CN112813276A - Method for disposing waste activated carbon - Google Patents
Method for disposing waste activated carbon Download PDFInfo
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- CN112813276A CN112813276A CN202011454335.2A CN202011454335A CN112813276A CN 112813276 A CN112813276 A CN 112813276A CN 202011454335 A CN202011454335 A CN 202011454335A CN 112813276 A CN112813276 A CN 112813276A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002910 solid waste Substances 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000003723 Smelting Methods 0.000 claims abstract description 18
- 239000006227 byproduct Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010791 quenching Methods 0.000 claims abstract description 14
- 230000000171 quenching effect Effects 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 13
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 11
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000009388 chemical precipitation Methods 0.000 claims abstract description 7
- 230000004907 flux Effects 0.000 claims abstract description 6
- 239000005416 organic matter Substances 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 10
- 235000012255 calcium oxide Nutrition 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 239000002920 hazardous waste Substances 0.000 abstract description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 26
- 239000003546 flue gas Substances 0.000 description 26
- 239000002912 waste gas Substances 0.000 description 15
- 239000002918 waste heat Substances 0.000 description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- 239000000428 dust Substances 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 9
- 239000004566 building material Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for disposing waste activated carbon, which comprises the following steps: mixing a mixture comprising waste activated carbon and multi-element solid waste with a flux, roasting and pre-reducing, wherein the waste activated carbon is activated carbon after organic matter is adsorbed, and the multi-element solid waste is generated in a chemical precipitation impurity removal process in a nickel-cobalt hydrometallurgy process; reducing and smelting the roasted product to obtain molten metal and molten slag; granulating and drying the molten metal to obtain the nickel-iron alloy, and quenching the molten slag to obtain a glassy state byproduct. The invention adopts the waste activated carbon and the multi-element solid waste to carry out the cooperative treatment, realizes the harmlessness, the recycling and the high value of the waste produced by using waste as well as hazardous waste, and can solve the problem of the treatment of the waste activated carbon and the multi-element solid waste in the prior nonferrous metallurgy industry.
Description
Technical Field
The invention belongs to the field of metallurgy and environment, and particularly relates to a method for treating waste activated carbon.
Background
In the process of nickel-cobalt hydrometallurgy, raw ores are subjected to acid leaching to obtain leachate with complex components, the leachate is subjected to a chemical precipitation process to preliminarily separate valuable metals such as nickel and cobalt and impurity metals such as iron and aluminum to respectively obtain multi-component solid wastes and a nickel-cobalt solution, the nickel-cobalt solution is subjected to a solvent extraction deep purification and enrichment process, an organic extractant is inevitably mixed in the obtained pure solution, organic matters in the pure solution are generally removed by using activated carbon in the industry, after the activated carbon is repeatedly used, a pore channel can be blocked and loses adsorption capacity, and the waste activated carbon contains an organic solvent, so the waste activated carbon is listed in a national hazardous waste record (2016 edition), and must be strictly managed according to relevant requirements of hazardous wastes. The existing reports and patents consider how to remove organic matters adsorbed by activated carbon, and the waste activated carbon is regenerated and recycled by a certain treatment method. The waste active carbon regeneration technology mainly comprises a thermal regeneration method, a solvent regeneration method, a biological regeneration method, a wet oxidation regeneration method, a catalytic wet oxidation regeneration method, an electrochemical regeneration method and a microwave ultraviolet radiation regeneration method. However, the above method is expensive, has poor regeneration effect, and the waste activated carbon cannot be regenerated for unlimited times, and finally, a large amount of non-reusable waste activated carbon is generated, and the organic solvent separated from the waste activated carbon is easy to cause secondary pollution.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology, and provide a method for disposing the waste activated carbon, so that the waste activated carbon is harmless and recyclable, and secondary pollution is avoided.
The idea of the inventor is as follows: the method is to realize the harmless treatment of the waste activated carbon to the minimum extent, and then the waste activated carbon is preferably used as a resource to be utilized in other processes, so that the value of the waste activated carbon can be exerted while the waste activated carbon is subjected to the harmless treatment. It was then unexpected that waste residues from a nickel cobalt hydrometallurgical process could be co-processed with spent activated carbon, perhaps to make waste from a spent. In fact, in the process of nickel cobalt hydrometallurgy, a chemical precipitation method is generally adopted to purify a leaching solution, a large amount of multi-element solid waste is generated in each chemical precipitation and impurity removal process, the solid waste inevitably adsorbs valuable metals such as nickel cobalt and the like, and is a very important secondary resource, but the treatment method of the solid waste by the domestic nickel cobalt hydrometallurgy enterprises mainly adopts stockpiling.
