CN115591911B - Full-recycling treatment method for waste tires - Google Patents
Full-recycling treatment method for waste tires Download PDFInfo
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- CN115591911B CN115591911B CN202211247930.8A CN202211247930A CN115591911B CN 115591911 B CN115591911 B CN 115591911B CN 202211247930 A CN202211247930 A CN 202211247930A CN 115591911 B CN115591911 B CN 115591911B
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- Prior art keywords
- synthesis gas
- leaching
- gasification
- gas
- condensable
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- 239000010920 waste tyre Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 118
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 118
- 238000002309 gasification Methods 0.000 claims abstract description 92
- 238000002386 leaching Methods 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 239000002893 slag Substances 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000009833 condensation Methods 0.000 claims abstract description 19
- 230000005494 condensation Effects 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 153
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002737 fuel gas Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 33
- 229910021529 ammonia Inorganic materials 0.000 abstract description 16
- 229910052725 zinc Inorganic materials 0.000 abstract description 14
- 238000002791 soaking Methods 0.000 abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000010949 copper Substances 0.000 description 26
- 238000007885 magnetic separation Methods 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 229910000831 Steel Inorganic materials 0.000 description 22
- 239000010959 steel Substances 0.000 description 22
- 238000001914 filtration Methods 0.000 description 21
- 239000003345 natural gas Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 239000002918 waste heat Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 230000000536 complexating effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- -1 steel wires Chemical class 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 9
- 238000009423 ventilation Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000004227 thermal cracking Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
-
- 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
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28B—STEAM OR VAPOUR CONDENSERS
- F28B1/00—Condensers in which the steam or vapour is separate from the cooling medium by walls, e.g. surface condenser
- F28B1/02—Condensers in which the steam or vapour is separate from the cooling medium by walls, e.g. surface condenser using water or other liquid as the cooling medium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/80—Rubber waste, e.g. scrap tyres
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of harmless and recycling of solid waste, and particularly relates to a full-amount recycling treatment method of waste tires. The processing method provided by the invention comprises the following steps: gasifying the waste tires by adopting a gasifying agent to obtain synthesis gas and gasified slag; the gasification temperature is more than or equal to 1100 ℃; condensing the synthesis gas to obtain liquid Zn and non-condensed synthesis gas, wherein the non-condensed synthesis gas comprises H 2 and CO; soaking gasification slag in ammonia water for leaching to obtain leaching liquid; and sequentially carrying out gas stripping and solid-liquid separation on the leaching solution to obtain mixed metal ore, wherein the mixed metal ore comprises Ni (OH) 2 and Cu (OH) 2. The invention adopts the mixed chemical treatment method of combining condensation, ammonia leaching metal and gas after high-temperature gasification, not only can effectively gasify the waste tires, but also can efficiently recycle valuable heavy metals such as Zn, ni, cu and the like, and can effectively recycle the non-condensable synthesis gas generated after gasification, thereby realizing the full-scale recycling treatment of the waste tires.
Description
Technical Field
The invention belongs to the technical field of harmless and recycling of solid waste, and particularly relates to a full-amount recycling treatment method of waste tires.
Background
Tires have a variety of good properties, wear resistance, corrosion resistance, resistance to organisms, mechanical resistance, etc., but these advantages also become a disadvantage when the service life of the tire is exhausted. After the scrap tire is produced, the landfill method is not suitable for disposing the scrap tire because the scrap tire also has the above characteristics. The burning of tires in the open air produces a great deal of waste gas which causes environmental pollution, and some heavy metals such as nickel and zinc can enter the ecological system during the burning process.
Since the heat value of the waste tires is about 25-30 MJ/kg, and the waste tires can be used as high-energy fuel, thermal cracking of the waste tires is considered as one of the most effective means for thoroughly eliminating the pollution thereof at present, and main products of thermal cracking process of the waste tires include cracked carbon black, cracked oil and cracked gas. However, the cracked carbon black obtained by thermal cracking of waste tires contains about 10% of ash (about 5% of zinc oxide, about 5% of white carbon black, etc.), and is only used as a reinforcing filler for lower rubber products or as a pigment for ink, and has low product value, and also the atmospheric pollution generated during thermal cracking of waste tires cannot be ignored.
