SU959821A1 - Catalyst for purifying gases from sulphur compounds - Google Patents

Description

(54) CATALYST FOR GAS CLEANING FROM CONNECTIONS

SULFUR

one

The invention relates to catalysts used to purify natural and process gases, and gases obtained during the processing and cracking of oil, from sulfur compounds, such as hydrogen sulfide, mercaptans, sulfur oxide, carbon disulfide.s

In industry, scavengers based on activated zinc oxide 1 are used for gas cleaning.

However, these absorbers are suitable, mainly, for gas cleaning at neckline temperatures (320-420 ° С) from hydrogen sulfide and partially from mercaptans.

To purify gases from organic sulfur compounds, the latter are preliminarily subjected to the same temperature of catalytic decomposition and hydrogenation 15 to hydrocarbons and hydrogen sulfide in the presence of a special catalyst, for example, aluminobol molybdenum.

In addition to the indicated absorbers, catalysts-adsorbents based on jo oxide zinc-aluminum system are known, which makes it possible to use a single-stage purification scheme 2.

However, such catalysts have a low (9-10%) sulfur-absorption capacity and can work only at elevated temperatures of 320-420 ° C.

The closest to the invention in its technical essence and the achieved effect is a catalyst for the purification of gases from sulfur compounds containing oxides of zinc, aluminum, chromium and / or nickel, and / or molybdenum, and / or cobalt, and / or copper. in the following ratio of components, wt. ° / p- zinc oxide 20-30; and / or nickel oxide 2-8; and / or molybdenum oxide 0.1-9.0; and / or cobalt oxide 1-2; and / or copper oxide 3,9-5,3; chromium oxide 7.6-10.2 and alumina - the rest. The temperature range of this catalyst is 290– 325 ° C 3.

The main disadvantages of the known catalyst are low sulfur content (6-10%) due to the low content of zinc oxide and low activity () at lower temperatures of 180-250 ° C. In addition, it is impossible to clean process gases containing CO, COj, Hj from sulfur compounds on such a catalyst, since there are side reactions that cause a change in the composition of the gas, for example, hydrogenation of CO, COj, etc.

The aim of the invention is to increase the activity of the catalyst.

This goal is achieved by the fact that the catalyst contains oxides of zinc, nickel, copper and aluminum in the following ratio, weight. /about :

Nickel oxide 0,, 0

Copper oxide4.4-10.0

Aluminum oxide 5.0-16.0

Zinc Oxide Else

The proposed catalyst in comparison with the known has a high activity. It has an increased sulfur content (28-303,) due to the increased content of active zinc oxide and provides a degree of purification close to 1007 at low temperatures of 180-250 ° C, not only natural gases, which are obtained during processing and cracking of oil, but also technological, containing Hj , CO and CO2 without changing their composition.

Thus, the proposed catalyst has a 3-4 times more activity than 3 times the known capacity in low-temperature activity and 180-250 ° C. In addition, it also removes sulfur compounds from process gases.

Example 1. In a 300 cm ammoniac carbonate solution containing 90 g / l CO2 and 1S9 g l NHi, the following components are introduced in portions, g: zinc oxide 70; copper oxide 10; basic nickel carbonate based on a 53.4% nickel oxide content of 7.49; active alumina 16. The resulting mixture is stirred at 45-50 ° C for 1.5-2 hours, then the temperature is raised to 80-85 ° C and stirred for another 1.5-2 hours. The resulting mass is dried at 100-110 ° C for 4-5 hours and calcined at 350-4 ° C ° C for the same time.

As a result, 100 g of catalyst mass is formed, containing, in terms of oxides, weight. / o: ZnO 70.0; CuO 10.0 AljOj 16.0; NiO 4.0. Bulk weight 1.25 kg / l, sulfur content 28.0%.

The resulting mass is tabletted with the addition of 1.5 g of graphite (tablet size 6X4 mm) or molded in the form of granules (diameter 5 mm). The strength of the tablets is 150-200 kg / cm 2 molded granules of 1.5 kg / mm diameter.

