Desulfurization adsorbents, methods of making and using the same

Abstract

This application provides a desulfurization adsorbent comprising an oxide active component and a support, wherein the mass ratio of the oxide active component to the support is 1:(5~1000). The oxide active component is selected from one or more oxides of alkali metals, alkaline earth metals, and Group III subgroup metals. The support is selected from one or more molecular sieves of type A, type X, type Y, activated carbon, and porous metal fluorides. The desulfurization adsorbent described in this application exhibits good adsorption effect, large adsorption capacity, and long breakthrough time for various organic sulfides.

Description

Technical Field

[0001] This application relates to an adsorbent, and more particularly to a desulfurization adsorbent, its preparation method, and its application. Background Technology

[0002] Hydrogen fluoride is an important product in the fluorochemical industry and an essential raw material in the manufacture of high-end fluorine-containing chemicals. It is typically produced from fluorite ore and sulfuric acid. Due to the varying quality of fluorite ore, which contains various substances such as calcium sulfide, zinc sulfide, and lead sulfide, hydrogen fluoride usually contains a certain amount of sulfur. In the production of some high-end fluorine-containing chemicals, sulfur can form complex fluorine-containing organic sulfides through various chemical reactions. Since the concentration of organic sulfides needs to be strictly controlled in actual applications, deep desulfurization is necessary to meet the sulfide content requirements of specific fields.

[0003] Fluorinated olefins / diolefins have broad application prospects in refrigerants, foaming agents, cleaning agents, and semiconductor manufacturing due to their good environmental and application performance. Currently, much research focuses on the manufacturing technology of fluorinated olefins / diolefins, with limited reports on the removal of sulfur-containing impurities. However, high-end manufacturing fields, such as precision electronic component cleaning, large-scale integrated circuit manufacturing, and chip manufacturing, have extremely strict requirements for the impurities in the fluorinated chemicals used. The content of sulfur compounds often needs to be controlled at the ppb level, or even required to be zero. Therefore, it is necessary to develop a deep desulfurization adsorbent for the desulfurization of fluorinated olefins / diolefins to meet the requirements of high-end manufacturing. Summary of the Invention

[0004] The specific technical solution of this application is as follows:

[0005] 1. A desulfurization adsorbent, wherein the desulfurization adsorbent comprises an oxide active component and a carrier, wherein the mass ratio of the oxide active component to the carrier is 1:(5~1000), the oxide active component is selected from one or more of alkali metal oxides, alkaline earth metal oxides, and group III subgroup metal oxides, and the carrier is selected from one or more of type A molecular sieves, type X molecular sieves, type Y molecular sieves, activated carbon, and porous metal fluorides.

[0006] 2. The desulfurization adsorbent according to item 1, wherein the alkali metal is selected from one or more of Li, Na, K, Rb, and Cs, the alkaline earth metal is selected from one or more of Be, Mg, Ca, Sr, and Ba, and the group III subgroup metal is selected from one or more of La, Ce, Pr, Nd, Y, and Sc.

[0007] Preferably, the alkali metal oxide is selected from one or more of Li₂O, Na₂O, K₂O, Rb₂O, and Cs₂O; the alkaline earth metal oxide is selected from one or more of BeO, MgO, CaO, SrO, and BaO; and the group III transition metal oxide is selected from one or more of La₂O₃, Ce₂O₃, Pr₂O₃, Nd₂O₃, Y₂O₃, Sc₂O₃, and CeO₂.

[0008] 3. The desulfurization adsorbent according to item 1, wherein the type A molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve and 5A molecular sieve; the type X molecular sieve is 10X molecular sieve and / or 13X molecular sieve; the type Y molecular sieve is NaY molecular sieve; the activated carbon is selected from one or more of coal carbon, wood carbon and coconut shell carbon; and the porous metal fluoride is selected from one or more of aluminum fluoride, chromium fluoride, magnesium fluoride and calcium fluoride.

[0009] 4. The desulfurization adsorbent according to item 1, wherein the mass ratio of the oxide active component to the carrier is (1~15):100.

[0010] 5. The desulfurization adsorbent according to item 1, wherein,

[0011] The desulfurization adsorbent is composed of the oxide active component and the carrier.

[0012] 6. The desulfurization adsorbent according to item 1, wherein,

[0013] The oxide active component is composed of oxides of alkali metals, oxides of alkaline earth metals, and oxides of Group III subgroup metals.

[0014] Preferably,

[0015] The mass ratio of the oxides of the alkali metal, the oxides of the alkaline earth metal, and the oxides of the Group III subgroup metal is (0.01~1):(1~5):(1~5).

[0016] 7. The desulfurization adsorbent according to any one of items 1-6, wherein the desulfurization adsorbent is prepared by the following method: the precursor soluble salt of the oxide active component is prepared into a precursor salt solution of the oxide active component according to the mass ratio of the oxide active component to the carrier in the desulfurization adsorbent; then the carrier is mixed and impregnated with the precursor salt solution of the oxide active component; after standing for a certain period of time, the mixture is dried and calcined to obtain the desulfurization adsorbent.

[0017] 8. The desulfurization adsorbent according to item 7, wherein the precursor soluble salt of the oxide active component is a nitrate and / or a carbonate.