Tire gasification is another recycling scheme for discarded tires. Gasification is a heat treatment technique that involves the passage of controlled amounts of gasifying agents (steam, air, etc.). Under gasification conditions, the raw materials are decomposed into three-phase products of gas (non-condensable synthetic gas), liquid (oil) and solid (carbon), generally speaking, the non-condensable synthetic gas is a main product of the gasification process, and meanwhile, oil phase and solid phase products can be co-produced by adjusting the gasification conditions. However, the hydrogen content of the non-condensable synthesis gas obtained by the gasification treatment is low at present, the standard of chemical utilization cannot be met, and the gasified residual gasified slag cannot be effectively utilized.
Therefore, no matter the cracking or gasification process of the tires, the bottleneck of incomplete resource utilization exists at present, and development of an effective disposal process for co-producing the waste tires with high added value products is an urgent need.
Disclosure of Invention
The invention aims to provide a method for processing the full amount of waste tires into resources, which can effectively gasify the waste tires, efficiently recycle valuable heavy metals such as Zn, ni, cu and the like, effectively recycle non-condensable synthesis gas generated after gasification, realize the full amount of recycling processing of the waste tires and has high economic value.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a full-quantity recycling treatment method for waste tires, which comprises the following steps:
gasifying the waste tires by adopting a gasifying agent to obtain synthesis gas and gasified slag; the gasification temperature is more than or equal to 1100 ℃;
Condensing the synthesis gas to obtain liquid Zn and non-condensed synthesis gas, wherein the non-condensed synthesis gas comprises H 2 and CO;
Immersing the gasified slag in ammonia water for leaching to obtain leaching liquid;
And sequentially carrying out gas stripping and solid-liquid separation on the leaching solution to obtain mixed metal ore, wherein the mixed metal ore comprises Ni (OH) 2 and Cu (OH) 2.
Preferably, the gasification temperature is 1100-1400 ℃.
Preferably, the gasifying agent is steam, and the mass ratio of the gasifying agent to the scrap tire is (1-1.2): 1.
Preferably, the temperature of the non-condensable synthesis gas is 450-500 ℃.
Preferably, the temperature of the leaching solution is 60-85 ℃.
Preferably, the gas used for stripping is N 2, and the temperature of stripping is 60-80 ℃.
Preferably, the leaching also yields a leaching residue, which after obtaining the leaching residue further comprises mixing the leaching residue with nitric acid to obtain a solution of SiO 2 and Ca (NO 3)2).
Preferably, the condensation is to exchange heat between the synthesis gas and water to obtain liquid Zn, non-condensable synthesis gas and water vapor, and the water vapor is used as the gasifying agent.
Preferably, the method further comprises: and taking the non-condensable synthesis gas as the gasified fuel gas.
The invention provides a full-quantity recycling treatment method for waste tires, which comprises the following steps: gasifying the waste tires by adopting a gasifying agent to obtain synthesis gas and gasified slag; the gasification temperature is more than or equal to 1100 ℃; condensing the synthesis gas to obtain liquid Zn and non-condensed synthesis gas, wherein the non-condensed synthesis gas comprises H 2 and CO; immersing the gasified slag in ammonia water for leaching to obtain leaching liquid; and sequentially carrying out gas stripping and solid-liquid separation on the leaching solution to obtain mixed metal ore, wherein the mixed metal ore comprises Ni (OH) 2 and Cu (OH) 2. The method for treating the full recycling of the waste tires gasifies the waste tires at the temperature of more than or equal to 1100 ℃ to obtain two products of synthesis gas and gasification slag; according to the invention, the synthetic gas is condensed to obtain liquid Zn so as to efficiently recycle Zn metal in the waste tires, and the condensed non-condensable synthetic gas contains H 2 and CO, so that the synthetic gas can be directly used as fuel gas and can be used for synthesizing products such as methane, synthetic ammonia, natural gas and the like; according to the invention, the gasified slag is leached by ammonia water, and the obtained leaching solution is sequentially subjected to gas stripping and solid-liquid separation to obtain the mixed metal ore containing Ni (OH) 2 and Cu (OH) 2, so that Cu metal and Ni metal in the waste tire are efficiently recovered. The treatment method provided by the invention adopts a mixed physical and chemical treatment method combining condensation, ammonia leaching, gas stripping and solid-liquid separation after high-temperature gasification, so that the waste tires can be effectively gasified, valuable heavy metals such as Zn, ni, cu and the like can be efficiently recovered, the non-condensable synthesis gas generated after gasification can be effectively recycled, the full-quantity recycling treatment of the waste tires is realized, and the economic value is high. According to the embodiment calculation, about 19kg of Zn and about 8kg of nickel-copper mixed metal ore can be recovered by treating 1t of waste tires, 2500-3000 Nm 3 of non-condensable synthesis gas is generated, and the generated non-condensable synthesis gas H 2 and CO can be recycled or used for synthesizing methane, synthetic ammonia, natural gas and other purposes; the treatment method provided by the invention utilizes the waste tires to extract products with high economic value, effectively improves the environmental pollution problem caused by accumulation and incineration of the waste tires, and has good application prospect and value.