The catalyst is tested during the purification process of a methanol synthesis process gas containing about %: CO 18-20; CO2 2.5-3.0; the rest is hydrogen. Test mode: catalyst volume 100 cm, volumetric speed 1000 h, pressure 20 atm, temperature 250 ° С. Sulfur content (in terms of sulfur); mg / organo-sulfur 7-10; hydrogen sulfide 20-35.

Within 200 hours of testing, the degree of organo-sulfur conversion reaches 98.3%, and the degree of absorption of total sulfur by the catalyst is at least 95.7.

The conversion degree is the ratio of the difference in sulfur content in organic sulfur substances in the source and purified gases to the sulfur content in organic sulfur substances in the source gas (%); under the purification degree, the ratio of the difference in the total sulfur content in the source and purified gases to the sulfur content in the source gas (%).

Quantitative and qualitative changes in the composition of the gas over the entire time of the test are not observed. After 200 hours of operation, the strength of the catalyst is reduced by no more than 15%. In addition, the catalyst is tested in the process of purification of natural gas with the dosing of 9-11% of hydrogen into it. The test conditions for pressure, temperature and space velocity are similar to those described. The content of sulfur compounds in gas, organic sulfur substances 17-23; hydrogen sulfide 1-3.

Within 20 hours of testing, the degree of conversion of organic sulfur compounds is 98.5%, and the degree of purification is 96.3%. Loss of strength - no more than 13% compared to the original.

Example 2. In a 300 cm ammonium carbonate solution with a content of CO and NHg the same as in Example 1, the components are introduced in portions, g: ZnO 80.0; CuO 10.0; the main nickel carbonate is based on the content of 53.4% NiO 9.3 and active A12Oz 5 in it. Further processing is similar to Example 1.

Get 100 g of catalyst mass containing based on the oxides of metals, weight. %: ZnO 80 .; CuO 10; AljOj 5; NiO 5. The bulk density is 1.20 kg / l, the sulfur-holding capacity is 30.0%. The catalyst was tested as in Example 1. The test temperature was 180 ° C. The content of organic sulfur in terms of elemental sulfur 5-8 mg / m, hydrogen sulfide 30-37 mgUm.

Within 200 hours of work, the degree of conversion of organic sulfur compounds reaches 98.9%, and the degree of absorption of total sulfur from gas by the catalyst is not less than 95.9%. Quantitative and qualitative changes in the composition of the gas over the entire time of the test are not observed. After 200 hours of testing, the strength of the catalyst is reduced by no more than 15%.

In addition, the catalyst was tested in a natural gas purification process under conditions similar to example 1, at a temperature of 180 ° C. The content of organic sulfur 15-28 mg / m, hydrogen sulfide 1 - 3 mg / m

Within 200 hours of the test, the conversion rate was 98.8%, the purification rate was 97.8%. Loss of strength of the catalyst is not more than 15%.

Example 3. In a 300 cm ammoniac carbonate solution with the same content of CO2 and NH.3 as in Example 1, the components are introduced in portions, g: Zn 75; CuO 7, basic nickel carbonate from the calculation of its content of 53.4%, NiO 5.6; active AljOa 15. Further processing is similar to the example of 1 Get 100 g of catalyst mass containing, based on metal oxides, weight. o / o: ZnO 75; CuO 7.0; AjOa 15; NiO 3. The bulk weight is 1.21 kg / l, the sulfur-holding capacity is 29.2%.

The catalyst is tested as in Example 1. The temperature of the test is 190 ° C. The content of organic sulfur compounds in terms of elemental sulfur is 7-12 mg / m, hydrogen sulfide is 30-40 mg / m.

Within 200 hours of testing, the degree of conversion of organosulphuric substances reaches 99.0%, and the degree of absorption of total sulfur by the catalyst is not less than 95.9%. No quantitative and qualitative change in the gas composition is observed. The strength of the catalyst decreases by no more than 15%.

In addition, the catalyst is tested in a natural gas purification process under conditions similar to Example 1. The temperature is 190 ° C.

Within 200 hours of the test, the conversion rate was 97.2%, the purification rate was 97.1. Loss of strength of the catalyst is 15%.

