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6RESEARCH AND APPLICATION OF MODIFIED HALLOIZITES IN ALKYLATION PROCESS
Huseynova G., Aliyeva N., Muxtarova G., Rashidova S., Gasimova G.
Institute of Petrochemical Processes Named after Acad. Y.H. Mamedaliyev of Azerbaijan National Academy of Sciences
ABSTRACT
The thermal properties of the halloizite sample were investigated using thermography method (TQ/DTQ/DTA). Based on the obtained curves, the change in the mass of samples of halloizites, not modified and modified with Al+CCU, depending on temperature, the amount of residue and heat expended, were determined. The study of X-ray curves shows that the intense maxima in the spectrum belong to the sample of halloizite Al2Si2(OH)5.
Al+CCl4 muhitinda modifikasiya olunmu§ halloizidda turbin yag fraksiyasinin katalitik krekinq qazlan ila alkilla§ma prosesi 30, 50 va 80°C temperaturda aparilib.The alkylation of the turbine oil fraction on the Al+CCl4+halloizite catalyst was carried out with catalytic cracking gases with an olefin content of 43.47%. It is shown that the alkylation of the oil fraction on modified halloizite at a temperature of 50oC allowed to increase the viscosity index from 32 to 84. The resalting alkylate with an additive composition can be successfully used for the lubrication of machines and mechanisms.
Keywords: Halloizite, modified Al+CCl4 halloizite, TQ/DTQ/DTA, X-ray, turbin oil fractions, alkylation, catalytic cracking gases, viscosity index.
Natural halloizites can serve as a basis for obtaining catalytic systems for various processes, including alkylation. In its natural form, halloizites do not have a pronounced catalytic activity in the processes of alkyl-ation of oil fractions with catalytic cracking gases. However, imparting acidic properties to them by treatment with the Al + CCl4 system increases their catalytic activity.
Base oils from Azerbaijani oils differ in their viscosity and temperature properties (with a low viscosity index). Therefore, the production of high-viscosity (OI) oils with low freezing point from Azerbaijani oils is possible only by changing the structure of hydrocarbons. The main direction that improves the quality of base oils is the development of chemical processes that convert their paraffin, naphthenic and aromatic hydrocarbons into isoparaffin and naphthenic hydrocarbons.
Purposeful impact on the conversion of oil fractions into hydrocarbons for the production of high-viscosity-temperature products is one of the key issues in the oil refining industry. Therefore, the creation of technology for the production of environmentally friendly, high-index oils using raw materials in our country is one of the urgent issues. The application of catalytic cracking propane-propylene (PPF) and butane-butylene (BBF) fractions in the production of quality oils is one of the promising areas for the use of these fractions.
It is known that one of the main components of oil fractions is naphthenic hydrocarbons. Naphthene, aromatic hydrocarbons and their alkyl derivatives play a key role in the formation of viscosity properties, as they do not contain large amounts of normal and isolated paraffin hydrocarbons. Polycyclic naphthenic, aromatic and naphthenic-aromatic hydrocarbons degrade the viscosity of oil fractions. Increasing the length and number
of side chains in aromatic hydrocarbons not only improves the viscosity-temperature properties, but also increases the viscosity.
Enrichment of oil fractions with isoparaffin hydrocarbons improves their rheological properties, evaporation, thermostability and other performance. Since paraffin, naphthene, and aromatic hydrocarbons in petroleum oils change during alkylation, it is interesting to study how these hydrocarbons change during alkylation in zeolite-type catalysts.
HAL 100 catalysts from group VIII metals (Pt, Pd, Ni) were introduced using the AlCVA^Os system [1]. Alkylation of iso-butane with olefins results in the formation of highly branched paraffin hydrocarbons with good antidetonization properties. The alkylation reaction of isobutane with olefins has been studied in zeolite-containing catalysts under extreme conditions. It was found that extreme conditions ensure long-term operation of the catalyst [2].
Niobium pentachloride or toluene on silicagel or aluminia has been found to be an active catalyst in alkylation with hexane- 1 [3]. Mono- and dihexyl derivatives of benzene and toluene were obtained.
Previously, the alkylation process of the distillate fraction of turbine T -22 oil was studied on catalysts Seokar 600 and Omnikat 210 P. The alkylation process was carried out in a periodic unit in a 250 ml reactor [46]. Gas supply is carried out in the presence of a reciprocating fluid pump, which allows you to adjust the ratio of gas consumption to oil fraction. The alkylation process was carried out in the range of 50 -150 ° C, the pressure in the reactor is 0.4- 0.7 MPa, the pressure of the supplied gas is 0.25- 0.70 MPa, the volume ratio of oil fractions to compressed liquid gases is 1: 1, 1: 2 and 1: 3.