The invention adopts the mixed chemical treatment method combining condensation, ammonia water metal and gas after gasification to realize the full recycling treatment method of the waste tires, has simple process flow, no pollution and no waste, and has great application value.
Further, the leaching also provides leaching residues, and the leaching residues are mixed with nitric acid to obtain SiO 2 and Ca (NO 3)2 solution, the treatment method provided by the invention further can recover SiO 2 and Ca (NO 3)2, and by calculation of the embodiment, the treatment method provided by the invention can treat about 15kg of SiO 2 and about 2kg of Ca (NO 3)2 crystal) of 1t waste tires.
Drawings
Fig. 1 is a schematic process flow diagram of a full-scale recycling method for waste tires according to an embodiment of the present invention.
Detailed Description
The invention provides a full-quantity recycling treatment method for waste tires, which comprises the following steps:
gasifying the waste tires by adopting a gasifying agent to obtain synthesis gas and gasified slag; the gasification temperature is more than or equal to 1100 ℃;
Condensing the synthesis gas to obtain liquid Zn and non-condensed synthesis gas, wherein the non-condensed synthesis gas comprises H 2 and CO;
Immersing the gasified slag in ammonia water for leaching to obtain leaching liquid;
And sequentially carrying out gas stripping and solid-liquid separation on the leaching solution to obtain mixed metal ore, wherein the mixed metal ore comprises Ni (OH) 2 and Cu (OH) 2.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention adopts gasifying agent to gasify waste tyre to obtain synthetic gas and gasified slag; the gasification temperature is more than or equal to 1100 ℃.
The present invention has no special requirement for the source of the scrap tire.
In the present invention, the particle size of the scrap tire is preferably 2 to 3cm.
The present invention preferably pretreats the scrap tires prior to the gasification. In the present invention, the pretreatment preferably includes: sequentially performing water washing, screening, crushing and magnetic separation. The invention has no special requirements on the specific implementation process of the water washing. The invention preferably removes large steel wires from scrap tires by screening. The invention has no special requirements for the specific implementation process of the crushing.
In the present invention, the particle size of the crushed scrap tire is preferably 2 to 3cm.
In the present invention, the magnetic separation is preferably performed in a magnetic separator, and the magnetic field strength of the magnetic separator is preferably 1 to 2T and the total exciting power of the magnetic separator is preferably 624W. The present invention preferably recovers metals having strong magnetism such as steel wires and iron wires which are not removed during screening by the magnetic separation.
In the present invention, the gasifying agent is particularly preferably water vapor.
In the present invention, the mass ratio of the gasifying agent to the scrap tire is preferably (1 to 1.2): 1, more preferably (1 to 1.1): 1.
In the present invention, the temperature of the gasification is preferably 1100 to 1400 ℃, more preferably 1100 to 1300 ℃, particularly preferably 1100 ℃, 1150 ℃, 1200 ℃ or 1250 ℃.
After synthesis gas is obtained, the synthesis gas is condensed to obtain liquid Zn and non-condensable synthesis gas, wherein the non-condensable synthesis gas comprises H 2 and CO.
In the present invention, the condensation is preferably heat exchanging the synthesis gas and water to obtain liquid Zn, non-condensable synthesis gas and water vapor, the water vapor being used as the gasifying agent.
