CN114891549A - Desulfurizing agent and preparation method and application thereof - Google Patents
Desulfurizing agent and preparation method and application thereof Download PDFInfo
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- CN114891549A CN114891549A CN202210360527.XA CN202210360527A CN114891549A CN 114891549 A CN114891549 A CN 114891549A CN 202210360527 A CN202210360527 A CN 202210360527A CN 114891549 A CN114891549 A CN 114891549A
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- Prior art keywords
- desulfurizing agent
- desulfurizer
- catalyst
- steel slag
- oxide
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- 230000003009 desulfurizing effect Effects 0.000 title claims description 57
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 74
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 49
- 239000010959 steel Substances 0.000 claims abstract description 49
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 43
- 230000023556 desulfurization Effects 0.000 claims abstract description 43
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000003245 coal Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 18
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 18
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 18
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012190 activator Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 68
- 238000002156 mixing Methods 0.000 claims description 29
- 238000002485 combustion reaction Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims 4
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 238000000227 grinding Methods 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000002802 bituminous coal Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- -1 desulfurization Chemical compound 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- 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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2042—Barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- 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
- B01D2255/20746—Cobalt
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention provides a desulfurizer and a preparation method and application thereof, wherein the desulfurizer comprises the following components: the mixed auxiliary agent comprises carbide slag and sodium carbonate; an activator comprising manganese ore and modified steel slag; the catalyst is one or more of cerium oxide, barium oxide and cobalt oxide. The desulfurizer provided by the invention has the advantages of cost saving, environmental protection and energy saving by utilizing industrial production byproducts, such as effective desulfurization components in carbide slag and steel slag, to desulfurize raw materials such as coal; the steel slag and the manganese ore are ground, so that the steel slag and the manganese ore can be conveniently and fully mixed with the catalyst and the mixed auxiliary agent, the utilization rate and the reaction rate of effective desulfurization components in the desulfurizer are improved, the effective desulfurization components in the sodium carbonate, the steel slag powder and the carbide slag can be effectively utilized through the synergistic effect of the catalyst and the activator at high temperature, and the utilization rate and the reaction rate of the effective desulfurization components in the desulfurizer are further improved.
Description
Technical Field
The invention relates to the technical field of air pollution treatment, in particular to a desulfurizer and a preparation method and application thereof.
Background
The flue gas generated in coal combustion or industrial manufacturing often contains sulfide, the sulfide is mainly derived from coal or petroleum and sulfur substances contained in industrial raw materials prepared from the coal or petroleum, and the sulfur substances are reacted in the combustion process or the industrial manufacturing process and converted into sulfide to be released. Sulfides, particularly hydrogen sulfide, sulfur dioxide and the like, can often cause catalyst poisoning and inactivation in a production process, waste gas containing the sulfides is directly discharged, the environment is easily polluted, air problems such as haze and the like are generated, in addition, the sulfides in the flue gas are also main substances for forming acid rain, and the acid rain not only seriously corrodes buildings and public facilities, but also destroys forests and crops in large areas, and seriously affects the health and property safety of human beings.
Coal is a main energy source in our country, has wide application fields, and is industrially used for power plant power generation, industrial boiler heat energy combustion and the like. 80% of coal in China is directly used for combustion, and the coal usually contains sulfur in different degrees, particularly the sulfur content of low-grade coal is the highest. At present, in order to reduce the production cost, most enterprises use a plurality of inferior coals and coal gangues with higher sulfur content. Therefore, the situation of sulfur dioxide pollution is more severe, and the problem of smoke desulfurization is highly regarded by various circles. Sulfur dioxide is listed as a main regulation and control of air pollutants in China, and the concentration level of sulfur dioxide in the atmosphere is used as an important index for evaluating the air quality. The control of the generation of sulfur dioxide, namely desulfurization, in various fields is an irresistible matter against the harm of the sulfur dioxide. The desulfurization after combustion, also called Flue gas desulfurization (FGD for short), is a process for removing sulfur and compounds in Flue gas, and in the FGD technology, the desulfurization is divided into the following five methods according to the type of the desulfurizing agent: with CaCO 3 (limestone) -based calcium process, MgO-based magnesium process, Na 2 SO 3 Sodium process based on NH 3 The basic ammonia process, the organic base process based on organic base.