Therefore, the inventor tries to carry out repeated experiments, and unexpectedly finds that by adopting the process disclosed by the invention, not only can waste treatment by waste and waste treatment by waste activated carbon and multi-element solid waste be simultaneously treated, but also valuable byproducts can be generated, and the resource recycling of the waste is really realized.
For the purpose, the technical scheme provided by the invention is as follows:
a method of disposing spent activated carbon comprising the steps of:
(1) mixing a mixture comprising waste activated carbon and multi-element solid waste with a flux, roasting and pre-reducing, wherein the waste activated carbon is activated carbon after organic matter is adsorbed, and the multi-element solid waste is generated in a chemical precipitation impurity removal process in a nickel-cobalt hydrometallurgy process and contains Ni, Fe, Co, Mn, Ca, S and C;
(2) reducing and smelting the roasted product to obtain molten metal and molten slag;
(3) granulating and drying the molten metal to obtain the nickel-iron alloy, and quenching the molten slag to obtain a glassy state byproduct.
Furthermore, the waste activated carbon is used for removing organic matters in the solution in the nickel-cobalt hydrometallurgy process and adsorbing the organic matters.
Further, the multi-element solid waste comprises the following main components in percentage by weight: 1.0 to 5.0 wt% of Ni, 5 to 20 wt% of Fe, 0.1 to 1.0 wt% of Co, 1.0 to 5.0 wt% of Mn, 20 to 30 wt% of Ca, 1.0 to 5.0 wt% of S and 5.0 to 10.0 wt% of C.
Further, the mass ratio of the dry mixture to the flux is 10-20: 1, the fusing agent is one or more of limestone, quicklime or hydrated lime.
Further, the roasting and the pre-reduction are carried out in a rotary kiln, the roasting temperature is 700-1000 ℃, and the time is 30-120 min.
Further, the reduction smelting temperature is 1300-1650 ℃, and the time is 30-60 min.
Further, the grades of nickel, iron, cobalt and manganese in the nickel-iron alloy are respectively 10.94-30.67 wt%, 57.33-81.28 wt%, 1.47-5.01 wt% and 2.85-4.70 wt%.
Further, the glassy byproduct comprises the following main components in percentage by weight: 0.06 to 0.16 wt% of Ni, 2.96 to 5.21 wt% of FeO, 0.03 to 0.10 wt% of Co, 0.85 to 1.40 wt% of MnO, and SiO2 38.42～40.38wt％、CaO 35.92～44.36wt％、Al2O38.51 to 12.87 wt%, MgO 1.76 to 4.85 wt%, and S0.19 to 0.33 wt%.
Further, the molten slag is quenched by water to form an amorphous structure with a glass state as a main component, and small-particle slag is formed.
Compared with the prior art, the invention has the advantages that:
(1) the waste activated carbon and the multi-element solid waste are cooperatively treated, so that the waste is prepared by using waste, and the harmless, recycling and high-value treatment of hazardous waste are realized; can solve the problem of disposal of waste activated carbon and multi-element solid waste in the prior nonferrous metallurgy industry, and is beneficial to the green development of the nonferrous metallurgy industry.
(2) The heat value of the waste active carbon is about 3000kcal/kg, the waste active carbon can be used as a substitute fuel and a reducing agent for charging, no fuel and reducing agent are required to be added, the active ingredients in the waste active carbon and the adsorbed waste organic solvent are fully utilized, and secondary pollution is avoided. The nickel and cobalt content in the multi-element solid waste is considerable, the multi-element solid waste can be used as a raw material to be fed into a furnace to produce a nickel-iron alloy with high added value, the gelling property is strong, and the multi-element solid waste can be directly used as a glassy state byproduct for building materials without being crushed. Therefore, the method has lower production cost and high economic value, is an optimal method for the cooperative treatment of solid waste and the utilization of harmless resources, can solve the problem of the treatment of waste activated carbon and multi-component solid waste in the prior nonferrous metallurgy industry, is beneficial to the green development of the nonferrous industry, and is worthy of popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Figure 1 is a process flow diagram for disposing of spent activated carbon in accordance with one embodiment of the present invention.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The process flow of the method for disposing waste activated carbon of one embodiment of the invention is shown in figure 1, and comprises the following steps:
s1: and uniformly mixing the waste activated carbon and the multi-element solid waste to obtain a mixture. The waste activated carbon is dangerous waste activated carbon which can not be used continuously after the organic matter is adsorbed and saturated, can be used for adsorbing an organic solvent after the organic matter in a solution is removed in a nickel-cobalt hydrometallurgy process, and can also be used for adsorbing the organic matter in other process flows. The multi-element solid waste is comprehensive tailings generated in the nickel-cobalt hydrometallurgy process, namely the multi-element solid waste generated in the chemical precipitation impurity removal process, and comprises the following main components: 1.0 to 5.0 wt% of Ni, 5 to 20 wt% of Fe, 0.1 to 1.0 wt% of Co, 1.0 to 5.0 wt% of Mn, 20 to 30 wt% of Ca, 1.0 to 5.0 wt% of S, and 5.0 to 10.0 wt% of C. Preferably, the mass ratio of the waste activated carbon to the multi-element solid waste is 1-10: 1.
