CN113801708B - Hazardous waste high-doping-ratio coal water slurry and preparation method thereof - Google Patents

Hazardous waste high-doping-ratio coal water slurry and preparation method thereof Download PDF

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CN113801708B
CN113801708B CN202111074586.2A CN202111074586A CN113801708B CN 113801708 B CN113801708 B CN 113801708B CN 202111074586 A CN202111074586 A CN 202111074586A CN 113801708 B CN113801708 B CN 113801708B
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slurry
coal
parts
hazardous waste
waste
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CN113801708A (en
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马国保
贺帅
孙宁
佘艳
黄河
周志江
周晴
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Fanjing New Energy Technology Zhejiang Co ltd
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Fanjing New Energy Technology Zhejiang Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/326—Coal-water suspensions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/28—Cutting, disintegrating, shredding or grinding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/34—Applying ultrasonic energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The invention discloses hazardous waste high-doping-ratio water-coal-slurry and a preparation method thereof, wherein the water-coal-slurry is prepared by mixing wet-milling coal slurry and hazardous waste organic synthesis slurry; the components of the wet-milled coal slurry comprise the following components in parts by weight: 235-245 parts of coal powder and 40-45 parts of water; the hazardous waste organic synthetic pulp comprises the following components: 25-35 parts of paint slag, 20-25 parts of oily sludge, 15-20 parts of clay oil sludge, 10-15 parts of waste activated carbon and 80-90 parts of water. The preparation method comprises the following steps: mixing and grading pulverized coal and water, and performing ball milling to obtain wet-milled coal slurry; paint slag, oil-containing sludge, clay oil sludge, waste activated carbon and water are mixed and stirred uniformly to obtain hazardous waste organic synthetic pulp; and mixing the wet-milled coal slurry and the hazardous waste organic synthesis slurry, uniformly stirring and ball-milling to obtain the hazardous waste high-doping-ratio coal water slurry. The invention mixes and matches different dangerous wastes and changes the grinding ball grading mode in the preparation process to prepare the coal water slurry with high mixing ratio, high stability and high fluidity.

Description

Hazardous waste high-doping-ratio coal water slurry and preparation method thereof
Technical Field
The invention relates to the technical field of hazardous waste treatment, in particular to hazardous waste high-doping-ratio coal water slurry and a preparation method thereof.
Background
Hazardous waste refers to waste having various toxic, flammable, explosive, corrosive, chemical reactivity and infectivity characteristics, as set forth in the national hazardous waste list or recognized according to the national hazardous waste identification standards and methods. Hazardous waste is of a wide variety and complex composition, with potential and delayed contamination. With the continuous and rapid development of economy in China and the continuous improvement of the living standard of people, the requirements of people on safety and environmental protection are more urgent than ever before, and the safe treatment and disposal of hazardous wastes is the only way for eliminating the harmfulness of the hazardous wastes. National laws and regulations and related policies have strongly encouraged resource recycling, such as the clear requirement of the environmental protection law of solid waste pollution on the full recovery and reasonable utilization of solid waste. The different types of hazardous wastes contain a plurality of components with utilization values, and if the hazardous wastes can be recycled and comprehensively utilized through reasonable and environment-friendly measures, the treatment pressure of the hazardous wastes can be reduced, the wastes can be changed into valuable materials, and objective economic benefits can be obtained.
After the hazardous waste and the coal are mixed to prepare the coal water slurry, the hazardous waste and the coal are subjected to cooperative treatment by using a coal water slurry gasification furnace, and carbon and hydrogen elements in the hazardous waste can be changed into CO and H 2 And the hazardous substances in the hazardous waste are decomposed or solidified into the glassy state slag by using useful gases, so that the hazardous waste treatment is thoroughly cleaned and the resource utilization is maximized, and the method is a brand-new waste treatment mode which is environment-friendly, energy-saving and capable of changing waste into valuables. For example, in the publication of "a coal water slurry of gasified coal blended with petrochemical waste and a pulping process thereof" disclosed in the chinese patent document, the publication No. CN106433822B includes coal, petrochemical waste, additives and water, wherein the petrochemical waste accounts for 0-6% but not zero of the total mass of the coal water slurry, and the additive amount is 0-1.5% but not zero of the total mass of dry coal.
