CN114262619A - Device and method for preparing high-content straight-chain alkane product by low-consumption pyrolysis of modified dust and mud compatible oily sludge - Google Patents
Device and method for preparing high-content straight-chain alkane product by low-consumption pyrolysis of modified dust and mud compatible oily sludge Download PDFInfo
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Abstract
The invention relates to a device and a method for preparing a high-content straight-chain alkane product by low-consumption pyrolysis of modified dust and sludge and oily sludge. Compared with the traditional dust and mud, the prepared modified dust and mud has higher porosity and surface activity and high orientation degree, plays a role of a thermosetting carrier, improves the heat and mass transfer capacity, reduces the energy consumption in the pyrolysis process, has a catalytic effect, promotes the ring-opening reaction of oil-containing sludge volatile components, and generates a high-content straight-chain alkane product. The pyrolysis slag and pyrolysis gas are sent into an activation device to generate active coke for wastewater treatment, and the metal simple substance is separated to realize high-value utilization of dust and mud; the produced gas is sent into a gas combustion device for combustion and energy supply.
Description
Technical Field
The invention belongs to the technical field of resource utilization of industrial solid wastes, and particularly relates to a device and a method for preparing a high-content straight-chain alkane product by low-consumption pyrolysis of modified dust and mud material and oil-containing sludge compatible with the modified dust and mud material.
Background
The solid waste produced in the industrial production process is called industrial solid waste. The industrial solid waste has various heterogeneity and extremely complex components and properties, and can be divided into inorganic industrial solid waste and organic industrial solid waste. Dust sludge and oily sludge are typical representatives of inorganic industrial solid wastes and organic industrial solid wastes, respectively.
Dust and smoke generated in the processes of sintering, iron making, steel making and the like, and rolled steel sheet and the like generated in the production process of rolled steel are often called dust mud. The annual output of the dust and mud in China is more than 8000 ten thousand tons according to 190 kilograms of dust and mud generated by each ton of steel. With the development of the steel industry, the dust and mud yield is gradually increased. In order to reasonably utilize resources and protect the environment to eliminate dust pollution, the full utilization of dust and mud is an indispensable component in the production of modern iron and steel enterprises. The conventional dust and mud recovery mode is a flotation/gravity combined separation process, and the consumption of a flotation agent is high. At present, the treatment is carried out independently, and the effective synergy with the organic industrial solid waste containing oil stains and the like is lacked.
The oily sludge is a mixture of petroleum hydrocarbon, soil organic matter, inorganic mineral matter, water, nitrogen, sulfur, chlorine, heavy metal elements and additives. Depending on the source of production, oily sludge can be classified into oilfield oily sludge (Oil field OS), Storage and transportation oily sludge (Storage and transportation OS), Refinery oily sludge (Refinery OS), and Accident oily sludge (Accident OS). According to the statistics of China ministry of ecological environment protection, the annual output of oily sludge in China industrial operation systems exceeds 600 million tons, and the historical total stock reaches 1.43 million tons. Oily sludge is listed in the list of national hazardous waste records because of its flammability, toxicity, difficult biodegradability, biotoxicity, etc. The average petroleum content of the oily sludge is about 10-30%, and a new technology suitable for recycling the oily sludge is urgently needed in view of the coexistence of potential resource and hazard. Hitherto, there have been developed a considerable number of methods for treating oily sludge, in which modulation-mechanical separation techniques, which have a high oil content of the residue after treatment, and heat treatment techniques, which mainly include incineration and pyrolysis techniques, which have a low utilization efficiency of treatment resources and generate secondary pollution such as dioxin, are widely used, and pyrolysis techniques, which have been receiving much attention due to their own characteristics. The oily sludge is decomposed into micromolecular pyrolysis gas and micromolecular pyrolysis oil under the high-temperature anoxic environment, the oil content in residues is low, and the secondary pollution to the atmosphere is reduced due to the fact that the reaction atmosphere is anoxic and the exhaust gas quantity is small. However, the pyrolysis technology also has the technical bottleneck, which is mainly reflected in that the added value of the pyrolysis product of the oily sludge is low and the energy consumption of the pyrolysis process is high. This is because the viscosity of the oily sludge is high, and the heat and mass transfer during the pyrolysis process is difficult.