The current power plants, steel plants and cement plants modify the flue gas desulfurization system to the standard of ultra-low emission (35 mg/m) because of the requirements of national environmental protection policy 3 Below), that is, sulfur dioxide discharged into the atmosphere should be 35mg/m regardless of the amount of sulfur fed 3 The following are in the eyeAfter the former ultralow emission is reformed, equipment runs for many years, a desulfurization equipment system is old successively, the running efficiency of the system is poor, related equipment is corroded or fails and the like, and the change of the sulfur content of power plant coal is too large, sometimes the sulfur feeding amount of a flue gas desulfurization system can exceed the standard suddenly, so that the current wet desulfurization system cannot meet the current actual desulfurization running requirement, in addition, the flow that most of domestic power plants need to report technical improvement cost again is long, the cost is high, for example, a newly-added desulfurization tower layer is used, the required improvement cost is at least ten million, the improvement cost is high and long, in addition, most of desulfurization towers do not have space and can meet the newly-added spray layer, and therefore, the condition of poor efficiency of the desulfurization system is solved by applying a novel desulfurization optimization scheme on the premise of the current wet desulfurization running.
Aiming at the problems, the invention provides a desulfurizing agent for realizing desulfurization in coal combustion and a preparation method and application thereof.
Disclosure of Invention
The invention aims to provide a desulfurizer, which is low in cost and is particularly suitable for high-temperature desulfurization at 700-1500 ℃, sulfur is pre-removed in the coal combustion process through the high-temperature desulfurizer, the removal efficiency can reach 50-80%, sulfur dioxide which subsequently enters a desulfurization tower can be effectively and easily removed, the pressure of desulfurization treatment of the subsequent desulfurization tower caused by unstable sulfur content of coal used in a power plant can be solved, and the electricity consumption cost and the desulfurizer cost related to desulfurization operation can be further reduced.
The invention also aims to provide a preparation method of the desulfurizing agent.
The invention also aims to provide application of the desulfurizing agent.
In order to achieve the above object, the present invention provides a desulfurizing agent comprising:
the mixed auxiliary agent comprises carbide slag and sodium carbonate;
an activator;
the catalyst is one or more of cerium oxide, barium oxide and cobalt oxide.
In some embodiments, the desulfurizing agent further comprises 53-78% of a mixing aid, 20-44% of an activator, and 2-10% of a catalyst by 100% of mass fraction.
In some embodiments, the desulfurizing agent further comprises 50-70% of carbide slag and 3-8% of sodium carbonate by 100% of mass fraction.
In some embodiments, further, the cerium oxide is cerium oxide; and/or, the barium oxide is barium oxide; and/or the cobalt oxide is cobalt oxide.
In some embodiments, the desulfurizing agent further comprises 1-3% by mass of cerium oxide, based on 100%; and/or the desulfurizing agent comprises 1-4% of barium oxide; and/or the desulfurizing agent comprises 1-3% of cobalt oxide.
In some embodiments, the activator further comprises manganese ore and modified steel slag having a particle size of 300 to 500 mesh.
In some embodiments, the desulfurizing agent further comprises 4-8% of manganese ore and 20-35% of modified steel slag by 100% of mass fraction.
In some embodiments, the activator is further ground to a particle size of 700 to 900 mesh.
Another object of the present invention is to provide a method for preparing a desulfurizing agent, comprising the steps of:
s1, providing a catalyst: mixing one or more of cerium oxide, barium oxide and cobalt oxide, and drying at 120-200 ℃ for 2-5 hours;
s2, providing an activator: providing modified steel slag with the granularity of 300-500 meshes, adding manganese ore into the steel slag, and grinding to obtain an activating agent with the grain size of 700-900 meshes;
s3, mixing: and (4) mixing and stirring the catalyst in the step S1 and the activating agent in the step S2 for 20-30 min, respectively and sequentially adding sodium carbonate and carbide slag, and mixing and stirring for 2-5 h.
Still another object of the present invention is to provide the use of a desulfurizing agent for desulfurization in a coal combustion process, in an amount of 2-6% of coal;
respectively, adding the desulfurizing agent in three sections according to the total amount of the desulfurizing agent:
1) before combustion, 30% of desulfurizer is uniformly mixed into the coal raw material;
2) after the mixture is put into a furnace for combustion, 50 percent of desulfurizer is added into the furnace;
3) 20% of desulfurizer is added into a horizontal flue at the upper end of the furnace.
The technical scheme of the invention at least has the following beneficial effects:
(1) the desulfurizer provided by the invention has the advantages of cost saving, environmental protection and energy saving by utilizing the effective desulfurization components in industrial production byproducts, such as carbide slag and steel slag, to desulfurize the combustion process of the raw materials such as coal.
