CN113817484A - Method for treating sulfur-containing organic solid waste and chromite processing waste residue through hydrogenation pyrolysis - Google Patents
Method for treating sulfur-containing organic solid waste and chromite processing waste residue through hydrogenation pyrolysis Download PDFInfo
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Abstract
The application discloses a method for treating sulfur-containing organic solid waste and chromite processing waste residue through hydropyrolysis, wherein the sulfur-containing organic solid waste is preheated and then sent into a pyrolysis furnace, heated to 550 ℃, and then stays for 5-10s, and a gas phase enters a cooling device for cold separation to obtain pyrolysis mixed gas and pyrolysis oil; the pyrolysis mixed gas enters a flue gas treatment device at the furnace tail, and the flue gas treatment device contains chromite processing waste residues; h in the mixed gas2S gas is oxidized into solid sulfur simple substance by hexavalent chromium in the flue gas treatment device or is adsorbed by chromite processing waste residue in the form of sulfate, the hexavalent chromium is reduced into trivalent chromium, and the treated mixed gas enters a gas collection device after passing through a dryer; the pyrolysis oil passes through a filter and an oil-water separator and then enters an oil storage tank for storage; and (4) discharging the solid phase remained in the pyrolysis furnace from the furnace bottom after pyrolysis into a solid collecting device for recycling.
Description
Technical Field
The invention belongs to the technical field of simultaneous treatment of waste tires and chromium slag, and particularly relates to a method for treating sulfur-containing organic solid waste and chromite processing waste slag through hydropyrolysis.
Background
With the rapid development of the automobile industry in China, the conservation quantity of automobiles in China is in a rapid growth trend. At the same time, the increased automobile inventory is likely to lead to scrap tire disposal problems. The current waste tires in China generate more than 1000 ten thousand tons every year, but the recovery rate of the waste tires is less than 50 percent. A large amount of waste tires are accumulated without treatment, mosquitoes are bred, pungent odor is emitted, and fire is easily caused. The components of the tire mainly comprise Natural Rubber (NR), synthetic rubber (styrene butadiene rubber SBR, butadiene rubber BR, isoprene rubber IR and the like), carbon black and various organic and inorganic auxiliary agents (a plasticizer, an anti-aging agent, sulfur, zinc oxide and the like). Therefore, the carbon content in the waste tire exceeds 80%, and the moisture and ash content are low, and the calorific value is high. Discarding or accumulating can result in a significant waste of resources.
At present, the waste tires are treated in a mode comprising rubber regeneration, tire retreading, production and pyrolysis of rubber powder. The most common method in China is rubber regeneration, but the rubber regeneration method has the advantages of low production profit, high labor intensity, long production period, high energy consumption, serious environmental pollution and incapability of regenerating tires after two times of regeneration. Compared with the other three methods, the pyrolysis method has higher economic value and environmental benefit.
The chromium slag is solid residue produced by mixing and calcining main materials and various auxiliary materials in the production process of chromium salt. The chromite processing technology necessarily produces chromium slag. The main component of the chromium slag is SiO2、Al2O3、CaO、MgO、Fe2O3、Cr2O6、Na2Cr2O7And the like. The chromium slag may have different compositions according to different processing techniques. Chromium slag from chromite processing is a hazardous waste, the toxicity of which is mainly derived from soluble hexavalent chromium therein.
Hexavalent chromium is a swallowable poison/inhalative toxicant, and skin contact may lead to allergies; more likely to cause genetic defects, inhalation may be carcinogenic, and there is a persistent risk to the environment. Hexavalent chromium is readily absorbed by the body and can invade the body through the digestive, respiratory, skin and mucous membranes.
Hexavalent chromium has strong oxidizability, and is reduced to trivalent chromium with weak toxicity and small fluidity by a chemical method to realize harmless treatment of hexavalent chromium at present.