The straight-chain alkane is one of oil-containing sludge pyrolysis products, and has important significance in chemical production. CN201120503691.9 discloses a device for continuously separating and extracting straight-chain alkane in naphtha, which indicates that the straight-chain alkane is used as a high-quality cracking raw material to most easily generate target products such as ethylene and the like in the industrial production process of the ethylene, thereby improving the yield of the ethylene, reducing the yield of poor-quality cracking gasoline, reducing the coking amount of a furnace tube, prolonging the start-up period and improving the economic benefit. In addition, the straight-chain alkane can also be used as an intermediate of aromatization reaction and can be applied to the preparation of protein/vitamin liquid concentrate. Therefore, if the content of straight-chain alkane in the oil-containing sludge pyrolysis oil can be increased, the additional value of the pyrolysis oil can be greatly improved.
CN201910885711.4 discloses a method for cooperative treatment of oil sludge pyrolysis and steel slag reduction, which comprises heating and softening oil sludge, mixing the oil sludge with steel slag with a certain particle size according to a proper proportion, placing the mixture on a continuous pyrolysis magnetic separation device, heating the mixture to a proper temperature, selecting a proper retention time and a proper magnetic field intensity of a magnetic separation tube, obtaining a pyrolysis oil gas product, and reducing the steel slag. The patent realizes the reduction of the oil sludge by means of pyrolysis, but still has the following problems: the addition of the steel slag does not increase the yield of the pyrolysis oil, and the content of straight-chain alkane in the pyrolysis oil is low. The conventional steel slag surface is covered by carbon black, carbonaceous sediments and various coking substances, so that original pores in the steel slag are blocked, the contact between the oily sludge and active sites in the steel slag is influenced, the catalytic effect of the steel slag is hindered, the separation of volatile matters is hindered in the pyrolysis process of the steel slag and the oily sludge, and the secondary pyrolysis of the volatile matters into micromolecular pyrolysis gas is promoted.
Disclosure of Invention
In view of the above problems and technical analysis, the present invention aims to provide a device and a method for preparing a high-content straight-chain alkane product by low-consumption pyrolysis of modified dust and sludge and oil-containing sludge. Compared with the traditional dust mud, the prepared modified dust mud removes most of carbon black, carbonaceous sediments and coking substances accumulated on the surface of the modified dust mud, greatly increases the porosity and surface activity of the dust mud, and has good ferric oxide crystallinity and high orientation degree. The modified dust and mud provides high-quality catalysis and heat load effects for the pyrolysis of the oily sludge, the heat and mass transfer effects in the pyrolysis process of the oily sludge are greatly improved, the energy consumption in the pyrolysis process is reduced, and the prepared pyrolysis oil is rich in straight-chain alkane components and has high added value. And after the pyrolysis slag and the pyrolysis gas are sent into an activation device, a metal simple substance and active coke are separated from a solid product, the active coke is used for a wastewater treatment device, the generated gas is sent into a gas combustion device for combustion, and the energy is reused for a calcining and pyrolysis device.
The technical scheme adopted by the invention is as follows:
a device for preparing a high-content straight-chain alkane product by low-consumption pyrolysis of modified dust and sludge compatible oily sludge comprises a crushing and screening device, a washing device, a calcining device, a premixing and drying device, a pyrolysis device, an oil-water separation device, an activation device, a gas recovery device, a gas combustion device, a sorting device and a wastewater treatment device;
the outlet of the crushing and screening device is communicated with a water washing device;
a liquid phase outlet of the washing device is introduced into the wastewater treatment device, and a solid phase outlet is introduced into the calcining device;
the solid phase outlet of the calcining device is introduced into the premixing and drying device;
the outlet of the premixing drying device is communicated with a pyrolysis device;
a gas phase outlet and a solid phase outlet of the pyrolysis device are both led into the activation device, and a liquid phase outlet is led into the oil-water separation device;
a gas phase outlet of the activation device is introduced into a gas recovery device, and a solid phase outlet is introduced into a sorting device;
the gas phase outlet of the gas recovery device is introduced into the gas combustion device;
an active coke outlet of the sorting device is introduced into a wastewater treatment device;
and a liquid phase outlet of the wastewater treatment device is introduced into the water washing device, and a solid phase outlet is introduced into the premixing drying device.