However, in the existing hazardous waste pulping technology, because the addition of hazardous waste can affect the dispersibility and fluidity of the coal water slurry and can also reduce the concentration of the coal slurry, the mixing ratio of the hazardous waste in the coal water slurry is generally lower, the improvement of the mixing ratio of the hazardous waste can cause the poor fluidity, stability and combustion performance of the coal water slurry, seriously restrict the treatment effect and increase the risk of unstable project operation.
Disclosure of Invention
The invention provides hazardous waste high-doping-ratio water-coal-slurry and a preparation method thereof, aiming at overcoming the problems that in the existing hazardous waste pulping technology, the doping ratio of hazardous waste in the water-coal-slurry is generally lower, the mobility, stability and combustion performance of the water-coal-slurry are poor due to the increase of the doping ratio of the hazardous waste, and the treatment effect is seriously restricted.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthetic slurry in a mass ratio of 275-290: 150-185; the components of the wet-milling coal slurry comprise the following components in parts by weight: 235-245 parts of coal powder and 40-45 parts of water; the hazardous waste organic synthesis slurry comprises the following components: 25-35 parts of paint slag, 20-25 parts of oily sludge, 15-20 parts of clay oil sludge, 10-15 parts of waste activated carbon and 80-90 parts of water.
In the hazardous waste organic synthetic pulp, paint slag belongs to HW12 waste in national hazardous waste entry, and contains a large amount of aromatic hydrocarbon and benzene substances; the oil-containing sludge and the clay oil sludge belong to HW08 waste in a hazardous waste directory, the clay has larger specific surface area and pore volume and stronger decolorization capacity and activity, is used for adsorbing unsaturated hydrocarbon substances of petroleum minerals in the petroleum industry and is commonly used for refining in the process of producing lubricating oil, base oil and the like, and the clay adsorbing the unsaturated hydrocarbon substances forms a filter cake, namely the clay oil sludge after being filtered; the oil-containing sludge and the clay oil sludge contain a large amount of benzene series, phenolic substances and the like; the activated carbon has good adsorption performance, can be applied to various fields for adsorbing various pollutants, and the hazardous waste types related to the waste activated carbon after adsorption comprise HW04, HW05, HW06, HW12, HW13, HW18, HW39, HW45, HW49 and the like.
Because the addition of dangerous wastes such as paint slag, oily sludge, clay oil sludge and the like generally causes the viscosity of the coal water slurry to be increased, the slurry concentration to be reduced and the stability to be reduced, the mixing ratio of the dangerous wastes in the coal water slurry is generally about 10 percent, and the coal water slurry can be ensured to have the slurry concentration, the fluidity and the stability which meet the requirements; according to the research of the invention, the hazardous waste organic synthetic slurry is prepared by compounding the hazardous waste organic synthetic slurry containing paint slag, oily sludge, clay oil sludge and waste activated carbon, and then the hazardous waste organic synthetic slurry is mixed with wet-milled coal slurry to prepare the coal water slurry, so that the effective components in the hazardous wastes can be fully utilized, the compatibility and coupling action are formed among the hazardous wastes, the influence of the addition of the hazardous wastes on the performance of the coal water slurry is reduced, the doping ratio of the hazardous wastes in the coal water slurry can be increased to about 20%, the adding proportion of the hazardous wastes in the coal water slurry is greatly increased on the premise of ensuring the concentration and stability of the coal water slurry, the use of coal resources is reduced, and the resource utilization and harmless treatment of the hazardous wastes are realized. Meanwhile, the adding proportion of each hazardous waste is controlled according to the property of each hazardous waste, so that the heat value of the prepared coal water slurry is ensured, and the obtained coal water slurry has good stability, high solid content, good fluidity and good combustion performance, and is beneficial to subsequent utilization.
Preferably, the water in the wet-milled coal slurry is formaldehyde wastewater; the water in the hazardous waste organic synthesis pulp comprises waste acid, sulfite process pulp waste liquid and waste organic solvent.
Preferably, the waste acid is waste sulfuric acid; the waste organic solvent is selected from one or more of acetone, ethyl acetate, butyl acetate and n-hexane; the mass ratio of the waste acid to the sulfite process pulp waste liquid to the waste organic solvent is 1-3: 4-5.