[0018] 9. The desulfurization adsorbent according to item 7, wherein the impregnation is an equal-volume impregnation method, the ratio of the volume of the precursor salt solution of the oxide active component to the volume of the saturated water absorption of the carrier is (1~1.2):1, and the standing time after impregnation is 12-36h.

[0019] 10. A method for preparing a desulfurization adsorbent, comprising:

[0020] Based on the mass ratio of oxide active component to carrier in the desulfurization adsorbent, the precursor soluble salt of oxide active component is prepared into precursor salt solution of oxide active component. Then, the carrier is mixed and impregnated with precursor salt solution of oxide active component. After standing for a certain period of time, the mixture is dried and calcined to obtain desulfurization adsorbent.

[0021] The desulfurization adsorbent comprises an oxide active component and a carrier, wherein the mass ratio of the oxide active component to the carrier is 1:(5~1000).

[0022] 11. The preparation method according to item 10, wherein the precursor soluble salt of the oxide active component is a nitrate and / or a carbonate.

[0023] 12. The preparation method according to item 10, wherein the impregnation is an equal-volume impregnation method, the ratio of the volume of the precursor salt solution of the oxide active component to the volume of the saturated water absorption of the carrier is (1~1.2):1, and the standing time after impregnation is 12-36 h.

[0024] 13. The preparation method according to item 10, wherein the oxide active component is selected from one or more of alkali metal oxides, alkaline earth metal oxides, and group III subgroup metal oxides, and the support is selected from one or more of type A molecular sieves, type X molecular sieves, type Y molecular sieves, activated carbon, and porous metal fluorides.

[0025] Preferably, the alkali metal is selected from one or more of Li, Na, K, Rb, and Cs; the alkaline earth metal is selected from one or more of Be, Mg, Ca, Sr, and Ba; and the Group III subgroup metal is selected from one or more of La, Ce, Pr, Nd, Y, and Sc.

[0026] More preferably, the alkali metal oxide is selected from one or more of Li2O, Na2O, K2O, Rb2O, and Cs2O; the alkaline earth metal oxide is selected from one or more of BeO, MgO, CaO, SrO, and BaO; and the group III transition metal oxide is selected from one or more of La2O3, Ce2O3, Pr2O3, Nd2O3, Y2O3, Sc2O3, and CeO2.

[0027] More preferably,

[0028] The type A molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve, and 5A molecular sieve; the type X molecular sieve is 10X molecular sieve and / or 13X molecular sieve; the type Y molecular sieve is NaY molecular sieve; the activated carbon is selected from one or more of coal carbon, wood carbon, and coconut shell carbon; the porous metal fluoride is selected from one or more of aluminum fluoride, chromium fluoride, magnesium fluoride, and calcium fluoride.

[0029] 14. The preparation method according to item 10, wherein the mass ratio of the oxide active component to the carrier is (1~15):100.

[0030] 15. The preparation method according to item 10, wherein the desulfurization adsorbent is composed of the oxide active component and the carrier.

[0031] 16. The preparation method according to item 10, wherein,

[0032] The oxide active component is composed of oxides of alkali metals, oxides of alkaline earth metals, and oxides of Group III subgroup metals.

[0033] Preferably,

[0034] The mass ratio of the oxides of the alkali metal, the oxides of the alkaline earth metal, and the oxides of the Group III subgroup metal is (0.01~1):(1~5):(1~5).

[0035] 17. The use of the desulfurization adsorbent according to any one of items 1-9, or the desulfurization adsorbent prepared by any one of items 10-16, in the adsorption of sulfur-containing substances in fluorinated olefins.

[0036] 18. The application according to item 17, wherein the fluorinated olefin is selected from trifluoroethylene (CF2=CFH), tetrafluoroethylene (CF2=CF2), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), cis-1,3,3,3-tetrafluoropropylene (Z-HFO-1234ze), trans-1,3,3,3-tetrafluoropropylene (E-HFO-1234ze), cis-1,1,1,2,3,4,4,4-octafluoro-2-butene (Z-CF3CF=CFCF3), trans-1,1,1,2,3,4,4,4-octafluoro-2-butene (… One or more of the following: E-CF3CF=CFCF3, cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-CF3CH=CHCF3), trans-1,1,1,4,4,4-hexafluoro-2-butene (E-CF3CH=CHCF3), 1,1,2,3,4,4-hexafluorocyclobutene (c-C4F6), octafluorocyclopentene (c-C5F8), hexafluorocyclopentene (c-C5F6H2), heptafluorocyclopentene (c-C5F7H), or 1,1,2,3,4,4-hexafluorobutadiene (CF2=CF-CF=CF2).

[0037] 19. The application according to item 18, wherein,

[0038] The sulfur-containing substances in trifluoroethylene (CF2=CFH) are mainly SO2; the sulfur-containing substances in 2,3,3,3-tetrafluoropropylene (HFO-1234yf) are mainly CF4SH.

[0039] The sulfur-containing substances in 2,3,3,3-tetrafluoropropylene (HFO-1234yf) are mainly perfluoromethanethiol (CF4SH).

[0040] The sulfur-containing substance in trans-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) is mainly perfluorothioacetone (C3F6S).

[0041] The sulfur-containing substances in 1,1,2,3,4,4-hexafluorobutadiene (CF2=CF-CF=CF2) are mainly bis(trifluoromethyl) disulfide.

