CN115253678A - Method for recycling zinc oxide desulfurizer and application - Google Patents
Method for recycling zinc oxide desulfurizer and application Download PDFInfo
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- CN115253678A CN115253678A CN202210939978.9A CN202210939978A CN115253678A CN 115253678 A CN115253678 A CN 115253678A CN 202210939978 A CN202210939978 A CN 202210939978A CN 115253678 A CN115253678 A CN 115253678A
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- Prior art keywords
- zinc oxide
- agent
- desulfurization
- recycling
- desulfurizer
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 264
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000004064 recycling Methods 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 156
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 141
- 230000023556 desulfurization Effects 0.000 claims abstract description 141
- 239000002699 waste material Substances 0.000 claims abstract description 91
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 20
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000005751 Copper oxide Substances 0.000 claims description 15
- 229910000431 copper oxide Inorganic materials 0.000 claims description 15
- 239000003345 natural gas Substances 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 68
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 30
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 28
- 239000007789 gas Substances 0.000 description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 24
- 239000000843 powder Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 235000011837 pasties Nutrition 0.000 description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 15
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 15
- 238000010298 pulverizing process Methods 0.000 description 15
- 229930192474 thiophene Natural products 0.000 description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 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 description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention belongs to the technical field of recycling of zinc oxide desulfurizer, and particularly relates to a method and application for recycling zinc oxide desulfurizer. The invention provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps of treating desulfurized waste agent with nitrogen or inert gas to obtain a desulfurization treatment agent and then removing mercury. After the zinc oxide desulfurizer is desulfurized, the product is metal sulfide. The surface treatment of the waste desulfurizing agent with hot nitrogen or inert gas may be carried out to eliminate mercury. The invention recycles the desulfurization waste agent for the first time to reduce the solid waste agent, and simultaneously treats the waste agent to be used as the mercury removal agent, thereby improving the economic value.
Description
Technical Field
The invention belongs to the technical field of desulfurizer recycling, and particularly relates to a method for recycling a zinc oxide desulfurizer and application thereof.
Background
Desulfurizing agents, generally agents that remove free sulfur or sulfur compounds from fuels, feedstocks, or other materials; the control and treatment of pollutants are mainly agents used for removing sulfur oxides in exhaust gas.
For example, the prior art discloses a deep evolution fine desulfurizing agent, which comprises 10-30 parts of aluminum oxide, 60-80 parts of nano zinc oxide, 1-6 parts of transition metal oxide, 1-10 parts of alkali metal or alkaline earth metal compound, 1-10 parts of lanthanide metal or oxide thereof, and at least one of germanium, tin, bismuth and antimony metal elements or oxide thereof.
However, in the prior art, few researches on a recycling method of a desulfurizing agent are carried out, mainly because the recycling cost of the desulfurizing agent is high and the operation is difficult, so that the conventional operation in the field is to directly bury the desulfurizing waste agent, and the desulfurizing agent is not effectively recycled.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the desulfurizing agents disclosed in the prior art are all buried directly and are not recycled, so that the method for recycling the zinc oxide desulfurizing agent and the application thereof are provided.
Therefore, the invention provides the following technical scheme,
the invention provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps,
the desulfurization waste agent is treated by nitrogen or inert gas at 110-120 ℃, and the obtained desulfurization treating agent is used as a mercury removing agent.
Optionally, the flow rate of the nitrogen or inert gas treatment is 60-100ml/min; the time for treating the nitrogen or the inert gas is 4-6h.
Optionally, the zinc oxide desulfurizing agent comprises zinc oxide.
Optionally, the zinc oxide desulfurizing agent further comprises at least one of transition metal oxides and alkali metal or alkaline earth metal oxides. Wherein the transition metal oxide is at least one of copper oxide, manganese oxide and nickel oxide; and/or the alkali metal or alkaline earth metal oxide is at least one of sodium oxide, potassium oxide and magnesium oxide.