Preferably, the waste activated carbon is waste activated carbon adsorbing VOCs, formaldehyde and benzene-containing waste gas.
When the wet-milling coal slurry and the hazardous waste organic synthetic slurry are prepared, liquid wastes such as formaldehyde wastewater, waste acid (HW34), sulfite process paper pulp waste liquid, waste organic solvent (HW06) and the like are compounded with coal and solid and semi-solid hazardous wastes, so that the consumption of clean water can be reduced, and the resource utilization of the wastes is realized. Meanwhile, in the hazardous waste organic synthesis slurry, aromatic hydrocarbons and benzene substances in paint residues, benzene series substances and phenolic substances in oil-containing sludge and clay oil sludge and the like can be subjected to sulfonation reaction with sulfuric acid in waste acid and sulfite in sulfite process paper pulp waste liquid, then are mixed with wet-milled coal slurry and then are condensed with formaldehyde in formaldehyde waste water, and the obtained sulfonated aromatic hydrocarbon formaldehyde condensate can play a role of a dispersing agent and a stabilizing agent in the coal water slurry. And in addition, the sulfite pulp waste liquid also contains a certain amount of lignosulfonate, and the lignosulfonate can be dehydrated with sulfonic acid groups in the generated sulfonated aromatic hydrocarbon formaldehyde condensate under an acidic condition, so that lignosulfonate is introduced to the sulfonated aromatic hydrocarbon formaldehyde condensate to serve as a branched chain, and the dispersion stability of the coal water slurry can be further improved through the steric hindrance effect of the long side chain of the grafted lignosulfonate. Therefore, the high-risk waste mixing ratio coal water slurry with good stability can be obtained under the condition of not adding an additive by compounding the components.
The invention also provides a preparation method of the hazardous waste high-doping-ratio coal water slurry, which comprises the following steps:
(1) mixing and ball-milling coal powder and water to obtain wet-milled coal slurry, wherein the step of ball-milling adopts grading ball milling of large balls with the diameter of 1.3-1.5 cm and medium balls with the diameter of 0.8-1.0 cm, and the number ratio of the large balls to the medium balls is 25-30: 35-40;
(2) paint slag, oil-containing sludge, clay oil sludge, waste activated carbon and water are mixed and stirred uniformly to obtain hazardous waste organic synthetic pulp;
(3) and mixing the wet-milled coal slurry and the hazardous waste organic synthesis slurry, uniformly stirring and ball-milling to obtain the hazardous waste high-doping-ratio coal water slurry.
In the process of preparing the wet-milling coal slurry, the invention adopts the large balls and the medium balls with different diameters to carry out grading ball milling, and enlarges the particle size range of the coal powder distribution in the wet-milling coal slurry by selecting a proper grading mode, so that the hazardous waste particles can fully fill the gaps among the coal powder after being mixed with the hazardous waste organic synthetic slurry, thereby adding the hazardous waste to the maximum extent and ensuring that the concentration of the finally synthesized coal water slurry meets the production requirement.
Preferably, the mass ratio of the material balls in the ball milling in the step (1) is 500: 620-630.
Preferably, the coal powder in the step (1) is sieved by a sieve of 10-20 meshes, and then is mixed with water for ball milling, wherein the ball milling time is 10-20 min.
Preferably, in the step (2), the stirring temperature is 80-100 ℃, and the stirring time is 1-2 h.
Preferably, the ultrasonic dispersion is performed while mixing and stirring in step (2). The method carries out ultrasonic dispersion in the process of preparing the hazardous waste organic synthesis slurry, and the organic solvent can desorb oil adsorbed in the argil under the assistance of ultrasonic waves, regenerate pore channels on the surface of the argil and recover the activity of the argil, so that the argil can play a role of a solid acid catalyst under the action of waste acid to catalyze the condensation of sulfonated aromatic hydrocarbon and formaldehyde, promote the generation of a sulfonated aromatic hydrocarbon formaldehyde condensate dispersant and be beneficial to improving the dispersibility and stability of the coal water slurry.
Preferably, the ultrasonic frequency is 40-80 kHz.
Preferably, the stirring temperature in the step (3) is 90-110 ℃, and the stirring time is 2-3 h; the ball milling time is 5-10 min.
