CN115487827A - Porous carbon composite catalytic material for converter gas recovery and preparation method and application thereof - Google Patents
Porous carbon composite catalytic material for converter gas recovery and preparation method and application thereof Download PDFInfo
- Publication number
- CN115487827A CN115487827A CN202211459324.2A CN202211459324A CN115487827A CN 115487827 A CN115487827 A CN 115487827A CN 202211459324 A CN202211459324 A CN 202211459324A CN 115487827 A CN115487827 A CN 115487827A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- converter
- cobalt
- nickel
- catalytic material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 113
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000463 material Substances 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 76
- 238000011084 recovery Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000003245 coal Substances 0.000 claims abstract description 50
- 239000000017 hydrogel Substances 0.000 claims abstract description 49
- 230000008016 vaporization Effects 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000009834 vaporization Methods 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 230000002195 synergetic effect Effects 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 89
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 238000007664 blowing Methods 0.000 claims description 44
- LMHKOBXLQXJSOU-UHFFFAOYSA-N [Co].[Ni].[Pt] Chemical compound [Co].[Ni].[Pt] LMHKOBXLQXJSOU-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- 239000007921 spray Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 229920000877 Melamine resin Polymers 0.000 claims description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003546 flue gas Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 238000000975 co-precipitation Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 150000003057 platinum Chemical class 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000009768 microwave sintering Methods 0.000 claims description 6
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 239000000428 dust Substances 0.000 abstract description 18
- 239000003034 coal gas Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000779 smoke Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000002309 gasification Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000002817 coal dust Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910020707 Co—Pt Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- 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
- C10K1/02—Dust removal
-
- 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
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
-
- 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
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of multi-metal catalysts, and particularly discloses a porous carbon composite catalytic material for converter gas recovery and a preparation method and application thereof. Through the concerted catalysis of Ni, co, pt, further improve coal catalytic gasification conversion effect, the even porous carbon structure has good adsorption effect to the smoke and dust simultaneously. In the converter gas recoveryIn the application, the porous carbon composite catalytic material, the activated coal powder and the composite hydrogel are blown into the vaporization flue of the converter, and the synergistic effect of the three materials is utilized to further promote CO 2 、O 2 The conversion efficiency to CO is improved, and the purity of the coal gas is improved.
Description
Technical Field
The invention relates to the technical field of multi-metal catalysts, in particular to a porous carbon composite catalytic material for converter gas recovery and a preparation method and application thereof.
Background
Converter gas is a byproduct generated in the converter steelmaking process,specifically, in the converter steelmaking process, carbon in the molten iron and the blown oxygen generate a mixed gas of carbon monoxide and a small amount of carbon dioxide at a high temperature, that is, converter gas. The converter gas is jetted from the converter mouth at 1450-1500 deg.c and has main components of CO 55-80% and CO 2 14-20%、N 2 5-18%、H 2 ＜1.5%，O 2 Less than 2.0 percent and simultaneously carries a large amount of ferric oxide dust. The converter gas is recycled and can be used as an important fuel and raw material for baking metallurgical packages of iron and steel enterprises, chemical products, fuel gas power generation and other industrial production.
However, converter gas needs to be cooled and dedusted to be used, and a converter vaporization flue is usually used for collecting high-temperature flue gas to the maximum extent. The collected high-temperature flue gas needs to capture the smoke dust therein, so that the quality of the coal gas meets the requirements of users; the content of CO is ensured, so that the unit calorific value in the recycled gas is high; meanwhile, the oxygen content in the coal gas is controlled to be out of the explosion limit range, and according to GB 51135-2015 technical Specification for purifying and recovering converter coal gas, when O in the coal gas is contained 2 When the content is more than 2 percent, the coal gas is stopped to be recycled.
At present, the recovery of converter gas is mainly realized by a wet purification system and a dry purification system, but the oxygen content is difficult to control and CO exists 2 The content is high. In the existing research, the recovery of converter gas is realized by blowing carbon materials into a converter vaporization flue, and the carbon in the coal powder and the O in the converter flue gas are enabled to be reacted by a catalyst 2 Reacting to form CO, and reacting with CO 2 CO is generated by the reaction, but the catalyst mostly adopts FeO and Fe in smoke dust 2 O 3 CaO and their compounds, the catalytic effect thereof and the recovery quality of converter gas are to be further improved.
The existing research shows that alkali metal elements, alkaline earth metal elements and transition metal elements of the eighth subgroup have certain effects on catalytic gasification of coal. However, compounds of alkali metal elements are easily volatilized, have a corrosive effect on gasification equipment, and the catalyst is easily deactivated at high temperatures, while transition metal elements are easily poisoned by sulfur (S) in coal.
Disclosure of Invention
In view of the above, the invention provides a porous carbon composite catalytic material for converter gas recovery, and a preparation method and application thereof. Through the concerted catalysis of Ni, co, pt, further improve coal catalytic gasification conversion effect, the even porous carbon structure has good adsorption effect to the smoke and dust simultaneously. In the application of converter gas recovery, the porous carbon composite catalytic material, the activated coal powder and the composite hydrogel are blown into the vaporization flue of the converter, and the synergistic effect of the three materials is utilized to further promote CO 2 、O 2 The conversion efficiency to CO is improved, and the purity of the coal gas is improved.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
in a first aspect, an embodiment of the invention provides a porous carbon composite catalytic material for converter gas recovery, which comprises a porous carbon material, wherein a nickel-cobalt-platinum metal system is loaded on the surface of the porous carbon material and inside holes;
wherein the nickel-cobalt-platinum metal system accounts for 0.5-1.2% of the mass of the porous carbon composite catalytic material.
