CN118105936B - Solid desulfurizing agent and preparation method thereof - Google Patents
Solid desulfurizing agent and preparation method thereof Download PDFInfo
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 claims description 4
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- DLNWMWYCSOQYSQ-UHFFFAOYSA-M benzyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 DLNWMWYCSOQYSQ-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 description 17
- 230000023556 desulfurization Effects 0.000 description 17
- 230000006872 improvement Effects 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a solid desulfurizing agent and a preparation method thereof, and belongs to the technical field of desulfurizing agents. Comprising the following steps: s1, uniformly mixing tetraethoxysilane, aluminum isopropoxide, ethanol, a pore-forming agent and water, adding ammonia water to adjust the pH value, heating and stirring for reaction, centrifuging, washing, drying and calcining to obtain a porous silica/alumina carrier; s2, adding the porous silica/alumina carrier into ethanol, adding a composite silane coupling agent, heating, stirring, reacting, centrifuging, washing and drying to obtain a modified porous silica/alumina carrier; s3, adding the modified porous silica/alumina carrier into water, adding soluble zinc salt and soluble ferric salt, adding citric acid, stirring and mixing uniformly, heating and volatilizing the solvent, calcining, and ball-milling to obtain the solid desulfurizing agent. The solid desulfurizing agent prepared by the invention has the advantages of good desulfurizing effect, high mechanical strength, simple reaction, wide raw material sources, low cost and the like.
Description
Technical Field
The invention relates to the technical field of desulfurizing agents, in particular to a solid desulfurizing agent and a preparation method thereof.
Background
The prior desulfurization technology mainly comprises the following steps: complexing removal method, alcohol amine refining, physical adsorption method, chemical absorption method, merox extraction-liquid phase catalytic oxidation method, hydrofining, catalytic desulfurization and the like, and the desulfurizing agents used are classified into the following three types: wet desulfurization, dry desulfurization, and other desulfurization methods (e.g., biological desulfurization, etc.).
In many dry desulfurization methods, adsorption desulfurization has a series of concerns of high desulfurization precision, simple process, easy operation, low energy consumption, repeated regeneration and use of adsorbent, and the like, and is particularly suitable for desulfurization processes with certain process requirements and high desulfurization precision, so that more attention is paid. The key of the adsorption desulfurization technology is to develop a high-efficiency desulfurizing agent, which has higher sulfur capacity, so that the regeneration frequency can be reduced, and the energy consumption is reduced. Meanwhile, the good adsorbent has higher adsorption selectivity, and the competitive adsorption of aromatic hydrocarbon, olefin and other compounds or the occurrence of hydrogenation and other side reactions are reduced as much as possible.
Although the active carbon desulfurization technology has certain efficiency for removing sulfur-containing compounds such as mercaptan and thioether, the active carbon desulfurization technology generally needs to take part in the reaction by oxygen, and is not recommended to be adopted in the desulfurization process of flammable and explosive components such as low-carbon olefin, and the active carbon adsorption removal technology purely relying on adsorption still has a series of problems of low selectivity, low penetrating sulfur capacity, low desulfurization rate and the like.
Disclosure of Invention
The invention aims to provide a solid desulfurizing agent and a preparation method thereof, and the solid desulfurizing agent has the advantages of good desulfurizing effect, high mechanical strength, simple reaction, wide raw material sources, low cost and the like.
The technical scheme of the invention is realized as follows:
The invention provides a preparation method of a solid desulfurizing agent, which comprises the following steps:
S1, preparing a porous silica/alumina carrier: uniformly mixing tetraethoxysilane, aluminum isopropoxide, ethanol, a pore-forming agent and water, adding ammonia water to regulate the pH value, heating and stirring for reaction, centrifuging, washing, drying and calcining to obtain a porous silica/alumina carrier;
S2, modification: adding the porous silica/alumina carrier prepared in the step S1 into ethanol, adding a composite silane coupling agent, heating, stirring, reacting, centrifuging, washing and drying to obtain a modified porous silica/alumina carrier;
S3, preparing a solid desulfurizing agent: adding the modified porous silica/alumina carrier prepared in the step S2 into water, adding soluble zinc salt and soluble ferric salt, adding citric acid, stirring and mixing uniformly, heating and volatilizing the solvent, calcining and ball-milling to obtain the solid desulfurizing agent.
As a further improvement of the invention, the mass ratio of the ethyl orthosilicate, the aluminum isopropoxide, the ethanol, the pore-forming agent, the water and the ammonia water in the step S1 is 10-12:7-10:100-120:2-4:12-15:15-20.
