CN117443154B - Natural gas desulfurizing agent and preparation method and application thereof - Google Patents
Natural gas desulfurizing agent and preparation method and application thereof Download PDFInfo
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- CN117443154B CN117443154B CN202311266114.6A CN202311266114A CN117443154B CN 117443154 B CN117443154 B CN 117443154B CN 202311266114 A CN202311266114 A CN 202311266114A CN 117443154 B CN117443154 B CN 117443154B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003345 natural gas Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 title claims description 9
- 230000003009 desulfurizing effect Effects 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 31
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 30
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000292 calcium oxide Substances 0.000 claims description 28
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 24
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 17
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 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 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 125000002081 peroxide group Chemical group 0.000 abstract 2
- 238000010301 surface-oxidation reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 19
- 229940097156 peroxyl Drugs 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 9
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 4
- 150000002978 peroxides Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002973 irritant agent Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
本发明提供了一种天然气脱硫剂及其制备方法和应用，属于能源净化技术领域。本发明制备得到的天然气脱硫剂为表面富氧化复合金属脱硫剂，其具有丰富的表面醇类官能团和过氧官能团，吸附和氧化能力较强，一方面能够将H2S化学吸附在脱硫剂表面形成金属硫化物，另一方面，在脱硫剂表面的过氧官能团和Fe2+/Fe3+的相互作用下，将H2S氧化为单质硫；脱硫剂表面双金属的协同作用，能够提高Fe2+/Fe3+的循环转化效率，提高脱硫剂的使用寿命和抗硫中毒特性。实施例结果表明，本发明提供的天然气脱硫剂天然气中H2S脱除效率高于99％。
The present invention provides a natural gas desulfurizer and a preparation method and application thereof, belonging to the field of energy purification technology. The natural gas desulfurizer prepared by the present invention is a surface-oxidation-rich composite metal desulfurizer, which has abundant surface alcohol functional groups and peroxide functional groups, and has strong adsorption and oxidation capabilities. On the one hand, H2S can be chemically adsorbed on the surface of the desulfurizer to form metal sulfides, and on the other hand, under the interaction between the peroxide functional groups on the surface of the desulfurizer and Fe2 + /Fe3 + , H2S is oxidized to elemental sulfur; the synergistic effect of the bimetallic on the surface of the desulfurizer can improve the circulation conversion efficiency of Fe2+ /Fe3 + , and improve the service life and anti-sulfur poisoning characteristics of the desulfurizer. The results of the embodiment show that the natural gas desulfurizer provided by the present invention has an H2S removal efficiency of more than 99% in natural gas.
Description
技术领域Technical Field
本发明涉及能源净化技术领域，特别涉及一种天然气脱硫剂及其制备方法和应用。The present invention relates to the technical field of energy purification, and in particular to a natural gas desulfurizing agent, a preparation method and application thereof.
背景技术Background technique
天然气是我国主要的能源，开采出来的天然气中含有较多的硫化物杂质，主要为硫化氢(H2S)。H2S是一种有毒的刺激性气体，不仅会造成大气环境的污染，也会在天然气的利用和输送过程中造成催化剂中毒和管器件腐蚀。含硫天然气燃烧后还会产生SO2，造成酸雨的产生。因此，为了实现环保要求和天然气利用需求，需要将天然气中的H2S深度净化脱除。Natural gas is the main energy source in China. The natural gas extracted contains a large amount of sulfide impurities, mainly hydrogen sulfide (H 2 S). H 2 S is a toxic and irritating gas that not only pollutes the atmospheric environment, but also causes catalyst poisoning and pipe corrosion during the use and transportation of natural gas. After the combustion of sulfur-containing natural gas, SO 2 is also produced, causing acid rain. Therefore, in order to meet environmental protection requirements and natural gas utilization needs, it is necessary to deeply purify and remove H 2 S in natural gas.
目前H2S的脱除方法包括干法、半干法和湿法。其中，半干法和湿法脱硫效率较高，但是其存在操作成本高、副产物种类多、二次污染等缺点。相比半干法和湿法脱硫技术，干法具有更高的抗中毒性能、更高的选择性、更低的操作成本和更少的二次污染。中国专利CN201610536607.0公开了“一种深度净化精脱硫剂及其制备方法”，该方法将ZnAl2O4、碱金属氧化物、重金属氧化物混合制备成精脱硫剂，实现了低温甲醇洗工艺中H2S的深度脱除。中国专利CN201710025806.X公开了“一种氧化锌基常温深度脱硫剂及其制备方法与应用”，该方法将锌盐、铝盐和助剂金属盐通过沉淀法制备氧化锌基复合脱硫剂，实现了低温条件下H2S的深度脱除。At present, the removal methods of H 2 S include dry method, semi-dry method and wet method. Among them, the semi-dry method and wet method have higher desulfurization efficiency, but they have disadvantages such as high operating cost, many types of by-products, and secondary pollution. Compared with semi-dry and wet desulfurization technologies, the dry method has higher anti-poisoning performance, higher selectivity, lower operating cost and less secondary pollution. Chinese patent CN201610536607.0 discloses "a deep purification fine desulfurizer and its preparation method", which mixes ZnAl 2 O 4 , alkali metal oxides, and heavy metal oxides to prepare a fine desulfurizer, and realizes the deep removal of H 2 S in the low-temperature methanol washing process. Chinese patent CN201710025806.X discloses "a zinc oxide-based room temperature deep desulfurizer and its preparation method and application", which prepares zinc oxide-based composite desulfurizer by precipitation method with zinc salt, aluminum salt and auxiliary metal salt, and realizes the deep removal of H 2 S under low temperature conditions.
然而，目前脱硫剂存在使用寿命低、抗硫中毒性差的缺陷。However, current desulfurizers have the disadvantages of short service life and poor resistance to sulfur poisoning.