A method for preparing a high-content straight-chain alkane product by low-consumption pyrolysis of modified dust and sludge and oily sludge comprises the following specific steps:
(1) the dust and mud are crushed and screened by the crushing and screening device and then are sent into the water washing device, the water washing device is used for removing soluble impurities blocking pore channels on the surface of the dust and mud, wastewater generated in the water washing process is sent into the wastewater treatment device, the dust and mud after being washed are sent into the calcining device and are calcined under the aerobic condition, carbon black, carbonaceous sediments and coking substances mixed in the dust and mud are fully contacted with oxygen at high temperature to generate oxidation reaction and then are removed, the pore channels blocked in the dust and mud are opened, the porosity and the surface activity of the dust and mud are greatly increased, and the orientation degree is high;
(2) the oily sludge and the calcined high-temperature modified dust sludge are fully mixed in a premixing drying device, the calcined high-temperature modified dust sludge plays a role of a thermosetting carrier, self heat is transferred to the oily sludge through heat transfer, the oily sludge is dehydrated and dried, the viscosity of the oily sludge is reduced, after the drying stage is finished, the mixture of the oily sludge and the dust sludge is sent into a pyrolysis device, the volatile component of the oily sludge is subjected to ring-opening reaction to generate a straight-chain alkane product, and simultaneously coke in pyrolysis slag and H in pyrolysis gas are subjected to ring-opening reaction2CO reduces the metal oxide in the dust mud into a metal simple substance; in the process, the mass transfer capacity of the pyrolysis process can be improved and the energy consumption of the pyrolysis process can be greatly reduced due to rich channels in the modified dust and mud, the modified dust and mud has a catalytic effect, the ring-opening reaction of volatile components of the oily sludge is promoted, and a high-content straight-chain alkane product is generated;
(3) pyrolysis liquid that the pyrolysis in-process produced passes through oil-water separator, separate water and straight chain alkane pyrolysis oil and retrieve it, pyrolysis gas and pyrolysis slag are sent into activation device jointly, the solid of activation device export separates metal simple substance and active coke through sorting unit, partial active coke sends into the effluent disposal unit, unnecessary active coke is retrieved, the gas of activation device export is unified to be sent into gas combustion device after gas recovery device retrieves and burns, the heat that the burning produced is used for calcining device, pyrolysis device and activation device again.
(4) The waste water inside the waste water recovery device is treated by using active coke, the treated clean water is sent to a washing device for recycling, the invalid active coke generated in the treatment process is sent to a premixing drying device, and the drying, pyrolysis and activation processes are repeated for regeneration and reuse.
The dust and mud refers to: the black brown powder is produced in the working procedures of sintering, iron making, steel making and the like, and is collected by dust collectors such as cloth bag dust collection, gravity dust collection, electric dust collection, ring cooling dust collection and the like, and the main components of the black brown powder are metal elements such as iron, calcium, silicon, aluminum, magnesium and the like.
The dust and mud are crushed and screened to obtain the dust and mud with the size of 60-100 meshes.
The volume ratio of the dust and mud to water for cleaning in the water washing device is 1: 10-50, and the washing frequency is more than 3.
The calcining temperature of the calcining device is 700-900 ℃, and the calcining time is 3-6 h.
The mixing proportion of the oily sludge and the calcined high-temperature modified dust sludge is as follows: the high-temperature modified dust and mud accounts for 5-20% of the mass of the oily sludge.
The oily sludge refers to: the oil, water and solid three-phase suspended emulsion stable dispersion system is produced by mixing crude oil or finished oil into soil or other medium. The water content is 40.0-90.0%, the oil content is 15.0-50.0%, the solid content is 5.0-46.0%, the pH is 6.5-7.5, and the odor is pungent.
The pyrolysis temperature is 400-700 ℃, the pyrolysis time is 30-120 min, the pyrolysis protective gas is nitrogen, and the flow rate is 100-200 mL/min.
The oil-water separation device adopts the processes of centrifugation, liquid separation, solvent extraction and rotary evaporation solvent removal, and the extracting agent is CH during solvent extraction2Cl2The rotary evaporation temperature is 40-60 ℃, the vacuum degree is 0.01-0.03 mPa, and the mark of the end of the rotary evaporation indicates that the quality of the residual liquid is not changed. The content of straight chain alkane in the pyrolysis oil can reach 40-60%.
