CN115253678B - Method for recycling zinc oxide desulfurizing agent and application - Google Patents
Method for recycling zinc oxide desulfurizing agent and application Download PDFInfo
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- CN115253678B CN115253678B CN202210939978.9A CN202210939978A CN115253678B CN 115253678 B CN115253678 B CN 115253678B CN 202210939978 A CN202210939978 A CN 202210939978A CN 115253678 B CN115253678 B CN 115253678B
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- zinc oxide
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- desulfurization
- desulfurizing agent
- oxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 288
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 220
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 144
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000004064 recycling Methods 0.000 title claims abstract description 41
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 118
- 230000023556 desulfurization Effects 0.000 claims abstract description 118
- 239000002699 waste material Substances 0.000 claims abstract description 91
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 55
- 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
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 5
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 21
- 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
- 239000002994 raw material Substances 0.000 description 33
- 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
- 239000007789 gas Substances 0.000 description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000002156 mixing Methods 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
- 239000002245 particle Substances 0.000 description 15
- 239000000843 powder Substances 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
- 238000000227 grinding Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 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
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 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
- 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
- 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
- 239000002184 metal Substances 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
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 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
- 239000007788 liquid Substances 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
- 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
- 238000002459 porosimetry Methods 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 zinc oxide desulfurizing agent recycling, and particularly relates to a method for recycling a zinc oxide desulfurizing agent and application thereof. The invention provides a method for recycling a zinc oxide desulfurizing agent, which comprises the following steps of treating a desulfurized waste agent after desulfurization by nitrogen or inert gas to obtain a desulfurizing agent and then removing mercury. After desulfurization, the product of the zinc oxide desulfurizing agent is metal sulfide. After the surface treatment of the desulfurization waste agent by hot nitrogen or inert gas, mercury removal treatment can be performed. The invention firstly recycles the desulfurization waste agent to reduce the solid waste agent, and simultaneously treats the waste agent and then is used as the mercury removal agent, thereby improving the economic value.
Description
Technical Field
The invention belongs to the technical field of desulfurization agent recycling, and particularly relates to a method for recycling a zinc oxide desulfurization agent and application thereof.
Background
Desulfurizing agents, generally, refer to agents that remove free sulfur or sulfur compounds from fuels, feedstocks, or other materials; the main reference in the control and treatment of pollutants is to agents used to remove sulfur oxides from exhaust gases.
For example, the prior art discloses a deep evolution fine desulfurizing agent comprising 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, antimony metal element or oxide thereof.
However, in the prior art, there are few researches on recycling methods of desulfurizing agents, mainly because of high recycling cost and difficult operation of the desulfurizing agents, so that the conventional operation in the field is to directly bury the desulfurizing waste agents, and the desulfurizing agents are not recycled effectively.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the desulfurizing agents disclosed in the prior art are directly buried 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 proposal,
The invention provides a method for recycling zinc oxide desulfurizing agent, which comprises the following steps,
The desulfurization waste agent is treated by nitrogen or inert gas at 110-120 ℃ to obtain the desulfurization treatment agent which is used as a mercury removal agent.
Optionally, the flow rate of the nitrogen or inert gas treatment is 60-100ml/min; the treatment time of the nitrogen or the inert gas is 4-6h.
Optionally, the zinc oxide desulfurizing agent comprises zinc oxide.
Optionally, 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.
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 percent.
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 desulfurizer further comprises a binder.
Optionally, the binder is silica sol, hydroxymethyl cellulose, or sodium carboxymethyl cellulose.
The zinc oxide desulfurizer of the invention is a conventional zinc oxide desulfurizer in the field, and is typically not limited, and 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 more 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 desulfurizing agent comprises the following steps:
mixing and kneading the raw materials, adding an adhesive, mixing and grinding, shaping and roasting to obtain the zinc oxide desulfurizing agent; 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 desulfurizing agent is converted into the desulfurizing waste agent with the surface product being metal sulfide after desulfurizing the sulfur-containing raw material gas.
Optionally, the desulfurization waste agent comprises 15-25% of sulfur in terms of elements.
Optionally, the desulfurization treatment agent is used as a natural gas mercury removal agent.
Optionally, natural gas is introduced in the mercury removal process, wherein the natural gas comprises 2000-3000 micrograms of mercury per cubic meter.
Optionally, the mercury removal pressure is normal pressure, and/or the mercury removal temperature is 30-40 ℃, and/or the mercury removal airspeed is 500-1000h -1.