Therefore, the invention has the following beneficial effects:
(1) the effective components in the hazardous wastes are fully utilized, so that compatibility and coupling effects are formed among the hazardous wastes, the influence of the addition of the hazardous wastes on the performance of the coal water slurry is reduced, the doping ratio of the hazardous wastes in the coal water slurry can be improved from 10% to about 20%, the adding proportion of the hazardous wastes in the coal water slurry is greatly improved on the premise of ensuring the concentration and stability of the coal water slurry, the use of coal resources is reduced, and the resource utilization and harmless treatment of the hazardous wastes are realized;
(2) in the process of preparing the wet-milling coal slurry, large balls and medium balls with different diameters are adopted for grading ball milling, and the particle size range of the coal dust distribution in the wet-milling coal slurry is expanded by selecting a proper grading mode, so that the hazardous waste particles mixed with the hazardous waste organic synthesis slurry can fully fill gaps among the coal dust, and the hazardous waste can be added to the maximum extent;
(3) through the compounding of the components, the high-risk waste mixing ratio coal water slurry with good stability can be obtained under the condition of not adding an additive.
Detailed Description
The invention is further described with reference to specific embodiments.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified. The raw material coal used in the examples of the present invention was nakedful coal.
Example 1:
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 282: 171; the components of the wet-milled coal slurry comprise the following components in parts by weight: 240 parts of coal powder and 42 parts of formaldehyde wastewater; the hazardous waste organic synthetic pulp comprises the following components: 30 parts of paint slag, 23 parts of middle-sea oil oily sludge, 18 parts of clay oil sludge, 15 parts of waste activated carbon adsorbing VOCs, 20 parts of waste sulfuric acid, 20 parts of sulfite process pulp waste liquid and 45 parts of waste acetone.
The preparation method of the hazardous waste high-doping-ratio coal water slurry comprises the following steps:
(1) crushing raw material coal and sieving the crushed raw material coal by a sieve of 10 meshes to obtain coal powder, adding the coal powder and formaldehyde wastewater into a ball mill in proportion, and mixing and ball-milling for 15min to obtain wet-milled coal slurry; the ball milling adopts the grading ball milling of large balls with the diameter of 1.5cm and medium balls with the diameter of 1.0cm, the number ratio of the large balls to the medium balls is 27:36, and the mass ratio of the material balls during ball milling is 500: 625;
(2) crushing the waste activated carbon, sieving the crushed waste activated carbon by a 40-mesh sieve, mixing paint slag, oily sludge, clay oil sludge and the waste activated carbon with waste sulfuric acid, sulfite pulp waste liquid and waste acetone according to a ratio, stirring the mixture at 90 ℃ for 1.5 hours, and simultaneously performing ultrasonic dispersion at an ultrasonic frequency of 60kHz to obtain hazardous waste organic synthetic pulp;
(3) and mixing the wet-milled coal slurry and the hazardous waste organic synthesis slurry, stirring for 2.5h at 100 ℃, and then performing ball milling for 8min to obtain the hazardous waste high-doping-ratio coal water slurry.
Example 2:
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 275: 150; the components of the wet-milled coal slurry comprise the following components in parts by weight: coal powder 235 and 40 parts of formaldehyde wastewater; the hazardous waste organic synthetic pulp comprises the following components: 25 parts of paint slag, 20 parts of middle-sea oil oily sludge, 15 parts of clay oil sludge, 10 parts of waste activated carbon adsorbing formaldehyde, 10 parts of waste sulfuric acid, 30 parts of sulfite process pulp waste liquid and 40 parts of waste ethyl acetate.
The preparation method of the hazardous waste high-doping-ratio coal water slurry comprises the following steps:
(1) crushing raw material coal and sieving the crushed raw material coal by a 20-mesh sieve to obtain coal powder, adding the coal powder and formaldehyde wastewater into a ball mill in proportion, and mixing and ball-milling for 10min to obtain wet-milled coal slurry; the ball milling method comprises the steps of performing grading ball milling on large balls with the diameter of 1.3cm and medium balls with the diameter of 0.8cm, wherein the number ratio of the large balls to the medium balls is 25:40, and the mass ratio of material balls during ball milling is 500: 620;
(2) crushing the waste activated carbon, sieving the crushed waste activated carbon by a 60-mesh sieve, mixing paint slag, oily sludge, clay oil sludge and the waste activated carbon with waste sulfuric acid, sulfite pulp waste liquid and waste ethyl acetate according to a ratio, stirring for 2 hours at 80 ℃, and simultaneously performing ultrasonic dispersion at an ultrasonic frequency of 40kHz to obtain hazardous waste organic synthetic pulp;
(3) and mixing the wet-milled coal slurry and the hazardous waste organic synthesis slurry, stirring for 3h at 90 ℃, and then performing ball milling for 5min to obtain the hazardous waste high-doping-ratio coal water slurry.