In the present invention, the temperature of the non-condensable synthesis gas after condensation is preferably 450 to 500 ℃, preferably 455 to 485 ℃.
In the invention, the non-condensable synthesis gas comprises H 2 and CO, and the volume percentage of H 2 in the non-condensable synthesis gas is preferably 10-30 vol%; the volume percentage of CO is preferably 15-40 vol%.
In the present invention, the present invention preferably further comprises: the non-condensable synthesis gas is preferably used as the gasified fuel gas.
In the present invention, the remaining non-condensable synthesis gas is preferably used for preparing methanol, synthesis ammonia and natural gas.
In the present invention, the condensation is particularly preferably: the non-condensable synthesis gas flows into a heat exchange chamber, the non-condensable synthesis gas is cooled by installing a tubular heat exchanger in the heat exchange chamber, water is used as a heat exchange medium, steam is generated as the gasifying agent for gasification, and the rest steam is preferably used for hot water supply. Waste heat utilization is realized.
In the invention, the liquid Zn obtained by condensation is accumulated and then the liquid Zn product is collected.
After gasified slag is obtained, the gasified slag is soaked in ammonia water for leaching, so that leaching liquid is obtained.
In the present invention, the mass concentration of the aqueous ammonia is preferably 35wt%.
After the leaching solution is obtained, the leaching solution is sequentially subjected to gas stripping and solid-liquid separation to obtain the mixed metal ore, wherein the mixed metal ore comprises Ni (OH) 2 and Cu (OH) 2.
In the present invention, the gas used for the stripping is preferably N 2.
In the present invention, the solid-liquid separation is preferably performed by filtration, and the present invention is not particularly limited to the specific implementation of the process.
In the present invention, the leaching preferably also gives a leaching residue, and the present invention preferably further comprises mixing the leaching residue with nitric acid to give a solution of SiO 2 and Ca (NO 3)2).
In the present invention, the molar concentration of nitric acid is preferably 1mol/L.
In the present invention, the leaching residue and nitric acid are mixed to obtain a mixed feed liquid, and the mixed feed liquid is preferably subjected to solid-liquid separation to obtain the SiO 2 and Ca (NO 3)2 solution.
In the present invention, after the Ca (NO 3)2 solution is obtained, the present invention preferably evaporates and crystallizes the Ca (NO 3)2 solution to obtain Ca (NO 3)2 crystals).
Compared with the prior art, the invention has the following advantages and effects:
The full-recycling treatment method for the waste tires provided by the invention has simple process flow.
The product obtained by the full recycling treatment method of the waste tires has great application value.
The method for processing the full-quantity recycling of the waste tires provided by the invention recycles the full-quantity waste tires, and has no pollution and no waste.
The method for treating the full amount of the waste tires for recycling carries out high-temperature gasification treatment on the waste tires to obtain products with higher utilization value, has high recycling utilization rate, can recycle about 19kg of ZnO, about 8kg of nickel-copper alloy ore, about 15kg of SiO 2 and about 2kg of Ca (NO 3)2 crystal) to generate 2500-3000 Nm 3 of non-condensable synthetic gas, can recycle the generated non-condensable synthetic gas H 2, CO and heat or be used for other purposes such as synthetic methane, synthetic ammonia, natural gas and the like, extracts materials with high economic value by using cheap and easily available raw materials, effectively improves the environmental pollution problem caused by accumulation and incineration of the waste tires, and has good application prospect and value.
The technical solutions provided by the present invention are described in detail below with reference to the drawings and examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Firstly, 1000kg of waste tires are pretreated, and the pretreatment comprises the steps of washing, removing large steel wires and crushing, wherein the crushing granularity is below 3 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. The waste tyre after magnetic separation is sent into a gasification chamber, the gasification temperature is 1100 ℃, and the ventilation quantity of the gasification agent steam is 1000kg. The gasified synthesis gas containing Zn, H 2 and CO flows into a heat exchange chamber, waste heat utilization and condensation are carried out on the synthesis gas through the heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 450 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol%, and CO is 15-40 vol%) is led out of the heat exchange chamber, 2860Nm 3 non-condensable synthesis gas is produced, part of the non-condensable synthesis gas can be reused in the gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 19kg of liquid Zn is obtained in the heat exchange chamber, and high-grade Zn can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 80 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, 10kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2 is obtained after the leaching solution is subjected to gas stripping and filtering at 65 ℃, 1mol/L nitric acid solution is added into leaching slag obtained by leaching for soaking, then the filtering is carried out to obtain 15kg of SiO 2, and 2kg of Ca (NO 3)2 crystal is obtained after the residual solution is subjected to evaporation crystallization.
