CN114849466A - Mercury remover and preparation method and application thereof - Google Patents
Mercury remover and preparation method and application thereof Download PDFInfo
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- CN114849466A CN114849466A CN202210444388.9A CN202210444388A CN114849466A CN 114849466 A CN114849466 A CN 114849466A CN 202210444388 A CN202210444388 A CN 202210444388A CN 114849466 A CN114849466 A CN 114849466A
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- mercury
- demercuration
- copper
- removing agent
- agent
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 4
- 150000000703 Cerium Chemical class 0.000 claims abstract description 3
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 26
- 238000005096 rolling process Methods 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 6
- 239000002803 fossil fuel Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- -1 preferably p-Al Inorganic materials 0.000 claims 2
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 32
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 230000004913 activation Effects 0.000 abstract description 10
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical class [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 21
- 239000008188 pellet Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 10
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 10
- 238000004898 kneading Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- AGVJBLHVMNHENQ-UHFFFAOYSA-N Calcium sulfide Chemical compound [S-2].[Ca+2] AGVJBLHVMNHENQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940079101 sodium sulfide Drugs 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/007—Removal of contaminants of metal compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
-
- 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
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a mercury removing agent and a preparation method and application thereof, wherein the mercury removing agent comprises the following components in percentage by total dry-basis mass of the mercury removing agent: 1-20 wt% of CuS, 1-10 wt% of S, 0.1-1 wt% of adsorption aid, 0.1-1 wt% of cerium salt and the balance of carrier; wherein: the ratio of the number of S atoms to the number of Cu atoms is (1.5 to 5): 1; the pore volume of the mercury removing agent is 0.5-0.8 ml/g; elemental sulfur is introduced and is used for oxidizing the inactivated cuprous sulfide into copper sulfide with demercuration activity, so that the utilization rate of the copper sulfide is improved, the consumption of copper element is reduced, the redox performance of sulfur is promoted by adding cerium oxide, the reaction activation energy of the cuprous sulfide and the elemental sulfur is reduced by adding an auxiliary agent, and the effective utilization rate of copper is improved.
Description
Technical Field
The invention relates to the technical field of demercuration, in particular to a demercuration agent and a preparation method and application thereof.
Background
The natural gas, the coking gas, the coke-oven gas, the coal gas and other fossil fuels contain trace harmful element mercury, and the mercury mainly exists in three forms, namely zero-valent mercury (Hg) 0 ) Mercury (Hg) in its oxidized state 2+ ) And particulate mercury (Hg) p ) Zero-valent mercury is the most difficult to treat among the three, has high volatility, is insoluble in water, and is not easy to be trapped and removed by dust removal and desulfurization equipment; the oxidized mercury has various compounds, is relatively stable, is mostly easy to dissolve in water and adsorb, can be adsorbed on the surface of particulate matters and removed by a dust remover or removed by wet desulphurization and washing; the mercury particles are easy to be adsorbed and removed by a dust remover.
Mercury is highly volatile, highly toxic, and highly corrosive. Mercury can not only corrode equipment and process pipelines to cause equipment pipeline leakage, but also cause catalyst poisoning in the process; meanwhile, mercury can cause diseases of the nervous system, and the emission of mercury can be circulated, enriched and accumulated in a biosphere, so that the harm to human bodies and the environment is increasingly obvious. Therefore, how to effectively remove mercury becomes a problem to be solved urgently in industrial production and environmental management processes.
Disclosure of Invention
The invention aims at the problem that the mercury exists in the fossil fuel to cause the fossil fuel to generate the mercury in the processing process, and provides the mercury removing agent which has high mercury capacity and high mercury removing efficiency.
On one hand, the invention discloses a mercury removing agent, which comprises the following components in percentage by weight based on the total dry mass of the mercury removing agent: 1-20 wt% of CuS, 1-10 wt% of S, 0.1-1 wt% of adsorption aid, 0.1-1 wt% of cerium oxide, and the balance of carrier; wherein: the ratio of the number of S atoms to the number of Cu atoms is (1.5 to 5): 1; the pore volume of the mercury removing agent is 0.5-0.8 ml/g.