Pyrolysis refers to a reaction in which an organic substance is heated in an inert atmosphere or a reducing atmosphere to break the polymer bonding state of the organic substance and decompose the organic substance into low-molecular substances. The products of the pyrolysis reaction are fuel gas, fuel oil and carbon black. Pyrolysis is the entire process of decomposition of a substance by heat, including an initial physical process, such as evaporation of moisture, intermediate thermal decomposition, and a final secondary reaction, repolymerization, or other reaction.
The main components of the tire are Natural Rubber (NR), synthetic rubber (SBR, BR, isoprene rubberIR, etc.), carbon black, and various organic and inorganic auxiliaries (plasticizers, antioxidants, sulfur, zinc oxide, etc.). The carbon content of the waste tires is over 80 percent, the moisture and ash content are very low, and the heat value is higher. The content of sulfur is about 1.5%, and the main inorganic substance is SiO2And ZnO.
The pyrolysis products of the waste tires in an inert atmosphere are about 45% of fuel oil, about 35% of carbon black and about 10% of combustible gas. The first stage of pyrolysis is a water analysis stage (about room temperature to 201 ℃), and the stage is mainly evaporation of bound water in rubber powder; the second stage is a pyrolysis stage (about 202-497 ℃), which is a main stage of pyrolysis, and the volatilization in the rubber powder is analyzed; the third stage is a carbonization stage (498-1000 ℃ or so), and pyrolysis residues are slowly decomposed to generate ash and fixed carbon.
During the hydropyrolysis, the added hydrogen can saturate the free radicals generated by the pyrolysis of the waste tires, and the secondary reaction caused by the mutual polymerization of the free radicals is avoided, so that the content of light components in the fuel oil is improved. Meanwhile, the addition of hydrogen can convert sulfur in the waste tires into toxic gas H with smelly eggs at high temperature2S：
H2+S→H2S (1)
The main component of the industrial waste residue generated by chromite processing is SiO2、Al2O3、CaO、MgO、Fe2O3、Cr2O6、Na2Cr2O7Wherein Cr is2O6And Na2Cr2O7Contains hexavalent chromium element. Hexavalent chromium has a strong toxicity and a strong oxidation property. Chromium slag under certain conditions for H2S has strong adsorption effect, and the reaction formula is as follows:
2CrO4 2-+3H2S+4H+→2Cr(OH)3(s)+3S(s)+2H2O (2)
8CrO4 2-+3H2S+10H++4H2O→8Cr(OH)3(s)+3SO4 2- (3)
after the reaction, the hexavalent chromium with strong toxicity can be reduced into trivalent chromium with weak toxicity and poor fluidity. H2S is oxidized into elemental sulfur or adsorbed in the form of sulfate.
Chinese patent CN104194419A discloses a waste tire cracking system, belonging to the technical field of waste recycling. The waste tire cracking system comprises the procedures of tire crushing, cracking reaction, oil product production, carbon black crushing, grinding, grading, granulator drying modification and the like, rubber is cracked into oil gas to form diesel oil and combustible gas, and carbon black in discharged carbon slag is thoroughly separated from steel wires to form a qualified carbon black, so that the aim of resource recycling is achieved.
Chinese patent CN110229691A discloses a waste tire anaerobic cracking treatment system, belonging to the field of waste tire treatment. The system comprises: the system comprises a pretreatment system, an anaerobic cracking system, a cracking product separation system, a cracking product storage system and an energy management system. The whole cracking system is in an anaerobic state, so that the condition that primary products generated by cracking tires continue to perform secondary reaction is avoided, and the anaerobic state completely avoids the generation of dioxin in the cracking process.
Chinese patent CN108203588A discloses a method for treating waste tires by nitrogen gas through low-temperature pyrolysis. The method comprises the steps of crushing waste tires into powder of 60-100 meshes, and mixing the powder with oil to obtain the oil cement. The prepared oil cement is pyrolyzed at 230-350 ℃, and has the advantages of low pyrolysis temperature, low pyrolysis gas yield, high pyrolysis oil yield and good pyrolysis carbon black quality.