Example 2
Firstly, 1000kg of waste tires are pretreated, and the pretreatment comprises the steps of washing, removing large steel wires and crushing, wherein the crushing granularity is below 2.5 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. The waste tyre after magnetic separation is sent into a gasification chamber, the gasification temperature is 1150 ℃, and the inlet amount of gasifying agent steam is 1050kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 455 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol%, and CO is 15-40 vol) is led out of the heat exchange chamber, 2913Nm 3 non-condensable synthesis gas is generated altogether, part of the non-condensable synthesis gas can be recycled to the gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 19.2kg of liquid Zn is obtained in the heat exchange chamber, and high-grade Zn can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 70 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, 10.5kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2 is obtained after the leaching solution is subjected to gas stripping and filtering at 60 ℃, 1mol/L nitric acid solution is added into leaching slag obtained by leaching for soaking, then the filtering is carried out to obtain 14.5kgSiO 2, and 2.1kg of Ca (NO 3)2 crystals) are obtained after the residual solution is subjected to evaporation and crystallization.
Example 3
Firstly, 1100kg of waste tires are pretreated, and the pretreatment comprises the steps of washing, removing large steel wires and crushing, wherein the crushing granularity is below 3 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. The waste tyre after magnetic separation is sent into a gasification chamber, the gasification temperature is 1150 ℃, and the ventilation quantity of the gasification agent steam is 1150kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 460 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol% and CO is 15-40 vol%) is led out of the heat exchange chamber, 3170Nm 3 non-condensable synthesis gas is produced altogether, part of the non-condensable synthesis gas can be reused in the gasification chamber in the step (3), and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 21.95kg of liquid Zn is obtained in the heat exchange chamber, and high-grade Zn can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 75 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, the leaching solution is subjected to gas stripping and filtration at 65 ℃ to obtain 11kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2, 1mol/L nitric acid solution is added into the leaching slag obtained by leaching for soaking, then the filtration is carried out to obtain 16kg of SiO 2, and the rest solution is subjected to evaporation crystallization to obtain 2.21kg of Ca (NO 3)2 crystals.
Example 4
Firstly, 1100kg of waste tires are pretreated, and the pretreatment comprises the steps of washing, removing large steel wires and crushing, wherein the crushing granularity is below 2.5 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. The waste tyre after magnetic separation is sent into a gasification chamber, the gasification temperature is 1200 ℃, and the ventilation quantity of gasification agent steam is 1100kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 460 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol% and CO is 15-40 vol%) is led out of the heat exchange chamber, so as to generate 3230Nm 3 non-condensable synthesis gas, wherein part of the non-condensable synthesis gas can be reused in the gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 22.2kg of liquid Zn is obtained in the heat exchange chamber, and high-grade Zn can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 70 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, 13.5kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2 is obtained after the leaching solution is subjected to gas stripping and filtering at 60 ℃, 1mol/L nitric acid solution is added into leaching slag obtained by leaching for soaking, then 16.5kg of SiO 2 is obtained by filtering, and 2.33kg of Ca (NO 3)2 crystals are obtained after the residual solution is subjected to evaporation and crystallization.
Example 5
Firstly, 1300kg of waste tires are pretreated, and the steps of washing, removing large steel wires and crushing are sequentially carried out, wherein the crushing granularity is below 3 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. And (3) delivering the waste tires subjected to magnetic separation into a gasification chamber, wherein the gasification temperature is 1200 ℃, and the ventilation quantity of the gasifying agent steam is 1350kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 470 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol% and CO is 15-40 vol%) is led out of the heat exchange chamber, so as to generate 3575Nm 3 non-condensable synthesis gas altogether, part of the non-condensable synthesis gas can be reused for gasification in the step gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 26kg of liquid Zn is obtained in the heat exchange chamber, and high-grade Zn can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 85 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching liquid, the leaching liquid is subjected to N 2 gas stripping and filtration at 75 ℃ to obtain 12.5kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2, 1mol/L nitric acid solution is added into leaching slag obtained by leaching for soaking, then filtration is carried out to obtain 19.5kgSiO 2, and the residual solution is subjected to evaporation crystallization to obtain 2.63kgCa (NO 3)2 crystals).