The invention has the beneficial effects that: the method is used for oxidizing the inactivated cuprous sulfide into the copper sulfide with demercuration activity by introducing the elemental sulfur, so that the utilization rate of the copper sulfide is improved, the consumption of copper element is reduced, the oxidation-reduction performance of sulfur is promoted by adding cerium oxide, the reaction activation energy of the cuprous sulfide and the elemental sulfur is reduced by adding an auxiliary agent, and the effective utilization rate of copper is improved, so that the method has good application potential in the field of demercuration, such as sewage treatment and fossil fuel.
On the other hand, the invention also discloses a preparation method of the mercury removing agent, which comprises the following steps:
mixing copper salt, sulfide and cerium oxide, and precipitating after the reaction is finished to obtain an active component;
mixing the active component, the adsorption additive and the carrier to prepare a demercuration precursor;
and activating the demercuration precursor to obtain the demercuration agent.
The invention has the beneficial effects that: the method has simple operation steps, the prepared mercury removing agent has stable performance, the controllability of the preparation process is enhanced, and the obtained mercury removing agent has large mercury capacity and high mercury removing precision.
Drawings
FIG. 1 is a graph showing the results of pore size distribution of the mercury removing agent of example 1;
figure 2 is a XRD result pattern of the mercury remover of example 1.
Detailed Description
The inventor of the present invention finds that the current demercuration methods in the process of solving the problem of mercury removal from fossil fuels can be classified into adsorption methods, low-temperature separation methods and membrane separation methods, and the adsorption methods mainly adopt fixed bed adsorption, anion resin adsorption and solution absorption processes, wherein the fixed bed adsorption is the main process method adopted at present. The adsorbent in the fixed bed adsorption method consists of a carrier and active ingredients, wherein the carrier mainly comprises active carbon and Al 2 O 3 And complexes thereof; the active components mainly comprise sulfide and metal oxide.
The activated carbon is used as a carrier, the preparation process is complex, the cost is high, the mechanical strength is poor, powder is easy to generate under the impact of high airflow, the granular mercury removing agent is crushed, and the active components are lost, so that the mercury removing efficiency is reduced, for example, the publication numbers are CN105771902A, CN105921107A, CN110343542A, CN113926304A, EP0794240A1, US20100113266A1 and US20100025302A 1.
Active Al 2 O 3 Mercury removing agent of Al 2 O 3 The carrier is used as a carrier, overcomes the defect of poor compressive strength of the activated carbon, has a certain amount of specific surface area and a specific pore structure, can highly disperse active components, can ensure the smoothness of a mass transfer channel in the demercuration process, and improves the demercuration precision and the mercury capacity. For example, chinese patent CN112108108A discloses a demercuration agent, the demercuration agent carrier has a multi-stage pore structure of micropores, mesopores and macropores, which can not only make the active component in a highly dispersed state, but also ensure the smoothness of the mass transfer channel in the demercuration process; the united states patent US20150217271a1 also discloses a mercury removing agent with a specific pore structure, which is composed of a core containing active components and a porous core communicated with the core, can effectively utilize the active components, improve the compressive strength of the adsorbent and simultaneously prevent the mercury particles from falling off after adsorption; but overall there are problems of low active ingredient utilization and low mercury capacity.
