CN113617217A - Desulfurizer containing nano zinc oxide and production process thereof - Google Patents
Desulfurizer containing nano zinc oxide and production process thereof Download PDFInfo
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- CN113617217A CN113617217A CN202110984691.3A CN202110984691A CN113617217A CN 113617217 A CN113617217 A CN 113617217A CN 202110984691 A CN202110984691 A CN 202110984691A CN 113617217 A CN113617217 A CN 113617217A
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- zinc oxide
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- nano zinc
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000011667 zinc carbonate Substances 0.000 claims abstract description 10
- 229910000010 zinc carbonate Inorganic materials 0.000 claims abstract description 10
- 235000004416 zinc carbonate Nutrition 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 21
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012778 molding material Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 230000003009 desulfurizing effect Effects 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- 238000006477 desulfuration reaction Methods 0.000 abstract description 11
- 230000023556 desulfurization Effects 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 230000007547 defect Effects 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 125000001741 organic sulfur group Chemical group 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 manganese oxide compound Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention relates to a desulfurizer containing nano zinc oxide and a production process thereof, belonging to the technical field of petrochemical industry desulfurization, and comprising the following raw materials in parts by weight: 100-120 parts of active component and 45-55 parts of 2% binder solution by mass fraction, wherein the active component is formed by mixing active nano zinc oxide, zinc carbonate and active filler according to the weight ratio of 100: 1-30: 10-20; one part of active nano zinc oxide is used as a new carrier through zinc carbonate to improve the reaction interface of the active nano zinc oxide, the other part of active nano zinc oxide can be compositely sintered with redundant sites in the carrier with a three-dimensional worm-shaped pore channel structure to form a ternary structure, and the ternary structure is cooperated with loaded manganese oxide to improve the sulfur removal performance.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry desulfurization, and particularly relates to a desulfurizer containing nano zinc oxide and a production process thereof.
Background
The zinc oxide desulfurizer takes zinc oxide as a main component and is added with a bonding agentFine desulfurizing agent prepared from components such as accelerator and the like. High desulfurization precision and simple use, and can be widely applied to the industries of ammonia synthesis, hydrogen production, methanol synthesis, coal chemical industry, petrochemical industry and the like to remove natural gas, petroleum fractions, oil field gas, refinery gas and synthesis gas (CO + H)2) Hydrogen sulfide and some organic sulfur in raw materials such as carbon dioxide.
Metal oxides such as zinc oxide, manganese oxide and the like have good desulfurization performance, but the temperature in the desulfurization process is 400-500 ℃ at present, which means that the use requirements on the aspects of heat resistance strength, oxidation resistance and the like of the desulfurization environment are higher, and pure metal oxides have the defects of easy sintering and low utilization rate, so that good desulfurization can not be carried out at the temperature.
Disclosure of Invention
In order to solve the technical problems, the invention provides a desulfurizer containing nano zinc oxide and a production process thereof.
The purpose of the invention can be realized by the following technical scheme:
a desulfurizer containing nano zinc oxide comprises the following raw materials in parts by weight: 100-120 parts of active component and 45-55 parts of 2% binder solution by mass fraction, wherein the active component is formed by mixing active nano zinc oxide, zinc carbonate and active filler according to the weight ratio of 100: 1-30: 10-20;
the active filler is prepared by the following steps:
step S1, sequentially adding hexadecyl trimethyl ammonium chloride and ethylene diamine tetraacetic acid tetrasodium salt into deionized water, stirring at a high speed of 550r/min for 30min by 450-;
in the step S1, hexadecyl trimethyl ammonium chloride and ethylene diamine tetraacetic acid tetrasodium salt are used as template agents, sodium silicate is added as a silicon source to prepare a crude product, then high-temperature calcination is carried out to prepare a carrier, the template agents are decomposed, and the prepared carrier is of a three-dimensional vermicular pore canal structure;
step S2, adding a manganese nitrate solution with the mass fraction of 50% and cerium nitrate hexahydrate into deionized water in sequence, stirring at a constant speed until the manganese nitrate solution and the cerium nitrate hexahydrate are dissolved, dripping a dilute nitric acid solution with the mass fraction of 30%, stirring at a constant speed and adding citric acid, continuing stirring for 1h, adding a carrier to form a mixed solution, heating in a water bath at 45-60 ℃, continuing stirring at a constant speed until a uniform sol is formed, and keeping the temperature for 1h to prepare a gel, wherein the weight ratio of the manganese nitrate solution, the cerium nitrate hexahydrate, the deionized water, the dilute nitric acid solution and the citric acid is controlled to be 7.35-7.38g, 2.20-2.25g, 30mL, 0.3-0.5mL, 5.5-5.8g, and the using amount of the carrier is one third of the weight sum of the manganese nitrate solution and the cerium nitrate hexahydrate;
and step S3, aging the gel at room temperature for 3 days, then placing the gel in a foaming box at 60 ℃ for foaming treatment for 3 hours, then heating to 110-120 ℃, preserving heat and treating for 7 hours, and finally calcining at 600 ℃ for 6 hours to obtain the active filler.