Preferably, in the nickel-cobalt-platinum metal system, the molar ratio of nickel, cobalt and platinum is 2-5.
Compared with the prior art, the invention further improves the catalytic gasification conversion effect of coal through the synergistic catalytic action of Ni, co and Pt, wherein cobalt can strengthen the stability of the spherical material, and the metal multi-active sites of nickel and platinum can play a better catalytic effect; the uniform porous carbon structure has good adsorption effect on smoke dust, improves the purity of coal gas, and can further reduce the content of oxides; the porous carbon structure enables the mass density of the carbon material to be small, the porosity to be large, the introduction amount of argon and nitrogen can be remarkably reduced, the gas consumption cost is reduced, and meanwhile, the reduction of the gas temperature can be slowed down.
The second aspect of the embodiment of the invention also provides a preparation method of the porous carbon composite catalytic material for recycling converter gas, which comprises the following steps:
s1, respectively dissolving soluble nickel salt, cobalt salt and platinum salt in water, and respectively and synchronously adding the soluble nickel salt, the cobalt salt and the platinum salt into the water with the pH value of 8.0-8.5 in an alkaline solution, O is introduced into the alkaline solution 2 Carrying out coprecipitation reaction under the condition of (1), filtering and drying to obtain a nickel-cobalt-platinum precursor;
s2, preparing spherical carbon-coated nickel-cobalt-platinum precursor powder by using the nickel-cobalt-platinum precursor, a citric acid solution and a melamine solution as raw materials through a spray drying process;
s3, compacting the precursor powder at 5-10% 2 Microwave sintering in 90-95% Ar mixed atmosphere, and grinding to obtain the Ni-Co-Pt porous carbon composite catalytic material, wherein the sintering temperature is 650-800 ℃, and the sintering time is 3-5h.
Compared with the prior art, the invention adopts a coprecipitation technology, and obtains the spherical nickel-cobalt-platinum precursor through the compounding of multiple metal ions of nickel, cobalt and platinum in O 2 More vacancies or defects can be introduced in the reaction under the condition, so that the catalytic effect of the material is enhanced; then preparing carbon-coated nickel-cobalt-platinum precursor powder by a spray drying process; finally at H 2 And sintering the precursor in Ar atmosphere to better fix/embed the spherical nickel-cobalt-platinum precursor into the porous carbon material with high specific area. The catalytic material prepared by the method has an excellent adsorption performance while obtaining a remarkable catalytic effect.
Preferably, the soluble nickel salt in the step S1 is nickel acetate, nickel chloride or nickel nitrate hydrate, and the concentration is 1-1.2mol/L; the soluble cobalt salt is hydrated cobalt nitrate or cobalt chloride, and the concentration is 0.8-1.0mol/L; the soluble platinum salt is chloroplatinic acid or ammonium chloroplatinate, and the concentration of the soluble platinum salt is 0.4-0.6mol/L;
controlling the flow rate of adding soluble nickel salt, cobalt salt and platinum salt into the alkaline solution to be 10-30mL/min;
the alkaline solution is ammonia water;
the reaction temperature of the coprecipitation reaction is 48-49 ℃, and the reaction time is 20-24h.
Preferably, the mass of the nickel-cobalt-platinum precursor in the step S2 is 1-3% of that of the carbon source which is citric acid and melamine; wherein the concentration of the citric acid solution prepared by citric acid is 0.8-1.2mol/L, the concentration of the melamine solution prepared by melamine is 1.2-1.8mol/L, and the volume ratio of the citric acid solution to the melamine solution is 1-1.8;
the inlet temperature of the spray drying process is 180-220 ℃, the feeding rate is 0.3-0.8L/h, and the air inlet flow is 350-500L/h.
Preferably, the compacting in step S3 is a treatment at 20-50 ℃ for 15-20min at 8-10 MPa.
The third aspect of the invention also provides the application of the converter gas in recovery and enrichment, in particular, the porous carbon composite catalytic material as claimed in any one of claims 1 to 2 is blown into a converter vaporization flue for collecting converter flue gas, and activated coal powder and composite hydrogel are used for removing CO in the converter flue gas 2 And O 2 Conversion to CO;
the composite hydrogel is compounded by 30-48 parts of ethylene glycol diglycidyl ether, 15-24 parts of sodium alginate, 1-4 parts of sodium citrate, 10-14 parts of pentaethylenehexamine, 10-14 parts of ammonium chloride and 10-14 parts of calcium chloride according to parts by weight.
Preferably, the porous carbon composite catalytic material, the activated coal powder and the composite hydrogel are subjected to synergistic treatment based on three spray guns, and the method specifically comprises the following steps:
blowing the porous carbon composite catalytic material into a vaporization flue of the converter by using a first spray gun and using nitrogen-argon mixed gas as a medium, wherein the blowing amount of the porous carbon composite catalytic material is 8 multiplied by 10 -7 -2×10 -6 kg/m 3 Converter gas with mixed gas flow of 5X 10 -2 -9×10 -2 m 3 Per kg of porous carbon composite catalytic material;
blowing activated coal powder into the vaporizing flue of the converter by a second spray gun by using nitrogen as a medium, wherein the blowing amount of the activated coal powder is 3 multiplied by 10 -4 -1×10 -3 kg/m 3 Converter gas with 4 x 10 gas flow rate -2 -8×10 -2 m 3 Per kg of activated coal fines;
blowing composite hydrogel into the vaporizing flue of the converter by a third spray gun by using nitrogen as a medium, wherein the blowing amount of the composite hydrogel material is 3 multiplied by 10 -7 -8×10 -7 kg/m 3 Converter gas with nitrogen flow of 3X 10 -3 -7×10 -3 m 3 Per kg of composite hydrogel.