The main physical and chemical properties and structural parameters of the products obtained from the
alkylation of turbine oil distillate fractions with zeolite catalysts Seokar 600 and Omnikat 210P with liquid gases of catalytic cracking were determined by IR, NMR and UV spectroscopy [7, 8].
Alkyllation was carried out on Seokar 600 and Omnikat 210P catalysts, which provide the maximum viscosity index of the oil fraction from 32 to 80 and 61 under optimal conditions. It has been shown that the kinematic viscosity and viscosity index of fat fractions increase during the alkylation process. This is due to the combination of catalytic cracking gases propylene, bu-tylene-olefin hydrocarbons in the side chain of aromatic hydrocarbons, the elongation of the side chain of aromatic hydrocarbons and the increase of alkyl sub-stituents.
Recently, catalysts ZSM-5, ZSM-11, MCM-22, MCM-49 containing 60% to 80% zeolite are widely used [9,10]. Zeolite catalysts contain Al2O3, SiO2 or amorphous aluminosilicate and modified compounds as a binding component.
The study of the process of alkylation of oil fractions in zeolite catalysts showed that a high increase in the viscosity index occurs in the presence of the maximum amount of olefin hydrocarbons in the catalytic cracking gases and their maximum conversion. In this case, the catalyst also plays a key role. In this case, the increase in the side alkyl chain with the combination of substitutes with alkyl naphthenes and alkylaromatic hydrocarbons further increases the viscosity index.
The formation time of the catalyst is 7 to 10 hours. However, the addition of 0.2 to 0.4% when preparing a new part of the catalyst reduces the recovery time of the previous catalyst (as an initiator) to 2 hours. The catalyst of the alkylation process is based on Al metal, CCl4 and halloizite. The catalysts were synthesized at 76.7 ° C according to the boiling point of CCl4 and the mass ratio of components Al: CCl4 - 1: 60^80. At the end of the reaction, add halloizite and mix for 3 hours. Then store the catalyst in a hermetically sealed container under the CCl4 layer.
To use the modified halloizite in the alkylation process, we first discharge CCl4, draw a mixture of hal-loizite and catalyst crystals, and add the required amount to the autoclave. The thermal properties of hal-loizite used to obtain catalysts were studied and X-ray phase analysis was performed.
The thermal properties of the halloizite sample were investigated using the room temperature thermog-raphy method (TQ/DTQ/DTA). Analysis in «STA 449F3» Jupiter thermoanalyst (owned by NETZSCH, Germany) in an inert gas (nitrogen medium) at room temperature up to 900 ° C at 10K/ min. was carried out with a rapid rise. Based on the resulting thermographic curves (thermograms), it is possible to determine the mass variability in the sample, the residue of the sample and the amount of heat consumed in this process (Figure 1).
Figure 1- The thermal properties of a halloizite
The obtained thermo grams allow to determine the picture of desorption of surface water and hydroxyls from the surface depending on the composition and temperature of the sample. According to the TQ/DTQ thermogram, the total mass loss of the halloizite sample is determined to be 10.81%, and the residue is 89.19%. The sample was resistant to ~ 450°C according to the TQ/ DTQ thermogram, with a mass loss of ~ 13% at low temperatures in the range of 59.2-124.2°C with a maximum of 90.2°C and poor contact with the surface. Physically adsorbed water molecules consist of hy-droxyl groups desorbed in the range of 124-400°C, 1.51% corresponding to a maximum of ~ 300-310°C.
In process IV, the main mass loss of halloizite, corresponding to a maximum of 511.7°C, occurs in the range from 454.2°C to 552.1°C. Mass loss in this interval was in two stages, 3.60% and 4.56%. Mass loss at temperatures from 552.1°C to 800.2°C is 2.44%.
According to the DTA curve, mass loss is an en-dothermic process, and the amount of heat dissipated for the main mass loss is 41.41 mcBc/mg at a maximum of 517.3 ° C in the range of 457.2- 607.2 ° C.
Figure 2 shows a diffractogram of X-ray phase analysis of a halloizite sample.
The X-ray was taken on a X- ray TD-3500 (made in China) diffractometer at room temperature in an angle range of 5 to 90 ° using a CuKa (a = 1.54184 A °) beam source and a Ni filter. The study of X-ray curves shows that the intense maxima in the spectrum belong to the sample of halloizite AbSi2(OH)5.