The above-mentioned publications focus on various aspects of pyrolysis of waste tires in an inert atmosphere (e.g., pyrolysis system, apparatus, treatment method, etc.), and none of the treatment methods relate to pyrolysis of waste tires in a hydrogenation atmosphere.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the method solves the problems that the recovery rate of the waste tires is less than 50 percent, the waste tires are accumulated without being treated, mosquitoes can be bred and pungent peculiar smell is emitted, fire is easily caused, great resource waste can be caused by discarding or accumulation, the rubber regeneration production profit is low, the labor intensity is high, the production period is long, the energy consumption is high, the environmental pollution is serious, the tires cannot be regenerated again after being regenerated for two times, hexavalent chromium is easily absorbed by a human body, and the hexavalent chromium can invade the human body through digestion, a respiratory tract, skin and mucous membrane; provides a method for the hydropyrolysis synergistic disposal of sulfur-containing organic solid waste and chromite processing waste residue.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
a method for treating sulfur-containing organic solid waste and chromite processing waste residue by virtue of hydropyrolysis, which comprises the following steps:
the first step is as follows: cleaning and slicing the sulfur-containing organic solid waste, then carrying out magnetic separation to separate out steel wires contained in the sulfur-containing organic solid waste, drying the residual substances at the temperature of 100-;
the second step is that: sending the preheated sulfur-containing organic solid waste into a pyrolysis furnace, blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace after the blowing process is finished, and heating the pretreated sulfur-containing organic solid waste at the heating rate of 10 ℃/min until the temperature reaches 550-;
the third step: after the heating temperature reaches 550-600 ℃, the sulfur-containing organic solid waste stays in the pyrolysis furnace for 5-10s, then the heating is stopped, and the pyrolysis reaction is complete;
the fourth step: the gas phase generated after pyrolysis enters a cooling device to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device at the tail of the furnace, and the flue gas treatment device contains chromite processing waste residue with the particle size of 150-; the sulfur in the sulfur-containing organic solid waste is converted into toxic gas H with the odor of rotten eggs during the hydropyrolysis2S, H in the mixed gas2S gas is oxidized into solid sulfur simple substance by hexavalent chromium in the chromite processing waste residue or is absorbed by the chromite processing waste residue in the form of sulfate in the smoke treatment deviceIn addition, the toxic hexavalent chromium is reduced into trivalent chromium with weak toxicity and poor fluidity, and the treated mixed gas is dried by a drier in the device through a drier to reach the water content<1% of the pyrolysis oil enters a gas collection device, and the pyrolysis oil separated from the cooling device passes through a filter and an oil-water separator and then enters an oil storage tank for storage;
the fifth step: the solid phase components remained in the pyrolysis furnace after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter a solid collecting device, and are recycled as fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to become a substitute of a pavement material.
Further, the chromite processing waste residue can adsorb and oxidize H2Solid waste of S gas.
Further, the catalyst is capable of adsorbing and oxidizing H2The solid waste of the S gas is one or more of chromium slag, steel slag and red mud.
Further, the final pyrolysis temperature in the third step was 550 ℃.
Further, the sulfur-containing organic solid waste is waste tires.
Further, the components of the chromite processing waste residue comprise SiO2、Al2O3、CaO、MgO、Fe2O3、Cr2O6、Na2Cr2O7One or more of them.
Further, in the first step, the drying temperature is 100-110 ℃, the drying is carried out for 30min until the water content is less than 3%, and in the fourth step, the drying agent in the dryer is a quicklime drying agent and is dried until the water content is less than 1%.