Preferably, the activated coal dust is prepared by spraying and pre-activating desulfurized coal dust by using 0.2-0.6mol/L KOH solution and then grinding;
the spraying solution accounts for 8-12% of the mass of the coal powder.
Preferably, the preparation process of the composite hydrogel material comprises the following steps:
dissolving ethylene glycol diglycidyl ether and pentaethylenehexamine in water, and stirring at the temperature of 45-55 ℃ for 60-120min at the stirring speed of 80-120r/min to obtain a clear mixed solution;
step two, adding the sodium alginate in parts by weight into the mixed solution, stirring, adding the sodium citrate in parts by weight after the solution is uniformly mixed, raising the temperature to 58-62 ℃, and carrying out aging treatment for 30-50min at the stirring speed of 100-120r/min to obtain a turbid solution;
and step three, synchronously adding the ammonium chloride and the calcium chloride in parts by weight into the turbid liquid, wherein the flow rate of calcium chloride powder is 4-7kg/h, the flow rate of ammonium chloride powder is 3-5kg/h, after the materials are added, the reaction temperature is increased to 65-68 ℃, the reaction is carried out for 60-120min, and the stirring speed is 120-150r/min, so as to obtain the composite hydrogel.
Preferably, the porous carbon composite catalytic material can be recycled after being cleaned by 1-4mol/L dilute hydrochloric acid or 0.5-2mol/L dilute sulfuric acid solution.
The catalytic material can be recycled after being washed by dilute acid solution to remove adsorbed oxide components.
Compared with the prior art, the porous carbon composite catalytic material, the activated coal powder and the composite hydrogel are blown into the converter vaporization flue, and the porous carbon composite catalytic material and the activated coal powder can be better bonded together under the action of the composite hydrogel by utilizing the synergistic action of the porous carbon composite catalytic material, the activated coal powder and the composite hydrogel, and meanwhile, the composite hydrogel can enhance the aggregation effect of gas molecules and smoke dust, so that the gas molecules and the smoke dust are more easily adsorbed by the activated coal powder or the catalytic material, and the CO is further promoted to be further adsorbed by the activated coal powder or the catalytic material 2 、O 2 Conversion efficiency to CO and improvement of gas purityAnd (4) degree.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Preparation of porous carbon composite catalytic material
1.0mol/L hydrated nickel nitrate, 0.8mol/L hydrated cobalt nitrate and 0.4mol/L chloroplatinic acid are taken as raw materials, and are respectively and synchronously added into ammonia water with the pH value of 8.0 according to the molar ratio of Ni, co and Pt metal ions of 2 2 Carrying out coprecipitation reaction under the condition of (1), wherein the coprecipitation reaction temperature is 48 ℃, and the reaction time is 24 hours, filtering and drying to obtain the nickel-cobalt-platinum precursor.
The method comprises the following steps of taking a prepared nickel-cobalt-platinum precursor, 0.8mol/L citric acid and 1.2mol/L melamine as raw materials, preparing spherical carbon-coated nickel-cobalt-platinum precursor powder by a spray drying process, wherein the inlet temperature is 180 ℃, the feeding rate is 0.3L/h, and the air inlet flow is 350L/h, wherein the mass of the nickel-cobalt-platinum precursor is 1% of the mass of a carbon source by taking the citric acid and the melamine, and the volume ratio of a citric acid solution to a melamine solution is 1.0.
Compacting the carbon-coated nickel-cobalt-platinum precursor powder for 15min at 8Mpa and 40 ℃ by adopting a hydraulic press; then at 5-10% 2 And (3) performing microwave sintering in an Ar mixed atmosphere accounting for 90-95 percent, and finally grinding to obtain the nickel-cobalt-platinum porous carbon composite catalytic material, wherein the sintering temperature is 650 ℃, and the sintering time is 5 hours.
(2) Preparation of activated coal fines
And (3) carrying out spray preactivation treatment on the desulfurized pulverized coal by adopting 0.4mol/L KOH solution, wherein the spray solution accounts for 10% of the mass of the pulverized coal.
Grinding using a ball mill: the rotating speed is 50r/min, the time is 40min, and the steel ball ratio is phi 100mm, phi 60mm, phi 40mm = 2.
(3) Preparation of composite hydrogel material
Step one, preparing the following raw materials in parts by weight: 40 parts of ethylene glycol diglycidyl ether, 21 parts of sodium alginate, 3 parts of sodium citrate, 12 parts of pentaethylenehexamine, 12 parts of ammonium chloride and 12 parts of calcium chloride.
And step two, dissolving the ethylene glycol diglycidyl ether and the pentaethylenehexamine in parts by weight in water, and stirring at the temperature of 50 ℃ for 90min at the stirring speed of 100r/min to obtain clear mixed liquor.