The activation temperature is 800-1200 ℃, and the activation time is 3-6 h.
The pyrolysis residue sorting device adopts a gravity sorting process, and metal simple substances and residual residues are sorted out by utilizing the difference of the densities of the metal simple substances and the pyrolysis residual values.
The invention has the advantages that: compared with the prior art, the invention provides a device and a method for preparing a high-content straight-chain alkane product by pyrolysis of modified dust and mud and oil-containing sludge, and the device and the method have the following advantages:
(1) realizing the harmlessness and reclamation of the oily sludge: in view of wide source and large yield of the oily sludge and coexistence of potential resource and hazard, a new technology suitable for harmless recycling treatment of the oily sludge is urgently needed. The modified dust mud is used as a catalyst in the pyrolysis process, so that the ring-opening reaction of volatile components in the oil-containing sludge is promoted, the pyrolysis oil with high content of straight-chain alkane is generated, and the additional value of the pyrolysis oil is improved. Meanwhile, the modified dust and mud has high porosity and surface activity, good ferric oxide crystallinity and high orientation degree, is an excellent thermosetting carrier in the pyrolysis process, and enriches pores to enhance the heat transfer and mass transfer effects in the pyrolysis process.
(2) The recycling of dust and mud is realized: the source of the dust and mud is wide, the annual output is large, the conventional recovery mode is a flotation/gravity combined separation process, and the consumption of the flotation agent is large. The modified dust and sludge with high porosity, high surface activity, high crystallinity and high orientation is successfully prepared by crushing, screening, washing and calcining, is used for the pyrolysis process of the oily sludge, and utilizes coke in the pyrolysis slag of the oily sludge and H in pyrolysis gas2And reducing substances such as CO and the like reduce metal oxides in the dust sludge into metal simple substances in the activation device, so that high-value utilization of the dust sludge is realized.
(3) Energy conservation, environmental protection and high economic value: oily sludge and calcined high temperatureThe modified dust and mud are fully mixed in the premixing and drying device, the calcined high-temperature modified dust and mud plays a role of a thermosetting carrier, self heat is transferred to the oily sludge through heat transfer, the oily sludge is dehydrated and dried, the viscosity of the oily sludge is reduced, and the energy consumption in the pyrolysis process is reduced. The gas at the outlet of the activation device is uniformly recovered by the gas recovery device and then sent to the gas combustion device for combustion, and the heat generated by combustion is reused for the calcining device, the pyrolysis device and the activation device. Coke in the pyrolysis slag and H in the pyrolysis gas2And reducing substances such as CO and the like reduce metal oxides in the dust mud into metal simple substances, and the pyrolysis liquid is separated by the oil/water separation unit to obtain high-content straight-chain alkane pyrolysis oil, so that the economic value is high. The waste water inside the waste water recovery device is treated by utilizing the active coke, the treated clean water is sent to the washing device for recycling, the invalid active coke generated in the treatment process is sent to the premixing drying device, and the waste water is repeatedly dried, pyrolyzed and activated and then is recycled, so that the water resource is saved, and the environment is protected.
Drawings
FIG. 1 is a schematic flow diagram of an apparatus and a method for preparing a high-content straight-chain alkane product by pyrolysis of modified dust and sludge and oily sludge.
FIG. 2 is an SEM image of a dust and sludge material before and after modification according to the present invention. Wherein, (a) is a scanning electron microscope picture (5000 times) of the dust and mud before modification, (b) is a scanning electron microscope picture (15000 times) of the dust and mud before modification, (c) is a scanning electron microscope picture (5000 times) of the dust and mud after modification, and (d) is a scanning electron microscope picture (15000 times) of the dust and mud after modification.