The thermal properties of the modified halloizite are shown in Figure 3. The thermal properties of modified halloizides differ from non-modified halloisides (Figures 1 and 3). The Al+CCl4 system of the modified halloizite marks the peaks of exo- and endo- processes occurring under the influence of temperature.
The initial mass loss of the catalyst sample is 97.3°C and 18.36% at 144.2°C. With a maximum of 144.2°C, the main mass loss of halloizite occurs in the range of 97.2°C to 162.4°C and 162.8°C to 198.1°C. Mass loss in this interval was in two stages, 1.80% and 2.45%.
According to the TQ/DTQ thermogram, 47.82% of the total mass loss of the halloizite+Al+CCU sample (temperature 600°C). The residual mass of the sample is 29.75% at 898.2°C.
[lab 1Б -N 1-hallozit 21.06.mdil 5lit 1 C0deq&1.CCdeq&C.2Cmm Monochromator OFF Theta-Theta
Figure 2 - X-ray phase diffractogram of a halloizite sample
Temperature /
Figure 3 - Thermal properties of Halloizite+Al+CCl4 sample
The process of alkylation of the distillate fraction of turbine oil with compressed gases obtained from catalytic cracking was carried out under the following conditions:__
Temperature, °C 30, 50, 80
Gas supply temperature, Mpa 0,5-0,6
Catalyst filling, q 5
Avtoclave filling time with catalytic cracking gases, minutes 30
Reaction time, hour 1
Physicochemical properties of distillate fractions of petroleum oils are given in Table 1.
Table 1
Quality indicators of distillate fractions of petroleum oils
Indicators Distillate T-22 turbine oil
Kinematik viscosity, mm2/s:
40°C 27,82
50°C 21,04
100°C 4,38
Viscosity index 32
Ignition temperature in open tigel, °C 194
Freezing temperature, °C - 40
Pickle number, mq KOH/1 q 2,97
Density at 20 oC, kq/m3 898,4
The composition of the primary catalytic cracking gases is given in Table 2.
The properties of alkylates obtained from the process of alkylation with catalytic cracking gases containing 43.47% olefins in the turbine oil distillate fraction are given in Table 3. As can be seen from Table 3, the
The properties of alkylates obtained from the process of alkylation with catalytic cracking gases containing 43.47% olefins in the turbine oil distillate fraction are given in Table 3. As can be seen from Table 3, the highest viscosity index (84) is achieved when alkylation is carried out at 50°C. Kinematic viscosities also have a maximum value at this temperature. As the temperature increases to 80°C, the kinematic viscosity and
highest viscosity index (84) is achieved when alkylation is carried out at 50°C. Kinematic viscosities also have a maximum value at this temperature. As the temperature increases to 80°C, the kinematic viscosity and viscosity index of the alkylate decreases. It was found that the viscosity of alkylates is significantly higher at all alkylation temperatures than the viscosity of the primary turbine oil fraction.
Table 2
viscosity index of the alkylate decreases. It was found that the viscosity of alkylates is significantly higher at all alkylation temperatures than the viscosity of the primary turbine oil fraction.
Thus, the catalytic system of the modified hal-loizite increases the catalytic activity of Al+CCl4 hal-loizite. In this case, the increase in the kinematic viscosity and viscosity index of alkylates is observed.
Composition of primary gases
Hydrocarbons Gas composition,% by volume
Ethylene-ethane 0,71
Propylene 17,58
Propane 16,85
Iso-butane 28,80
Butene-1 13,27
N-butane 9,91
Trans-butene-2 7,38
Sys-butene-2 5,12
3-methilbutene-1 0,07
Iso-pentane 0,26
2-methilbutene-1 0,04
Penten-1 0,01
Table 3
Alkylation conditions and physical and chemical properties of alkylates obtained under these conditions
T, °C P, MPa Physical -chemical properties
p420, kq/m3 n20 ' D Kinematic viscosity, mm2/s Viscosity indeks
40°C 100°C
Turbine oil distillate fraction 898,4 1,4926 27,82 4,38 32
30 0,5-0,6 890,0 1,4894 37,36 5,34 65
50 0,5-0,6 893,9 1,4904 40,70 5,95 84,4
80 0,5-0,6 895,3 1,4914 30,03 4,75 56
Thus, the catalytic system of the modified hal-loizite increases the catalytic activity of Al+CCU hal-loizite. In this case, the increase in the kinematic viscosity and viscosity index of alkylates is observed
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