Has the advantages that:
the application provides a method for coprocessing sulfur-containing organic solid waste and chromite processing waste residues through hydropyrolysis, and compared with the prior art, the method has the following beneficial effects:
1. the existing waste tire pyrolysis technology is mainly to carry out pyrolysis in a nitrogen atmosphere. The pyrolysis products are typically 45% fuel oil, 35% carbon black, 10% combustible gas. When the waste tires are pyrolyzed in the inert atmosphere, the viscosity, the oxygen content and the coking rate of the liquid oil generated after pyrolysis are high. The method realizes the pyrolysis of the waste tires in the hydrogenation atmosphere, controls the final temperature of the pyrolysis to be between 400 ℃ and 800 ℃, utilizes the added hydrogen to saturate the free radicals generated by the pyrolysis of the waste tires, avoids the mutual polymerization of the free radicals to generate a secondary reaction, and can improve the yield of the pyrolysis fuel oil and simultaneously improve the content of light components in the fuel oil. The light oil has carbon atoms of C5 and C6, has higher combustion efficiency compared with heavy oil such as diesel oil, does not generate any waste gas during combustion, and is clean and safe. By means of hydropyrolysis treatment, the hazardous waste and waste tires are converted into combustible gas, fuel oil and carbon black with high calorific value, and the hazardous waste and waste tires can be used as alternative fuels or raw materials for industrial production, so that resource recycling is realized.
2. The used tires contain about 1.5% of elemental sulfur. The existing waste tire pyrolysis technology does not relate to the treatment of sulfur element. Untreated elemental sulfur may remain in the solid phase of the carbon black or in the gaseous phase of the pyrolysis gas, eventually leading to the generation of acid gases. In the invention, the hydrogenation atmosphere is used for ensuring that the sulfur element is converted into H2And (4) S gas. In the flue gas treatment device, the toxic H is adsorbed and oxidized by the chromium slag generated by mixing and calcining the main material and various auxiliary materials in the production process of chromium salt2And (4) S gas. Meanwhile, hexavalent chromium which is originally toxic in the chromium slag is reduced into trivalent chromium which is weak in toxicity and poor in fluidity. The cooperative treatment of the two dangerous wastes of the waste tires and the chromite processing waste residues is completed.
3. The application discloses a method for cooperatively treating waste tires and chromite processing waste residues, which simultaneously treats two dangerous wastes of the waste tires and the chromite residues, and realizes resource utilization of the waste tires and harmless treatment of iron ore processing waste residues.
4. The pyrolysis is carried out in the hydrogenation atmosphere, so that the yield of the pyrolysis oil and the content of light components in the pyrolysis oil are improved, the viscosity, the oxygen content and the coking rate of the pyrolysis oil are effectively reduced, and the pyrolysis oil can be widely used.
5. The pyrolysis is carried out in a hydrogenation atmosphere (such as 10% hydrogen and 90% nitrogen), oxygen does not exist in a reaction system, and toxic substance dioxin cannot be generated due to low temperature.
6. The final temperature of the pyrolysis reaction is low, so that the pyrolysis reaction is basically complete, and the energy can be saved. The final temperature of the pyrolysis reaction is controlled to be 400-800 ℃, and the yield of the pyrolysis oil can be ensured.
Description of the drawings:
fig. 1 is a diagram of a scrap tire pyrolysis system according to the present invention.
Description of reference numerals: 1. the system comprises a preheater, 2, a pyrolysis furnace, 3, a cooling device, 4, a flue gas treatment device, 5, a dryer, 6, a gas collection device, 7, a filter, 8, an oil-water separator, 9, an oil storage tank and 10, a solid collection device.
Detailed Description
The following will further explain the embodiments and working procedures of the present invention by referring to examples.