FIG. 3 is an XRD pattern of the dust and mud material of the present invention before and after modification.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1:
a device and a method for preparing a high-content straight-chain alkane product by pyrolysis of modified dust and sludge compatible oily sludge comprise a crushing and screening device, a washing device, a calcining device, a premixing and drying device, a pyrolysis device, an oil-water separation device, an activation device, a gas recovery device, a gas combustion device, a sorting device and a wastewater treatment device;
the oily sludge selected in the experiment is black brown at normal temperature and accompanied by pungent odor of petroleum gas at the bottom of a certain oil refinery in Panjin, Liaoning province, the water content of the oily sludge is measured by Kaerfei titration, the solid content of the oily sludge is tested by Soxhlet extraction, the oil content is calculated by a differential subtraction method, and the water content, the oil content and the solid content of the oily sludge are respectively 50.98%, 29.60% and 19.42%. The selected dust mud is the dust removed by a gravity dust remover of a certain iron and steel enterprise, and XRF detection results show that the Fe is Fe2O3The content was 70.17%. And (3) putting the dust and mud into a ball mill, crushing for 60min at the rotating speed of 300r/min, screening by using a screen, and selecting the dust and mud with the particle size of 60-100 meshes. Weighing 20g of sieved dust mud, washing the dust mud for 6 times by using deionized water in a vacuum filtration mode, wherein the use amount of the deionized water in each washing is 1000mL, sending wastewater into a wastewater treatment device, feeding the washed dust mud into a calcining device, calcining at 800 ℃ for 4h to obtain modified dust mud, and SEM analysis results (figure 2) of dust mud materials before and after modification show that the smooth surface of the modified dust mud is damaged, the surface is rough, and various irregular groove-shaped and large loose structures are presented. XRD analysis results (figure 3) of the dust and mud materials before and after modification show that the dust and mud materials after modification are clear in phase distribution, good in ferric oxide crystallinity and high in orientation degree. Compared with the prior modification, the modified Fe-Fe alloy has stronger diffraction peaks at the 2 theta of 33.19 degrees and 35.65 degrees, which correspond to Fe2O3The main characteristic peaks of the structure.
Weighing 5g of oily sludge, fully mixing with 0.25g of calcined high-temperature modified dust sludge in a premixing drying device after a homogenizing unit, dehydrating and drying the oily sludge and reducing the viscosity of the oily sludge, sending the mixture of the oily sludge and the dust sludge into a pyrolysis device after the drying stage is finished, wherein the pyrolysis temperature is 500 ℃, and N is used2As carrier gas, the flow rate is 100mL/min, the retention time is 60min, and pyrolysis gas, pyrolysis liquid and pyrolysis slag are obtained. Centrifuging pyrolysis solution with oil/water separator at 3000r/min for 20min, separating, and using CH2Cl2Extracting the pyrolysis oil by using a solvent, and performing rotary evaporation to remove the solvent, wherein the rotary evaporation temperature is 40 ℃, the vacuum degree is 0.02mPa, and the rotary evaporation is considered to be finished when the quality of the residual liquid is not changed.
Taking another 5g of oily sludge, carrying out pyrolysis reaction on the oily sludge and 0.25g of unactivated sludge after a homogenizing unit, wherein the pyrolysis temperature is 500 ℃, and N is used2As carrier gas, the flow rate is 100mL/min, the retention time is 60min, and pyrolysis gas, pyrolysis liquid and pyrolysis slag are obtained. Centrifuging pyrolysis solution with oil/water separator at 3000r/min for 20min, separating, and using CH2Cl2Extracting the pyrolysis oil by using a solvent, and performing rotary evaporation to remove the solvent, wherein the rotary evaporation temperature is 40 ℃, the vacuum degree is 0.02mPa, and the rotary evaporation is considered to be finished when the quality of the residual liquid is not changed.
Taking another 5g of oily sludge, homogenizing in a homogenizing unit, and introducing into a pyrolysis device at 500 deg.C using N2As carrier gas, the flow rate is 100mL/min, the retention time is 60min, and pyrolysis gas, pyrolysis liquid and pyrolysis slag are obtained. Centrifuging pyrolysis solution with oil/water separator at 3000r/min for 20min, separating, and using CH2Cl2Extracting the pyrolysis oil by using a solvent, and performing rotary evaporation to remove the solvent, wherein the rotary evaporation temperature is 40 ℃, the vacuum degree is 0.02mPa, and the rotary evaporation is considered to be finished when the quality of the residual liquid is not changed.
