Method for upgrading coal tar pitch and oil sludge by co-pyrolysis and carbon black raw material

Abstract

The present application belongs to the technical field of energy products, and particularly relates to a method for upgrading coal pitch and oil sludge by co-pyrolysis and a carbon black raw material, comprising the following steps: S1, pre-degradation: degrading organic alkali, thick oil ester, inorganic heavy metal ions and fillers in the oil sludge by actinomycetes and bacillus; the classification name of the bacillus is Bacillus arthriticus, the preservation address is China Center for Type Culture Collection, and the preservation number is CCTCC NO: M20232038; S2, co-pyrolysis: co-pyrolyzing the oil sludge after pre-degradation in step S1 under oxygen-rich fuel gas and carbon black tail gas CO2 and coal pitch, and obtaining a derivative. Through pre-degradation, co-pyrolysis, fractional distillation or reaction rectification, the utilization rate of oil product resources of the waste oil sludge is 85-90%, and the remaining 10-15% is used as filler carbon black.

Description

Technical Field

[0001] The invention belongs to the technical field of energy products, and specifically relates to a method for co-pyrolysis and upgrading of coal tar pitch and oil sludge, and a carbon black raw material. Background Art

[0002] Lignite humic acid is used as an oilfield additive in oil drilling. Therefore, the waste sludge from the mining site contains organic pollutants such as heavy oil and polycyclic aromatic hydrocarbons, as well as soluble inorganic salts such as Cl - , SO4, Na+ and Ca 2+ Etc. Using immobilized microbial technology for oil recovery and utilizing chemical or physical means to treat contaminated sludge in situ is one of the ways to alleviate waste sludge pollution.

[0003] Ren Lijun et al. from Tianjin University of Science and Technology isolated three strains of petroleum hydrocarbon-degrading bacteria from oily sludge in Bohai Oilfield and identified them as Corynebacterium, Brevibacterium and Pseudomonas through 16S rRNA gene sequence. The single factor experiment determined that the degradation rates of total petroleum hydrocarbons in oily sludge at 37°C, salinity 1-3%, pH 6-8; 32°C and 30 days were 39.69% and 53.29%, respectively. The degradation effect of mixed bacteria was significantly higher than that of single strain, with a degradation rate of 58.08%. GC-MS analysis showed that mixed bacteria had significant degradation of n-C12 ~ n-C34 normal alkanes, and had strong degradation ability for polycyclic aromatic hydrocarbons such as naphthalene, acenaphthene, chrysene and benzofluoranthene (Ren Lijun, Liu Xianbin, Tian Shengyan, Isolation of petroleum-degrading bacteria from oily sludge and their degradation characteristics. Journal of Environmental Engineering, 2015, 9(7): 3538-3544. However, there are limitations on the raw materials of oily sludge and the degradation of organic matter such as petroleum polycyclic aromatic hydrocarbons, and the degradation of inorganic heavy metal compounds in drilling mud oil sludge is not involved.

[0004] The utility model patent with patent application number CN207552228 discloses a device for making carbon black from oil sludge, which can utilize oil and combustion materials to prevent oil sludge from polluting the environment, but does not have any process or parameters.

[0005] Yu Yinguo of Jiangsu Guoruite Environmental Engineering Technology Co., Ltd. believes that the conventional waste pyrolysis process for oil sludge treatment not only has a huge investment cost in kerosene and fuel, but also produces harmful fly ash and particulate pollutants containing dioxins and other substances during the pyrolysis process. The treatment of oil sludge can be improved from both environmental and economic aspects by replacing the equipment of the pyrolysis furnace or improving the process (Research and Application of Low-temperature Pyrolysis Treatment Technology of Oil Sludge Solid Waste [J]. Engineering Technology, 2022 (2): 248-251). It is currently in the process of proposal and exploration, and does not involve high-condensate oil sludge. Summary of the invention

[0008] In view of the above technical problems, on the one hand, the purpose of the present invention is to provide a method for co-pyrolysis and upgrading of coal tar and oil sludge, which utilizes the properties of actinomycetes that can reduce salt, alkali and other inorganic heavy metal compounds, and the property of Bacillus aeruginosa that can convert inorganic silicon into organic silicon, to treat drilling mud sludge, and to reduce the coal tar and oil sludge by co-pyrolysis and upgrading; on the other hand, the purpose of the present invention is to provide a carbon black raw material.