Example 4. In a 300 cm ammonium carbonate solution with the same content of CO2 and NHg as in Example 1, the components are introduced in portions, g: ZnO 80; CuO 8; ASjOj 10 of basic nickel carbonate based on a 53.4% NiO 3.7 content. Further processing is similar to example 1.

Get 100 g of the catalyst mass containing, based on the metal oxides in, weight. %: ZnO 80; CuO 8, AlaOj 10; 2. Bulk weight 1.23 kg / l; graining capacity 28.9.

The catalyst is tested in the same conditions as in example 1. The test temperature is 210 ° C, the content of organic sulfur substances in terms of elemental sulfur is 10-17 mg / m, hydrogen sulfide is 25-38 mg / m. Within 200 hours of testing, the degree of conversion of organosulphuric substances is 99.2%, and the degree of purification is 95.3%. No quantitative and qualitative change in the gas composition is observed. After 200 hours of testing, the strength of the catalyst decreases by no more than 15%.

In addition, the catalyst was tested in a natural gas purification process under conditions similar to Example 1 at 210 ° C. Within 200 hours of testing, the conversion rate is 98.2%, and the purification rate is

95.2%. Loss of strength of the catalyst is not more than 15%.

Example 5. Analogously to the proposed example 1. The composition of the catalyst and the method of its preparation corresponds to example 1 of the known invention.

Example 6. The tests were carried out under conditions similar to those proposed for example 2. The composition of the catalyst and the method of its preparation corresponds to example 3 of the known invention.

Example 7. The tests are carried out under conditions similar to those of Example 3. The composition of the catalyst and the method of its preparation corresponds to Example 4 of the known invention.

Example 8. The tests are carried out under conditions similar to those of Example 4. The composition of the catalyst and the method of its preparation corresponds to Example 14 of the known invention.

Comparative data of the proposed and known catalysts are given in the table (the volumetric gas velocity during testing of all samples is 1000 h).

It follows from the table that the proposed catalysts are significantly higher than the known ones: in terms of the sulfur-holding capacity, almost 3 times, and in the degree of purification, not less than 2 times.

Example 9. In a 300 cm ammonium carbonate solution with the same content of COa and NHg as in Example I, the components are introduced in portions, g: ZnO 79.5; CuO 5.4; AljOj 14.0, basic nickel carbonate based on its content of 53.4% NiO 1.1. Further processing is similar to example 1. Get 100 g of the catalyst mass, based on the oxides of metals, weight. %: ZnO 80.0; CuO 5.4; AEjOa 14.0 and NiO 0.6. Bulk weight 1.21 kg / l, sulfur content 28.1%.

The catalyst was tested as in Example 1. The test temperature was 250 ° C. The content of organic sulfur compounds in terms of elemental sulfur 7-11 mg / m of hydrogen sulfide 21-37 mg / m.

Claims (3)

Within 200 hours of testing, the degree of conversion of organosulphuric substances is 99.3%, the degree of purification is 95.5%. No quantitative and qualitative change in gas is observed. After 200 hours of testing, the strength of the catalyst decreases by no more than 15%. In addition, the catalyst is tested in a natural gas purification process under conditions similar to example 1 at 250 ° C. Within 200 hours of testing, the conversion rate is 98.3%, and the purification rate is 95.0%. Loss of strength of the catalyst - no more than 15. Claims of the invention Catalyst for the purification of gases from sulfur compounds, including oxides of zinc, nickel, copper, and aluminum, O7, which, in order to increase the activity of the catalyst, it contains components in the following ratio, wt. %: Nickel oxide 0,6-5,0 Copper oxide 5,4-10,0 Alumina oxide 5-16, Zinc oxide Ostalnoy Sources of information taken into account during the examination 1. Reference book of nitric oxide, T. 1, M., "Chem , L 967, s. 294-295. 2. USSR author's certificate number 447393, cl. C O7 C 7/00, 1971. 3. USSR author's certificate number 652960, cl. In 01 J 2104, 1979 (prototype).