Toshmatov Davlatjon Abduraufovich, junior researcher, doctoral student of the Laboratory of Chemical Technology of Institute of general and inorganic chemistry of Uzbekistan Academy of sciences E-mail: [email protected] Yusupov Farhod Maxkamovich, doctor of technical science Head of the Laboratory of Chemical Technology of Institute of general and inorganic chemistry of Uzbekistan Academy of sciences E-mail: [email protected] Baymatova Gulnoza Achedovna, junior researcher of the Laboratory of Chemical Technology of Institute of general and inorganic chemistry of Uzbekistan
Academy of sciences E-mail: [email protected]
PROCESSING OF OIL SLUDGE FOR THE CONSTRUCTION OF INTERFIELD ROADS
Abstract: As a secondary raw material for the first time, commercial sludge is widely analyzed to determine its group composition and physicochemical properties. Oil sludge contains many high-molecular derivatives of oils, such as condensed aromatic and naphthenic, asphaltene, resinous hydrocarbons. At the same time, a technology has been proposed for processing field sludge into oil-mineralized binders, by oxidizing them with atmospheric oxygen in moderate conditions. We have developed a technological scheme of a model installation for the production of oil-mineralized binders. The novelty of this development is that for the first time it has been proposed to obtain oil-mineralized binders and a technological scheme that works according to the method of converting sludge into a selective product - an oxidized binder for use in interfield road construction.
Keywords: oil, industrial sludge, oil-mineralized binder, asphaltenes, hydrocarbons.
Oil-mineral binders are obtained from the bituminous oil leum-mineral binders are based on the oxidative oligomeriza-residue, tar and heavy oils by the oxidative condensation of tion reaction of heavy fractions of petroleum hydrocarbons. their hydrocarbons. The process takes place with a moderate One of the ways to obtain oil-mineralized binders from
supply of air heated at 280-320 °C and a reaction time of 6-8 oil sludge is a method of obtaining from oil-water emulsions hours [1]. In the Republic, there is a problem of shortage of (prototype) used for the manufacture of road surfaces [2]. raw materials for asphalt bitumen production due to the deep For the first time we use commercial oil sludge as a raw
processing of crude oil. Therefore, this problem is relevant and material for its transformation into oil-mineralized binder. is of great practical importance. Methods for producing petro- Table 1 gives their group composition and Table 2 shows
its fuel fractions.
Table 1.- Group composition of sludge
Name of group hydrocarbon composition Varieties of sludge,%
Ground Fishing
High molecular weight paraffin 42-50 25-40
Condensed aromatic 8-10 20-25
Naphthenic aromatic 15-17 15-17
Asphaltene-resinous 13-15 30-35
Table 2.- Characteristic of fuel fractions of commercial sludge (primary pursuit direct steam)
The name of indicators Types of motor straps
Heavy gasoline Kerosene Diesel fuel
Fraction temperature, °C 120-200 220-260 220-340
Specific gravity, df, g/sm3 0.740 0.810 0.835
Refractive index, nD° 1.4285 1.4420 1.4655
Condition - liquid: Yellow-mobile Red-mobile Slightly brown oil
The essence of the proposed method of obtaining bituminous mineral binder from oil sludge consists of:
- rationing them for humidity and mechanical impurities;
- high-speed catalytic oxidation of oil sludge with intensive contact with oxygen in a mobile unit is quite mild
(280-320 °C and 6-8 hours) of the reaction;
- taring after normalization of the properties of the resulting oil-mineralized binder [3].
The proposed method differs from the known (prototype) methods for producing mineralized binder by the following qualities:
- significantly reduced the cost of the method of development, because the process is localized and it can be used in the fields;
Table 3.- Characteristics of hydroi
- reduced cost of oil-mineralized binder;
- the volume of output increases due to the introduction of a new raw material volume - oil sludge into the raw material base for the production of oil-mineralized binder.
The composition and properties of commercial sludge, which contain up to 10-12% of higher paraffins, 25-30% of condensed naphthenes, up to 40% of condensed aromatic hydrocarbons, up to 10% of higher oily fractions, up to 15% of asphaltenes and up to 5% of petroleum resins, have been established.
From the dried tank oil sludge by thermal method, 14% were detected and hydrocarbon fractions with a boiling point up to 360 0C, which are dark brown liquids with a specific odor, were investigated.
bon fuel recovered from oil sludge
Indicators of fuel fraction of oil sludge The output of the fraction by distillation,% Specific weight, kg/m3 Refractive index, n2° d Hydrocarbons, C/H,% Cetane number
Indicators Kerosene fraction T. n.k, oC: 190 4.2 824 1.4526 88/12
210 9.1 845 1.4605 90/10 56.4
230 33.2 868 1.4655 90.5/9.5 57.0
250 52.5 872 1.4682 90.8/9.2 56.9
258 66.8 - - - -
Indicators Diesel fraction T. n.k, oC: 250 70.4 880 1.4825 90/10 54.0
280 84.6 892 1.4950 91/9.0 53.5
310 98.1 905 1.4995 91.2/8.8 52.7
340 95.3 922 - - -
T. n.k, 360 97.8 - - 91.4/8.6 -
As can be seen from the table, the light fraction of the tank sludge consists mainly of kerosene and diesel fuel [4].