In step S2, manganese nitrate solution and cerous nitrate hexahydrate are used as raw materials, citric acid is added as a complexing agent, a carrier is added to prepare a gel, and finally calcination treatment is performed to prepare an active filler, the active filler is a carrier-supported manganese oxide composite with a three-dimensional vermicular pore structure in structure, the carrier has the three-dimensional vermicular pore structure, so that the carrier still has sufficient specific surface area and pore channels after being loaded with manganese oxide to provide sufficient reaction space and diffusion conditions for desulfurization of the carrier, and the common knowledge shows that pure metal oxide has good desulfurization performance, but has the defects of easy sintering and low utilization rate, so that the carrier prepared supports the carrier, and the defect can be well solved.
Further, the binder solution with the mass fraction of 2% is a sodium carboxymethylcellulose aqueous solution with the mass fraction of 2%.
Further, the specific surface area of the active nano zinc oxide is 70-80m2/g。
A production process of a desulfurizer containing nano zinc oxide comprises the following steps:
firstly, adding an active component into a binder solution, and uniformly stirring to obtain a mixture;
secondly, placing the mixture in a four-column hydraulic strip extruding machine, extruding and molding under the pressure of 2000KN to prepare a molding material;
thirdly, standing the prepared molding material at room temperature for 12-24h, and curing to obtain a blank;
and fourthly, roasting the prepared blank at 500 ℃ for 3-5 hours by adopting an up-and-down infrared heating mode to prepare the desulfurizer.
The invention has the beneficial effects that:
the desulfurizer of the invention is prepared by roasting active components and a binder, etc. as raw materials, the sodium carboxymethylcellulose is used as the binder, after roasting, the sodium carboxymethylcellulose is burnt and lost, the content of zinc oxide is not influenced, active nano zinc oxide, zinc carbonate and active fillers in the active components have good removal effect on sulfur components in gas, the active fillers have a carrier-supported manganese oxide compound with a three-dimensional worm-shaped pore passage structure, the carrier has the three-dimensional worm-shaped pore passage structure, so that the carrier still has enough specific surface area and pore passages after being loaded with manganese oxide to provide enough reaction space and diffusion conditions for desulfuration, and pure metal oxide has good desulfuration performance, but has the defects of easy sintering and low utilization rate, so the prepared carrier can load the carrier, can well solve the defects, when the desulfurizer of the desulfurizer and the active nano zinc oxide, After the zinc carbonate and the active filler are sintered, one part of active nano zinc oxide is used as a new carrier through the zinc carbonate to improve the reaction interface of the active nano zinc oxide, the other part of active nano zinc oxide can be compositely sintered with redundant sites in the carrier with the three-dimensional vermicular pore channel structure to form a ternary structure, and the ternary structure is cooperated with the loaded manganese oxide to improve the sulfur removal performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of the production process of a desulfurizing agent containing nano-zinc oxide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The active filler is prepared by the following steps:
step S1, sequentially adding hexadecyl trimethyl ammonium chloride and ethylene diamine tetraacetic acid tetrasodium salt into deionized water, stirring at a high speed of 450r/min for 30min, slowly adding sodium silicate, continuously stirring for 30min, transferring to a high-pressure reaction kettle, heating to 100 ℃, crystallizing at the temperature for 48h to obtain a crude product, filtering, washing with deionized water for three times, drying, heating to 550 ℃ at a speed of 5 ℃/min, calcining for 6h to obtain a carrier, and controlling the dosage ratio of the hexadecyl trimethyl ammonium chloride, the ethylene diamine tetraacetic acid tetrasodium salt, the deionized water and the sodium silicate to be 12.5 g: 45 g: 300 mL: 16.30;
step S2, sequentially adding a manganese nitrate solution with the mass fraction of 50% and cerium nitrate hexahydrate into deionized water, stirring at a constant speed until the manganese nitrate solution and the cerium nitrate hexahydrate are dissolved, dropwise adding a dilute nitric acid solution with the mass fraction of 30%, stirring at a constant speed and adding citric acid, continuing stirring for 1h, adding a carrier to form a mixed solution, heating in a 45 ℃ water bath, stirring at a constant speed until a uniform sol is formed, continuing keeping the temperature for 1h to prepare a gel, and controlling the weight ratio of the manganese nitrate solution, the cerium nitrate hexahydrate, the deionized water, the dilute nitric acid solution and the citric acid to be 7.35g, 2.20g, 30mL, 0.3mL, 5.5g, wherein the dosage of the carrier is one third of the sum of the weight of the manganese nitrate solution and the cerium nitrate hexahydrate;
and step S3, aging the gel at room temperature for 3 days, then placing the gel in a foaming box with the temperature of 60 ℃ for foaming treatment for 3 hours, then heating to 110 ℃, preserving heat and treating for 7 hours, and finally calcining at the temperature of 600 ℃ for 6 hours to obtain the active filler.