发明内容Summary of the invention
有鉴于此，本发明目的在于提供一种天然气脱硫剂及其制备方法和应用。本发明制备方法简单，成本低，所得天然气脱硫剂不仅能高效脱除天然气中的H2S，还具有高抗硫性，使用寿命长，能有效解决天然气脱硫净化的问题。In view of this, the present invention aims to provide a natural gas desulfurizer and its preparation method and application. The preparation method of the present invention is simple and low in cost. The obtained natural gas desulfurizer can not only efficiently remove H2S from natural gas, but also has high sulfur resistance and long service life, and can effectively solve the problem of natural gas desulfurization and purification.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
本发明提供了一种天然气脱硫剂的制备方法，包括以下步骤：The present invention provides a method for preparing a natural gas desulfurizer, comprising the following steps:
将混合金属硝酸盐、碳酸钠混合，将所得混合粉末溶解于有机溶剂中，得到混合金属盐溶液；所述混合金属硝酸盐包括硝酸铁和其他金属硝酸盐；所述有机溶剂包括N-甲基二乙醇胺和/或无水乙醇；所述其他金属硝酸盐为硝酸铜、硝酸锌、硝酸铝和硝酸镍中的一种或几种；Mixing a mixed metal nitrate and sodium carbonate, and dissolving the obtained mixed powder in an organic solvent to obtain a mixed metal salt solution; the mixed metal nitrate comprises iron nitrate and other metal nitrates; the organic solvent comprises N-methyldiethanolamine and/or anhydrous ethanol; the other metal nitrate is one or more of copper nitrate, zinc nitrate, aluminum nitrate and nickel nitrate;
将氧化钙、双氧水与水混合，得到含过氧自由基的氢氧化钙溶液；Mixing calcium oxide, hydrogen peroxide and water to obtain a calcium hydroxide solution containing peroxyl radicals;
在通入臭氧的条件下，将所述混合金属盐溶液、含过氧自由基的氢氧化钙溶液混合，进行沉淀反应，去除所得沉淀反应液的有机溶剂和水分，得到天然气脱硫剂。Under the condition of introducing ozone, the mixed metal salt solution and the calcium hydroxide solution containing peroxyl radicals are mixed to carry out precipitation reaction, and the organic solvent and water in the obtained precipitation reaction liquid are removed to obtain a natural gas desulfurizer.
优选的，所述硝酸铁与其他硝酸盐的质量比为2～5:1。Preferably, the mass ratio of the ferric nitrate to other nitrates is 2 to 5:1.
优选的，所述混合金属硝酸盐和碳酸钠的质量比为1:0.5～2；Preferably, the mass ratio of the mixed metal nitrate to sodium carbonate is 1:0.5-2;
所述混合粉末与有机溶剂的质量比为1:5～10。The mass ratio of the mixed powder to the organic solvent is 1:5-10.
优选的，所述氧化钙与双氧水的质量比为1:1～4；Preferably, the mass ratio of calcium oxide to hydrogen peroxide is 1:1 to 4;
所述氧化钙、双氧水与水混合时，水的质量为氧化钙与双氧水总质量的5～10倍。When the calcium oxide, hydrogen peroxide and water are mixed, the mass of the water is 5 to 10 times the total mass of the calcium oxide and hydrogen peroxide.
优选的，所述混合金属盐溶液与含过氧自由基的氢氧化钙溶液的质量比为1:0.5～3。Preferably, the mass ratio of the mixed metal salt solution to the calcium hydroxide solution containing peroxyl radicals is 1:0.5-3.
优选的，以1kg混合金属盐溶液、含过氧自由基的氢氧化钙溶液的混合液计，所述臭氧的通入流量为50～100mL/min。Preferably, based on 1 kg of the mixed solution of the mixed metal salt solution and the calcium hydroxide solution containing peroxyl radicals, the ozone introduction flow rate is 50-100 mL/min.
优选的，所述去除所得沉淀反应液的有机溶剂和水分后，还包括对所得固体进行自然晾晒，所述自然晾晒的时间为24～48h。Preferably, after removing the organic solvent and water from the precipitation reaction solution, the method further comprises airing the solid obtained naturally, and the time for the natural airing is 24 to 48 hours.
本发明提供了上述制备方法制备得到的天然气脱硫剂，成分包括钙基多孔载体和负载在所述钙基多孔载体表面和内部孔隙的混合金属氧化物，所述钙基多孔载体成分包括CaCO3和/或Ca(OH)2，所述钙基多孔载体表面具有醇类官能团和过氧官能团；The present invention provides a natural gas desulfurizer prepared by the above preparation method, which comprises a calcium-based porous carrier and a mixed metal oxide loaded on the surface and internal pores of the calcium-based porous carrier, wherein the calcium-based porous carrier comprises CaCO 3 and/or Ca(OH) 2 , and the surface of the calcium-based porous carrier has an alcohol functional group and a peroxide functional group;
所述混合金属氧化物包括二价铁氧化物、三价铁氧化物和其他金属氧化物，所述其他金属为铜、锌、铝和镍中的一种或几种。The mixed metal oxides include divalent iron oxides, trivalent iron oxides and other metal oxides, and the other metals are one or more of copper, zinc, aluminum and nickel.
本发明提供了上述天然气脱硫剂在脱除H2S中的应用。The present invention provides the use of the natural gas desulfurizing agent in removing H 2 S.
优选的，所述天然气脱硫剂的工作温度为常温～150℃，工作压力为常压～8.0MPa。Preferably, the working temperature of the natural gas desulfurizer is between room temperature and 150° C., and the working pressure is between normal pressure and 8.0 MPa.