[0009] In order to solve the above technical problems, the technical solution adopted by the present invention is: A method for co-pyrolysis and upgrading of coal tar pitch and oil sludge, comprising the following steps: S1. Pre-degradation: Degradation of organic alkali, heavy oil esters, inorganic heavy metal ions and fillers in oil sludge by actinomycetes and Bacillus; The classification name of the Bacillus is Bacillus altei, the deposit address is China Center for Type Culture Collection, the deposit number is CCTCC NO: M20232038, and the deposit date is October 25, 2023; S2, co-pyrolysis: the oil sludge pre-degraded in step S1 is co-pyrolyzed with coal tar in the presence of oxygen-rich fuel gas and carbon black tail gas CO2 to obtain a derivative.

[0010] Preferably, in step S1, the actinomycetes are subjected to 16S rDNA fragment amplification optimization.

[0011] Preferably, in step S1, under the action of actinomycetes and Bacillus aeruginosa, at a CFU of 1.0 / kg of oil sludge, at a temperature of 10-40°C, a pH of 7.0-10.0, and a time of 40-60 min, the hydrophilic hydroxyl group (-OH) thereof converts the -SiO2 wrapped in the filler into Si(OR)4+H2O; In the step S2, the organic base and the heavy oil ester are chimeric and modified by reacting the oxygen-rich fuel gas and the carbon black tail gas CO2.

[0012] Preferably, in step S1, trace amounts of miscellaneous salts in the oil sludge can be used as a culture medium for actinomycetes and Bacillus agglomerans, wherein the mass percentages are as follows: chloride ion 0.02%, sulfate ion, sodium ion 0.10%, calcium ion 0.05%, and the actinomycete recycling phase is transferred to the non-oil phase during the culture.

[0013] Preferably, in step S2, the derivatives obtained by pyrolysis include "straight-chain alkanoic acid" derivatives, "straight-chain oleamide" derivatives and "benzonaphthalene" derivatives.

[0014] Preferably, in step S2, the mass ratio of oil sludge to coal tar is 2:1, and the ratio of straight-chain hydrocarbons to aromatic hydrocarbons in the product is 1.5:1, which is a high-quality ink carbon black raw material with a DBP absorption value of 125-130 cm / 100g.

[0015] A printing ink carbon black raw material can be prepared by co-pyrolysis of coal tar and oil sludge according to the above-mentioned method for co-pyrolysis and upgrading, and then purification through a fractionation tower.

[0016] A conductive carbon black raw material is co-pyrolyzed according to the above-mentioned method for co-pyrolysis and upgrading of coal tar pitch and oil sludge, and then further purified in a reactive distillation tower to obtain a conductive carbon black raw material for high-voltage submarine cable shielding material.

[0017] Compared with the prior art, the present invention has the following beneficial effects: It is first degraded under the action of actinomycetes and Bacillus aggregati; it is co-pyrolyzed with coal tar in the presence of oxygen-rich carbon black exhaust CO2, and "straight-chain alkanoic acid" and "straight-chain oleamide" derivatives, as well as "benzonaphthalene" derivatives, are formed.

[0018] The production system of coal tar carbon black has been improved and utilized. The co-pyrolysis quality improvement technology has been used to improve the quality of ink carbon black to meet the quality requirements of conductive carbon black used in semi-conductive shielding materials for high-voltage cables. The oxygen-rich fuel and carbon black tail gas CO2 are effectively adjusted to improve the quality of sludge, save energy and reduce emissions, and increase the economy of by-product filler carbon black.

[0019] The mass ratio of oil sludge to coal tar is 2:1, and the ratio of straight-chain hydrocarbons to aromatic hydrocarbons in the product is 1.5:1. It is a high-quality carbon black raw material for ink, and the DBP absorption value is 125-130cm / 100g.

[0020] After further purification in a reactive distillation tower, the conductive carbon black raw material for high-voltage submarine cable shielding material is produced, with a pH value (according to GB / T 3780.7 standard) of 7.0-8.0, oil absorption value-DBP absorption value (according to GB / T 3780 standard) of 138-148 cm / 100g, ash content (according to GB / T3780.10 standard) <0.1%, volume resistivity (according to JB / T 10738, GB / T3048.3 standard) 2.6-3.0Ω·cm, particle size 30-40nm, 325 mesh sieve residue content <6ppm, reaching the quality of conductive carbon black raw material for high-voltage submarine cable shielding material.

[0021] Through pre-degradation, co-pyrolysis, fractionation or reactive distillation, the utilization rate of oil resources in waste sludge is 85-90%, and the remaining 10-15% is used as filler carbon black. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1It is a schematic diagram of the operation flow of the process equipment of the present invention; Figure 2 This is a GC-MS representation of the co-pyrolysis product "straight-chain alkanoic acid" derivative of the present invention; Figure 3 This is a GC-MS representation of the co-pyrolysis product "straight-chain oleamide" derivative of the present invention; Figure 4 This is a GC-MS representation of the co-pyrolysis product "benzonaphthalene" derivative of the present invention; Among them: 1 is carbon black tail gas, 2 is nitrogen, 3 is waste oil sludge, 4 is a fractionation or reactive distillation tower, 5 is a pyrolysis furnace, 6 is a dust collector, 7 is oxygen-enriched fuel gas control, 8 is a condenser, 9 is a compressor, and 10 is recyclable CO2. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments.