As a further improvement of the invention, the temperature of the heating and stirring reaction in the step S1 is 40-50 ℃ for 5-7h, the temperature of the calcination is 500-600 ℃ for 1-2h.
As a further improvement of the present invention, the pore-forming agent in step S1 is at least one selected from cetyltrimethylammonium chloride, cetyldimethylbenzyl ammonium bromide, and cetyltrimethylsodium chloride.
As a further improvement of the invention, the mass ratio of the porous silica carrier to the silane coupling agent in the step S2 is 100:7-10; the temperature of the heating and stirring reaction is 35-45 ℃ and the time is 0.5-1h.
As a further improvement of the invention, the silane coupling agent in the step S2 is at least two selected from KH550, KH560, KH570, KH580, KH590, KH602 and KH792, preferably, a mixture of KH602 and KH792, and the mass ratio is 7-10:3-5.
As a further improvement of the invention, in the step S3, the mass ratio of the modified porous silica/alumina carrier, the soluble zinc salt, the soluble iron salt and the citric acid is 100:15-20:12-15:25-30, the heating temperature is 60-70 ℃, the calcining temperature is 400-500 ℃, the time is 2-4h, and the ball milling time is 1-3h.
As a further improvement of the present invention, the soluble zinc salt in step S3 is selected from at least one of zinc chloride, zinc sulfate, zinc nitrate, and the soluble iron salt is selected from at least one of ferric chloride, ferric sulfate, and ferric nitrate.
As a further improvement of the invention, the method specifically comprises the following steps:
S1, preparing a porous silica/alumina carrier: uniformly mixing 10-12 parts by weight of tetraethoxysilane, 7-10 parts by weight of aluminum isopropoxide, 100-120 parts by weight of ethanol, 2-4 parts by weight of pore-forming agent and 12-15 parts by weight of water, adding 15-20 parts by weight of ammonia water to adjust the pH value, heating to 40-50 ℃, stirring for reacting for 7-10 hours, centrifuging, washing, drying, and calcining at 500-600 ℃ for 1-2 hours to obtain the porous silica/alumina carrier;
S2, modification: adding 100 parts by weight of the porous silica/alumina carrier prepared in the step S1 into 200 parts by weight of ethanol, adding 7-10 parts by weight of a composite silane coupling agent, heating to 35-45 ℃, stirring and reacting for 0.5-1h, centrifuging, washing and drying to prepare a modified porous silica/alumina carrier;
the composite silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 7-10:3-5;
S3, preparing a solid desulfurizing agent: adding 100 parts by weight of the modified porous silica/alumina carrier prepared in the step S2 into 200 parts by weight of water, adding 15-20 parts by weight of soluble zinc salt and 12-15 parts by weight of soluble ferric salt, adding 25-30 parts by weight of citric acid, stirring and mixing uniformly, heating to 60-70 ℃, volatilizing the solvent, calcining at 400-500 ℃ for 2-4 hours, and ball-milling for 1-3 hours to prepare the solid desulfurizing agent.
The invention further protects the solid desulfurizing agent prepared by the preparation method.
The invention has the following beneficial effects: the invention prepares a solid desulfurizing agent, uses the porous nano silicon dioxide prepared by a sol-gel method as a carrier, has the advantages of large specific surface area and more active reaction sites, is modified by a composite silane coupling agent, has abundant amino groups on the surface, fixes Zn and Fe ions through chelation, forms xerogel under the complexing action of citric acid, and calcines to prepare the nano silicon dioxide solid desulfurizing agent with zinc oxide and ferric oxide immobilized, and has the advantages of good desulfurizing effect, high mechanical strength, simple reaction, wide raw material sources, lower cost and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a solid desulfurizing agent, which specifically comprises the following steps:
S1, preparing a porous silica/alumina carrier: uniformly mixing 10 parts by weight of tetraethoxysilane, 7 parts by weight of aluminum isopropoxide, 100 parts by weight of ethanol, 2 parts by weight of hexadecyl trimethyl ammonium chloride and 12 parts by weight of water, adding 15 parts by weight of ammonia water to adjust the pH value, heating to 40 ℃, stirring and reacting for 7 hours, centrifuging, washing, drying, and calcining at 500 ℃ for 1 hour to obtain a porous silica/alumina carrier;
S2, modification: adding 100 parts by weight of the porous silica/alumina carrier prepared in the step S1 into 200 parts by weight of ethanol, adding 7 parts by weight of a composite silane coupling agent, heating to 35 ℃, stirring and reacting for 0.5h, centrifuging, washing and drying to prepare a modified porous silica/alumina carrier;
The composite silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 7:3;
S3, preparing a solid desulfurizing agent: adding 100 parts by weight of the modified porous silica/alumina carrier prepared in the step S2 into 200 parts by weight of water, adding 15 parts by weight of zinc chloride and 12 parts by weight of ferric chloride, adding 25 parts by weight of citric acid, stirring and mixing uniformly, heating to 60 ℃, volatilizing the solvent, calcining at 400 ℃ for 2 hours, and ball-milling for 1 hour to prepare the solid desulfurizing agent.