本发明提供了一种天然气脱硫剂的制备方法，包括以下步骤：将混合金属硝酸盐、碳酸钠混合，将所得混合粉末溶解于有机溶剂中，得到混合金属盐溶液；所述混合金属硝酸盐包括硝酸铁和其他金属硝酸盐；所述有机溶剂包括N-甲基二乙醇胺和/或无水乙醇；所述其他金属硝酸盐为硝酸铜、硝酸锌、硝酸铝和硝酸镍中的一种或几种；将氧化钙、双氧水与水混合，得到含过氧自由基的氢氧化钙溶液；在通入臭氧的条件下，将所述混合金属盐溶液、含过氧自由基的氢氧化钙溶液混合，进行沉淀反应，去除所得沉淀反应液的有机溶剂和水分，得到天然气脱硫剂。本发明通过加入碳酸钠，在混合的过程中碳酸钠与金属硝酸盐形成金属胶体，形成的金属胶体主要为碳酸盐和附着在碳酸盐表面的游离态离子，胶体形式能够保证金属盐及金属离子的高度分散性。胶体中的碳酸盐和氢氧化钙反应可以生成碳酸钙和金属氢氧化物，氧化钙遇水生成氢氧化钙，由于双氧水的加入，水中的过氧自由基就会与氢氧化钙结合产生含过氧自由基的氢氧化钙，同时臭氧也能够进一步补充溶液中的过氧自由基，提高含过氧自由基的氢氧化钙的含量。双氧水和臭氧在与氢氧化钙结合的过程中还会在氢氧化钙内部产生大量游离氧气，这些游离氧气在干燥过程中随着水分的蒸发会产生大量的孔隙，促使脱硫剂具有多孔结构。The present invention provides a method for preparing a natural gas desulfurizer, comprising the following steps: mixing a mixed metal nitrate and sodium carbonate, dissolving the obtained mixed powder in an organic solvent to obtain a mixed metal salt solution; the mixed metal nitrate includes iron nitrate and other metal nitrates; the organic solvent includes N-methyldiethanolamine and/or anhydrous ethanol; the other metal nitrates are one or more of copper nitrate, zinc nitrate, aluminum nitrate and nickel nitrate; mixing calcium oxide, hydrogen peroxide and water to obtain a calcium hydroxide solution containing peroxyl radicals; mixing the mixed metal salt solution and the calcium hydroxide solution containing peroxyl radicals under the condition of passing ozone, performing a precipitation reaction, removing the organic solvent and water of the obtained precipitation reaction liquid, and obtaining a natural gas desulfurizer. The present invention forms a metal colloid by adding sodium carbonate, and in the mixing process, the sodium carbonate and the metal nitrate form a metal colloid, and the formed metal colloid is mainly carbonate and free ions attached to the surface of the carbonate, and the colloidal form can ensure the high dispersibility of the metal salt and the metal ion. The carbonate in the colloid reacts with calcium hydroxide to generate calcium carbonate and metal hydroxide. Calcium oxide generates calcium hydroxide when it meets water. Due to the addition of hydrogen peroxide, the peroxyl radicals in the water will combine with calcium hydroxide to generate calcium hydroxide containing peroxyl radicals. At the same time, ozone can further supplement the peroxyl radicals in the solution and increase the content of calcium hydroxide containing peroxyl radicals. In the process of combining with calcium hydroxide, hydrogen peroxide and ozone will also generate a large amount of free oxygen inside the calcium hydroxide. These free oxygen will generate a large number of pores as the water evaporates during the drying process, which makes the desulfurizer have a porous structure.
本发明制备得到的天然气脱硫剂为表面富氧化复合金属脱硫剂，其具有丰富的表面醇类官能团和过氧官能团，吸附和氧化能力较强，一方面能够将H2S化学吸附在脱硫剂表面形成金属硫化物，另一方面，在脱硫剂表面的过氧官能团和Fe2+/Fe3+的相互作用下，将H2S氧化为单质硫；脱硫剂表面双金属的协同作用，能够提高Fe2+/Fe3+的循环转化效率，提高脱硫剂的使用寿命和抗硫中毒特性。实施例结果表明，本发明提供的天然气脱硫剂天然气中H2S脱除效率高于99％。The natural gas desulfurizer prepared by the present invention is a surface-enriched oxide composite metal desulfurizer, which has abundant surface alcohol functional groups and peroxide functional groups, and has strong adsorption and oxidation capabilities. On the one hand, H2S can be chemically adsorbed on the surface of the desulfurizer to form metal sulfide, and on the other hand, under the interaction between the peroxide functional groups on the surface of the desulfurizer and Fe2 + /Fe3 + , H2S is oxidized to elemental sulfur; the synergistic effect of the double metal on the surface of the desulfurizer can improve the circulation conversion efficiency of Fe2+ /Fe3 + , and improve the service life and anti-sulfur poisoning characteristics of the desulfurizer. The results of the embodiment show that the natural gas desulfurizer provided by the present invention has a H2S removal efficiency in natural gas higher than 99%.
同时，本发明提供的制备方法操作简单、条件温和、成本低廉，易于实现工业化批量化生产；有机溶剂N-甲基二乙醇胺、无水乙醇和水分可以通过冷凝的方式收集后循环使用，天然气中的H2S在净化过程中得到脱除及资源化利用，产物清洁，无二次污染，工艺绿色环保。Meanwhile, the preparation method provided by the present invention is simple to operate, has mild conditions, is low in cost, and is easy to realize industrialized batch production; the organic solvent N-methyldiethanolamine, anhydrous ethanol and water can be collected by condensation and then recycled, and H2S in natural gas is removed and recycled during the purification process, the product is clean, has no secondary pollution, and the process is green and environmentally friendly.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例1脱硫剂的H2S去除效率；FIG1 is a diagram showing the H 2 S removal efficiency of the desulfurizer of Example 1 of the present invention;
图2为本发明实施例2脱硫剂的H2S去除效率；FIG2 is a graph showing the H 2 S removal efficiency of the desulfurizer of Example 2 of the present invention;
图3为本发明实施例3脱硫剂的H2S去除效率。FIG. 3 shows the H 2 S removal efficiency of the desulfurizer of Example 3 of the present invention.
