Process for removing hydrogen sulfide from sour gases
A process for removing hydrogen sulfide (H 2 S) from a H 2 S-containing gas composition includes charging a liquid to a reactor under continuous agitation and dispersing particles of a cobalt-based zeolitic imidazolate framework-67 (ZIF-67) in the liquid to form a ZIF-67 mixture. The method further includes introducing the H 2 S-containing gas composition to the reactor containing the ZIF-67 mixture under continuous agitation and passing the H 2 S-containing gas composition through the ZIF-67 mixture. In addition, the method includes adsorbing the H 2 S from the H 2 S-containing gas composition onto the ZIF-67 to remove the H 2 S from the H 2 S-containing gas composition and form a purified gas composition.
1. A process for removing hydrogen sulfide (H 2 S) from a H 2 S-containing gas composition, comprising:
charging a liquid to a reactor under continuous agitation;
dispersing particles of a cobalt-based zeolitic imidazolate framework-67 (ZIF-67) in the liquid to form a ZIF-67 mixture;
continuously agitating the ZIF-67 mixture;
introducing the H 2 S-containing gas composition to the reactor containing the ZIF-67 mixture under continuous agitation and passing the H 2 S-containing gas composition through the ZIF-67 mixture;
adsorbing the H 2 S from the H 2 S-containing gas composition onto the ZIF-67 to remove the H 2 S from the H 2 S-containing gas composition and form a purified gas composition.
2. The process of claim 1 , wherein the ZIF-67 particles have a mean particle size in a range of 5 to 150 nm.
3. The process of claim 1 , wherein the ZIF-67 particles having:
a porous structure; and
a mean pore size in a range of 0.5 to 5 nm.
4. The process of claim 1 , wherein the ZIF-67 is supported on at least one support selected from the group consisting of a graphene-based material, an alumina, a carbon nanotube, an activated carbon, a metal organic framework (MOF), a zeolitic nanotube, and a covalent organic polymer (COP).
5. The process of claim 4 , wherein the supported ZIF-67 has a delaminated structure comprising charged crystalline particles, in which a distance between laminated layers is in a range of 0.5 to 50 nm.
6. The process of claim 4 , wherein the graphene-based material comprises at least one selected from the group consisting of graphene, graphyne, graphydiyne, graphene oxide, reduced graphene oxide, and exfoliated graphite.
7. The process of claim 4 , wherein a weight ratio of the ZIF-67 to the support is from 20:1 to 1:20.
8. The process of claim 1 , wherein the liquid comprises at least one selected from the group consisting of tap water, ground water, distilled water, deionized water, saltwater, hard water, fresh water, and wastewater.
9. The process of claim 1 , wherein the reactor is a stirred tank reactor in the form of a vertical cylindrical reactor containing at least one propeller agitator disposed therein, wherein the vertical cylindrical reactor has a bottom portion, a vertically oriented cylindrical body portion and a top portion, wherein the bottom portion is cone shaped or pyramidal, wherein a plurality of recirculation tubes fluidly connects the bottom portion of the vertical cylindrical reactor with the body portion of the vertical cylindrical reaction.
10. The process of claim 1 , wherein the H 2 S-containing gas composition is natural gas.
11. The process of claim 1 , wherein the H 2 S-containing gas composition further comprises at least one gas selected from the group consisting of nitrogen, argon, methane, ethane, ethylene, propylene, propane, butane, butene, butadiene, and isobutylene.
12. The process of claim 1 , wherein the H 2 S is present in the gas composition at a concentration in a range of 10 to 200 parts per million by volume (ppmv) based on a total volume of the gas composition.
13. The process of claim 1 , wherein the H 2 S-containing gas composition is introduced to the reactor at a rate of 0.4 to 2.0 milliliters per minute (mL/min) per milligram of the ZIF-67.
14. The process of claim 1 , wherein the ZIF-67 is present in the liquid at a concentration in a range of 0.1 to 10 milligrams per milliliter (mg/mL).
15. The process of claim 1 , wherein during the introducing and adsorbing the ZIF-67 is in contact with the H 2 S-containing gas composition at a temperature in a range of from 15 to 40° C. and under a pressure of 0.9 to 1.2 bar.
16. The process of claim 1 , further comprising:
preparing the ZIF-67 by:
mixing and dissolving a cobalt salt in a first liquid to form a first solution;
mixing and dissolving an imidazole compound in a second solution comprising ammonia to form a second solution;
adding the first solution to the second solution under agitation to form a mixture;
reacting the cobalt salt from the first solution with the imidazole compound from the second solution to form a ZIF-67 in a ZIF-67-containing aqueous composition;
removing the ZIF-67 from the ZIF-67-containing aqueous composition and washing to form a wet ZIF-67;
heating and drying the wet ZIF-67 to form the ZIF-67.
17. The process of claim 16 , wherein the cobalt salt is at least one selected from the group consisting of cobalt sulfate, cobalt acetate, cobalt citrate, cobalt iodide, cobalt chloride, cobalt perchlorate, cobalt nitrate, cobalt phosphate, cobalt triflate, cobalt bis(trifluoromethanesulfonyl)imide, cobalt tetrafluoroborate, cobalt bromide, and/or its hydrate.
18. The process of claim 16 , wherein the imidazole compound comprises an imidazole of formula (I) and a benzimidazole of formula (II):
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkoxy, a hydroxyl, a halogen, a nitro, and a cyano.
19. The process of claim 16 , wherein:
a molar ratio of the cobalt salt to the imidazole compound present in the first mixture is in a range of 1:2 to 1:6; and
the imidazole compound is 2-methylimidazole.
20. The process of claim 16 , wherein the ZIF-67 having:
a specific surface area in a range of 800 to 1600 m 2 /g;
a cumulative specific pore volume in a range of 0.2 to 1 cm 3 /g; and
an average pore diameter of 0.5 to 5 nm.