Example 3:
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 290: 185; the components of the wet-milled coal slurry comprise the following components in parts by weight: coal powder 245 and 45 parts of formaldehyde wastewater; the hazardous waste organic synthetic pulp comprises the following components: 35 parts of paint slag, 25 parts of middle-sea oil oily sludge, 20 parts of clay oil sludge, 15 parts of waste activated carbon adsorbing formaldehyde, 30 parts of waste sulfuric acid, 10 parts of sulfite process pulp waste liquid and 50 parts of waste acetone.
The preparation method of the hazardous waste high-doping-ratio coal water slurry comprises the following steps:
(1) crushing raw material coal and sieving the crushed raw material coal by a sieve of 10 meshes to obtain coal powder, adding the coal powder and formaldehyde wastewater into a ball mill in proportion, and mixing and ball-milling for 20min to obtain wet-milled coal slurry; the ball milling adopts the grading ball milling of large balls with the diameter of 1.5cm and medium balls with the diameter of 1.0cm, the number ratio of the large balls to the medium balls is 30:35, and the mass ratio of the material balls during ball milling is 500: 630;
(2) crushing the waste activated carbon, sieving the crushed waste activated carbon by a 40-mesh sieve, mixing paint slag, oily sludge, clay oil sludge and the waste activated carbon with waste sulfuric acid, sulfite pulp waste liquid and waste ethyl acetate according to a ratio, stirring for 1 hour at 100 ℃, and simultaneously performing ultrasonic dispersion at an ultrasonic frequency of 80kHz to obtain hazardous waste organic synthetic pulp;
(3) and mixing the wet-milled coal slurry and the hazardous waste organic synthesis slurry, stirring for 2h at 110 ℃, and then performing ball milling for 10min to obtain the hazardous waste high-doping-ratio coal water slurry.
Example 4:
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 282: 171; the components of the wet-milled coal slurry comprise the following components in parts by weight: 240 parts of coal powder and 42 parts of water; the hazardous waste organic synthetic pulp comprises the following components: 30 parts of paint slag, 23 parts of oily sludge of the middle-sea oil, 18 parts of clay oil sludge, 15 parts of waste activated carbon adsorbing VOCs and 85 parts of water.
The preparation method of the hazardous waste high-doping-ratio coal water slurry comprises the following steps:
(1) crushing raw material coal and sieving the crushed raw material coal by a sieve of 10 meshes to obtain coal powder, adding the coal powder and water into a ball mill in proportion, and mixing and ball-milling for 15min to obtain wet-milled coal slurry; the ball milling adopts the grading ball milling of large balls with the diameter of 1.5cm and medium balls with the diameter of 1.0cm, the number ratio of the large balls to the medium balls is 27:36, and the mass ratio of the material balls during ball milling is 500: 625;
(2) crushing the waste activated carbon, sieving the crushed waste activated carbon by a 40-mesh sieve, mixing paint slag, oil-containing sludge, clay oil sludge and the waste activated carbon with water according to a ratio, stirring the mixture at 90 ℃ for 1.5 hours, and simultaneously performing ultrasonic dispersion at an ultrasonic frequency of 60kHz to obtain dangerous waste organic synthetic pulp;
(3) and mixing the wet-milled coal slurry and the hazardous waste organic synthesis slurry, stirring for 2.5 hours at 100 ℃, and then performing ball milling for 8 minutes to obtain the hazardous waste high-doping-ratio coal water slurry.
Example 5:
the procedure in step (2) of example 5 was carried out without ultrasonic dispersion while stirring, and the rest was the same as in example 1.