The invention also provides application of the desulfurization treatment agent obtained by the zinc oxide desulfurization agent recycling method in natural gas mercury removal working conditions.
The technical proposal provided by the invention has the following advantages,
1. The invention provides a method for recycling a zinc oxide desulfurizing agent, which comprises the following steps of treating a desulfurized waste agent after desulfurization with nitrogen or inert gas to obtain a desulfurizing agent and then removing mercury. After desulfurization, the product of the zinc oxide desulfurizing agent is metal sulfide. After the surface treatment of the desulfurization waste agent by hot nitrogen or inert gas, mercury removal treatment can be performed. The invention firstly recycles the desulfurization waste agent to reduce the solid waste agent, and simultaneously treats the waste agent and then is used as the mercury removal agent, thereby improving the economic utilization value.
2. According to the method for recycling the zinc oxide desulfurizer, the molecular sieve in the zinc oxide desulfurizer has a large specific surface area and a regular pore structure, so that the zinc oxide desulfurizer has a proper pore structure, gas sulfide can better react with active components, the metal sulfide obtained after the reaction is stable in structure, pore collapse is not easy to occur, the recycling of the desulfurization waste agent after the reaction is facilitated, and the mercury removal effect is high.
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, the microwave heat treatment is adopted, the crystal grains of the sample are more dispersed, no obvious agglomeration phenomenon exists, the boundary is clear, the structure is regular, the crystal appearance is uniform, and the high desulfurization performance is shown.
4. According to the method for recycling the zinc oxide desulfurizing agent, the desulfurizing agent obtained by the method is applied to the natural gas mercury removal working condition, and the removal accuracy can reach 0.01ppb.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 5 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 80ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
60g of nano zinc oxide (particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are kneaded for 45min, 50g of silica sol is added, mixed and milled for 30min until paste is formed, extruded into phi 4 strip shape, baked in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the temperature is raised to 380 ℃ and the baking time is 4h, thus obtaining the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 21%.
Example 2
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 4 hours at the temperature of 110 ℃ under the condition that the flow rate of nitrogen is 60ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
Mixing 60g of nano zinc oxide (particle size of 4 nm), 25g of molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate for 45min, adding 29g of silica sol, simultaneously adding 71g of sodium carboxymethyl cellulose, mixing and grinding for 30min until paste is formed, extruding the paste into phi 4 strips, roasting in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating time is 4h, and the nano zinc oxide desulfurizer is obtained.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 22%.
Example 3
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 5 hours at the temperature of 110 ℃ under the condition that the flow rate of nitrogen is 70ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
Mixing 60g of nano zinc oxide (particle size of 2 nm), 25g of molecular sieve powder, 15g of copper oxide and 5g of potassium carbonate for 45min, adding 12.5g of silica sol, adding 76g of sodium carboxymethyl cellulose, mixing and grinding for 30min until paste is formed, extruding the paste into phi 4 strips, roasting in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating time is 4h, and the nano zinc oxide desulfurizer is obtained.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 24%.
Example 4
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 5 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 80ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
Mixing 52g of nano zinc oxide (particle size of 2 nm), 35g of molecular sieve powder, 15g of manganese oxide and 5g of sodium carbonate for 45min, adding 72g of sodium carboxymethyl cellulose, mixing and grinding for 30min until the mixture becomes paste, extruding the paste into phi 4 strips, roasting in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating time is 400 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 25%.
Example 5
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 6 hours at the temperature of 110 ℃ under the condition that the flow rate of nitrogen is 90ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
50g of nano zinc oxide (particle size is 3 nm), 33g of molecular sieve powder, 10g of copper oxide and 5g of sodium bicarbonate are kneaded for 45min, 82g of sodium carboxymethyl cellulose is added, mixed and milled for 30min until paste is formed, extruded into phi 4 strip shape, baked in a microwave high-temperature furnace, and heated to 430 ℃ at an initial temperature of 30 ℃ and a heating rate of 2 ℃/min for 4h, thus obtaining the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 24%.
Example 6
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 4 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 80ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
Mixing 70g of nano zinc oxide (particle size of 4 nm), 20g of molecular sieve powder, 10g of nickel oxide and 5g of sodium carbonate for 45min, adding 72g of sodium carboxymethyl cellulose, mixing and grinding for 30min until the mixture becomes paste, extruding the paste into phi 4 strips, roasting in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating time is 400 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 22%.
