SU561727A1 - Method of oil refining - Google Patents

Description

(54) METHOD FOR PROCESSING OIL

one

The invention relates to a method of refining petroleum, in which simultaneously with the separation into fractions, light petroleum products are purified from sulfur, sulfur compounds, and resinous substances.

Light petroleum products (gasoline, kerosene, diesel fuel) isolated from sulfur oils have a high content of total and mercaptan sulfur. For example, the content of mercaptans in kerosene, isolated from a mixture of oils from the Romashkinskoye and West Siberian fields, is 0.006-0.008 weight. %, the norm according to GOST not more than 0.005 weight. % The increased content of sulfur compounds pesiKO impairs the performance of petroleum products, leads to a reduction in the life of engines as a result of the rapid deterioration of the main parts and a decrease in their economic performance, as well as to the contamination of the air pool with acidic combustion products.

The known method of purification of oil and products of its primary processing from sulfur, sulfur compounds, nitrogen and oxygen-containing compounds and naphthenic acids, characterized by that TO 1 oil or products of its primary processing 1 is subjected to processing by carbonyls of transition metals or their mixtures, - transition metal complexes, salts or all-strong complexes of the platinum group metals at 80-120 ° C, followed by separation of the purified product from the resulting reaction mixture.

At the same time, in individual fractions of the resulting light oil products, an excess of reagents used for purification may accumulate, and chelating agents are used to remove them. In addition, this refining method is applicable mainly to oil fractions, i.e., to distillates, and not to crude (non-distilled) oil, and is not compatible with the distillation of oil.

The aim of the invention is to eliminate these drawbacks. The basis of the invention

the task was to create a purification method, which, in principle, eliminates the possibility of metal-containing reagents getting into the target purified n products. One variant of the proposed method is

that the oil is reacted with non-volatile reactants under distillation conditions: At the same time, they will improve the quality of the recovered oil products by binding sulfur and resinous substances to heavy non-volatile complexes; In another embodiment, the oil treatment mode is changed as compared to the prototype (increase the processing temperature and system pressure) in order to increase the cleaning efficiency and cause thermal decomposition of small amounts of unreacted volatile cleaning reagents. According to the invention, 0.02-0.2 wt. Is added to desalted and dewatered or crude oil (if the desalination process is combined with a direct race). % non-volatile derivatives of metal carbonyls; further distillation of oil lead by conventional means. It is also possible to introduce the reagent into the preheated oil (up to 250-350 ° C at a pressure of 0.5-1.5 atm); it is possible to use metal carbonyls and their volatile derivatives, as well as other l-complexes of transition metals; further distillation of oil lead conventional methods and. As non-volatile derivatives of metal carbonyls, it is advisable to use salts of the composition MLn M5 (CO) jn), where M is Ni, Co, Mn, Fe; L - ammonia, pyridine, piperidine, morpholine, 7-picoline, ethylenediamine, monoethanol, yn, diethyiolamine, triethanol amine and other amines; , t: 3-13; (or salts with carbonyl hydride amines of the composition LH2Rec (CO) c, where L is ammonia, monoethanolamine, diztanolamine, triethanolamine, trialkylamines (methyl, ethyl, propyl, n-butyl). It is advisable to use carbonyls V as volatile in the conditions of carbonyl metal distillation, , Cr, Mo, W, Mn, Fe, Re, Co, Ni, and mixtures thereof, as well as polydermal and cluster carbonyls. H 2 S and sulfur, the content of mercaptan sulfur decreases 5 to 10 times and the content of total sulfur decreases 2-10 times, the content of resinous substances decreases. Such distillation remains unchanged. As a rule, as a result of the described treatment, the octane number of the gasoline fraction is increased by 10-20 points by the motor method. FIG. 1-4 depict an installation for carrying out the proposed method for processing oil, various options. The following symbols are used in the figures: 1 — heat exchangers, 2 — topping column, 3 — main distillation column, 4 — tube furnace, 5 — electrohydrators, 6 — capacity for the reagent. The product lines are indicated by arrows: A - gasoline, B - kerosene, B - diesel fuel, G - fuel oil, D - oil. Under industrial conditions, this method can be implemented as one of the following options. A concentrated solution of the reagent in water or petroleum, prepared with heating in a separate tank 6, is fed by a dosing pump to a reception (Fig. I) or to the output (Fig. 2) of a raw pump (raw pumps) of a Pefti distillation unit. Further reheating is carried out in the usual way. In this case, the reagent can also be supplied along with a solution of soda, usually introduced into the process to suppress hydrochloric acid corrosion. The concentrated reagent solution in the oil product, prepared in the vessel 6, is fed to the furnace pump intake, which pumps the stripped hot oil from the evaporator to the furnace and then to the main distillation column (Fig. 3); It is also possible to use a combined reagent loader system (Fig. 4). The invention has a large economic effect, since it allows to obtain purified gasoline and kerosene at existing oil refineries without significant technological changes, which meet the requirements of GOST, and thus saves money spent on their purification, releasing the corresponding power of existing treatment plants other petroleum products, such as diesel fuel. Example 1. 1500 g of desalted and dehydrated oil are mixed with 2.6 g of the salt of composition Mn (C5H5M) (CO) and dispersed to 350 ° C in ten-degree fractions (on an APH-2 apparatus according to GOST 11011-64). From the obtained fractions, gasoline is compounded (from the beginning of boiling (NC) to 150 ° C), kerosene (150-230 ° C) and diesel fuel (230-350 ° C). Products and distillation residue - fuel oil is analyzed according to all GOST indicators. The average fractions obtained according to this and the following examples 2-5, are given in table. I and 2. Example 2. 1500 g of desalted and dehydrated oil are mixed with 3 g of salt (C2H5) зMH2Rec (CO) 11 and dispersed to 350 ° C in ten-degree fractions (using an APH-2 apparatus according to GOST 11011-64). Compounds of gasoline (from n. To 150 ° C), kerosene (150-230 ° C) and diesel fuel (230-350 ° C) are compounded from the fractions obtained. Products and distillation residue - fuel oil is analyzed according to all GOST indicators. Example 3. 1500 g of crude oil and 1.2 g of decarbonyl manganese are heat treated in a closed vessel at 280 ° C for 30 minutes. The oil is then dispersed to ten-degree fractions (on the apparatus. The quality of oil fractions obtained