Example 1:
the method for treating the sulfur-containing organic solid waste and the chromite processing waste residue by the cooperation of the hydropyrolysis comprises the following steps:
the first step is as follows: cleaning and slicing the waste tires, then carrying out magnetic separation to separate steel wires contained in the waste tires, drying the residual substances at the temperature of 100-;
the second step is that: sending the preheated waste tires into a pyrolysis furnace 2, blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace 2 after the blowing process is finished, and heating the pretreated waste tires at the heating rate of 10 ℃/min until the temperature reaches 550-;
the third step: after the heating temperature reaches 550-600 ℃, the waste tires stay in the pyrolysis furnace 2 for 5-10s, then the heating is stopped, and the pyrolysis reaction is complete;
the fourth step: the gas phase generated after pyrolysis enters a cooling device 3 to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device 4 at the tail of the furnace, the flue gas treatment device 4 contains waste chromite processing waste with the grain diameter of 150-375 mu m and the water content of 20-30 percentSlag; the sulfur in the waste tires is converted into toxic gas H with the odor of the smelly eggs during the hydro-pyrolysis2S, H in the mixed gas2S gas is oxidized into solid sulfur simple substance by hexavalent chromium in the chromite processing waste residue or is adsorbed by the chromite processing waste residue in the form of sulfate in the smoke treatment device 4, toxic hexavalent chromium is reduced into trivalent chromium with weak toxicity and poor liquidity, and the treated mixed gas is dried by a drying agent in the device through a dryer 5 until the water content is reduced to the water content<1% of the pyrolysis oil enters a gas collecting device 6, and the pyrolysis oil separated from the cooling device 3 passes through a filter 7 and an oil-water separator 8 and then enters an oil storage tank 9 for storage;
the fifth step: the solid phase components remained in the pyrolysis furnace 2 after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter the solid collecting device 10, and are recycled to be used as fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to be used as a substitute of a pavement material.
Example 2:
the method for treating the sulfur-containing organic solid waste and the chromite processing waste residue by the cooperation of the hydropyrolysis comprises the following steps:
the first step is as follows: cleaning and crushing the sulfur-containing organic solid waste, drying the residual substances at the temperature of 100-;
the second step is that: sending the preheated sulfur-containing organic solid waste into a pyrolysis furnace 2, blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace 2 after the blowing process is finished, and heating the pretreated sulfur-containing organic solid waste at the heating rate of 10 ℃/min until the temperature reaches 550-600 ℃;
the third step: after the heating temperature reaches 550-600 ℃, the sulfur-containing organic solid waste stays in the pyrolysis furnace 2 for 5-10s, then the heating is stopped, and the pyrolysis reaction is complete;
the fourth step: the gas phase generated after pyrolysis enters a cooling device 3 to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device 4 at the tail of the furnace, the flue gas treatment device 4 contains particles with the particle size of 150-375 mu m and the water content of 20-30 percentChromium slag; the sulfur in the sulfur-containing organic solid waste is converted into toxic gas H with the odor of rotten eggs during the hydropyrolysis2S, H in the mixed gas2S gas is oxidized into solid sulfur simple substance by hexavalent chromium in the chromium slag or is adsorbed by the chromium slag in the form of sulfate in the flue gas treatment device 4, toxic hexavalent chromium is reduced into trivalent chromium with weak toxicity and poor liquidity, and the treated mixed gas is dried by a drying agent in the device through a dryer 5 until the water content is reduced to<1% of the pyrolysis oil enters a gas collecting device 6, and the pyrolysis oil separated from the cooling device 3 passes through a filter 7 and an oil-water separator 8 and then enters an oil storage tank 9 for storage;
the fifth step: the solid phase components remained in the pyrolysis furnace 2 after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter the solid collecting device 10, and are recycled to be used as fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to be used as a substitute of a pavement material.
Example 3:
the method for treating the sulfur-containing organic solid waste and the steelmaking waste residue by the cooperation of the hydropyrolysis comprises the following steps:
the first step is as follows: cleaning and crushing the sulfur-containing organic solid waste, drying the residual substances at the temperature of 100-;
the second step is that: sending the preheated sulfur-containing organic solid waste into a pyrolysis furnace 2, blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace 2 after the blowing process is finished, and heating the pretreated sulfur-containing organic solid waste at the heating rate of 10 ℃/min until the temperature reaches 550-600 ℃;
the third step: after the heating temperature reaches 550-600 ℃, the sulfur-containing organic solid waste stays in the pyrolysis furnace 2 for 5-10s, then the heating is stopped, and the pyrolysis reaction is complete;
the fourth step: the gas phase generated after pyrolysis enters a cooling device 3 to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device 4 at the tail of the furnace, and the flue gas treatment device 4 contains steel slag with the particle size of 100-150 mu m and the water content of 15-25%; in sulfur-containing organic solid wastesThe sulfur is converted into toxic gas H with the odor of the rotten eggs during the hydro-pyrolysis2S, H in the mixed gas2S gas reacts with ferric hydroxide in the steel slag in the flue gas treatment device 4 to be converted into solid ferrous sulfide, and the treated mixed gas is dried by a drying agent in the device through a dryer 5 to reach the moisture content<1% of the pyrolysis oil enters a gas collecting device 6, and the pyrolysis oil separated from the cooling device 3 passes through a filter 7 and an oil-water separator 8 and then enters an oil storage tank 9 for storage;
the fifth step: the solid phase components remained in the pyrolysis furnace 2 after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter the solid collecting device 10, and are recycled to be used as fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to be used as a substitute of a pavement material.