[0042] 20. The application of the desulfurization adsorbent described in any one of items 1-9, or the desulfurization adsorbent prepared by the method described in any one of items 10-16, in the adsorption of SO2 in trifluoroethylene (CF2=CFH);

[0043] Preferably,

[0044] The adsorption temperature is 10-40℃; the adsorption pressure is 0.05-1.0 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1 .

[0045] 21. The application of the desulfurization adsorbent described in any one of items 1-9, or the desulfurization adsorbent prepared by the method described in any one of items 10-16, in the adsorption of perfluoromethanethiol (CF4SH) in HFO-1234yf;

[0046] Preferably,

[0047] The adsorption temperature is 0-40℃; the adsorption pressure is 0.05-0.2 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1 .

[0048] 22. The application of the desulfurization adsorbent according to any one of items 1-9, or the desulfurization adsorbent prepared by any one of items 10-16, in the adsorption of thioperfluoroacetone (C3F6S) in E-HFO-1336mzz;

[0049] Preferably,

[0050] The adsorption temperature is 10-40℃; the adsorption pressure is 0.05-0.2 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1 .

[0051] 23. The application of the desulfurization adsorbent according to any one of items 1-9, or the desulfurization adsorbent prepared by the method according to any one of items 10-16, in the adsorption of bis(trifluoromethyl) disulfide (C2F6S2) in CF2=CF-CF=CF2;

[0052] Preferably,

[0053] The adsorption temperature is 10-40℃; the adsorption pressure is 0.05-0.2 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1 .

[0054] Invention Effects

[0055] The desulfurization adsorbent described in this application has a simple preparation process, good reproducibility, and low manufacturing cost.

[0056] The desulfurization adsorption described in this application has the characteristics of good adsorption effect, large adsorption capacity and long breakthrough time for a variety of organic sulfides.

[0057] This application uses adsorption to remove sulfide impurities, which has advantages such as lower equipment investment, lower energy consumption, and simpler operation compared to traditional distillation. Detailed Implementation

[0058] The following description provides exemplary embodiments of this application, including various details to aid understanding, and should be considered merely exemplary. Therefore, those skilled in the art will recognize that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of this application. Similarly, for clarity and brevity, descriptions of well-known functions and structures are omitted in the following description.

[0059] This application provides a desulfurization adsorbent comprising an oxide active component and a support, wherein the mass ratio of the oxide active component to the support is 1:(5~1000). The oxide active component is selected from one or more oxides of alkali metals, alkaline earth metals, and group III transition metals. The support is selected from one or more molecular sieves of type A, type X, type Y, activated carbon, and porous metal fluorides. In this application, the main function of the desulfurization adsorbent is to deeply remove sulfides from fluorinated olefins, while also improving the surface properties of the adsorbent, inhibiting isomerization reactions, and increasing the adsorption yield.

[0060] In some embodiments of this application, the mass ratio of the oxide active component to the support is (1~15):100; for example, the mass ratio of the oxide active component to the support can be 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, 1:100, 1:150, etc. :200, 1:250, 1:300, 1:350, 1:400, 1:450, 1:500, 1:550, 1:600, 1:650, 1:700, 1:750, 1:800, 1:850, 1:900, 1:950, 1:1000, 3:100, 7:100, 8:100, 9:100, 11:100, 12:100, 13:100, 14:100, 15:100, or any range between them.

[0061] In some embodiments of this application, the alkali metal is selected from one or more of Li, Na, K, Rb, and Cs; the alkaline earth metal is selected from one or more of Be, Mg, Ca, Sr, and Ba; and the group III subgroup metal is selected from one or more of La, Ce, Pr, Nd, Y, and Sc.

[0062] In some embodiments of this application, the alkali metal oxide is selected from one or more of Li2O, Na2O, K2O, Rb2O, and Cs2O; the alkaline earth metal oxide is selected from one or more of BeO, MgO, CaO, SrO, and BaO; and the group III subgroup metal oxide is selected from one or more of La2O3, Ce2O3, Pr2O3, Nd2O3, Y2O3, Sc2O3, and CeO2.

[0063] In some embodiments of this application, the type A molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve, and 5A molecular sieve; the type X molecular sieve is 10X molecular sieve and / or 13X molecular sieve; the type Y molecular sieve is NaY molecular sieve; the activated carbon is selected from one or more of coal carbon, lignocarbon, and coconut shell carbon; and the porous metal fluoride is selected from one or more of aluminum fluoride, chromium fluoride, magnesium fluoride, and calcium fluoride.

[0064] In some embodiments of this application, the desulfurization adsorbent is composed of the oxide active component and the carrier.

[0065] In some embodiments of this application, the oxide active component is composed of oxides of alkali metals, oxides of alkaline earth metals, and oxides of group III subgroup metals.