The yield of the oil-containing sludge pyrolysis oil is 33.11 percent, the yield of the pyrolysis residue is 41.84 percent, the yield of pyrolysis gas is 4.31 percent, the conversion rate of petroleum compounds is 62.93 percent, and the pyrolysis oil is subjected to component analysis by using a gas chromatography-mass spectrometer. The oil phase product was diluted in a volume ratio of 1:20 using high purity helium as a carrier gas at a flow rate of 1.2mL/min, equipped with an HP-5MS column (30 m.times.0.25 mm. times.0.25 μm), chromatographically pure dichloromethane as the organic solvent. The adopted temperature-rising program is as follows: keeping at 40 deg.C for 2min, heating to 300 deg.C at a heating rate of 4 deg.C/min, and standing for 5 min. Qualitative compound identification was performed using the NIST05 database. The results showed that the straight chain paraffin content in the pyrolysis oil was 39.08%.
After 0.25g of unactivated dust mud is added, the yield of the pyrolysis oil of the oily sludge is 32.82%, the yield of the pyrolysis residue is 42.02%, the yield of the pyrolysis gas is 4.65%, and the conversion rate of petroleum compounds is 63.02%. The pyrolysis oil was subjected to composition analysis using a gas chromatograph-mass spectrometer. The oil phase product was diluted in a volume ratio of 1:20 using high purity helium as a carrier gas at a flow rate of 1.2mL/min, equipped with an HP-5MS column (30 m.times.0.25 mm. times.0.25 μm), chromatographically pure dichloromethane as the organic solvent. The adopted temperature-rising program is as follows: keeping at 40 deg.C for 2min, heating to 300 deg.C at a heating rate of 4 deg.C/min, and standing for 5 min. Qualitative compound identification was performed using the NIST05 database. The results showed that the straight chain paraffin content in the pyrolysis oil was 39.22%.
After 0.25g of activated dust and sludge are added, the yield of pyrolysis oil of the oily sludge is 37.77%, the yield of pyrolysis slag is 38.69%, the yield of pyrolysis gas is 3.62%, and the conversion rate of petroleum compounds is 69.61%. The pyrolysis oil was subjected to composition analysis using a gas chromatograph-mass spectrometer. The oil phase product was diluted in a volume ratio of 1:20 using high purity helium as a carrier gas at a flow rate of 1.2mL/min, equipped with an HP-5MS column (30 m.times.0.25 mm. times.0.25 μm), chromatographically pure dichloromethane as the organic solvent. The adopted temperature-rising program is as follows: keeping at 40 deg.C for 2min, heating to 300 deg.C at a heating rate of 4 deg.C/min, and standing for 5 min. Qualitative compound identification was performed using the NIST05 database. The results show that the straight chain paraffin content in the pyrolysis oil was 44.52%.
The pyrolysis slag and the pyrolysis gas are jointly sent into an activation device, the activation temperature is 1100 ℃, the residues are prepared into active coke, then the active coke and metal simple substances are separated out through a separation device, part of the active coke is sent into a wastewater treatment unit, the redundant active coke is recovered, the gas at the outlet of the activation device is uniformly recovered through a gas recovery device and then sent into a gas combustion device for combustion, and the heat generated by combustion is reused for a calcining device, a pyrolysis device and the activation device. The waste water inside the waste water recovery device is treated by using active coke, the treated clean water is sent to a washing device for recycling, the invalid active coke generated in the treatment process is sent to a premixing drying device, and the drying, pyrolysis and activation processes are repeated for regeneration and reuse.