具体实施方式Detailed ways
本发明提供了一种天然气脱硫剂的制备方法，包括以下步骤：The present invention provides a method for preparing a natural gas desulfurizer, comprising the following steps:
将混合金属硝酸盐、碳酸钠混合，将所得混合粉末溶解于有机溶剂中，得到混合金属盐溶液；所述混合金属硝酸盐包括硝酸铁和其他金属硝酸盐；所述有机溶剂包括N-甲基二乙醇胺和/或无水乙醇；所述其他金属硝酸盐为硝酸铜、硝酸锌、硝酸铝和硝酸镍中的一种或几种；Mixing a mixed metal nitrate and sodium carbonate, and dissolving the obtained mixed powder in an organic solvent to obtain a mixed metal salt solution; the mixed metal nitrate comprises iron nitrate and other metal nitrates; the organic solvent comprises N-methyldiethanolamine and/or anhydrous ethanol; the other metal nitrate is one or more of copper nitrate, zinc nitrate, aluminum nitrate and nickel nitrate;
将氧化钙、双氧水与水混合，得到含过氧自由基的氢氧化钙溶液；Mixing calcium oxide, hydrogen peroxide and water to obtain a calcium hydroxide solution containing peroxyl radicals;
在通入臭氧的条件下，将所述混合金属盐溶液、含过氧自由基的氢氧化钙溶液混合，进行沉淀反应，去除所得沉淀反应液的有机溶剂和水分，得到天然气脱硫剂。Under the condition of introducing ozone, the mixed metal salt solution and the calcium hydroxide solution containing peroxyl radicals are mixed to carry out precipitation reaction, and the organic solvent and water in the obtained precipitation reaction liquid are removed to obtain a natural gas desulfurizer.
在本发明中，所述混合金属硝酸盐包括硝酸铁和其他金属硝酸盐，所述其他金属硝酸盐优选为硝酸铜、硝酸锌、硝酸铝和硝酸镍中的一种或几种。在本发明中，所述硝酸铁与其他硝酸盐的质量比优选为2～5:1，更优选为3～4:1。In the present invention, the mixed metal nitrate includes iron nitrate and other metal nitrates, and the other metal nitrates are preferably one or more of copper nitrate, zinc nitrate, aluminum nitrate and nickel nitrate. In the present invention, the mass ratio of the iron nitrate to the other nitrates is preferably 2 to 5:1, more preferably 3 to 4:1.
在本发明中，所述混合金属硝酸盐和碳酸钠的质量比优选为1:0.5～2，更优选为1:1～1.5。在本发明中，所述碳酸钠的作用是将金属硝酸盐形成胶体。在本发明中，当混合金属硝酸盐和碳酸钠的质量比为1:0.5～2时，由于碳酸钠的剂量低于完全反应的消耗量，因此胶体中还会有部分的离子态的金属存在，可以增强金属的可迁移特性。In the present invention, the mass ratio of the mixed metal nitrate to sodium carbonate is preferably 1:0.5-2, more preferably 1:1-1.5. In the present invention, the role of the sodium carbonate is to form a colloid of the metal nitrate. In the present invention, when the mass ratio of the mixed metal nitrate to sodium carbonate is 1:0.5-2, since the dosage of sodium carbonate is lower than the consumption of the complete reaction, part of the ionic metal will still exist in the colloid, which can enhance the transferability of the metal.
在本发明中，所述有机溶剂包括N-甲基二乙醇胺和/或无水乙醇。In the present invention, the organic solvent includes N-methyldiethanolamine and/or anhydrous ethanol.
在本发明中，所述混合粉末与有机溶剂的质量比优选为1:5～10，更优选为1:6～8。In the present invention, the mass ratio of the mixed powder to the organic solvent is preferably 1:5-10, more preferably 1:6-8.
在本发明中，所述混合粉末溶解于有机溶剂的方式优选为搅拌混合，所述搅拌速度优选为500～800r/min，更优选为600～700r/min；搅拌时间优选为1～3h，更优选为2h；在本发明中，所述混合优选在常温常压下进行。In the present invention, the mixed powder is preferably dissolved in the organic solvent by stirring and mixing, and the stirring speed is preferably 500-800 r/min, more preferably 600-700 r/min; the stirring time is preferably 1-3 h, more preferably 2 h; in the present invention, the mixing is preferably carried out at room temperature and pressure.
本发明将氧化钙、双氧水与水混合，得到含过氧自由基的氢氧化钙溶液。在本发明中，所述氧化钙与双氧水的质量比优选为1:1～4，更优选为1:2～3。在本发明中，所述水优选为纯净水，所述水的质量优选为氧化钙与双氧水总质量的5～10倍，更优选为6～8倍。在本发明中，所述混合优选为搅拌混合，所述搅拌的速度优选为200～400r/min，更优选为300r/min；搅拌时间优选为0.5～2h，更优选为1～1.5h；在本发明中，所述混合优选在常温常压下进行。The present invention mixes calcium oxide, hydrogen peroxide and water to obtain a calcium hydroxide solution containing peroxyl radicals. In the present invention, the mass ratio of calcium oxide to hydrogen peroxide is preferably 1:1-4, more preferably 1:2-3. In the present invention, the water is preferably pure water, and the mass of the water is preferably 5-10 times the total mass of calcium oxide and hydrogen peroxide, more preferably 6-8 times. In the present invention, the mixing is preferably stirring mixing, and the stirring speed is preferably 200-400r/min, more preferably 300r/min; the stirring time is preferably 0.5-2h, more preferably 1-1.5h; in the present invention, the mixing is preferably carried out at normal temperature and pressure.