Optionally, the zinc oxide desulfurizer comprises 50-80% of zinc oxide, 10-15% of transition metal oxide and 5-10% of alkali metal or alkaline earth metal oxide by mass percentage.
Optionally, the zinc oxide desulfurizer further comprises a carrier;
optionally, the carrier is a molecular sieve carrier;
optionally, the carrier is an X-type molecular sieve or a Y-type molecular sieve;
optionally, the specific surface area of the carrier is 400-600m 2 /g。
Optionally, the mass percentage of the carrier in the zinc oxide desulfurizer is 5-35%.
Optionally, the zinc oxide desulfurizing agent further comprises a binder.
Optionally, the binder is silica sol, hydroxymethyl cellulose, and sodium carboxymethyl cellulose.
The zinc oxide desulfurizer of the invention is a conventional zinc oxide desulfurizer in the field, and typically, but not limitatively, the zinc oxide desulfurizer can comprise the following raw materials in parts by weight:
optionally, the zinc oxide is nano zinc oxide, and the particle size of the zinc oxide is not greater than 4nm.
Optionally, the transition metal compound is at least one of basic copper carbonate, copper oxide, manganese carbonate, manganese oxide, nickel carbonate and nickel oxide.
Optionally, the alkali metal or alkaline earth metal compound is at least one of sodium carbonate, potassium carbonate, sodium bicarbonate, magnesium oxide and magnesium carbonate.
Optionally, the preparation method of the zinc oxide desulfurizer comprises the following steps:
after the raw materials are kneaded, an adhesive is added for mixing and grinding, shaping and roasting, the zinc oxide desulfurizer is obtained; wherein, the roasting adopts microwave heat treatment.
Optionally, the roasting temperature is 380-430 ℃; and/or the roasting time is 3-4h.
Optionally, the zinc oxide desulfurizer is converted into the desulfurization waste agent with a surface product of metal sulfide after desulfurization of the sulfur-containing raw material gas.
Optionally, the waste desulfurization agent contains 15-25% of sulfur calculated by elements.
Optionally, the desulfurization treatment agent is used as a natural gas mercury removal agent.
Optionally, in the demercuration process, natural gas is introduced, wherein the natural gas comprises 2000-3000 micrograms/cubic meter of mercury.
Optionally, the demercuration pressure is normal pressure, and/or the demercuration temperature is 30-40 ℃, and/or the demercuration space velocity is 500-1000h -1 。
The invention also provides application of the desulfurization treatment agent obtained by the method for recycling the zinc oxide desulfurizer in the working condition of natural gas demercuration.
The technical proposal provided by the invention has the advantages that,
1. the invention provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps of treating desulfurized waste agent with nitrogen or inert gas to obtain a desulfurization treating agent and then carrying out mercury removal. After the zinc oxide desulfurizer is desulfurized, the product is metal sulfide. The surface treatment of the waste desulfurizing agent with hot nitrogen or inert gas may be carried out to eliminate mercury. The method recycles the desulfurization waste agent for the first time to reduce the solid waste agent, and simultaneously treats the waste agent to be used as the mercury removing agent, thereby improving the economic utilization value.
2. In the method for recycling the zinc oxide desulfurizer, the molecular sieve in the zinc oxide desulfurizer has large specific surface area and regular pore structure, so that the zinc oxide desulfurizer has a proper pore structure, the gas sulfide can better react with the active component, and the metal sulfide obtained after the reaction has a stable structure, is not easy to have pore collapse, is beneficial to reutilization of the waste desulfurization agent after the reaction, and has a high demercuration effect.
3. In the method for recycling the zinc oxide desulfurizer, the preparation method of the zinc oxide desulfurizer has the advantages of simple process, short preparation period, low energy consumption, easy operation and implementation in actual production and no environmental pollution in the whole process. Meanwhile, in the roasting process, microwave heat treatment is adopted, so that the crystal grains of the sample are relatively dispersed, the obvious agglomeration phenomenon is avoided, the boundary is clear, the structure is regular, the crystal appearance is uniform, and the high desulfurization performance is shown.