Note 1. Hydrogen sulphide and water-soluble acids and alkalis are absent in all the fractions obtained. The distillation residue (350 ° C) of oil without treatment contains 2.30% by weight of total sulfur, the oil treated according to the invention, and 2.35% by weight. % sulfur.

2. Test on a copper plate withstand all the fractions

3. Mechanical impurities are absent in all fractions.

Table 1 on the apparatus ARN-2 from desalted oil

The quality of fuel oil f-5, obtained using distillation residues

oil, subjected to pretreatment according to the invention (weight

the ratio of diesel fuel and fuel oil 1: 1; test method GOST 6258-52).

ARN-2 according to GOST 11011-64). From the obtained fractions, gasoline is compounded (from oil up to 150 ° C), kerosene (150-230 ° C) and diesel fuel (230-350 ° C). Products and distillation residue - fuel oil is analyzed according to all GOST indicators.

Example 4. 700 g of desalted and dehydrated oil are mixed with 0.8 g of salt (POS2P4YPz) НРез (СО) 11, heat treated in a closed vessel at 300 ° С for 15 minutes and then gasoline fractions (from . to. to 150 ° C) n kerosene (150-230 ° C). Products are analyzed for all indicators GOST.

Example 5. 1500 g of crude oil and 2 g of iron pentacarbonyl are heat treated in a closed vessel at 300 ° C for 40 minutes. Then, the oil is dispersed to ten degrees (fractions) on an APH-2 apparatus according to GOST 11011-64). From the obtained fractions, gasoline is comained (from n. To 150 ° C), kerosene (150-230), and diesel fuel (230-350 ° C). Products and residue Distillation — fuel oil is analyzed for all GOST indicators;

table 2

Claims (3)

1. A method of refining oil, including purification from sulfurous and partially reactive nitrogen and oxygen-containing compounds and naphthenic acids by treating with non-transition metal compounds and subsequent distillation by conventional methods, characterized in that, in order to simplify the process technology, the oil carbonyl metal-containing reagents, volatile or non-volatile under the conditions of crude distillation, in an amount of 0.02-0.2 wt. %, moreover, in the case of the introduction of volatile reagents, the mixture is subjected to preliminary heat treatment at 250–350 ° C and a pressure of 1.5–7 atm. 2. A process according to claim 1, characterized in that carbonyls of V, Cr, Mo, W, Mn, Re, Fe, Co, Ni and their mixtures are used as carbonyl reagents, as well as polycarbonate and cluster carbonyls, and their volatile derivatives are used by arenemetallcarbonyls, cyclopentadienylmethylcarbonyls, dienmetallicarbovdl and rdefiymetallkaronily listed above. 3. A method according to claim 1, characterized in that iB as nonvolatile metal carbonyl derivatives, salts of the composition (CO) are used, where M is Ni, Co, Mn, Fe; L - ammonia, pyridine, piperidine, morpholine, -r-q u-picolip, ethylenediamine, monoethanolamn, metaldiethanols .n, triethanolamine and other amines; t 3-13; or salts with carbonyl hydride amine compounds LH2Rep (CO) 11, where L is ammonia, monoethanolamine, diethanolamine, triethanolamine, trialkylamines, where alkyl is methyl egil, propyl, n-butyl.