(2) According to the desulfurizer provided by the invention, the modified steel slag and manganese ore are ground to 700-900 meshes, so that the desulfurizer can be uniformly distributed on the surfaces of raw materials such as coal and the like, and the utilization rate and the reaction rate of effective desulfurization components in the desulfurizer are improved.
(3) According to the desulfurizer provided by the invention, one or more of cerium oxide, barium oxide and cobalt oxide are used as a catalyst and added into the desulfurizer, and the catalyst can further improve the utilization rate and reaction rate of effective desulfurization components in the desulfurizer under the action of high temperature in a furnace.
(4) The desulfurizer provided by the invention, sulfur in raw materials such as coal and the like and sulfate generated by the desulfurizer under the high-temperature action in the furnace enter the horizontal flue along with the air flow, and the sulfate can continuously react with the desulfurizer added in the horizontal flue at the upper end of the furnace to play a role in further desulfurization.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to thereby define the scope of the invention more clearly.
The modified steel slag can be directly purchased from the market or prepared by the following method:
1) adding a boron modifier into the high-temperature converter steel slag, and then cooling to 600-800 ℃ to obtain mixed steel slag;
2) placing the mixed steel slag obtained in the step 1) in a sealed environment for spray water thermal braising (the steam pressure is 0.2-0.3Mpa) for treatment for 8-12h to obtain powdered modified steel slag;
wherein B in the boron modifier 2 O 3 Accounting for more than 0.8 percent.
Illustratively, the modified steel slag of the invention is prepared as follows: high-temperature converter steel slag generated in a steel plant is placed in a slag pot, and 0.5 percent of boron modifier (B in the boron modifier) is added into the slag pot 2 O 3 More than 0.8 percent) is added, when the slag is cooled to about 600 ℃, water is sprayed into the slag tank for sealing, the water in the slag tank is changed into water vapor by the waste heat of the steel slag, and the steam pressure in the slag tank is adjusted to about 0.2Mpa by a steam discharge pipe arranged on the slag tank. The thermal stress generated by the self heat of the steel slag enables the large steel slag to be cracked, simultaneously a large amount of saturated steam permeates into the steel slag to react with free calcium oxide and free magnesium oxide in the steel slag to generate volume expansion stress, so that the steel slag is further pulverized, and the whole slag stewing time is 12 hours, thereby obtaining the modified steel slag.
Example 1
Providing a desulfurizing agent:
mixing 2% of cerium oxide, 2% of barium oxide and 1% of cobalt oxide, adding the mixture into a reaction kettle, and drying the mixture at 150 ℃ for 3 hours to obtain a catalyst; grinding 35% of the modified steel slag until the particle size of the modified steel slag reaches 350 meshes, mixing the ground modified steel slag with 5% of manganese ore, and continuing grinding until the particle size of the mixture reaches 800 meshes to obtain an activating agent; and mixing and stirring the catalyst and the activator for 30min, adding 5% of sodium carbonate and 50% of carbide slag, and fully mixing and stirring for 5h to obtain the desulfurizer 1.
Example 2
Providing a desulfurizing agent:
mixing 2% of cerium oxide, 2% of barium oxide and 1% of cobalt oxide, adding the mixture into a reaction kettle, and drying at 180 ℃ for 2.5 hours to obtain a catalyst; grinding 25% of the modified steel slag until the particle size of the modified steel slag reaches 400 meshes, mixing the ground modified steel slag with 5% of manganese ore, and continuing grinding until the particle size of the mixture reaches 800 meshes to obtain an activating agent; and mixing and stirring the catalyst and the activator for 30min, adding 5% of sodium carbonate and 60% of carbide slag, and fully mixing and stirring for 5h to obtain the desulfurizer 2.
Example 3
Providing a desulfurizing agent:
mixing 1% of cerium oxide, 2% of barium oxide and 2% of cobalt oxide, adding the mixture into a reaction kettle, and drying at 150 ℃ for 3 hours to obtain a catalyst; grinding 20% of the modified steel slag until the particle size of the modified steel slag reaches 350 meshes, mixing the ground modified steel slag with 5% of manganese ore, and continuing grinding until the particle size of the mixture reaches 800 meshes to obtain an activating agent; and mixing and stirring the catalyst and the activator for 30min, adding 5% of sodium carbonate and 65% of carbide slag, and fully mixing and stirring for 5h to obtain the desulfurizer 3.