s2: and putting the mixture into a steam dryer for steam drying to obtain dry materials and dry waste gas. The heat source used in the steam drying process is low-pressure steam, and the water content of the obtained dry material is 20-30 wt% of the total weight.
S3: and (3) after the dry materials and the flux are mixed, conveying the mixture to a rotary kiln for roasting, removing free water and crystal water in the dry materials, and performing pre-reduction to obtain a kiln product and kiln discharge smoke. Preferably, the mass ratio of the dry materials to the fusing agents is 10-20: 1, the fusing agent can be one or more of limestone, quick lime and hydrated lime, the roasting temperature is preferably 700-1000 ℃, and the roasting time is preferably 30-120 min.
S4: and washing and condensing the dry waste gas, and discharging the dry waste gas after reaching the standard.
S5: and conveying the kiln products into an electric furnace through a hot material conveying system, and producing molten metal, molten slag and electric furnace flue gas after reduction smelting. The reduction smelting temperature is 1300-1650 ℃, and the reduction smelting treatment time is 30-60 min.
S6: and heating the flue gas discharged from the kiln by a secondary combustion chamber, conveying the flue gas into a waste heat boiler to recover waste heat and reduce the temperature, conveying the flue gas into a dust collecting system after quenching and adsorption, and finally discharging the flue gas after desulfurization and reaching the standard. The heating temperature of the secondary combustion chamber is 600-plus-900 ℃, the temperature is reduced to 300-plus-600 ℃, and the dust collecting system is a cloth bag for collecting dust.
S7: and conveying the molten metal into a granulating system for granulation and drying to obtain the nickel-iron alloy. The grain size of the obtained nickel-iron alloy is generally 5-20mm, and the grades of nickel, iron, cobalt and manganese are respectively 10.94-30.67 wt%, 57.33-81.28 wt%, 1.47-5.01 wt% and 2.85-4.70 wt%.
S8: and water quenching the slag to produce glassy byproducts which are sold as building auxiliary materials. The glassy state byproduct comprises 0.06-0.16 wt% of Ni, 2.96-5.21 wt% of FeO, 0.03-0.10 wt% of Co, 0.85-1.40 wt% of MnO and SiO2(38.42～40.38wt％)、CaO(35.92～44.36wt％)、Al2O3(8.51～12.87wt％)、MgO(1.76～4.85wt％)、S(0.19～0.33wt％)。
S9: and directly conveying the electric furnace flue gas into the rotary kiln for waste heat recovery and reutilization.
Wherein, the drying adopts a steam drier to mainly remove part of free water in the raw materials. The roasting-prereduction adopts a rotary kiln to mainly remove residual free water and crystal water in raw materials, preheat the raw materials, and selectively reduce partial nickel and iron, namely partial ferronickel oxide can be reduced into metallic ferronickel. The electric furnace smelting is to reduce nickel oxide into metallic nickel and partial iron oxide into metallic iron, and separate slag and ferronickel to produce crude ferronickel and glassy by-products. After water quenching is carried out on molten slag for smelting ferronickel in an electric furnace, because the melt cannot be crystallized in the process of rapid cooling, an amorphous structure mainly in a glass state is formed, and the higher the cooling speed of the melt is, the lower the crystal content in the slag is, and the higher the glass content is; and because of rapid cooling, the small granular slag is formed and can be directly used as the auxiliary material of the building material without being crushed. The glassy state by-product has the characteristics of high gelling property, porosity, light and crisp texture and easy breakage, and is mainly applied to cement admixtures, concrete admixtures, slag wool and microcrystalline glass. The ferronickel alloy is the main raw material for producing stainless steel.