[0066] In some embodiments of this application, the mass ratio of the alkali metal oxide, alkaline earth metal oxide, and Group III subgroup metal oxide is (0.01~1):(1~5):(1~5); for example, the mass ratio of the alkali metal oxide, alkaline earth metal oxide, and Group III subgroup metal oxide can be 0.01:1:1, 0.01:1:2, 0.01:1:3, 0.01:1:4, 0.01:1:5, 0.01:2:1, 0.01:2:2, 0.01:2:3, 0.01:2:4, 0.01:2:5, 0.01:3:1, 0.01:3:2, 0.0 1:3:3, 0.01:3:4, 0.01:3:5, 0.01:4:1, 0.01:4:2, 0.01:4:3, 0.01:4:4, 0.01:4:5, 0.01:5:1, 0.01:5:2, 0.01:5:3, 0.01:5:4, 0.01:5:5, 0.1:1:1, 0.1:1:2, 0.1:1:3, 0.1:1:4, 0.1:1:5, 0.1:2:1, 0.1:2:2, 0.1:2:3, 0.1:2:4, 0.1:2:5, 0.1:3:1, 0.1:3:2, 0.1:3:3, 0.1:3: 4, 0.1:3:5, 0.1:4:1, 0.1:4:2, 0.1:4:3, 0.1:4:4, 0.1:4:5, 0.1:5:1, 0.1:5:2, 0.1:5:3, 0.1:5:4, 0.1:5:5, 0.5:1:1, 0.5:1:2, 0.5:1:3, 0.5:1:4, 0.5:1:5, 0.5:2:1, 0.5:2:2, 0.5:2:3, 0.5:2:4, 0.5:2:5, 0.5:3:1, 0.5:3:2, 0.5:3:3, 0.5:3:4, 0.5:3:5, 0.5:4:1, 0.5:4: 2, 0.5:4:3, 0.5:4:4, 0.5:4:5, 0.5:5:1, 0.5:5:2, 0.5:5:3, 0.5:5:4, 0.5:5:5, 1:1:1, 1:1:2, 1:1:3, 1:1:4, 1:1:5, 1:2:1, 1:2:2, 1:2:3, 1:2:4, 1:2:5, 1:3:1, 1:3:2, 1:3:3, 1:3:4, 1:3:5, 1:4:1, 1:4:2, 1:4:3, 1:4:4, 1:4:5, 1:5:1, 1:5:2, 1:5:3, 1:5:4, 1:5:5 or any range thereof.

[0067] This application provides a method for preparing the above-mentioned desulfurization adsorbent. The desulfurization adsorbent is prepared according to the following method: the precursor soluble salt of the oxide active component is prepared into a precursor salt solution of the oxide active component according to the mass ratio of the oxide active component to the carrier in the desulfurization adsorbent. Then, the carrier and the precursor salt solution of the oxide active component are mixed and impregnated. After standing for a certain period of time, the mixture is dried and calcined to obtain the desulfurization adsorbent.

[0068] In some embodiments of this application, the precursor soluble salt of the oxide active component is a nitrate and / or a carbonate.

[0069] In some embodiments of this application, the impregnation is an equal-volume impregnation method, where the volume ratio of the precursor salt solution of the oxide active component to the saturated water absorption volume of the carrier is (1~1.2):1, and the standing time after impregnation is 12-36 h; for example, the volume ratio of the precursor salt solution of the oxide active component to the saturated water absorption volume of the carrier is 1:1, 1.1:1, 1.2:1, or any range thereof; the standing time after impregnation can be 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h, 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h, 30 h, 31 h, 32 h, 33 h, 34 h, 35 h, 36 h, or any range thereof.

[0070] The inventor, teacher, defines the precursor salt solution of the active component of the oxide as a solution of the oxide precursor, such as nitrate, nitrite, and carbonate of the active component of the oxide.

[0071] The saturated water absorption volume of a carrier refers to the mass difference of the carrier before and after water absorption, divided by the density of water, which gives the water absorption volume.

[0072] This application provides the application of desulfurization adsorbents in the adsorption of sulfur-containing substances in fluorinated olefins.

[0073] In some embodiments of this application, the fluorinated olefin is selected from trifluoroethylene (CF2=CFH), tetrafluoroethylene (CF2=CF2), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), cis-1,3,3,3-tetrafluoropropylene (Z-HFO-1234ze), trans-1,3,3,3-tetrafluoropropylene (E-HFO-1234ze), cis-1,1,1,2,3,4,4,4-octafluoro-2-butene (Z-CF3CF=CFCF3), and trans-1,1,1,2,3,4,4,4-octafluoro-2-butene (…). One or more of the following: E-CF3CF=CFCF3, cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-CF3CH=CHCF3), trans-1,1,1,4,4,4-hexafluoro-2-butene (E-CF3CH=CHCF3), 1,1,2,3,4,4-hexafluorocyclobutene (c-C4F6), octafluorocyclopentene (c-C5F8), hexafluorocyclopentene (c-C5F6H2), heptafluorocyclopentene (c-C5F7H), or 1,1,2,3,4,4-hexafluorobutadiene (CF2=CF-CF=CF2).

[0074] In some embodiments of this application, the sulfur-containing substances in trifluoroethylene (CF2=CFH) are mainly SO2; the sulfur-containing substances in 2,3,3,3-tetrafluoropropylene (HFO-1234yf) are mainly CF4SH; the sulfur-containing substances in trans-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) are mainly perfluorothioacetone (C3F6S); and the sulfur-containing substances in 1,1,2,3,4,4-hexafluorobutadiene (CF2=CF-CF=CF2) are mainly bis(trifluoromethyl) disulfide.

[0075] This application provides an application of the above-mentioned desulfurization adsorbent in the adsorption of SO2 in trifluoroethylene (CF2=CFH); preferably, the adsorption temperature is 10-40℃; the adsorption pressure is 0.05-1.0 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1 For example, the adsorption temperature can be any range of 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃ or above; the adsorption pressure can be any range of 0.05MPa, 0.1MPa, 0.5MPa, 1MPa or above; and the adsorption space velocity can be 200 h⁻¹. -1 300 h -1 400h -1 500 h -1 600 h -1 700 h -1 800 h -1 900 h -11000 h -1 or any range thereof.