The preparation methods of the mercury removing agent are different, and Chinese patents CN109663475A and CN105498469B disclose the preparation methods of the mercury removing agent, which are simple to operate, but have the defects of large active component particles and low active component utilization rate, by directly mixing the active component, the carrier and the structural auxiliary agent in proportion, then adding the adhesive, rolling the balls on a ball rolling machine for forming and roasting to obtain the mercury removing agent; chinese patent CN111394144A discloses a mercury removing agent, in the preparation process of the mercury removing agent, 12-14% of active component Cu and 1.5-6% of Zn are loaded on dentiform sphere or spherical Al by an impregnation method 2 O 3 On a carrier, then introducing high-purity H 2 S gas sulfurization to form CuS and ZnS, and the mercury removing agent can penetrate through the thickness of 30cm mercury removing agent to reduce the mercury content to 0.01ug/m 3 The mercury capacity can reach 6.5%. However, the preparation process of the mercury removing agent is complex, the influence factors of the vulcanization process are more, and H is 2 S is expensive, has bad smell and is environmentally friendlyThe influence of the determination; chinese patent CN104475007 improves the vulcanization mode, copper salt, basic copper carbonate and calcium hydroxide react to prepare a copper-containing precursor, and then the copper-containing precursor reacts with vulcanizing agents such as thiourea, sodium sulfide, thioacetamide and the like to prepare active copper sulfide, the copper is incompletely vulcanized, the activity of the generated copper sulfide is not high, and a large amount of inactive components such as alkali metal or alkaline earth metal are contained in the product; chinese patent CN106311280A discloses a demercuration agent and a preparation method thereof, wherein active CuS is prepared by a coprecipitation method, and then a carrier, a binder, a forming aid and the like are added for forming.
The inventor of the invention finds that when the existing mercury removing agent and the preparation method thereof have the problems, the mercury removing efficiency is obviously and greatly improved when elemental sulfur and copper sulfide are combined for mercury removal, and the activation energy of the reaction can be reduced after manganese dioxide is added as an auxiliary agent; it has also been found that the reaction of elemental sulfur and mercury is more complete and promoted by the addition of cerium oxide.
The invention discloses a mercury removing agent, which comprises a carrier, wherein the carrier refers to a skeleton of an active component, supports the active component, enables the active component to be dispersed, and provides main mechanical strength for the mercury removing agent; as used herein, the term "active component" refers to a compound that reacts with mercury to form a mercury-containing compound that is removed from the feedstock to be treated to effect mercury removal; suitably, the support may be, but is not limited to, at least one of alumina, alumina sol and aluminium nitrate, suitably alumina, more suitably rho-Al 2 O 3 In order to further improve the carrier pore canal openness, promote the diffusion of mercury in the mercury removal agent, improve the mercury removal efficiency and improve the mechanical strength of the mercury removal agent, rho-Al 2 O 3 The pores with a median pore diameter of greater than 10nm make up 80%, suitably 85%, more suitably 90% of the total number of pores in the support.
The carrier is loaded with at least an active component, which can be but is not limited to CuS, elemental sulfur, and cerium oxide, suitably CuS and elemental sulfur, more suitably a combination of CuS, elemental sulfur, and cerium oxide; in the present invention, 2CuS + Hg → HgS + Cu 2 S(1)；
It is thus understood that elemental sulfur is capable of converting Cu into 2 The S is reactivated into CuS for continuous demercuration, thereby improving the demercuration rate of mercury, reducing the consumption of copper, saving raw materials and prolonging the time of a demercuration period.
The mercury removing agent is calculated by taking the total dry-basis mass of the mercury removing agent as a reference, wherein the dry basis refers to solid dry substances obtained after the mercury removing agent is dried to remove water, and the total dry-basis mass of the mercury removing agent refers to the sum of the solid dry substances obtained after the mercury removing agent is dried to remove water; the content of CuS in the mercury removing agent can be 1-20 wt%, suitably 5-14 wt%, more suitably 8-10 wt%; the content of the elemental sulfur may be 1 to 10 wt%, suitably 2 to 7 wt%, more suitably 4 to 6 wt%; the cerium oxide may be present in an amount of 0.1 to 1 wt%, suitably 0.1 to 0.6 wt%, more suitably 0.3 to 0.5 wt%.
In order to further reduce the activation energy of the reaction between cuprous sulfide and elemental sulfur, the mercury removing agent according to the present invention further comprises an adsorption auxiliary agent, and as used herein, the "adsorption auxiliary agent" refers to a substance capable of promoting the forward progress of the reaction, such as a catalyst, and reduces the activation energy required by the reaction to promote the forward progress of the reaction; suitably, the adsorption aid may be, but is not limited to, manganese dioxide, suitably the adsorption aid comprises 0.1 to 1 wt%, suitably 0.1 to 0.6 wt%, more suitably 0.3 to 0.5 wt% of the total mass of the mercury removal agent on a dry basis.