Example 7
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 5 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 90ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
Mixing 80g of nano zinc oxide (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 carboxymethyl cellulose, mixing and grinding for 30min until the paste is formed, extruding the paste into phi 4 strips, roasting in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating time is 400 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 23%.
Example 8
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 6 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 90ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
Mixing 70g of nano zinc oxide (particle size of 3 nm), 18.8g of molecular sieve powder, 10g of copper oxide and 10.5g of magnesium carbonate for 45min, adding 62g of sodium carboxymethyl cellulose, mixing and grinding for 30min until paste is formed, extruding the paste into phi 4 strips, roasting in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating time is 4h, and the nano zinc oxide desulfurizer is obtained.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 22%.
Example 9
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 5 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 80ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
60g of nano zinc oxide (with the grain diameter of 6 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are kneaded for 45min, 50g of silica sol is added, mixed and milled for 30min until paste is formed, extruded into phi 4 strip shape, baked in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the temperature is raised to 380 ℃ and the baking time is 4h, thus obtaining the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 20%.
Example 10
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 5 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 80ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
60g of nano zinc oxide (particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are kneaded for 45min, 50g of silica sol is added, and then mixed and milled for 30min until paste is formed, then extruded into phi 4 strip shape, dried for 2 h by a drying box, and then baked for 4h by a muffle furnace at 380 ℃ to obtain the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 20%.
Example 11
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 4 hours at the temperature of 120 ℃ under the condition that the flow rate of nitrogen is 100ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
50g of nano zinc oxide (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 carboxymethyl cellulose is added, then mixed and milled for 30min until paste is formed, then extruded into phi 4 strip shape, baked in a microwave high-temperature furnace, and heated to 430 ℃ at an initial temperature of 30 ℃ and a heating rate of 2 ℃/min for 4h, thus obtaining the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 24%.
Example 12
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 6 hours at the temperature of 110 ℃ under the condition that the flow rate of nitrogen is 60ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
Mixing 80g of nano zinc oxide (particle size of 4 nm), 20g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate for 45min, adding 60g of sodium carboxymethyl cellulose, mixing and grinding for 30min until paste is formed, extruding the paste into phi 4 strips, roasting in a microwave high-temperature furnace, wherein the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the heating time is 430 ℃, and the roasting time is 4h, so that the nano zinc oxide desulfurizer is obtained.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a 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 desulfurizing agent, comprising the following steps that a desulfurizing waste agent is treated for 5 hours at the temperature of 120 ℃ under the argon flow rate of 70ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
60g of nano zinc oxide (particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are kneaded for 45min, 50g of silica sol is added, mixed and milled for 30min until paste is formed, extruded into phi 4 strip shape, baked in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the temperature is raised to 380 ℃ and the baking time is 4h, thus obtaining the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 23%.
Comparative example 1
The embodiment provides a recycling method of a zinc oxide desulfurizing agent, which comprises the following steps that a desulfurizing waste agent is treated for 5 hours at normal temperature under the condition that the flow rate of nitrogen is 80ml/min, and the obtained desulfurizing agent is used as a mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
60g of nano zinc oxide (particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are kneaded for 45min, 50g of silica sol is added, mixed and milled for 30min until paste is formed, extruded into phi 4 strip shape, baked in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the temperature is raised to 380 ℃ and the baking time is 4h, thus obtaining the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a desulfurization waste agent, wherein the sulfur content of the desulfurization waste agent is 21%.
Comparative example 2
The comparative example provides a recycling method of zinc oxide desulfurizing agent, comprising the following steps that the desulfurizing waste agent is directly used as mercury removing agent.
Wherein the desulfurization waste agent is obtained by converting a zinc oxide desulfurizing agent after desulfurization. The raw material composition, the preparation method and the formation process of the desulfurization waste agent of the zinc oxide desulfurizing agent are as follows:
60g of nano zinc oxide (particle size is 3 nm), 17g of X-type molecular sieve powder, 10g of copper oxide and 5g of sodium carbonate are kneaded for 45min, 50g of silica sol is added, mixed and milled for 30min until paste is formed, extruded into phi 4 strip shape, baked in a microwave high-temperature furnace, the initial temperature is 30 ℃, the heating rate is 2 ℃/min, the temperature is raised to 380 ℃ and the baking time is 4h, thus obtaining the nano zinc oxide desulfurizer.
