
14. Pat. AzR. № Í 00139. Motor yanacaqlari ûçûn an-tidetonasion kompozisiya //Rüstamov A.Í., Süleymanov G.Z., Babayev Э.1, Haciyev O.M., Abdul-layev R.Í., Mammadov D.N., Litviçkov Y.N. 2007.
15. Pat. AzR. i 0079. Manqan metal-üzvi birlaçma asasin-da antidetonator kompozisiyasi // Süleymanov G.Z., Babazada Н.Э., Yaqubov E.A., Hüceynov !Э. 2002.
16. Pat. AzR. i 0105. Monoalkilferrosen-4-metil-, 2,4-dife-nilpentilferrosenin birmarhalali alinma üsulu // Sü-leymanov G.Z., Эsgarov Q.R., §ahtaxtinski T.N., Quli-yev A.M., Litvishkov Y.N., Muradxanov R.M. 2004.
17. Pat. AzR. i 0154. Kükürdlü neft mahsullarinin elementar kükürda qadar katalitik demerkaptanizasi-
yasi üsulu // Süleymanov G.Z., Quibanov Z.H., Quli-yev A.§., Litvi§kov Y.N., Muradxanov R.M. 2007.
18. Сулейманов Г.З., Алиев А.М., Аскеров Г.Р., Кулиев А.С., Курбанов З.Г., Рустамова А.И. Исследование процесса демеркаптанизации до элементарной серы некоторых нефтепродуктов с помощью каталитической системы (Mn-Fe)- и (Ее-Со)-безводный клиноптилолит // Хим. пром-сть. 2008. № 8. С. 16-20.
19. Peter Sternicka T. Ferrocens. //John Willey -Sons Ltd, Weri PO19 8 SQ England, 2008. 785 p.
20. Перевалова Э.Г., Решетова М.Д., Гранберг К.И. Метод элементоорганической химии. Же-лезоорганические соединения. Ферроцен. М.: Наука, 1983. 544 с.
21. Johnson J.C. Metallocene Technology (Chemical Technology Review). New Jersey: Noyes Data Corp., 1973. No 11. P. 222.
22. Курбанов З.Г. Исследование реакции дихлор-ида железа с циклопентадиеном, активированным пиридином в абсолютированном изопро-паноле //Журн. общ. химии. 2011. Т. 81. №. 9. С. 1425-1427.
23. Cookson R.C., Hudes J., Whitear B.R.D. Проблемы дизельных топлив // Proc. Chem. Soc. 1961. No 1. P. 117-122.
24. Шекилиев Ф.И., Курбанов З.Г., Рустамова А.И., Мамедов Э.Ш., Сулейманов Г.З., Абду-лазимова Е.А. iki valentli damir, manqan va kobaltin metalüzvi birla§masinin ekstraksiya üsulu ila ayrilmasi prosesinin tadqiqi // Докл. НАН Азербайджана. 2006. № 5-6. С. 72-76.
25. Pat. AzR. 0098. Ferrosenin tullantisiz texnologiya ila alinmasi üsulu va qurgusu /Süleymanov G.Z., Tagiyev D.B., Hüseynova T.H., Kalbaliyev Q.i., Muradxanov R.M. 2015.
FERROSEN VO SiMANTREN TORKiBLi NANOKOMPOZiSiYA MOHLULLARI. ONLARIN ALINMASI VO DiZEL YANACAQLARI U£UN i§LONMi§ QAZLARIN NEYTRALLA§DIRICISI KiMi iSTiFADOSi
iMKANLARI
G.Z.Suleymanov, Z.Q.Qurbanov, R.M.Muradxanov, A.R.Rzayeva
I§da ferrosenin yeni alkil, oksialkil, karbinol (karbinolat), klaster va iki nuvali toramalarinin va simantrenin karbinol va karbinolat toramalarinin sintezi taqiq olunmu§dur. Dizel yanacaqlari ugun i§lanmi§ qazlarin neytralla§dirilmasi kimi istifada olunan nanokompozisiya mahlullarinin alinmasi tadqiqatinin naticalari verilmi§dir Ferrosenin (simantrenin) va onun bazi toramalarinin tullantisiz alinma texnologiyasinin aspektlari da 6yranilmi§dir.
Agar sozlar: nanokompozisiya mahsullari, ferrosenin (simantrenin) karbinol, karbinolat toramalari, antidetonasiya neytraUa§dinci, motor va dizel yanacaqlari ugun i§hnmi§ qazlari.
ФЕРРОЦЕН- И ЦИМАНТРЕНСОДЕРЖАЩИЕ НАНОКОМПОЗИЦИОННЫЕ РАСТВОРЫ. ПРИГОТОВЛЕНИЕ И ВОЗМОЖНОСТЬ ИСПОЛЬЗОВАНИЯ ИХ В КАЧЕСТВЕ НЕЙТРАЛИЗАТОРОВ
ВЫХЛОПНЫХ ГАЗОВ ДЛЯ ДИЗЕЛЬНЫХ ТОПЛИВ
Г.З.Сулейманов, З.Г.Курбанов, Р.М.Мурадханов, A-Р.Рзаева
Рассмотрены в основном вопросы синтеза новых алкильных, оксиалкильных, карбинольных (карбинолятных) кластерных и биядерных производных ферроцена, карбинольных и карбинолятных производных цимантрена. Приведены данные по приготовлению нанокомпозиционных растворов, используемых в качестве нейтрализаторов выхлопных газов для дизельных топлив. Рассмотрены также некоторые аспекты безотходной технологии получения ферроцена (цимантрена) и некоторых их производных.
Ключевые слова: нанокомпозиционные растворы, карбинольные, карбинолятные производные ферроцена (цимантрена), анидетонация, нейтрализаторы, выхлопные газы моторных и дизельных топлив.