本发明在通入臭氧的条件下，将所述混合金属盐溶液、含过氧自由基的氢氧化钙溶液混合，进行沉淀反应，去除所得沉淀反应液的有机溶剂和水分，得到天然气脱硫剂。在本发明中，以1kg混合金属盐溶液、含过氧自由基的氢氧化钙溶液混合的混合液计，所述臭氧的通入流量优选为50～100mL/min，更优选为60～80mL/min。The present invention mixes the mixed metal salt solution and the calcium hydroxide solution containing peroxyl radicals under the condition of introducing ozone, performs precipitation reaction, removes the organic solvent and water of the obtained precipitation reaction liquid, and obtains a natural gas desulfurizer. In the present invention, the introduction flow rate of the ozone is preferably 50-100 mL/min, more preferably 60-80 mL/min, based on 1 kg of the mixed liquid of the mixed metal salt solution and the calcium hydroxide solution containing peroxyl radicals.
在本发明中，所述混合金属盐溶液与含过氧自由基的氢氧化钙溶液混合的质量比优选为1:0.5～3，更优选为1:2。在本发明中，所述混合的方式优选为搅拌混合，所述搅拌的速率优选为800～1500r/min，更优选为1000～1200r/min。In the present invention, the mass ratio of the mixed metal salt solution to the calcium hydroxide solution containing peroxyl radicals is preferably 1:0.5-3, more preferably 1:2. In the present invention, the mixing method is preferably stirring mixing, and the stirring rate is preferably 800-1500r/min, more preferably 1000-1200r/min.
本发明优选在搅拌的条件下进行所述沉淀反应。在本发明中，所述沉淀反应的时间优选为10～30min，更优选为20min；在本发明中，所述沉淀反应优选在常温常压下进行。In the present invention, the precipitation reaction is preferably carried out under stirring. In the present invention, the precipitation reaction time is preferably 10 to 30 minutes, more preferably 20 minutes; in the present invention, the precipitation reaction is preferably carried out at room temperature and pressure.
在本发明中，去除所得沉淀反应液的有机溶剂和水分的方式优选为真空干燥。本发明对所述真空干燥的方式没有特殊的要求，使用本领域技术人员熟知的真空干燥方式即可。在本发明中，真空干燥得到的纯净水和有机溶剂可以循环利用。In the present invention, the method for removing the organic solvent and water from the obtained precipitation reaction solution is preferably vacuum drying. The present invention has no special requirements for the vacuum drying method, and a vacuum drying method well known to those skilled in the art can be used. In the present invention, the pure water and organic solvent obtained by vacuum drying can be recycled.
在本发明中，所述去除所得混合液的有机溶剂和水分后，还包括对所得固体进行自然晾晒，所述自然晾晒的时间优选为24～48h；在本发明中，所述自然晾晒优选在通风干燥环境下进行。In the present invention, after removing the organic solvent and water from the obtained mixed liquid, the obtained solid is further subjected to natural drying, and the natural drying time is preferably 24 to 48 hours; in the present invention, the natural drying is preferably carried out in a ventilated and dry environment.
本发明提供了上述制备方法制备得到的天然气脱硫剂，成分包括钙基多孔载体和负载在所述钙基多孔载体表面和内部孔隙的混合金属氧化物，所述钙基多孔载体成分包括CaCO3和/或Ca(OH)2，所述钙基多孔载体表面具有醇类官能团和过氧官能团；所述混合金属氧化物包括二价铁氧化物和三价铁氧化物。The present invention provides a natural gas desulfurizer prepared by the above preparation method, which comprises a calcium-based porous carrier and a mixed metal oxide loaded on the surface and internal pores of the calcium-based porous carrier, wherein the calcium-based porous carrier comprises CaCO 3 and/or Ca(OH) 2 , and the surface of the calcium-based porous carrier has alcohol functional groups and peroxide functional groups; the mixed metal oxide comprises divalent iron oxide and trivalent iron oxide.
在本发明中，由于用作形成金属胶体的碳酸钠的含量是低于完全反应所需的量的，所以会导致有一部分Fe3+在醇溶液的环境下通过羟基官能团的作用被还原成Fe2+，因此催化剂表面是存在一定量的Fe2+的。同时，把当前脱硫剂用在脱除H2S的过程中，H2S中的S2-也能够将部分Fe3+还原为Fe2+，从而实现Fe2+和Fe3+在脱硫剂上的共存。In the present invention, since the content of sodium carbonate used to form the metal colloid is lower than the amount required for complete reaction, part of Fe 3+ is reduced to Fe 2+ by the action of hydroxyl functional groups in the environment of alcohol solution, so there is a certain amount of Fe 2+ on the catalyst surface. At the same time, when the current desulfurizer is used in the process of removing H 2 S, S 2- in H 2 S can also reduce part of Fe 3+ to Fe 2+ , thereby achieving the coexistence of Fe 2+ and Fe 3+ on the desulfurizer.
本发明提供了上述天然气脱硫剂在脱除H2S中的应用。The present invention provides the use of the natural gas desulfurizing agent in removing H 2 S.
在本发明中，所述天然气脱硫剂的工作温度优选为常温～150℃，工作压力优选为常压～8.0MPa。In the present invention, the working temperature of the natural gas desulfurizer is preferably room temperature to 150° C., and the working pressure is preferably normal pressure to 8.0 MPa.