In order to make elemental sulfur and copper elements utilized as much as possible, the ratio of the sum of sulfur atoms to the number of copper atoms in the CuS and elemental sulfur is (1.5-5): 1, more suitably, 2: 1.
in order to simplify the steps of the preparation process and enhance the controllability of the performance of the obtained mercury removing agent, the invention also provides a preparation method of the mercury removing agent, which comprises the following steps:
s1, mixing copper salt, sulfide and cerium salt, and precipitating after the reaction is finished to obtain an active component;
suitably, the copper salt includes, but is not limited to, at least one of copper nitrate, copper acetate and basic copper carbonate, suitably copper nitrate; as used herein, the "sulfide" refers to a compound in which sulfur is present as a negative ion and a metal is present as a positive ion, the two being combined, suitably the metals include, but are not limited to, alkali and alkaline earth metals, such as sodium, potassium, magnesium and calcium; suitably, the sulphide includes, but is not limited to, sodium sulphide, magnesium sulphide and calcium sulphide, suitably the sulphide is sodium sulphide.
Suitably, the precipitate obtained after the end of the reaction may, but need not necessarily, be washed in a drying step, in particular a washing step, and may be selected in particular according to the content of the starting material in the filtrate of the filtration.
S2, mixing the active component, the adsorption auxiliary agent and the carrier to prepare a demercuration precursor;
as used herein, the "demercuration precursor" refers to a substance whose active component has not been activated, and requires a specific treatment, such as calcination at a certain temperature, for activation; suitably, the shape of the demercuration precursor may be any shape, such as cylindrical, spherical, and square, suitably spherical.
The mixing may be carried out by simple stirring or may be carried out in other mixing-assisting equipment, such as kneaders, suitably kneaders; the mercury removal precursor may be formed by one of, but not limited to, a rolling ball forming method, an oil column forming method, and a bar-pellet-shaping method, and suitably, the rolling ball forming method, as used herein, refers to a method in which a spherical mercury removal precursor is formed by a corresponding apparatus, such as a rotary disc ball rolling machine; suitably, the diameter of the spheres is 1.5-3.5 mm, suitably 2.0-3.0 mm.
And S3, activating the demercuration precursor to obtain the demercuration agent.
As used herein, the "activation" refers to a process that activates the activity of an active component, e.g., calcination, suitably calcination; the temperature during the roasting process is 170-210 ℃, suitably 180-200 ℃, more suitably 200 ℃, and the roasting time can be adjusted according to the preparation amount, suitably 0.5-15 hours, more suitably 2-3 hours; in order to make the activation more effective, a water removal treatment may be performed before the activation, for example, by drying, the temperature of the drying process is 100-.
Examples
Example 1
Under the condition of stirring, sequentially mixing 210g of copper nitrate trihydrate, 700g of deionized water, 26g of sulfur, 2.3g of cerium oxide and 195g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; mixing the above obtained active component with 2.5g MnO 2 And 430g of powder rho-Al 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-A1.
Comparative example 1
Under the condition of stirring, sequentially mixing 210g of copper nitrate trihydrate, 700g of deionized water and 195g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; the active component obtained above and 430g of powder rho-Al were mixed 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-B1.
Comparative example 2
Under stirring, 210g of copper nitrate trihydrate,Mixing 700g of deionized water, 26g of sulfur and 195g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; the active component obtained above and 430g of powder rho-Al were mixed 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-B2.
Example 2
Under the condition of stirring, mixing 271g of copper nitrate trihydrate, 580g of deionized water, 26g of sulfur, 2.3g of cerium oxide and 252g of sodium sulfide nonahydrate in sequence, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; mixing the active component obtained above with 2.5g MnO 2 410g of powder of rho-Al 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-A2.
Example 3
Under the condition of stirring, mixing 136g of copper nitrate trihydrate, 830g of deionized water, 26g of sulfur, 4.2g of cerium oxide and 126g of sodium sulfide nonahydrate in sequence, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; mixing the active component obtained above with 4gMnO 2 455g of powder of rho-Al 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-A3.
