SU952948A1 - Process for recovering vanadylporphiric complexes from crude oil - Google Patents

Description

This invention relates to methods for removing vanadyl porphyrin complexes from oils using sorbents.

There is a known method for removing metals and metal blocks from petroleum and petroleum products using hydrofining of crude oil during hydrocatalytic processing under pressure tl.

There is also known a method for removing porphyrin complexes of iron, nickel, vanadium from asphaltenic petroleum oils by deasphalting them, followed by contacting with hydrochloric acid, which coagulates metallic porphyrins 2.

The closest to the proposed technical essence and the achieved effect is a method of extracting vanadyl porphyrin complexes from oil by treating it at 20-35 ° C in succession with twenty-two portions of the sorbent, which uses airgel, with each portion being separated from the treated NW product.

The disadvantages of this method are the relatively low degree of extraction of vanadylporphyrin complexes (96%) and the duration of the process - twenty-two times the treatment with a sorbent takes more than 7 hours.

The purpose of the invention is to increase the recovery rate and reduce the time spent on the process.

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This goal is achieved by the method of extracting vanadylporphyrin complexes from oil by o6pa6otKH at 20-35 With successive portions of the sorbent, which is based on the waste of titanium aluminum

15 production, containing oxides yulumini, iron, titanium and silicon in the following ratio, wt.% "Alumina O, 3-3.0 iron oxide 0.3-1.0) titanium dioxide 2.0-4.0j

20 silicon dioxide - the rest, when the ratio of the sorbent oil is 1: 10-12, with the separation of each portion of the processed product.

The proposed method allows n6

25 compared with the known increase in the degree of extraction of vanadyl porphyrin complexes to 97.2-98% and reduce the time of the process from 7 to 4 hours, while the number of treatments is reduced

30 from 27 to 4.5 treatments. Oil or a model solution is sequentially treated in portions of a benthus comprising oxides of silicon, aluminum, iron and titanium in the following ratios of incoming components, wt%: SiOr 90.0-96; 0.3-3.0; 0.3-1.0; TiO 2.0-4.0, which is a waste of metallurgical production. The treatment is carried out by 4-5-fold mechanical mixing of the mentioned sorbent, with oil or oil product at a ratio of 1: 10-12 at 20-35 ° C for 1 hour. Each new portion of the sorbate is contacted after it is separated from the waste oil by filtration . In the filtrate, the contents of vanadyl porphyrin complexes are determined by a known method of hot extraction with alcohol and acetone, followed by spectrophotometry with t4J. The extraction rate is 9799% by weight. The indicated ranges of oscillations of the concentrations of the components that make up the used sorbent, which is a waste of metallurgical titanium-aluminum production, do not introduce noticeable deviations in the process of sorption of vanadyl porphyrin complexes from oils and model solutions and are equivalent, therefore, in all the examples described below ts results on the extraction of vanadyl porphyrins from oils using the selected sorbent of the following composition, wt.% SiO-i 94.4; 2.3; 0.3; TiO, 3 j O. Example, 100 ml of oil from the Zhanazhol field (Western Kazakhstan) with a concentration of 6.375 mg of vanadyl porphyrin complexes at and atmospheric pressure for 1 h are in contact with 10 g of the above-mentioned sorbent at the following ratios of incoming components, wt.% G SiOa 94.4; A1,2.0z, 3; 0.3; NIGHT 3.0. Each time after an hour of contact in the filtered oil, the content of vanadyl porphyrin complexes is determined by a spectrophotometric method. The results are shown in table 1. Table 1

The data show that the proposed method, by contact with the 4th portion of the mi- sorbent, allows to extract up to 98.0% of the vanadyl porphyrin complexes. Contact with the 5th portion of the sorbent does not increase the degree of extraction.

Example 2. Under the conditions of Example 1, 110 ml of oil are contacted with 10 g of sorbent successively in 4 portions. Extraction of vanadylporphyrin complexes occurs at 97.5%.

Example 3. Under the conditions of Example 1, 120 ml of oil are contacted with 10 g of sorbent successively in 4 portions. Extraction of vanadylporphyrin complexes occurs at 97.2%.

Example4. Under the conditions of Example 1, a model benzene solution of vanadyl porphyrin complexes isolated by the method of hot extraction with alcohol and acetone from Kalamkas oil is contacted with the sorbent specified in Example 1. The content of vanadylporphyrin complexes in the model solution is 18.6 mg. Results The data of Table 2 show that the full absorption of vanadyl porphyrins from the model solution occurs after contact with 4 portions of the mentioned sorbent. Example 5 Under the conditions of Example 1, vanadyl porphyrin complexes were extracted from a model solution of vanadyl porphyrins isolated from Kalaskas oil and purified by chromatography. The contact time is 1 h, t 20 ° С, the ratio of sorbent: model solution is 1:10. The concentration of vanadyl porphyrin complexes in the model solution is 10.02 mg per 100 g of the original oil. Example Under the conditions of example 1, the extraction was carried out. The contact time of each batch, min 200

The final degree of extraction of van. Dilporphyrin complexes from petroleum, wt.%

Total process time, min

Data on the degree of extraction of vananadylporphyrin complexes and the extraction of α-porphyrins from model solutions are given in Table 2.

table 2

20

20

20

50

96

94

88

83

77

440

320

200 195 200 200

The procedure for carrying out the proposed method is given in Table 4. dilporphyrin complexes at a ratio of sorbent; oil is 1:10, the degree of sorption at a given temperature is 98.0%, the process of sorption is carried out in 4 portions. Example. Under the conditions of Example 1, vanadylporphyrin complexes were extracted at 30 ° C, sorbent: oil ratio was 1:10, degree of sorption was 98.2%. Example Under the conditions of Example 1, vanadyl porphyrin complexes were extracted at 35 ° C, the degree of sorption was 98.2%. Data on the degree of extraction of vanadylporphyrin complexes and the time of the known method are given in Table 3. Table

The final degree of extraction, wt.%

Claims (4)

Total process time, min. Formula of the invention. Method of extracting vanadyl porphyry complexes from oil by treating it at 20-35 ° C by successive portions of sorbent with separating each portion of the processed product, characterized in that in order to increase the recovery rate and reduce the time spent of the method, as a sorbent, use of titanium-aluminum production waste, containing oxides of aluminyl / iron, titanium and silicon in the following ratio, wt.%: alumina 0.3-3.0; iron oxide 0.3-1.0; titanium dioxide 2,0Table4 55.7 68,8 87.4 98.0 180 120 240 4.0; silicon dioxide - the rest, and the treatment is carried out with respect to the sorbent: oil, equal to 1: 10-12, Sources of information taken into account during the examination 1. US patent 3496099, cl. 208-251, cl. From 10 G 23/00, published 1970. 2. US Patent 3095368,. cl. 203-252, cl. From 10 G 25/00, published 1957. 3. USSR author's certificate number 499289, cl. C 10 G 25/05, 1974 (prototype). 4. Manual analysis of petroleum. L., Nedra, 1966, p. 215-219.