下面结合实施例对本发明提供的天然气脱硫剂及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The natural gas desulfurizer provided by the present invention, its preparation method and application are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
实施例1Example 1
将混合金属硝酸盐(硝酸铁和硝酸铜，质量比2:1)和碳酸钠按照质量比1:2混合，形成混合固体粉末A。将混合固体粉末A按质量比1:8溶解于N-甲基二乙醇胺，在常温常压下以500r/min转速搅拌3h，作为溶液B。将氧化钙和双氧水按照质量比1:4混合，并加入氧化钙和双氧水质量总和的10倍的纯净水，在常温常压下以300r/min转速搅拌2h，作为溶液C。将溶液B和溶液C按照质量比1:3在常温常压下以800r/min转速搅拌20min，搅拌过程中向混合液中通入气体流量为60mL/kg/min的臭氧，作为溶液D。将溶液D通过真空干燥的方式脱去水分和N-甲基二乙醇胺，得到固体E。将固体E置于通风干燥环境下自然晾晒24h，即得到天然气脱硫剂。Mixed metal nitrates (ferric nitrate and copper nitrate, mass ratio 2:1) and sodium carbonate are mixed in a mass ratio of 1:2 to form a mixed solid powder A. The mixed solid powder A is dissolved in N-methyldiethanolamine in a mass ratio of 1:8, and stirred at 500r/min for 3h at room temperature and pressure to obtain solution B. Calcium oxide and hydrogen peroxide are mixed in a mass ratio of 1:4, and pure water 10 times the mass of calcium oxide and hydrogen peroxide is added, and stirred at 300r/min for 2h at room temperature and pressure to obtain solution C. Solution B and solution C are stirred at a mass ratio of 1:3 at a speed of 800r/min for 20min at room temperature and pressure, and ozone with a gas flow rate of 60mL/kg/min is introduced into the mixed solution during stirring to obtain solution D. Solution D is dehydrated and N-methyldiethanolamine is removed by vacuum drying to obtain solid E. Solid E is placed in a ventilated and dry environment for natural drying for 24h to obtain a natural gas desulfurizer.
脱硫剂的活性测试在固定床石英反应器中进行，反应条件为：H2S浓度10000ppm、空速100000h-1、反应温度30℃，H2S的去除率结果见图1，从图中可以看出H2S去除率达到100％，且能维持48h，这表明脱硫剂对H2S的去除有明显的效果。The activity test of the desulfurizer was carried out in a fixed bed quartz reactor. The reaction conditions were: H 2 S concentration 10000ppm, space velocity 100000h -1 , reaction temperature 30°C. The H 2 S removal rate results are shown in Figure 1. It can be seen from the figure that the H 2 S removal rate reached 100% and could be maintained for 48 hours, which shows that the desulfurizer has a significant effect on the removal of H 2 S.
所得天然气脱硫剂的XRF元素分析结果如表1所示。The XRF elemental analysis results of the obtained natural gas desulfurizer are shown in Table 1.
表1催化剂元素分析Table 1 Elemental analysis of catalyst
实施例2Example 2
将混合金属硝酸盐(硝酸铁和硝酸锌，质量比5:1)和碳酸钠按照质量比1:1混合，形成混合固体粉末A。将混合固体粉末A按质量比1:10溶解于无水乙醇，在常温常压下以600r/min转速搅拌2h，作为溶液B。将氧化钙和双氧水按照质量比1:2混合，并加入氧化钙和双氧水质量总和的5倍的纯净水，在常温常压下以400r/min转速搅拌1h，作为溶液C。将溶液B和溶液C按照质量比1:1在常温常压下以1200r/min转速搅拌10min，搅拌过程中向混合液中通入气体流量为50mL/kg/min的臭氧，作为溶液D。将溶液D通过真空干燥的方式脱去水分和无水乙醇，得到固体E。将固体E置于通风干燥环境下自然晾晒36h，即得到天然气脱硫剂。Mixed metal nitrates (iron nitrate and zinc nitrate, mass ratio 5:1) and sodium carbonate are mixed in a mass ratio of 1:1 to form a mixed solid powder A. The mixed solid powder A is dissolved in anhydrous ethanol in a mass ratio of 1:10, and stirred at 600r/min for 2h at room temperature and pressure to obtain solution B. Calcium oxide and hydrogen peroxide are mixed in a mass ratio of 1:2, and pure water 5 times the total mass of calcium oxide and hydrogen peroxide is added, and stirred at 400r/min for 1h at room temperature and pressure to obtain solution C. Solution B and solution C are stirred at a mass ratio of 1:1 at a speed of 1200r/min for 10min at room temperature and pressure, and ozone with a gas flow rate of 50mL/kg/min is introduced into the mixed solution during stirring to obtain solution D. Solution D is dehydrated and anhydrous ethanol is removed by vacuum drying to obtain solid E. Solid E is placed in a ventilated and dry environment for natural drying for 36h to obtain a natural gas desulfurizer.
脱硫剂的活性测试在固定床石英反应器中进行，反应条件为：H2S浓度10000ppm、空速100000h-1、反应温度80℃，H2S的去除率结果见图2，从图中可以看出H2S去除率达到100％，且能维持63h，这表明脱硫剂对H2S的去除有明显的效果。The activity test of the desulfurizer was carried out in a fixed bed quartz reactor. The reaction conditions were: H 2 S concentration 10000ppm, space velocity 100000h -1 , reaction temperature 80°C. The H 2 S removal rate results are shown in Figure 2. It can be seen from the figure that the H 2 S removal rate reached 100% and could be maintained for 63h, which shows that the desulfurizer has a significant effect on the removal of H 2 S.