Example 1:
the method for disposing waste activated carbon of the embodiment has a process flow as shown in fig. 1, and utilizes the RKEF process to cooperatively dispose the waste activated carbon and multi-element solid waste, and comprises the following steps:
s1: taking multielement solid waste containing Ni (2.84 wt%), Fe (10.91 wt%), Co (0.38 wt%), Mn (1.75 wt%), Ca (24.92 wt%), S (2.46 wt%) and C (8.73 wt%) and waste activated carbon which is saturated by adsorbed organic matters according to the mass ratio of 5: 1, uniformly mixing to obtain a mixture;
s2: putting the mixture into a steam dryer for steam drying to obtain dry materials with the water content of 22% and dry waste gas;
s3: mixing dry materials and limestone according to a mass ratio of 15: 1, uniformly mixing the ingredients, and conveying the mixture to a rotary kiln for roasting at 800 ℃ for 60min to obtain a kiln product and kiln discharge smoke;
s4: washing and condensing the dry waste gas, and then discharging the dry waste gas after reaching the standard;
s5: conveying the kiln product into an electric furnace for reduction smelting through a hot material conveying system, wherein the smelting temperature is 1600 ℃, and the time is 45min, so as to obtain molten metal, molten slag and electric furnace flue gas;
s6: heating the flue gas discharged from the kiln to 850 ℃ through a secondary combustion chamber, sending the flue gas to a waste heat boiler for recovering waste heat, cooling to 500 ℃, carrying out shock cooling and activated carbon adsorption, then sending the flue gas into a cloth bag dust collector for dust collection, and finally carrying out desulfurization and standard emission;
s7: conveying the molten metal into a granulating system for granulation and drying to obtain a nickel-iron alloy with the particle size of 5-20mm, wherein the grades of nickel, iron, cobalt and manganese are respectively 21.14 wt%, 68.77 wt%, 2.54 wt% and 4.05 wt%, the impurity element content is Si (0.39 wt%), S (0.6 wt%) and C (2.5 wt%);
s8: water quenching the slag in a water quenching slag pool to obtain glassy state side products, wherein the glassy state side products comprise Ni (0.11 wt%), FeO (3.04 wt%), Co (0.05 wt%), MnO (1.21 wt%), and SiO2(40.03wt％)、CaO(39.78wt％)、Al2O3(9.46 wt%), MgO (1.76 wt%), S (0.2 wt%), can be sold as building material auxiliary materials;
s9: the flue gas of the electric furnace is directly conveyed into the rotary kiln for waste heat recovery and reutilization.
Example 2:
the method for disposing waste activated carbon of the embodiment has a process flow as shown in fig. 1, utilizes an RKEF process to cooperatively dispose waste activated carbon and multi-element solid waste, and has a process flow as shown in fig. 1, and comprises the following steps:
s1: taking multielement solid waste containing Ni (3.95 wt%), Fe (15.76 wt%), Co (0.68 wt%), Mn (2.03 wt%), Ca (20.45 wt%), S (3.22 wt%) and C (6.01 wt%) and waste activated carbon which is saturated by adsorbed organic matters according to the mass ratio of 1: 1, uniformly mixing to obtain a mixture;
s2: putting the mixture into a steam dryer for steam drying to obtain dry materials with the water content of 27% and dry waste gas;
s3: mixing dry materials and hydrated lime according to a mass ratio of 20: 1, uniformly mixing the ingredients, and conveying the mixture to a rotary kiln for roasting at 900 ℃ for 90min to obtain a kiln product and kiln discharge smoke;
s4: washing and condensing the dry waste gas, and then discharging the dry waste gas after reaching the standard;
s5: conveying the kiln product into an electric furnace for reduction smelting through a hot material conveying system, wherein the smelting temperature is 1550 ℃, and the time is 60min, so as to obtain molten metal, molten slag and electric furnace flue gas;
s6: heating the flue gas discharged from the kiln to 900 ℃ by a secondary combustion chamber, sending the flue gas to a waste heat boiler for recovering waste heat, cooling to 600 ℃, carrying out shock cooling and activated carbon adsorption, then sending the flue gas into a cloth bag dust collector for dust collection, and finally carrying out desulfurization and standard emission;
s7: conveying the molten metal into a granulating system for granulation and drying to obtain a nickel-iron alloy with the particle size of 5-20mm, wherein the grades of nickel, iron, cobalt and manganese are respectively 29.40 wt%, 59.35 wt%, 3.55 wt% and 4.70 wt%, the impurity element content is Si (0.46 wt%), S (0.79 wt%) and C (1.72 wt%);
s8: water quenching the slag in a water quenching slag pool to obtain glassy state byproducts with the component contents of Ni (0.15 wt%), FeO (4.39 wt%), Co (0.09 wt%), MnO (1.40 wt%), and SiO2(38.42wt％)、CaO(35.92wt％)、Al2O3(10.41wt％)、MgO(4.85wt％) S (0.26 wt%) can be sold as a building material auxiliary material;
s9: the flue gas of the electric furnace is directly conveyed into the rotary kiln for waste heat recovery and reutilization.