[0024] A method for co-pyrolysis and upgrading of coal tar pitch and oil sludge, comprising the following steps: S1. Organic alkali, heavy oil esters, heavy metal ions, etc. in oil sludge are first degraded under the action of actinomycetes and Bacillus; S2, when co-pyrolyzed with coal tar pitch in the presence of oxygen-rich carbon black tail gas CO2, "straight-chain alkanoic acid", "straight-chain oleamide" derivatives are formed, as well as "benzonaphthalene" derivatives (such as Figure 2-4 as shown).

[0025] Specifically: The actinomycetes that degrade organic alkali, heavy oil esters, and inorganic heavy metal ions in oil sludge were optimized for 16SrDNA fragment amplification. The classification name of Bacillus is Bacillus agnesiensis, the preservation address is China Center for Type Culture Collection, the preservation number is CCTCC NO: M20232038, and the preservation date is October 25, 2023.

[0026] Through this method, the utilization rate of oil resources in waste sludge can be increased to 85-90% (the remaining 10-15% is used as filler carbon black). After purification in a distillation tower, it can be made into high-quality ink carbon black raw materials, and by further purification in a reactive distillation tower for conductive carbon black raw materials, the quality of conductive carbon black raw materials for high-voltage submarine cable shielding materials can be achieved.

[0027] like Figure 1 As shown, the process equipment used mainly includes a fractionation or reactive distillation tower 4, a pyrolysis furnace 5 (which regularly removes usable carbon black particles), a dust collector 6, a condenser 8 and a compressor 9. 1 and 2 are the inlet and outlet of carbon black tail gas and nitrogen; 3 is the inlet of waste oil sludge (which has been acted on by actinomycetes and bacillus), and 10 is the transport of recyclable CO2.

[0028] For further elaboration, the following embodiments are listed for illustration.

[0029] Embodiment 1: In this embodiment, 100 parts of used lignite humic acid drilling mud waste oil sludge and coal tar pitch, including 65 parts of water-containing thick oil, 2 parts of kaolin and heavy metal compounds, 2 parts of actinomycetes with a water content of 95% and 1 part of Bacillus arnoldii (preservation number: 20232038) were used at a temperature of 30°C, pH 7.0, and the reaction time was 35 minutes. -1 , Ca 2+ ,SO4 2+ The oil was transferred to the non-oil phase actinomycetes and Bacillus aggregatifolia layer, and then pyrolyzed with 30 parts of coal tar containing polycyclic aromatic hydrocarbons (PAHs) at 500°C by oxygen-rich fuel gas and CO2 tail gas to form "straight-chain alkanoic acid", "straight-chain oleamide" derivatives, and "benzonaphthalene" derivatives. After purification by a fractionating tower, the utilization rate of waste sludge oil resources was 87%. As a raw material for ink carbon black, the DBP absorption value was 125cm / 100g. When added to the coating, it can improve the covering, weather resistance and corrosion resistance of the coating, and produce 15% filler carbon black by-product. Embodiment 2: In this embodiment, 100 parts of used lignite humic acid drilling mud waste oil sludge and coal tar pitch, including 65 parts of water-containing thick oil, 2 parts of kaolin and heavy metal compounds, 2 parts of actinomycetes with a water content of 95% and 1 part of Bacillus arnoldii (preservation number: 20232038) were used at a concentration of U1.0 / kg oil sludge, at a temperature of 35°C, pH 7.5, and for 50 minutes, to react with Cl -1 , Ca 2+ ,SO4 2+ Then, it is transferred to the non-oil phase actinomycetes and Bacillus aggregatifolia layer, and then co-pyrolyzed with 30 parts of coal tar containing polycyclic aromatic hydrocarbons (PAHs) at 550°C, regulated by oxygen-rich fuel gas and CO2 tail gas, to form "straight-chain alkanoic acid", "straight-chain oleamide" derivatives, as well as "benzonaphthalene" derivatives, etc. After purification by a distillation tower, the utilization rate of the oil resources of the waste sludge is 90%. As a raw material for ink carbon black, the DBP absorption value is 130cm / 100g, and 10% filler carbon black is also produced as a by-product.