Example 4
Providing a desulfurizing agent:
mixing 1% of cerium oxide, 1% of barium oxide and 1% of cobalt oxide, adding the mixture into a reaction kettle, and drying at 150 ℃ for 3 hours to obtain a catalyst; grinding 30% of modified steel slag until the particle size of the modified steel slag reaches 450 meshes, mixing the ground modified steel slag with 7% of manganese ore, and continuing grinding until the particle size of the mixture reaches 800 meshes to obtain an activating agent; and mixing and stirring the catalyst and the activator for 30min, adding 5% of sodium carbonate and 55% of carbide slag, and fully mixing and stirring for 5h to obtain the desulfurizer 4.
Example 5
Providing a desulfurizing agent:
mixing 1% of cerium oxide, 1% of barium oxide and 2% of cobalt oxide, adding the mixture into a reaction kettle, and drying at 150 ℃ for 3 hours to obtain a catalyst; grinding 35% of the modified steel slag until the particle size of the modified steel slag reaches 500 meshes, mixing the ground modified steel slag with 6% of manganese ore, and continuing grinding until the particle size of the mixture reaches 800 meshes to obtain an activating agent; and mixing and stirring the catalyst and the activator for 30min, adding 5% of sodium carbonate and 50% of carbide slag, and fully mixing and stirring for 5h to obtain the desulfurizer 5.
Application example 1
Adopting a desulfurizing agent 1, wherein the adding amount of the desulfurizing agent 1 is 2 percent of the mass of the coal raw material, and specifically adding the desulfurizing agent in three sections: before combustion, 0.6% of desulfurizer 1 is uniformly mixed into the bituminous coal; after the mixture is put into a furnace for combustion, 1 percent of desulfurizer 1 is injected into the furnace; and finally, adding 0.4 percent of desulfurizer 1 into a horizontal flue at the upper end of the furnace, and monitoring the content of sulfur dioxide at an outlet.
After the desulfurizer 1 is added into a coal mill and ground, the desulfurizer 1 can be uniformly distributed on coal raw materials, effective desulfurization components in sodium carbonate, modified steel slag and carbide slag can be more effectively utilized and reacted under the high-temperature catalysis of cerium oxide, barium oxide and cobalt oxide after the coal raw materials are put into a furnace and combusted, meanwhile, under the distribution action of alkaline substances such as aluminum, sodium, silicon and the like in the desulfurizer injected into flue gas and fly ash, sulfur and the desulfurizer in the coal raw materials form sulfate to form coal slag, part of the sulfur and the desulfurizer continuously react with the desulfurizer injected into the flue gas and the desulfurizer injected into a subsequent horizontal flue, and under the application of the desulfurizer and a desulfurization mode (three sections of areas are respectively catalyzed), an improved high-temperature desulfurization effect can be achieved.
Application example 2
The difference from the application example 1 is that the addition amount of the desulfurizing agent 1 is 3% of the mass of the coal raw material.
Application example 3
The difference from application example 1 is that a desulfurizing agent 2 is used, and the amount of the desulfurizing agent 2 added is 3% of the coal raw material.
Application example 4
The difference from application example 1 is that a desulfurizing agent 3 is used, and the amount of the desulfurizing agent 3 added is 4% of the coal raw material.
Application example 5
Except that a desulfurizing agent 4 was used and the amount of the desulfurizing agent 4 added was 4% as compared with application example 1.
Application example 6
The difference from application example 1 was that a desulfurizing agent 5 was used, and the amount of the desulfurizing agent 5 added was 5%.
Application example 7
The difference from application example 1 was that the amount of desulfurizing agent 1 added was 6%.
Comparative example 1
The adding amount of the desulfurizer 1 is 6% of the mass of the coal raw material, the desulfurizer 1 is completely and uniformly mixed with the bituminous coal, and the content of the sulfur oxide at the outlet is monitored.
The test results are shown in table 1.