Example 2
The active filler is prepared by the following steps:
step S1, sequentially adding hexadecyltrimethylammonium chloride and ethylenediaminetetraacetic acid tetrasodium salt into deionized water, stirring at a high speed of 500r/min for 30min, slowly adding sodium silicate, continuously stirring for 30min, transferring to a high-pressure reaction kettle, heating to 100 ℃, crystallizing at the temperature for 48h to obtain a crude product, filtering, washing with deionized water for three times, drying, heating to 550 ℃ at a speed of 5 ℃/min, calcining for 6h to obtain a carrier, and controlling the dosage ratio of the hexadecyltrimethylammonium chloride, the ethylenediaminetetraacetic acid tetrasodium salt, the deionized water and the sodium silicate to be 12.68 g: 45.3 g: 300 mL: 16.33;
step S2, sequentially adding a manganese nitrate solution with the mass fraction of 50% and cerium nitrate hexahydrate into deionized water, stirring at a constant speed until the manganese nitrate solution and the cerium nitrate hexahydrate are dissolved, dropwise adding a dilute nitric acid solution with the mass fraction of 30%, stirring at a constant speed and adding citric acid, continuing stirring for 1h, adding a carrier to form a mixed solution, heating in a water bath at 50 ℃, stirring at a constant speed until a uniform sol is formed, continuing keeping the temperature for 1h to prepare a gel, and controlling the weight ratio of the manganese nitrate solution, the cerium nitrate hexahydrate, the deionized water, the dilute nitric acid solution and the citric acid to be 7.36g, 2.23g, 30mL, 0.4mL, 5.6g, wherein the dosage of the carrier is one third of the sum of the weight of the manganese nitrate solution and the cerium nitrate hexahydrate;
and step S3, aging the gel at room temperature for 3 days, then placing the gel in a foaming box at 60 ℃ for foaming treatment for 3 hours, then heating to 115 ℃, preserving heat and treating for 7 hours, and finally calcining at 600 ℃ for 6 hours to obtain the active filler.
Example 3
The active filler is prepared by the following steps:
step S1, sequentially adding hexadecyl trimethyl ammonium chloride and ethylene diamine tetraacetic acid tetrasodium salt into deionized water, stirring at a high speed of 550r/min for 30min, slowly adding sodium silicate, continuously stirring for 30min, transferring to a high-pressure reaction kettle, heating to 100 ℃, crystallizing at the temperature for 48h to obtain a crude product, filtering, washing with deionized water for three times, drying, heating to 550 ℃ at a speed of 5 ℃/min, calcining for 6h to obtain a carrier, and controlling the dosage ratio of the hexadecyl trimethyl ammonium chloride, the ethylene diamine tetraacetic acid tetrasodium salt, the deionized water and the sodium silicate to be 12.8 g: 45.5 g: 300 mL: 16.35;
step S2, sequentially adding a manganese nitrate solution with the mass fraction of 50% and cerium nitrate hexahydrate into deionized water, stirring at a constant speed until the manganese nitrate solution and the cerium nitrate hexahydrate are dissolved, dropwise adding a dilute nitric acid solution with the mass fraction of 30%, stirring at a constant speed and adding citric acid, continuing stirring for 1h, adding a carrier to form a mixed solution, heating in a water bath at 60 ℃, continuing stirring at a constant speed until uniform sol is formed, keeping the temperature for 1h to prepare gel, and controlling the weight ratio of the manganese nitrate solution, the cerium nitrate hexahydrate, the deionized water, the dilute nitric acid solution and the citric acid to be 7.38g, 2.25g, 30mL, 0.5mL, 5.8g, wherein the dosage of the carrier is one third of the sum of the weight of the manganese nitrate solution and the cerium nitrate hexahydrate;
and step S3, aging the gel at room temperature for 3 days, then placing the gel in a foaming box at 60 ℃ for foaming treatment for 3 hours, then heating to 110-120 ℃, preserving heat and treating for 7 hours, and finally calcining at 600 ℃ for 6 hours to obtain the active filler.