Example 4
Under the condition of stirring, sequentially mixing 90g of copper nitrate trihydrate, 920g of deionized water, 35g of sulfur, 4.2g of cerium oxide and 84g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; mixing the active component obtained above with 4gMnO 2 470g of powder of rho-Al 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-A4.
Example 5
Under the condition of stirring, sequentially mixing 210g of copper nitrate trihydrate, 700g of deionized water, 26g of sulfur, 2.3g of cerium oxide and 195g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; mixing the active component obtained above with 2.5g MnO 2 430g of pseudo-boehmite is uniformly mixed by a wet method, kneaded on a small kneader and rolled on a small turntable ball rolling machine to form a sphere with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-A5.
Example 6
Under the condition of stirring, sequentially mixing 210g of copper nitrate trihydrate, 700g of deionized water, 26g of sulfur, 2.3g of cerium oxide and 195g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; mixing the active component obtained above with 2.5g MnO 2 、430gγ-Al 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-A6.
Comparative example 3
Under the condition of stirring, sequentially mixing 210g of copper nitrate trihydrate, 700g of deionized water, 26g of sulfur and 195g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; mixing the active component obtained above with 2.5g MnO 2 430g of powder of rho-Al 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; placing the formed pellets in an industrial oven at 110 deg.CAfter drying for 2 hours, the mixture was calcined at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-B3.
Comparative example 4
Under the condition of stirring, sequentially mixing 210g of copper nitrate trihydrate, 700g of deionized water, 26g of sulfur, 2.3g of cerium oxide and 195g of sodium sulfide nonahydrate, stirring for 1h, standing for 12h, filtering, washing and drying to obtain an active component; the active component obtained above and 430g of powder rho-Al were mixed 2 O 3 Uniformly mixing by a wet method, kneading on a small kneader, and rolling on a small turntable ball rolling machine to form a ball shape with the diameter of 1.5-3.5 mm; drying the formed pellets in an industrial oven at 110 ℃ for 2 hours, and then roasting the pellets at 200 ℃ for 2 hours to obtain the mercury removing agent which is recorded as DHg-B4.
Now, DHg-A1 prepared in example 1 is characterized, and the results are shown in FIG. 1 and FIG. 2, wherein FIG. 1 is measured by mercury intrusion method, and it can be seen from FIG. 1 that the pore size distribution range of the mercury removing agent-A1 is wide, and a large number of pores with pore size of more than 10nm are contained, so that not only can a large specific surface area be ensured, but also the molecular diffusion after Hg is absorbed is facilitated; as can be seen from FIG. 2, the diffraction peak of CuS in the demercuration agent-A1 is not obvious, which shows that CuS crystal grains are smaller, and the active component is highly dispersed on the surface of the carrier, thereby improving the utilization rate of the active component and increasing the demercuration efficiency.
The mercury removing agents respectively prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to mercury removing performance tests on a micro evaluation device under the following test conditions: normal temperature and normal pressure, gas flow rate of 30ml/min, mercury removal agent filling amount of 20ml, mercury content of 1-1.5ug/g, stopping adsorption reaction when outlet mercury content is more than 10ng/g, and taking 1 test period, wherein the experimental results are shown in table 1.
TABLE 1 comparison of demercuration adsorbents for examples 1-6 and comparative examples 1-4
In table 1, it is to be noted that: the smaller the average mercury content at the outlet in the 1 period shows that the mercury removing effect of the mercury removing agent is better.
As can be seen from table 1, in example 1, when cerium oxide, elemental sulfur and manganese dioxide were added, the average outlet mercury content was significantly reduced and the mercury capacity was significantly increased in period 1, as compared with comparative example 1, and it was found that the addition of cerium oxide, elemental sulfur and manganese dioxide significantly improved the mercury removal rate, as compared with comparative example 1.
Example 1 compared to comparative example 2, it can be seen that when cerium oxide and elemental sulfur were added, the average outlet mercury content was significantly reduced and the mercury capacity was significantly increased in period 1, but the average outlet mercury content and mercury capacity in period 1 of comparative example 2 were significantly better than that of comparative example 1, indicating that the addition of manganese dioxide helped to increase the average outlet mercury content and mercury capacity in period 1.