Comparative example 1 (no paint residue added):
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 282: 171; the components of the wet-milled coal slurry comprise the following components in parts by weight: 240 parts of coal powder and 42 parts of formaldehyde wastewater; the hazardous waste organic synthetic pulp comprises the following components: 53 parts of middle-sea oil oily sludge, 18 parts of clay oil sludge, 15 parts of waste activated carbon adsorbing VOCs, 20 parts of waste sulfuric acid, 20 parts of sulfite pulp waste liquid and 45 parts of waste acetone. The preparation method was the same as in example 1.
Comparative example 2 (no addition of oily sludge):
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 282: 171; the components of the wet-milled coal slurry comprise the following components in parts by weight: 240 parts of coal powder and 42 parts of formaldehyde wastewater; the hazardous waste organic synthetic pulp comprises the following components: 53 parts of paint slag, 18 parts of clay oil sludge, 15 parts of waste activated carbon adsorbing VOCs, 20 parts of waste sulfuric acid, 20 parts of sulfite pulp waste liquid and 45 parts of waste acetone. The preparation method was the same as in example 1.
Comparative example 3 (no clay sludge added):
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 282: 171; the components of the wet-milled coal slurry comprise the following components in parts by weight: 240 parts of coal powder and 42 parts of formaldehyde wastewater; the hazardous waste organic synthetic pulp comprises the following components: 30 parts of paint slag, 41 parts of oily sludge of the middle-sea oil, 15 parts of waste activated carbon adsorbing VOCs, 20 parts of waste sulfuric acid, 20 parts of sulfite pulp waste liquid and 45 parts of waste acetone. The preparation method was the same as in example 1.
Comparative example 4 (no waste activated carbon added):
the hazardous waste high-doping-ratio coal water slurry is prepared by mixing wet-milled coal slurry and hazardous waste organic synthesis slurry in a mass ratio of 282: 171; the components of the wet-milled coal slurry comprise the following components in parts by weight: 240 parts of coal powder and 42 parts of formaldehyde wastewater; the hazardous waste organic synthetic pulp comprises the following components: 30 parts of paint slag, 23 parts of middle-sea oil oily sludge, 33 parts of clay oil sludge, 20 parts of waste sulfuric acid and 20 parts of sulfite process pulp waste liquid
And 45 parts of waste acetone. The preparation method was the same as in example 1.
Comparative example 5 (without grading ball milling):
in step (1) of comparative example 5, ball milling was performed using only large balls having a diameter of 1.5cm, and the rest was the same as in example 1.
The performance indexes of solid and semi-solid hazardous wastes used in the above examples and comparative examples were analyzed, and the performance of the obtained coal water slurry was tested, with the results shown in tables 1 and 2.
Wherein, the solid content is measured by a water meter, namely, about 2 g of sample is weighed and dried for 30 minutes at 105 ℃, and the residual weight is the solid content; the apparent viscosity of the slurry was determined using a Brookfield R/S-CC + type rheometer (C40 rotor)Shear rate of 100s -1 Viscosity at room temperature.
The fluidity and stability (24-hour stability) of the slurry were observed and graded as A + 、A、A - 、B + 、B、B - 、C + 、C、C - 、D + 、D、D - 12 stages in total; fluidity from A + ～D - In the order of decrease, A + For rapid continuous flow, D - Is completely non-flowing; stability from A + ～D - In the order of decreasing, A + To avoid precipitation and precipitation, D - To produce a hard precipitate and cannot be restored to the original state by stirring the slurry.
Table 1: and (5) hazardous waste performance index test results.
Figure BDA0003261773510000071
Table 2: and (5) testing the performance of the coal water slurry.
Figure BDA0003261773510000072
As can be seen from tables 1 and 2, in examples 1 to 3, the mixing ratio of hazardous wastes in the coal water slurry prepared by the formula and the method can reach 20%, and the coal water slurry has high solid content, high heat value, good stability and good fluidity and is beneficial to subsequent utilization. In the preparation process of the coal water slurry in the embodiment 4, clean water is adopted, under the same hazardous waste mixing ratio condition, the solid content, the fluidity and the stability of the coal water slurry are all reduced compared with those in the embodiment 1, and probably because the introduction of sulfuric acid, sulfite, formaldehyde and the like is lacked, the effective components in the hazardous waste cannot react to generate a dispersing agent, so that the performance of the coal water slurry is reduced. The preparation process of the hazardous waste organic synthesis slurry in the embodiment 5 does not carry out ultrasonic dispersion, and the performances of the coal water slurry are also reduced compared with those of the embodiment 1, probably because the auxiliary action of ultrasonic wave is lacked, the activity of the argil is not recovered enough, and the argil cannot play a role in catalyzing the solid acid catalyst, so that the content of the generated dispersant is insufficient, and the performances of the coal water slurry are influenced.