Example 4:
the method for treating sulfur-containing organic solid waste and red mud by using hydropyrolysis comprises the following steps:
the first step is as follows: cleaning and crushing the sulfur-containing organic solid waste, drying the residual substances at 110-;
the second step is that: sending the preheated sulfur-containing organic solid waste into a pyrolysis furnace 2, blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace 2 after the blowing process is finished, and heating the pretreated sulfur-containing organic solid waste at the heating rate of 10 ℃/min until the temperature reaches 550-600 ℃;
the third step: after the heating temperature reaches 550-600 ℃, the sulfur-containing organic solid waste stays in the pyrolysis furnace 2 for 5-10s, then the heating is stopped, and the pyrolysis reaction is complete;
the fourth step: the gas phase generated after pyrolysis enters a cooling device 3 to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device 4 at the tail of the furnace, and the flue gas treatment device 4 contains red mud with the water content of 10-15%; the sulfur in the sulfur-containing organic solid waste is converted into toxic gas H with the odor of rotten eggs during the hydropyrolysis2S, H in the mixed gas2The S gas is mixed with the red mud in the flue gas treatment device 4The ferric oxide is converted into solid ferrous sulfide through reaction or is converted into solid calcium sulfide through reaction with calcium carbonate in the red mud, and the treated mixed gas is dried by a drier 5 in the device until the water content is reduced<1% of the pyrolysis oil enters a gas collecting device 6, and the pyrolysis oil separated from the cooling device 3 passes through a filter 7 and an oil-water separator 8 and then enters an oil storage tank 9 for storage;
the fifth step: the solid phase components remained in the pyrolysis furnace 2 after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter the solid collecting device 10, and are recycled to be used as fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to be used as a substitute of a pavement material.
Example 5:
the method for treating the sulfur-containing organic solid waste and the chromite processing waste residue by the cooperation of the hydropyrolysis comprises the following steps:
the first step is as follows: cleaning and crushing the sulfur-containing organic solid waste, drying the residual substances at 110-;
the second step is that: sending the preheated sulfur-containing organic solid waste into a pyrolysis furnace 2, blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace 2 after the blowing process is finished, and heating the pretreated sulfur-containing organic solid waste at the heating rate of 10 ℃/min until the temperature reaches 550-600 ℃;
the third step: after the heating temperature reaches 550-600 ℃, the sulfur-containing organic solid waste stays in the pyrolysis furnace 2 for 5-10s, then the heating is stopped, and the pyrolysis reaction is complete;
the fourth step: the gas phase generated after pyrolysis enters a cooling device 3 to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device 4 at the tail of the furnace, and the flue gas treatment device 4 contains chromite processing waste residue with the particle size of 150-; the sulfur in the sulfur-containing organic solid waste is converted into toxic gas H with the odor of rotten eggs during the hydropyrolysis2S, H in the mixed gas2S gas is oxidized into solid sulfur sheets by hexavalent chromium in chromite processing waste residue in the flue gas treatment device 4The chromium or the chromium is adsorbed by the chromite processing waste residue in the form of sulfate, the toxic hexavalent chromium is reduced into the trivalent chromium with weak toxicity and poor liquidity, and the treated mixed gas is dried by a drying agent in the device through a drier 5 until the water content is reduced to<1% of the pyrolysis oil enters a gas collecting device 6, and the pyrolysis oil separated from the cooling device 3 passes through a filter 7 and an oil-water separator 8 and then enters an oil storage tank 9 for storage; the components of the chromite processing waste residue comprise SiO2、Al2O3、CaO、MgO、Fe2O3、Cr2O6、Na2Cr2O7One or more of the above;
the fifth step: the solid phase components remained in the pyrolysis furnace 2 after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter the solid collecting device 10, and are recycled to be used as fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to be used as a substitute of a pavement material.