Example 2:
5g of oily sludge is weighed, and after a homogenizing unit, the oily sludge is modified with 0.5g of calcined high temperatureFully mixing the oil-containing sludge in a premixing and drying device, dehydrating and drying the oil-containing sludge and reducing the viscosity of the oil-containing sludge, sending the mixture of the oil-containing sludge and the sludge into a pyrolysis device after the drying stage is finished, wherein the pyrolysis temperature is 500 ℃, and N is used2As carrier gas, the flow rate is 100mL/min, the retention time is 60min, and pyrolysis gas, pyrolysis liquid and pyrolysis slag are obtained. Centrifuging pyrolysis solution with oil/water separator at 3000r/min for 20min, separating to remove water, and adding CH2Cl2Extracting the pyrolysis oil by using a solvent, and performing rotary evaporation to remove the solvent, wherein the rotary evaporation temperature is 40 ℃, the vacuum degree is 0.02mPa, and the rotary evaporation is considered to be finished when the quality of the residual liquid is not changed. The yield of pyrolysis oil is 43.55%, the yield of pyrolysis slag is 37.48%, the yield of pyrolysis gas is 2.43%, and the conversion rate of petroleum compounds is 77.31%. The pyrolysis oil was subjected to composition analysis using a gas chromatograph-mass spectrometer. The oil phase product was diluted in a volume ratio of 1:20 using high purity helium as a carrier gas at a flow rate of 1.2mL/min, equipped with an HP-5MS column (30 m.times.0.25 mm. times.0.25 μm), chromatographically pure dichloromethane as the organic solvent. The adopted temperature-rising program is as follows: keeping at 40 deg.C for 2min, heating to 300 deg.C at a heating rate of 4 deg.C/min, and standing for 5 min. Qualitative compound identification was performed using the NIST05 database. The results show that the straight chain paraffin content in the pyrolysis oil was 54.30%.
The pyrolysis slag and the pyrolysis gas are jointly sent into an activation device, the activation temperature is 1100 ℃, the residues are prepared into active coke, then the active coke and metal simple substances are separated out through a separation device, part of the active coke is sent into a wastewater treatment unit, the redundant active coke is recovered, the gas at the outlet of the activation device is uniformly recovered through a gas recovery device and then sent into a gas combustion device for combustion, and the heat generated by combustion is reused for a calcining device, a pyrolysis device and the activation device. The waste water inside the waste water recovery device is treated by using active coke, the treated clean water is sent to a washing device for recycling, the invalid active coke generated in the treatment process is sent to a premixing drying device, and the drying, pyrolysis and activation processes are repeated for regeneration and reuse.
TABLE 1 yield of pyrolysis oil and straight-chain paraffin content obtained in inventive examples 1 and 2
Claims (10)
1. The device for preparing the high-content straight-chain alkane product by low-consumption pyrolysis of the modified dust and sludge compatible with the oily sludge is characterized by comprising a crushing and screening device, a washing device, a calcining device, a premixing and drying device, a pyrolysis device, an oil-water separation device, an activation device, a gas recovery device, a gas combustion device, a sorting device and a wastewater treatment device;
the outlet of the crushing and screening device is communicated with a water washing device;
a liquid phase outlet of the washing device is introduced into the wastewater treatment device, and a solid phase outlet is introduced into the calcining device;
the solid phase outlet of the calcining device is introduced into the premixing and drying device;
the outlet of the premixing drying device is communicated with a pyrolysis device;
a gas phase outlet and a solid phase outlet of the pyrolysis device are both led into the activation device, and a liquid phase outlet is led into the oil-water separation device;
a gas phase outlet of the activation device is introduced into a gas recovery device, and a solid phase outlet is introduced into a sorting device;
the gas phase outlet of the gas recovery device is introduced into the gas combustion device;
an active coke outlet of the sorting device is introduced into a wastewater treatment device;
and a liquid phase outlet of the wastewater treatment device is introduced into the water washing device, and a solid phase outlet is introduced into the premixing drying device.