4. The method for recycling the zinc oxide desulfurizer provided by the invention has the advantages that the desulfurization treating agent obtained by the method is applied to the natural gas demercuration working condition, and the removal precision can reach 0.01ppb.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 5 hours at the nitrogen flow rate of 80ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 50g of silica sol is added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, the mixture is roasted in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating is 380 ℃, and the roasting time is 4 hours, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene is at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 21%.
Example 2
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 4 hours at the nitrogen flow rate of 60ml/min and the temperature of 110 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 4 nm), 25g of molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 29g of silica sol is added, 71g of sodium carboxymethylcellulose is added at the same time, then the mixture is mixed and ground for 30min to form paste, then the paste is extruded into a phi 4 strip shape, the paste is roasted in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating is carried out to 400 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene is at the space velocity of 20000h -1 And carrying out desulfurization treatment at 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 22%.
Example 3
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 5 hours at the nitrogen flow rate of 70ml/min and the temperature of 110 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 2 nm), 25g of molecular sieve powder, 15g of copper oxide and 5g of potassium carbonate are mixed and kneaded for 45min, 12.5g of silica sol is added, 76g of sodium carboxymethylcellulose is added at the same time, then the mixture is mixed and ground for 30min until the mixture is pasty, then the pasty mixture is extruded into a phi 4 strip shape, the mixture is roasted in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the temperature is raised to 400 ℃, and the roasting time is 4 hours, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 24%.
Example 4
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 5 hours at the nitrogen flow rate of 80ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
52g of nano zinc oxide (the particle size is 2 nm), 35g of molecular sieve powder, 15g of manganese oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 72g of sodium carboxymethylcellulose are added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, the mixture is roasted in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating is 400 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene is at the space velocity of 20000h -1 And carrying out desulfurization treatment at 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 25%.
Example 5
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that a waste desulfurization agent is treated for 6 hours at a nitrogen flow rate of 90ml/min and a temperature of 110 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
50g of nano zinc oxide (the particle size is 3 nm), 33g of molecular sieve powder, 10g of copper oxide and 5g of sodium bicarbonate are mixed and kneaded for 45min, 82g of sodium carboxymethylcellulose is added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, and the mixture is roasted in a microwave high-temperature furnace at the initial temperature of 30 ℃, the heating rate of 2 ℃/min, the temperature of 430 ℃ and the roasting time of 4h to obtain the nano zinc oxide desulfurizer.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 24%.
Example 6
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 4 hours at the nitrogen flow rate of 80ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
70g of nano zinc oxide (the particle size is 4 nm), 20g of molecular sieve powder, 10g of nickel oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 72g of sodium carboxymethylcellulose are added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, the mixture is roasted in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating is 400 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene is at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 22%.
Example 7
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 5 hours at the nitrogen flow rate of 90ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
mixing and kneading 80g of nano zinc oxide (the particle size is 3 nm), 7g of molecular sieve powder, 18g of basic copper carbonate and 5g of magnesium oxide for 45min, adding 72g of sodium carboxymethylcellulose, mixing and grinding for 30min until the mixture is pasty, extruding the pasty mixture into a phi 4 strip shape, roasting the mixture in a microwave high-temperature furnace at the initial temperature of 30 ℃, the heating rate of 2 ℃/min, the heating rate of 400 ℃ and the roasting time of 4h, and obtaining the nano zinc oxide desulfurizer.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene is at the space velocity of 20000h -1 And carrying out desulfurization treatment at 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 23%.
Example 8
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 6 hours at the nitrogen flow rate of 90ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
70g of nano zinc oxide (the particle size is 3 nm), 18.8g of molecular sieve powder, 10g of copper oxide and 10.5g of magnesium carbonate are kneaded for 45min, 62g of sodium carboxymethylcellulose are added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, and the mixture is roasted in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating is 400 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene is at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 22%.