And step three, adding the sodium alginate in parts by weight into the mixed solution, stirring, adding the sodium citrate in parts by weight after the solution is uniformly mixed, raising the temperature to 60 ℃, and aging for 40min at the stirring speed of 110r/min to obtain the turbid solution.
And step four, synchronously adding the ammonium chloride and the calcium chloride in parts by weight into the turbid liquid, wherein the flow rate of calcium chloride powder is 6kg/h, the flow rate of ammonium chloride powder is 4kg/h, after the materials are added, raising the reaction temperature to 66 ℃, reacting for 90min, and stirring at the speed of 150r/min to obtain the composite hydrogel.
(4) Converter gas recovery enrichment
And blowing the prepared porous carbon composite catalytic material, activated coal powder and composite hydrogel into a converter vaporization flue for collecting converter flue gas, and converting CO2 and O2 in the converter flue gas into CO. The method specifically comprises the following steps of performing synergistic treatment on a porous carbon composite catalytic material, activated coal powder and composite hydrogel based on three spray guns:
blowing the porous carbon composite catalytic material into a vaporization flue of the converter by using a first spray gun and using nitrogen-argon mixed gas as a medium, wherein the blowing amount of the porous carbon composite catalytic material is 2 multiplied by 10 -6 kg/m 3 Converter gas with mixed gas flow of 9X 10 -2 m 3 Per kg of porous carbon composite catalytic material;
blowing activated coal powder into the vaporizing flue of the converter by a second spray gun by using nitrogen as a medium, wherein the blowing amount of the activated coal powder is 1 multiplied by 10 -3 kg/m 3 Converter gas with gas flow rate of 8 x 10 -2 m 3 The included angle between the blowing angle and the first spray gun is 15 degrees;
passing through a third spray gun by using nitrogen asBlowing composite hydrogel into the vaporizing flue of the converter, wherein the blowing amount of the composite hydrogel material is 8 multiplied by 10 -7 kg/m 3 Converter gas with nitrogen flow of 7X 10 -3 m 3 Per kg of composite hydrogel.
The converter used for smelting is a 150t converter, 7 times of tests are carried out according to the conditions, and the average gas recovery rate is 139Nm 3 T, the main components of the recovered gas are CO 65-89% in volume percentage 2 3-7%，O 2 0.2-0.4%, hydrogen and nitrogen as the rest, and the average dust content is 3mg/m 3 。
Example 2
(1) Preparation of porous carbon composite catalytic material
1.2mol/L hydrated nickel nitrate, 1.0mol/L hydrated cobalt nitrate and 0.6mol/L chloroplatinic acid are taken as raw materials, and are respectively and synchronously added into ammonia water with the pH value of 8.5 according to the molar ratio of Ni, co and Pt metal ions of 5 2 Carrying out coprecipitation reaction at 49 ℃ for 20h, filtering and drying to obtain the nickel-cobalt-platinum precursor.
The method comprises the following steps of taking a prepared nickel-cobalt-platinum precursor, 1.2mol/L citric acid and 1.8mol/L melamine as raw materials, preparing spherical carbon-coated nickel-cobalt-platinum precursor powder through a spray drying process, wherein the inlet temperature is 220 ℃, the feeding rate is 0.8L/h, and the air inlet flow is 500L/h, wherein the mass of the nickel-cobalt-platinum precursor is 3% of that of the carbon source by taking the citric acid and the melamine, and the volume ratio of the citric acid solution to the melamine solution is 1.8.
Compacting the carbon-coated nickel-cobalt-platinum precursor powder for 18min at 10Mpa and 30 ℃ by adopting a hydraulic press; then by 10% of 2 +90 percent, microwave sintering in Ar mixed atmosphere, and finally grinding to obtain the nickel-cobalt-platinum porous carbon composite catalytic material, wherein the sintering temperature is 800 ℃, and the sintering time is 3 hours.
(2) Activated coal dust and a composite hydrogel material were prepared according to the method in example 1.
(3) Converter gas recovery enrichment
And blowing the prepared porous carbon composite catalytic material, activated coal powder and composite hydrogel into a converter vaporization flue for collecting converter flue gas, and converting CO2 and O2 in the converter flue gas into CO. The method specifically comprises the following steps of performing synergistic treatment on a porous carbon composite catalytic material, activated coal powder and composite hydrogel based on three spray guns:
blowing the porous carbon composite catalytic material into a vaporization flue of the converter by using a first spray gun and using nitrogen-argon mixed gas as a medium, wherein the blowing amount of the porous carbon composite catalytic material is 8 multiplied by 10 -7 kg/m 3 Converter gas with mixed gas flow of 5X 10 -2 m 3 Per kg of porous carbon composite catalytic material;
blowing activated coal powder into the vaporizing flue of the converter by a second spray gun by using nitrogen as a medium, wherein the blowing amount of the activated coal powder is 3 multiplied by 10 -4 kg/m 3 Converter gas with 4 x 10 gas flow rate -2 m 3 Per kg of activated coal fines;
blowing composite hydrogel into the vaporization flue of the converter by a third spray gun by using nitrogen as a medium, wherein the blowing amount of the composite hydrogel material is 3 multiplied by 10 -7 kg/m 3 Converter gas with nitrogen flow of 3X 10 -3 m 3 Per kg of composite hydrogel.