2. The method for preparing the high-content straight-chain alkane product by low-consumption pyrolysis of the modified dust sludge and the oil-containing sludge is characterized by being realized by the device of claim 1, and comprises the following steps:
(1) the dust and mud are crushed and screened by the crushing and screening device and then are sent into the water washing device, the water washing device is used for removing soluble impurities blocking pore channels on the surface of the dust and mud, wastewater generated in the water washing process is sent into the wastewater treatment device, the dust and mud after being washed are sent into the calcining device and are calcined under the aerobic condition, carbon black, carbonaceous sediments and coking substances mixed in the dust and mud are fully contacted with oxygen at high temperature to generate oxidation reaction and then are removed, the pore channels blocked in the dust and mud are opened, the porosity and the surface activity of the dust and mud are greatly increased, and the orientation degree is high;
(2) the oily sludge and the calcined high-temperature modified dust sludge are fully mixed in a premixing drying device, the calcined high-temperature modified dust sludge plays a role of a thermosetting carrier, self heat is transferred to the oily sludge through heat transfer, the oily sludge is dehydrated and dried, the viscosity of the oily sludge is reduced, after the drying stage is finished, the mixture of the oily sludge and the dust sludge is sent into a pyrolysis device, the volatile component of the oily sludge is subjected to ring-opening reaction to generate a straight-chain alkane product, and simultaneously coke in pyrolysis slag and H in pyrolysis gas are subjected to ring-opening reaction2CO reduces the metal oxide in the dust mud into a metal simple substance; in the process, the mass transfer capacity of the pyrolysis process can be improved and the energy consumption of the pyrolysis process can be greatly reduced due to rich channels in the modified dust and mud, the modified dust and mud has a catalytic effect, the ring-opening reaction of volatile components of the oily sludge is promoted, and a high-content straight-chain alkane product is generated;
(3) the pyrolysis liquid generated in the pyrolysis process passes through an oil-water separation device, water and straight-chain alkane pyrolysis oil are separated and recovered, pyrolysis gas and pyrolysis slag are jointly sent to an activation device, a solid at the outlet of the activation device is separated into a metal simple substance and active coke through a separation device, part of the active coke is sent to a wastewater treatment unit, redundant active coke is recovered, gas at the outlet of the activation device is uniformly recovered through a gas recovery device and then sent to a gas combustion device for combustion, and heat generated by combustion is reused for a calcining device, the pyrolysis device and the activation device;
(4) the waste water inside the waste water recovery device is treated by using active coke, the treated clean water is sent to a washing device for recycling, the invalid active coke generated in the treatment process is sent to a premixing drying device, and the drying, pyrolysis and activation processes are repeated for regeneration and reuse.
3. The method for preparing the product with high content of straight-chain alkane through low consumption pyrolysis of the modified dust and sludge and the oily sludge as claimed in claim 2, wherein the size of the dust and sludge is 60-100 meshes after crushing and screening.
4. The method for preparing the product with high content of straight-chain alkane through low-consumption pyrolysis of the modified dust, mud and oily sludge as claimed in claim 2, wherein the volume ratio of the dust, mud and water cleaned in each time in the water washing device is 1: 10-50, and the washing times are more than 3 times.
5. The method for preparing the product with high content of straight-chain alkane through low consumption pyrolysis of the modified dust sludge and the oil-containing sludge as claimed in claim 2, wherein the calcining temperature of the calcining device is 700-900 ℃, and the calcining time is 3-6 h.
6. The method for preparing the product with high content of straight chain alkane by low consumption pyrolysis of the modified dust and mud and the oily sludge as claimed in claim 2, wherein the mixing ratio of the oily sludge and the calcined high-temperature modified dust and mud is as follows: the high-temperature modified dust and mud accounts for 5-20% of the mass of the oily sludge.
7. The method for preparing the product with high content of straight chain alkane through low consumption pyrolysis of the modified dust and sludge and the oily sludge as claimed in claim 2, wherein the pyrolysis temperature is 400-700 ℃, the pyrolysis time is 30-120 min, the pyrolysis protective gas is nitrogen, and the flow rate is 100-200 mL/min.
8. The method for preparing the product with high content of straight-chain alkane by low consumption pyrolysis of the modified dust and sludge combined with the oily sludge according to claim 2, wherein the oil-water separation device adopts the processes of centrifugation, liquid separation, solvent extraction and rotary evaporation solvent removal; the extractant is CH in solvent extraction2Cl2The rotary evaporation temperature is 40-60 ℃, the vacuum degree is 0.01-0.03 mPa, and the mark of the end of the rotary evaporation indicates that the quality of the residual liquid is not changed; straight chain alkane content in pyrolysis oil40 to 60 percent.
9. The method for preparing the product with high content of straight chain alkane through low consumption pyrolysis of the modified dust, mud and oily sludge as claimed in claim 2, wherein the activation temperature is 800-1200 ℃ and the activation time is 3-6 h.
10. The method for preparing the product with high content of straight-chain alkane through low consumption pyrolysis of the modified dust and sludge combined with the oily sludge as claimed in claim 2, wherein the pyrolysis residue sorting device adopts a gravity sorting process, and utilizes the density difference between the metal simple substance and the pyrolysis residue value to sort out the metal simple substance and the residual residue.
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