Example 6
Firstly, 1300kg of waste tires are pretreated, and the steps of washing, removing large steel wires and crushing are sequentially carried out, wherein the crushing granularity is below 2.5 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. The waste tyre after magnetic separation is sent into a gasification chamber, the gasification temperature is 1250 ℃, and the ventilation quantity of gasification agent steam is 1400kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 475 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-15 vol%, and CO is 15-40 vol) is led out of the heat exchange chamber, 3900Nm 3 non-condensable synthesis gas is produced altogether, part of the non-condensable synthesis gas can be recycled to the gasification chamber in the step (3), and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 26.2kg of liquid Zn is obtained in the heat exchange chamber, and high-grade Zn can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 65 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, 13kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2 is obtained after the leaching solution is subjected to gas stripping and filtering at 60 ℃, 1mol/L nitric acid solution is added into the leaching slag obtained by leaching for soaking, then the filtering is carried out to obtain 19.5kg of SiO 2, and 2.66kg of Ca (NO 3)2 crystals) are obtained after the residual solution is subjected to evaporation crystallization.
Example 7
Firstly, 1400kg of waste tires are pretreated, and the steps of washing, removing large steel wires and crushing are sequentially carried out, wherein the crushing granularity is below 3 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. And (3) delivering the waste tires subjected to magnetic separation into a gasification chamber, wherein the gasification temperature is 1200 ℃, and the introducing amount of gasification agent steam is 1500kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 480 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol%, and CO is 15-40 vol%) is led out of the heat exchange chamber, so that 3920Nm 3 non-condensable synthesis gas is produced, part of the non-condensable synthesis gas can be reused in the gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 28kg of liquid Zn is obtained in the heat exchange chamber, and high-grade ZnO can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 80 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, the leaching solution is subjected to gas stripping and filtration at 70 ℃ to obtain 14.5kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2, 1mol/L nitric acid solution is added into the leaching slag obtained by leaching for soaking, then filtration is carried out to obtain 21.0kg of SiO 2, and the rest solution is subjected to evaporation crystallization to obtain 2.84kg of Ca (NO 3)2 crystals).
Example 8
Firstly, 1400kg of waste tires are pretreated, and the steps of washing, removing large steel wires and crushing are sequentially carried out, wherein the crushing granularity is below 2.5 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. The waste tyre after magnetic separation is sent into a gasification chamber, the gasification temperature is 1250 ℃, and the inlet amount of gasifying agent steam is 1500kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 485 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol%, and CO is 15-40 vol%) is led out of the heat exchange chamber, and 4200Nm 3 non-condensable synthesis gas is produced altogether, part of the non-condensable synthesis gas can be reused in the gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 28.2kg of liquid Zn is obtained in the heat exchange chamber, and high-grade ZnO can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 70 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, the leaching solution is subjected to gas stripping and filtration at 70 ℃ to obtain 14kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2, 1mol/L nitric acid solution is added into the leaching slag obtained by leaching for soaking, then filtration is carried out to obtain 21.5kg of SiO 2, and the rest solution is subjected to evaporation crystallization to obtain 2.84kg of Ca (NO 3)2 crystals).
Example 9
Firstly, 1600kg of waste tires are pretreated, and the pretreatment comprises the steps of washing, removing large steel wires and crushing, wherein the crushing granularity is below 2.7 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. The waste tyre after magnetic separation is sent into a gasification chamber, the gasification temperature is 1350 ℃, and the inlet amount of gasifying agent steam is 1700kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 485 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol%, and CO is 15-40 vol%) is led out of the heat exchange chamber, 4785Nm 3 non-condensable synthesis gas is produced altogether, part of the non-condensable synthesis gas can be reused in the gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 32kg of liquid Zn is obtained in the heat exchange chamber, and high-grade ZnO can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 65 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, the leaching solution is subjected to gas stripping and filtration at 65 ℃ to obtain 16kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2, 1mol/L nitric acid solution is added into the leaching slag obtained by leaching for soaking, then the filtration is carried out to obtain 24kg of SiO 2, and the rest solution is subjected to evaporation crystallization to obtain 3.25kg of Ca (NO 3)2 crystals.