Example 9
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 5 hours at the nitrogen flow rate of 80ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 6 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 50g of silica sol is added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, the mixture is roasted in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating is 380 ℃, and the roasting time is 4 hours, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 20%.
Example 10
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 5 hours at the nitrogen flow rate of 80ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 50g of silica sol is added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, the phi 4 strip shape is dried for 2 hours by a drying box, and then the mixture is roasted for 4 hours at 380 ℃ by a muffle furnace, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh powder containing 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 20%.
Example 11
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated for 4 hours at the nitrogen flow rate of 100ml/min and the temperature of 120 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
50g of nano zinc oxide (the particle size is 4 nm), 35g of X-type molecular sieve powder, 15g of copper oxide and 10g of sodium carbonate are kneaded for 45min, 60g of sodium carboxymethylcellulose are added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, and the mixture is roasted in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating rate is 430 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 24%.
Example 12
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that a waste desulfurization agent is treated for 6 hours at a nitrogen flow rate of 60ml/min and a temperature of 110 ℃, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
80g of nano zinc oxide (the particle size is 4 nm), 20g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are kneaded for 45min, 60g of sodium carboxymethylcellulose are added, then the mixture is mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, and the mixture is roasted in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating rate is 430 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh powder containing 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 25%.
Example 13
The comparative example provides a recycling method of a zinc oxide desulfurizer, which comprises the following steps that the desulfurization waste agent is treated for 5 hours at the temperature of 120 ℃ at the flow rate of argon gas of 70ml/min, and the obtained desulfurization treating agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 50g of silica sol is added, then mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, and the mixture is roasted in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating rate is 380 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene is at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 23%.
Comparative example 1
The embodiment provides a method for recycling a zinc oxide desulfurizer, which comprises the following steps that the waste desulfurization agent is treated at normal temperature for 5 hours at the nitrogen flow rate of 80ml/min, and the obtained desulfurization treatment agent is used as a mercury removal agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 50g of silica sol is added, then mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, and the mixture is roasted in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating rate is 380 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh, and adding 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 21%.
Comparative example 2
This comparative example provides a method for recycling a zinc oxide desulfurizing agent, comprising the step of using the desulfurization waste agent directly as a mercury removing agent.
Wherein the waste desulfurization agent is obtained by converting a zinc oxide desulfurizer after desulfurization. The raw material composition, the preparation method and the formation process of the waste desulfurization agent are as follows:
60g of nano zinc oxide (the particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are mixed and kneaded for 45min, 50g of silica sol is added, then mixed and ground for 30min until the mixture is pasty, then the mixture is extruded into a phi 4 strip shape, and the mixture is roasted in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating rate is 380 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
Pulverizing the zinc oxide desulfurizer to 40-60 mesh powder containing 280mg/m 3 Hydrogen sulfide, 10mg/m 3 Carbonyl sulfide and a total concentration of 10mg/m 3 The raw gas of mercaptan and thiophene at the space velocity of 20000h -1 And carrying out desulfurization treatment at the temperature of 30 ℃ to obtain the desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 21%.
Test example 1
The desulfurization treatment agents obtained in examples 1 to 13 and comparative examples 1 to 2 were placed in a reactor, and then natural gas having a mercury content of 2500. Mu.g/m was introduced into the reactor to conduct a reaction at 40 ℃ under normal pressure 3 The reaction space velocity is 1000h -1 。
The desulfurization effect of the zinc oxide desulfurizer obtained by desulfurization in examples 1 to 13 and comparative examples 1 to 2 was tested, and the indexes of the mercury removal effect were the tail gas outlet accuracy and the mercury capacity.