Example 3:
the method for disposing waste activated carbon of the embodiment has a process flow as shown in fig. 1, utilizes an RKEF process to cooperatively dispose waste activated carbon and multi-element solid waste, and has a process flow as shown in fig. 1, and comprises the following steps:
s1: taking multielement solid waste containing Ni (1.47 wt%), Fe (18.68 wt%), Co (0.22 wt%), Mn (1.28 wt%), Ca (26.54 wt%), S (1.59 wt%) and C (5.17 wt%) and waste activated carbon which is saturated by adsorbed organic matters according to the mass ratio of 10: 1, uniformly mixing to obtain a mixture;
s2: putting the mixture into a steam dryer for steam drying to obtain a dry material with the water content of 25% and dry waste gas;
s3: mixing dry materials and raw limestone according to a mass ratio of 19: 1, uniformly mixing the ingredients, conveying the mixture to a rotary kiln for roasting at 750 ℃ for 120min to obtain a kiln product and kiln discharge smoke;
s4: washing and condensing the dry waste gas, and then discharging the dry waste gas after reaching the standard;
s5: conveying the kiln product into an electric furnace for reduction smelting through a hot material conveying system, wherein the smelting temperature is 1650 ℃, and the time is 30min, so as to obtain molten metal, molten slag and electric furnace flue gas;
s6: heating the flue gas discharged from the kiln to 850 ℃ through a secondary combustion chamber, sending the flue gas to a waste heat boiler for recovering waste heat, cooling to 500 ℃, carrying out shock cooling and activated carbon adsorption, then sending the flue gas into a cloth bag dust collector for dust collection, and finally carrying out desulfurization and standard emission;
s7: conveying the molten metal into a granulating system for granulation and drying to obtain a nickel-iron alloy with the particle size of 5-20mm, wherein the grades of nickel, iron, cobalt and manganese are respectively 10.94 wt%, 81.28 wt%, 1.47 wt% and 2.96 wt%, the impurity element content is Si (0.71 wt%), S (0.39 wt%) and C (1.48 wt%);
s8: water quenching the slag in a water quenching slag pool to obtain glassy state side product with Ni (0.06 wt%), FeO (5.21 wt%), Co (0.03 wt%) and MnO (0.89 wt%)wt％)、SiO2(40.38wt％)、CaO(35.99wt％)、Al2O3(12.87 wt%), MgO (2.21 wt%), S (0.33 wt%), can be sold as building material auxiliary materials;
s9: the flue gas of the electric furnace is directly conveyed into the rotary kiln for waste heat recovery and reutilization.