The converter used for smelting is a 150t converter, 7 times of tests are carried out according to the conditions, and the average gas recovery rate is 130m 3 Per ton of steel, the main components of the recovered gas are 63-85% of CO and CO according to volume percentage 2 4-10%、O 2 0.3-0.4%, the rest is hydrogen, nitrogen and the like, and the average dust content is 5mg/m 3 。
Example 3
(1) Preparation of porous carbon composite catalytic material
1.1mol/L hydrated nickel nitrate, 0.9mol/L hydrated cobalt nitrate and 0.5mol/L chloroplatinic acid are taken as raw materials, and are respectively and synchronously added into ammonia water with the pH value of 8.3 according to the molar ratio of Ni, co and Pt metal ions of 4 2 The coprecipitation reaction is carried out under the condition of (1), the temperature of the coprecipitation reaction is 49 ℃, the reaction time is 22h, and the nickel-cobalt-platinum precursor is obtained after filtration and drying.
The method comprises the following steps of taking a prepared nickel-cobalt-platinum precursor, 1.0mol/L citric acid and 1.5mol/L melamine as raw materials, preparing spherical carbon-coated nickel-cobalt-platinum precursor powder through a spray drying process, wherein the inlet temperature is 200 ℃, the feeding rate is 0.5L/h, and the air inlet flow is 420L/h, wherein the mass of the nickel-cobalt-platinum precursor is 2% of the mass of a carbon source taking citric acid and melamine, and the volume ratio of a citric acid solution to a melamine solution is 1.5.
Compacting the carbon-coated nickel-cobalt-platinum precursor powder for 18min at 10Mpa and 30 ℃ by adopting a hydraulic press; then by 7% of 2 +93% by microwave sintering in Ar mixed atmosphere, and finally grinding to obtain the nickel-cobalt-platinum porous carbon composite catalytic material, wherein the sintering temperature is 700 ℃ and the sintering time is 4h.
(2) Activated coal dust and composite hydrogel materials were prepared as in example 1.
(3) Recovery and enrichment of converter gas
And blowing the prepared porous carbon composite catalytic material, activated coal powder and composite hydrogel into a converter vaporization flue for collecting converter flue gas, and converting CO2 and O2 in the converter flue gas into CO. The method specifically comprises the following steps of performing synergistic treatment on a porous carbon composite catalytic material, activated coal powder and composite hydrogel based on three spray guns:
blowing the porous carbon composite catalytic material into a vaporization flue of the converter by using a first spray gun and using nitrogen-argon mixed gas as a medium, wherein the blowing amount of the porous carbon composite catalytic material is 1.4 multiplied by 10 -6 kg/m 3 Converter gas with mixed gas flow of 7X 10 -2 m 3 Per kg of porous carbon composite catalytic material;
blowing activated coal powder into the vaporization flue of the converter by a second spray gun by taking nitrogen as a medium, wherein the blowing amount of the activated coal powder is 7 multiplied by 10 -4 kg/m 3 Converter gas with gas flow of 6 x 10 -2 m 3 Per kg of activated coal fines;
blowing composite hydrogel into the vaporizing flue of the converter by a third spray gun by using nitrogen as a medium, wherein the blowing amount of the composite hydrogel material is 5 multiplied by 10 -7 kg/m 3 Converter gas with nitrogen flow of 5X 10 -3 m 3 Per kg of composite hydrogel.
Converter for smeltingIn a 150t converter, 7 tests were carried out under the above conditions, and the average amount of recovered coal gas was 135m 3 Per ton steel, the main components of the recovered gas are CO 65-87% and CO according to volume percentage 2 3-8%、O 2 0.3-0.5%, hydrogen and nitrogen as the rest, and the average dust content is 4mg/m 3 。
Example 4
(1) Preparation of porous carbon composite catalytic material
1.1mol/L nickel chloride, 0.9mol/L cobalt chloride and 0.5mol/L ammonium chloroplatinate are taken as raw materials, and are respectively and synchronously added into ammonia water with the pH value of 8.3 according to the molar ratio of Ni, co and Pt metal ions of 4 2 The coprecipitation reaction is carried out under the condition of (1), the temperature of the coprecipitation reaction is 49 ℃, the reaction time is 22h, and the nickel-cobalt-platinum precursor is obtained after filtration and drying.
The method comprises the following steps of taking a prepared nickel-cobalt-platinum precursor, 1.0mol/L citric acid and 1.5mol/L melamine as raw materials, preparing spherical carbon-coated nickel-cobalt-platinum precursor powder through a spray drying process, wherein the inlet temperature is 200 ℃, the feeding rate is 0.5L/h, and the air inlet flow is 420L/h, wherein the mass of the nickel-cobalt-platinum precursor is 2% of the mass of a carbon source taking citric acid and melamine, and the volume ratio of a citric acid solution to a melamine solution is 1.5.
Compacting the carbon-coated nickel-cobalt-platinum precursor powder for 18min at 10Mpa and 30 ℃ by adopting a hydraulic press; then at 7% H 2 +93% by microwave sintering in Ar mixed atmosphere, and finally grinding to obtain the nickel-cobalt-platinum porous carbon composite catalytic material, wherein the sintering temperature is 700 ℃ and the sintering time is 4h.
(2) Activated coal dust and a composite hydrogel material were prepared according to the method in example 1.