Example 2
The embodiment provides a preparation method of a solid desulfurizing agent, which specifically comprises the following steps:
S1, preparing a porous silica/alumina carrier: uniformly mixing 11 parts by weight of tetraethoxysilane, 8.5 parts by weight of aluminum isopropoxide, 110 parts by weight of ethanol, 3 parts by weight of hexadecyldimethylbenzyl ammonium chloride and 13 parts by weight of water, adding 17 parts by weight of ammonia water to adjust the pH value, heating to 45 ℃, stirring and reacting for 8 hours, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5 hours to obtain a porous silica/alumina carrier;
s2, modification: adding 100 parts by weight of the porous silica/alumina carrier prepared in the step S1 into 200 parts by weight of ethanol, adding 8.5 parts by weight of a composite silane coupling agent, heating to 40 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare a modified porous silica/alumina carrier;
the composite silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 9:4;
s3, preparing a solid desulfurizing agent: adding 100 parts by weight of the modified porous silica/alumina carrier prepared in the step S2 into 200 parts by weight of water, adding 17 parts by weight of zinc nitrate and 13 parts by weight of ferric nitrate, adding 27 parts by weight of citric acid, stirring and mixing uniformly, heating to 65 ℃, volatilizing the solvent, calcining at 450 ℃ for 3 hours, and ball-milling for 2 hours to prepare the solid desulfurizing agent.
Comparative example 1
The difference from example 2 is that zinc nitrate is not added in step S3.
The method comprises the following steps:
S1, preparing a porous silica/alumina carrier: uniformly mixing 11 parts by weight of tetraethoxysilane, 8.5 parts by weight of aluminum isopropoxide, 110 parts by weight of ethanol, 3 parts by weight of hexadecyldimethylbenzyl ammonium chloride and 13 parts by weight of water, adding 17 parts by weight of ammonia water to adjust the pH value, heating to 45 ℃, stirring and reacting for 8 hours, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5 hours to obtain a porous silica/alumina carrier;
s2, modification: adding 100 parts by weight of the porous silica/alumina carrier prepared in the step S1 into 200 parts by weight of ethanol, adding 8.5 parts by weight of a composite silane coupling agent, heating to 40 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare a modified porous silica/alumina carrier;
the composite silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 9:4;
S3, preparing a solid desulfurizing agent: adding 100 parts by weight of the modified porous silica/alumina carrier prepared in the step S2 into 200 parts by weight of water, adding 30 parts by weight of ferric nitrate, adding 27 parts by weight of citric acid, stirring and mixing uniformly, heating to 65 ℃, volatilizing the solvent, calcining at 450 ℃ for 3 hours, and ball-milling for 2 hours to prepare the solid desulfurizing agent.
Comparative example 2
In comparison with example 2, the difference is that no ferric nitrate was added in step S3.
The method comprises the following steps:
S1, preparing a porous silica/alumina carrier: uniformly mixing 11 parts by weight of tetraethoxysilane, 8.5 parts by weight of aluminum isopropoxide, 110 parts by weight of ethanol, 3 parts by weight of hexadecyldimethylbenzyl ammonium chloride and 13 parts by weight of water, adding 17 parts by weight of ammonia water to adjust the pH value, heating to 45 ℃, stirring and reacting for 8 hours, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5 hours to obtain a porous silica/alumina carrier;
s2, modification: adding 100 parts by weight of the porous silica/alumina carrier prepared in the step S1 into 200 parts by weight of ethanol, adding 8.5 parts by weight of a composite silane coupling agent, heating to 40 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare a modified porous silica/alumina carrier;
the composite silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 9:4;
S3, preparing a solid desulfurizing agent: adding 100 parts by weight of the modified porous silica/alumina carrier prepared in the step S2 into 200 parts by weight of water, adding 30 parts by weight of zinc nitrate, adding 27 parts by weight of citric acid, stirring and mixing uniformly, heating to 65 ℃, volatilizing the solvent, calcining at 450 ℃ for 3 hours, and ball-milling for 2 hours to prepare the solid desulfurizing agent.