TABLE 1 content of inlet sulfur dioxide for each application example
| Serial number | Sulfur content in the furnace/ppm | Sulfur content/ppm in the outlet | Desulfurization rate/%) |
| Application example 1 | 250 | 130 | 48 |
| Application example 2 | 250 | 100 | 60 |
| Application example 3 | 250 | 114 | 54 |
| Application example 4 | 250 | 80 | 68 |
| Application example 5 | 250 | 91 | 64 |
| Application example 6 | 250 | 50 | 80 |
| Application example 7 | 250 | 25 | 90 |
| Comparative example 1 | 250 | 180 | 28 |
As can be seen from Table 1, the desulfurizer provided by the invention is particularly suitable for desulfurization treatment at the temperature of 700-. (ii) a
According to the desulfurizer of the application examples 1, 2 and 7, experimental results show that the better desulfurization effect is achieved along with the increase of the content of the desulfurizer;
according to the desulfurizer of the application examples 2 and 3, experimental results show that the desulfurization effect of the desulfurizer 1 is better than that of the desulfurizer 2, because the content of the activating agent in the desulfurizer 1 is higher, the desulfurizer can act synergistically with the catalyst, so that effective desulfurization components in sodium carbonate, steel slag powder and carbide slag are effectively utilized under the action of high temperature;
according to the application example 7, compared with the comparative example 1, the experimental results show that the desulfurization effect of the desulfurizing agent can be improved by adding the desulfurizing agent in a stepwise manner, because the desulfurizing agent can be uniformly distributed on the bituminous coal due to the small particle size when the first part of the desulfurizing agent can be mixed with the bituminous coal; under the action of high temperature, the effective desulfurization components in the sodium carbonate, the steel slag powder and the carbide slag are effectively utilized through the synergistic effect of the catalyst and the activator by the second part of the desulfurizer; the third part of desulfurizer can enter the horizontal flue along with the sulfuric acid generated by the desulfurization reaction in the furnace, and the desulfurizer in the horizontal flue further reacts with the sulfate to play a role in further desulfurization.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A desulfurizing agent, comprising:
the mixed auxiliary agent comprises carbide slag and sodium carbonate;
an activator;
the catalyst is one or more of cerium oxide, barium oxide and cobalt oxide.
2. The desulfurizing agent according to claim 1, wherein the desulfurizing agent comprises 53-78% of a mixed additive, 20-44% of an activator, and 2-10% of a catalyst by 100% by mass.
3. The desulfurizing agent according to claim 1, wherein the desulfurizing agent comprises 50-70% by mass of carbide slag and 3-8% by mass of sodium carbonate, based on 100% by mass.
4. The desulfurization agent of claim 1, wherein the cerium oxide is cerium oxide; and/or the presence of a catalyst in the reaction mixture,
the barium oxide is barium oxide; and/or the presence of a catalyst in the reaction mixture,
the cobalt oxide is cobalt oxide.
5. The desulfurizing agent according to claim 4, wherein the desulfurizing agent comprises 1-3% by mass of cerium oxide, based on 100%; and/or the presence of a catalyst in the reaction mixture,
the desulfurizer comprises 1-4% of barium oxide; and/or the presence of a catalyst in the reaction mixture,
the desulfurizer comprises 1-3% of cobalt oxide.
6. The desulfurizing agent according to claim 1, wherein the activating agent comprises manganese ore and modified steel slag with a particle size of 300-500 meshes.
7. The desulfurizing agent according to claim 6, wherein the desulfurizing agent comprises, based on 100% by mass, 4-8% of manganese ore and 20-35% of modified steel slag.
8. The desulfurizing agent according to claim 1, wherein the activating agent is ground to a particle size of 700-900 mesh.
9. A method for preparing the desulfurizing agent according to claim 1, comprising the steps of:
s1, providing a catalyst: mixing one or more of cerium oxide, barium oxide and cobalt oxide, and drying at 120-200 ℃ for 2-5 hours;
s2, providing an activator: providing modified steel slag with the granularity of 300-500 meshes, and adding manganese ore into the modified steel slag to obtain an activating agent with the grain size of 700-900 meshes;
s3, mixing: and (4) mixing and stirring the catalyst in the step S1 and the activating agent in the step S2 for 20-30 min, respectively and sequentially adding sodium carbonate and carbide slag, and mixing and stirring for 2-5 h.
10. The application of the desulfurizing agent according to any one of claims 1 to 8, wherein the desulfurizing agent is used for desulfurizing coal in a combustion process, and the amount of the desulfurizing agent is 2-6% of the mass of a coal raw material;
respectively, adding the desulfurizing agent in three sections according to the total amount of the desulfurizing agent:
1) before combustion, 30% of desulfurizer is added into the coal raw material;
2) after the mixture is put into a furnace for combustion, 50 percent of desulfurizer is added into the furnace;
3) 20 percent of desulfurizer is added into a horizontal flue at the upper end of the furnace.
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