实施例3Example 3
将混合金属硝酸盐(硝酸铁和硝酸铝，质量比4:1)和碳酸钠按照质量比1:0.5混合，形成混合固体粉末A。将混合固体粉末A按质量比1:5溶解于N-甲基二乙醇胺，在常温常压下以800r/min转速搅拌1h，作为溶液B。将氧化钙和双氧水按照质量比1:1混合，并加入氧化钙和双氧水质量总和的7倍的纯净水，在常温常压下以200r/min转速搅拌0.5h，作为溶液C。将溶液B和溶液C按照质量比1:0.5在常温常压下以1500r/min转速搅拌30min，搅拌过程中向混合液中通入气体流量为100mL/kg/min的臭氧，作为溶液D。将溶液D通过真空干燥的方式脱去水分和N-甲基二乙醇胺，得到固体E。将固体E置于通风干燥环境下自然晾晒48h，即得到天然气脱硫剂。Mixed metal nitrates (iron nitrate and aluminum nitrate, mass ratio 4:1) and sodium carbonate are mixed in a mass ratio of 1:0.5 to form a mixed solid powder A. The mixed solid powder A is dissolved in N-methyldiethanolamine in a mass ratio of 1:5, and stirred at 800r/min for 1h at room temperature and pressure to obtain solution B. Calcium oxide and hydrogen peroxide are mixed in a mass ratio of 1:1, and pure water 7 times the total mass of calcium oxide and hydrogen peroxide is added, and stirred at 200r/min for 0.5h at room temperature and pressure to obtain solution C. Solution B and solution C are stirred at a mass ratio of 1:0.5 at a speed of 1500r/min for 30min at room temperature and pressure, and ozone with a gas flow rate of 100mL/kg/min is introduced into the mixed solution during stirring to obtain solution D. Solution D is dehydrated and N-methyldiethanolamine is removed by vacuum drying to obtain solid E. Solid E is placed in a ventilated and dry environment and naturally dried for 48h to obtain a natural gas desulfurizer.
脱硫剂的活性测试在固定床石英反应器中进行，反应条件为：H2S浓度10000ppm、空速100000h-1、反应温度45℃，H2S的去除率结果见图3，从图中可以看出H2S去除率达到100％，且能维持54h，这表明脱硫剂对H2S的去除有明显的效果。The activity test of the desulfurizer was carried out in a fixed bed quartz reactor. The reaction conditions were: H 2 S concentration 10000ppm, space velocity 100000h -1 , reaction temperature 45°C. The H 2 S removal rate results are shown in Figure 3. It can be seen from the figure that the H 2 S removal rate reached 100% and could be maintained for 54h, which shows that the desulfurizer has a significant effect on the removal of H 2 S.
对比例1Comparative Example 1
将硝酸铜和碳酸钠按照质量比1:2混合，形成混合固体粉末A。将混合固体粉末A按质量比1:8溶解于N-甲基二乙醇胺，在常温常压下以500r/min转速搅拌3h，作为溶液B。将氧化钙和双氧水按照质量比1:4混合，并加入氧化钙和双氧水质量总和的10倍的纯净水，在常温常压下以300r/min转速搅拌2h，作为溶液C。将溶液B和溶液C按照质量比1:3在常温常压下以800r/min转速搅拌20min，搅拌过程中向混合液中通入气体流量为60mL/kg/min的臭氧，作为溶液D。将溶液D通过真空干燥的方式脱去水分和N-甲基二乙醇胺，得到固体E。将固体E置于通风干燥环境下自然晾晒24h，即得到天然气脱硫剂。Copper nitrate and sodium carbonate were mixed in a mass ratio of 1:2 to form a mixed solid powder A. The mixed solid powder A was dissolved in N-methyldiethanolamine in a mass ratio of 1:8, and stirred at 500r/min for 3h at room temperature and pressure to obtain solution B. Calcium oxide and hydrogen peroxide were mixed in a mass ratio of 1:4, and pure water 10 times the mass of calcium oxide and hydrogen peroxide was added, and stirred at 300r/min for 2h at room temperature and pressure to obtain solution C. Solution B and solution C were stirred at a mass ratio of 1:3 at a speed of 800r/min for 20min at room temperature and pressure, and ozone with a gas flow rate of 60mL/kg/min was introduced into the mixed solution during stirring to obtain solution D. Solution D was dehydrated and N-methyldiethanolamine was removed by vacuum drying to obtain solid E. Solid E was placed in a ventilated and dry environment for natural drying for 24h to obtain a natural gas desulfurizer.
脱硫剂的活性测试在固定床石英反应器中进行，反应条件为：H2S浓度10000ppm、空速100000h-1、反应温度30℃，未添加硝酸铁的脱硫剂的H2S去除率最高只能达到87％。The activity test of the desulfurizer was carried out in a fixed bed quartz reactor. The reaction conditions were: H 2 S concentration 10000 ppm, space velocity 100000 h -1 , reaction temperature 30° C. The H 2 S removal rate of the desulfurizer without adding ferric nitrate could only reach 87% at most.
对比例2Comparative Example 2
将硝酸铁和碳酸钠按照质量比1:2混合，形成混合固体粉末A。将混合固体粉末A按质量比1:8溶解于N-甲基二乙醇胺，在常温常压下以500r/min转速搅拌3h，作为溶液B。将氧化钙和双氧水按照质量比1:4混合，并加入氧化钙和双氧水质量总和的10倍的纯净水，在常温常压下以300r/min转速搅拌2h，作为溶液C。将溶液B和溶液C按照质量比1:3在常温常压下以800r/min转速搅拌20min，搅拌过程中向混合液中通入气体流量为60mL/kg/min的臭氧，作为溶液D。将溶液D通过真空干燥的方式脱去水分和N-甲基二乙醇胺，得到固体E。将固体E置于通风干燥环境下自然晾晒24h，即得到天然气脱硫剂。Ferric nitrate and sodium carbonate were mixed in a mass ratio of 1:2 to form a mixed solid powder A. The mixed solid powder A was dissolved in N-methyldiethanolamine in a mass ratio of 1:8, and stirred at 500r/min for 3h at room temperature and pressure to obtain solution B. Calcium oxide and hydrogen peroxide were mixed in a mass ratio of 1:4, and pure water 10 times the mass of calcium oxide and hydrogen peroxide was added, and stirred at 300r/min for 2h at room temperature and pressure to obtain solution C. Solution B and solution C were stirred at a mass ratio of 1:3 at a speed of 800r/min for 20min at room temperature and pressure, and ozone with a gas flow rate of 60mL/kg/min was introduced into the mixed solution during stirring to obtain solution D. Solution D was dehydrated and N-methyldiethanolamine was removed by vacuum drying to obtain solid E. Solid E was placed in a ventilated and dry environment for natural airing for 24h to obtain a natural gas desulfurizer.