Example 10
Firstly, 1600kg of waste tires are pretreated, and the pretreatment comprises the steps of washing, removing large steel wires and crushing, wherein the crushing granularity is below 2.5 cm. And removing magnetic metals such as steel wires, iron wires and the like through magnetic separation recovery. And (3) delivering the waste tires subjected to magnetic separation into a gasification chamber, wherein the gasification temperature is 1370 ℃, and the ventilation quantity of the gasifying agent steam is 1600kg. The non-condensable synthesis gas containing Zn, H 2 and CO obtained by gasification flows into a heat exchange chamber, waste heat utilization condensation is carried out on the non-condensable synthesis gas through a heat exchanger, liquid Zn and non-condensable synthesis gas are obtained, and the temperature of the non-condensable synthesis gas obtained at a gas outlet of the heat exchange chamber is 485 ℃.
After heat exchange, the obtained non-condensable synthesis gas (H 2 is 10-30 vol%, and CO is 15-40 vol%) is led out of the heat exchange chamber, so that 4800Nm 3 non-condensable synthesis gas is produced, part of the non-condensable synthesis gas can be reused in the gasification chamber, and the rest is used for preparing methanol, synthetic ammonia, natural gas and the like. 32.3kg of liquid Zn is obtained in the heat exchange chamber, and high-grade Zn can be recovered after cooling to 60 ℃. The gasified slag obtained by gasification is cooled to 80 ℃ after being separated from a gasification chamber, the gasified slag is immersed in ammonia water (the mass percentage content is 35 wt%) and the ammonia water is used for complexing Ni 2+ and Cu 2+ to obtain leaching solution, the leaching solution is subjected to gas stripping and filtration at 70 ℃ to obtain 16.5kg of mixed metal ore of Ni (OH) 2 and Cu (OH) 2, the leaching slag obtained by leaching is added with 1mol/L nitric acid solution for soaking, then the filtration is carried out to obtain 24kg of SiO 2, and the rest solution is evaporated and crystallized to obtain 3.25kg of Ca (NO 3)2 crystals).
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (7)
1. The full-amount recycling treatment method for the waste tires is characterized by comprising the following steps of:
gasifying the waste tires by adopting a gasifying agent to obtain synthesis gas and gasified slag; the gasification temperature is more than or equal to 1100 ℃;
condensing the synthesis gas to obtain liquid Zn and non-condensed synthesis gas, wherein the non-condensed synthesis gas comprises H 2 and CO; the condensation is to exchange heat between the synthesis gas and water to obtain liquid Zn, non-condensable synthesis gas and water vapor, wherein the water vapor is used as the gasifying agent;
Immersing the gasified slag in ammonia water for leaching to obtain leaching liquid; the leaching also obtains leaching slag, and the leaching slag is mixed with nitric acid to obtain SiO 2 and Ca (NO 3)2 solution;
And sequentially carrying out gas stripping and solid-liquid separation on the leaching solution to obtain mixed metal ore, wherein the mixed metal ore comprises Ni (OH) 2 and Cu (OH) 2.
2. The process of claim 1, wherein the gasification temperature is 1100-1400 ℃.
3. A treatment method according to claim 1 or 2, wherein the mass ratio of the gasifying agent to the scrap tire is (1-1.2): 1.
4. The process of claim 1, wherein the non-condensable syngas is at a temperature of 450 ℃ to 500 ℃.
5. The process of claim 1, wherein the leaching temperature is 60-85 ℃.
6. The process of claim 1 or 5, wherein the gas used for stripping is N 2 and the temperature of the stripping is 60-80 ℃.
7. The method of processing according to claim 1, further comprising: and taking the non-condensable synthesis gas as the gasified fuel gas.
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