Comparative example 4
Referring to fig. 1, the invention is a desulfurizer containing nano zinc oxide, comprising the following raw materials in parts by weight: 100 parts of active component and 45 parts of binder solution with the mass fraction of 2%, wherein the active component is formed by mixing active nano zinc oxide, zinc carbonate and the active filler prepared in the example 1 according to the weight ratio of 100: 1: 10;
the desulfurizer containing the nano zinc oxide is prepared by the following steps:
firstly, adding an active component into a binder solution with the mass fraction of 2%, and uniformly stirring to obtain a mixture;
secondly, placing the mixture in a four-column hydraulic strip extruding machine, extruding and molding under the pressure of 2000KN to prepare a molding material;
thirdly, standing the prepared molding material at room temperature for 12 hours, and curing to obtain a blank;
and fourthly, roasting the prepared blank at 500 ℃ for 3 hours by adopting an up-and-down infrared heating mode to prepare the desulfurizer.
Comparative example 5
Referring to fig. 1, the invention is a desulfurizer containing nano zinc oxide, comprising the following raw materials in parts by weight: 110 parts of active component and 50 parts of binder solution with the mass fraction of 2%, wherein the active component is formed by mixing active nano zinc oxide, zinc carbonate and the active filler prepared in the example 1 according to the weight ratio of 100: 20: 15;
the desulfurizer containing the nano zinc oxide is prepared by the following steps:
firstly, adding an active component into a binder solution with the mass fraction of 2%, and uniformly stirring to obtain a mixture;
secondly, placing the mixture in a four-column hydraulic strip extruding machine, extruding and molding under the pressure of 2000KN to prepare a molding material;
thirdly, standing the prepared molding material at room temperature for 18 hours, and curing to obtain a blank;
and fourthly, roasting the prepared blank at 500 ℃ for 3 hours by adopting an up-and-down infrared heating mode to prepare the desulfurizer.
Comparative example 6
Referring to fig. 1, the invention is a desulfurizer containing nano zinc oxide, comprising the following raw materials in parts by weight: 120 parts of active component and 55 parts of binder solution with the mass fraction of 2%, wherein the active component is formed by mixing active nano zinc oxide, zinc carbonate and the active filler prepared in the example 1 according to the weight ratio of 100: 30: 20;
the desulfurizer containing the nano zinc oxide is prepared by the following steps:
firstly, adding an active component into a binder solution with the mass fraction of 2%, and uniformly stirring to obtain a mixture;
secondly, placing the mixture in a four-column hydraulic strip extruding machine, extruding and molding under the pressure of 2000KN to prepare a molding material;
thirdly, standing the prepared molding material at room temperature for 24 hours, and curing to obtain a blank;
and fourthly, roasting the prepared blank at 500 ℃ for 5 hours by adopting an up-and-down infrared heating mode to prepare the desulfurizer.
Comparative example 1
Compared with example 1, the active component of the comparative example is replaced by active nano zinc oxide.
Comparative example 2
This comparative example is a commercially available desulfurizing agent produced by a company.
The sulfur removal capacity, organic sulfur and total sulfur capacity of examples 4 to 6 and comparative examples 1 to 2 were measured, and the results are shown in the following tables 1, 2 and 3:
40000ppm of H for raw material gas2S, 150ppm of COS, 100ppm of ethanethiol, 100ppm of propanethiol and 100ppm of methyl sulfide (the balance is high-purity N)2) Space velocity of 5000h-1The temperature is 220 ℃, the pressure is normal, the loading amount of the desulfurizer is 0.8g, the sulfur content of the tail gas at the outlet is respectively controlled to be 10ppb at the reaction end point of the desulfurizer, and the sulfur content in the tail gas is analyzed by adopting a chromatography.
The sulfur capacity calculation formula is as follows:
S＝(V*C)/M
s: sulfur capacity,%;
v: the volume of gas;
c: h in gas2Concentration of S, mg/m3；
M: the loading amount of the desulfurizer;
(1) h in the mixed gas2Removing S gas;
TABLE 1
From Table 1 above, it can be seen that examples 1-3 are for H2S has good removing effect.