脱硫剂的活性测试在固定床石英反应器中进行，反应条件为：H2S浓度10000ppm、空速100000h-1、反应温度30℃，未添加其他硝酸盐的脱硫剂的H2S去除率达到100％，仅能维持11h。The activity test of the desulfurizer was carried out in a fixed bed quartz reactor. The reaction conditions were: H 2 S concentration 10000 ppm, space velocity 100000 h -1 , reaction temperature 30°C. The H 2 S removal rate of the desulfurizer without adding other nitrates reached 100%, which could only be maintained for 11 hours.
对比例3Comparative Example 3
将混合金属硝酸盐(硝酸铁和硝酸铜，质量比8:1)和碳酸钠按照质量比1:2混合，形成混合固体粉末A。将混合固体粉末A按质量比1:8溶解于N-甲基二乙醇胺，在常温常压下以500r/min转速搅拌3h，作为溶液B。将氧化钙和双氧水按照质量比1:4混合，并加入氧化钙和双氧水质量总和的10倍的纯净水，在常温常压下以300r/min转速搅拌2h，作为溶液C。将溶液B和溶液C按照质量比1:3在常温常压下以800r/min转速搅拌20min，搅拌过程中向混合液中通入气体流量为60mL/kg/min的臭氧，作为溶液D。将溶液D通过真空干燥的方式脱去水分和N-甲基二乙醇胺，得到固体E。将固体E置于通风干燥环境下自然晾晒24h，即得到天然气脱硫剂。Mixed metal nitrates (iron nitrate and copper nitrate, mass ratio 8:1) and sodium carbonate are mixed in a mass ratio of 1:2 to form a mixed solid powder A. Dissolve the mixed solid powder A in N-methyldiethanolamine in a mass ratio of 1:8, and stir at 500r/min for 3h at room temperature and pressure to obtain solution B. Calcium oxide and hydrogen peroxide are mixed in a mass ratio of 1:4, and pure water 10 times the mass of calcium oxide and hydrogen peroxide is added, and stirred at 300r/min for 2h at room temperature and pressure to obtain solution C. Solution B and solution C are stirred at a mass ratio of 1:3 at a speed of 800r/min for 20min at room temperature and pressure, and ozone with a gas flow rate of 60mL/kg/min is introduced into the mixed solution during stirring to obtain solution D. Solution D is dehydrated and N-methyldiethanolamine is removed by vacuum drying to obtain solid E. Solid E is placed in a ventilated and dry environment for natural drying for 24h to obtain a natural gas desulfurizer.
脱硫剂的活性测试在固定床石英反应器中进行，反应条件为：H2S浓度10000ppm、空速100000h-1、反应温度30℃，未在最佳混合硝酸盐质量比范围内的脱硫剂的H2S去除率达到100％，仅能维持15h。The activity test of the desulfurizer was carried out in a fixed bed quartz reactor. The reaction conditions were: H 2 S concentration 10000 ppm, space velocity 100000 h -1 , reaction temperature 30°C. The H 2 S removal rate of the desulfurizer that was not within the optimal mixed nitrate mass ratio range reached 100%, which could only be maintained for 15 hours.
对比例4Comparative Example 4
将混合金属硝酸盐(硝酸铁和硝酸铜，质量比2:1)和碳酸钠按照质量比1:2混合，形成混合固体粉末A。将混合固体粉末A按质量比1:8溶解于纯净水，在常温常压下以500r/min转速搅拌3h，作为溶液B。将氧化钙和双氧水按照质量比1:4混合，并加入氧化钙和双氧水质量总和的10倍的纯净水，在常温常压下以300r/min转速搅拌2h，作为溶液C。将溶液B和溶液C按照质量比1:3在常温常压下以800r/min转速搅拌20min，搅拌过程中向混合液中通入气体流量为60mL/kg/min的臭氧，作为溶液D。将溶液D通过真空干燥的方式脱去水分，得到固体E。将固体E置于通风干燥环境下自然晾晒24h，即得到天然气脱硫剂。Mixed metal nitrates (iron nitrate and copper nitrate, mass ratio 2:1) and sodium carbonate are mixed in a mass ratio of 1:2 to form a mixed solid powder A. Dissolve the mixed solid powder A in pure water in a mass ratio of 1:8, and stir at a speed of 500r/min for 3h at room temperature and pressure to obtain solution B. Mix calcium oxide and hydrogen peroxide in a mass ratio of 1:4, add pure water 10 times the mass of calcium oxide and hydrogen peroxide, and stir at a speed of 300r/min for 2h at room temperature and pressure to obtain solution C. Stir solution B and solution C in a mass ratio of 1:3 at a speed of 800r/min at room temperature and pressure for 20min, and pass ozone with a gas flow rate of 60mL/kg/min into the mixed solution during stirring to obtain solution D. Remove moisture from solution D by vacuum drying to obtain solid E. Place solid E in a ventilated and dry environment for natural drying for 24h to obtain a natural gas desulfurizer.
脱硫剂的活性测试在固定床石英反应器中进行，反应条件为：H2S浓度10000ppm、空速100000h-1、反应温度30℃，未添加醇类溶剂的脱硫剂的H2S去除率只能达到96％。The activity test of the desulfurizer was carried out in a fixed bed quartz reactor. The reaction conditions were: H 2 S concentration 10000 ppm, space velocity 100000 h -1 , reaction temperature 30° C. The H 2 S removal rate of the desulfurizer without adding alcohol solvent could only reach 96%.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
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| CN101754809A (en) * | 2007-07-23 | 2010-06-23 | 朗盛德国有限责任公司 | Method for producing chelate resins |
| CN103920454A (en) * | 2014-04-29 | 2014-07-16 | 哈尔滨理工大学 | Composite copper-based desulfurizing agent for removing sulfur-containing repugnant substances at normal temperature and preparation method of composite copper-based desulfurizing agent |
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