[0076] This application provides the application of the above-mentioned desulfurization adsorbent in the adsorption of perfluoromethanethiol (CF4SH) in HFO-1234yf; preferably, the adsorption temperature is 0-40℃; the adsorption pressure is 0.05-0.2 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1 For example, the adsorption temperature can be 0℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃ or any range therein; the adsorption pressure can be 0.05MPa, 0.1MPa, 0.2MPa or any range therein; and the adsorption space velocity can be 200 h⁻¹. -1 300 h -1 400 h -1 500 h -1 600 h -1 700 h -1 800 h -1 900 h -1 1000 h -1 or any range thereof.

[0077] This application provides the application of the above-mentioned desulfurization adsorbent in the adsorption of thioperfluoroacetone (C3F6S) in E-HFO-1336mzz; preferably, the adsorption temperature is 10-40℃; the adsorption pressure is 0.05-0.2 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1 For example, the adsorption temperature can be any range of 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃ or above; the adsorption pressure can be any range of 0.05MPa, 0.1MPa, 0.2MPa or above; and the adsorption space velocity can be 200 h⁻¹. -1 300 h -1 400 h -1 500 h -1 600 h -1 700 h -1 800 h -1 900 h -1 1000 h -1 or any range thereof.

[0078] This application provides the application of the above-mentioned desulfurization adsorbent in the adsorption of bis(trifluoromethyl) disulfide (C2F6S2) in CF2=CF-CF=CF2; preferably, the adsorption temperature is 10-40℃; the adsorption pressure is 0.05-0.2 MPa; and the adsorption space velocity is 200-1000 h⁻¹. -1For example, the adsorption temperature can be any range of 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃ or above; the adsorption pressure can be any range of 0.05MPa, 0.1MPa, 0.2MPa or above; and the adsorption space velocity can be 200 h⁻¹. -1 300 h -1 400 h -1 500 h -1 600 h -1 700 h -1 800 h -1 900 h -1 1000 h -1 or any range thereof.

[0079] Example

[0080] This application provides a general and / or specific description of the materials and test methods used in the experiments. In the following examples, unless otherwise specified, % represents wt%, i.e., weight percentage. Reagents or instruments used, unless otherwise specified, are all commercially available conventional reagent products.

[0081] Example 1

[0082] Weigh out 7.9 g RbNO3, 29.3 g Ca(NO3)2, and 50.7 g Y(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 1# desulfurization adsorbent, 2.5%Rb2O-5%CaO-7.5% Y2O3 / 4A.

[0083] 2.5%Rb2O-5%CaO-7.5%Y2O3 / 4A means: relative to 100 parts by weight of 4A molecular sieve, Rb2O is 2.5 parts by weight, CaO is 5 parts by weight, and Y2O3 is 7.5 parts by weight; the same applies below.

[0084] Example 2

[0085] Weigh out 7.9 g RbNO3, 29.3 g Ca(NO3)2, and 39.8 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 2# desulfurization adsorbent, 2.5%Rb2O-5%CaO-7.5% La2O3 / 4A.

[0086] Example 3

[0087] Weigh out 7.9 g RbNO3, 29.3 g Ca(NO3)2, and 37.8 g Ce(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 3# desulfurization adsorbent, 2.5%Rb2O-5%CaO-7.5%CeO2 / 4A.

[0088] Example 4

[0089] Weigh out 7.9 g RbNO3, 29.3 g Ca(NO3)2, and 37.8 g Ce(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h. Cool to 200 ℃ and treat with 5% H2 / 95% N2 gas at 100 mL / min for 6 h to obtain sample 4# desulfurization adsorbent, 2.5% Rb2O-5% CaO-7.5% Ce2O3 / 4A.

[0090] Example 5

[0091] 79.6 g of La(NO3)3·6H2O was dissolved in 250 g of deionized water, and 180 g of 4A molecular sieve was added. The mixture was allowed to stand for 24 h to soak. The soaked mixture was dried in an oven at 80 ℃ for 12 h, and then calcined in a muffle furnace at 350 ℃ for 24 h to obtain sample 5# desulfurization adsorbent, 15% La2O3 / 4A.

[0092] Example 6

[0093] 87.9 g of Ca(NO3)2 was weighed and dissolved in 250 g of deionized water, and 180 g of 4A molecular sieve was added. The mixture was allowed to stand for 24 h to soak. The soaked mixture was dried in an oven at 80 ℃ for 12 h, and then calcined in a muffle furnace at 350 ℃ for 24 h to obtain sample 6# desulfurization adsorbent, 15% CaO / 4A.

[0094] Example 7

[0095] 47.4 g of RbNO3 was dissolved in 250 g of deionized water, and 180 g of 4A molecular sieve was added. The mixture was allowed to stand for 24 h to soak. The soaked mixture was dried in an oven at 80 ℃ for 12 h, and then calcined in a muffle furnace at 350 ℃ for 24 h to obtain sample 7# desulfurization adsorbent, 15% Rb2O / 4A.

[0096] Example 8

[0097] Weigh 44.0 g Ca(NO3)2 and 39.8 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 8# desulfurization adsorbent, 7.5% CaO - 7.5% La2O3 / 4A.