On a gas chromatograph mass spectrophotometer HP GC/MS6890/5973. Under the following conditions: Column - HP 5% Phenyl Methyl Siloxane 30m x 0.25^m x 250 mm
Capillary. Injection: 2 ^k. Oven: from 70 oC to 260 oC, 150 oC /min. Mobile phase: Not (helium). Detector: a mass selective detector with a turbo pump. Computer base: laid 250 thousand known individual spectra on willey 275 L. Used to compare the obtained spectrum and its decryption.
Figure 5. Chromatogram of sludge fuel fraction
According to the chromatogram, fractions of reservoir oil sludge in light fractions were detected in the fuel fraction of the tank sludge; their fractions are in%: heptane - 1.04, cyclopropane 2.05, dimethylhexane - 0.9, nonane - 1.69, decane 3.15, cycloheptatriene - 1.86, dimethyloctane - 2.41, undec-ane - 3.69, dimethylbenzene - 3.05, methyldecane - 1.73, ge-neicosane - 3.55, dodecane - 14.62, methylundecane - 11.31, tridecane - 48.60. The sum of the detected components is 99.99%. Thus, according to this method, highly efficient processing and utilization of commercial sludge is achieved and bitumen-mineral binder with quality indicators used to cover asphalt concrete roads is obtained [4].
Examples of the method for preparing mineral bonding from the industrial petroleum
Example 1. 1500 ml of oil sludge is loaded into the reactor of the laboratory installation and it is heated to 2600 0C with a spiral electric heater. When the temperature limit is reached, the oil sludge is continuously drip-forcibly fed by an oxidizing agent heated by up to 2800 oC - with oxygenation of air by bubbling (air consumption 15 l/min) for 35 hours. In the continuous reactor, the reaction of oxidative condensation proceeds relatively high molecular weight compounds of industrial sludge. The end of the reaction of oxidative conden-
sation of oil sludge hydrocarbons in its pento-octomers with a molecular weight of 3000-4500 g/mol is an indicator of the limit of volume saturation, when equilibrium is observed between the volume of incoming air and its blocking volumes from the reactor. At the same time, oil-mineralized binder continuously flows from the bottom of the reactor.
Indicators obtained petroleum mineralized binder:
- specific weight is 1135 kg/m3;
- softening temperature 520 oC;
- dropping point 720 oC;
- viscosity VZ-4, 800 oC 64 sec.;
- mol. mass 4300 g/mol
- needle penetration in 10 mm 540 oC
Example 2. In similar conditions of loading of industrial sludge into the reactor, oxidative condensation is carried out at a different reaction temperature of280 oC. 6-8 h. The result is a bitumen mineral binder with the following indicators:
- specific weight 1155 kg/m3
- softening temperature 54 oC
- dropping point 80 oC
- viscosity according to VZ-4 at 80 oC 70 sec.
- penetration (10 mm needle) 55 oC
- mol. mass 4900 g/mol
Example 3. In the above conditions of loading in the reactor sludge after separation of the fuel fraction, the reaction of oxidative condensation of its dodicomer and above. The reaction is carried out at a temperature of 3000 oC and 45 hours with an air flow rate of 2 l/min. The result is a viscous mass of dark color - oil-mineralized binder with the following indicators of properties:
- specific weight 1170 kg/m3
- softening temperature 58 oC
- dropping point 86 oC
- viscosity according to VZ-4 at 80 oC 75 sec.
- penetration (10 mm needle) 56 oC
- mol. mass 5200 g/mol.
From this it can be seen that for the samples taken, the oil-mineralized binder is obtained with the corresponding indicators that meet the requirements of road construction:
- a method of obtaining oil-mineralized binder from the oil sludge by oxidizing the oil sludge with air oxygen at T = 280oC for 8 hours. At an oxidizer consumption of 1500 m3/t;
- oil-mineralized binder from commercial oil sludge is not inferior in its operational properties to well-known analogues:
- softening temperature 52-56 oC;
- penetration, mm 24-25 oC;
- dropping of75-80 oC;
- (indicators are defined by standard ISO methods).
Thus, for the first time, a method of producing a cheaper
mineralized mineral mixture - a sandy oxidized binder from commercial sludge (up to 10-12%), sandy - oil sludge impregnation (20-30%), a mineral mixture (25-30%), crushed stone (20-30%) and cement (up to 10%). Here, sludge with its natural bitumen (oxidized asphaltenes and resinous compounds) is represented as a binder of mineral additives in sand concrete.
References:
1. Pat. 2171700 of the Russian Federation. The method of treatment of trap oils oil sludge out of barns BI number 22, 2001.
2. Gun R. E. Oil bitumens.- M.: Chemistry, 1973.- 432 p.
3. No. 3808012 / 29-33 Method of preparation of oil-mineral mixture / Gaitenko V. Z. and others. C04B26 Bull. No. 26 of 15.07.0987.
4. Toshmatov D. A., Yusupov F. M., Baymatov G. A. The prepetion and properties of oil-mineralized binders from commercial oil sludge. Universum journal. 7(52) - Moscow. 2018.