Example 4:
the method for disposing waste activated carbon of the embodiment has a process flow as shown in fig. 1, utilizes an RKEF process to cooperatively dispose waste activated carbon and multi-element solid waste, and has a process flow as shown in fig. 1, and comprises the following steps:
s1: taking multielement solid waste containing Ni (4.12 wt%), Fe (10.63 wt%), Co (0.75 wt%), Mn (1.23 wt%), Ca (21.08 wt%), S (3.85 wt%) and C (9.72 wt%) and waste activated carbon which is saturated by adsorbed organic matters according to the mass ratio of 3: 1, uniformly mixing to obtain a mixture;
s2: putting the mixture into a steam dryer for steam drying to obtain a dry material with the water content of 20% and dry waste gas;
s3: mixing dry materials and limestone according to a mass ratio of 13: 1, uniformly mixing the ingredients, conveying the mixture to a rotary kiln for roasting, wherein the roasting temperature is 950 ℃, and the roasting time is 45min, so as to obtain a kiln product and kiln discharge smoke;
s4: washing and condensing the dry waste gas, and then discharging the dry waste gas after reaching the standard;
s5: conveying the kiln product into an electric furnace for reduction smelting through a hot material conveying system, wherein the smelting temperature is 1550 ℃, and the time is 60min, so as to obtain molten metal, molten slag and electric furnace flue gas;
s6: heating the flue gas discharged from the kiln to 900 ℃ by a secondary combustion chamber, sending the flue gas to a waste heat boiler for recovering waste heat, cooling to 550 ℃, carrying out shock cooling and activated carbon adsorption, then sending the flue gas into a cloth bag dust collector for dust collection, and finally carrying out desulfurization and standard emission;
s7: conveying the molten metal into a granulating system for granulation and drying to obtain a nickel-iron alloy with the particle size of 5-20mm, wherein the grades of nickel, iron, cobalt and manganese are respectively 30.67 wt%, 57.33 wt%, 5.01 wt% and 2.85 wt%, the impurity element content is Si (0.39 wt%), S (0.94 wt%) and C (2.78 wt%);
s8: water of molten slag passing through water quenching slag poolObtaining glassy state byproducts after quenching, wherein the components of the glassy state byproducts comprise Ni (0.16 wt%), FeO (2.96 wt%), Co (0.10 wt%), MnO (0.85 wt%), SiO2(38.69wt％)、CaO(44.36wt％)、Al2O3(8.51 wt%), MgO (2.18 wt%), S (0.19 wt%), can be sold as building material auxiliary materials;
s9: the flue gas of the electric furnace is directly conveyed into the rotary kiln for waste heat recovery and reutilization.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (9)
1. A method of disposing spent activated carbon comprising the steps of:
(1) mixing a mixture comprising waste activated carbon and multi-element solid waste with a flux, roasting and pre-reducing, wherein the waste activated carbon is activated carbon after organic matter is adsorbed, and the multi-element solid waste is generated in a chemical precipitation impurity removal process in a nickel-cobalt hydrometallurgy process and contains Ni, Fe, Co, Mn, Ca, S and C;
(2) reducing and smelting the roasted product to obtain molten metal and molten slag;
(3) granulating and drying the molten metal to obtain the nickel-iron alloy, and quenching the molten slag to obtain a glassy state byproduct.
2. A method of disposing waste activated carbon as claimed in claim 1, wherein the waste activated carbon is waste activated carbon adsorbing organic substances after removing organic substances from a solution in a nickel cobalt hydrometallurgy process.
3. A method of disposing spent activated carbon as claimed in claim 1 or claim 2 wherein the multi-component solid waste has a major component content of: 1.0 to 5.0 wt% of Ni, 5 to 20 wt% of Fe, 0.1 to 1.0 wt% of Co, 1.0 to 5.0 wt% of Mn, 20 to 30 wt% of Ca, 1.0 to 5.0 wt% of S and 5.0 to 10.0 wt% of C.
4. A method for disposing spent activated carbon as claimed in claim 3 wherein the mass ratio of said mixed material dry material to flux is 10-20: 1, the fusing agent is one or more of limestone, quicklime or hydrated lime.
5. A method for the disposal of spent activated carbon as defined in claim 3 wherein the calcination and pre-reduction is carried out in a rotary kiln at a calcination temperature of 700-.
6. A method for disposing spent activated carbon as defined in claim 3 wherein said reduction smelting temperature is 1300-1650 ℃ for 30-60 min.
7. A method of disposing spent activated carbon as claimed in claim 3, wherein the grades of nickel, iron, cobalt and manganese in the ferronickel alloy are 10.94-30.67 wt%, 57.33-81.28 wt%, 1.47-5.01 wt% and 2.85-4.70 wt%, respectively.
8. A method of disposing spent activated carbon as claimed in claim 3 wherein said glassy byproduct has a major component content of: 0.06 to 0.16 wt% of Ni, 2.96 to 5.21 wt% of FeO, 0.03 to 0.10 wt% of Co, 0.85 to 1.40 wt% of MnO, and SiO238.42～40.38wt％、CaO 35.92～44.36wt％、Al2O38.51 to 12.87 wt%, MgO 1.76 to 4.85 wt%, and S0.19 to 0.33 wt%.
9. A method of disposing spent activated carbon as claimed in claim 8 wherein the slag is water quenched to form an amorphous structure dominated by a glassy state and to form a small particle slag.
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| CN115959829A (en) * | 2022-12-27 | 2023-04-14 | 重庆科技学院 | Method for recovering pig iron-aluminum slag and waste carbon slag produced in recovery process of retired lithium battery |
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