[0098] Example 9

[0099] Weigh 44.0 g Ca(NO3)2 and 39.8 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 9# desulfurization adsorbent, 7.5%Rb2O-7.5%La2O3 / 4A.

[0100] Example 10

[0101] Weigh out 0.79 g RbNO3, 2.93 g Ca(NO3)2, and 3.98 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 10# desulfurization adsorbent, 0.25%Rb2O-0.5%CaO-0.75% La2O3 / 4A.

[0102] Example 11

[0103] Weigh 1.19 g RbNO3, 4.4 g Ca(NO3)2, and 5.97 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 11# desulfurization adsorbent, 0.375%Rb2O-0.75%CaO-0.56%La2O3 / 4A.

[0104] Example 12

[0105] Weigh out 7.9 g RbNO3, 58.6 g Ca(NO3)2, and 13.3 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 12# desulfurization adsorbent, 2.5%Rb2O-10%CaO-2.5% La2O3 / 4A.

[0106] Example 13

[0107] Weigh out 7.9 g RbNO3, 29.3 g Mg(NO3)2, and 39.8 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 13# desulfurization adsorbent, 2.5%Rb2O-5%MgO-7.5% La2O3 / 4A.

[0108] Example 14

[0109] Weigh out 9.66 g KNO3, 29.3 g Ca(NO3)2, and 39.8 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 14# desulfurization adsorbent, 2.5% K2O - 5% CaO - 7.5% La2O3 / 4A.

[0110] Example 15

[0111] Weigh out 12.3 g NaNO3, 29.3 g Ca(NO3)2, and 39.8 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 4A molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 15# desulfurization adsorbent, 2.5% Na2O-5% CaO-7.5% La2O3 / 4A.

[0112] Example 16

[0113] Weigh out 7.9 g RbNO3, 29.3 g Ca(NO3)2, and 39.8 g La(NO3)3·6H2O, dissolve them in 250 g deionized water, add 180 g 10X molecular sieve, and let stand for 24 h to impregnate. Dry the impregnated mixture in an oven at 80 ℃ for 12 h, and then calcine it in a muffle furnace at 350 ℃ for 24 h to obtain sample 16# desulfurization adsorbent, 2.5% Rb2O-5% CaO-7.5% La2O3 / 10X.

[0114] Table 1

[0115] .

[0116] Application examples

[0117] Application Example 1

[0118] A fixed-bed adsorption column with an inner diameter of 25 mm and a length of 600 mm was used, with an adsorbent loading of 100 g. The adsorption temperature was 20℃, the adsorption pressure was 0.1 MPa, and the space velocity was 200 h⁻¹. -1 The adsorption effects of each adsorbent on different sulfur-containing compounds in CF2=CFH, HFO-1234yf, CF3CH=CHCF3, and CF2=CF-CF=CF2 were investigated, and quantitative analysis was performed using gas chromatography. See Table 2-5 for details.

[0119] Table 2. Adsorption effect of each adsorbent on SO2 in CF2=CFH

[0120] .

[0121] Gas chromatography analysis showed no significant change in CF2=CFH before and after adsorption, indicating that the adsorbent did not induce the polymerization reaction of CF2=CFH. However, the SO2 content in CF2=CFH decreased from the initial 0.1% to less than 200 ppmv, demonstrating the significant adsorption effect of the desulfurization adsorbent on SO2 in CF2=CFH. Alkali metal oxides Rb2O, K2O, and Na2O, alkaline earth metal oxides CaO and MgO, and rare earth metal oxides La2O3, Y2O3, CeO2, and Ce2O3 all showed some adsorption effect on SO2. Among them, the adsorption effect of Rb2O, CaO, MgO, and rare earth metal oxides, when combined in a certain proportion and loaded onto a molecular sieve, was even better. Furthermore, as time progressed, the adsorption capacity gradually saturated, and the adsorption effect fluctuated slightly, but the overall adsorption effect remained very significant.

[0122] Table 3. Adsorption efficiency of each adsorbent for perfluoromethanethiol (CF4SH) in HFO-1234yf

[0123] .

[0124] Chromatographic analysis showed that HFO-1234yf did not undergo significant changes before and after adsorption, indicating that the adsorbent did not cause HFO-1234yf to undergo polymerization or isomerization. However, the perfluoromethanethiol content in HFO-1234yf decreased from the initial 0.05% to below 120 ppmv. Sample #2 showed the best adsorption effect, controlling the perfluoromethanethiol content below 10 ppmv. Alkali metal oxides Rb₂O, K₂O, and Na₂O, alkaline earth metal oxides CaO and MgO, and rare earth metal oxides La₂O₃, Y₂O₃, CeO₂, and Ce₂O₃ all exhibited significant adsorption effects on perfluoromethanethiol. Among these, the adsorption effect of Rb₂O, CaO, MgO, and rare earth metal oxides, when combined in a certain proportion and loaded onto a molecular sieve, was even better.

[0125] Table 4. Adsorption efficiency of each adsorbent for perfluorothioacetone (C3F6S) in E-HFO-1336mzz

[0126] .