(3) Converter gas recovery enrichment
And blowing the prepared porous carbon composite catalytic material, activated coal powder and composite hydrogel into a converter vaporization flue for collecting converter flue gas, and converting CO2 and O2 in the converter flue gas into CO. The method specifically comprises the following steps of performing synergistic treatment on a porous carbon composite catalytic material, activated coal powder and composite hydrogel based on three spray guns:
through the first stepA spray gun, which takes nitrogen-argon mixed gas as a medium and blows the porous carbon composite catalytic material into the vaporization flue of the converter, wherein the blowing amount of the porous carbon composite catalytic material is 1.4 multiplied by 10 -6 kg/m 3 Converter gas with mixed gas flow of 7 x 10 -2 m 3 Per kg of porous carbon composite catalytic material;
blowing activated coal powder into the vaporizing flue of the converter by a second spray gun by using nitrogen as a medium, wherein the blowing amount of the activated coal powder is 7 multiplied by 10 -4 kg/m 3 Converter gas with gas flow of 6 x 10 -2 m 3 Per kg of activated coal fines;
blowing composite hydrogel into the vaporizing flue of the converter by a third spray gun by using nitrogen as a medium, wherein the blowing amount of the composite hydrogel material is 5 multiplied by 10 -7 kg/m 3 Converter gas with nitrogen flow of 5X 10 -3 m 3 Per kg of composite hydrogel.
The converter used for smelting is a 150t converter, 7 times of tests are carried out according to the conditions, and the average gas recovery rate is 134m 3 Per ton of steel, the main components of the recovered gas are 62-84% of CO and CO according to volume percentage 2 5-10%、O 2 0.4-0.6%, hydrogen and nitrogen as the rest, and the average dust content is 5mg/m 3 。
Comparative example 1
The test for the recovery of converter gas was carried out under the conditions in example 3 without blowing the porous carbon composite catalyst material, and the average amount of recovered gas was 128m 3 Per ton steel, the main components of the recovered gas are 54-72% of CO and CO according to volume percentage 2 7-13%、O 2 0.5-0.7%, average dust content of 6mg/m 3 。
Compared with the comparative example 1, the embodiment 3 has the advantages that the recovery amount of coal gas per ton steel is increased by 5.5 percent, the content of CO is obviously improved, and CO is obviously reduced 2 And O 2 The content of the active carbon is obviously reduced, and the dust content is reduced by 33 percent.
Comparative example 2
The test for the recovery of converter gas was carried out under the conditions in example 3 without blowing the porous carbon composite catalytic material and the composite hydrogel, and the average amount of recovered gas was 127m 3 Per ton of steel, recoveryThe main components of the coal gas are 53-70% of CO and CO according to volume percentage 2 9-14%、O 2 0.4-0.8%, and average dust content of 8mg/m 3 。
Compared with the comparative example 2, the recovery amount of each ton of steel gas is increased by 6.3 percent, the content of CO is obviously improved, and the CO content is obviously improved 2 And O 2 The content of the active carbon is obviously reduced, and the dust content is reduced by 50 percent.
Comparative example 3
The test of the recovery of converter gas was carried out under the conditions of example 3 without blowing the activated coal powder, the porous carbon composite catalytic material and the composite hydrogel, and the average amount of the recovered gas was 116m 3 Per ton steel, the main components of the recovered gas are 40-60% of CO and CO according to volume percentage 2 15-20%、O 2 0.6-0.9%, and average dust content of 8mg/m 3 。
Compared with the comparative example 3, the recovery amount of each ton of steel gas is increased by 16.4 percent, the content of CO is obviously improved, and the CO content is obviously increased 2 And O 2 The content of (A) is obviously reduced, and the dust content is reduced by 50%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A porous carbon composite catalytic material for converter gas recovery is characterized by comprising a porous carbon material, wherein a nickel-cobalt-platinum metal system is loaded on the surface of the porous carbon material and in holes;
wherein the nickel-cobalt-platinum metal system accounts for 0.5-1.2% of the mass of the porous carbon composite catalytic material.
2. The porous carbon composite catalytic material for recovering converter gas according to claim 1, wherein in the nickel-cobalt-platinum metal system, the molar ratio of nickel, cobalt and platinum is 2-5.
3. The method for preparing a porous carbon composite catalytic material for converter gas recovery according to any one of claims 1 to 2, characterized by comprising the steps of:
s1, respectively dissolving soluble nickel salt, cobalt salt and platinum salt in water, respectively and synchronously adding the soluble nickel salt, the cobalt salt and the platinum salt into an alkaline solution with the pH value of 8.0-8.5, and introducing O into the alkaline solution 2 Carrying out coprecipitation reaction under the condition of (1), filtering and drying to obtain a nickel-cobalt-platinum precursor;
s2, preparing spherical carbon-coated nickel-cobalt-platinum precursor powder by using the nickel-cobalt-platinum precursor, a citric acid solution and a melamine solution as raw materials through a spray drying process;
s3, compacting the precursor powder at 5-10% 2 Microwave sintering in 90-95% Ar mixed atmosphere, and grinding to obtain the nickel-cobalt-platinum porous carbon composite catalytic material, wherein the sintering temperature is 650-800 ℃, and the sintering time is 3-5h.
4. The preparation method of the porous carbon composite catalytic material for converter gas recovery as recited in claim 3, wherein in step S1 the soluble nickel salt is nickel acetate, nickel chloride or nickel nitrate hydrate, and the concentration is 1-1.2mol/L; the soluble cobalt salt is hydrated cobalt nitrate or cobalt chloride, and the concentration is 0.8-1.0mol/L; the soluble platinum salt is chloroplatinic acid or ammonium chloroplatinate, and the concentration of the soluble platinum salt is 0.4-0.6mol/L;
controlling the flow of adding soluble nickel salt, cobalt salt and platinum salt into the alkaline solution to be 10-30mL/min;
the alkaline solution is ammonia water;
the reaction temperature of the coprecipitation reaction is 48-49 ℃, and the reaction time is 20-24h.