In example 4, compared with comparative example 3, when the dosage of the copper nitrate trihydrate in example 4 is less than half of that in comparative example 3, but the average mercury content at the outlet in 1 period is still obviously lower than that in comparative example 3 by adding the cerium oxide, and the mercury capacity is only slightly lower than that in comparative example 3, the mercury capacity can be obviously improved by adding the cerium oxide, so that the mercury removal rate is improved.
Example 1 compared to comparative example 4, the average outlet mercury content was significantly reduced and the mercury capacity was significantly increased over 1 cycle when manganese dioxide was added, indicating that the addition of manganese dioxide helped to increase the mercury removal rate.
In conclusion, the elemental sulfur is introduced to oxidize the active cuprous sulfide into the copper sulfide with demercuration activity, so that the utilization rate of the copper sulfide is improved, the consumption of copper element is reduced, the redox performance of sulfur is promoted by adding cerium oxide, the reaction activation energy of the cuprous sulfide and the elemental sulfur is reduced by adding an auxiliary agent, and the effective utilization rate of copper is improved.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The mercury removing agent is characterized by comprising the following components in percentage by weight based on the total dry mass of the mercury removing agent: 1-20 wt% of CuS, 1-10 wt% of S, 0.1-1 wt% of adsorption aid, 0.1-1 wt% of cerium oxide, and the balance of carrier;
wherein: the ratio of the number of S atoms to the number of Cu atoms is (1.5 to 5): 1;
the pore volume of the mercury removing agent is 0.5-0.8 ml/g.
2. The mercury removal agent of claim 1, wherein the adsorption aid comprises MnO 2 。
3. Mercury remover according to claim 1 or 2, characterized in that the carrier comprises at least one of alumina, preferably p-Al, aluminium sol and aluminium nitrate 2 O 3 。
4. The mercury removal agent of claim 3, wherein the rho-Al is 2 O 3 The rho-Al is occupied by pores with the medium pore diameter of more than 10nm 2 O 3 80% of the total number of pores.
5. A process for the preparation of a mercury-removing agent as claimed in any one of claims 1 to 4, characterized in that the process comprises:
mixing copper salt, sulfide and cerium salt, and precipitating after the reaction is finished to obtain an active component;
mixing the active component, the adsorption additive and the carrier to prepare a demercuration precursor;
and activating the demercuration precursor to obtain the demercuration agent.
6. The preparation method according to claim 5, wherein the step of activating the demercuration precursor to obtain the demercuration agent comprises a drying process and a roasting process which are sequentially carried out on the demercuration precursor.
7. The preparation method according to claim 6, wherein the temperature in the drying process is 100-250 ℃, preferably 110-150 ℃, and the drying time is 0.5-15 hours, preferably 2-3 hours; the temperature in the roasting process is 170-210 ℃, preferably 180-200 ℃, and the roasting time is 0.5-15 hours, preferably 2-3 hours.
8. The preparation method according to claim 5, wherein the step of mixing the active component, the adsorption aid and the carrier to prepare the demercuration precursor comprises the following steps:
and mixing the active component, the adsorption aid and the carrier, and then preparing the demercuration precursor by one of a rolling ball forming method, an oil column forming method and extrusion, granulation and shaping.
9. The method according to claim 5, wherein the copper salt comprises at least one of copper nitrate, copper acetate and basic copper carbonate, preferably copper nitrate; the sulfide includes at least one of an alkali metal sulfide and an alkaline earth metal sulfide, preferably sodium sulfide.
10. Use of a mercury removal agent as defined in any one of claims 1-4 for removing mercury from fossil fuels.
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| CN112108108A (en) * | 2020-09-28 | 2020-12-22 | 西安元创化工科技股份有限公司 | Copper sulfide mercury removing agent and preparation method thereof |
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| CN101687173A (en) * | 2007-05-14 | 2010-03-31 | 康宁股份有限公司 | Comprise adsorbent, its preparation method and the application thereof of active carbon |
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