[0127] Chromatographic analysis showed that CF3CH=CHCF3 did not undergo significant changes before and after adsorption, indicating that the adsorbent did not cause polymerization or isomerization of CF3CH=CHCF3. However, the content of thioperfluoroacetone in CF3CH=CHCF3 decreased from the initial 0.23% to below 50 ppmv. Sample #1 showed the best adsorption effect, controlling the thioperfluoroacetone content below 1 ppm. Alkali metal oxides Rb2O, K2O, and Na2O, alkaline earth metal oxides CaO and MgO, and rare earth metal oxides La2O3, Y2O3, CeO2, and Ce2O3 all exhibited significant adsorption effects on thioperfluoroacetone. Among these, the adsorption effect of Rb2O, CaO, MgO, and rare earth metal oxides, when combined in a certain proportion and loaded onto a molecular sieve, was even better.

[0128] Table 5. Adsorption efficiency of each adsorbent for bis(trifluoromethyl) disulfide (C2F6S2) in CF2=CF-CF=CF2

[0129] .

[0130] Chromatographic analysis showed that CF2=CF-CF=CF2 did not change significantly before and after adsorption, indicating that the adsorbent did not cause polymerization or isomerization of CF2=CF-CF=CF2. However, the C2F6S2 content in CF2=CF-CF=CF2 decreased from the initial 0.03% to below 60 ppmv. Sample #4 showed the best adsorption effect, controlling the C2F6S2 content below 10 ppm. Alkali metal oxides Rb2O, K2O, and Na2O, alkaline earth metal oxides CaO and MgO, and rare earth metal oxides La2O3, Y2O3, CeO2, and Ce2O3 all showed significant adsorption effects on C2F6S2. Among these, Rb2O, CaO, MgO, and rare earth metal oxides, when combined in a certain proportion and loaded onto the molecular sieve, exhibited superior adsorption performance for C2F6S2.

[0131] Application Example 2

[0132] Using 2.5%Rb₂O-5%CaO-7.5%CeO₂ / 4A from Example 3 as the adsorbent, the adsorption effect on SO₂ in CF₂=CFH was compared under different temperatures, pressures, and space velocities. The results are shown in Table 6.

[0133] Table 6. Adsorption effect of the adsorbent in Example 3 on SO2 in CF2=CFH

[0134] .

[0135] Table 6 data shows that lowering the temperature is beneficial for SO2 adsorption, while raising the temperature causes SO2 to desorb from the adsorbent, affecting the adsorption efficiency. Increasing the adsorption pressure has little impact on SO2 adsorption; considering equipment and operating costs, desulfurization adsorption can be carried out at a lower pressure. Increasing the space velocity is detrimental to the complete adsorption of SO2; a space velocity of 1000 h⁻¹ is particularly problematic. -1 At that time, the product still contained 214.2 ppmv of SO2. The temperature used in No. 2 is closer to room temperature and is easy to achieve in actual production. The temperature in No. 1 is 10 °C, which requires additional cooling and will increase operating costs.

[0136] Application Example 3

[0137] Using 2.5%Rb2O-5%CaO-7.5%CeO2 / 4A from Example 3 as the adsorbent, the adsorption effect of perfluoromethanethiol (CF4SH) in HFO-1234yf under different temperatures, pressures, and space velocities was compared. The results are shown in Table 7.

[0138] Table 7. Adsorption effect of the adsorbent in Example 3 on perfluoromethanethiol (CF4SH) in HFO-1234yf

[0139] .

[0140] Table 7 shows that lowering the temperature also benefits CF4SH adsorption, while increasing the temperature causes CF4SH to desorb from the adsorbent, affecting the adsorption efficiency. Increasing the adsorption pressure helps CF4SH adsorption; however, considering equipment and operating costs, desulfurization adsorption can be carried out at a lower pressure. Excessive space velocity is detrimental to the complete adsorption of CF4SH; a space velocity of 1000 h⁻¹ is particularly problematic. -1 At that time, the product still contained 159.2 ppmv of CF4SH.

[0141] Application Example 4

[0142] Using 2.5%Rb2O-5%CaO-7.5%La2O3 / 4A from Example 2 as the adsorbent, the adsorption effect on thioperfluoroacetone (C3F6S) in E-HFO-1336mzz was compared under different temperatures, pressures, and space velocities. The results are shown in Table 8.

[0143] Table 8. Adsorption effect of the adsorbent in Example 2 on perfluorothioacetone (C3F6S) in E-HFO-1336mzz

[0144] .

[0145] Table 8 shows that lowering the temperature also favors the adsorption of C3F6S. Since the boiling point of C3F6S is 6-7 °C, the adsorption temperature needs to be above 7 °C to ensure it remains gaseous; however, increasing the temperature will cause C3F6S to desorb from the adsorbent. Increasing the adsorption pressure also promotes C3F6S adsorption. The saturated vapor pressure of E-HFO-1336mzz is relatively low, and experiments were conducted only at 0.05-0.12 MPa, with no C3F6S detected in the products. Excessive space velocity (1000 h⁻¹) is detrimental to C3F6S adsorption. -1 At that time, the product still contained 45.2 ppmv of C3F6S. "Not detected" means the impurity concentration was below the detection limit of the analytical instrument.

[0146] Application Example 5

[0147] Using 2.5%Rb2O-5%CaO-7.5%La2O3 / 4A from Example 2 as the adsorbent, the adsorption effect on bis(trifluoromethyl) disulfide (C2F6S2) in CF2=CF-CF=CF2 was compared under different temperatures, pressures, and space velocities. The results are shown in Table 9.