Example 6:
the method for treating the sulfur-containing organic solid waste and the chromite processing waste residue by the cooperation of the hydropyrolysis comprises the following steps:
the first step is as follows: cleaning and slicing the waste tires, then carrying out magnetic separation to separate steel wires contained in the waste tires, drying the residual substances at 110-;
the second step is that: sending the preheated waste tires into a pyrolysis furnace 2, blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace 2 after the blowing process is finished, and heating the pretreated waste tires at the heating rate of 10 ℃/min until the temperature reaches 550-;
the third step: after the heating temperature reaches 550-600 ℃, the waste tires stay in the pyrolysis furnace 2 for 5-10s, then the heating is stopped, and the pyrolysis reaction is complete;
the fourth step: the gas phase generated after pyrolysis enters a cooling device 3 to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device 4 at the tail of the furnace, the flue gas treatment device 4 contains particles with the particle size of 150-20-30% of chromium slag; the sulfur in the waste tires is converted into toxic gas H with the odor of the smelly eggs during the hydro-pyrolysis2S, H in the mixed gas2S gas is oxidized into solid sulfur simple substance by hexavalent chromium in the chromium slag or is adsorbed by the chromium slag in the form of sulfate in the flue gas treatment device 4, toxic hexavalent chromium is reduced into trivalent chromium with weak toxicity and poor liquidity, and the treated mixed gas is dried by a drying agent in the device through a dryer 5 until the water content is reduced to<1% of the pyrolysis oil enters a gas collecting device 6, and the pyrolysis oil separated from the cooling device 3 passes through a filter 7 and an oil-water separator 8 and then enters an oil storage tank 9 for storage;
the fifth step: the solid phase components remained in the pyrolysis furnace 2 after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter the solid collecting device 10, and are recycled to be used as fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to be used as a substitute of a pavement material.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by the person skilled in the art shall be covered by the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A method for the hydropyrolysis cooperative disposal of sulfur-containing organic solid waste and chromite processing waste residue is characterized by comprising the following steps:
the first step is as follows: cleaning and slicing the sulfur-containing organic solid waste, then performing magnetic separation to separate steel wires contained in the sulfur-containing organic solid waste, drying the residual substances at the temperature of 100-110 ℃ for 30min until the water content is less than 3%, and then preheating the residual substances to the temperature of 180-200 ℃ in a preheater (1);
the second step is that: sending the preheated sulfur-containing organic solid waste into a pyrolysis furnace (2), blowing for 5min under nitrogen, introducing 10% hydrogen into the pyrolysis furnace (2) after the blowing process is finished, and heating the pretreated sulfur-containing organic solid waste at the heating rate of 10 ℃/min until the temperature reaches 550-600 ℃;
the third step: after the heating temperature reaches 550-600 ℃, the sulfur-containing organic solid waste stays in the pyrolysis furnace (2) for 5-10s, then the heating is stopped, and the pyrolysis reaction is completed;
the fourth step: the gas phase generated after pyrolysis enters a cooling device (3) to be cooled to room temperature, and pyrolysis mixed gas and pyrolysis oil are separated; the separated pyrolysis mixed gas enters a flue gas treatment device (4) at the tail of the furnace, and the flue gas treatment device (4) contains chromite processing waste residue with the particle size of 150-375 mu m and the water content of 20-30%; the sulfur in the sulfur-containing organic solid waste is converted into toxic gas H with the odor of rotten eggs during the hydropyrolysis2S, H in the mixed gas2S gas is oxidized into solid sulfur simple substance by hexavalent chromium in the chromite processing waste residue or is adsorbed by the chromite processing waste residue in the form of sulfate in the smoke treatment device (4), toxic hexavalent chromium is reduced into trivalent chromium with weak toxicity and poor liquidity, and the treated mixed gas is dried by a drying agent in the device to reach the moisture content through a dryer (5)<1% of the pyrolysis oil enters a gas collection device (6), and the pyrolysis oil separated from the cooling device (3) passes through a filter (7) and an oil-water separator (8) and then enters an oil storage tank (9) for storage;
the fifth step: the solid phase components remained in the pyrolysis furnace (2) after pyrolysis are carbon black, zinc oxide and silicon dioxide, are discharged from the furnace bottom, enter a solid collecting device (10), and are recycled as the fuel of the pyrolysis furnace or added into asphalt as an asphalt reinforcing agent to become a substitute of a pavement material.