(2) Removing organic sulfur in mixed gas:
TABLE 2
| Temperature/. degree.C | Penetration of sulfur capacity/%) | Exit precision/ppb | |
| Example 4 | 220 | 26.71 | 10 |
| Example 5 | 220 | 26.73 | 10 |
| Example 6 | 220 | 26.75 | 10 |
| Comparative example 1 | 220 | 25.11 | 10 |
| Comparative example 2 | 220 | 22.31 | 10 |
It can be seen from table 2 above that examples 1-3 have good effect of removing organic sulfur from the mixed gas.
(3) Removing total sulfur in the gas;
TABLE 3
| Temperature/. degree.C | Penetration of sulfur capacity/%) | Exit precision/ppb | |
| Example 4 | 220 | 46.31 | 10 |
| Example 5 | 220 | 46.28 | 10 |
| Example 6 | 220 | 46.25 | 10 |
| Comparative example 1 | 220 | 33.10 | 10 |
| Comparative example 2 | 220 | 31.25 | 10 |
From table 3 above, it can be seen that examples 4-6 of the present application have a good effect on the removal of total sulfur from a gas.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. The desulfurizer containing nano zinc oxide is characterized by comprising the following raw materials in parts by weight: 100-120 parts of active component and 45-55 parts of 2% binder solution by mass fraction, wherein the active component is formed by mixing active nano zinc oxide, zinc carbonate and active filler according to the weight ratio of 100: 1-30: 10-20;
the active filler is prepared by the following steps:
step S1, sequentially adding hexadecyltrimethylammonium chloride and ethylenediaminetetraacetic acid tetrasodium salt into deionized water, stirring at a high speed of 550r/min for 30min at 450-;
step S2, adding a manganese nitrate solution with the mass fraction of 50% and cerium nitrate hexahydrate into deionized water in sequence, stirring at a constant speed until the manganese nitrate and the cerium nitrate are dissolved, dropwise adding a dilute nitric acid solution with the mass fraction of 30%, stirring at a constant speed, adding citric acid, continuing stirring for 1h, adding a carrier to form a mixed solution, heating in a water bath at 45-60 ℃, stirring at a constant speed until uniform sol is formed, and continuing keeping the temperature for 1h to obtain gel;
and step S3, calcining the gel at 600 ℃ for 6h to obtain the active filler.
2. The desulfurizing agent according to claim 1, wherein the step S3 comprises the following steps: and aging the gel at room temperature for 3 days, then placing the gel in a foaming box at 60 ℃ for foaming treatment for 3 hours, then heating to 110-120 ℃, and preserving heat for 7 hours.
3. The desulfurizer containing nano zinc oxide as claimed in claim 1, wherein the binder solution with a mass fraction of 2% is sodium carboxymethylcellulose aqueous solution with a mass fraction of 2%.
4. The desulfurizing agent according to claim 1, wherein the amount ratio of cetyltrimethylammonium chloride, ethylenediaminetetraacetic acid tetrasodium salt, deionized water and sodium silicate in step S1 is controlled to 12.5-12.8 g: 45-45.5 g: 300 mL: 16.30-16.35.
5. The desulfurizing agent according to claim 1, wherein in step S2, the weight ratio of the manganese nitrate solution, the cerium nitrate hexahydrate, the deionized water, the dilute nitric acid solution and the citric acid is controlled to be 7.35-7.38g, 2.20-2.25g, 30mL, 0.3-0.5mL, 5.5-5.8g, and the amount of the carrier is one third of the sum of the weight of the manganese nitrate solution and the cerium nitrate hexahydrate.
6. The desulfurizing agent according to claim 1, wherein the specific surface area of the active nano-zinc oxide is 70-80m2/g。
7. The production process of the desulfurizing agent containing nano-zinc oxide according to claim 1, comprising the steps of:
firstly, adding an active component into a binder solution, and uniformly stirring to obtain a mixture;
secondly, placing the mixture in a four-column hydraulic strip extruding machine, extruding and molding under the pressure of 2000KN to prepare a molding material;
thirdly, standing the prepared molding material at room temperature for 12-24h, and curing to obtain a blank;
and fourthly, roasting the prepared blank at 500 ℃ for 3-5 hours by adopting an up-and-down infrared heating mode to prepare the desulfurizer.
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Denomination of invention: A desulfurizer containing nano zinc oxide and its production process Effective date of registration: 20231227 Granted publication date: 20230915 Pledgee: Bank of China Limited by Share Ltd. Jiyuan branch Pledgor: JIYUAN LUTAI NANO MATERIAL CO.,LTD. Registration number: Y2023980074439 |