The calculation method of the tail gas outlet precision comprises the following steps:
17.5mL of potassium permanganate absorption solution was added to the gas absorption bottle, and 400L of off-gas was sampled through the gas absorption bottle using a wet gas flow meter. The absorption solution was transferred to a 200mL volumetric flask, and the gas absorption flask was washed with deionized water and the wash was incorporated into the 200mL volumetric flask. Hydroxylamine hydrochloride solution was added dropwise until colorless. And (5) using deionized water to fix the volume to the scale. Accurately transferring 5.00mL of sample to a mercury detector (model CG-1C, manufacturer: jiangsu gold instrument) reduction bottle for measuring mercury. The corresponding mercury content (ng) was obtained from the mercury photometer.
The mercury capacity calculation method comprises the following steps:
sample mercury capacity X C1 The numerical value is expressed in (%) and is calculated as follows:
wherein:
g-the amount of mercury measured by a mercury-sensing instrument, in nanograms (ng);
m-sample mass in grams (g);
v-sample size in milliliters (mL).
The specific test results are shown in the following table:
as can be seen from the above table, the zinc oxide desulfurizer is obtained after extrusion molding of 50-80% of zinc oxide, 10-15% of transition metal, 5-10% of alkaline earth metal and 10-40% of molecular sieve. After desulfurization, the mercury removing agent is obtained after hot nitrogen treatment. The demercuration precision can reach 0.01ppb, and the mercury capacity can reach 7.6-8.3%. If the treatment is not carried out in an inert atmosphere, or the desulfurization waste agent is treated at normal temperature, the demercuration precision can only reach 0.05ppb, and the mercury capacity can only reach 5.1%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A method for recycling a zinc oxide desulfurizer is characterized by comprising the following steps of,
the desulfurization waste agent is treated by nitrogen or inert gas at 110-120 ℃, and the obtained desulfurization treating agent is used as a mercury removing agent.
2. The method for recycling the zinc oxide desulfurizing agent according to claim 1, wherein the flow rate of the nitrogen or inert gas treatment is 60-100ml/min;
the time for treating the nitrogen or the inert gas is 4-6h.
3. The method for recycling the zinc oxide desulfurizing agent according to claim 1 or 2, wherein the zinc oxide desulfurizing agent comprises zinc oxide.
4. The method for recycling zinc oxide desulfurizer as claimed in claim 3, wherein the zinc oxide desulfurizer further comprises at least one of transition metal oxide, alkali metal or alkaline earth metal oxide,
wherein the transition metal oxide is at least one of copper oxide, manganese oxide and nickel oxide;
and/or the alkali metal or alkaline earth metal oxide is at least one of sodium oxide, potassium oxide and magnesium oxide.
5. The method for recycling the zinc oxide desulfurizer according to claim 4, wherein the zinc oxide desulfurizer comprises 50 to 80% by mass of zinc oxide, 10 to 15% by mass of transition metal oxide, and 5 to 10% by mass of alkali metal or alkaline earth metal oxide.
6. The method for recycling the zinc oxide desulfurizer according to claim 3, wherein the zinc oxide desulfurizer further comprises a carrier;
optionally, the carrier is a molecular sieve carrier;
optionally, the carrier is an X-type molecular sieve or a Y-type molecular sieve;
optionally, the mass percentage of the carrier in the zinc oxide desulfurizer is 5-35%.
7. The method for recycling the zinc oxide desulfurizer according to any one of claims 1 to 6, wherein the desulfurization waste agent contains 20 to 25% of sulfur in terms of element.
8. The method for recycling the zinc oxide desulfurizing agent according to any one of claims 1 to 7, wherein the zinc oxide desulfurizing agent is used as a natural gas mercury removing agent.
9. The method for recycling the zinc oxide desulfurizing agent according to claim 8, wherein in the demercuration process, natural gas is introduced, and the natural gas comprises 2000-3000 micrograms of mercury per cubic meter.
10. The method for recycling the zinc oxide desulfurizer as claimed in claim 9, wherein the demercuration pressure is normal pressure, and/or the demercuration temperature is 30-40 ℃, and/or the demercuration space velocity is 500-1000h -1 。
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