2. The hydropyrolysis method for the co-disposal of sulfur-containing organic solid waste and chromite processing slag according to claim 1, wherein: the chromite processing waste residue can adsorb and oxidize H2Solid waste of S gas.
3. The hydropyrolysis method for the co-disposal of sulfur-containing organic solid waste and chromite processing slag according to claim 2, wherein: said being capable of adsorbing and oxidizing H2The solid waste of the S gas is one or more of chromium slag, steel slag and red mud.
4. The hydropyrolysis method for the co-disposal of sulfur-containing organic solid waste and chromite processing slag according to claim 1, wherein: the final pyrolysis temperature in the third step is 550 ℃.
5. The hydropyrolysis method for the co-disposal of sulfur-containing organic solid waste and chromite processing slag according to claim 1, wherein: the sulfur-containing organic solid waste is waste tires.
6. The hydropyrolysis method for the co-disposal of sulfur-containing organic solid waste and chromite processing slag according to claim 1, wherein: the components of the chromite processing waste residue comprise SiO2、Al2O3、CaO、MgO、Fe2O3、Cr2O6、Na2Cr2O7One or more of them.
7. The hydropyrolysis method for the co-disposal of sulfur-containing organic solid waste and chromite processing slag according to claim 1, wherein: in the first step, the drying temperature is 110-.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381335A (en) * | 2013-07-17 | 2013-11-06 | 山东大学 | Method for removing hydrogen sulfide through chromium slag |
| CN204434552U (en) * | 2014-12-26 | 2015-07-01 | 北京神雾环境能源科技集团股份有限公司 | Rotating bed pyrolysis oven and junked tire pyrolysis system |
| CN106110864A (en) * | 2016-06-28 | 2016-11-16 | 昆明理工大学 | A kind of method utilizing chromium dreg slurry to process flue gas |
| CN106824979A (en) * | 2017-01-04 | 2017-06-13 | 长沙汇聚环境技术有限公司 | A kind of cooperative disposal method of Cr VI slag and biomass castoff |
-
2021
- 2021-09-14 CN CN202111075086.0A patent/CN113817484A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381335A (en) * | 2013-07-17 | 2013-11-06 | 山东大学 | Method for removing hydrogen sulfide through chromium slag |
| CN204434552U (en) * | 2014-12-26 | 2015-07-01 | 北京神雾环境能源科技集团股份有限公司 | Rotating bed pyrolysis oven and junked tire pyrolysis system |
| CN106110864A (en) * | 2016-06-28 | 2016-11-16 | 昆明理工大学 | A kind of method utilizing chromium dreg slurry to process flue gas |
| CN106824979A (en) * | 2017-01-04 | 2017-06-13 | 长沙汇聚环境技术有限公司 | A kind of cooperative disposal method of Cr VI slag and biomass castoff |
Non-Patent Citations (1)
| Title |
|---|
| 王凤超等: "废轮胎热解技术及炭黑产物的品质提升与应用研究进展", 《化工学报》 * |
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