[0148] Table 9. Adsorption effect of the adsorbent in Example 2 on bis(trifluoromethyl) disulfide (C2F6S2) in CF2=CF-CF=CF2

[0149] .

[0150] Table 9 shows that lowering the temperature also favors the adsorption of C2F6S2. Since the boiling point of CF2=CF-CF=CF2 is 6.5 ℃, the adsorption temperature needs to be above 7 ℃ to ensure the feedstock is gaseous; however, increasing the temperature will cause C2F6S2 to desorb from the adsorbent. Furthermore, increasing the adsorption pressure promotes the adsorption of C2F6S2, while the saturated vapor pressure of CF2=CF-CF=CF2 is less than 0.2 MPa at 20 ℃, and the experiments were conducted at 0.02-0.12 MPa. The data in the table show that pressure changes have little effect on the concentration of C2F6S2 in the product. Excessive space velocity is detrimental to the adsorption of C2F6S2; a space velocity of 1000 h⁻¹ is particularly detrimental. -1 At that time, the product still contained 68.3 ppmv of C2F6S2.

[0151] Although the embodiments of this application have been described above in conjunction with the specific embodiments described, this application is not limited to the specific embodiments and application fields described above. The specific embodiments described above are merely illustrative and instructive, and not restrictive. Those skilled in the art can make many other forms based on the teachings of this specification and without departing from the scope of protection of the claims of this application, and these are all within the scope of protection of this application.

Claims

1. The application of a desulfurization adsorbent in adsorbing sulfur-containing substances in fluorinated olefins, characterized in that, The desulfurization adsorbent comprises an oxide active component and a carrier. The oxide active component is composed of oxides of alkali metals, oxides of alkaline earth metals, and oxides of Group III subgroup metals. The carrier is selected from one or more of type A molecular sieves, type X molecular sieves, type Y molecular sieves, activated carbon, and porous metal fluorides; The mass ratio of the oxide active component to the carrier is (2.25~15):100, and is not 2.25:

100.

2. The application according to claim 1, characterized in that, The alkali metal is selected from one or more of Li, Na, K, Rb, and Cs; the alkaline earth metal is selected from one or more of Be, Mg, Ca, Sr, and Ba; and the Group III subgroup metal is selected from one or more of La, Ce, Pr, Nd, Y, and Sc.

3. The application according to claim 1, characterized in that, The alkali metal oxide is selected from one or more of Li2O, Na2O, K2O, Rb2O, and Cs2O; the alkaline earth metal oxide is selected from one or more of BeO, MgO, CaO, SrO, and BaO; and the group III subgroup metal oxide is selected from one or more of La2O3, Ce2O3, Pr2O3, Nd2O3, Y2O3, Sc2O3, and CeO2.

4. The application according to claim 1, characterized in that, The type A molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve, and 5A molecular sieve; the type X molecular sieve is 10X molecular sieve and / or 13X molecular sieve; the type Y molecular sieve is NaY molecular sieve; the activated carbon is selected from one or more of coal carbon, wood carbon, and coconut shell carbon; the porous metal fluoride is selected from one or more of aluminum fluoride, chromium fluoride, magnesium fluoride, and calcium fluoride.

5. The application according to claim 1, characterized in that, The desulfurization adsorbent is composed of the oxide active component and the carrier.

6. The application according to claim 1, characterized in that, The mass ratio of the oxides of the alkali metal, the oxides of the alkaline earth metal, and the oxides of the Group III subgroup metal is (0.01~1):(1~5):(1~5).

7. The application according to any one of claims 1-6, characterized in that, The desulfurization adsorbent is prepared according to the following method: the precursor soluble salt of the oxide active component is prepared into a precursor salt solution of the oxide active component according to the mass ratio of the oxide active component to the carrier. Then, the carrier is mixed and impregnated with the precursor salt solution of the oxide active component. After standing for a certain period of time, the mixture is dried and calcined to obtain the desulfurization adsorbent.

8. The application according to claim 7, characterized in that, The precursor soluble salt of the oxide active component is a nitrate.

9. The application according to claim 7, characterized in that, The impregnation is an equal-volume impregnation method, where the volume ratio of the precursor salt solution of the oxide active component to the saturated water absorption volume of the carrier is (1~1.2):1, and the standing time after impregnation is 12-36h.

10. The application according to claim 1, characterized in that, The fluorinated olefin is selected from one or more of the following: trifluoroethylene, tetrafluoroethylene, 2,3,3,3-tetrafluoropropylene, cis-1,3,3,3-tetrafluoropropylene, trans-1,3,3,3-tetrafluoropropylene, cis-1,1,1,2,3,4,4,4-octafluoro-2-butene, trans-1,1,1,2,3,4,4,4-octafluoro-2-butene, cis-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,2,3,4,4-hexafluorocyclobutene, octafluorocyclopentene, hexafluorocyclopentene, heptafluorocyclopentene, or 1,1,2,3,4,4-hexafluorobutadiene.

11. The application according to claim 10, characterized in that, The sulfur-containing substance in trifluoroethylene is mainly SO2; The sulfur-containing substances in 2,3,3,3-tetrafluoropropylene are mainly perfluoromethanethiol; The sulfur-containing substance in trans-1,1,1,4,4,4-hexafluoro-2-butene is mainly thioperfluoroacetone. The sulfur-containing substances in 1,1,2,3,4,4-hexafluorobutadiene are mainly bis(trifluoromethyl) disulfide.