Test example 1
The solid desulfurizing agents prepared in examples 1-2 and comparative examples 1-2 of the present invention were subjected to performance test, and the results are shown in Table 1.
TABLE 1
| Group of | Intensity (N/cm) | Bulk Density (Kg/L) | Penetration sulfur capacity (%) | Specific surface area (%) | Desulfurization rate (%) |
| Example 1 | 92 | 0.59 | 62 | 889 | 99.8 |
| Example 2 | 95 | 0.56 | 65 | 894 | 99.9 |
| Comparative example 1 | 88 | 0.62 | 56 | 867 | 87.2 |
| Comparative example 2 | 86 | 0.65 | 55 | 859 | 85.6 |
As can be seen from the above table, the solid desulfurizing agents prepared in examples 1-2 of the present invention have better comprehensive properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. The preparation method of the solid desulfurizing agent is characterized by comprising the following steps:
S1, preparing a porous silica/alumina carrier: uniformly mixing tetraethoxysilane, aluminum isopropoxide, ethanol, a pore-forming agent and water, adding ammonia water to regulate the pH value, heating and stirring for reaction, centrifuging, washing, drying and calcining to obtain a porous silica/alumina carrier; the pore-forming agent is at least one selected from cetyltrimethylammonium chloride, cetyldimethylbenzyl ammonium chloride and cetyldimethylbenzyl ammonium bromide;
s2, modification: adding the porous silica/alumina carrier prepared in the step S1 into ethanol, adding a composite silane coupling agent, heating, stirring, reacting, centrifuging, washing and drying to obtain a modified porous silica/alumina carrier; the composite silane coupling agent is selected from
At least two of KH550, KH602, KH 792;
S3, preparing a solid desulfurizing agent: adding the modified porous silica/alumina carrier prepared in the step S2 into water, adding soluble zinc salt and soluble ferric salt, adding citric acid, stirring and mixing uniformly, heating and volatilizing a solvent, calcining and ball-milling to prepare a solid desulfurizing agent; the mass ratio of the modified porous silica/alumina carrier to the soluble zinc salt to the soluble ferric salt to the citric acid is 100:15-20:12-15:25-30, the heating temperature is 60-70 ℃, the calcining temperature is 400-500 ℃, the time is 2-4h, and the ball milling time is 1-3h.
2. The preparation method according to claim 1, wherein the mass ratio of the ethyl orthosilicate, the aluminum isopropoxide, the ethanol, the pore-forming agent, the water and the ammonia water in the step S1 is 10-12:7-10:100-120:2-4:12-15:15-20.
3. The method according to claim 1, wherein the temperature of the heating and stirring reaction in step S1 is 40-50 ℃ for 5-7 hours, the temperature of the calcination is 500-600 ℃ for 1-2 hours.
4. The preparation method according to claim 1, wherein the mass ratio of the porous silica/alumina carrier and the composite silane coupling agent in the step S2 is 100:7-10; the temperature of the heating and stirring reaction is 35-45 ℃ and the time is 0.5-1h.
5. The method according to claim 1, wherein the composite silane coupling agent in step S2 is KH602
And KH792 in a mass ratio of 7-10:3-5.
6. The preparation method according to claim 1, wherein the soluble zinc salt in step S3 is at least one selected from zinc chloride, zinc sulfate and zinc nitrate, and the soluble iron salt is at least one selected from ferric chloride, ferric sulfate and ferric nitrate.
7. A solid desulfurizing agent produced by the production process according to any one of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102430412A (en) * | 2011-09-16 | 2012-05-02 | 中国海洋石油总公司 | Method for preparing desulfurizer capable of absorbing catalytic cracking gas at high selection |
| CN114849777A (en) * | 2022-04-25 | 2022-08-05 | 贵州大学 | 2D lamellar structure silicon dioxide-based desulfurization catalyst and preparation method thereof |
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| JP3563923B2 (en) * | 1997-06-11 | 2004-09-08 | 三菱重工業株式会社 | Desulfurizing agent and method for producing the same |
| JP4657413B2 (en) * | 2000-02-15 | 2011-03-23 | 堺化学工業株式会社 | Desulfurization agent and method for producing the same |
| US7147769B2 (en) * | 2003-08-25 | 2006-12-12 | Conocophillips Company | Desulfurization and novel methods for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102430412A (en) * | 2011-09-16 | 2012-05-02 | 中国海洋石油总公司 | Method for preparing desulfurizer capable of absorbing catalytic cracking gas at high selection |
| CN114849777A (en) * | 2022-04-25 | 2022-08-05 | 贵州大学 | 2D lamellar structure silicon dioxide-based desulfurization catalyst and preparation method thereof |
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