5. The preparation method of the porous carbon composite catalytic material for recycling converter gas as claimed in claim 3, wherein the mass of the nickel-cobalt-platinum precursor in the step S2 is 1-3% of the mass of the carbon source which is citric acid and melamine; wherein the concentration of the citric acid solution prepared by citric acid is 0.8-1.2mol/L, the concentration of the melamine solution prepared by melamine is 1.2-1.8mol/L, and the volume ratio of the citric acid solution to the melamine solution is 1-1.8;
the inlet temperature of the spray drying process is 180-220 ℃, the feeding rate is 0.3-0.8L/h, and the air inlet flow is 350-500L/h.
6. A method for recovering and enriching converter gas is characterized by comprising the following steps: blowing the porous carbon composite catalytic material as claimed in any one of claims 1 to 2, activated coal powder and composite hydrogel into a converter vaporization flue for collecting converter flue gas, for removing CO in the converter flue gas 2 And O 2 Conversion to CO;
the composite hydrogel is prepared by compounding 30-48 parts by weight of ethylene glycol diglycidyl ether, 15-24 parts by weight of sodium alginate, 1-4 parts by weight of sodium citrate, 10-14 parts by weight of pentaethylenehexamine, 10-14 parts by weight of ammonium chloride and 10-14 parts by weight of calcium chloride.
7. The method for recovering and enriching converter gas according to claim 6, wherein the porous carbon composite catalytic material, the activated coal powder and the composite hydrogel are subjected to synergistic treatment based on three spray guns, and the method specifically comprises the following steps:
blowing the porous carbon composite catalytic material into a converter vaporization flue by using a first spray gun and using nitrogen-argon mixed gas as a medium, wherein the blowing amount of the porous carbon composite catalytic material is 8 multiplied by 10 -7 -2×10 -6 kg/m 3 Converter gas with mixed gas flow of 5X 10 -2 -9×10 -2 m 3 Per kg of porous carbon composite catalytic material;
blowing activated coal powder into the vaporization flue of the converter by a second spray gun by taking nitrogen as a medium, wherein the blowing amount of the activated coal powder is 3 multiplied by 10 -4 -1×10 -3 kg/m 3 Converter gas with gas flow of 4X 10 -2 -8×10 -2 m 3 Per kg of activated coal fines;
blowing composite hydrogel into the vaporizing flue of the converter by a third spray gun by using nitrogen as a medium, wherein the blowing amount of the composite hydrogel material is 3 multiplied by 10 -7 -8×10 -7 kg/m 3 Converter gas with nitrogen flow of 3X 10 -3 -7×10 -3 m 3 Perkg composite hydrogel。
8. The method for recovering and enriching converter gas according to any one of claims 6 to 7, wherein the activated pulverized coal is prepared by performing spray pre-activation treatment on desulfurized pulverized coal with 0.2 to 0.6mol/L KOH solution, and then grinding;
the spraying solution accounts for 8-12% of the mass of the coal powder.
9. The method for recovering and enriching converter gas according to any one of claims 6 to 7, wherein the preparation process of the composite hydrogel material comprises the following steps:
dissolving ethylene glycol diglycidyl ether and pentaethylenehexamine in water, and stirring at the temperature of 45-55 ℃ for 60-120min at the stirring speed of 80-120r/min to obtain a clear mixed solution;
step two, adding the sodium alginate in parts by weight into the mixed solution, stirring, adding the sodium citrate in parts by weight after the solution is uniformly mixed, raising the temperature to 58-62 ℃, and carrying out aging treatment for 30-50min at the stirring speed of 100-120r/min to obtain a turbid solution;
and step three, synchronously adding the above parts by weight of ammonium chloride and calcium chloride into the turbid liquid, wherein the flow rate of calcium chloride powder is 4-7kg/h, the flow rate of ammonium chloride powder is 3-5kg/h, after the materials are added, raising the reaction temperature to 65-68 ℃, reacting for 60-120min, and stirring at 120-150r/min to obtain the composite hydrogel.