[0030] Embodiment three: In this embodiment, 100 parts of used lignite humic acid drilling mud waste oil sludge and coal tar pitch, including 65 parts of water-containing thick oil, 2 parts of kaolin and heavy metal compounds, 2 parts of actinomycetes with a water content of 95% and 1 part of Bacillus arnoldii (preservation number: 20232038) were used at a concentration of U1.0 / kg oil sludge, at a temperature of 40°C, pH 8.0, and for 40 minutes, Cl -1, Ca 2+ ,SO4 2+ and the like are transferred to the non-oil phase actinomycetes and Bacillus arnoldii layer, and then co-pyrolyzed with 30 parts of coal tar containing polycyclic aromatic hydrocarbons (PAHs) at 550°C, regulated by oxygen-rich fuel gas and CO2 tail gas, to form "straight-chain alkanoic acid", "straight-chain oleamide" derivatives, as well as "benzonaphthalene" derivatives, etc. The co-pyrolysis oil is further purified in a reactive distillation tower, with pH 8.0, oil absorption value - DBP absorption value of 146 cm / 100g, particle size of 38nm, ash content <0.1%, resistivity of 3.0Ω·cm, 325 mesh sieve residue content <6ppm, reaching the quality of conductive carbon black raw material for high-voltage submarine cable shielding materials; the oil utilization rate is 85%, and the remaining 15% is used as filler carbon black.

[0031] Only the preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments.

Claims

1. A method for co-pyrolysis and upgrading of coal tar pitch and oil sludge, characterized in that: The following steps are involved: S1. Pre-degradation: Degradation of organic alkali, heavy oil esters, inorganic heavy metal ions and fillers in oil sludge by actinomycetes and Bacillus; The classification name of the Bacillus is Bacillus altei, the deposit address is China Center for Type Culture Collection, the deposit number is CCTCC NO: M20232038, and the deposit date is October 25, 2023; S2, co-pyrolysis: the oil sludge pre-degraded in step S1 is co-pyrolyzed with coal tar in the presence of oxygen-rich fuel gas and carbon black tail gas CO2 to obtain a derivative.

2. The method for co-pyrolysis and upgrading of coal tar pitch and oil sludge according to claim 1, characterized in that: In the step S1, the actinomycetes were optimized for 16S rDNA fragment amplification.

3. The method for co-pyrolysis and upgrading of coal tar pitch and oil sludge according to claim 1, characterized in that: In the step S1, under the action of actinomycetes and Bacillus alfa, at a CFU of 1.0 / kg of oil sludge, at a temperature of 10-40°C, a pH of 7.0-10.0, and a time of 40-60 minutes, the hydrophilic hydroxyl group (-OH) of the actinomycetes and Bacillus alfa converts the -SiO2 wrapped in the filler into Si(OR)4+H2O; In the step S2, the organic base and the heavy oil ester are chimeric and modified by reacting the oxygen-rich fuel gas and the carbon black tail gas CO2.

4. The method for co-pyrolysis and upgrading of coal tar pitch and oil sludge according to claim 1, characterized in that: In step S1, trace amounts of miscellaneous salts in the oil sludge can be used as a culture medium for actinomycetes and Bacillus agglomerans, wherein the mass percentages are as follows: 0.02% chloride ion, 0.10% sulfate ion and sodium ion, and 0.05% calcium ion, and the actinomycete recycling phase is transferred to the non-oil phase during the culture.

5. The method for co-pyrolysis and upgrading of coal tar pitch and oil sludge according to claim 1, characterized in that: In step S2, the derivatives obtained by pyrolysis include "straight-chain alkanoic acid" derivatives, "straight-chain oleamide" derivatives and "benzonaphthalene" derivatives.

6. The method for co-pyrolysis and upgrading of coal tar pitch and oil sludge according to claim 1, characterized in that: In step S2, the mass ratio of oil sludge to coal tar is 2:1, and the ratio of straight-chain hydrocarbons to aromatic hydrocarbons in the product is 1.5:1, which is a high-quality ink carbon black raw material with a DBP absorption value of 125-130 cm / 100g.

7. A carbon black raw material for ink, characterized in that: According to the method for co-pyrolysis and upgrading of coal tar pitch and oil sludge as claimed in any one of claims 1 to 7, after co-pyrolysis, the raw material for printing ink carbon black can be prepared by purification in a fractionating tower.

8. A conductive carbon black raw material, characterized in that: According to the method for co-pyrolysis and upgrading of coal tar pitch and oil sludge according to any one of claims 1 to 7, after co-pyrolysis, further purification is carried out in a reactive distillation tower to obtain a conductive carbon black raw material for high-voltage submarine cable shielding material.

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