SU857230A1 - Method of desulfurizing light hydrocarbons - Google Patents

Description

The invention relates to the field of purification of petroleum hydrocarbons from sulfur compounds and can be used in industry. A known method for the liquid-phase purification of a gasoline fraction from sulfur compounds on a copper-aluminosilicate adsorbent obtained by impregnating a carrier with a solution of Cu (NO) 2 and subsequent reduction in current. in which zeolite of type X in iron-substituted form is used as an adsorbent. For purification, a fraction of 70-1300s of gasoline of thermal cracking of the Angarsk Petrochemical Combine with soda is used AJ Niemi total sulfur 0.35%. This fraction is used as a cheese for the production of alcohols by the oxysynthesis method, where the total sulfur content is limited to 0.05%. The adsorption of sulfur compounds is carried out under dynamic conditions, passing the cleaned fraction through the stationary layer of the adsorbent at a speed of 3.2 ml / min-cm (the bulk feed rate is 3.08 × 1). The best results were obtained when using as an adsorbent a type X zeolite with a content of 3.86% FegO (maximum content of the active component). Dynamic capacity until exhausted, sulfur adsorption activity at the same time is 2.09 g per 100 g of adsorbent 2. A disadvantage of the known methods is The degree of desulfurization is relatively low. The purpose of the invention is to increase the degree of desulfurization. The goal is achieved by using an adsorbent containing 10–20 wt.% Copper sulfate deposited on a zeolite carrier, 10-30 wt.% Type Y zeolite, in the method of desulfurizing light hydrocarbons by percolating them through a zeolite adsorbent. uniformly dispersed in an amorphous aluminosilicate matrix. Samples of the zeolite-containing ositol are treated with a solution of ammonium chloride to remove "atgl", then the active component (copper sulfate) is applied by impregnation, dried and calcined under certain conditions. The samples obtained are tested to determine the dynamic sulfur adsorption capacity by varying the volumetric rate and the sulfur content of the hydrocarbon fraction to be purified.

Example 1. 100 g of a synthesized zeolite-containing carrier consisting of 10 wt.% NaY zeolite and 90 wt.% Amorphous aluminosilicate (granule size 2-3 mm), is treated with 1 l of 0.1 M ammonium chloride solution at room temperature for 2 After the fivefold treatment, the sodium content for the air-dry sample is 0.36% by weight. For the / fat sample, in the amount of 50 g, pour 90 ml of 0.5 M copper sulphate solution. The sample is kept in the solution for 2 hours, then the solution is evaporated, the adsorbent is dried for 6 hours at 120 ° C and calcined for 2 hours at. Getting adsorbent A-1, containing 15 wt.% CuSO on a zeolite-containing carrier.

10 cm of the adsorbent is placed into a glass percolation column. Across the stationary layer of the adsorbent, petroleum ether (, p TO-IOO C) with a sulfur content of 0.055 wt.% With a volume of

Adsorption lead

speed 2.5 h

at room temperature and atmospheric pressure. The content of mercaptan sulfur in the purified fraction is checked every hour by potentiometric titration (0.01 N silver ammine solution). Purification is carried out until the sulfur adsorption activity is exhausted. At the end of the experiment, the total volume of the hydrocarbon fraction passed through the adsorbent and the content of mercaptan sulfur in it are determined. The value of the dynamic sulfur adsorption capacity is determined on the basis of the weight of the adsorbent and the amount of the adsorbed organic sulfur compound (calculated as elemental sulfur). The dynamic sulfur adsorption capacity of granular adsorbate A - is 15 wt. Cu 50 on a zeolite-containing carrier (10 wt.% Type Y zeolite and 90 wt.% Amorphous silica-alumina) is 31.6 mg of mercaptan sulfur per 1 g of adsorbent.

Example 2. 100 g of a synthesized zeolite-containing carrier consisting of 15 wt.% NaY zeolite and 85 wt.% Amorphous aluminosilicate (granule size 2-3 mm), is treated with an ammonium chloride solution as described above. After a fivefold treatment with the solution, the sodium content is 0.40% by weight for the air-dry sample.

Cy50d is applied to the obtained sample by the impregnation method. All operations are carried out as described above.

An adsorbent containing 15% by weight of CuS04 on a zeolite-containing carrier is obtained. Dynamic sulfur adsorption. The capacity of granulated adsorbent A-2, which is 15 wt.% CuSOj on a zeolite-containing carrier (15 wt.% type Y zeolite and 85 amorphous silica-alumina), is 44.1 mg of mercaptan sulfur per 1 g of adsorbent.

Example 3. 100 g of a synthesized zeolite-containing carrier consisting of 18% by weight of a Y-type zeolite and 82% by weight of an amorphous aluminosilicate (granule size 2-3 mm) are treated with a solution of ammonium chloride. After treatment with NH solution for five times. The sodium content for the air-dry sample is 0.44% by weight.

Siozd is applied to the obtained sample by the impregnation method. All operations

0 is carried out as described in Example 1. An adsorbent A-3 is obtained containing 15% by weight of CuSQ4 on a zeolite-containing carrier. The dynamic sulfur adsorption capacity of granular adsorbent A-3, which is 15 wt.% CuSO on a zeolite-containing carrier (18 wt.% Y-type zeolite and 82 wt.% Of amorphous aluminosilicate), is 54.3 mg of mercaptan sulfur per 1 g of adsorbent .

0 Example 4. 100 g of a synthesized zeolite-containing carrier, consisting of 20 wt.% NaY zeolite and 80 wt.% Amorphous aluminosilicate (granule size 2-3 mm), is treated with ammonium chloride solution as described in example 1. After five times treatment with the solution NH-C8 sodium content is

air-dry sample of 0.53 wt.%.

CuSOj is deposited onto the obtained sample by the impregnation method. All operations are carried out as described in Example 1.

Receive adsorbent A-4, contents of 45 to 15 wt.% CiS on the zeolite-containing carrier.

The dynamic sulfur adsorption capacity of granular adsorbent A-4, which is 15 wt.% 50 Cu 50 on a zeolite-containing carrier (20 wt.% Y-type zeolite and 80 wt.% Amorphous silica-alumina) is 37.6 mg of mercaptan sulfur per 1 g of adsorbent.

 Example 5. 100 g of a synthesized zeolite-containing carrier consisting of 30 wt.% NaY zeolite and 70 wt.% Amorphous aluminosilicate (granule size 2-3 mm), is treated with a solution of ammonium chloride as described in example 1.

After five times treatment with the solution, the sodium content is for an air-dry sample.

65 O, 71 May.%.

Claims (1)

Claim A method of desulphurizing light coal, hydrogen by percolating them through a zeolite adsorbent, characterized in that, in order to increase the degree of desulfurization, an adsorbent is used containing 1020 wt.% Copper sulfate deposited on a zeolite carrier, representing 10-30 wt.% Type zeolite Y uniformly dispersed in an amorphous aluminosilicate matrix.