The zinc oxide desulfurizer prepared by the method is crushed to 40-60 meshes, and raw material gas containing 280mg/m 3 of hydrogen sulfide, 10mg/m 3 of carbonyl sulfide and mercaptan and thiophene with the total concentration of 10mg/m 3 is subjected to desulfurization treatment at the airspeed of 20000h -1 and the temperature of 30 ℃ to obtain a 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 was introduced into the reactor, and the reaction was carried out under normal pressure conditions at 40℃with a mercury content of 2500. Mu.g/m 3 and a reaction space velocity of 1000h -1.
The zinc oxide desulfurizing agents after desulfurization of examples 1 to 13 and comparative examples 1 to 2 were tested for the removal effect of mercury, and the removal effect index of mercury was the exhaust gas outlet accuracy and mercury capacity.
The calculation method of the tail gas outlet precision comprises the following steps:
17.5mL of potassium permanganate absorption liquid was added to the gas absorption bottle, and 400L of outlet gas was sampled by a wet gas flow meter through the gas absorption bottle. The absorbent was transferred to a 200mL volumetric flask, the gas absorbent flask was washed with deionized water, and the wash solution 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 the sample to a mercury measuring instrument (model CG-1C, manufacturer: jiangsu gold separating instrument) reduction bottle for measuring mercury. The corresponding mercury content (ng) was obtained by mercury porosimetry.
The mercury capacity calculating method comprises the following steps:
Sample mercury capacity X C1, numerical value expressed in (%), is calculated as:
Wherein:
g, measuring mercury quantity by a mercury meter, wherein the unit is nanogram (ng);
m-sample mass in grams (g);
V-sample amount in milliliters (mL).
The specific test results are shown in the following table:
As can be seen from the table, the zinc oxide desulfurizing agent is obtained after extrusion molding, wherein the zinc oxide content is 50-80%, the transition metal content is 10-15%, the alkaline earth metal content is 5-10% and the molecular sieve content is 10-40%. After desulfurization, the mercury removing agent is obtained after hot nitrogen treatment. The mercury removal precision can reach 0.01ppb, and the mercury capacity can reach 7.6% -8.3%. If the desulfurization waste agent is not treated by inert atmosphere or treated at normal temperature, the mercury removal precision can only reach 0.05ppb, and the mercury capacity can only reach 5.1%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
1. A method for recycling zinc oxide desulfurizing agent is characterized by comprising the following steps,
Treating the desulfurization waste agent by inert gas at 110-120 ℃ to obtain a desulfurization treatment agent which is used as a mercury removal agent;
the treatment time of the inert gas is 4-6 hours;
the desulfurization waste agent comprises 20-25% of sulfur in terms of elements;
The zinc oxide desulfurizing agent comprises zinc oxide;
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 percent;
The transition metal oxide is at least one of copper oxide, manganese oxide and nickel oxide;
the alkali metal or alkaline earth metal oxide is at least one of sodium oxide, potassium oxide and magnesium oxide;
the zinc oxide desulfurizing agent also comprises a carrier;
the carrier is a molecular sieve carrier.
2. The method for recycling zinc oxide desulfurization agent according to claim 1, wherein the flow rate of the inert gas treatment is 60-100ml/min.
3. The method for recycling zinc oxide desulfurizing agent according to claim 1, wherein the carrier is an X-type molecular sieve or a Y-type molecular sieve.
4. The method for recycling zinc oxide desulfurizer according to claim 1, wherein the mass percent of the carrier in the zinc oxide desulfurizer is 5-35%.
5. The method for recycling zinc oxide desulfurization agent according to any one of claims 1 to 4, characterized by being used as a natural gas mercury removal agent.
6. The method for recycling zinc oxide desulfurizing agent according to claim 5, wherein natural gas is introduced in the process of removing mercury, and the natural gas comprises 2000-3000 micrograms of mercury per cubic meter.
7. The method for recycling zinc oxide desulfurizing agent according to claim 6, wherein the mercury removal pressure is normal pressure.
8. The method for recycling zinc oxide desulfurization agent according to claim 6, wherein the mercury removal temperature is 30-40 ℃.
9. The method for recycling zinc oxide desulfurizing agent according to claim 6, wherein the mercury removal airspeed is 500-1000 h -1.
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| CN104338435A (en) * | 2014-07-01 | 2015-02-11 | 太原理工大学 | Method for removing mercury in flue gas by use of waste desulfurizer after being used for recycling elemental sulfur |
| CN112058273A (en) * | 2020-08-26 | 2020-12-11 | 中国科学院山西煤炭化学研究所 | Blast furnace gas desulfurization catalyst and preparation method and application thereof |
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