In comparative examples 1-4, the types and proportions of the hazardous wastes in the hazardous waste organic synthetic slurry are changed, and the performance of the finally prepared water-coal-slurry is reduced compared with that in example 1, which shows that the water-coal-slurry can obtain good service performance under the synergistic effect of the hazardous waste components in the invention. Comparative example 5 a grading ball milling method is not used in the process of preparing the wet-milled coal slurry, the size range distribution of the pulverized coal is narrow, the particle filling efficiency is reduced, and the gaps among the particles are large, so that the solid content of the coal water slurry is reduced and the stability is deteriorated.

Claims (9)

1. The hazardous waste high-doping-ratio coal water slurry is characterized by being prepared by mixing wet-milled coal slurry and hazardous waste organic synthetic slurry in a mass ratio of 275-290: 150-185; the components of the wet-milling coal slurry comprise the following components in parts by weight: 235-245 parts of coal powder and 40-45 parts of water; the hazardous waste organic synthesis slurry comprises the following components: 25-35 parts of paint slag, 20-25 parts of oily sludge, 15-20 parts of clay oil sludge, 10-15 parts of waste activated carbon and 80-90 parts of water;
the water in the wet-milled coal slurry is formaldehyde wastewater;
the water in the hazardous waste organic synthesis pulp comprises waste acid, sulfite process pulp waste liquid and waste organic solvent; the waste acid is waste sulfuric acid.
2. The hazardous waste high-doping-ratio coal-water slurry as claimed in claim 1, wherein the waste organic solvent is one or more selected from acetone, ethyl acetate, butyl acetate and n-hexane; the mass ratio of the waste acid to the sulfite process pulp waste liquid to the waste organic solvent is 1-3: 4-5.
3. The preparation method of the hazardous waste high-doping-ratio coal water slurry as claimed in claim 1 or 2, which is characterized by comprising the following steps of:
(1) mixing and ball-milling the coal powder and water in the wet-milled coal slurry to obtain the wet-milled coal slurry, wherein large balls with the diameter of 1.3-1.5 cm and medium balls with the diameter of 0.8-1.0 cm are adopted for ball milling in a grading manner, and the number ratio of the large balls to the medium balls is 25-30: 35-40;
(2) mixing and stirring paint slag, oil-containing sludge, clay oil sludge, waste activated carbon and water in the hazardous waste organic synthetic pulp uniformly to obtain hazardous waste organic synthetic pulp;
(3) and mixing the wet-milled coal slurry and the hazardous waste organic synthesis slurry, uniformly stirring and ball-milling to obtain the hazardous waste high-doping-ratio coal water slurry.
4. The preparation method of the hazardous waste high-doping-ratio coal water slurry as claimed in claim 3, wherein the mass ratio of material balls during ball milling in the step (1) is 500: 620-630.
5. The preparation method of the hazardous waste high-doping-ratio coal water slurry according to claim 3 or 4, characterized in that the coal powder in the step (1) is sieved by a sieve of 10-20 meshes and then mixed with water in the wet-milled coal slurry for ball milling for 10-20 min.
6. The preparation method of the hazardous waste high-doping-ratio coal water slurry as claimed in claim 3, wherein the stirring temperature in the step (2) is 80-100 ℃, and the stirring time is 1-2 hours.
7. The preparation method of the hazardous waste high-doping-ratio coal-water slurry according to claim 3 or 6, characterized in that the mixing and stirring in the step (2) are performed while ultrasonic dispersion is performed.
8. The preparation method of the hazardous waste high-doping-ratio coal water slurry as claimed in claim 7, wherein the ultrasonic frequency is 40-80 kHz.
9. The preparation method of the hazardous waste high-doping-ratio coal water slurry according to claim 3, wherein the stirring temperature in the step (3) is 90-110 ℃, and the stirring time is 2-3 hours; the ball milling time is 5-10 min.
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