10. The method for recovering and enriching converter gas as recited in claim 6, wherein the porous carbon composite catalytic material can be recycled after being cleaned by 1-4mol/L diluted hydrochloric acid or 0.5-2mol/L diluted sulfuric acid solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211459324.2A CN115487827B (en) | 2022-11-16 | 2022-11-16 | Porous carbon composite catalytic material for converter gas recovery and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211459324.2A CN115487827B (en) | 2022-11-16 | 2022-11-16 | Porous carbon composite catalytic material for converter gas recovery and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115487827A true CN115487827A (en) | 2022-12-20 |
| CN115487827B CN115487827B (en) | 2023-03-24 |
Family
ID=85116335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211459324.2A Active CN115487827B (en) | 2022-11-16 | 2022-11-16 | Porous carbon composite catalytic material for converter gas recovery and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115487827B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117535470A (en) * | 2024-01-10 | 2024-02-09 | 河北科技大学 | Converter gas upgrading increment method and system based on photocatalytic carbon dioxide conversion |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102448880A (en) * | 2009-05-26 | 2012-05-09 | 创业发展联盟技术有限公司 | Carbon material and method for producing the same |
| CN102513099A (en) * | 2011-11-24 | 2012-06-27 | 浙江大学 | Novel metal catalyst loaded by mesoporous carbon and preparation method thereof |
| CN106910899A (en) * | 2017-02-27 | 2017-06-30 | 广西大学 | A kind of preparation method of N doping bivalve Rotating fields nanocatalyst |
| CN109225224A (en) * | 2018-10-24 | 2019-01-18 | 北方民族大学 | Wooden macroporous carbon catalysis electrode material and its preparation method and application |
| CN110034306A (en) * | 2019-03-13 | 2019-07-19 | 上海交通大学 | The preparation method and application of the composite material of the porous carbon coating cobalt nano-particle of N doping |
| CN110694772A (en) * | 2019-10-21 | 2020-01-17 | 大峘集团有限公司 | Production process of slag and steel slag micropowder |
| CN113522287A (en) * | 2021-06-24 | 2021-10-22 | 中科合成油技术有限公司 | Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof |
-
2022
- 2022-11-16 CN CN202211459324.2A patent/CN115487827B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102448880A (en) * | 2009-05-26 | 2012-05-09 | 创业发展联盟技术有限公司 | Carbon material and method for producing the same |
| CN102513099A (en) * | 2011-11-24 | 2012-06-27 | 浙江大学 | Novel metal catalyst loaded by mesoporous carbon and preparation method thereof |
| CN106910899A (en) * | 2017-02-27 | 2017-06-30 | 广西大学 | A kind of preparation method of N doping bivalve Rotating fields nanocatalyst |
| CN109225224A (en) * | 2018-10-24 | 2019-01-18 | 北方民族大学 | Wooden macroporous carbon catalysis electrode material and its preparation method and application |
| CN110034306A (en) * | 2019-03-13 | 2019-07-19 | 上海交通大学 | The preparation method and application of the composite material of the porous carbon coating cobalt nano-particle of N doping |
| CN110694772A (en) * | 2019-10-21 | 2020-01-17 | 大峘集团有限公司 | Production process of slag and steel slag micropowder |
| CN113522287A (en) * | 2021-06-24 | 2021-10-22 | 中科合成油技术有限公司 | Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117535470A (en) * | 2024-01-10 | 2024-02-09 | 河北科技大学 | Converter gas upgrading increment method and system based on photocatalytic carbon dioxide conversion |
| CN117535470B (en) * | 2024-01-10 | 2024-03-15 | 河北科技大学 | Converter gas upgrading increment method and system based on photocatalytic carbon dioxide conversion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115487827B (en) | 2023-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055848B (en) | Rare-earth doped low-temperature denitration catalyst and preparation method thereof | |
| CN102441396B (en) | The application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method | |
| CN115487827B (en) | Porous carbon composite catalytic material for converter gas recovery and preparation method and application thereof | |
| CN103230813A (en) | Preparation method of alkali-poisoning-resistant denitrifying catalyst applicable to cement kilns | |
| CN111939907A (en) | Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof | |
| CN105597769A (en) | Preparing method for flake-feature nano-composite metal oxide catalyst CeO2-Co3O4 | |
| CN112403487A (en) | Medium-low temperature vanadium-free desulfurization and denitrification catalyst and preparation method thereof | |
| CN105903478B (en) | Medium-low temperature SCR catalyst with wider use temperature and preparation method thereof | |
| CN107983354B (en) | Preparation method of alkali poisoning resistant copper-based spinel low-temperature denitration catalyst | |
| WO2022141978A1 (en) | Nickel-doped brownmillerite-type oxygen carrier, and preparation method therefor and application thereof | |
| CN102862960B (en) | Application and preparation of high-activity composite oxide oxygen carrier in chemical link circulation hydrogen production | |
| CN113600198A (en) | Biomass tar reforming catalyst and preparation method thereof | |
| CN113877623B (en) | Preparation method and application of catalyst for purifying tail gas of submerged arc furnace | |
| CN110252317B (en) | Ce-Fe-based catalyst for efficiently removing nitrogen oxides at low temperature | |
| CN111905721A (en) | Catalyst for low-temperature denitration and demercuration of titanium dioxide nano array and preparation method thereof | |
| CN114377684A (en) | MnCoO for removing CO at low temperaturexCatalyst and preparation method thereof | |
| CN115318303B (en) | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof | |
| CN107744819B (en) | Preparation method of environment-friendly denitration catalyst | |
| CN102442640B (en) | Application of composite metal oxide oxygen carrier to recycle chemistry chain hydrogen production and preparation thereof | |
| CN103480368B (en) | A kind of low-carbon (LC) gaseous mixture catalytic combustion deoxygenation catalyst and preparation method thereof | |
| CN113941338B (en) | Denitration and dust removal integrated ceramic tube catalyst and preparation method thereof, and flue gas denitration and dust removal method | |
| CN102862956A (en) | Application of oxygen carrier with perovskite structure in chemical looping hydrogen production and preparation thereof | |
| CN114100625B (en) | Cobalt-molybdenum-based perovskite sulfur-tolerant shift reaction catalyst and preparation method thereof | |
| CN106622313B (en) | A kind of oxygen carrier for hydrogen production of chemical chain, preparation method and application | |
| CN102851085B (en) | Renewable calcium high-temperature coal gas desulfurizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |